COMMONWEALTH of VIRGINIA...research papers Mr. Gullett has published on the subject matter. 4. I have spoken with our air modeling group at DEQ regarding the models currently in use
6
COMMONWEALTH of VIRGINIA DEPARTMENT OF ENVIRONMENTAL QUALITY Street address: 629 East Main Street, Richmond, Virginia 23219 Mailing address: P.O. Box 1105, Richmond, Virginia 23218 Fax: 804-698-4019 - TDD (804) 698-4021 www.deq.virginia.gov David K. Paylor Director (804) 698-4020 1-800-592-5482 Molly Joseph Ward Secretary of Natural Resources March 12, 2015 VIA ELECTRONIC MAIL Mr. Jay Stewart Environmental Manager BAE Systems, Ordnance Systems, Inc. Radford Army Ammunition Plant 4050 Pepper’s Ferry Road Radford, Virginia 24141 Re: Radford Army Ammunition Plant, Radford, VA EPA ID No. VA1210020730, Extension Request for Renewal Application for Reissuance of Facility’s Open Burning Grounds Permit Dear Mr. Stewart: The DEQ received your request for a 120 day extension for the Radford Army Ammunition Plant’s (RAAP) submission of the renewal application for the Open Burning Grounds (OBG) Permit, dated March 2, 2015, via electronic mail on March 9, 2015. As detailed in your request letter, the extension is being requested to allow for additional time to complete the OBG renewal permit application. The extension request is in addition to the already approved 60 day extension, which revised the application submittal to a deadline of June 29, 2015, which was granted in a letter transmitted via electronic mail on February 4, 2015 in order to address issues raised in the Notice of Deficiency for the Energetic Waste Incinerator permit application that are applicable to the OBG as well. While RAAP has requested a 120 day extension for the application deadline, to extend the application submittal deadline to October 28, 2015, the DEQ has determined that an extension of this length is not warranted at this time based on the justification provided. As a result the current deadline for RAAP’s submission of the OBG renewal permit application will remain June 29, 2015. However, as specified in the previous 60 day extension approval letter, dated February 4, 2015, RAAP may submit an additional extension request with proper justification for review by DEQ prior to the expiration of the current deadline.
DEPARTMENT OF ENVIRONMENTAL QUALITY Street address 629 East Main Street Richmond Virginia 23219
Mailing address PO Box 1105 Richmond Virginia 23218
Fax 804-698-4019 - TDD (804) 698-4021
wwwdeqvirginiagov
David K Paylor
Director
(804) 698-4020
1-800-592-5482
Molly Joseph Ward
Secretary of Natural Resources
March 12 2015
VIA ELECTRONIC MAIL
Mr Jay Stewart
Environmental Manager
BAE Systems Ordnance Systems Inc
Radford Army Ammunition Plant
4050 Pepperrsquos Ferry Road
Radford Virginia 24141
Re Radford Army Ammunition Plant Radford VA
EPA ID No VA1210020730 Extension Request for Renewal Application for
Reissuance of Facilityrsquos Open Burning Grounds Permit
Dear Mr Stewart
The DEQ received your request for a 120 day extension for the Radford Army Ammunition
Plantrsquos (RAAP) submission of the renewal application for the Open Burning Grounds (OBG)
Permit dated March 2 2015 via electronic mail on March 9 2015 As detailed in your request
letter the extension is being requested to allow for additional time to complete the OBG renewal
permit application The extension request is in addition to the already approved 60 day
extension which revised the application submittal to a deadline of June 29 2015 which was
granted in a letter transmitted via electronic mail on February 4 2015 in order to address issues
raised in the Notice of Deficiency for the Energetic Waste Incinerator permit application that are
applicable to the OBG as well While RAAP has requested a 120 day extension for the
application deadline to extend the application submittal deadline to October 28 2015 the DEQ
has determined that an extension of this length is not warranted at this time based on the
justification provided
As a result the current deadline for RAAPrsquos submission of the OBG renewal permit application
will remain June 29 2015 However as specified in the previous 60 day extension approval
letter dated February 4 2015 RAAP may submit an additional extension request with proper
justification for review by DEQ prior to the expiration of the current deadline
Mr Jay Stewart March 12 2015
Page 2
Additionally your extension request letter detailed that RAAP had not received contact information for another RCRA OBOD permitted facility which has since ceased their OBOD operations from DEQ yet The contact information was transmitted twice via electronic mail on September 29 2014 included in the second listed item and again on December 18 2914 A copy of these email transmittals has been attached to this letter for your reference If you have any questions regarding this letter please contact me at (804) 698-4467 or by e-mail at AshbyScottdeqvirginiagov
Sincerely
Mr Ashby Scott Title V Coordinator Office of Waste Permitting and Compliance
Attachments
Archived Electronic Mail Transmittal to Mr Jay Stewart dated September 29 2014 Archived Electronic Mail Transmittal to Mr Rob Davie dated December 18 2014
cc Central Hazardous Waste Files Andrea Barbieri EPA Region III (3LC50) Aziz Farahmand DEQ Blue Ridge Regional Office Leslie Romanchik Russ McAvoy Jutta Schneider Kurt Kochan DEQ CO
Jim McKenna Radford Army Ammunition Plant
Archived Monday March 09 2015 35016 PMFrom Scott Ashby (DEQ)Sent Monday September 29 2014 20600 PMTo Stewart Jay (US SSA)Cc McKenna Jim McAvoy Russell (DEQ) Farahmand Aziz (DEQ) Schneider Jutta (DEQ)Kochan Kurt (DEQ) michelegehringcoterie-envcom Mike Lawless (mlawlessdaacom)Janet Frazier (jfrazierdaacom) barbieriandreaepagov Alberts Matt (US SSA)Romanchik Leslie (DEQ) Iyer Sonal (DEQ) Williams Justin (DEQ)Subject Radford Army Ammunition Plant (VA1210020730) OBOD Permit Call-in - September25th Conference CallImportance NormalAttachments Section_Odoc Section_Ndoc Section_Mdoc Section_J_K_LdocSection_Idoc Section_Hdoc Section_Gdoc Section_Fdoc Section_EdocSection_Ddoc Section_Cdoc Checklistdocx Subpart_X_Miscellaneous_UnitspdfSection_A_Bdoc Aurell EFs from Aerial and Ground es402101kpdf Aurell MilitaryWaste online ver es303131kpdf Aurell Gullett et al Chemosphere 85 806-811 2011pdf
___________________________________
Mr Stewart
As a follow up to our conference call on September 25th regarding the RCRA permit forthe open burning grounds at your facility the following information in included to answerthe questions that were brought up during the call
1 The permitting checklists have been attached to this email for your reference Onechecklist is a generalized version for RCRA facilities the second checklist is specific toSubpart X miscellaneous units
2 The contact information for the facility which intends to close an openburningopen detonation ground and ship their energetic wastes off-site to be treated isMr Tim Holden Environmental Safety Manager Aerojet ndash Virginia Operations Phone 540-854-2037 Email timholdenaerojetcom Please contact Mr Holden with anyquestions you have regarding off-site treatment of their waste stream and any analysiswhich was done regarding on-site versus off-site treatment
3 The contact information for the EPA monitoring program for OBOD sites is MrBrian K Gullett PhD US EPA Office of Research and Development National RiskManagement Research Laboratory Phone 919-541-1534 Emailgullettbrianepagov Please contact Mr Gullett for information about the OBODmonitoring program and how RAAP may participate Attached are copies of the
RCRA ID No Facility Name Page O- of O-15
SECTOWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION O SUBPART CC AIR EMISSION STANDARDS
Section and
Requirement
Federal
Regulation
Review
Consideration a
Location in Application b
See Attached Comment
Number c
O-1Standards Apply to All Facilities That Treat Store or Dispose of Hazardous Waste in Tanks Surface Impoundments or Containers Subject to 264 Subparts I J or K Except as Provided Otherwise
27014(a) 27027 2641080 (a) - (d)
Exclusions from 2641080(a) are listed at 2641080(b) (eg a container that has a design capacity less than or equal to 01 cubic meters [m3])
O-2Following is a List of Units that are Exempt from the 2641084-2641087 Standards
27014(a) 27027 2641082(c)
O-2aA Tank Surface Impoundment or Container for Which All Hazardous Waste Entering the Unit Has an Average Volatile Organic Concentration at the Point of Waste Origination of less than 500 Parts per Million by Weight (ppmw)
27014(a) 27027 2641082(c)(1)
Waste determination procedures are specified at 2641083
O-2bA Tank Surface Impoundment or Container for Which the Organic Content of all the Hazardous Waste Entering the Waste Management Unit has been Reduced by an Organic Destruction or Removal Process that Achieves Specified Criteria
27014(a) 27027 2641082(c)(2)
Waste determination procedures are specified at 2651084(b)(2)-(b)(9)
O-2cA Tank Used for Biological Treatment of Hazardous Waste that Destroys or Degrades the Organics Contained in the Hazardous Waste such that the Requirements of 2641082(c)(2)(iv) are Met
27014(a) 27027 2641082(c)(3)
Waste determination procedures are specified at 2641083(b) and 2641083(a)
O-2dA Tank Surface Impoundment or Container for Which all Hazardous Waste Placed in the Unit Meets Applicable Organic Concentration Limits or has been Treated by Appropriate Treatment Technology
27014(a) 27027 2641082(c)(4)
Waste determination procedures are specified at Part 268
O-2eA Tank Located Inside an Enclosure Vented to a Control Device that is Used for Bulk Feed of Hazardous Waste to a Waste Incinerator that Meets Specified Criteria
27014(a) 27027 2641082(c)(5)
Design and operation of the control device and enclosure shall satisfy Part 61 Subpart FF 52741 Appendix B and other conditions as specified
O-3Several Waste Determination Procedures are Explained in Detail and Must be Followed in Order to Demonstrate the Various Subpart CC Exemptions andor Control Requirements
27014(a) 27027 2641083 2651084
In general an owner or operator need not undergo waste determination procedures unless they are pursuing an exemption from the Subpart CC regulations
O-4Tanks that Satisfy the Conditions at 2641084(b)(1)(i-iii) Can Use Tank Level 1 or Tank Level 2 Controls Tanks that do not Satisfy Conditions Shall Use Tank Level 2 Controls
27014(a) 27027 2641084(b)(1) (2)
O-5aThe Conditions at 264108(b)(1)(i-iii) Provide that Hazardous Waste in the Tank Shall
27014(a) 27027 2641084(b)(1)
O-5a(1)Have Maximum Organic Vapor Pressure Which is less than Maximum Organic Vapor Pressure Limit for Tankrsquos Design Capacity Category
27014(a) 27027 2641084(b)(1)
(i)
O-5a(2)Not be Heated to Temperature Greater than Temperature at Which Maximum Organic Vapor Pressure of Waste is Determined for Purposes of Compliance
27014(a) 27027 2641084(b)(1)
(ii)
O-5a(3)Not be Treated Using a Waste Stabilization Process as Defined in 2651081
27014(a) 27027 2641084(b)(1)
(iii)
A waste stabilization process includes mixing hazardous waste with binders or other materials and curing resulting hazardous waste and binder mixture
O-5bMaximum Organic Vapor Pressure Determination
27014(a) 27027 2641084(c) (1)
Must be determined before first time waste placed in tank and retested whenever changes could cause it to increase above the maximum vapor pressure limit [2641084(b)(1)(i)]
O-5b(1)Tank Level 1 OwnerOperator Shall Equip Tanks with Fixed Roof and Closure Devices as Needed
27014(a) 27027 2641084(c)
(2) (3)
Fixed roofclosure devices shall form continuous barrier over entire waste in tank contain no visible open spaces between roof section joints or between interface of roof edge and tank wall contain openings with closure devices or closed-vent system and be made of suitable materials
O-5b(2)Tank Level 2 OwnerOperator Shall Use One of the Following Tanks
27014(a) 27027 2641084(d)
O-5b(2)(i)Fixed Roof Tank Equipped with Internal Floating Roof
27027(a)(1) 2641084(d)(1) (e)
Internal floating roof shall be designed to float on liquid surface except when supported by leg supports be equipped with continuous seal between tank wall and floating roof edge and meet other design specifications
O-5b(2)(ii)Tank Equipped with an External Floating Roof
27027(a)(1) 2641084(d)(2) (f)
External floating roof shall be designed to float on all liquid surface except when supported by leg supports be equipped with two continuous seals and meet other design specifications
O-5b(3)Tank Vented Through Closed-Vent System to a Control Device
27014(a) 27027 2641084(d)(3) (g)
Fixed roofclosure devices shall form continuous barrier over entire liquid surface be made of suitable materials and satisfy 2641087 standards
O-5cPressure Tank
27014(a) 27027 2641084(d)(4) (h)
Tank shall be designed not to bend to atmosphere as result of compression of vapor headspace in tank and be equipped with closure devices as needed
O-5dTank Located Inside an Enclosure that is Vented Through a Closed-Vent System to an Enclosed Combustion Control Device
27014(a) 27027 2641084(d)(5) (1)
Tank shall be located in enclosure that is vented through closed vent system to enclosed combustion device and enclosure shall be equipped with safety devices as needed
O-5eTank Level 1 OwnerOperator Shall
27014(a) 27027 2641084(c)
(1)(3)
O-5e(1)Determine Maximum Organic Vapor Pressure for Hazardous Waste Initially and Whenever Changes could Cause the Vapor Pressure to Increase Above the Maximum Organic Vapor Pressure Limit
27014(a) 27027 2641084(c)(1)
Maximum organic vapor pressure shall be determined using 2641083(c) procedures
O-5e(2)Ensure that Whenever Hazardous Waste is in Tank the Fixed Roof is Installed with Each Closure Device Secured in Closed Position
Exceptions are listed at 2641084(c)(3)(i-iii)
O-5e(3)Inspect the Air Emission Control Equipment
27014(a) 27027 2641084(c)(4)
O-5fTank Level 2 OwnerOperators Shall Adhere to the Following Operating Procedures for Each Unit Type
27014(a) 27027 2641084(e)(i)
O-5f(1)Fixed Roof Tank Equipped with Internal Floating Roof
27014(a) 27027 2641084(e) (2)(3)
When floating roof is resting on leg supports filling emptying or refilling shall be continuous and completed as soon as practical when roof is floating automatic bleeder vents shall be set closed and prior to filling openings in roof shall be secured Inspect the floating roof
O-5f(2)Tank Equipped with an External Floating Roof
27014(a) 27027 2641084(f)
(2)(3)
When floating roof is resting on leg supports filling emptying or refilling shall be continuous and completed as soon as practical when closure device is open for access equipment and devices shall be closed and secured as specified and seals shall provide a continuous and complete cover as specified Inspect the floating roof
O-5f(3)Tank Vented Through Closed-Vent System to a Control Device
27014(a) 27027 2641084(g)
(2) (3)
When hazardous waste is in tank fixed roof shall be installed with closure devices secured in closed position and vapor headspace underneath fixed roof vented to control device except as specified Inspect and monitor the air emission control equipment
O-5f(4)Pressure Tank
27014(a) 27027 2641084(h)
(2) (3)
When hazardous waste is in tank it shall be operated as closed system that does not vent to atmosphere except to avoid an unsafe condition
O-5f(5)Tank Located Inside an Enclosure that is Vented Through a Closed-Vent System to an Enclosed Combustion Control Device
27027(a)(3) 2641084(i)
Enclosure shall be operated in accordance with 52741 Appendix B and comply with applicable closed-vent requirements Safety devices may be operated as needed Inspect and monitor the system and control device
O-5f(6)Shall be Conducted Using Continuous Hard-Piping or Another Closed System that Does Not Allow Exposure of Hazardous Waste to Environment
27014(a) 27027 2641084(j)(1)
Requirements do not apply under the conditions specified at 2641084(j)(2)
O-6aOwnerOperators Shall Install Either of the Following Controls
27014(a) 27027 2641085(b)(d)
O-6a(1)Floating Membrane Cover
27027(a)(4) 2641085
(b)(1) (c)(1)
Floating membrane cover shall float on liquid surface and form continuous barrier over entire liquid be made of synthetic membrane material contain no visible open spaces and be equipped with closure devices and cover drains as needed
O-6a(2)Cover That Is Vented Through a Closed-Vent System to a Control Device
27014(a) 27027 2641085
(b)(2) and (d)(2)
Coverclosure devices shall form continuous barrier over entire liquid surface be equipped with closure device be made of suitable material and be designed in compliance with 2641087
O-6bOwnerOperators Shall Adhere to the Following Operating Procedures for Each Control Type
27014(a) 27027 2641085
(c) (d)
O-6b(1)Floating Membrane Cover
27014(a) 27027 2641085(c)
(2) (3)
When hazardous waste is in surface impoundment floating membrane cover shall float on liquid and each closure device shall be secured in closed position except as specified Inspect the cover
O-6b(2)Cover that is Vented Through a Closed-Vent System to a Control Device
27014(a) 27027 2641085(d) (2) (3)
When hazardous waste is in surface impoundment cover shall be installed with each closure device secured in closed position and vapor headspace underneath the cover vented to control device except as specified Closed-vent system and control device shall be operated in accordance with 2641087 Inspect and monitor the control device
O-7Shall be Conducted Using Continuous Hard-Piping or Another Closed System
27014(a) 27027 2641085(c)
(1)
Requirements do not apply under conditions specified at 2641085(e)(2)
O-8aContainer Level 1 Standards Apply to
27014(a) 27027 2641086(b)(1)
O-8a(1)Container with Design Capacity Greater than 01 m3 and less than or Equal to 046 m3
27014(a) 27027 2641086(b)(1)
(i)
O-8a(2)Container with Design Capacity Greater than 046 m3 that is not in Light Material Service
27014(a) 27027 2641086(b)(1)
(ii)
O-8abContainer Level 2 Standards Apply to Container with a Design Capacity Greater than 046 m3 that is in Light Material Service
27014(a) 27027 2641086(b)(1)
(iii)
O-8cContainer Level 3 Standards Apply to Container with Design Capacity Greater than 01 m3 that is Used for Stabilization
27014(a) 27027 2641086(b)(2)
Level 3 standards apply at those times during waste stabilization process when hazardous waste in container is exposed to atmosphere
O-9Identify Each Container Area Subject to Subpart CC
27027(a)(2)
O-9aContainer Level 1 A Container Using Level 1 Controls is Defined as One of the Following
27027(a)(2) 2641086(c)
(1)
O-9a(1)Container that Meets Department of Transportation Regulations on Packaging
27027(a)(2) 2641086(c)
(1)(i)(f)
Container shall meet Part 178 or Part 179 and be managed in accordance with Parts 107 172 173 and 180
O-9a(2)Container Equipped with Cover and Closure Devices
27027(a)(2) 2641086(c)
(1)(ii)(2)
Container shall be equipped with covers and closure devices as needed
O-9a(3)Open-Top Container Equipped with Organic-Vapor Suppressing Barrier
27027(a)(2) 2641086(c)
(1)(iii)(2)
Container shall be equipped with covers and closure devices as needed
O-9bContainer Level 2 A Container Using Level 2 Controls is Defined as One of the Following
27027(a)(2) 2641086
(d)(1)(f)(g)
O-9b(1)Container that Needs Department of Transportation (DOT) Regulations on Packaging
27027(a)(2) 2641086(d)(1)
(i)(f)
Containers shall meet Part 178 or Part 179 and be managed in accordance with Parts 107 172 173 and 180
O-9b(2)Container that Operates with No Detectable Organic Emissions
27027(a)(2) 2641086(d)(1)
(ii)(g)
Owneroperator shall follow the procedures at 2641086(g) and 2651084(d) to determine no detectable organic emissions
O-9b(3)Container that has been Demonstrated Within the Preceding 12 Months to be Vapor-Tight
27027(a)(2) 2641086(d)(1)
(iii) and (h)
Owneroperator shall follow procedures at 2641086(h) and Part 60 Appendix A Method 27 to demonstrate container is vapor-tight
O-9cContainer Level 3 A Container Using Level 3 Controls is Defined as One of the Following
27027(a)(2) 2641086(e)
(1) (2)
O-9c(1)Container that is Vented Directly Through a Closed-Vent System to a Control Device
27027(a)(2) 2641086(e)
(1)(i)
The closed-vent system and control device shall be designed in accordance with 2641087 Safety devices may be installed as needed
O-9c(2)Container that is Vented Inside an Enclosure Which is Exhausted Through a Closed-Vent System to a Control Device
27027(a)(2) 27027(a)(3) 2641086(e)
(1)(ii)
The containerenclosure must be designed in accordance with 52741 Appendix B and 2641087 Safety devices may be installed as needed
O-10aContainer Level 1 OwnerOperators Shall Install Covers and Closure Devices for the Container and Secure and Maintain Each Closure Device in Closed Position Except as Specified
27014(a) 27027 2641086(c)
(3) (4)
The closure device or cover may be opened for the purpose of adding or removing hazardous waste or for maintenance or to avoid unsafe conditions
O-10bContainer Level 2 OwnerOperator Shall Install All Covers and Closure Devices for the Container and Maintain and Secure Each Closure Device in Closed Position Except as Specified
27014(a) 27027 2641086(d)(2) (3)
Transfer of hazardous waste in or out of container shall be conducted in such a manner as to minimize exposure to atmosphere as practical The closure device or cover may be opened for the purpose of adding or removing hazardous waste or for maintenance or to avoid unsafe conditions
O-10cContainer Level 3 OwnerOperators Shall Operate the System in Accordance with 52741 Appendix B 2641087 and 2651081 as Needed
27014(a) 27027 2641086(e)
(3)(4) (5)
O-11aStandards Apply to Each Closed-Vent System and Control Device Used to Control Air Emissions under Part 264 Subpart CC
27014(a) 27027 2641087(a)
O-11(b)Closed-Vent Systems Shall
27027(a)(5) 2641087(b)
O-11b(1)Route Gases Vapors and Fumes to Control Device
27027(a) 2641087(b)(1)
O-11b(2)Be Designed and Operated in Accordance with 2641033(k)
27027(a) 2641087(b)(2)
The Subpart AA standards for closed-vent systems must be satisfied
O-11b(3)Meet the Requirements for Bypass Devices if Applicable
27027(a) 2641087(b)(3)
Each bypass device shall be equipped with either a flow indicator or a seal or locking device
O-12aThe Control Device Shall be One of the Following
27027(a)(5) 2641087(c)(1)
O-12a(1)A Control Device Designed and Operated to Reduce Total Organic Content on Inlet Vapor Stream Vented to the Control Device by at Least 95 Percent by Weight
27027(a)(5) 2641087(c)
(1)(i)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified
O-12a(2)An Enclosed Combustion Device
27027(a)(5) 2641087(c)
(1)(ii)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified Control device shall be designed and operated in accordance with 2641033(c)
O-12a(3)A Flare
27027(a)(5) 2641087(c)
(1)(iii)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified
O-12bEach Closed-Vent System and Control Device Shall Comply with the Operating Requirements of 2641087(c)(2)
27027(a)(5) 2641087(c)
(2)
Planned routine maintenance of control device shall not exceed 240 hours per year system malfunctions shall be corrected as soon as practicable and system shall be operated such that gases vapors or fumes are not actively vented to control device during planned maintenance or system malfunction except as specified
O-12cA Carbon Adsorption System
27027(a)(5) 2641087(c)
(3)
Carbon replacement and removal shall follow prescribed requirements in 2641033(g) (h) and (n)
O-12dEach Control Device Shall be Operated and Maintained in Accordance with 2641033(j) Except for Certain Devices Identified (eg Flare)
27027(a)(5) 2641087(c)
(4)
2641033(j) requires the owneroperator to prepare documentation describing the control devicersquos operation and to identify the process parameter(s) that indicate its proper operation and maintenance
O-12eThe OwnerOperator Shall Demonstrate that a Control Device Achieves the Performance Requirements Using a Performance Test or Design Analysis Except for Specific Devices Identified (eg flare)
27027(a)(5) 2641087(c)
(5)
For performance test owneroperator shall use the test specified at 264103(c) For design analysis owneroperator shall use an analysis that meets requirements specified at 2641035(b)(4)(iii) In addition the US Environmental Protection Agency (EPA) prescribes unit-specific performance demonstration requirements for certain unit types at 2641087(c)(5)
O-12fIf Design Analysis is Not Sufficient then a Performance Test is Required
27027(a)(5) 2641087(c) (6)
The EPA regional administrator shall determine if a performance test is required to demonstrate control devicersquos performance
O-12hInspect and Monitor the Control Device
27027(a)(5) 2641087(c) (7)
Control devices shall be inspected and monitored at least once a day
O-13Each Tank Surface Impoundment and Container Shall be Inspected Monitored and Repaired in Accordance with the 264 Subpart CC Requirements
27027 2641088
Inspection monitoring and repair requirements specific to each unit are located in the standards sections of the regulation 2641084 through 2641087 Owneroperator shall develop and implement written plan and schedule to perform inspections and monitoring required The plan and schedule shall be incorporated into facilityrsquos inspection plan
O-14Each OwnerOperator Shall Comply with the Recordkeeping Requirements Specified at 2641089
27027 2641089
Except as specified records shall be maintained in facilityrsquos operating record for a minimum of 3 years Various records are required depending on the type of unit and control device
O-14aEach of the Following OwnerOperators Shall Comply with the Reporting Requirements at 2641090
27027 2641090
O-14a(1)Each OwnerOperator Managing Hazardous Waste in a Tank Surface Impoundment or Container Exempted from Using Air Emission Controls under 2641082(c)
27027 2641090(a)
Owneroperator shall report to EPA each noncompliance identified under 2641082(c)
O-14a(2)Each Owneroperator Using Air Emission Controls on a Tank in Accordance with 2641084(c)
27027 2641090(b)
Owneroperator shall report to EPA each noncompliance identified under 2641084(B)
O-14a(3)Each Owneroperator Using a Control Device in Accordance with 2641087
27027 2641090
(c)(d)
Owneroperator shall submit semiannual written report to EPA except as specified
O-14bEach OwnerOperator shall Provide an Emission Monitoring Plan
27027(a)(6)
Applies to Method 21 and control device monitoring methods
O-14cSubpart CC Implementation Plan
27027(a)(7)
Required when facility cannot comply with Subpart CC by date of permit issuance
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
RCRA ID No Facility Name Page N- of N-7
SECTNWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION N SUBPART BB EQUIPMENT LEAKS
Section and
Requirement
Federal
Regulation
Review
Consideration a
Location in Application b
See Attached Comment Numberc
N-1aApplicability
27014(a) 27025 2641050(b)(d)
Except as otherwise specified this subpart applies to equipment that contains or contacts hazardous waste with organic concentrations of at least 10 percent by weight that are managed in one of the following if these operations are conducted in a unit subject to the permitting requirements of 270 a unit (including a hazardous waste recycling unit) that is not exempt from permitting under 26234(a) and is located at a hazardous waste management facility otherwise subject to permitting requirements and a unit that is exempt from permitting under 26234(a) such as a 90-day tank or container
N-1bDefinition of Equipment
27014(a) 27025 2641031 2641051
Examples include valve pump compressor pressure relief device sampling connection system open-ended valve or line or flange
N-1cEquipment in a Vacuum or Equipment that Contains or Contacts Hazardous Waste with an Organic Concentration of at Least 10 Percent by Weight for a Period of Less than 300 Hours per Calendar Year is Excluded from Requirements at 2641052 to 2641060
27014(a) 27025 2641050(f)
Equipment shall be identified in a log in facilityrsquos operating record as required by 2641064(g) in order to qualify for exclusion
N-2aMonthly Monitoring for Leaks
27025(d) 2641052(a)
(1)
N-2bVisual Inspection for Pump Seal Leakage on a Weekly Basis
27025(d) 2641052(a)(2)
N-2cLeak Detection
27025(d) 2641052(b) 2641063
Leak detected if (1) leak detection instrument reads 10000 parts per million (ppm) or greater or (2) there are indications of liquid dripping from the pump seal
N-2dLeak Repair as Soon as Practicable
27025(d) 2641052(c) 2641059
Repairs are to be made within 15 calendar days after detection Repair extensions are allowed under conditions specified in 2641059
N-2eSpecific Exceptions to these Standards
27025(d) 2641052(d - f)
Exceptions to these standards are dual mechanical seal systems or no detectable emissions
N-3aBarrier Fluid Pressure Greater than the Compressor Stuffing Box Pressure
27025(d) 2641053(b)
(1)
N-3bBarrier Fluid System Connected by a Closed-Vent System to a Control Device as Described in Subpart AA
27025(d) 2641053(b)
(2)
N-3cNo Detectable Atmospheric Emissions of Hazardous Contaminants from the Barrier System
27025(d) 2641053(b)
(3)
N-3dSensors Checked Daily or an Audible Alarm Checked Monthly
27025(d) 2641053(d - c)
N-3eLeak Detection
27025(d) 2641053(f)
A leak is detected if sensor indicates failure of (1) seal system or (2) barrier fluid system
N-3fLeak Repair as Soon as Practicable
27025(d) 2641053(g)
(1) 2641059
Repairs are to be made within 15 calendar days after detection Repair extensions are allowed under conditions specified in 2641059
N-3gSpecific Exceptions to these Standards
27025(d) 2641053(h - i)
Exceptions to these standards are certain closed vent systems or no detectable emissions
N-4aExcept During Pressure Releases No Pressure Relief Device Shall Release Detectable Emissions
27025(d) 2641054(a)
Emissions shall be less than 500 ppm above background levels
N-4bWithin 5 Calendar Days after a Pressure Release No Detectable Emissions Shall Emanate from Pressure Released Device
27025(d) 2641054(b)
Emissions shall be less than 500 ppm above background levels
N-4cSpecific Exceptions to These Standards
27025(d) 2641054(c)
Exceptions to these standards are certain closed vent systems
N-5aEach Sampling Connecting System Shall Be Equipped with a Closed-Purge Closed Loop or Closed-Vent System Closed-Vent Systems and Control Devices are also Subject to 2641033
27025(d) 2641055(a - b) 2641060
Each closed-purge closed-loop or closed-vent system shall either (1) return purged process fluid directly to process line (2) collect and recycle purged process liquid or (3) be designed and operated to capture and transport all purged process fluid to a waste management unit or control device that satisfies applicable requirements
N-5bExemption for Qualified Sampling Systems
27025(d) 2641055(c)
In situ sampling systems and sampling systems without purges are exempt from requirements of 2641055(a)(b)
N-6aOpen-Ended Valve or Line
27025(d) 2641056(a) (c)
A double block or bleed system must comply with the open-ended valve or line requirements
N-6bSecond Valve
27025(d) 2641056(b)
A second valve shall be operated such that primary valve shall be closed before second valve is opened
N-7Monitoring Schedule Based on Detection of Leaks and Predetermined Schedule
27025(d) 2641057(a - e)
A reading of 10000 ppm denotes a detected leak
N-7dSpecific Exceptions to the Monitoring Schedule
27025(d) 2640157(f - h) 2641061 2641062
Exceptions to schedule include unsafe-to-monitor valves no detectable emissions and difficult-to-monitor valves
N-8aMonitoring
27025(d) 2641058(a) 2641063(b)
Monitoring is required within 5 days after leak is found by sight sound smell or other detection method
N-8bLeak Detection
27025(d) 2641058(b)
A leak is detected if a leak detection instrument reads 10000 ppm or greater
N-8cLeak Repair as Soon as Practicable
27025(d) 2641058(c) 2641059
Repairs are to be made within 15 calendar days after detection The first attempt at repair shall be made no later than 5 calendar days after each leak is detected Repair extensions are allowed under conditions specified in 2641059
N-8dAny Connector that is Inaccessible or is Ceramic or Ceramic-Lined is Exempt from the Monitoring Requirements of 2641058(a) and 2641064
27025(d) 2641058(e)
Examples of ceramic-lined connectors include porcelain glass or glass-lined connectors
N-9Specific Allowances for Delay of Repair for Various Types of Equipment
27025(d) 2641059
N-10When Closed-Vent Systems and Control Devices are Used they Must Comply with the Requirements in Subpart AA
27025(e) 2641033 2641060
N-11An OwnerOperator may Elect to Comply with this Alternative Monitoring Program
27025(e) 2641061
No greater than 2 percent of the valves are allowed to leak per monitoring period
N-12An OwnerOperator may Elect to Comply with this Alternative Work Practice
27025(e) 2641062
Relief of monitoring frequency is allowed if less than 2 percent of the valves are leaking
N-13Owner Complies with Recordkeeping Requirements
27025(a) 2641064
Depending on the type of requirement various records must be maintained in the facility operating record
N-13aSemiannual Report
27025(a) 2641065
A semiannual report is only required if leaks from equipment have gone unrepaired or a control device operates outside the design specifications
N-13bImplementation Schedule
27025(b)
An implementation schedule shall be provided if facility cannot install closed-vent system and control device to comply with provisions of Part 264 Subpart BB on the effective date that facility becomes subject to provisions of Parts 264 and 265
N-13cPerformance Test Plan
27025(c)
A performance test plan shall be provided if the owneroperator applies for permission to use a control device for other than a thermal vapor incinerator flare boiler process heater condenser or carbon adsorption system and chooses to use test data to determine the organic removal efficiency achieved by the control device
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
RCRA ID No Facility Name Page N- of N-7
SECTNWPDReviewer
Checklist Revision Date (December 1997)
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
RCRA ID No Facility Name Page M- of M-8
SECTMWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION M SUBPART AA PROCESS VENTS
Section and
Requirement
Federal Regulation
Review
Consideration a
Location in Application b
See Attached Comment Numberc
M-1Definition of Process Vent
27014(a) 2641030 2641031
A process vent is any open-ended pipe or stack that is vented to atmosphere either directly through a vacuum-producing system or through a tank
M-2ApplicabilitymdashProcess Vents Associated with the Following Six Operations that Manage Hazardous Waste with Organic Concentrations of at Least 10 Parts per Million by Weight if these Operations are Conducted in a Unit Subject to the Permitting Requirements of 270 a Unit (including a Hazardous Waste Recycling Unit) that is Not Exempt from Permitting Under 26234(a) and is Located at a Hazardous Waste Management Facility Otherwise Subject to Permitting Requirements and a Unit that is Exempt from Permitting Under 26234(a)
27014(a) 2641030(b) 2641031
Concentrations should be determined by a time-weighted average annually or when waste or process changes
M-2aDistillationmdasha Batch or Continuous Operation Which Separates One or More Feed Stream(s) into Two or More Exit Streams Each Exit Stream Having Component Concentrations Different from Those in the Feed Stream(s)
27024(b)(3) 2641030(b) 2641031
Include process description
M-2bFractionationmdasha Distillation Operation or Method Used to Separate a Mixture of Several Volatile Components of Different Boiling Points in Successive Stages
27024(b)(3) 2641030(b) 2641031
Include process description
M-2cThin-Film Evaporationmdasha Distillation Operation that Employs a Heating Surface Consisting of a Large Diameter Tube that May be Either Straight or Tapered Horizontal or Vertical
27024(b)(3) 2641030(b) 2641031
Include process description
M-2dSolvent Extractionmdashan Operation or Method of Separation in Which a Solid or Solution Contacts a Liquid Solvent (The Two Being Mutually Insoluble) to Preferentially Dissolve and Transfer One or More Components into the Solvent
27024(b)(3) 2641030(b) 2641031
Include process description
M-2eAir Strippingmdasha Desorption Operation Employed to Transfer One or More Volatile Components from a Liquid Mixture into a Gas (Air) Either with or Without the Application of Heat to the Liquid
27024(b)(3) 2641030(b) 2641031
Include process description
M-2fStream Strippingmdasha Distillation Operation in Which Vaporization of the Volatile Constituents of a Liquid Mixture Takes Place by the Introduction of Steam Directly into the Charge
27024(b)(3) 2641030(b) 2641031
Include process description
M-3aReduce Total Organic Emission below 14 Kilogram per Hour (3 Pounds per Hour) and 28 Million Grams per Year (31 Tons per Year) or
27024(b) 2641032(a)
(1)(c)
Engineering calculations or performance tests may be used to determine vent emissions and emissions reductions or total organic compound concentrations achieved by add-on control devices
M-3bReduce Total Organic Emissions of 95 Percent by Weight with the Use of a Control Device
27024(b) 2641032(a)
(2)(b)
Engineering calculations or performance tests may be used to determine vent emissions and emissions reductions or total organic compound concentrations achieved by add-on control devices
M-3cReduce Emissions for Various Control Devices with Closed-vent Systems under the Following Operational Conditions
27024(b) 2641032(a - b) 2641033
(b - j)
Closed-vent systems are optional devices but shall comply with regulations if they are used
M-3c(1)Control Device Involving Vapor Recovery (Condenser or Adsorber) Shall Recover at Least 95 Percent by Weight of the Organic Vapors
27024(b) 2641032(a)
(1)(b)
A less than 95 percent recovery is permissible if control devices meet emission limits set in 2641032(a)(1)
M-3c(2)Enclosed Combustion Device (A Vapor Incinerator Boiler or Process Heater) Shall Recover at Least 95 Percent by Weight of Organic Emissions
27024(d) 2641033(c)
The device shall achieve 20 parts per million by weight or 12 second residence time at 760 EC
M-3c(3)A Flare Shall Operate under the Following Four Conditions (1) No Visible Emissions (2) a Flame Present at all Times (3) an Acceptable Net Heating Value and (4) Appropriate Exit Velocity
27024(d) 2641033(d)
M-4Inspection Readings Shall Be Conducted at Least Daily Vent Stream Flow Information Shall be Provided at Least Hourly
27024(d) 2641033(f)
(1)(3)
M-4aContinuous Monitoring for the Following Control Devices
27024(d) 2641033(f)(2)
M-4a(1)Thermal Vapor Incinerator (One Temperature Sensor)
27024(d) 2641033(f)(2)(i)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(2)Catalytic Vapor Incinerator (Two Temperature Sensor)
27024(d) 2641033(f)(2)(i)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(3)Flare (Heat Sensing Device)
2641033(f)(2)(iii)
M-4a(4)Boiler or Process Heater with Heater Input Capacity Equal or Greater than 44 Megawatts (Recorder Which Indicates Good Combustion Practices)
27024(d) 2641033(f)(2)(v)
M-4a(5)Condenser (Device with Recorder to Measure the Concentration of Organic Compounds in the Condenser Exhaust Vent Stream or Temperature Monitoring Device Equipped with Recorder to Measure Temperature in the Condenser Exhaust Vent Stream)
27024(d) 2641033(f)(2)(vi)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(6)Carbon Adsoprtion System (Device to Measure Organic Vapors or a Recorder that Verifies Predetermined Regeneration Cycle)
27024(d) 2641033(f)(2)(vii)
M-4bAlternate Monitoring of Control Device
27024(c) 2641033(i)
Describe measurement of applicable monitoring parameters
M-4cInspection of the Following Control Devices
27024(d) 2641033(g - h)
M-4c(1)Regenerable Carbon Adsorption System
27024(d) 2641033(g)
Carbon replacement schedule must be acceptable
M-4c(2)Nonregenerable Carbon Adsoprtion System
27024(d) 2641033(h)
Carbon shall be replaced when breakthrough is observed or on an acceptable schedule
M-5Basic Design and Operation
M-5aThe Closed-Vent System Shall be Designed to Operate According to Either of the Following
27024(d) 2641033(k)
M-5a(1)With No Detectable Emissions
27024(d) 2641033(k)(1)
Emissions shall be less than 500 parts per million above background
M-5a(2)At a Pressure below Atmospheric Pressure
27024(d) 2641033(k)(2)
System shall be equipped with at least one pressure gauge or other measurement device that can be read from a readily accessible location to verify negative pressure is being maintained in system during operation
M-5bOwneroperator Shall Monitor and Inspect Each System
27024(d) 2641033(1)
The monitoring and inspection shall be done (1) by date the system is subject to regulation (2) annually and (3) other times requested by the US Environmental Protection Agency regional administrator Various inspection and monitoring requirements apply depending upon the type of closed-vent system employed All detected defects shall be repaired according to the schedule prescribed in 2641033(l)(3)
M-5cClosed-Vent System Shall be Operated at all Times When Emissions May be Vented to Them
27024(d) 2641033(m)
M-5dCarbon Adsorption System Used to Control Air Pollutant Emissions
27024(d) 2641033(n)
Owneroperator must document that all carbon that is a hazardous waste and removed from the control device is managed in one of these approved manners 2641033(n)(1) (2) or (3)
M-6Any Components of a Closed-Vent System that are Designated as Unsafe to Monitor are Exempt from the Monitoring Requirements of 1033(l)(1)(i)(B) if Certain Conditions are Met
27024(d) 2641033(o)
Applies to system if its components are unsafe to monitor and it adheres to written plan that requires monitoring using the procedures in 2641033(l)(1)(ii)(B) as frequently as practicable during safe-to-monitor times
M-7aOwneroperator Complies with Record Keeping Requirements
27024(d) 2641033 2641035
Depending on the type of control devices and closed vent systems used various records must be maintained in the facility operating record
M-7bSemiannual Report is Submitted According to Subpart AA Requirements
27014(a) 2641036
A semiannual report is only required if a control device operates outside the design specifications
M-7cImplementation Schedule is Provided
27024(a) 2641033(a)(2)
A schedule shall be provided when facilities cannot install a closed-vent system and control device to comply with Part 264 on date facility is subject to requirements
M-7dPerformance Test Plan is Provided
27024(c) 2641035(b)(3)
A performance test plan shall be provided where owneroperator applies for permission to use control device other than thermal vapor incinerator catalytic vapor incinerator flare boiler process heater condenser or carbon adsorption system and chooses to use test data to determine organic removal efficiency achieved by control device
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
Revised 12001
J CORRECTIVE ACTION FOR SOLID WASTE MANAGEMENT UNITS
J-1 Solid Waste Management Units 9 VAC 20-60-264 and 1010M 40 CFR 264101
Identify all solid waste management units at the facility including hazardous and non-hazardous units as well as active and inactive units if known A solid waste management unit may include any of the following
Landfill
Surface Impoundment
Waste pile
Land treatment unit
Tank (including 90-day accumulation tank)
Injection well
Incinerator
Wastewater treatment tank
Container storage area
Waste handling area
Transfer station and
Waste recycling operation
J-1a Characterize the Solid Waste Management Unit
For each solid waste management unit submit the following information
Type of each unit
Location of each existing or closed unit on the topographic map [See comment B-2]
Engineering drawings of the unit if available
Dimensions and materials of construction of each unit
Dates when the unit was in operation
Quantity or volume of waste if known
J-1b No Solid Waste Management Units
Describe the methodology used to determine that no existing or former solid waste management units exist at the facility (eg review of old solid waste permits blueprints)
J-2 Releases
Provide all information available including releases reported under CERCLA Section 103 on whether or not releases have occurred from any solid waste management units at the facility Reasonable efforts to identify releases must be made even if releases have not been verified (A release may include spilling leaking pumping pouring emitting emptying discharging injecting escaping leaching dumping or disposing into the environment It does not include releases otherwise permitted or authorized under law)
J-2a Characterize Releases
Information on releases must include the following types of available information concerning prior or current releases
Date of the release
Type of waste constituent released
Nature of the release
-spill
-overflow
-ruptured pipe or tank
-result of the units construction (eg unlined surface impoundment leaky tank)
Groundwater monitoring and other analytical data available to describe nature and extent of release If other than groundwater monitoring data please describe
Physical evidence of distressed vegetation and soil contamination
Historical evidence of releases such as tanker truck accidents
Any state local or federal enforcement action that may address releases
Any public citizen complaints about the facility that could indicate a release and
Any information showing the migration of a release
J-2b No Releases
Describe the methodology used to determine that releases from solid waste management units are not present (eg review of groundwater monitoring data)
K OTHER FEDERAL LAWS 9 VAC 20-60-1010I13 and 1200C1c
Demonstrate compliance with the requirements of applicable Federal laws such as the Wild and Scenic Rivers Act National Historic Preservation Act of 1966 Endangered Species Act Coastal Zone Management Act and Fish and Wildlife Coordination Act
L PART B CERTIFICATION 9 VAC 20-60-1030A and 1030B
Applications must be accompanied by a certification letter as specified in 1030D The required signatures are as follows (1) for a corporation a principal executive officer (at least at the level of vice-president) (2) for a partnership or sole proprietorship a general partner or the proprietor respectively (3) for a municipal state Federal or other public agency either a principal executive officer or ranking elected official
Mr Jay Stewart March 12 2015
Page 2
Additionally your extension request letter detailed that RAAP had not received contact information for another RCRA OBOD permitted facility which has since ceased their OBOD operations from DEQ yet The contact information was transmitted twice via electronic mail on September 29 2014 included in the second listed item and again on December 18 2914 A copy of these email transmittals has been attached to this letter for your reference If you have any questions regarding this letter please contact me at (804) 698-4467 or by e-mail at AshbyScottdeqvirginiagov
Sincerely
Mr Ashby Scott Title V Coordinator Office of Waste Permitting and Compliance
Attachments
Archived Electronic Mail Transmittal to Mr Jay Stewart dated September 29 2014 Archived Electronic Mail Transmittal to Mr Rob Davie dated December 18 2014
cc Central Hazardous Waste Files Andrea Barbieri EPA Region III (3LC50) Aziz Farahmand DEQ Blue Ridge Regional Office Leslie Romanchik Russ McAvoy Jutta Schneider Kurt Kochan DEQ CO
Jim McKenna Radford Army Ammunition Plant
Archived Monday March 09 2015 35016 PMFrom Scott Ashby (DEQ)Sent Monday September 29 2014 20600 PMTo Stewart Jay (US SSA)Cc McKenna Jim McAvoy Russell (DEQ) Farahmand Aziz (DEQ) Schneider Jutta (DEQ)Kochan Kurt (DEQ) michelegehringcoterie-envcom Mike Lawless (mlawlessdaacom)Janet Frazier (jfrazierdaacom) barbieriandreaepagov Alberts Matt (US SSA)Romanchik Leslie (DEQ) Iyer Sonal (DEQ) Williams Justin (DEQ)Subject Radford Army Ammunition Plant (VA1210020730) OBOD Permit Call-in - September25th Conference CallImportance NormalAttachments Section_Odoc Section_Ndoc Section_Mdoc Section_J_K_LdocSection_Idoc Section_Hdoc Section_Gdoc Section_Fdoc Section_EdocSection_Ddoc Section_Cdoc Checklistdocx Subpart_X_Miscellaneous_UnitspdfSection_A_Bdoc Aurell EFs from Aerial and Ground es402101kpdf Aurell MilitaryWaste online ver es303131kpdf Aurell Gullett et al Chemosphere 85 806-811 2011pdf
___________________________________
Mr Stewart
As a follow up to our conference call on September 25th regarding the RCRA permit forthe open burning grounds at your facility the following information in included to answerthe questions that were brought up during the call
1 The permitting checklists have been attached to this email for your reference Onechecklist is a generalized version for RCRA facilities the second checklist is specific toSubpart X miscellaneous units
2 The contact information for the facility which intends to close an openburningopen detonation ground and ship their energetic wastes off-site to be treated isMr Tim Holden Environmental Safety Manager Aerojet ndash Virginia Operations Phone 540-854-2037 Email timholdenaerojetcom Please contact Mr Holden with anyquestions you have regarding off-site treatment of their waste stream and any analysiswhich was done regarding on-site versus off-site treatment
3 The contact information for the EPA monitoring program for OBOD sites is MrBrian K Gullett PhD US EPA Office of Research and Development National RiskManagement Research Laboratory Phone 919-541-1534 Emailgullettbrianepagov Please contact Mr Gullett for information about the OBODmonitoring program and how RAAP may participate Attached are copies of the
RCRA ID No Facility Name Page O- of O-15
SECTOWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION O SUBPART CC AIR EMISSION STANDARDS
Section and
Requirement
Federal
Regulation
Review
Consideration a
Location in Application b
See Attached Comment
Number c
O-1Standards Apply to All Facilities That Treat Store or Dispose of Hazardous Waste in Tanks Surface Impoundments or Containers Subject to 264 Subparts I J or K Except as Provided Otherwise
27014(a) 27027 2641080 (a) - (d)
Exclusions from 2641080(a) are listed at 2641080(b) (eg a container that has a design capacity less than or equal to 01 cubic meters [m3])
O-2Following is a List of Units that are Exempt from the 2641084-2641087 Standards
27014(a) 27027 2641082(c)
O-2aA Tank Surface Impoundment or Container for Which All Hazardous Waste Entering the Unit Has an Average Volatile Organic Concentration at the Point of Waste Origination of less than 500 Parts per Million by Weight (ppmw)
27014(a) 27027 2641082(c)(1)
Waste determination procedures are specified at 2641083
O-2bA Tank Surface Impoundment or Container for Which the Organic Content of all the Hazardous Waste Entering the Waste Management Unit has been Reduced by an Organic Destruction or Removal Process that Achieves Specified Criteria
27014(a) 27027 2641082(c)(2)
Waste determination procedures are specified at 2651084(b)(2)-(b)(9)
O-2cA Tank Used for Biological Treatment of Hazardous Waste that Destroys or Degrades the Organics Contained in the Hazardous Waste such that the Requirements of 2641082(c)(2)(iv) are Met
27014(a) 27027 2641082(c)(3)
Waste determination procedures are specified at 2641083(b) and 2641083(a)
O-2dA Tank Surface Impoundment or Container for Which all Hazardous Waste Placed in the Unit Meets Applicable Organic Concentration Limits or has been Treated by Appropriate Treatment Technology
27014(a) 27027 2641082(c)(4)
Waste determination procedures are specified at Part 268
O-2eA Tank Located Inside an Enclosure Vented to a Control Device that is Used for Bulk Feed of Hazardous Waste to a Waste Incinerator that Meets Specified Criteria
27014(a) 27027 2641082(c)(5)
Design and operation of the control device and enclosure shall satisfy Part 61 Subpart FF 52741 Appendix B and other conditions as specified
O-3Several Waste Determination Procedures are Explained in Detail and Must be Followed in Order to Demonstrate the Various Subpart CC Exemptions andor Control Requirements
27014(a) 27027 2641083 2651084
In general an owner or operator need not undergo waste determination procedures unless they are pursuing an exemption from the Subpart CC regulations
O-4Tanks that Satisfy the Conditions at 2641084(b)(1)(i-iii) Can Use Tank Level 1 or Tank Level 2 Controls Tanks that do not Satisfy Conditions Shall Use Tank Level 2 Controls
27014(a) 27027 2641084(b)(1) (2)
O-5aThe Conditions at 264108(b)(1)(i-iii) Provide that Hazardous Waste in the Tank Shall
27014(a) 27027 2641084(b)(1)
O-5a(1)Have Maximum Organic Vapor Pressure Which is less than Maximum Organic Vapor Pressure Limit for Tankrsquos Design Capacity Category
27014(a) 27027 2641084(b)(1)
(i)
O-5a(2)Not be Heated to Temperature Greater than Temperature at Which Maximum Organic Vapor Pressure of Waste is Determined for Purposes of Compliance
27014(a) 27027 2641084(b)(1)
(ii)
O-5a(3)Not be Treated Using a Waste Stabilization Process as Defined in 2651081
27014(a) 27027 2641084(b)(1)
(iii)
A waste stabilization process includes mixing hazardous waste with binders or other materials and curing resulting hazardous waste and binder mixture
O-5bMaximum Organic Vapor Pressure Determination
27014(a) 27027 2641084(c) (1)
Must be determined before first time waste placed in tank and retested whenever changes could cause it to increase above the maximum vapor pressure limit [2641084(b)(1)(i)]
O-5b(1)Tank Level 1 OwnerOperator Shall Equip Tanks with Fixed Roof and Closure Devices as Needed
27014(a) 27027 2641084(c)
(2) (3)
Fixed roofclosure devices shall form continuous barrier over entire waste in tank contain no visible open spaces between roof section joints or between interface of roof edge and tank wall contain openings with closure devices or closed-vent system and be made of suitable materials
O-5b(2)Tank Level 2 OwnerOperator Shall Use One of the Following Tanks
27014(a) 27027 2641084(d)
O-5b(2)(i)Fixed Roof Tank Equipped with Internal Floating Roof
27027(a)(1) 2641084(d)(1) (e)
Internal floating roof shall be designed to float on liquid surface except when supported by leg supports be equipped with continuous seal between tank wall and floating roof edge and meet other design specifications
O-5b(2)(ii)Tank Equipped with an External Floating Roof
27027(a)(1) 2641084(d)(2) (f)
External floating roof shall be designed to float on all liquid surface except when supported by leg supports be equipped with two continuous seals and meet other design specifications
O-5b(3)Tank Vented Through Closed-Vent System to a Control Device
27014(a) 27027 2641084(d)(3) (g)
Fixed roofclosure devices shall form continuous barrier over entire liquid surface be made of suitable materials and satisfy 2641087 standards
O-5cPressure Tank
27014(a) 27027 2641084(d)(4) (h)
Tank shall be designed not to bend to atmosphere as result of compression of vapor headspace in tank and be equipped with closure devices as needed
O-5dTank Located Inside an Enclosure that is Vented Through a Closed-Vent System to an Enclosed Combustion Control Device
27014(a) 27027 2641084(d)(5) (1)
Tank shall be located in enclosure that is vented through closed vent system to enclosed combustion device and enclosure shall be equipped with safety devices as needed
O-5eTank Level 1 OwnerOperator Shall
27014(a) 27027 2641084(c)
(1)(3)
O-5e(1)Determine Maximum Organic Vapor Pressure for Hazardous Waste Initially and Whenever Changes could Cause the Vapor Pressure to Increase Above the Maximum Organic Vapor Pressure Limit
27014(a) 27027 2641084(c)(1)
Maximum organic vapor pressure shall be determined using 2641083(c) procedures
O-5e(2)Ensure that Whenever Hazardous Waste is in Tank the Fixed Roof is Installed with Each Closure Device Secured in Closed Position
Exceptions are listed at 2641084(c)(3)(i-iii)
O-5e(3)Inspect the Air Emission Control Equipment
27014(a) 27027 2641084(c)(4)
O-5fTank Level 2 OwnerOperators Shall Adhere to the Following Operating Procedures for Each Unit Type
27014(a) 27027 2641084(e)(i)
O-5f(1)Fixed Roof Tank Equipped with Internal Floating Roof
27014(a) 27027 2641084(e) (2)(3)
When floating roof is resting on leg supports filling emptying or refilling shall be continuous and completed as soon as practical when roof is floating automatic bleeder vents shall be set closed and prior to filling openings in roof shall be secured Inspect the floating roof
O-5f(2)Tank Equipped with an External Floating Roof
27014(a) 27027 2641084(f)
(2)(3)
When floating roof is resting on leg supports filling emptying or refilling shall be continuous and completed as soon as practical when closure device is open for access equipment and devices shall be closed and secured as specified and seals shall provide a continuous and complete cover as specified Inspect the floating roof
O-5f(3)Tank Vented Through Closed-Vent System to a Control Device
27014(a) 27027 2641084(g)
(2) (3)
When hazardous waste is in tank fixed roof shall be installed with closure devices secured in closed position and vapor headspace underneath fixed roof vented to control device except as specified Inspect and monitor the air emission control equipment
O-5f(4)Pressure Tank
27014(a) 27027 2641084(h)
(2) (3)
When hazardous waste is in tank it shall be operated as closed system that does not vent to atmosphere except to avoid an unsafe condition
O-5f(5)Tank Located Inside an Enclosure that is Vented Through a Closed-Vent System to an Enclosed Combustion Control Device
27027(a)(3) 2641084(i)
Enclosure shall be operated in accordance with 52741 Appendix B and comply with applicable closed-vent requirements Safety devices may be operated as needed Inspect and monitor the system and control device
O-5f(6)Shall be Conducted Using Continuous Hard-Piping or Another Closed System that Does Not Allow Exposure of Hazardous Waste to Environment
27014(a) 27027 2641084(j)(1)
Requirements do not apply under the conditions specified at 2641084(j)(2)
O-6aOwnerOperators Shall Install Either of the Following Controls
27014(a) 27027 2641085(b)(d)
O-6a(1)Floating Membrane Cover
27027(a)(4) 2641085
(b)(1) (c)(1)
Floating membrane cover shall float on liquid surface and form continuous barrier over entire liquid be made of synthetic membrane material contain no visible open spaces and be equipped with closure devices and cover drains as needed
O-6a(2)Cover That Is Vented Through a Closed-Vent System to a Control Device
27014(a) 27027 2641085
(b)(2) and (d)(2)
Coverclosure devices shall form continuous barrier over entire liquid surface be equipped with closure device be made of suitable material and be designed in compliance with 2641087
O-6bOwnerOperators Shall Adhere to the Following Operating Procedures for Each Control Type
27014(a) 27027 2641085
(c) (d)
O-6b(1)Floating Membrane Cover
27014(a) 27027 2641085(c)
(2) (3)
When hazardous waste is in surface impoundment floating membrane cover shall float on liquid and each closure device shall be secured in closed position except as specified Inspect the cover
O-6b(2)Cover that is Vented Through a Closed-Vent System to a Control Device
27014(a) 27027 2641085(d) (2) (3)
When hazardous waste is in surface impoundment cover shall be installed with each closure device secured in closed position and vapor headspace underneath the cover vented to control device except as specified Closed-vent system and control device shall be operated in accordance with 2641087 Inspect and monitor the control device
O-7Shall be Conducted Using Continuous Hard-Piping or Another Closed System
27014(a) 27027 2641085(c)
(1)
Requirements do not apply under conditions specified at 2641085(e)(2)
O-8aContainer Level 1 Standards Apply to
27014(a) 27027 2641086(b)(1)
O-8a(1)Container with Design Capacity Greater than 01 m3 and less than or Equal to 046 m3
27014(a) 27027 2641086(b)(1)
(i)
O-8a(2)Container with Design Capacity Greater than 046 m3 that is not in Light Material Service
27014(a) 27027 2641086(b)(1)
(ii)
O-8abContainer Level 2 Standards Apply to Container with a Design Capacity Greater than 046 m3 that is in Light Material Service
27014(a) 27027 2641086(b)(1)
(iii)
O-8cContainer Level 3 Standards Apply to Container with Design Capacity Greater than 01 m3 that is Used for Stabilization
27014(a) 27027 2641086(b)(2)
Level 3 standards apply at those times during waste stabilization process when hazardous waste in container is exposed to atmosphere
O-9Identify Each Container Area Subject to Subpart CC
27027(a)(2)
O-9aContainer Level 1 A Container Using Level 1 Controls is Defined as One of the Following
27027(a)(2) 2641086(c)
(1)
O-9a(1)Container that Meets Department of Transportation Regulations on Packaging
27027(a)(2) 2641086(c)
(1)(i)(f)
Container shall meet Part 178 or Part 179 and be managed in accordance with Parts 107 172 173 and 180
O-9a(2)Container Equipped with Cover and Closure Devices
27027(a)(2) 2641086(c)
(1)(ii)(2)
Container shall be equipped with covers and closure devices as needed
O-9a(3)Open-Top Container Equipped with Organic-Vapor Suppressing Barrier
27027(a)(2) 2641086(c)
(1)(iii)(2)
Container shall be equipped with covers and closure devices as needed
O-9bContainer Level 2 A Container Using Level 2 Controls is Defined as One of the Following
27027(a)(2) 2641086
(d)(1)(f)(g)
O-9b(1)Container that Needs Department of Transportation (DOT) Regulations on Packaging
27027(a)(2) 2641086(d)(1)
(i)(f)
Containers shall meet Part 178 or Part 179 and be managed in accordance with Parts 107 172 173 and 180
O-9b(2)Container that Operates with No Detectable Organic Emissions
27027(a)(2) 2641086(d)(1)
(ii)(g)
Owneroperator shall follow the procedures at 2641086(g) and 2651084(d) to determine no detectable organic emissions
O-9b(3)Container that has been Demonstrated Within the Preceding 12 Months to be Vapor-Tight
27027(a)(2) 2641086(d)(1)
(iii) and (h)
Owneroperator shall follow procedures at 2641086(h) and Part 60 Appendix A Method 27 to demonstrate container is vapor-tight
O-9cContainer Level 3 A Container Using Level 3 Controls is Defined as One of the Following
27027(a)(2) 2641086(e)
(1) (2)
O-9c(1)Container that is Vented Directly Through a Closed-Vent System to a Control Device
27027(a)(2) 2641086(e)
(1)(i)
The closed-vent system and control device shall be designed in accordance with 2641087 Safety devices may be installed as needed
O-9c(2)Container that is Vented Inside an Enclosure Which is Exhausted Through a Closed-Vent System to a Control Device
27027(a)(2) 27027(a)(3) 2641086(e)
(1)(ii)
The containerenclosure must be designed in accordance with 52741 Appendix B and 2641087 Safety devices may be installed as needed
O-10aContainer Level 1 OwnerOperators Shall Install Covers and Closure Devices for the Container and Secure and Maintain Each Closure Device in Closed Position Except as Specified
27014(a) 27027 2641086(c)
(3) (4)
The closure device or cover may be opened for the purpose of adding or removing hazardous waste or for maintenance or to avoid unsafe conditions
O-10bContainer Level 2 OwnerOperator Shall Install All Covers and Closure Devices for the Container and Maintain and Secure Each Closure Device in Closed Position Except as Specified
27014(a) 27027 2641086(d)(2) (3)
Transfer of hazardous waste in or out of container shall be conducted in such a manner as to minimize exposure to atmosphere as practical The closure device or cover may be opened for the purpose of adding or removing hazardous waste or for maintenance or to avoid unsafe conditions
O-10cContainer Level 3 OwnerOperators Shall Operate the System in Accordance with 52741 Appendix B 2641087 and 2651081 as Needed
27014(a) 27027 2641086(e)
(3)(4) (5)
O-11aStandards Apply to Each Closed-Vent System and Control Device Used to Control Air Emissions under Part 264 Subpart CC
27014(a) 27027 2641087(a)
O-11(b)Closed-Vent Systems Shall
27027(a)(5) 2641087(b)
O-11b(1)Route Gases Vapors and Fumes to Control Device
27027(a) 2641087(b)(1)
O-11b(2)Be Designed and Operated in Accordance with 2641033(k)
27027(a) 2641087(b)(2)
The Subpart AA standards for closed-vent systems must be satisfied
O-11b(3)Meet the Requirements for Bypass Devices if Applicable
27027(a) 2641087(b)(3)
Each bypass device shall be equipped with either a flow indicator or a seal or locking device
O-12aThe Control Device Shall be One of the Following
27027(a)(5) 2641087(c)(1)
O-12a(1)A Control Device Designed and Operated to Reduce Total Organic Content on Inlet Vapor Stream Vented to the Control Device by at Least 95 Percent by Weight
27027(a)(5) 2641087(c)
(1)(i)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified
O-12a(2)An Enclosed Combustion Device
27027(a)(5) 2641087(c)
(1)(ii)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified Control device shall be designed and operated in accordance with 2641033(c)
O-12a(3)A Flare
27027(a)(5) 2641087(c)
(1)(iii)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified
O-12bEach Closed-Vent System and Control Device Shall Comply with the Operating Requirements of 2641087(c)(2)
27027(a)(5) 2641087(c)
(2)
Planned routine maintenance of control device shall not exceed 240 hours per year system malfunctions shall be corrected as soon as practicable and system shall be operated such that gases vapors or fumes are not actively vented to control device during planned maintenance or system malfunction except as specified
O-12cA Carbon Adsorption System
27027(a)(5) 2641087(c)
(3)
Carbon replacement and removal shall follow prescribed requirements in 2641033(g) (h) and (n)
O-12dEach Control Device Shall be Operated and Maintained in Accordance with 2641033(j) Except for Certain Devices Identified (eg Flare)
27027(a)(5) 2641087(c)
(4)
2641033(j) requires the owneroperator to prepare documentation describing the control devicersquos operation and to identify the process parameter(s) that indicate its proper operation and maintenance
O-12eThe OwnerOperator Shall Demonstrate that a Control Device Achieves the Performance Requirements Using a Performance Test or Design Analysis Except for Specific Devices Identified (eg flare)
27027(a)(5) 2641087(c)
(5)
For performance test owneroperator shall use the test specified at 264103(c) For design analysis owneroperator shall use an analysis that meets requirements specified at 2641035(b)(4)(iii) In addition the US Environmental Protection Agency (EPA) prescribes unit-specific performance demonstration requirements for certain unit types at 2641087(c)(5)
O-12fIf Design Analysis is Not Sufficient then a Performance Test is Required
27027(a)(5) 2641087(c) (6)
The EPA regional administrator shall determine if a performance test is required to demonstrate control devicersquos performance
O-12hInspect and Monitor the Control Device
27027(a)(5) 2641087(c) (7)
Control devices shall be inspected and monitored at least once a day
O-13Each Tank Surface Impoundment and Container Shall be Inspected Monitored and Repaired in Accordance with the 264 Subpart CC Requirements
27027 2641088
Inspection monitoring and repair requirements specific to each unit are located in the standards sections of the regulation 2641084 through 2641087 Owneroperator shall develop and implement written plan and schedule to perform inspections and monitoring required The plan and schedule shall be incorporated into facilityrsquos inspection plan
O-14Each OwnerOperator Shall Comply with the Recordkeeping Requirements Specified at 2641089
27027 2641089
Except as specified records shall be maintained in facilityrsquos operating record for a minimum of 3 years Various records are required depending on the type of unit and control device
O-14aEach of the Following OwnerOperators Shall Comply with the Reporting Requirements at 2641090
27027 2641090
O-14a(1)Each OwnerOperator Managing Hazardous Waste in a Tank Surface Impoundment or Container Exempted from Using Air Emission Controls under 2641082(c)
27027 2641090(a)
Owneroperator shall report to EPA each noncompliance identified under 2641082(c)
O-14a(2)Each Owneroperator Using Air Emission Controls on a Tank in Accordance with 2641084(c)
27027 2641090(b)
Owneroperator shall report to EPA each noncompliance identified under 2641084(B)
O-14a(3)Each Owneroperator Using a Control Device in Accordance with 2641087
27027 2641090
(c)(d)
Owneroperator shall submit semiannual written report to EPA except as specified
O-14bEach OwnerOperator shall Provide an Emission Monitoring Plan
27027(a)(6)
Applies to Method 21 and control device monitoring methods
O-14cSubpart CC Implementation Plan
27027(a)(7)
Required when facility cannot comply with Subpart CC by date of permit issuance
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
RCRA ID No Facility Name Page N- of N-7
SECTNWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION N SUBPART BB EQUIPMENT LEAKS
Section and
Requirement
Federal
Regulation
Review
Consideration a
Location in Application b
See Attached Comment Numberc
N-1aApplicability
27014(a) 27025 2641050(b)(d)
Except as otherwise specified this subpart applies to equipment that contains or contacts hazardous waste with organic concentrations of at least 10 percent by weight that are managed in one of the following if these operations are conducted in a unit subject to the permitting requirements of 270 a unit (including a hazardous waste recycling unit) that is not exempt from permitting under 26234(a) and is located at a hazardous waste management facility otherwise subject to permitting requirements and a unit that is exempt from permitting under 26234(a) such as a 90-day tank or container
N-1bDefinition of Equipment
27014(a) 27025 2641031 2641051
Examples include valve pump compressor pressure relief device sampling connection system open-ended valve or line or flange
N-1cEquipment in a Vacuum or Equipment that Contains or Contacts Hazardous Waste with an Organic Concentration of at Least 10 Percent by Weight for a Period of Less than 300 Hours per Calendar Year is Excluded from Requirements at 2641052 to 2641060
27014(a) 27025 2641050(f)
Equipment shall be identified in a log in facilityrsquos operating record as required by 2641064(g) in order to qualify for exclusion
N-2aMonthly Monitoring for Leaks
27025(d) 2641052(a)
(1)
N-2bVisual Inspection for Pump Seal Leakage on a Weekly Basis
27025(d) 2641052(a)(2)
N-2cLeak Detection
27025(d) 2641052(b) 2641063
Leak detected if (1) leak detection instrument reads 10000 parts per million (ppm) or greater or (2) there are indications of liquid dripping from the pump seal
N-2dLeak Repair as Soon as Practicable
27025(d) 2641052(c) 2641059
Repairs are to be made within 15 calendar days after detection Repair extensions are allowed under conditions specified in 2641059
N-2eSpecific Exceptions to these Standards
27025(d) 2641052(d - f)
Exceptions to these standards are dual mechanical seal systems or no detectable emissions
N-3aBarrier Fluid Pressure Greater than the Compressor Stuffing Box Pressure
27025(d) 2641053(b)
(1)
N-3bBarrier Fluid System Connected by a Closed-Vent System to a Control Device as Described in Subpart AA
27025(d) 2641053(b)
(2)
N-3cNo Detectable Atmospheric Emissions of Hazardous Contaminants from the Barrier System
27025(d) 2641053(b)
(3)
N-3dSensors Checked Daily or an Audible Alarm Checked Monthly
27025(d) 2641053(d - c)
N-3eLeak Detection
27025(d) 2641053(f)
A leak is detected if sensor indicates failure of (1) seal system or (2) barrier fluid system
N-3fLeak Repair as Soon as Practicable
27025(d) 2641053(g)
(1) 2641059
Repairs are to be made within 15 calendar days after detection Repair extensions are allowed under conditions specified in 2641059
N-3gSpecific Exceptions to these Standards
27025(d) 2641053(h - i)
Exceptions to these standards are certain closed vent systems or no detectable emissions
N-4aExcept During Pressure Releases No Pressure Relief Device Shall Release Detectable Emissions
27025(d) 2641054(a)
Emissions shall be less than 500 ppm above background levels
N-4bWithin 5 Calendar Days after a Pressure Release No Detectable Emissions Shall Emanate from Pressure Released Device
27025(d) 2641054(b)
Emissions shall be less than 500 ppm above background levels
N-4cSpecific Exceptions to These Standards
27025(d) 2641054(c)
Exceptions to these standards are certain closed vent systems
N-5aEach Sampling Connecting System Shall Be Equipped with a Closed-Purge Closed Loop or Closed-Vent System Closed-Vent Systems and Control Devices are also Subject to 2641033
27025(d) 2641055(a - b) 2641060
Each closed-purge closed-loop or closed-vent system shall either (1) return purged process fluid directly to process line (2) collect and recycle purged process liquid or (3) be designed and operated to capture and transport all purged process fluid to a waste management unit or control device that satisfies applicable requirements
N-5bExemption for Qualified Sampling Systems
27025(d) 2641055(c)
In situ sampling systems and sampling systems without purges are exempt from requirements of 2641055(a)(b)
N-6aOpen-Ended Valve or Line
27025(d) 2641056(a) (c)
A double block or bleed system must comply with the open-ended valve or line requirements
N-6bSecond Valve
27025(d) 2641056(b)
A second valve shall be operated such that primary valve shall be closed before second valve is opened
N-7Monitoring Schedule Based on Detection of Leaks and Predetermined Schedule
27025(d) 2641057(a - e)
A reading of 10000 ppm denotes a detected leak
N-7dSpecific Exceptions to the Monitoring Schedule
27025(d) 2640157(f - h) 2641061 2641062
Exceptions to schedule include unsafe-to-monitor valves no detectable emissions and difficult-to-monitor valves
N-8aMonitoring
27025(d) 2641058(a) 2641063(b)
Monitoring is required within 5 days after leak is found by sight sound smell or other detection method
N-8bLeak Detection
27025(d) 2641058(b)
A leak is detected if a leak detection instrument reads 10000 ppm or greater
N-8cLeak Repair as Soon as Practicable
27025(d) 2641058(c) 2641059
Repairs are to be made within 15 calendar days after detection The first attempt at repair shall be made no later than 5 calendar days after each leak is detected Repair extensions are allowed under conditions specified in 2641059
N-8dAny Connector that is Inaccessible or is Ceramic or Ceramic-Lined is Exempt from the Monitoring Requirements of 2641058(a) and 2641064
27025(d) 2641058(e)
Examples of ceramic-lined connectors include porcelain glass or glass-lined connectors
N-9Specific Allowances for Delay of Repair for Various Types of Equipment
27025(d) 2641059
N-10When Closed-Vent Systems and Control Devices are Used they Must Comply with the Requirements in Subpart AA
27025(e) 2641033 2641060
N-11An OwnerOperator may Elect to Comply with this Alternative Monitoring Program
27025(e) 2641061
No greater than 2 percent of the valves are allowed to leak per monitoring period
N-12An OwnerOperator may Elect to Comply with this Alternative Work Practice
27025(e) 2641062
Relief of monitoring frequency is allowed if less than 2 percent of the valves are leaking
N-13Owner Complies with Recordkeeping Requirements
27025(a) 2641064
Depending on the type of requirement various records must be maintained in the facility operating record
N-13aSemiannual Report
27025(a) 2641065
A semiannual report is only required if leaks from equipment have gone unrepaired or a control device operates outside the design specifications
N-13bImplementation Schedule
27025(b)
An implementation schedule shall be provided if facility cannot install closed-vent system and control device to comply with provisions of Part 264 Subpart BB on the effective date that facility becomes subject to provisions of Parts 264 and 265
N-13cPerformance Test Plan
27025(c)
A performance test plan shall be provided if the owneroperator applies for permission to use a control device for other than a thermal vapor incinerator flare boiler process heater condenser or carbon adsorption system and chooses to use test data to determine the organic removal efficiency achieved by the control device
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
RCRA ID No Facility Name Page N- of N-7
SECTNWPDReviewer
Checklist Revision Date (December 1997)
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
RCRA ID No Facility Name Page M- of M-8
SECTMWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION M SUBPART AA PROCESS VENTS
Section and
Requirement
Federal Regulation
Review
Consideration a
Location in Application b
See Attached Comment Numberc
M-1Definition of Process Vent
27014(a) 2641030 2641031
A process vent is any open-ended pipe or stack that is vented to atmosphere either directly through a vacuum-producing system or through a tank
M-2ApplicabilitymdashProcess Vents Associated with the Following Six Operations that Manage Hazardous Waste with Organic Concentrations of at Least 10 Parts per Million by Weight if these Operations are Conducted in a Unit Subject to the Permitting Requirements of 270 a Unit (including a Hazardous Waste Recycling Unit) that is Not Exempt from Permitting Under 26234(a) and is Located at a Hazardous Waste Management Facility Otherwise Subject to Permitting Requirements and a Unit that is Exempt from Permitting Under 26234(a)
27014(a) 2641030(b) 2641031
Concentrations should be determined by a time-weighted average annually or when waste or process changes
M-2aDistillationmdasha Batch or Continuous Operation Which Separates One or More Feed Stream(s) into Two or More Exit Streams Each Exit Stream Having Component Concentrations Different from Those in the Feed Stream(s)
27024(b)(3) 2641030(b) 2641031
Include process description
M-2bFractionationmdasha Distillation Operation or Method Used to Separate a Mixture of Several Volatile Components of Different Boiling Points in Successive Stages
27024(b)(3) 2641030(b) 2641031
Include process description
M-2cThin-Film Evaporationmdasha Distillation Operation that Employs a Heating Surface Consisting of a Large Diameter Tube that May be Either Straight or Tapered Horizontal or Vertical
27024(b)(3) 2641030(b) 2641031
Include process description
M-2dSolvent Extractionmdashan Operation or Method of Separation in Which a Solid or Solution Contacts a Liquid Solvent (The Two Being Mutually Insoluble) to Preferentially Dissolve and Transfer One or More Components into the Solvent
27024(b)(3) 2641030(b) 2641031
Include process description
M-2eAir Strippingmdasha Desorption Operation Employed to Transfer One or More Volatile Components from a Liquid Mixture into a Gas (Air) Either with or Without the Application of Heat to the Liquid
27024(b)(3) 2641030(b) 2641031
Include process description
M-2fStream Strippingmdasha Distillation Operation in Which Vaporization of the Volatile Constituents of a Liquid Mixture Takes Place by the Introduction of Steam Directly into the Charge
27024(b)(3) 2641030(b) 2641031
Include process description
M-3aReduce Total Organic Emission below 14 Kilogram per Hour (3 Pounds per Hour) and 28 Million Grams per Year (31 Tons per Year) or
27024(b) 2641032(a)
(1)(c)
Engineering calculations or performance tests may be used to determine vent emissions and emissions reductions or total organic compound concentrations achieved by add-on control devices
M-3bReduce Total Organic Emissions of 95 Percent by Weight with the Use of a Control Device
27024(b) 2641032(a)
(2)(b)
Engineering calculations or performance tests may be used to determine vent emissions and emissions reductions or total organic compound concentrations achieved by add-on control devices
M-3cReduce Emissions for Various Control Devices with Closed-vent Systems under the Following Operational Conditions
27024(b) 2641032(a - b) 2641033
(b - j)
Closed-vent systems are optional devices but shall comply with regulations if they are used
M-3c(1)Control Device Involving Vapor Recovery (Condenser or Adsorber) Shall Recover at Least 95 Percent by Weight of the Organic Vapors
27024(b) 2641032(a)
(1)(b)
A less than 95 percent recovery is permissible if control devices meet emission limits set in 2641032(a)(1)
M-3c(2)Enclosed Combustion Device (A Vapor Incinerator Boiler or Process Heater) Shall Recover at Least 95 Percent by Weight of Organic Emissions
27024(d) 2641033(c)
The device shall achieve 20 parts per million by weight or 12 second residence time at 760 EC
M-3c(3)A Flare Shall Operate under the Following Four Conditions (1) No Visible Emissions (2) a Flame Present at all Times (3) an Acceptable Net Heating Value and (4) Appropriate Exit Velocity
27024(d) 2641033(d)
M-4Inspection Readings Shall Be Conducted at Least Daily Vent Stream Flow Information Shall be Provided at Least Hourly
27024(d) 2641033(f)
(1)(3)
M-4aContinuous Monitoring for the Following Control Devices
27024(d) 2641033(f)(2)
M-4a(1)Thermal Vapor Incinerator (One Temperature Sensor)
27024(d) 2641033(f)(2)(i)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(2)Catalytic Vapor Incinerator (Two Temperature Sensor)
27024(d) 2641033(f)(2)(i)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(3)Flare (Heat Sensing Device)
2641033(f)(2)(iii)
M-4a(4)Boiler or Process Heater with Heater Input Capacity Equal or Greater than 44 Megawatts (Recorder Which Indicates Good Combustion Practices)
27024(d) 2641033(f)(2)(v)
M-4a(5)Condenser (Device with Recorder to Measure the Concentration of Organic Compounds in the Condenser Exhaust Vent Stream or Temperature Monitoring Device Equipped with Recorder to Measure Temperature in the Condenser Exhaust Vent Stream)
27024(d) 2641033(f)(2)(vi)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(6)Carbon Adsoprtion System (Device to Measure Organic Vapors or a Recorder that Verifies Predetermined Regeneration Cycle)
27024(d) 2641033(f)(2)(vii)
M-4bAlternate Monitoring of Control Device
27024(c) 2641033(i)
Describe measurement of applicable monitoring parameters
M-4cInspection of the Following Control Devices
27024(d) 2641033(g - h)
M-4c(1)Regenerable Carbon Adsorption System
27024(d) 2641033(g)
Carbon replacement schedule must be acceptable
M-4c(2)Nonregenerable Carbon Adsoprtion System
27024(d) 2641033(h)
Carbon shall be replaced when breakthrough is observed or on an acceptable schedule
M-5Basic Design and Operation
M-5aThe Closed-Vent System Shall be Designed to Operate According to Either of the Following
27024(d) 2641033(k)
M-5a(1)With No Detectable Emissions
27024(d) 2641033(k)(1)
Emissions shall be less than 500 parts per million above background
M-5a(2)At a Pressure below Atmospheric Pressure
27024(d) 2641033(k)(2)
System shall be equipped with at least one pressure gauge or other measurement device that can be read from a readily accessible location to verify negative pressure is being maintained in system during operation
M-5bOwneroperator Shall Monitor and Inspect Each System
27024(d) 2641033(1)
The monitoring and inspection shall be done (1) by date the system is subject to regulation (2) annually and (3) other times requested by the US Environmental Protection Agency regional administrator Various inspection and monitoring requirements apply depending upon the type of closed-vent system employed All detected defects shall be repaired according to the schedule prescribed in 2641033(l)(3)
M-5cClosed-Vent System Shall be Operated at all Times When Emissions May be Vented to Them
27024(d) 2641033(m)
M-5dCarbon Adsorption System Used to Control Air Pollutant Emissions
27024(d) 2641033(n)
Owneroperator must document that all carbon that is a hazardous waste and removed from the control device is managed in one of these approved manners 2641033(n)(1) (2) or (3)
M-6Any Components of a Closed-Vent System that are Designated as Unsafe to Monitor are Exempt from the Monitoring Requirements of 1033(l)(1)(i)(B) if Certain Conditions are Met
27024(d) 2641033(o)
Applies to system if its components are unsafe to monitor and it adheres to written plan that requires monitoring using the procedures in 2641033(l)(1)(ii)(B) as frequently as practicable during safe-to-monitor times
M-7aOwneroperator Complies with Record Keeping Requirements
27024(d) 2641033 2641035
Depending on the type of control devices and closed vent systems used various records must be maintained in the facility operating record
M-7bSemiannual Report is Submitted According to Subpart AA Requirements
27014(a) 2641036
A semiannual report is only required if a control device operates outside the design specifications
M-7cImplementation Schedule is Provided
27024(a) 2641033(a)(2)
A schedule shall be provided when facilities cannot install a closed-vent system and control device to comply with Part 264 on date facility is subject to requirements
M-7dPerformance Test Plan is Provided
27024(c) 2641035(b)(3)
A performance test plan shall be provided where owneroperator applies for permission to use control device other than thermal vapor incinerator catalytic vapor incinerator flare boiler process heater condenser or carbon adsorption system and chooses to use test data to determine organic removal efficiency achieved by control device
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
Revised 12001
J CORRECTIVE ACTION FOR SOLID WASTE MANAGEMENT UNITS
J-1 Solid Waste Management Units 9 VAC 20-60-264 and 1010M 40 CFR 264101
Identify all solid waste management units at the facility including hazardous and non-hazardous units as well as active and inactive units if known A solid waste management unit may include any of the following
Landfill
Surface Impoundment
Waste pile
Land treatment unit
Tank (including 90-day accumulation tank)
Injection well
Incinerator
Wastewater treatment tank
Container storage area
Waste handling area
Transfer station and
Waste recycling operation
J-1a Characterize the Solid Waste Management Unit
For each solid waste management unit submit the following information
Type of each unit
Location of each existing or closed unit on the topographic map [See comment B-2]
Engineering drawings of the unit if available
Dimensions and materials of construction of each unit
Dates when the unit was in operation
Quantity or volume of waste if known
J-1b No Solid Waste Management Units
Describe the methodology used to determine that no existing or former solid waste management units exist at the facility (eg review of old solid waste permits blueprints)
J-2 Releases
Provide all information available including releases reported under CERCLA Section 103 on whether or not releases have occurred from any solid waste management units at the facility Reasonable efforts to identify releases must be made even if releases have not been verified (A release may include spilling leaking pumping pouring emitting emptying discharging injecting escaping leaching dumping or disposing into the environment It does not include releases otherwise permitted or authorized under law)
J-2a Characterize Releases
Information on releases must include the following types of available information concerning prior or current releases
Date of the release
Type of waste constituent released
Nature of the release
-spill
-overflow
-ruptured pipe or tank
-result of the units construction (eg unlined surface impoundment leaky tank)
Groundwater monitoring and other analytical data available to describe nature and extent of release If other than groundwater monitoring data please describe
Physical evidence of distressed vegetation and soil contamination
Historical evidence of releases such as tanker truck accidents
Any state local or federal enforcement action that may address releases
Any public citizen complaints about the facility that could indicate a release and
Any information showing the migration of a release
J-2b No Releases
Describe the methodology used to determine that releases from solid waste management units are not present (eg review of groundwater monitoring data)
K OTHER FEDERAL LAWS 9 VAC 20-60-1010I13 and 1200C1c
Demonstrate compliance with the requirements of applicable Federal laws such as the Wild and Scenic Rivers Act National Historic Preservation Act of 1966 Endangered Species Act Coastal Zone Management Act and Fish and Wildlife Coordination Act
L PART B CERTIFICATION 9 VAC 20-60-1030A and 1030B
Applications must be accompanied by a certification letter as specified in 1030D The required signatures are as follows (1) for a corporation a principal executive officer (at least at the level of vice-president) (2) for a partnership or sole proprietorship a general partner or the proprietor respectively (3) for a municipal state Federal or other public agency either a principal executive officer or ranking elected official
Archived Monday March 09 2015 35016 PMFrom Scott Ashby (DEQ)Sent Monday September 29 2014 20600 PMTo Stewart Jay (US SSA)Cc McKenna Jim McAvoy Russell (DEQ) Farahmand Aziz (DEQ) Schneider Jutta (DEQ)Kochan Kurt (DEQ) michelegehringcoterie-envcom Mike Lawless (mlawlessdaacom)Janet Frazier (jfrazierdaacom) barbieriandreaepagov Alberts Matt (US SSA)Romanchik Leslie (DEQ) Iyer Sonal (DEQ) Williams Justin (DEQ)Subject Radford Army Ammunition Plant (VA1210020730) OBOD Permit Call-in - September25th Conference CallImportance NormalAttachments Section_Odoc Section_Ndoc Section_Mdoc Section_J_K_LdocSection_Idoc Section_Hdoc Section_Gdoc Section_Fdoc Section_EdocSection_Ddoc Section_Cdoc Checklistdocx Subpart_X_Miscellaneous_UnitspdfSection_A_Bdoc Aurell EFs from Aerial and Ground es402101kpdf Aurell MilitaryWaste online ver es303131kpdf Aurell Gullett et al Chemosphere 85 806-811 2011pdf
___________________________________
Mr Stewart
As a follow up to our conference call on September 25th regarding the RCRA permit forthe open burning grounds at your facility the following information in included to answerthe questions that were brought up during the call
1 The permitting checklists have been attached to this email for your reference Onechecklist is a generalized version for RCRA facilities the second checklist is specific toSubpart X miscellaneous units
2 The contact information for the facility which intends to close an openburningopen detonation ground and ship their energetic wastes off-site to be treated isMr Tim Holden Environmental Safety Manager Aerojet ndash Virginia Operations Phone 540-854-2037 Email timholdenaerojetcom Please contact Mr Holden with anyquestions you have regarding off-site treatment of their waste stream and any analysiswhich was done regarding on-site versus off-site treatment
3 The contact information for the EPA monitoring program for OBOD sites is MrBrian K Gullett PhD US EPA Office of Research and Development National RiskManagement Research Laboratory Phone 919-541-1534 Emailgullettbrianepagov Please contact Mr Gullett for information about the OBODmonitoring program and how RAAP may participate Attached are copies of the
RCRA ID No Facility Name Page O- of O-15
SECTOWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION O SUBPART CC AIR EMISSION STANDARDS
Section and
Requirement
Federal
Regulation
Review
Consideration a
Location in Application b
See Attached Comment
Number c
O-1Standards Apply to All Facilities That Treat Store or Dispose of Hazardous Waste in Tanks Surface Impoundments or Containers Subject to 264 Subparts I J or K Except as Provided Otherwise
27014(a) 27027 2641080 (a) - (d)
Exclusions from 2641080(a) are listed at 2641080(b) (eg a container that has a design capacity less than or equal to 01 cubic meters [m3])
O-2Following is a List of Units that are Exempt from the 2641084-2641087 Standards
27014(a) 27027 2641082(c)
O-2aA Tank Surface Impoundment or Container for Which All Hazardous Waste Entering the Unit Has an Average Volatile Organic Concentration at the Point of Waste Origination of less than 500 Parts per Million by Weight (ppmw)
27014(a) 27027 2641082(c)(1)
Waste determination procedures are specified at 2641083
O-2bA Tank Surface Impoundment or Container for Which the Organic Content of all the Hazardous Waste Entering the Waste Management Unit has been Reduced by an Organic Destruction or Removal Process that Achieves Specified Criteria
27014(a) 27027 2641082(c)(2)
Waste determination procedures are specified at 2651084(b)(2)-(b)(9)
O-2cA Tank Used for Biological Treatment of Hazardous Waste that Destroys or Degrades the Organics Contained in the Hazardous Waste such that the Requirements of 2641082(c)(2)(iv) are Met
27014(a) 27027 2641082(c)(3)
Waste determination procedures are specified at 2641083(b) and 2641083(a)
O-2dA Tank Surface Impoundment or Container for Which all Hazardous Waste Placed in the Unit Meets Applicable Organic Concentration Limits or has been Treated by Appropriate Treatment Technology
27014(a) 27027 2641082(c)(4)
Waste determination procedures are specified at Part 268
O-2eA Tank Located Inside an Enclosure Vented to a Control Device that is Used for Bulk Feed of Hazardous Waste to a Waste Incinerator that Meets Specified Criteria
27014(a) 27027 2641082(c)(5)
Design and operation of the control device and enclosure shall satisfy Part 61 Subpart FF 52741 Appendix B and other conditions as specified
O-3Several Waste Determination Procedures are Explained in Detail and Must be Followed in Order to Demonstrate the Various Subpart CC Exemptions andor Control Requirements
27014(a) 27027 2641083 2651084
In general an owner or operator need not undergo waste determination procedures unless they are pursuing an exemption from the Subpart CC regulations
O-4Tanks that Satisfy the Conditions at 2641084(b)(1)(i-iii) Can Use Tank Level 1 or Tank Level 2 Controls Tanks that do not Satisfy Conditions Shall Use Tank Level 2 Controls
27014(a) 27027 2641084(b)(1) (2)
O-5aThe Conditions at 264108(b)(1)(i-iii) Provide that Hazardous Waste in the Tank Shall
27014(a) 27027 2641084(b)(1)
O-5a(1)Have Maximum Organic Vapor Pressure Which is less than Maximum Organic Vapor Pressure Limit for Tankrsquos Design Capacity Category
27014(a) 27027 2641084(b)(1)
(i)
O-5a(2)Not be Heated to Temperature Greater than Temperature at Which Maximum Organic Vapor Pressure of Waste is Determined for Purposes of Compliance
27014(a) 27027 2641084(b)(1)
(ii)
O-5a(3)Not be Treated Using a Waste Stabilization Process as Defined in 2651081
27014(a) 27027 2641084(b)(1)
(iii)
A waste stabilization process includes mixing hazardous waste with binders or other materials and curing resulting hazardous waste and binder mixture
O-5bMaximum Organic Vapor Pressure Determination
27014(a) 27027 2641084(c) (1)
Must be determined before first time waste placed in tank and retested whenever changes could cause it to increase above the maximum vapor pressure limit [2641084(b)(1)(i)]
O-5b(1)Tank Level 1 OwnerOperator Shall Equip Tanks with Fixed Roof and Closure Devices as Needed
27014(a) 27027 2641084(c)
(2) (3)
Fixed roofclosure devices shall form continuous barrier over entire waste in tank contain no visible open spaces between roof section joints or between interface of roof edge and tank wall contain openings with closure devices or closed-vent system and be made of suitable materials
O-5b(2)Tank Level 2 OwnerOperator Shall Use One of the Following Tanks
27014(a) 27027 2641084(d)
O-5b(2)(i)Fixed Roof Tank Equipped with Internal Floating Roof
27027(a)(1) 2641084(d)(1) (e)
Internal floating roof shall be designed to float on liquid surface except when supported by leg supports be equipped with continuous seal between tank wall and floating roof edge and meet other design specifications
O-5b(2)(ii)Tank Equipped with an External Floating Roof
27027(a)(1) 2641084(d)(2) (f)
External floating roof shall be designed to float on all liquid surface except when supported by leg supports be equipped with two continuous seals and meet other design specifications
O-5b(3)Tank Vented Through Closed-Vent System to a Control Device
27014(a) 27027 2641084(d)(3) (g)
Fixed roofclosure devices shall form continuous barrier over entire liquid surface be made of suitable materials and satisfy 2641087 standards
O-5cPressure Tank
27014(a) 27027 2641084(d)(4) (h)
Tank shall be designed not to bend to atmosphere as result of compression of vapor headspace in tank and be equipped with closure devices as needed
O-5dTank Located Inside an Enclosure that is Vented Through a Closed-Vent System to an Enclosed Combustion Control Device
27014(a) 27027 2641084(d)(5) (1)
Tank shall be located in enclosure that is vented through closed vent system to enclosed combustion device and enclosure shall be equipped with safety devices as needed
O-5eTank Level 1 OwnerOperator Shall
27014(a) 27027 2641084(c)
(1)(3)
O-5e(1)Determine Maximum Organic Vapor Pressure for Hazardous Waste Initially and Whenever Changes could Cause the Vapor Pressure to Increase Above the Maximum Organic Vapor Pressure Limit
27014(a) 27027 2641084(c)(1)
Maximum organic vapor pressure shall be determined using 2641083(c) procedures
O-5e(2)Ensure that Whenever Hazardous Waste is in Tank the Fixed Roof is Installed with Each Closure Device Secured in Closed Position
Exceptions are listed at 2641084(c)(3)(i-iii)
O-5e(3)Inspect the Air Emission Control Equipment
27014(a) 27027 2641084(c)(4)
O-5fTank Level 2 OwnerOperators Shall Adhere to the Following Operating Procedures for Each Unit Type
27014(a) 27027 2641084(e)(i)
O-5f(1)Fixed Roof Tank Equipped with Internal Floating Roof
27014(a) 27027 2641084(e) (2)(3)
When floating roof is resting on leg supports filling emptying or refilling shall be continuous and completed as soon as practical when roof is floating automatic bleeder vents shall be set closed and prior to filling openings in roof shall be secured Inspect the floating roof
O-5f(2)Tank Equipped with an External Floating Roof
27014(a) 27027 2641084(f)
(2)(3)
When floating roof is resting on leg supports filling emptying or refilling shall be continuous and completed as soon as practical when closure device is open for access equipment and devices shall be closed and secured as specified and seals shall provide a continuous and complete cover as specified Inspect the floating roof
O-5f(3)Tank Vented Through Closed-Vent System to a Control Device
27014(a) 27027 2641084(g)
(2) (3)
When hazardous waste is in tank fixed roof shall be installed with closure devices secured in closed position and vapor headspace underneath fixed roof vented to control device except as specified Inspect and monitor the air emission control equipment
O-5f(4)Pressure Tank
27014(a) 27027 2641084(h)
(2) (3)
When hazardous waste is in tank it shall be operated as closed system that does not vent to atmosphere except to avoid an unsafe condition
O-5f(5)Tank Located Inside an Enclosure that is Vented Through a Closed-Vent System to an Enclosed Combustion Control Device
27027(a)(3) 2641084(i)
Enclosure shall be operated in accordance with 52741 Appendix B and comply with applicable closed-vent requirements Safety devices may be operated as needed Inspect and monitor the system and control device
O-5f(6)Shall be Conducted Using Continuous Hard-Piping or Another Closed System that Does Not Allow Exposure of Hazardous Waste to Environment
27014(a) 27027 2641084(j)(1)
Requirements do not apply under the conditions specified at 2641084(j)(2)
O-6aOwnerOperators Shall Install Either of the Following Controls
27014(a) 27027 2641085(b)(d)
O-6a(1)Floating Membrane Cover
27027(a)(4) 2641085
(b)(1) (c)(1)
Floating membrane cover shall float on liquid surface and form continuous barrier over entire liquid be made of synthetic membrane material contain no visible open spaces and be equipped with closure devices and cover drains as needed
O-6a(2)Cover That Is Vented Through a Closed-Vent System to a Control Device
27014(a) 27027 2641085
(b)(2) and (d)(2)
Coverclosure devices shall form continuous barrier over entire liquid surface be equipped with closure device be made of suitable material and be designed in compliance with 2641087
O-6bOwnerOperators Shall Adhere to the Following Operating Procedures for Each Control Type
27014(a) 27027 2641085
(c) (d)
O-6b(1)Floating Membrane Cover
27014(a) 27027 2641085(c)
(2) (3)
When hazardous waste is in surface impoundment floating membrane cover shall float on liquid and each closure device shall be secured in closed position except as specified Inspect the cover
O-6b(2)Cover that is Vented Through a Closed-Vent System to a Control Device
27014(a) 27027 2641085(d) (2) (3)
When hazardous waste is in surface impoundment cover shall be installed with each closure device secured in closed position and vapor headspace underneath the cover vented to control device except as specified Closed-vent system and control device shall be operated in accordance with 2641087 Inspect and monitor the control device
O-7Shall be Conducted Using Continuous Hard-Piping or Another Closed System
27014(a) 27027 2641085(c)
(1)
Requirements do not apply under conditions specified at 2641085(e)(2)
O-8aContainer Level 1 Standards Apply to
27014(a) 27027 2641086(b)(1)
O-8a(1)Container with Design Capacity Greater than 01 m3 and less than or Equal to 046 m3
27014(a) 27027 2641086(b)(1)
(i)
O-8a(2)Container with Design Capacity Greater than 046 m3 that is not in Light Material Service
27014(a) 27027 2641086(b)(1)
(ii)
O-8abContainer Level 2 Standards Apply to Container with a Design Capacity Greater than 046 m3 that is in Light Material Service
27014(a) 27027 2641086(b)(1)
(iii)
O-8cContainer Level 3 Standards Apply to Container with Design Capacity Greater than 01 m3 that is Used for Stabilization
27014(a) 27027 2641086(b)(2)
Level 3 standards apply at those times during waste stabilization process when hazardous waste in container is exposed to atmosphere
O-9Identify Each Container Area Subject to Subpart CC
27027(a)(2)
O-9aContainer Level 1 A Container Using Level 1 Controls is Defined as One of the Following
27027(a)(2) 2641086(c)
(1)
O-9a(1)Container that Meets Department of Transportation Regulations on Packaging
27027(a)(2) 2641086(c)
(1)(i)(f)
Container shall meet Part 178 or Part 179 and be managed in accordance with Parts 107 172 173 and 180
O-9a(2)Container Equipped with Cover and Closure Devices
27027(a)(2) 2641086(c)
(1)(ii)(2)
Container shall be equipped with covers and closure devices as needed
O-9a(3)Open-Top Container Equipped with Organic-Vapor Suppressing Barrier
27027(a)(2) 2641086(c)
(1)(iii)(2)
Container shall be equipped with covers and closure devices as needed
O-9bContainer Level 2 A Container Using Level 2 Controls is Defined as One of the Following
27027(a)(2) 2641086
(d)(1)(f)(g)
O-9b(1)Container that Needs Department of Transportation (DOT) Regulations on Packaging
27027(a)(2) 2641086(d)(1)
(i)(f)
Containers shall meet Part 178 or Part 179 and be managed in accordance with Parts 107 172 173 and 180
O-9b(2)Container that Operates with No Detectable Organic Emissions
27027(a)(2) 2641086(d)(1)
(ii)(g)
Owneroperator shall follow the procedures at 2641086(g) and 2651084(d) to determine no detectable organic emissions
O-9b(3)Container that has been Demonstrated Within the Preceding 12 Months to be Vapor-Tight
27027(a)(2) 2641086(d)(1)
(iii) and (h)
Owneroperator shall follow procedures at 2641086(h) and Part 60 Appendix A Method 27 to demonstrate container is vapor-tight
O-9cContainer Level 3 A Container Using Level 3 Controls is Defined as One of the Following
27027(a)(2) 2641086(e)
(1) (2)
O-9c(1)Container that is Vented Directly Through a Closed-Vent System to a Control Device
27027(a)(2) 2641086(e)
(1)(i)
The closed-vent system and control device shall be designed in accordance with 2641087 Safety devices may be installed as needed
O-9c(2)Container that is Vented Inside an Enclosure Which is Exhausted Through a Closed-Vent System to a Control Device
27027(a)(2) 27027(a)(3) 2641086(e)
(1)(ii)
The containerenclosure must be designed in accordance with 52741 Appendix B and 2641087 Safety devices may be installed as needed
O-10aContainer Level 1 OwnerOperators Shall Install Covers and Closure Devices for the Container and Secure and Maintain Each Closure Device in Closed Position Except as Specified
27014(a) 27027 2641086(c)
(3) (4)
The closure device or cover may be opened for the purpose of adding or removing hazardous waste or for maintenance or to avoid unsafe conditions
O-10bContainer Level 2 OwnerOperator Shall Install All Covers and Closure Devices for the Container and Maintain and Secure Each Closure Device in Closed Position Except as Specified
27014(a) 27027 2641086(d)(2) (3)
Transfer of hazardous waste in or out of container shall be conducted in such a manner as to minimize exposure to atmosphere as practical The closure device or cover may be opened for the purpose of adding or removing hazardous waste or for maintenance or to avoid unsafe conditions
O-10cContainer Level 3 OwnerOperators Shall Operate the System in Accordance with 52741 Appendix B 2641087 and 2651081 as Needed
27014(a) 27027 2641086(e)
(3)(4) (5)
O-11aStandards Apply to Each Closed-Vent System and Control Device Used to Control Air Emissions under Part 264 Subpart CC
27014(a) 27027 2641087(a)
O-11(b)Closed-Vent Systems Shall
27027(a)(5) 2641087(b)
O-11b(1)Route Gases Vapors and Fumes to Control Device
27027(a) 2641087(b)(1)
O-11b(2)Be Designed and Operated in Accordance with 2641033(k)
27027(a) 2641087(b)(2)
The Subpart AA standards for closed-vent systems must be satisfied
O-11b(3)Meet the Requirements for Bypass Devices if Applicable
27027(a) 2641087(b)(3)
Each bypass device shall be equipped with either a flow indicator or a seal or locking device
O-12aThe Control Device Shall be One of the Following
27027(a)(5) 2641087(c)(1)
O-12a(1)A Control Device Designed and Operated to Reduce Total Organic Content on Inlet Vapor Stream Vented to the Control Device by at Least 95 Percent by Weight
27027(a)(5) 2641087(c)
(1)(i)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified
O-12a(2)An Enclosed Combustion Device
27027(a)(5) 2641087(c)
(1)(ii)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified Control device shall be designed and operated in accordance with 2641033(c)
O-12a(3)A Flare
27027(a)(5) 2641087(c)
(1)(iii)
Owneroperator shall demonstrate compliance using either performance test or design analysis except as specified
O-12bEach Closed-Vent System and Control Device Shall Comply with the Operating Requirements of 2641087(c)(2)
27027(a)(5) 2641087(c)
(2)
Planned routine maintenance of control device shall not exceed 240 hours per year system malfunctions shall be corrected as soon as practicable and system shall be operated such that gases vapors or fumes are not actively vented to control device during planned maintenance or system malfunction except as specified
O-12cA Carbon Adsorption System
27027(a)(5) 2641087(c)
(3)
Carbon replacement and removal shall follow prescribed requirements in 2641033(g) (h) and (n)
O-12dEach Control Device Shall be Operated and Maintained in Accordance with 2641033(j) Except for Certain Devices Identified (eg Flare)
27027(a)(5) 2641087(c)
(4)
2641033(j) requires the owneroperator to prepare documentation describing the control devicersquos operation and to identify the process parameter(s) that indicate its proper operation and maintenance
O-12eThe OwnerOperator Shall Demonstrate that a Control Device Achieves the Performance Requirements Using a Performance Test or Design Analysis Except for Specific Devices Identified (eg flare)
27027(a)(5) 2641087(c)
(5)
For performance test owneroperator shall use the test specified at 264103(c) For design analysis owneroperator shall use an analysis that meets requirements specified at 2641035(b)(4)(iii) In addition the US Environmental Protection Agency (EPA) prescribes unit-specific performance demonstration requirements for certain unit types at 2641087(c)(5)
O-12fIf Design Analysis is Not Sufficient then a Performance Test is Required
27027(a)(5) 2641087(c) (6)
The EPA regional administrator shall determine if a performance test is required to demonstrate control devicersquos performance
O-12hInspect and Monitor the Control Device
27027(a)(5) 2641087(c) (7)
Control devices shall be inspected and monitored at least once a day
O-13Each Tank Surface Impoundment and Container Shall be Inspected Monitored and Repaired in Accordance with the 264 Subpart CC Requirements
27027 2641088
Inspection monitoring and repair requirements specific to each unit are located in the standards sections of the regulation 2641084 through 2641087 Owneroperator shall develop and implement written plan and schedule to perform inspections and monitoring required The plan and schedule shall be incorporated into facilityrsquos inspection plan
O-14Each OwnerOperator Shall Comply with the Recordkeeping Requirements Specified at 2641089
27027 2641089
Except as specified records shall be maintained in facilityrsquos operating record for a minimum of 3 years Various records are required depending on the type of unit and control device
O-14aEach of the Following OwnerOperators Shall Comply with the Reporting Requirements at 2641090
27027 2641090
O-14a(1)Each OwnerOperator Managing Hazardous Waste in a Tank Surface Impoundment or Container Exempted from Using Air Emission Controls under 2641082(c)
27027 2641090(a)
Owneroperator shall report to EPA each noncompliance identified under 2641082(c)
O-14a(2)Each Owneroperator Using Air Emission Controls on a Tank in Accordance with 2641084(c)
27027 2641090(b)
Owneroperator shall report to EPA each noncompliance identified under 2641084(B)
O-14a(3)Each Owneroperator Using a Control Device in Accordance with 2641087
27027 2641090
(c)(d)
Owneroperator shall submit semiannual written report to EPA except as specified
O-14bEach OwnerOperator shall Provide an Emission Monitoring Plan
27027(a)(6)
Applies to Method 21 and control device monitoring methods
O-14cSubpart CC Implementation Plan
27027(a)(7)
Required when facility cannot comply with Subpart CC by date of permit issuance
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
RCRA ID No Facility Name Page N- of N-7
SECTNWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION N SUBPART BB EQUIPMENT LEAKS
Section and
Requirement
Federal
Regulation
Review
Consideration a
Location in Application b
See Attached Comment Numberc
N-1aApplicability
27014(a) 27025 2641050(b)(d)
Except as otherwise specified this subpart applies to equipment that contains or contacts hazardous waste with organic concentrations of at least 10 percent by weight that are managed in one of the following if these operations are conducted in a unit subject to the permitting requirements of 270 a unit (including a hazardous waste recycling unit) that is not exempt from permitting under 26234(a) and is located at a hazardous waste management facility otherwise subject to permitting requirements and a unit that is exempt from permitting under 26234(a) such as a 90-day tank or container
N-1bDefinition of Equipment
27014(a) 27025 2641031 2641051
Examples include valve pump compressor pressure relief device sampling connection system open-ended valve or line or flange
N-1cEquipment in a Vacuum or Equipment that Contains or Contacts Hazardous Waste with an Organic Concentration of at Least 10 Percent by Weight for a Period of Less than 300 Hours per Calendar Year is Excluded from Requirements at 2641052 to 2641060
27014(a) 27025 2641050(f)
Equipment shall be identified in a log in facilityrsquos operating record as required by 2641064(g) in order to qualify for exclusion
N-2aMonthly Monitoring for Leaks
27025(d) 2641052(a)
(1)
N-2bVisual Inspection for Pump Seal Leakage on a Weekly Basis
27025(d) 2641052(a)(2)
N-2cLeak Detection
27025(d) 2641052(b) 2641063
Leak detected if (1) leak detection instrument reads 10000 parts per million (ppm) or greater or (2) there are indications of liquid dripping from the pump seal
N-2dLeak Repair as Soon as Practicable
27025(d) 2641052(c) 2641059
Repairs are to be made within 15 calendar days after detection Repair extensions are allowed under conditions specified in 2641059
N-2eSpecific Exceptions to these Standards
27025(d) 2641052(d - f)
Exceptions to these standards are dual mechanical seal systems or no detectable emissions
N-3aBarrier Fluid Pressure Greater than the Compressor Stuffing Box Pressure
27025(d) 2641053(b)
(1)
N-3bBarrier Fluid System Connected by a Closed-Vent System to a Control Device as Described in Subpart AA
27025(d) 2641053(b)
(2)
N-3cNo Detectable Atmospheric Emissions of Hazardous Contaminants from the Barrier System
27025(d) 2641053(b)
(3)
N-3dSensors Checked Daily or an Audible Alarm Checked Monthly
27025(d) 2641053(d - c)
N-3eLeak Detection
27025(d) 2641053(f)
A leak is detected if sensor indicates failure of (1) seal system or (2) barrier fluid system
N-3fLeak Repair as Soon as Practicable
27025(d) 2641053(g)
(1) 2641059
Repairs are to be made within 15 calendar days after detection Repair extensions are allowed under conditions specified in 2641059
N-3gSpecific Exceptions to these Standards
27025(d) 2641053(h - i)
Exceptions to these standards are certain closed vent systems or no detectable emissions
N-4aExcept During Pressure Releases No Pressure Relief Device Shall Release Detectable Emissions
27025(d) 2641054(a)
Emissions shall be less than 500 ppm above background levels
N-4bWithin 5 Calendar Days after a Pressure Release No Detectable Emissions Shall Emanate from Pressure Released Device
27025(d) 2641054(b)
Emissions shall be less than 500 ppm above background levels
N-4cSpecific Exceptions to These Standards
27025(d) 2641054(c)
Exceptions to these standards are certain closed vent systems
N-5aEach Sampling Connecting System Shall Be Equipped with a Closed-Purge Closed Loop or Closed-Vent System Closed-Vent Systems and Control Devices are also Subject to 2641033
27025(d) 2641055(a - b) 2641060
Each closed-purge closed-loop or closed-vent system shall either (1) return purged process fluid directly to process line (2) collect and recycle purged process liquid or (3) be designed and operated to capture and transport all purged process fluid to a waste management unit or control device that satisfies applicable requirements
N-5bExemption for Qualified Sampling Systems
27025(d) 2641055(c)
In situ sampling systems and sampling systems without purges are exempt from requirements of 2641055(a)(b)
N-6aOpen-Ended Valve or Line
27025(d) 2641056(a) (c)
A double block or bleed system must comply with the open-ended valve or line requirements
N-6bSecond Valve
27025(d) 2641056(b)
A second valve shall be operated such that primary valve shall be closed before second valve is opened
N-7Monitoring Schedule Based on Detection of Leaks and Predetermined Schedule
27025(d) 2641057(a - e)
A reading of 10000 ppm denotes a detected leak
N-7dSpecific Exceptions to the Monitoring Schedule
27025(d) 2640157(f - h) 2641061 2641062
Exceptions to schedule include unsafe-to-monitor valves no detectable emissions and difficult-to-monitor valves
N-8aMonitoring
27025(d) 2641058(a) 2641063(b)
Monitoring is required within 5 days after leak is found by sight sound smell or other detection method
N-8bLeak Detection
27025(d) 2641058(b)
A leak is detected if a leak detection instrument reads 10000 ppm or greater
N-8cLeak Repair as Soon as Practicable
27025(d) 2641058(c) 2641059
Repairs are to be made within 15 calendar days after detection The first attempt at repair shall be made no later than 5 calendar days after each leak is detected Repair extensions are allowed under conditions specified in 2641059
N-8dAny Connector that is Inaccessible or is Ceramic or Ceramic-Lined is Exempt from the Monitoring Requirements of 2641058(a) and 2641064
27025(d) 2641058(e)
Examples of ceramic-lined connectors include porcelain glass or glass-lined connectors
N-9Specific Allowances for Delay of Repair for Various Types of Equipment
27025(d) 2641059
N-10When Closed-Vent Systems and Control Devices are Used they Must Comply with the Requirements in Subpart AA
27025(e) 2641033 2641060
N-11An OwnerOperator may Elect to Comply with this Alternative Monitoring Program
27025(e) 2641061
No greater than 2 percent of the valves are allowed to leak per monitoring period
N-12An OwnerOperator may Elect to Comply with this Alternative Work Practice
27025(e) 2641062
Relief of monitoring frequency is allowed if less than 2 percent of the valves are leaking
N-13Owner Complies with Recordkeeping Requirements
27025(a) 2641064
Depending on the type of requirement various records must be maintained in the facility operating record
N-13aSemiannual Report
27025(a) 2641065
A semiannual report is only required if leaks from equipment have gone unrepaired or a control device operates outside the design specifications
N-13bImplementation Schedule
27025(b)
An implementation schedule shall be provided if facility cannot install closed-vent system and control device to comply with provisions of Part 264 Subpart BB on the effective date that facility becomes subject to provisions of Parts 264 and 265
N-13cPerformance Test Plan
27025(c)
A performance test plan shall be provided if the owneroperator applies for permission to use a control device for other than a thermal vapor incinerator flare boiler process heater condenser or carbon adsorption system and chooses to use test data to determine the organic removal efficiency achieved by the control device
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
RCRA ID No Facility Name Page N- of N-7
SECTNWPDReviewer
Checklist Revision Date (December 1997)
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
RCRA ID No Facility Name Page M- of M-8
SECTMWPDReviewer
Checklist Revision Date (December 1997)
CHECKLIST FOR REVIEW OF FEDERAL RCRA PERMIT APPLICATIONS
SECTION M SUBPART AA PROCESS VENTS
Section and
Requirement
Federal Regulation
Review
Consideration a
Location in Application b
See Attached Comment Numberc
M-1Definition of Process Vent
27014(a) 2641030 2641031
A process vent is any open-ended pipe or stack that is vented to atmosphere either directly through a vacuum-producing system or through a tank
M-2ApplicabilitymdashProcess Vents Associated with the Following Six Operations that Manage Hazardous Waste with Organic Concentrations of at Least 10 Parts per Million by Weight if these Operations are Conducted in a Unit Subject to the Permitting Requirements of 270 a Unit (including a Hazardous Waste Recycling Unit) that is Not Exempt from Permitting Under 26234(a) and is Located at a Hazardous Waste Management Facility Otherwise Subject to Permitting Requirements and a Unit that is Exempt from Permitting Under 26234(a)
27014(a) 2641030(b) 2641031
Concentrations should be determined by a time-weighted average annually or when waste or process changes
M-2aDistillationmdasha Batch or Continuous Operation Which Separates One or More Feed Stream(s) into Two or More Exit Streams Each Exit Stream Having Component Concentrations Different from Those in the Feed Stream(s)
27024(b)(3) 2641030(b) 2641031
Include process description
M-2bFractionationmdasha Distillation Operation or Method Used to Separate a Mixture of Several Volatile Components of Different Boiling Points in Successive Stages
27024(b)(3) 2641030(b) 2641031
Include process description
M-2cThin-Film Evaporationmdasha Distillation Operation that Employs a Heating Surface Consisting of a Large Diameter Tube that May be Either Straight or Tapered Horizontal or Vertical
27024(b)(3) 2641030(b) 2641031
Include process description
M-2dSolvent Extractionmdashan Operation or Method of Separation in Which a Solid or Solution Contacts a Liquid Solvent (The Two Being Mutually Insoluble) to Preferentially Dissolve and Transfer One or More Components into the Solvent
27024(b)(3) 2641030(b) 2641031
Include process description
M-2eAir Strippingmdasha Desorption Operation Employed to Transfer One or More Volatile Components from a Liquid Mixture into a Gas (Air) Either with or Without the Application of Heat to the Liquid
27024(b)(3) 2641030(b) 2641031
Include process description
M-2fStream Strippingmdasha Distillation Operation in Which Vaporization of the Volatile Constituents of a Liquid Mixture Takes Place by the Introduction of Steam Directly into the Charge
27024(b)(3) 2641030(b) 2641031
Include process description
M-3aReduce Total Organic Emission below 14 Kilogram per Hour (3 Pounds per Hour) and 28 Million Grams per Year (31 Tons per Year) or
27024(b) 2641032(a)
(1)(c)
Engineering calculations or performance tests may be used to determine vent emissions and emissions reductions or total organic compound concentrations achieved by add-on control devices
M-3bReduce Total Organic Emissions of 95 Percent by Weight with the Use of a Control Device
27024(b) 2641032(a)
(2)(b)
Engineering calculations or performance tests may be used to determine vent emissions and emissions reductions or total organic compound concentrations achieved by add-on control devices
M-3cReduce Emissions for Various Control Devices with Closed-vent Systems under the Following Operational Conditions
27024(b) 2641032(a - b) 2641033
(b - j)
Closed-vent systems are optional devices but shall comply with regulations if they are used
M-3c(1)Control Device Involving Vapor Recovery (Condenser or Adsorber) Shall Recover at Least 95 Percent by Weight of the Organic Vapors
27024(b) 2641032(a)
(1)(b)
A less than 95 percent recovery is permissible if control devices meet emission limits set in 2641032(a)(1)
M-3c(2)Enclosed Combustion Device (A Vapor Incinerator Boiler or Process Heater) Shall Recover at Least 95 Percent by Weight of Organic Emissions
27024(d) 2641033(c)
The device shall achieve 20 parts per million by weight or 12 second residence time at 760 EC
M-3c(3)A Flare Shall Operate under the Following Four Conditions (1) No Visible Emissions (2) a Flame Present at all Times (3) an Acceptable Net Heating Value and (4) Appropriate Exit Velocity
27024(d) 2641033(d)
M-4Inspection Readings Shall Be Conducted at Least Daily Vent Stream Flow Information Shall be Provided at Least Hourly
27024(d) 2641033(f)
(1)(3)
M-4aContinuous Monitoring for the Following Control Devices
27024(d) 2641033(f)(2)
M-4a(1)Thermal Vapor Incinerator (One Temperature Sensor)
27024(d) 2641033(f)(2)(i)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(2)Catalytic Vapor Incinerator (Two Temperature Sensor)
27024(d) 2641033(f)(2)(i)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(3)Flare (Heat Sensing Device)
2641033(f)(2)(iii)
M-4a(4)Boiler or Process Heater with Heater Input Capacity Equal or Greater than 44 Megawatts (Recorder Which Indicates Good Combustion Practices)
27024(d) 2641033(f)(2)(v)
M-4a(5)Condenser (Device with Recorder to Measure the Concentration of Organic Compounds in the Condenser Exhaust Vent Stream or Temperature Monitoring Device Equipped with Recorder to Measure Temperature in the Condenser Exhaust Vent Stream)
27024(d) 2641033(f)(2)(vi)
Sensor shall have accuracy of plusmn 1 percent EC or plusmn 05 EC whichever is greater
M-4a(6)Carbon Adsoprtion System (Device to Measure Organic Vapors or a Recorder that Verifies Predetermined Regeneration Cycle)
27024(d) 2641033(f)(2)(vii)
M-4bAlternate Monitoring of Control Device
27024(c) 2641033(i)
Describe measurement of applicable monitoring parameters
M-4cInspection of the Following Control Devices
27024(d) 2641033(g - h)
M-4c(1)Regenerable Carbon Adsorption System
27024(d) 2641033(g)
Carbon replacement schedule must be acceptable
M-4c(2)Nonregenerable Carbon Adsoprtion System
27024(d) 2641033(h)
Carbon shall be replaced when breakthrough is observed or on an acceptable schedule
M-5Basic Design and Operation
M-5aThe Closed-Vent System Shall be Designed to Operate According to Either of the Following
27024(d) 2641033(k)
M-5a(1)With No Detectable Emissions
27024(d) 2641033(k)(1)
Emissions shall be less than 500 parts per million above background
M-5a(2)At a Pressure below Atmospheric Pressure
27024(d) 2641033(k)(2)
System shall be equipped with at least one pressure gauge or other measurement device that can be read from a readily accessible location to verify negative pressure is being maintained in system during operation
M-5bOwneroperator Shall Monitor and Inspect Each System
27024(d) 2641033(1)
The monitoring and inspection shall be done (1) by date the system is subject to regulation (2) annually and (3) other times requested by the US Environmental Protection Agency regional administrator Various inspection and monitoring requirements apply depending upon the type of closed-vent system employed All detected defects shall be repaired according to the schedule prescribed in 2641033(l)(3)
M-5cClosed-Vent System Shall be Operated at all Times When Emissions May be Vented to Them
27024(d) 2641033(m)
M-5dCarbon Adsorption System Used to Control Air Pollutant Emissions
27024(d) 2641033(n)
Owneroperator must document that all carbon that is a hazardous waste and removed from the control device is managed in one of these approved manners 2641033(n)(1) (2) or (3)
M-6Any Components of a Closed-Vent System that are Designated as Unsafe to Monitor are Exempt from the Monitoring Requirements of 1033(l)(1)(i)(B) if Certain Conditions are Met
27024(d) 2641033(o)
Applies to system if its components are unsafe to monitor and it adheres to written plan that requires monitoring using the procedures in 2641033(l)(1)(ii)(B) as frequently as practicable during safe-to-monitor times
M-7aOwneroperator Complies with Record Keeping Requirements
27024(d) 2641033 2641035
Depending on the type of control devices and closed vent systems used various records must be maintained in the facility operating record
M-7bSemiannual Report is Submitted According to Subpart AA Requirements
27014(a) 2641036
A semiannual report is only required if a control device operates outside the design specifications
M-7cImplementation Schedule is Provided
27024(a) 2641033(a)(2)
A schedule shall be provided when facilities cannot install a closed-vent system and control device to comply with Part 264 on date facility is subject to requirements
M-7dPerformance Test Plan is Provided
27024(c) 2641035(b)(3)
A performance test plan shall be provided where owneroperator applies for permission to use control device other than thermal vapor incinerator catalytic vapor incinerator flare boiler process heater condenser or carbon adsorption system and chooses to use test data to determine organic removal efficiency achieved by control device
Notes
aConsiderations in addition to the requirements presented in the regulations
bFor each requirement this column must indicate one of the following NA for not applicable IM for information missing or the exact location of the information in the application
cIf application is deficient in an area prepare a comment describing the deficiency attach it to the checklist and reference the comment in this column
Revised 12001
J CORRECTIVE ACTION FOR SOLID WASTE MANAGEMENT UNITS
J-1 Solid Waste Management Units 9 VAC 20-60-264 and 1010M 40 CFR 264101
Identify all solid waste management units at the facility including hazardous and non-hazardous units as well as active and inactive units if known A solid waste management unit may include any of the following
Landfill
Surface Impoundment
Waste pile
Land treatment unit
Tank (including 90-day accumulation tank)
Injection well
Incinerator
Wastewater treatment tank
Container storage area
Waste handling area
Transfer station and
Waste recycling operation
J-1a Characterize the Solid Waste Management Unit
For each solid waste management unit submit the following information
Type of each unit
Location of each existing or closed unit on the topographic map [See comment B-2]
Engineering drawings of the unit if available
Dimensions and materials of construction of each unit
Dates when the unit was in operation
Quantity or volume of waste if known
J-1b No Solid Waste Management Units
Describe the methodology used to determine that no existing or former solid waste management units exist at the facility (eg review of old solid waste permits blueprints)
J-2 Releases
Provide all information available including releases reported under CERCLA Section 103 on whether or not releases have occurred from any solid waste management units at the facility Reasonable efforts to identify releases must be made even if releases have not been verified (A release may include spilling leaking pumping pouring emitting emptying discharging injecting escaping leaching dumping or disposing into the environment It does not include releases otherwise permitted or authorized under law)
J-2a Characterize Releases
Information on releases must include the following types of available information concerning prior or current releases
Date of the release
Type of waste constituent released
Nature of the release
-spill
-overflow
-ruptured pipe or tank
-result of the units construction (eg unlined surface impoundment leaky tank)
Groundwater monitoring and other analytical data available to describe nature and extent of release If other than groundwater monitoring data please describe
Physical evidence of distressed vegetation and soil contamination
Historical evidence of releases such as tanker truck accidents
Any state local or federal enforcement action that may address releases
Any public citizen complaints about the facility that could indicate a release and
Any information showing the migration of a release
J-2b No Releases
Describe the methodology used to determine that releases from solid waste management units are not present (eg review of groundwater monitoring data)
K OTHER FEDERAL LAWS 9 VAC 20-60-1010I13 and 1200C1c
Demonstrate compliance with the requirements of applicable Federal laws such as the Wild and Scenic Rivers Act National Historic Preservation Act of 1966 Endangered Species Act Coastal Zone Management Act and Fish and Wildlife Coordination Act
L PART B CERTIFICATION 9 VAC 20-60-1030A and 1030B
Applications must be accompanied by a certification letter as specified in 1030D The required signatures are as follows (1) for a corporation a principal executive officer (at least at the level of vice-president) (2) for a partnership or sole proprietorship a general partner or the proprietor respectively (3) for a municipal state Federal or other public agency either a principal executive officer or ranking elected official
Facility Name ___________________________ Reference No ___________________________
1 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
APPLICATION REVIEW CHECKLIST
HAZARDOUS WASTE PROGRAM
Facility Name ________________________________________________________________________________________ Facility ID No ___________________ VADEQ Permit No ___________________ Reference No _________________ Application Type ________________________________________________________ Date ________________________ (NewModifyRenewal)
40 CFR 264 Subpart X
MISCELLANEOUS UNITS
Virginia Department
ofEnvironmental Quality
Administrative Reviewer ____________________________ Start Date ________________ Completion Date ________ Technical Reviewer ________________________________ Start Date ________________ Completion Date ________ Issuance Deadline __________________________________
RCRA ID Number
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA (MU 1) APPLICABILITY - 264600 Applies to facilities that treat store or dispose of hazardous waste in miscellaneous units except as 2641 provides otherwise
Facility Name ___________________________ Reference No ___________________________
2 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
Environmental Performance Standards - 264601
A miscellaneous unit (MU) must be located designed constructed operated maintained and closed in a manner to ensure protection of human health and the environment
Permits are to contain the design and operating requirements responses to releases and other requirements as necessary
Permits shall include requirements of subparts I through O 270 and 146 that are appropriate
Protection of human health and the environment includes but is not limited to
MU 2 264601(a) Prevention of any releases into the groundwater or subsurface environment considering
MU 3 264601(a)(1) The volume and physical and chemical characteristics of the waste in the unit including its potential for migration through containing structures
MU 4 264601(a)(2) The hydrologic and geologic characteristics of the unit and the surrounding area
MU 5 264601(a)(3) The existing quality of groundwater including other sources of contamination and their cumulative impact on the groundwater
MU 6 264601(a)(4) The quantity and direction of groundwater flow
MU 7 264601(a)(5) The proximity to and withdrawal rates of current and potential groundwater users
MU 8 264601(a)(6) The pattern of land use in the region
MU 9 264601(a)(7) The potential for waste constituents to migrate or deposit into the subsurface physical structure and into the root zone of food-chain crops and other vegetation
MU 10 264601(a)(8) The potential for health risks due to exposure
Facility Name ___________________________ Reference No ___________________________
3 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
MU 11 264601(a)(9) The potential for damage to animals wildlife crops vegetation and physical structures
MU 12 264601(b) Prevention of any releases to surface waters wetlands or soil surface considering
MU 13 264601(b)(1) The volume and physical and chemical characteristics of the waste in the unit
MU 14 264601(b)(2) The effectiveness and reliability of the containing and collection system
MU 15 264601(b)(3) The hydrologic characteristics of the unit and the surrounding area including topography
MU 16 264601(b)(4) The pattern of precipitation in the region
MU 17 264601(b)(5) The quantity quality and direction of groundwater flow
MU 18 264601(b)(6) The proximity of the unit to surface waters
MU 19 264601(b)(7) The current and potential use of surface waters and their established quality standards
MU 20 264601(b)(8) The existing quality of surface waters and surface soils including other sources of contamination and their cumulative impact those media
MU 21 264601(b)(9) The patterns of land use in the region
MU 22 264601(b)(10) The potential for health risks due to exposure
MU 23 264601(b)(11) The potential for damage to animals wildlife crops vegetation and physical structures
MU 24 264601(c) Prevention of any releases to air considering
Facility Name ___________________________ Reference No ___________________________
4 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
MU 25 264601(c)(1) The volume and physical and chemical characteristics of the waste in the unit including its potential for emission and dispersal of gases aerosols and particulates
MU 26 264601(c)(2) The effectiveness and reliability of the containing system to prevent emissions
MU 27 264601(c)(3) The operating characteristics of the unit
MU 28 264601(c)(4) The atmospheric meteorologic and topographic characteristics of the unit and surrounding area
MU 29 264601(c)(5) The existing quality of air including other sources of contamination and their cumulative impact on air
MU 30 264601(c)(6) The potential for health risks due to exposure
MU 31 264601(c)(7) The potential for damage to animals wildlife crops vegetation and physical structures
Monitoring testing analytical data inspection response and reporting procedures and frequencies must be in compliance with 264601 26415 26433 26475 26476 26477 and 264101 as well other additional requirements
(MU 33) POST-CLOSURE CARE - 264603
Must comply with 264601 during the post-closure care period
The post-closure plan under 264118 must specify the procedures to satisfy this requirement
9 VAC 20-60-12 et seq and 40 CFR 261 et seq as adopted by reference
A PART A APPLICATION 9 VAC 20-60-980 and 1000
B Facility Description
B-1 General Description 9 VAC 20-60-1010B1
Describe the facility including the nature of the business Off-site facilities should identify the types of industry served on-site facilities should briefly describe the process(es) involved in the generation of hazardous waste
B-2 Topographic Map 9 VAC 20-60-1010I
B-2a General Requirements 9 VAC 20-60-1010I
Show the facility and a distance of 1000 feet around it at a scale of 1 inch equal to not more than 200 feet The map must include contours sufficient to show surface water flow in the vicinity of and from each operational unit (eg contours of 5 feet if relief is greater than 20 feet contours of 2 feet if the relief is greater than 20 feet) The map must include contours sufficient to show surface water flow around facility unit operations map date 100-year floodplain area surface waters surrounding land uses a wind rose map orientation and legal boundaries of facility site The map must also indicate location of access control injection and withdrawal wells buildings structures sewers (storm sanitary and process) loading and unloading areas fire control facilities flood control or drainage barriers run-off control systems and location of (proposed) new and existing hazardous waste management units and solid waste management units Note Multiple maps may be submitted but all must be at a scale of one inch equals not more than 200 feet
B-2b Additional Requirements for Land Disposal Facilities 9 VAC 20-60-264 and 1010K3 and 1010K4 40 CFR 26495 and 26497
The topographic map must also indicate the waste management area boundaries property boundaries proposed point of compliance proposed groundwater monitoring well locations the locations of the uppermost aquifer and aquifers hydraulically interconnected beneath the facility (including flow direction and rate) and if present the extent of the plume of contamination that has entered the groundwater from a regulated unit Note Multiple maps may be submitted but all must be at a scale of one inch equals not more than 200 feet
B-3 Location Information
B-3a Seismic Standard 9 VAC 20-60-264 and 270 40 CFR 26418(a) and 27014(b)(11)(i) and (ii)
New facilities must identify the political jurisdiction (county township or election district) in which the facility will be located If the facility will be located in an area listed in CFR Part 264 Appendix VI prove that the faclity is located at least 3000 feet from any faults that have had displacement in Holocene time or that no such faults pass within 200 feet of proposed hazardous waste treatment storage or disposal areas Proof may be based on geologic studies aerial photographs filed observations or subsurface investigations All information must be acceptable to a geologist experienced in evaluating seismic activity
B-3b Floodplain Standard 9 VAC 20-60-264 and 1010C1 40 CFR 26418(b) and 270(b)(11)(iii)
Document whether or not the facility is located within a 100-year floodplain and include the source of data (Federal Insurance Administration Map or equivalent maps and calculations)
B-3b(1) Demonstration of Compliance 9 VAC 20-60-264 and 1010C3 40 CFR 26418(b) and 270(b)(11)(iv)
For facilities located within the 100-year floodplain describe how the facility is designed constructed operated and maintained to prevent washout of any hazardous waste during a flood
B-3b(1)(a) Flood Proofing and Flood Protection Measures 9 VAC 20-60-1010C2a and b
Provide a structural or other engineering study indicating the various hydrodynamic and hydrostatic forces expected in a 100-year flood and showing how the design of the hazardous waste units and flood proofing and protection devices at the facility will prevent washout or
B-3b(1)(b) Flood Plan 9 VAC 20-60-1010C2c
Describe the procedures to be followed to remove hazardous waste to safety before the facility is flooded including timing related to flood levels estimated time to move the waste the location to which the waste will be moved demonstration that those facilities will be eligible to receive hazardous waste the planned procedures equipment and personnel to be used and the potential for accidental discharge of the waste during movement
B-3b(2) Plan for Future Compliance With Floodplain Standard 9 VAC 20-60-1010C3
For facilities located within the 100-year floodplain that do not comply with the floodplain standard show how and when the facility will be brought into compliance
B-3b(3) Waiver for Land Storage and Disposal Facilities 9 VAC 20-60-264 40 CFR 264
If a waiver from the Floodplain Standard is requested the owner or operator must demonstrate that there will be no adverse effects on human health or the environment if washout occurs and that procedures are in effect to safely remove the waste before flood waters reach the facility Note that wastes must be removed to a facility that has interim status or is permitted The following factors must be considered in this demonstration the volume and physical and chemical characteristics of the waste the concentration of hazardous constituents that would potentially affect surface waters the impact of such concentrations on the current or potential uses of and water quality standards established for the affected surface waters and the impact of hazardous constituents on the sediments of affected surface waters or the soils of the 100-year floodplain
B-4 Traffic Information 9 VAC 20-60-1010B10
Describe the traffic pattern on-site including estimated volume traffic control signs signals and procedures adequacy of access roadway surfaces and load-bearing capacity for expected traffic on-site
Facility Name ___________________________ Reference No ___________________________
2 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
Environmental Performance Standards - 264601
A miscellaneous unit (MU) must be located designed constructed operated maintained and closed in a manner to ensure protection of human health and the environment
Permits are to contain the design and operating requirements responses to releases and other requirements as necessary
Permits shall include requirements of subparts I through O 270 and 146 that are appropriate
Protection of human health and the environment includes but is not limited to
MU 2 264601(a) Prevention of any releases into the groundwater or subsurface environment considering
MU 3 264601(a)(1) The volume and physical and chemical characteristics of the waste in the unit including its potential for migration through containing structures
MU 4 264601(a)(2) The hydrologic and geologic characteristics of the unit and the surrounding area
MU 5 264601(a)(3) The existing quality of groundwater including other sources of contamination and their cumulative impact on the groundwater
MU 6 264601(a)(4) The quantity and direction of groundwater flow
MU 7 264601(a)(5) The proximity to and withdrawal rates of current and potential groundwater users
MU 8 264601(a)(6) The pattern of land use in the region
MU 9 264601(a)(7) The potential for waste constituents to migrate or deposit into the subsurface physical structure and into the root zone of food-chain crops and other vegetation
MU 10 264601(a)(8) The potential for health risks due to exposure
Facility Name ___________________________ Reference No ___________________________
3 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
MU 11 264601(a)(9) The potential for damage to animals wildlife crops vegetation and physical structures
MU 12 264601(b) Prevention of any releases to surface waters wetlands or soil surface considering
MU 13 264601(b)(1) The volume and physical and chemical characteristics of the waste in the unit
MU 14 264601(b)(2) The effectiveness and reliability of the containing and collection system
MU 15 264601(b)(3) The hydrologic characteristics of the unit and the surrounding area including topography
MU 16 264601(b)(4) The pattern of precipitation in the region
MU 17 264601(b)(5) The quantity quality and direction of groundwater flow
MU 18 264601(b)(6) The proximity of the unit to surface waters
MU 19 264601(b)(7) The current and potential use of surface waters and their established quality standards
MU 20 264601(b)(8) The existing quality of surface waters and surface soils including other sources of contamination and their cumulative impact those media
MU 21 264601(b)(9) The patterns of land use in the region
MU 22 264601(b)(10) The potential for health risks due to exposure
MU 23 264601(b)(11) The potential for damage to animals wildlife crops vegetation and physical structures
MU 24 264601(c) Prevention of any releases to air considering
Facility Name ___________________________ Reference No ___________________________
4 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
MU 25 264601(c)(1) The volume and physical and chemical characteristics of the waste in the unit including its potential for emission and dispersal of gases aerosols and particulates
MU 26 264601(c)(2) The effectiveness and reliability of the containing system to prevent emissions
MU 27 264601(c)(3) The operating characteristics of the unit
MU 28 264601(c)(4) The atmospheric meteorologic and topographic characteristics of the unit and surrounding area
MU 29 264601(c)(5) The existing quality of air including other sources of contamination and their cumulative impact on air
MU 30 264601(c)(6) The potential for health risks due to exposure
MU 31 264601(c)(7) The potential for damage to animals wildlife crops vegetation and physical structures
Monitoring testing analytical data inspection response and reporting procedures and frequencies must be in compliance with 264601 26415 26433 26475 26476 26477 and 264101 as well other additional requirements
(MU 33) POST-CLOSURE CARE - 264603
Must comply with 264601 during the post-closure care period
The post-closure plan under 264118 must specify the procedures to satisfy this requirement
9 VAC 20-60-12 et seq and 40 CFR 261 et seq as adopted by reference
A PART A APPLICATION 9 VAC 20-60-980 and 1000
B Facility Description
B-1 General Description 9 VAC 20-60-1010B1
Describe the facility including the nature of the business Off-site facilities should identify the types of industry served on-site facilities should briefly describe the process(es) involved in the generation of hazardous waste
B-2 Topographic Map 9 VAC 20-60-1010I
B-2a General Requirements 9 VAC 20-60-1010I
Show the facility and a distance of 1000 feet around it at a scale of 1 inch equal to not more than 200 feet The map must include contours sufficient to show surface water flow in the vicinity of and from each operational unit (eg contours of 5 feet if relief is greater than 20 feet contours of 2 feet if the relief is greater than 20 feet) The map must include contours sufficient to show surface water flow around facility unit operations map date 100-year floodplain area surface waters surrounding land uses a wind rose map orientation and legal boundaries of facility site The map must also indicate location of access control injection and withdrawal wells buildings structures sewers (storm sanitary and process) loading and unloading areas fire control facilities flood control or drainage barriers run-off control systems and location of (proposed) new and existing hazardous waste management units and solid waste management units Note Multiple maps may be submitted but all must be at a scale of one inch equals not more than 200 feet
B-2b Additional Requirements for Land Disposal Facilities 9 VAC 20-60-264 and 1010K3 and 1010K4 40 CFR 26495 and 26497
The topographic map must also indicate the waste management area boundaries property boundaries proposed point of compliance proposed groundwater monitoring well locations the locations of the uppermost aquifer and aquifers hydraulically interconnected beneath the facility (including flow direction and rate) and if present the extent of the plume of contamination that has entered the groundwater from a regulated unit Note Multiple maps may be submitted but all must be at a scale of one inch equals not more than 200 feet
B-3 Location Information
B-3a Seismic Standard 9 VAC 20-60-264 and 270 40 CFR 26418(a) and 27014(b)(11)(i) and (ii)
New facilities must identify the political jurisdiction (county township or election district) in which the facility will be located If the facility will be located in an area listed in CFR Part 264 Appendix VI prove that the faclity is located at least 3000 feet from any faults that have had displacement in Holocene time or that no such faults pass within 200 feet of proposed hazardous waste treatment storage or disposal areas Proof may be based on geologic studies aerial photographs filed observations or subsurface investigations All information must be acceptable to a geologist experienced in evaluating seismic activity
B-3b Floodplain Standard 9 VAC 20-60-264 and 1010C1 40 CFR 26418(b) and 270(b)(11)(iii)
Document whether or not the facility is located within a 100-year floodplain and include the source of data (Federal Insurance Administration Map or equivalent maps and calculations)
B-3b(1) Demonstration of Compliance 9 VAC 20-60-264 and 1010C3 40 CFR 26418(b) and 270(b)(11)(iv)
For facilities located within the 100-year floodplain describe how the facility is designed constructed operated and maintained to prevent washout of any hazardous waste during a flood
B-3b(1)(a) Flood Proofing and Flood Protection Measures 9 VAC 20-60-1010C2a and b
Provide a structural or other engineering study indicating the various hydrodynamic and hydrostatic forces expected in a 100-year flood and showing how the design of the hazardous waste units and flood proofing and protection devices at the facility will prevent washout or
B-3b(1)(b) Flood Plan 9 VAC 20-60-1010C2c
Describe the procedures to be followed to remove hazardous waste to safety before the facility is flooded including timing related to flood levels estimated time to move the waste the location to which the waste will be moved demonstration that those facilities will be eligible to receive hazardous waste the planned procedures equipment and personnel to be used and the potential for accidental discharge of the waste during movement
B-3b(2) Plan for Future Compliance With Floodplain Standard 9 VAC 20-60-1010C3
For facilities located within the 100-year floodplain that do not comply with the floodplain standard show how and when the facility will be brought into compliance
B-3b(3) Waiver for Land Storage and Disposal Facilities 9 VAC 20-60-264 40 CFR 264
If a waiver from the Floodplain Standard is requested the owner or operator must demonstrate that there will be no adverse effects on human health or the environment if washout occurs and that procedures are in effect to safely remove the waste before flood waters reach the facility Note that wastes must be removed to a facility that has interim status or is permitted The following factors must be considered in this demonstration the volume and physical and chemical characteristics of the waste the concentration of hazardous constituents that would potentially affect surface waters the impact of such concentrations on the current or potential uses of and water quality standards established for the affected surface waters and the impact of hazardous constituents on the sediments of affected surface waters or the soils of the 100-year floodplain
B-4 Traffic Information 9 VAC 20-60-1010B10
Describe the traffic pattern on-site including estimated volume traffic control signs signals and procedures adequacy of access roadway surfaces and load-bearing capacity for expected traffic on-site
Facility Name ___________________________ Reference No ___________________________
3 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
MU 11 264601(a)(9) The potential for damage to animals wildlife crops vegetation and physical structures
MU 12 264601(b) Prevention of any releases to surface waters wetlands or soil surface considering
MU 13 264601(b)(1) The volume and physical and chemical characteristics of the waste in the unit
MU 14 264601(b)(2) The effectiveness and reliability of the containing and collection system
MU 15 264601(b)(3) The hydrologic characteristics of the unit and the surrounding area including topography
MU 16 264601(b)(4) The pattern of precipitation in the region
MU 17 264601(b)(5) The quantity quality and direction of groundwater flow
MU 18 264601(b)(6) The proximity of the unit to surface waters
MU 19 264601(b)(7) The current and potential use of surface waters and their established quality standards
MU 20 264601(b)(8) The existing quality of surface waters and surface soils including other sources of contamination and their cumulative impact those media
MU 21 264601(b)(9) The patterns of land use in the region
MU 22 264601(b)(10) The potential for health risks due to exposure
MU 23 264601(b)(11) The potential for damage to animals wildlife crops vegetation and physical structures
MU 24 264601(c) Prevention of any releases to air considering
Facility Name ___________________________ Reference No ___________________________
4 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
MU 25 264601(c)(1) The volume and physical and chemical characteristics of the waste in the unit including its potential for emission and dispersal of gases aerosols and particulates
MU 26 264601(c)(2) The effectiveness and reliability of the containing system to prevent emissions
MU 27 264601(c)(3) The operating characteristics of the unit
MU 28 264601(c)(4) The atmospheric meteorologic and topographic characteristics of the unit and surrounding area
MU 29 264601(c)(5) The existing quality of air including other sources of contamination and their cumulative impact on air
MU 30 264601(c)(6) The potential for health risks due to exposure
MU 31 264601(c)(7) The potential for damage to animals wildlife crops vegetation and physical structures
Monitoring testing analytical data inspection response and reporting procedures and frequencies must be in compliance with 264601 26415 26433 26475 26476 26477 and 264101 as well other additional requirements
(MU 33) POST-CLOSURE CARE - 264603
Must comply with 264601 during the post-closure care period
The post-closure plan under 264118 must specify the procedures to satisfy this requirement
9 VAC 20-60-12 et seq and 40 CFR 261 et seq as adopted by reference
A PART A APPLICATION 9 VAC 20-60-980 and 1000
B Facility Description
B-1 General Description 9 VAC 20-60-1010B1
Describe the facility including the nature of the business Off-site facilities should identify the types of industry served on-site facilities should briefly describe the process(es) involved in the generation of hazardous waste
B-2 Topographic Map 9 VAC 20-60-1010I
B-2a General Requirements 9 VAC 20-60-1010I
Show the facility and a distance of 1000 feet around it at a scale of 1 inch equal to not more than 200 feet The map must include contours sufficient to show surface water flow in the vicinity of and from each operational unit (eg contours of 5 feet if relief is greater than 20 feet contours of 2 feet if the relief is greater than 20 feet) The map must include contours sufficient to show surface water flow around facility unit operations map date 100-year floodplain area surface waters surrounding land uses a wind rose map orientation and legal boundaries of facility site The map must also indicate location of access control injection and withdrawal wells buildings structures sewers (storm sanitary and process) loading and unloading areas fire control facilities flood control or drainage barriers run-off control systems and location of (proposed) new and existing hazardous waste management units and solid waste management units Note Multiple maps may be submitted but all must be at a scale of one inch equals not more than 200 feet
B-2b Additional Requirements for Land Disposal Facilities 9 VAC 20-60-264 and 1010K3 and 1010K4 40 CFR 26495 and 26497
The topographic map must also indicate the waste management area boundaries property boundaries proposed point of compliance proposed groundwater monitoring well locations the locations of the uppermost aquifer and aquifers hydraulically interconnected beneath the facility (including flow direction and rate) and if present the extent of the plume of contamination that has entered the groundwater from a regulated unit Note Multiple maps may be submitted but all must be at a scale of one inch equals not more than 200 feet
B-3 Location Information
B-3a Seismic Standard 9 VAC 20-60-264 and 270 40 CFR 26418(a) and 27014(b)(11)(i) and (ii)
New facilities must identify the political jurisdiction (county township or election district) in which the facility will be located If the facility will be located in an area listed in CFR Part 264 Appendix VI prove that the faclity is located at least 3000 feet from any faults that have had displacement in Holocene time or that no such faults pass within 200 feet of proposed hazardous waste treatment storage or disposal areas Proof may be based on geologic studies aerial photographs filed observations or subsurface investigations All information must be acceptable to a geologist experienced in evaluating seismic activity
B-3b Floodplain Standard 9 VAC 20-60-264 and 1010C1 40 CFR 26418(b) and 270(b)(11)(iii)
Document whether or not the facility is located within a 100-year floodplain and include the source of data (Federal Insurance Administration Map or equivalent maps and calculations)
B-3b(1) Demonstration of Compliance 9 VAC 20-60-264 and 1010C3 40 CFR 26418(b) and 270(b)(11)(iv)
For facilities located within the 100-year floodplain describe how the facility is designed constructed operated and maintained to prevent washout of any hazardous waste during a flood
B-3b(1)(a) Flood Proofing and Flood Protection Measures 9 VAC 20-60-1010C2a and b
Provide a structural or other engineering study indicating the various hydrodynamic and hydrostatic forces expected in a 100-year flood and showing how the design of the hazardous waste units and flood proofing and protection devices at the facility will prevent washout or
B-3b(1)(b) Flood Plan 9 VAC 20-60-1010C2c
Describe the procedures to be followed to remove hazardous waste to safety before the facility is flooded including timing related to flood levels estimated time to move the waste the location to which the waste will be moved demonstration that those facilities will be eligible to receive hazardous waste the planned procedures equipment and personnel to be used and the potential for accidental discharge of the waste during movement
B-3b(2) Plan for Future Compliance With Floodplain Standard 9 VAC 20-60-1010C3
For facilities located within the 100-year floodplain that do not comply with the floodplain standard show how and when the facility will be brought into compliance
B-3b(3) Waiver for Land Storage and Disposal Facilities 9 VAC 20-60-264 40 CFR 264
If a waiver from the Floodplain Standard is requested the owner or operator must demonstrate that there will be no adverse effects on human health or the environment if washout occurs and that procedures are in effect to safely remove the waste before flood waters reach the facility Note that wastes must be removed to a facility that has interim status or is permitted The following factors must be considered in this demonstration the volume and physical and chemical characteristics of the waste the concentration of hazardous constituents that would potentially affect surface waters the impact of such concentrations on the current or potential uses of and water quality standards established for the affected surface waters and the impact of hazardous constituents on the sediments of affected surface waters or the soils of the 100-year floodplain
B-4 Traffic Information 9 VAC 20-60-1010B10
Describe the traffic pattern on-site including estimated volume traffic control signs signals and procedures adequacy of access roadway surfaces and load-bearing capacity for expected traffic on-site
Facility Name ___________________________ Reference No ___________________________
4 A Reviewerrsquos Initials ________ Tracking Date ________
T Reviewerrsquos Initials ________ Tracking Date ________
ITEM
FEDERAL
REGULATIONS 40 CFR
STATE
REGULATIONS
GENERAL DESCRIPTION
INFO
LOCATION
ADMIN COMPLETE
TECHNICALLY COMPLETE
REMARKS
YESNONA YESNONA
MU 25 264601(c)(1) The volume and physical and chemical characteristics of the waste in the unit including its potential for emission and dispersal of gases aerosols and particulates
MU 26 264601(c)(2) The effectiveness and reliability of the containing system to prevent emissions
MU 27 264601(c)(3) The operating characteristics of the unit
MU 28 264601(c)(4) The atmospheric meteorologic and topographic characteristics of the unit and surrounding area
MU 29 264601(c)(5) The existing quality of air including other sources of contamination and their cumulative impact on air
MU 30 264601(c)(6) The potential for health risks due to exposure
MU 31 264601(c)(7) The potential for damage to animals wildlife crops vegetation and physical structures
Monitoring testing analytical data inspection response and reporting procedures and frequencies must be in compliance with 264601 26415 26433 26475 26476 26477 and 264101 as well other additional requirements
(MU 33) POST-CLOSURE CARE - 264603
Must comply with 264601 during the post-closure care period
The post-closure plan under 264118 must specify the procedures to satisfy this requirement
9 VAC 20-60-12 et seq and 40 CFR 261 et seq as adopted by reference
A PART A APPLICATION 9 VAC 20-60-980 and 1000
B Facility Description
B-1 General Description 9 VAC 20-60-1010B1
Describe the facility including the nature of the business Off-site facilities should identify the types of industry served on-site facilities should briefly describe the process(es) involved in the generation of hazardous waste
B-2 Topographic Map 9 VAC 20-60-1010I
B-2a General Requirements 9 VAC 20-60-1010I
Show the facility and a distance of 1000 feet around it at a scale of 1 inch equal to not more than 200 feet The map must include contours sufficient to show surface water flow in the vicinity of and from each operational unit (eg contours of 5 feet if relief is greater than 20 feet contours of 2 feet if the relief is greater than 20 feet) The map must include contours sufficient to show surface water flow around facility unit operations map date 100-year floodplain area surface waters surrounding land uses a wind rose map orientation and legal boundaries of facility site The map must also indicate location of access control injection and withdrawal wells buildings structures sewers (storm sanitary and process) loading and unloading areas fire control facilities flood control or drainage barriers run-off control systems and location of (proposed) new and existing hazardous waste management units and solid waste management units Note Multiple maps may be submitted but all must be at a scale of one inch equals not more than 200 feet
B-2b Additional Requirements for Land Disposal Facilities 9 VAC 20-60-264 and 1010K3 and 1010K4 40 CFR 26495 and 26497
The topographic map must also indicate the waste management area boundaries property boundaries proposed point of compliance proposed groundwater monitoring well locations the locations of the uppermost aquifer and aquifers hydraulically interconnected beneath the facility (including flow direction and rate) and if present the extent of the plume of contamination that has entered the groundwater from a regulated unit Note Multiple maps may be submitted but all must be at a scale of one inch equals not more than 200 feet
B-3 Location Information
B-3a Seismic Standard 9 VAC 20-60-264 and 270 40 CFR 26418(a) and 27014(b)(11)(i) and (ii)
New facilities must identify the political jurisdiction (county township or election district) in which the facility will be located If the facility will be located in an area listed in CFR Part 264 Appendix VI prove that the faclity is located at least 3000 feet from any faults that have had displacement in Holocene time or that no such faults pass within 200 feet of proposed hazardous waste treatment storage or disposal areas Proof may be based on geologic studies aerial photographs filed observations or subsurface investigations All information must be acceptable to a geologist experienced in evaluating seismic activity
B-3b Floodplain Standard 9 VAC 20-60-264 and 1010C1 40 CFR 26418(b) and 270(b)(11)(iii)
Document whether or not the facility is located within a 100-year floodplain and include the source of data (Federal Insurance Administration Map or equivalent maps and calculations)
B-3b(1) Demonstration of Compliance 9 VAC 20-60-264 and 1010C3 40 CFR 26418(b) and 270(b)(11)(iv)
For facilities located within the 100-year floodplain describe how the facility is designed constructed operated and maintained to prevent washout of any hazardous waste during a flood
B-3b(1)(a) Flood Proofing and Flood Protection Measures 9 VAC 20-60-1010C2a and b
Provide a structural or other engineering study indicating the various hydrodynamic and hydrostatic forces expected in a 100-year flood and showing how the design of the hazardous waste units and flood proofing and protection devices at the facility will prevent washout or
B-3b(1)(b) Flood Plan 9 VAC 20-60-1010C2c
Describe the procedures to be followed to remove hazardous waste to safety before the facility is flooded including timing related to flood levels estimated time to move the waste the location to which the waste will be moved demonstration that those facilities will be eligible to receive hazardous waste the planned procedures equipment and personnel to be used and the potential for accidental discharge of the waste during movement
B-3b(2) Plan for Future Compliance With Floodplain Standard 9 VAC 20-60-1010C3
For facilities located within the 100-year floodplain that do not comply with the floodplain standard show how and when the facility will be brought into compliance
B-3b(3) Waiver for Land Storage and Disposal Facilities 9 VAC 20-60-264 40 CFR 264
If a waiver from the Floodplain Standard is requested the owner or operator must demonstrate that there will be no adverse effects on human health or the environment if washout occurs and that procedures are in effect to safely remove the waste before flood waters reach the facility Note that wastes must be removed to a facility that has interim status or is permitted The following factors must be considered in this demonstration the volume and physical and chemical characteristics of the waste the concentration of hazardous constituents that would potentially affect surface waters the impact of such concentrations on the current or potential uses of and water quality standards established for the affected surface waters and the impact of hazardous constituents on the sediments of affected surface waters or the soils of the 100-year floodplain
B-4 Traffic Information 9 VAC 20-60-1010B10
Describe the traffic pattern on-site including estimated volume traffic control signs signals and procedures adequacy of access roadway surfaces and load-bearing capacity for expected traffic on-site
Emission Factors from Aerial and Ground Measurements of Field andLaboratory Forest Burns in the Southeastern US PM25 Black andBrown Carbon VOC and PCDDPCDFJohanna Aurelldagger and Brian K Gullett
US Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United States
S Supporting Information
ABSTRACT Aerial- and ground-sampled emissions from three prescribed forest burns inthe southeastern US were compared to emissions from laboratory open burn tests usingbiomass from the same locations A comprehensive array of emissions including PM25black carbon (BC) brown carbon (BrC) carbon dioxide (CO2) volatile organiccompounds (VOCs) and polychlorinated dibenzo-p-dioxins (PCDDs) and polychlori-nated dibenzofurans (PCDFs) were sampled using ground-based and aerostat-loftedplatforms for determination of emission factors The PM25 emission factors ranged from 14to 47 gkg biomass up to three times higher than previously published studies Thebiomass type was the primary determinant of PM25 rather than whether the emissionsample was gathered from the laboratory or the field and from aerial- or ground-basedsampling The BC and BrC emission factors ranged from 12 to 21 gkg biomass and 10to 14 gkg biomass respectively A decrease in BC and BrC emission factors withdecreased combustion efficiency was found from both field and laboratory data VOCemission factors increased with decreased combustion efficiency No apparent differences in averaged emission factors wereobserved between the field and laboratory for BC BrC and VOCs The average PCDDPCDF emission factors ranged from006 to 46 ng TEQkg biomass
INTRODUCTIONPrescribed forest burns are used to avoid wildfires and keepecological sustainability to maintain ecosystem habitats foranimal and plant species Wildfires and prescribed forest burnsgenerate a complex mix of emissions and some of the majorpollutants are particulate matter (PM) such as PM25 (PM withan aerodynamic diameter less than or equal to 25 μm) blackcarbon (BC) brown carbon (BrC) carbon dioxide (CO2)volatile organic compounds (VOCs) and semivolatile organiccompounds (SVOCs) such as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans(PCDFs) Measurement of pollutant emission factors allowsprediction of exposure and possible harm to human health andthe environment and use in emission inventory calculationsHowever obtaining emission factors from wildfires andprescribed forest burns is difficult Proper distances must bemaintained for personnel and equipment safety while at thesame time the sampling equipment must be close enough to thesource to obtain detectable emission levels This also raisesquestions of representativeness as the less hazardoussmoldering phase of the fire may be disproportionatelysampled particularly by close-proximity ground-based sam-pling These challenges together with the relatively high costsfor measuring emissions from field forest burns suggestpossible advantages to conducting laboratory burn simulationsfor emission sampling However the laboratory burns may havequestions of representativeness as only a small fraction of
biomass can be burned compared to the field burns and thedifferences in their underlying fuel bedsTarget pollutants from forest burns are selected based on
their health environment and climate effects PM25 is a criteriapollutant regulated by the US EPA due to its health effectsWhen inhaled PM25 can enter the lungs potentially carryingmetals and other toxic pollutants which can cause adversehealth effects PM25 can also cause decreased visibility in theform of haze According to the US EPArsquos National EmissionsInventory (NEI)1 12 and 17 of the PM25 emissions in theUSA (2008) were emitted from prescribed forest burns andwildfires respectively making forest burns the largest source ofPM25 emissions in the USA This can be compared to 92 ofPM25 from transportation sources1 The southeastern part ofthe USA is responsible for 26 of the PM25 emissions fromforest burns1 However only limited and varied emission factordata are available from this area A small-scale laboratory forestburn study of mixed biomass species from South Eastern UShad an average PM25emission factor of 99 gkg biomass2
While two other small-scale laboratory forest burn with biomassspecies from North Carolina (NC) and Florida (FL) showedhigher emission factors and average of 20minus22 gkg biomass34
Received May 10 2013Revised June 26 2013Accepted July 1 2013Published July 29 2013
Article
pubsacsorgest
copy 2013 American Chemical Society 8443 dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus8452
These emission factors are higher than the emission factorsfound from airborne5 tower based6 and ground based7 fieldmeasurements at prescribed forest burns from South EasternUS (11 gkg biomass 14 gkg biomass and 9minus16g kgbiomass) which in turn is ten times higher than the emissionfactors found from ground based sampling from prescribedburning in Georgia (090 gkg biomass)8
Black carbon is an efficient light-absorbing aerosol in theinfrared (IR) spectrum known to be a major contributor toglobal climate change9 Brown carbon is defined as light-absorbing organic matter aerosols from various sources foundin the ultraviolet (UV) spectrum10 which is starting to getmore attention as a possible contributor to global warm-ing10minus12 Only a few BC emission factors from wildfires andprescribed forest burns have been reported Kondo et al13
reported values of 180 ngm3 BCppm CO2 or 011 g BCkgbiomass consumed (using a biomass carbon fraction of 050)for boreal forest fires while others have reported values of037minus066 gkg biomass1415 for savanna and tropical forestburns In the absence of BC emission factors elemental carbon(EC) and PM25 data are usually used to calculateestimate BCinventories Elemental carbon is batch-sampled onto a filter andmeasured by thermal-optical transmission techniques4 whereasBC is measured continuously with an optical technique such asan aethalometer which records changes in the optical lightattenuation on a disposable filter A number of studies havereported EC emission factors from wildfires and prescribedforest burns in Brazil16 Africa17 Georgia (US)8 andPortugal18 as well as laboratory small-scale biomass burnswith biomass species from South Eastern US2minus4 Theseemission factors ranged almost 2 orders of magnitude from0035 to 15 g ECkg biomass consumed with no differencebetween field and laboratory emission levelsThe majority of the compounds on the US EPArsquos list of
hazardous air pollutions (HAPs) are VOCs19 Some of theVOCs such as benzene 13-butadiene and acrolein are toxic to
humans while others such as xylene toluene and 124-trimethyl benzene can form fine PM and ground level ozonewhich is a criteria pollutant tied to respiratory ailments20 TheNEI estimated that 96 and 16 of VOC emissions in theUSA (2008) were emitted from prescribed forest burns andwildfires respectively of which 23 originate from thesoutheastern USA Only a limited number of forest burnVOC emission factors from the HAP list are available in theliterature The few VOC emission factors are derived fromdifferent biomass sources and vary considerably ie thebenzene emission factor was 018 gkg biomass from African21
savanna forest burns 065 gkg biomass from laboratory burnsof Brazil tropical forest species22 22 gkg biomass from pinedominated forest burns in GA (US)8 and 028minus080 gkgbiomass from prescribed burns in SC (US) Yokelson et al2223
studied VOC emissions from field and laboratory burns ofBrazilian tropical forest biomass finding higher benzeneemission factors from the laboratory study than from thefield studyPCDDsPCDFs are recognized as toxic bioaccumulative
and persistent in the environment Combustion sources such asopen burning of biomass have been identified as the majorsource of global PCDDsPCDFs24 However emission factordata such as from prescribed field forest burning and laboratoryforest burns are limited and of broad range25minus27 from 055 to25 ng toxic equivalent (TEQ)kg biomass Only one of thesestudies compared emission factors derived from the field withlaboratory measurements finding no difference27
This study aimed to obtain emission factors from prescribedforest burns and compare these to emissions obtained fromsmall-scale laboratory burns using the same biomass sourceField measurements were conducted via either aerial-basedmeasurements to achieve proportional emission sampling fromboth flaming and smoldering phases or ground-based measure-ments at three different locations in the southeastern part of theUS The same sampling equipment was used for both field and
measures the light attenuation in aerosols accumulated onto aquartz filter at the infrared wavelength of 880 nm
black carbon AE52a continuous every 10 s see above IR 880 nmbrown carbon AE52a continuous every 10 s measures the light attenuation in aerosols accumulated onto a
quartz filter at the ultraviolet wavelength of 370 nmPM1 PM25 PM7 PM10and TSPi
Aerocet 531b continuous every 2 min light-scattering laser photometer
PM25j DustTrak 8520c continuous every
secondlight-scattering laser photometer
PM25 Impactord 47 mm Teflon filter(pore size 20 μm)
electrochemical oxidation of CO range of 0minus1000 ppm
ambient pressureelevation and location
MTi-Gg continuous everysecond
global position system attitude and heading reference system(AHRS) static pressure sensor
aAethlabs US bMet One Instruments Inc US cTSI Inc US dSKC Inc US eLICOR Biosciences US fTransducer Technology inc US gXsensNetherlands hLeland Legacy pump SKC Inc US) iused in FL and NC jUsed in SC kResponse time 20minus30 s
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528444
laboratory measurements to avoid method differences Acomprehensive list of pollutants was simultaneously collectedto allow for intercomparisons
EXPERIMENTAL SECTIONThree field sampling campaigns of prescribed forest burns wereconducted at three different locations of the southeastern partof the US (1) Eglin Air Force Base (February 2011) locatedon the northwestern part of Florida (FL) on the Gulf of Mexicocoast (2) Marine Corps Base Camp Lejeune (FebruaryMarch2011) located on the Atlantic Ocean coast (east coast) ofNorth Carolina (NC) and (3) Fort Jackson (OctoberNovember 2011) located in the central part of South Carolina(SC) approximately 200 km from the Atlantic Ocean coastTwo to three different areas were burned on separate days foreach location Combustible biomass was collected at each of thelocations and brought back to the US EPArsquos open burn testfacility (OBTF) in Research Triangle Park NC for small scaleburn testsAerial and Ground-Based Sampling Methods A 43 m
diameter tethered aerostat (Kingfisher Model Aerial ProductsInc US) was used as an aerial sampling platform and an allterrain vehicle (ATV) was used as a ground sampling platform(Supporting Information (SI) Figure S1) The helium-filledaerostat and the ATV carried duplicate sampling instrumenta-tion packages each termed the ldquoFlyerrdquo (SI Figure S2) Theground based platform transported the Flyer on a standattached on the back of an ATV at an approximate height of 25m above ground level Emission sampling was not performedwhile in transport to avoid gasoline fumes from the exhaustThe aerostat sampling method has been described in detailelsewhere2829 In summary the aerostat lofts the Flyer intoplumes and is maneuvered by a tether attached to a remote-controlled winch on an ATV For the NC study data wererecorded every second onto an on-board stand-alone datalogger (HOBO U12minus013 Onset Computer CorporationUS) For the FL and SC studies the Flyer was updated withan onboard USB-based data acquisition (DAQ) card (Measure-ment Computing USB-2537) controlled by an on-boardcomputer running a LabView generated data acquisition andcontrol program This update also included a ground-basedcomputer used to view data in real time and control thesampling via a wireless remote desktop connection Thecomputer data were logged at a rate of 10 Hz Additionally toavoid dilution of samples when not in the plume the batchsamplers were automatically turned on and off by a carbondioxide (CO2) ldquotriggerrdquo at a user-set plume concentrationInstrumentation For these sampling efforts the Flyer was
equipped for continuous measurement of CO2 BC and particlesize distribution semicontinuous measurement of CO andbatch sampling of PM25 VOCs and PCDDPCDF (Table 1)The CO2 was measured at a range set to 0minus4500 ppm andunderwent three-point calibration for CO2 on a daily basisaccording to US EPA Method 3A30 The CO2 unit (Table 1)had an accuracy of less than 3 of reading a precision of 1 ppmand a response time of one second CO was measured using anelectrochemical sensor with a response time of 20minus30 s Thelong response time of the sensor precluded its usefulness in thefield where concentrations could vary significantly in less than1 s The CO sensor underwent a three-point calibration beforeuse according to US EPA Method 3A30 The PCDDPCDFsampler used a 48 V (DC) Windjammer brushless directcurrent blower (AMETEK Inc US) resulting in a nominal
sampling rate of 085 m3min Flow rate was measured by a 0minus622 Pa pressure differential transducer (Setra Model 265 US)across a Herschel Standard Venturi tube with a throat andupstream diameter of 31 and 45 mm respectively The pressuredifferential voltage equivalent was recorded on the onboardcomputer or HOBO data logger and calibrated with a Rootsmeter (Model 5M Dresser Measurement US) The Flyer onthe aerostat was run on a 48 V 10 Amp-h Li-ion rechargeablebattery which has a battery capacity for approximately onehour of PCDDPCDF sampling The ground-based Flyer wasrun with four 12 V 75 Amp-h in series deep cycle marinebatteries with approximately 4minus5 h of sampling Summacanisters were equipped with an electronic solenoid valvepressure transducer and a frit filter All instruments were time-synchronized each day
Analyses The PCDDPCDF samples were extracted andcleaned up by a modified US EPA Method TO-9A35 andanalyzed using high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS)36 Trip andfield blanks were collected and analyzed for PCDDPCDFQuantities of raw biomass 202 183 and 51 g from NC FLand SC respectively were Soxhlet-extracted using US EPAMethod 354037 and spiked and analyzed for PCDDPCDFaccording to US EPA Method TO-9A35 The 2005 WorldHealth Organization (WHO) 2005 toxic equivalent factors(TEFs)38 were used to determine the PCDDPCDF TEQemission factors Not all TEF-weighted PCDDPCDFcongeners were detected in all samples The congeners thatwere not detected (ND) were set to zero in the text but SITables S1minusS3 show the PCDDPCDF values both at ND = 0and ND = limit of detection) All data were normalized to 1atm and 211 degC and background-corrected by subtractingambient air concentrations Values of the raw biomass forPCDDPCDF content were normalized using the raw carbonfraction of each biomass (SI Table S1)
Biomass The major species in FL and SC were LongleafPine (Pinus palustris) Turkey Oak (Quercus laevis) and SandLive Oak (Quercus geminata) while the NC biomass consistedof Loblolly Pine seedlings (Pinus taeda) Red Bay (Perseaborbonia) Inkberry (Ilex glabra) and Red Maple (Acerrubrum) The SC burn sites had not been burnt in the last50 years and were considered ldquounmanagedrdquo stands with theexpectation that their burns would more represent behavior ofan uncontrolled fireCombustible biomass was collected from a 91 times 91 m2 area
at all three locations and transported to the OBTF at US EPARTP NC for burn testing within seven days The biomass fromeach of the locations (approximately 30 to 60 kg) was dividedby standard cone and quarter methods for ultimate (SI TableS1) and PCDDPCDF analyses in the unburnt biomass and forcombustion testing in the OBTF Three replicate OBTF testswere each comprised of multiple sequential 14minus15 kgbiomass charges at the same area density as in the field
Field Burn Description Solely the aerostat-based samplingmethod was used in the FL and NC studies while only theground based sampling platform was used in SC due to airspacerestrictions Aerostat sampling was conducted downwind of theprescribed burn areas on the borderline of the burn area alongan open field or a road The average aerostat sampling altitudewas higher for the FL burns (115 m maximum 327 m) than forthe NC burns (13 m maximum 46 m) due to plume rise Theground-based sampling equipment was approximately 2 mabove ground level at all times Ground-based sampling at SC
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was performed downwind of the burn area on firebreak roadsTwo simultaneous Flyer samples were combined for two ofthree sampling days in SC to obtain detectable PCDDPCDFlevels The SC burns were presupposed to be of higherintensity than those in FL and NC since the forest had nohistory of prescribed burn treatmentOpen Burn Test Facility A 70 m3 enclosed OBTF
described in detail elsewhere39 was used for simulatingprescribed forest burns (SI Figure S1) The OBTF wasequipped with a high-volume blower that pulls ambient air intothe OBTF This blower and small fans located inside the facilityensured complete mixing and oxygen concentrations close toambient Burn tests were performed 6minus7 days after biomasscollection at the same area density as found in the field Becausethe small charge sizes used in the OBTF do not necessarilyprovide sufficient mass of PCDDPCDF emissions to avoidnondetectable congeners emissions from multiple charge burnswere composited to obtain a single measurement The biomasscharges were burned one after the other a new charge wasloaded when the CO2 concentration decreased to approx-imately 500 ppm The small burn charges were used to mimicthe field area density and keep the temperature inside thefacility below 50 degC around the sampling equipment to avoidoverheating Flyer electronics and the sampling media Theburns were performed on an aluminum-foil-covered steel plateand the aluminum foil was replaced before each burn testThe same sampling instrumentation was used in the OBTF
as in the field The Flyer was placed inside the facility near theair exit duct For the SC biomass burn tests two PCDDPCDF
samples were collected simultaneously using two Flyers Twopostburn OBTF ambient air background samples werecollected for a total of 5minus10 h inside the uncleaned OBTFover three separate days
Calculations The concentration ratios of the cosampledtarget analytes and the CO2 above ambient levels (ΔCO2)(plus Summa canister ΔCO for VOCs) were used to deriveemission factors according to the carbon mass balanceapproach40 Emission factors are expressed in terms of pollutantmass per mass of biomass where the latter indicates the mass ofbiomass consumed by the fire The carbon mass balanceassumes that all combusted carbon in the biomass is emitted tothe atmosphere as CO2 CO methane and total hydrocarbons(THCs) and that the carbon and pollutants are completelymixed in the plume Calculations from a previous forestlaboratory burn study show that 90minus996 of the total carbonemitted (sum of CO and CO2) was CO2
4 and that THCconcentration was 2minus4 times lower than the CO concentrationThus carbon concentrations from CO and THC were minimaland only CO2 measurements were needed to approximate thetotal mass of carbon emitted Neglecting CO and trace VOCscould have an approximate 10 effect on the emission factor avalue within the total error of the method and likely thereproducibility of the event The biomass composition carbonfractions (Fc) in the preburnedraw biomass (SI Table S1)were then used to calculate emission factors (EFs) bymultiplying Fc with the mass of analyte per mass of carbonThe semicontinuous CO measurements acquired from the
Table 2 Resultsa
aOBTF minus Open burn test facility FL minus North West Florida NC minus East North Carolina SC minus Central South Carolina NM minus not measured FR minusFailed recovery (recovery under method limits) bLimit of detection values within parentheses for those samples with not detected congenerscComposite sample from two field days dParallel sampling of PCDDPCDF - two PCDDPCDF samples collected during the same time eAllOBTF emission factors shown in SI Table S10
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OBTF tests were used only to calculate the modifiedcombustion efficiency (MCE) (ΔCO2(ΔCO2 + ΔCO))The VOC samples were unique in that the summa canister
data provided both CO2 and measurable CO concentrationsallowing emission factors to be assigned to flaming andsmoldering modes by calculating the MCE where the flamingmode has a MCE gt 095 and the smoldering mode has a MCElt 090Custom correction factors for the continuous measured PM
were derived as by manufacture instruction to improve themeasurement accuracy from prescribed forest burns Thesecorrection factors were conducted by dividing the averagecontinuous PM25 concentration by the PM25 by filterconcentration during the same collection time (for eachcollected filter) The average correction factor for the DustTrak8520 and the Aerocet 531 was 20 plusmn 056 and 63 plusmn 22respectivelyThe black carbon data were postprocessed for noise using an
optimized noise-reduction averaging algorithm program41 Nocorrection for particle loading on the filters was made since theBC concentration did not change with an increased lightattenuation value (ATN) reported from the AE51 and AE52
RESULTS AND DISCUSSIONNine prescribed burns were sampled at three separate locationsas well as companion laboratory burns with site-gatheredbiomass At the field sites aerial ground-only or both aerial-and ground-based sampling were conducted as site constraintsallowed (Table 2)Particulate Matter The continuous PM25 and CO2
concentrations were highest for the ground-based fieldsampling in SC and lowest for the aerostat-based sampling inFL (SI Figure S3) likely due to the comparative proximity ofthe ground-based sampler to the source The average PM25emission factors from the three different field burn locationsand the OBTF derived from the ratio of the PM mass to thecarbon collected as CO2 ranged from 14 to 47 gkg biomass(Figure 1) These emission factors are mostly higher than
previously reported from prescribed and wildfire forest burns inthe US Portugal and Mexico at 066minus16 gkg bio-mass5minus84243 but overlapping those from previous OBTFforest burns of different biomass types 11minus34 gkg biomass4
A 3-fold difference in average PM25 emission factors wasobserved between the three field values Field and correspond-ing OBTF PM25 emission factors were quite similar also
showing a 3-fold range ANOVA analyses were performed ontwenty-one OBTF and fifteen field PM25 samples from thethree field burn locations No statistical differences (α = 005)were observed between PM25 emission factors derived in thefield and the OBTF suggesting the adequacy of the laboratorysimulation A statistical difference between the OBTF-derivedemission factors was found between FL and both SC and NCThe field-derived emission factors were only statisticallydifferent between the FL and SC biomass sources Theseresults indicate that it is the biomass composition itself ratherthan the laboratory-versus field-based sampling distinctions thatdrive the PM25 emission factor levels As none of the testingafforded opportunities for both aerial and ground basedsampling future research should compare emission factorsderived from simultaneous use of both of these methods
Black and Brown Carbon The field and OBTF averageBC and BrC emission factors ranged from 12 to 21 gkgbiomass and 10 to 14 gkg biomass respectively (Figure 2)
These BC emission factors are generally higher than previouslyreported for forest burn EC and estimated BC emission factorsof 0035minus13 gkg biomass34816minus18 and 037minus066 gkgbiomass1415 respectively The BC emission factors determinedhere are in the same range as medium-and high-duty dieseltrucks 092minus2340414445 gkg fuel4041 ANOVA analysisshowed a slight difference (F = 533) in BC emission factorsbetween the SC OBTF and its corresponding field data but notfor the FL and NC field versus OBTF data There werestatistical differences in OBTF BC emission levels for the NCbiomass with those from FL and SC but no such differenceswere observed for the field dataFigures 3A and B show time-resolved BC BrC ΔCO2
ΔCO and MCE concentrations and emission factor datarespectively for a representative OBTF burn of SC biomass Alldata reach a rapid peak at the onset of combustion As theemission factor data are mass-loss-normalized (Figure 3B) theinitial peaks indicate that the early onset emissions areproportionately higher than subsequent emissions The earlypeak BC and BrC emission factors are more than 2 to 10 timeshigher respectively than their whole-run averages indicatingthat fire intensity characteristics have a significant impact onemissions The BC and BrC concentrations decline exponen-tially with the MCE and time or as the ΔCO2 concentration
Figure 1 PM25 emission factors from field and OBTF forest burns forthree different biomass sources northwestern Florida (FL) the NorthCarolina east coast (NC) and Central South Carolina (SC) Error barsdenote one standard deviation (NC SC) or range of data (FL)
Figure 2 Black and brown carbon emission factors from the threebiomass sources northwestern Florida (FL) North Carolina east coast(NC) and Central South Carolina (SC) sampled in the field and inthe OBTF Error bars denote one standard deviation (SC) or range ofdata (FL NC)
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decreases (Figure 3A) The OBTF laboratory data (Figure 3B)show an exponential decrease in BC and BrC emission factorswith a decrease in MCE and also reveal that while the BC andBrC concentrations are low at the start of a burn the MCE isthe highest (Figure 3A)Figure 4AB shows the comparable BC BrC CO2 and CO
concentrations and emission factor data respectively for thefield tests at SC The concentration data show predictably morefluctuation than the OBTF data (Figure 3A) as the former issubject to turbulent mixing while the latter is a well-stirredscenario MCE values from the Summa canister CO and CO2
grab samples were compared to the same-time BC and BrCvalues (Figure 4CD) A linear trend between BC and BrCemission factors with MCE is observed with higher values at
the start of a field burn The higher BC and BrC emissionfactors at higher MCE values suggest that more intense forestburns with higher fuel burn rates such as occur during wildfiresmay result in greater releases of BC and BrC than duringprescribed burning Additional scatter plots are available in SIFigure S4The paired BC to PM25 mass percentages for the field and
OBTF respectively were FL 18 (plusmn66) and 84 (plusmn34)NC 84 (plusmn32) and 77 (plusmn23) and SC 34(plusmn071) and 33 (plusmn12) The BrCPM25 mass fractionsat SC for the field and OBTF were 31 (plusmn20) and 23(plusmn079) respectively These BCPM25 mass percentagesfrom NC and FL are higher than the ECPM25 masspercentages found in the US EPA SPECIATE version 4346
Figure 3 A OBTF samples of continuous (10 s average) ΔCO2 ΔCO black carbon (BC) and brown carbon (BrC) concentration traces versustime and modified combustion efficiency (MCE) B OBTF time- and MCE-resolved BC and BrC emission factors with ΔCO2 and ΔCOconcentrations
Figure 4 Continuous (10 s average) ΔCO2 BC and BrC concentration traces (A) and BC and BrC emission factors with ΔCO2 (B) from arepresentative SC field emission sampling episode Scatter plots of BC and BrC concentrations vs MCE (D) and average BC and BrC emissionfactors vs MCE (C) during summa canister sampling in SC
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Table
3FieldandOBTFVOC
Emission
Factorsin
μgg
Biomassb
NCfi
eld
SCfi
eld
NCO
BTF
SCO
BTF
MCEgt095
MCElt090
MCEgt090
MCE=090
MCElt090
MCEgt095
MCElt090
MCEgt095
MCEgt0
90lt095
MCElt090
compound
average
AD
average
AD
average
AD
average
AD
average
AD
average
AD
MCE
0980
0004
0886
0011
0928
0007
0904
0004
0874
0011
0951
0889
00952
0932
0855
acroleina
627
599
697
170
385
53435
183
585
349
312
1023
154
256
381
332
propene
479
522
538
156
323
47360
80595
41
350
965
197
230
323
307
benzenea
370
369
526
262
245
23276
79441
92284
776
102
225
290
199
13-butadienea
195
222
246
6199
23114
46195
55
121
378
4797
153
108
vinylacetatea
330
455
363
82250
29256
36ND
166
830
75183
323
425
acetonitrile
165
188
172
57115
17106
16177
1054
165
013
3756
83toluenea
271
371
232
107
150
062
148
38277
51123
369
42121
171
153
2-butanone
(MEK)
128
161
124
3972
58
7354
157
4951
234
6752
8299
xylenea
6474
7817
7932
73125
131
1037
126
1557
8499
naphthalene
6468
102
6838
40
3592
6314
44116
2742
4733
styrenea
6467
8437
4042
4097
8226
102
286
2037
5341
α-pinene
6129
101
100
5632
78282
7255
26
2412
3459
40acrylonitrilea
5441
5611
2915
2450
4314
2549
91
1624
18ethylbenzenea
2729
3294
2231
2054
4217
2676
45
1926
22D-limonene
3548
4164
4319
4855
109
8397
6833
4990
114
chloromethanea
3429
4320
94
47
86
014
1133
1454
34
93
1416
124-trimethylbenzene
78
77
1027
14041
94
22
1616
37
1630
54
81
121
135-trimethylbenzene
22
26
28
55
34
028
24
072
40
062
080
33
087
13
19
30
cumenea
22
23
29
59
23
012
23
084
41
092
22
60
0079
21
29
26
methylene
chlorid
e22
34
40
36
024
042
0028
00079
0053
005
ND
0079
032
ND
ND
ND
brom
omethanea
22
23
26
53
15
034
18
012
30
14
ND
15
30
13
23
23
aIncluded
intheEP
Alistof
hazardousairpollutantsbADabsolutedifference
(twosamples)MCE
modified
combustioneffi
ciencyN
Dnot
detectedornotdetected
abovebackground
levelsN
Ceast
coastof
North
CarolinaSC
centralSouthCarolinaOBTF
open
burn
testfacility
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528449
database (source category = forest fires) of 12minus45 (ID4463minus44684) which were derived from laboratory (OBTF)tests while the SC ratios are similar to those in SPECIATE Asimilar ECPM25 percentage 39 was found from prescribedburning conducted in Georgia (USA)8 The higher ratios foundin our work seem to be due to higher BC rather than ECemission factors levels given the similar PM25 emission factorsdiscussed above This difference could be due to the differentsampling methodslight-scattering (BC) in this study versusthermaloptical transmission (EC) in Hays et al4 Thesedifferences suggest the need for a comparative investigation ofparallel BC and EC measurements from combustion sourcesVOC Ten field and six OBTF summa canister samples were
taken for VOC determination for the NC and SC campaigns(canister samples at FL could not be taken due to weightrestrictions on the aerostat) Acrolein benzene vinyl acetate(on the US EPArsquos hazardous air pollutant list) and propenehad the highest emission factors (425minus380 ugg biomass) of allVOCs analyzed (Table 3) The sixteen VOC samples weredivided according to MCE resulting in 1minus2 samples in eachMCE category (Table 3) The SC field results had no sampleswith MCE gt095 likely due more to the limitations of ground-only sampling than distinctions in the combustion character-istics of this unmanaged site No apparent differences wereobserved between field and OBTF samples for the differentMCE categories although more replicates would be needed fora robust statistical analysis A trend in decreased VOC emissionfactors with increased MCE was found when all of the collectedsamples were correlated (see SI Figure S5 for four VOCs) Theaverage field emission factor for acrolein was 350 μgg biomasswhich was in the same range as that for open burning ofmunicipal waste 310 μgg biomass47 and prescribed burning inSC 323minus472 μgg biomass48 but lower than that found fromtropical forest fires 960 μgg biomass22 The 13-butadiene hadan average emission factor from both field and OBTF of 310 plusmn182 μgg biomass higher than reported from previousprescribed and wild forest burns in the US58 and Mexico49
(67minus100 μgg biomass) and from Mexican crop residue fires(114 μgg biomass43) yet similar to open burning of municipalwaste (300 μgg biomass47) and prescribed burning of SCforest (110minus240 μgkg biomass48) Some other individualVOCs such as benzene and α-pinene were in the same rangeas emission factors from prescribed forest burning in GeorgiaUS8 All VOCs analyzed are shown in SI Tables S8minusS9PCDDPCDF Emissions The average PCDDPCDF
emission factors from the three different biomass sources andboth field (N = 5) and OBTF (N = 7) testing ranged from 006to 46 ng TEQkg biomass (ND = 0 Table 2 and SI TablesS2minusS4) Emissions exceeded the level anticipated fromvolatilization of PCDDPCDF in the raw biomass (Figure 5)which indicates that formation occurs during combustion ratherthan due to evaporation from the green biomassThese emission factors are on the lower range of similar
OBTF and field studies with US forest biomass at 040minus25 ngTEQkg biomass25minus27 (the lowest emission factor 006 ngTEQkg biomass was obtained from an OBTF sample burningNC biomass with only 6 of 17 TEF congeners detected) Therange of emission factors derived herein overlap those ofresidential wood heating appliances such as wood heaters (039ng TEQkg)50 wood stoves (025 ng TEQkg)51 andfireplaces (088 ng TEQkg)51
To discern potential emission factor differences betweenaerial- and ground-based field samples more simultaneous
aerial- and ground-based sampling is necessary The fieldsamples were of limited number and for the aerial samplesconsisted of one single composite (FL) sample from twodifferent burn days with 14 of 17 TEF congeners detected andtwo replicates (NC) with only 4 and 6 of 17 TEF congenersdetected Further none of the aerial and ground samples weretaken from the same fireThe PCDDPCDF emission factors showed similar levels
between aerial measurements in the field and OBTF samplesfor each of the biomass sources (FL and NC) except for theSC ground-based field and OBTF measurements as shown inFigure 5 The emission factors from the three SC ground fieldsamples showed an increase of up to seven times from the firstto last sample (068 22 and 46 ng TEQkg biomass)reflecting the qualitative observations of increasing smokethickness throughout the campaign (Table 3) In addition thetotal PCDD to PCDF and PCDD TEQ to PCDF TEQ massratios in these samples increased with increased emission factorlevels (SI Tables S4 and S7) A higher emission factor and agreater PCDD TEQ to PCDF TEQ ratio during smolderingversus flaming stages was found in an earlier study by Gullett etal26 burning standing trees in EPArsquos OBTF Thus the twohigher emission factors derived from the SC field study (22TEQkg biomass and 46 ng TEQkg biomass) may be due tosampling a larger portion of the smoldering stage rather thanthe flaming stage The SC OBTF emission levels (average 032ng TEQkg biomass) and PCDDPCDF ratios (12) are alsosimilar to the initial SC ground-based field sample (068 ngTEQkg biomass) which suggests the difficulty of collecting arepresentative PCDDPCDF sample from ground- rather thanaerial-based samplingThe slight emission level difference between FL and SC
biomass from the OBTF could be due to chlorine content inthe fuel 645 ppm and 111 ppm respectively (Table 2 andFigure 5) which is in agreement with a OBTF biomass studyshowing that increased chlorine content in the fuel increasesthe PCDDPCDF emissions39 The PCDDPCDF ratio wasalso higher in the FL OBTF samples (57 plusmn 17) than the SCbiomass samples (12 plusmn 02) which is in agreement with alaboratory study showing that an increased chlorine content inthe fuel enhances the formation of PCDDs over PCDFs52
More definitive conclusions regarding the effect of biomass
Figure 5 PCDDPCDF emission factors from three differentlocations on the eastern part of the USA northwestern Florida(FL) the North Carolina east coast (NC) and Central South Carolina(SC) ND not detectable congeners LOD limit of detection
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chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
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Environmental Science amp Technology Article
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of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
These emission factors are higher than the emission factorsfound from airborne5 tower based6 and ground based7 fieldmeasurements at prescribed forest burns from South EasternUS (11 gkg biomass 14 gkg biomass and 9minus16g kgbiomass) which in turn is ten times higher than the emissionfactors found from ground based sampling from prescribedburning in Georgia (090 gkg biomass)8
Black carbon is an efficient light-absorbing aerosol in theinfrared (IR) spectrum known to be a major contributor toglobal climate change9 Brown carbon is defined as light-absorbing organic matter aerosols from various sources foundin the ultraviolet (UV) spectrum10 which is starting to getmore attention as a possible contributor to global warm-ing10minus12 Only a few BC emission factors from wildfires andprescribed forest burns have been reported Kondo et al13
reported values of 180 ngm3 BCppm CO2 or 011 g BCkgbiomass consumed (using a biomass carbon fraction of 050)for boreal forest fires while others have reported values of037minus066 gkg biomass1415 for savanna and tropical forestburns In the absence of BC emission factors elemental carbon(EC) and PM25 data are usually used to calculateestimate BCinventories Elemental carbon is batch-sampled onto a filter andmeasured by thermal-optical transmission techniques4 whereasBC is measured continuously with an optical technique such asan aethalometer which records changes in the optical lightattenuation on a disposable filter A number of studies havereported EC emission factors from wildfires and prescribedforest burns in Brazil16 Africa17 Georgia (US)8 andPortugal18 as well as laboratory small-scale biomass burnswith biomass species from South Eastern US2minus4 Theseemission factors ranged almost 2 orders of magnitude from0035 to 15 g ECkg biomass consumed with no differencebetween field and laboratory emission levelsThe majority of the compounds on the US EPArsquos list of
hazardous air pollutions (HAPs) are VOCs19 Some of theVOCs such as benzene 13-butadiene and acrolein are toxic to
humans while others such as xylene toluene and 124-trimethyl benzene can form fine PM and ground level ozonewhich is a criteria pollutant tied to respiratory ailments20 TheNEI estimated that 96 and 16 of VOC emissions in theUSA (2008) were emitted from prescribed forest burns andwildfires respectively of which 23 originate from thesoutheastern USA Only a limited number of forest burnVOC emission factors from the HAP list are available in theliterature The few VOC emission factors are derived fromdifferent biomass sources and vary considerably ie thebenzene emission factor was 018 gkg biomass from African21
savanna forest burns 065 gkg biomass from laboratory burnsof Brazil tropical forest species22 22 gkg biomass from pinedominated forest burns in GA (US)8 and 028minus080 gkgbiomass from prescribed burns in SC (US) Yokelson et al2223
studied VOC emissions from field and laboratory burns ofBrazilian tropical forest biomass finding higher benzeneemission factors from the laboratory study than from thefield studyPCDDsPCDFs are recognized as toxic bioaccumulative
and persistent in the environment Combustion sources such asopen burning of biomass have been identified as the majorsource of global PCDDsPCDFs24 However emission factordata such as from prescribed field forest burning and laboratoryforest burns are limited and of broad range25minus27 from 055 to25 ng toxic equivalent (TEQ)kg biomass Only one of thesestudies compared emission factors derived from the field withlaboratory measurements finding no difference27
This study aimed to obtain emission factors from prescribedforest burns and compare these to emissions obtained fromsmall-scale laboratory burns using the same biomass sourceField measurements were conducted via either aerial-basedmeasurements to achieve proportional emission sampling fromboth flaming and smoldering phases or ground-based measure-ments at three different locations in the southeastern part of theUS The same sampling equipment was used for both field and
measures the light attenuation in aerosols accumulated onto aquartz filter at the infrared wavelength of 880 nm
black carbon AE52a continuous every 10 s see above IR 880 nmbrown carbon AE52a continuous every 10 s measures the light attenuation in aerosols accumulated onto a
quartz filter at the ultraviolet wavelength of 370 nmPM1 PM25 PM7 PM10and TSPi
Aerocet 531b continuous every 2 min light-scattering laser photometer
PM25j DustTrak 8520c continuous every
secondlight-scattering laser photometer
PM25 Impactord 47 mm Teflon filter(pore size 20 μm)
electrochemical oxidation of CO range of 0minus1000 ppm
ambient pressureelevation and location
MTi-Gg continuous everysecond
global position system attitude and heading reference system(AHRS) static pressure sensor
aAethlabs US bMet One Instruments Inc US cTSI Inc US dSKC Inc US eLICOR Biosciences US fTransducer Technology inc US gXsensNetherlands hLeland Legacy pump SKC Inc US) iused in FL and NC jUsed in SC kResponse time 20minus30 s
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528444
laboratory measurements to avoid method differences Acomprehensive list of pollutants was simultaneously collectedto allow for intercomparisons
EXPERIMENTAL SECTIONThree field sampling campaigns of prescribed forest burns wereconducted at three different locations of the southeastern partof the US (1) Eglin Air Force Base (February 2011) locatedon the northwestern part of Florida (FL) on the Gulf of Mexicocoast (2) Marine Corps Base Camp Lejeune (FebruaryMarch2011) located on the Atlantic Ocean coast (east coast) ofNorth Carolina (NC) and (3) Fort Jackson (OctoberNovember 2011) located in the central part of South Carolina(SC) approximately 200 km from the Atlantic Ocean coastTwo to three different areas were burned on separate days foreach location Combustible biomass was collected at each of thelocations and brought back to the US EPArsquos open burn testfacility (OBTF) in Research Triangle Park NC for small scaleburn testsAerial and Ground-Based Sampling Methods A 43 m
diameter tethered aerostat (Kingfisher Model Aerial ProductsInc US) was used as an aerial sampling platform and an allterrain vehicle (ATV) was used as a ground sampling platform(Supporting Information (SI) Figure S1) The helium-filledaerostat and the ATV carried duplicate sampling instrumenta-tion packages each termed the ldquoFlyerrdquo (SI Figure S2) Theground based platform transported the Flyer on a standattached on the back of an ATV at an approximate height of 25m above ground level Emission sampling was not performedwhile in transport to avoid gasoline fumes from the exhaustThe aerostat sampling method has been described in detailelsewhere2829 In summary the aerostat lofts the Flyer intoplumes and is maneuvered by a tether attached to a remote-controlled winch on an ATV For the NC study data wererecorded every second onto an on-board stand-alone datalogger (HOBO U12minus013 Onset Computer CorporationUS) For the FL and SC studies the Flyer was updated withan onboard USB-based data acquisition (DAQ) card (Measure-ment Computing USB-2537) controlled by an on-boardcomputer running a LabView generated data acquisition andcontrol program This update also included a ground-basedcomputer used to view data in real time and control thesampling via a wireless remote desktop connection Thecomputer data were logged at a rate of 10 Hz Additionally toavoid dilution of samples when not in the plume the batchsamplers were automatically turned on and off by a carbondioxide (CO2) ldquotriggerrdquo at a user-set plume concentrationInstrumentation For these sampling efforts the Flyer was
equipped for continuous measurement of CO2 BC and particlesize distribution semicontinuous measurement of CO andbatch sampling of PM25 VOCs and PCDDPCDF (Table 1)The CO2 was measured at a range set to 0minus4500 ppm andunderwent three-point calibration for CO2 on a daily basisaccording to US EPA Method 3A30 The CO2 unit (Table 1)had an accuracy of less than 3 of reading a precision of 1 ppmand a response time of one second CO was measured using anelectrochemical sensor with a response time of 20minus30 s Thelong response time of the sensor precluded its usefulness in thefield where concentrations could vary significantly in less than1 s The CO sensor underwent a three-point calibration beforeuse according to US EPA Method 3A30 The PCDDPCDFsampler used a 48 V (DC) Windjammer brushless directcurrent blower (AMETEK Inc US) resulting in a nominal
sampling rate of 085 m3min Flow rate was measured by a 0minus622 Pa pressure differential transducer (Setra Model 265 US)across a Herschel Standard Venturi tube with a throat andupstream diameter of 31 and 45 mm respectively The pressuredifferential voltage equivalent was recorded on the onboardcomputer or HOBO data logger and calibrated with a Rootsmeter (Model 5M Dresser Measurement US) The Flyer onthe aerostat was run on a 48 V 10 Amp-h Li-ion rechargeablebattery which has a battery capacity for approximately onehour of PCDDPCDF sampling The ground-based Flyer wasrun with four 12 V 75 Amp-h in series deep cycle marinebatteries with approximately 4minus5 h of sampling Summacanisters were equipped with an electronic solenoid valvepressure transducer and a frit filter All instruments were time-synchronized each day
Analyses The PCDDPCDF samples were extracted andcleaned up by a modified US EPA Method TO-9A35 andanalyzed using high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS)36 Trip andfield blanks were collected and analyzed for PCDDPCDFQuantities of raw biomass 202 183 and 51 g from NC FLand SC respectively were Soxhlet-extracted using US EPAMethod 354037 and spiked and analyzed for PCDDPCDFaccording to US EPA Method TO-9A35 The 2005 WorldHealth Organization (WHO) 2005 toxic equivalent factors(TEFs)38 were used to determine the PCDDPCDF TEQemission factors Not all TEF-weighted PCDDPCDFcongeners were detected in all samples The congeners thatwere not detected (ND) were set to zero in the text but SITables S1minusS3 show the PCDDPCDF values both at ND = 0and ND = limit of detection) All data were normalized to 1atm and 211 degC and background-corrected by subtractingambient air concentrations Values of the raw biomass forPCDDPCDF content were normalized using the raw carbonfraction of each biomass (SI Table S1)
Biomass The major species in FL and SC were LongleafPine (Pinus palustris) Turkey Oak (Quercus laevis) and SandLive Oak (Quercus geminata) while the NC biomass consistedof Loblolly Pine seedlings (Pinus taeda) Red Bay (Perseaborbonia) Inkberry (Ilex glabra) and Red Maple (Acerrubrum) The SC burn sites had not been burnt in the last50 years and were considered ldquounmanagedrdquo stands with theexpectation that their burns would more represent behavior ofan uncontrolled fireCombustible biomass was collected from a 91 times 91 m2 area
at all three locations and transported to the OBTF at US EPARTP NC for burn testing within seven days The biomass fromeach of the locations (approximately 30 to 60 kg) was dividedby standard cone and quarter methods for ultimate (SI TableS1) and PCDDPCDF analyses in the unburnt biomass and forcombustion testing in the OBTF Three replicate OBTF testswere each comprised of multiple sequential 14minus15 kgbiomass charges at the same area density as in the field
Field Burn Description Solely the aerostat-based samplingmethod was used in the FL and NC studies while only theground based sampling platform was used in SC due to airspacerestrictions Aerostat sampling was conducted downwind of theprescribed burn areas on the borderline of the burn area alongan open field or a road The average aerostat sampling altitudewas higher for the FL burns (115 m maximum 327 m) than forthe NC burns (13 m maximum 46 m) due to plume rise Theground-based sampling equipment was approximately 2 mabove ground level at all times Ground-based sampling at SC
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528445
was performed downwind of the burn area on firebreak roadsTwo simultaneous Flyer samples were combined for two ofthree sampling days in SC to obtain detectable PCDDPCDFlevels The SC burns were presupposed to be of higherintensity than those in FL and NC since the forest had nohistory of prescribed burn treatmentOpen Burn Test Facility A 70 m3 enclosed OBTF
described in detail elsewhere39 was used for simulatingprescribed forest burns (SI Figure S1) The OBTF wasequipped with a high-volume blower that pulls ambient air intothe OBTF This blower and small fans located inside the facilityensured complete mixing and oxygen concentrations close toambient Burn tests were performed 6minus7 days after biomasscollection at the same area density as found in the field Becausethe small charge sizes used in the OBTF do not necessarilyprovide sufficient mass of PCDDPCDF emissions to avoidnondetectable congeners emissions from multiple charge burnswere composited to obtain a single measurement The biomasscharges were burned one after the other a new charge wasloaded when the CO2 concentration decreased to approx-imately 500 ppm The small burn charges were used to mimicthe field area density and keep the temperature inside thefacility below 50 degC around the sampling equipment to avoidoverheating Flyer electronics and the sampling media Theburns were performed on an aluminum-foil-covered steel plateand the aluminum foil was replaced before each burn testThe same sampling instrumentation was used in the OBTF
as in the field The Flyer was placed inside the facility near theair exit duct For the SC biomass burn tests two PCDDPCDF
samples were collected simultaneously using two Flyers Twopostburn OBTF ambient air background samples werecollected for a total of 5minus10 h inside the uncleaned OBTFover three separate days
Calculations The concentration ratios of the cosampledtarget analytes and the CO2 above ambient levels (ΔCO2)(plus Summa canister ΔCO for VOCs) were used to deriveemission factors according to the carbon mass balanceapproach40 Emission factors are expressed in terms of pollutantmass per mass of biomass where the latter indicates the mass ofbiomass consumed by the fire The carbon mass balanceassumes that all combusted carbon in the biomass is emitted tothe atmosphere as CO2 CO methane and total hydrocarbons(THCs) and that the carbon and pollutants are completelymixed in the plume Calculations from a previous forestlaboratory burn study show that 90minus996 of the total carbonemitted (sum of CO and CO2) was CO2
4 and that THCconcentration was 2minus4 times lower than the CO concentrationThus carbon concentrations from CO and THC were minimaland only CO2 measurements were needed to approximate thetotal mass of carbon emitted Neglecting CO and trace VOCscould have an approximate 10 effect on the emission factor avalue within the total error of the method and likely thereproducibility of the event The biomass composition carbonfractions (Fc) in the preburnedraw biomass (SI Table S1)were then used to calculate emission factors (EFs) bymultiplying Fc with the mass of analyte per mass of carbonThe semicontinuous CO measurements acquired from the
Table 2 Resultsa
aOBTF minus Open burn test facility FL minus North West Florida NC minus East North Carolina SC minus Central South Carolina NM minus not measured FR minusFailed recovery (recovery under method limits) bLimit of detection values within parentheses for those samples with not detected congenerscComposite sample from two field days dParallel sampling of PCDDPCDF - two PCDDPCDF samples collected during the same time eAllOBTF emission factors shown in SI Table S10
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528446
OBTF tests were used only to calculate the modifiedcombustion efficiency (MCE) (ΔCO2(ΔCO2 + ΔCO))The VOC samples were unique in that the summa canister
data provided both CO2 and measurable CO concentrationsallowing emission factors to be assigned to flaming andsmoldering modes by calculating the MCE where the flamingmode has a MCE gt 095 and the smoldering mode has a MCElt 090Custom correction factors for the continuous measured PM
were derived as by manufacture instruction to improve themeasurement accuracy from prescribed forest burns Thesecorrection factors were conducted by dividing the averagecontinuous PM25 concentration by the PM25 by filterconcentration during the same collection time (for eachcollected filter) The average correction factor for the DustTrak8520 and the Aerocet 531 was 20 plusmn 056 and 63 plusmn 22respectivelyThe black carbon data were postprocessed for noise using an
optimized noise-reduction averaging algorithm program41 Nocorrection for particle loading on the filters was made since theBC concentration did not change with an increased lightattenuation value (ATN) reported from the AE51 and AE52
RESULTS AND DISCUSSIONNine prescribed burns were sampled at three separate locationsas well as companion laboratory burns with site-gatheredbiomass At the field sites aerial ground-only or both aerial-and ground-based sampling were conducted as site constraintsallowed (Table 2)Particulate Matter The continuous PM25 and CO2
concentrations were highest for the ground-based fieldsampling in SC and lowest for the aerostat-based sampling inFL (SI Figure S3) likely due to the comparative proximity ofthe ground-based sampler to the source The average PM25emission factors from the three different field burn locationsand the OBTF derived from the ratio of the PM mass to thecarbon collected as CO2 ranged from 14 to 47 gkg biomass(Figure 1) These emission factors are mostly higher than
previously reported from prescribed and wildfire forest burns inthe US Portugal and Mexico at 066minus16 gkg bio-mass5minus84243 but overlapping those from previous OBTFforest burns of different biomass types 11minus34 gkg biomass4
A 3-fold difference in average PM25 emission factors wasobserved between the three field values Field and correspond-ing OBTF PM25 emission factors were quite similar also
showing a 3-fold range ANOVA analyses were performed ontwenty-one OBTF and fifteen field PM25 samples from thethree field burn locations No statistical differences (α = 005)were observed between PM25 emission factors derived in thefield and the OBTF suggesting the adequacy of the laboratorysimulation A statistical difference between the OBTF-derivedemission factors was found between FL and both SC and NCThe field-derived emission factors were only statisticallydifferent between the FL and SC biomass sources Theseresults indicate that it is the biomass composition itself ratherthan the laboratory-versus field-based sampling distinctions thatdrive the PM25 emission factor levels As none of the testingafforded opportunities for both aerial and ground basedsampling future research should compare emission factorsderived from simultaneous use of both of these methods
Black and Brown Carbon The field and OBTF averageBC and BrC emission factors ranged from 12 to 21 gkgbiomass and 10 to 14 gkg biomass respectively (Figure 2)
These BC emission factors are generally higher than previouslyreported for forest burn EC and estimated BC emission factorsof 0035minus13 gkg biomass34816minus18 and 037minus066 gkgbiomass1415 respectively The BC emission factors determinedhere are in the same range as medium-and high-duty dieseltrucks 092minus2340414445 gkg fuel4041 ANOVA analysisshowed a slight difference (F = 533) in BC emission factorsbetween the SC OBTF and its corresponding field data but notfor the FL and NC field versus OBTF data There werestatistical differences in OBTF BC emission levels for the NCbiomass with those from FL and SC but no such differenceswere observed for the field dataFigures 3A and B show time-resolved BC BrC ΔCO2
ΔCO and MCE concentrations and emission factor datarespectively for a representative OBTF burn of SC biomass Alldata reach a rapid peak at the onset of combustion As theemission factor data are mass-loss-normalized (Figure 3B) theinitial peaks indicate that the early onset emissions areproportionately higher than subsequent emissions The earlypeak BC and BrC emission factors are more than 2 to 10 timeshigher respectively than their whole-run averages indicatingthat fire intensity characteristics have a significant impact onemissions The BC and BrC concentrations decline exponen-tially with the MCE and time or as the ΔCO2 concentration
Figure 1 PM25 emission factors from field and OBTF forest burns forthree different biomass sources northwestern Florida (FL) the NorthCarolina east coast (NC) and Central South Carolina (SC) Error barsdenote one standard deviation (NC SC) or range of data (FL)
Figure 2 Black and brown carbon emission factors from the threebiomass sources northwestern Florida (FL) North Carolina east coast(NC) and Central South Carolina (SC) sampled in the field and inthe OBTF Error bars denote one standard deviation (SC) or range ofdata (FL NC)
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528447
decreases (Figure 3A) The OBTF laboratory data (Figure 3B)show an exponential decrease in BC and BrC emission factorswith a decrease in MCE and also reveal that while the BC andBrC concentrations are low at the start of a burn the MCE isthe highest (Figure 3A)Figure 4AB shows the comparable BC BrC CO2 and CO
concentrations and emission factor data respectively for thefield tests at SC The concentration data show predictably morefluctuation than the OBTF data (Figure 3A) as the former issubject to turbulent mixing while the latter is a well-stirredscenario MCE values from the Summa canister CO and CO2
grab samples were compared to the same-time BC and BrCvalues (Figure 4CD) A linear trend between BC and BrCemission factors with MCE is observed with higher values at
the start of a field burn The higher BC and BrC emissionfactors at higher MCE values suggest that more intense forestburns with higher fuel burn rates such as occur during wildfiresmay result in greater releases of BC and BrC than duringprescribed burning Additional scatter plots are available in SIFigure S4The paired BC to PM25 mass percentages for the field and
OBTF respectively were FL 18 (plusmn66) and 84 (plusmn34)NC 84 (plusmn32) and 77 (plusmn23) and SC 34(plusmn071) and 33 (plusmn12) The BrCPM25 mass fractionsat SC for the field and OBTF were 31 (plusmn20) and 23(plusmn079) respectively These BCPM25 mass percentagesfrom NC and FL are higher than the ECPM25 masspercentages found in the US EPA SPECIATE version 4346
Figure 3 A OBTF samples of continuous (10 s average) ΔCO2 ΔCO black carbon (BC) and brown carbon (BrC) concentration traces versustime and modified combustion efficiency (MCE) B OBTF time- and MCE-resolved BC and BrC emission factors with ΔCO2 and ΔCOconcentrations
Figure 4 Continuous (10 s average) ΔCO2 BC and BrC concentration traces (A) and BC and BrC emission factors with ΔCO2 (B) from arepresentative SC field emission sampling episode Scatter plots of BC and BrC concentrations vs MCE (D) and average BC and BrC emissionfactors vs MCE (C) during summa canister sampling in SC
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528448
Table
3FieldandOBTFVOC
Emission
Factorsin
μgg
Biomassb
NCfi
eld
SCfi
eld
NCO
BTF
SCO
BTF
MCEgt095
MCElt090
MCEgt090
MCE=090
MCElt090
MCEgt095
MCElt090
MCEgt095
MCEgt0
90lt095
MCElt090
compound
average
AD
average
AD
average
AD
average
AD
average
AD
average
AD
MCE
0980
0004
0886
0011
0928
0007
0904
0004
0874
0011
0951
0889
00952
0932
0855
acroleina
627
599
697
170
385
53435
183
585
349
312
1023
154
256
381
332
propene
479
522
538
156
323
47360
80595
41
350
965
197
230
323
307
benzenea
370
369
526
262
245
23276
79441
92284
776
102
225
290
199
13-butadienea
195
222
246
6199
23114
46195
55
121
378
4797
153
108
vinylacetatea
330
455
363
82250
29256
36ND
166
830
75183
323
425
acetonitrile
165
188
172
57115
17106
16177
1054
165
013
3756
83toluenea
271
371
232
107
150
062
148
38277
51123
369
42121
171
153
2-butanone
(MEK)
128
161
124
3972
58
7354
157
4951
234
6752
8299
xylenea
6474
7817
7932
73125
131
1037
126
1557
8499
naphthalene
6468
102
6838
40
3592
6314
44116
2742
4733
styrenea
6467
8437
4042
4097
8226
102
286
2037
5341
α-pinene
6129
101
100
5632
78282
7255
26
2412
3459
40acrylonitrilea
5441
5611
2915
2450
4314
2549
91
1624
18ethylbenzenea
2729
3294
2231
2054
4217
2676
45
1926
22D-limonene
3548
4164
4319
4855
109
8397
6833
4990
114
chloromethanea
3429
4320
94
47
86
014
1133
1454
34
93
1416
124-trimethylbenzene
78
77
1027
14041
94
22
1616
37
1630
54
81
121
135-trimethylbenzene
22
26
28
55
34
028
24
072
40
062
080
33
087
13
19
30
cumenea
22
23
29
59
23
012
23
084
41
092
22
60
0079
21
29
26
methylene
chlorid
e22
34
40
36
024
042
0028
00079
0053
005
ND
0079
032
ND
ND
ND
brom
omethanea
22
23
26
53
15
034
18
012
30
14
ND
15
30
13
23
23
aIncluded
intheEP
Alistof
hazardousairpollutantsbADabsolutedifference
(twosamples)MCE
modified
combustioneffi
ciencyN
Dnot
detectedornotdetected
abovebackground
levelsN
Ceast
coastof
North
CarolinaSC
centralSouthCarolinaOBTF
open
burn
testfacility
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528449
database (source category = forest fires) of 12minus45 (ID4463minus44684) which were derived from laboratory (OBTF)tests while the SC ratios are similar to those in SPECIATE Asimilar ECPM25 percentage 39 was found from prescribedburning conducted in Georgia (USA)8 The higher ratios foundin our work seem to be due to higher BC rather than ECemission factors levels given the similar PM25 emission factorsdiscussed above This difference could be due to the differentsampling methodslight-scattering (BC) in this study versusthermaloptical transmission (EC) in Hays et al4 Thesedifferences suggest the need for a comparative investigation ofparallel BC and EC measurements from combustion sourcesVOC Ten field and six OBTF summa canister samples were
taken for VOC determination for the NC and SC campaigns(canister samples at FL could not be taken due to weightrestrictions on the aerostat) Acrolein benzene vinyl acetate(on the US EPArsquos hazardous air pollutant list) and propenehad the highest emission factors (425minus380 ugg biomass) of allVOCs analyzed (Table 3) The sixteen VOC samples weredivided according to MCE resulting in 1minus2 samples in eachMCE category (Table 3) The SC field results had no sampleswith MCE gt095 likely due more to the limitations of ground-only sampling than distinctions in the combustion character-istics of this unmanaged site No apparent differences wereobserved between field and OBTF samples for the differentMCE categories although more replicates would be needed fora robust statistical analysis A trend in decreased VOC emissionfactors with increased MCE was found when all of the collectedsamples were correlated (see SI Figure S5 for four VOCs) Theaverage field emission factor for acrolein was 350 μgg biomasswhich was in the same range as that for open burning ofmunicipal waste 310 μgg biomass47 and prescribed burning inSC 323minus472 μgg biomass48 but lower than that found fromtropical forest fires 960 μgg biomass22 The 13-butadiene hadan average emission factor from both field and OBTF of 310 plusmn182 μgg biomass higher than reported from previousprescribed and wild forest burns in the US58 and Mexico49
(67minus100 μgg biomass) and from Mexican crop residue fires(114 μgg biomass43) yet similar to open burning of municipalwaste (300 μgg biomass47) and prescribed burning of SCforest (110minus240 μgkg biomass48) Some other individualVOCs such as benzene and α-pinene were in the same rangeas emission factors from prescribed forest burning in GeorgiaUS8 All VOCs analyzed are shown in SI Tables S8minusS9PCDDPCDF Emissions The average PCDDPCDF
emission factors from the three different biomass sources andboth field (N = 5) and OBTF (N = 7) testing ranged from 006to 46 ng TEQkg biomass (ND = 0 Table 2 and SI TablesS2minusS4) Emissions exceeded the level anticipated fromvolatilization of PCDDPCDF in the raw biomass (Figure 5)which indicates that formation occurs during combustion ratherthan due to evaporation from the green biomassThese emission factors are on the lower range of similar
OBTF and field studies with US forest biomass at 040minus25 ngTEQkg biomass25minus27 (the lowest emission factor 006 ngTEQkg biomass was obtained from an OBTF sample burningNC biomass with only 6 of 17 TEF congeners detected) Therange of emission factors derived herein overlap those ofresidential wood heating appliances such as wood heaters (039ng TEQkg)50 wood stoves (025 ng TEQkg)51 andfireplaces (088 ng TEQkg)51
To discern potential emission factor differences betweenaerial- and ground-based field samples more simultaneous
aerial- and ground-based sampling is necessary The fieldsamples were of limited number and for the aerial samplesconsisted of one single composite (FL) sample from twodifferent burn days with 14 of 17 TEF congeners detected andtwo replicates (NC) with only 4 and 6 of 17 TEF congenersdetected Further none of the aerial and ground samples weretaken from the same fireThe PCDDPCDF emission factors showed similar levels
between aerial measurements in the field and OBTF samplesfor each of the biomass sources (FL and NC) except for theSC ground-based field and OBTF measurements as shown inFigure 5 The emission factors from the three SC ground fieldsamples showed an increase of up to seven times from the firstto last sample (068 22 and 46 ng TEQkg biomass)reflecting the qualitative observations of increasing smokethickness throughout the campaign (Table 3) In addition thetotal PCDD to PCDF and PCDD TEQ to PCDF TEQ massratios in these samples increased with increased emission factorlevels (SI Tables S4 and S7) A higher emission factor and agreater PCDD TEQ to PCDF TEQ ratio during smolderingversus flaming stages was found in an earlier study by Gullett etal26 burning standing trees in EPArsquos OBTF Thus the twohigher emission factors derived from the SC field study (22TEQkg biomass and 46 ng TEQkg biomass) may be due tosampling a larger portion of the smoldering stage rather thanthe flaming stage The SC OBTF emission levels (average 032ng TEQkg biomass) and PCDDPCDF ratios (12) are alsosimilar to the initial SC ground-based field sample (068 ngTEQkg biomass) which suggests the difficulty of collecting arepresentative PCDDPCDF sample from ground- rather thanaerial-based samplingThe slight emission level difference between FL and SC
biomass from the OBTF could be due to chlorine content inthe fuel 645 ppm and 111 ppm respectively (Table 2 andFigure 5) which is in agreement with a OBTF biomass studyshowing that increased chlorine content in the fuel increasesthe PCDDPCDF emissions39 The PCDDPCDF ratio wasalso higher in the FL OBTF samples (57 plusmn 17) than the SCbiomass samples (12 plusmn 02) which is in agreement with alaboratory study showing that an increased chlorine content inthe fuel enhances the formation of PCDDs over PCDFs52
More definitive conclusions regarding the effect of biomass
Figure 5 PCDDPCDF emission factors from three differentlocations on the eastern part of the USA northwestern Florida(FL) the North Carolina east coast (NC) and Central South Carolina(SC) ND not detectable congeners LOD limit of detection
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528450
chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
REFERENCES(1) US EPA 1970minus2012 Average annual emissions all criteriapollutants httpwwwepagovttnchie1trends (accessed October17 2012)(2) Hosseini S Urbanski S P Dixit P Qi L Burling IYokelson R Shrivastava M Jung H Weise D R Miller WCocker D Laboratory characterization of PM emissions fromcombustion of wildland biomass fuels J Geophys Res 2013DOI101002jgrd50481(3) McMeeking G R Kreidenweis S M Baker S Carrico C MChow J C Collett J L Hao W M Holden A S Kirchstetter T
W Malm W C Moosmuller H Sullivan A P Wold C EEmissions of trace gases and aerosols during the open combustion ofbiomass in the laboratory J Geophys Res 2009 114(4) Hays M D Geron C D Linna K J Smith N D Schauer JJ Speciation of gas-phase and fine particle emissions from burning offoliar fuels Environ Sci Technol 2002 36 (11) 2281minus2295(5) Burling I R Yokelson R J Akagi S K Urbanski S P WoldC E Griffith D W T Johnson T J Reardon J Weise D RAirborne and ground-based measurements of the trace gases andparticles emitted by prescribed fires in the United States Atmos ChemPhys 2011 11 (23) 12197minus12216(6) Urbanski S P Hao W M Baker S Chemical composition ofwildland fire emissions In Developments in Environmental ScienceBytnerowicz A Arbaugh M Riebau A Andersen C Eds ElsevierNew York 2009 Vol 8 pp 79minus107(7) Geron C Hays M Air emissions from organic soil burning onthe coastal plain of North Carolina Atmos Environ 2013 64 192minus199(8) Lee S Baumann K Schauer J J Sheesley R J Naeher L PMeinardi S Blake D R Edgerton E S Russell A G Clements MGaseous and particulate emissions from prescribed burning in GeorgiaEnviron Sci Technol 2005 39 (23) 9049minus9056(9) Ramanathan V Carmichael G Global and regional climatechanges due to black carbon Nat Geosci 2008 1 (4) 221minus227(10) Andreae M O Gelencser A Black carbon or brown carbonThe nature of light-absorbing carbonaceous aerosols Atmos ChemPhys 2006 6 3131minus3148(11) Alexander D T L Crozier P A Anderson J R Browncarbon spheres in East Asian outflow and their optical propertiesScience 2008 321 (5890) 833minus836(12) Kirchstetter T W Novakov T Hobbs P V Evidence that thespectral dependence of light absorption by aerosols is affected byorganic carbon J Geophys Res 2004 109 (D21)(13) Kondo Y Matsui H Moteki N Sahu L Takegawa NKajino M Zhao Y Cubison M J Jimenez J L Vay S Diskin GS Anderson B Wisthaler A Mikoviny T Fuelberg H E BlakeD R Huey G Weinheimer A J Knapp D J Brune W HEmissions of black carbon organic and inorganic aerosols frombiomass burning in North America and Asia in 2008 J Geophys Res2011 116(14) Akagi S K Yokelson R J Wiedinmyer C Alvarado M JReid J S Karl T Crounse J D Wennberg P O Emission factorsfor open and domestic biomass burning for use in atmospheric modelsAtmos Chem Phys 2011 11 (9) 4039minus4072(15) Andreae M O Merlet P Emission of trace gases and aerosolsfrom biomass burning Global Biogeochem Cyc 2001 15 (4) 955minus966(16) Ferek R J Reid J S Hobbs P V Blake D R Liousse CEmission factors of hydrocarbons halocarbons trace gases andparticles from biomass burning in Brazil J Geophys Res 1998 103(D24) 32107minus32118(17) Andreae M O Andreae T W Annegarn H Beer JCachier H le Canut P Elbert W Maenhaut W Salma IWienhold F G Zenker T Airborne studies of aerosol emissionsfrom savanna fires in southern Africa 2 Aerosol chemicalcomposition J Geophys Res 1998 103 (D24) 32119minus32128(18) Alves C Vicente A Nunes T Goncalves C Fernandes AP Mirante F Tarelho L Sanchez de la Campa A M Querol XCaseiro A Monteiro C Evtyugina M Pio C Summer 2009wildfires in Portugal Emission of trace gases and aerosol compositionAtmos Environ 2011 45 (3) 641minus649(19) US EPA Hazardous Air Pollution List Clean Air Act Title 42The Public Health and Welfare US Government Printing OfficeWashington DC 2008(20) Pappas G P Herbert R J Henderson W Koenig J StoverB Barnhart S The respiratory effects of volatile organic compoundsInt J Occup Env Heal 2000 6 (1) 1minus8(21) Sinha P Hobbs P V Yokelson R J Bertschi I T Blake DR Simpson I J Gao S Kirchstetter T W Novakov T Emissions
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528451
of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
laboratory measurements to avoid method differences Acomprehensive list of pollutants was simultaneously collectedto allow for intercomparisons
EXPERIMENTAL SECTIONThree field sampling campaigns of prescribed forest burns wereconducted at three different locations of the southeastern partof the US (1) Eglin Air Force Base (February 2011) locatedon the northwestern part of Florida (FL) on the Gulf of Mexicocoast (2) Marine Corps Base Camp Lejeune (FebruaryMarch2011) located on the Atlantic Ocean coast (east coast) ofNorth Carolina (NC) and (3) Fort Jackson (OctoberNovember 2011) located in the central part of South Carolina(SC) approximately 200 km from the Atlantic Ocean coastTwo to three different areas were burned on separate days foreach location Combustible biomass was collected at each of thelocations and brought back to the US EPArsquos open burn testfacility (OBTF) in Research Triangle Park NC for small scaleburn testsAerial and Ground-Based Sampling Methods A 43 m
diameter tethered aerostat (Kingfisher Model Aerial ProductsInc US) was used as an aerial sampling platform and an allterrain vehicle (ATV) was used as a ground sampling platform(Supporting Information (SI) Figure S1) The helium-filledaerostat and the ATV carried duplicate sampling instrumenta-tion packages each termed the ldquoFlyerrdquo (SI Figure S2) Theground based platform transported the Flyer on a standattached on the back of an ATV at an approximate height of 25m above ground level Emission sampling was not performedwhile in transport to avoid gasoline fumes from the exhaustThe aerostat sampling method has been described in detailelsewhere2829 In summary the aerostat lofts the Flyer intoplumes and is maneuvered by a tether attached to a remote-controlled winch on an ATV For the NC study data wererecorded every second onto an on-board stand-alone datalogger (HOBO U12minus013 Onset Computer CorporationUS) For the FL and SC studies the Flyer was updated withan onboard USB-based data acquisition (DAQ) card (Measure-ment Computing USB-2537) controlled by an on-boardcomputer running a LabView generated data acquisition andcontrol program This update also included a ground-basedcomputer used to view data in real time and control thesampling via a wireless remote desktop connection Thecomputer data were logged at a rate of 10 Hz Additionally toavoid dilution of samples when not in the plume the batchsamplers were automatically turned on and off by a carbondioxide (CO2) ldquotriggerrdquo at a user-set plume concentrationInstrumentation For these sampling efforts the Flyer was
equipped for continuous measurement of CO2 BC and particlesize distribution semicontinuous measurement of CO andbatch sampling of PM25 VOCs and PCDDPCDF (Table 1)The CO2 was measured at a range set to 0minus4500 ppm andunderwent three-point calibration for CO2 on a daily basisaccording to US EPA Method 3A30 The CO2 unit (Table 1)had an accuracy of less than 3 of reading a precision of 1 ppmand a response time of one second CO was measured using anelectrochemical sensor with a response time of 20minus30 s Thelong response time of the sensor precluded its usefulness in thefield where concentrations could vary significantly in less than1 s The CO sensor underwent a three-point calibration beforeuse according to US EPA Method 3A30 The PCDDPCDFsampler used a 48 V (DC) Windjammer brushless directcurrent blower (AMETEK Inc US) resulting in a nominal
sampling rate of 085 m3min Flow rate was measured by a 0minus622 Pa pressure differential transducer (Setra Model 265 US)across a Herschel Standard Venturi tube with a throat andupstream diameter of 31 and 45 mm respectively The pressuredifferential voltage equivalent was recorded on the onboardcomputer or HOBO data logger and calibrated with a Rootsmeter (Model 5M Dresser Measurement US) The Flyer onthe aerostat was run on a 48 V 10 Amp-h Li-ion rechargeablebattery which has a battery capacity for approximately onehour of PCDDPCDF sampling The ground-based Flyer wasrun with four 12 V 75 Amp-h in series deep cycle marinebatteries with approximately 4minus5 h of sampling Summacanisters were equipped with an electronic solenoid valvepressure transducer and a frit filter All instruments were time-synchronized each day
Analyses The PCDDPCDF samples were extracted andcleaned up by a modified US EPA Method TO-9A35 andanalyzed using high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS)36 Trip andfield blanks were collected and analyzed for PCDDPCDFQuantities of raw biomass 202 183 and 51 g from NC FLand SC respectively were Soxhlet-extracted using US EPAMethod 354037 and spiked and analyzed for PCDDPCDFaccording to US EPA Method TO-9A35 The 2005 WorldHealth Organization (WHO) 2005 toxic equivalent factors(TEFs)38 were used to determine the PCDDPCDF TEQemission factors Not all TEF-weighted PCDDPCDFcongeners were detected in all samples The congeners thatwere not detected (ND) were set to zero in the text but SITables S1minusS3 show the PCDDPCDF values both at ND = 0and ND = limit of detection) All data were normalized to 1atm and 211 degC and background-corrected by subtractingambient air concentrations Values of the raw biomass forPCDDPCDF content were normalized using the raw carbonfraction of each biomass (SI Table S1)
Biomass The major species in FL and SC were LongleafPine (Pinus palustris) Turkey Oak (Quercus laevis) and SandLive Oak (Quercus geminata) while the NC biomass consistedof Loblolly Pine seedlings (Pinus taeda) Red Bay (Perseaborbonia) Inkberry (Ilex glabra) and Red Maple (Acerrubrum) The SC burn sites had not been burnt in the last50 years and were considered ldquounmanagedrdquo stands with theexpectation that their burns would more represent behavior ofan uncontrolled fireCombustible biomass was collected from a 91 times 91 m2 area
at all three locations and transported to the OBTF at US EPARTP NC for burn testing within seven days The biomass fromeach of the locations (approximately 30 to 60 kg) was dividedby standard cone and quarter methods for ultimate (SI TableS1) and PCDDPCDF analyses in the unburnt biomass and forcombustion testing in the OBTF Three replicate OBTF testswere each comprised of multiple sequential 14minus15 kgbiomass charges at the same area density as in the field
Field Burn Description Solely the aerostat-based samplingmethod was used in the FL and NC studies while only theground based sampling platform was used in SC due to airspacerestrictions Aerostat sampling was conducted downwind of theprescribed burn areas on the borderline of the burn area alongan open field or a road The average aerostat sampling altitudewas higher for the FL burns (115 m maximum 327 m) than forthe NC burns (13 m maximum 46 m) due to plume rise Theground-based sampling equipment was approximately 2 mabove ground level at all times Ground-based sampling at SC
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was performed downwind of the burn area on firebreak roadsTwo simultaneous Flyer samples were combined for two ofthree sampling days in SC to obtain detectable PCDDPCDFlevels The SC burns were presupposed to be of higherintensity than those in FL and NC since the forest had nohistory of prescribed burn treatmentOpen Burn Test Facility A 70 m3 enclosed OBTF
described in detail elsewhere39 was used for simulatingprescribed forest burns (SI Figure S1) The OBTF wasequipped with a high-volume blower that pulls ambient air intothe OBTF This blower and small fans located inside the facilityensured complete mixing and oxygen concentrations close toambient Burn tests were performed 6minus7 days after biomasscollection at the same area density as found in the field Becausethe small charge sizes used in the OBTF do not necessarilyprovide sufficient mass of PCDDPCDF emissions to avoidnondetectable congeners emissions from multiple charge burnswere composited to obtain a single measurement The biomasscharges were burned one after the other a new charge wasloaded when the CO2 concentration decreased to approx-imately 500 ppm The small burn charges were used to mimicthe field area density and keep the temperature inside thefacility below 50 degC around the sampling equipment to avoidoverheating Flyer electronics and the sampling media Theburns were performed on an aluminum-foil-covered steel plateand the aluminum foil was replaced before each burn testThe same sampling instrumentation was used in the OBTF
as in the field The Flyer was placed inside the facility near theair exit duct For the SC biomass burn tests two PCDDPCDF
samples were collected simultaneously using two Flyers Twopostburn OBTF ambient air background samples werecollected for a total of 5minus10 h inside the uncleaned OBTFover three separate days
Calculations The concentration ratios of the cosampledtarget analytes and the CO2 above ambient levels (ΔCO2)(plus Summa canister ΔCO for VOCs) were used to deriveemission factors according to the carbon mass balanceapproach40 Emission factors are expressed in terms of pollutantmass per mass of biomass where the latter indicates the mass ofbiomass consumed by the fire The carbon mass balanceassumes that all combusted carbon in the biomass is emitted tothe atmosphere as CO2 CO methane and total hydrocarbons(THCs) and that the carbon and pollutants are completelymixed in the plume Calculations from a previous forestlaboratory burn study show that 90minus996 of the total carbonemitted (sum of CO and CO2) was CO2
4 and that THCconcentration was 2minus4 times lower than the CO concentrationThus carbon concentrations from CO and THC were minimaland only CO2 measurements were needed to approximate thetotal mass of carbon emitted Neglecting CO and trace VOCscould have an approximate 10 effect on the emission factor avalue within the total error of the method and likely thereproducibility of the event The biomass composition carbonfractions (Fc) in the preburnedraw biomass (SI Table S1)were then used to calculate emission factors (EFs) bymultiplying Fc with the mass of analyte per mass of carbonThe semicontinuous CO measurements acquired from the
Table 2 Resultsa
aOBTF minus Open burn test facility FL minus North West Florida NC minus East North Carolina SC minus Central South Carolina NM minus not measured FR minusFailed recovery (recovery under method limits) bLimit of detection values within parentheses for those samples with not detected congenerscComposite sample from two field days dParallel sampling of PCDDPCDF - two PCDDPCDF samples collected during the same time eAllOBTF emission factors shown in SI Table S10
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OBTF tests were used only to calculate the modifiedcombustion efficiency (MCE) (ΔCO2(ΔCO2 + ΔCO))The VOC samples were unique in that the summa canister
data provided both CO2 and measurable CO concentrationsallowing emission factors to be assigned to flaming andsmoldering modes by calculating the MCE where the flamingmode has a MCE gt 095 and the smoldering mode has a MCElt 090Custom correction factors for the continuous measured PM
were derived as by manufacture instruction to improve themeasurement accuracy from prescribed forest burns Thesecorrection factors were conducted by dividing the averagecontinuous PM25 concentration by the PM25 by filterconcentration during the same collection time (for eachcollected filter) The average correction factor for the DustTrak8520 and the Aerocet 531 was 20 plusmn 056 and 63 plusmn 22respectivelyThe black carbon data were postprocessed for noise using an
optimized noise-reduction averaging algorithm program41 Nocorrection for particle loading on the filters was made since theBC concentration did not change with an increased lightattenuation value (ATN) reported from the AE51 and AE52
RESULTS AND DISCUSSIONNine prescribed burns were sampled at three separate locationsas well as companion laboratory burns with site-gatheredbiomass At the field sites aerial ground-only or both aerial-and ground-based sampling were conducted as site constraintsallowed (Table 2)Particulate Matter The continuous PM25 and CO2
concentrations were highest for the ground-based fieldsampling in SC and lowest for the aerostat-based sampling inFL (SI Figure S3) likely due to the comparative proximity ofthe ground-based sampler to the source The average PM25emission factors from the three different field burn locationsand the OBTF derived from the ratio of the PM mass to thecarbon collected as CO2 ranged from 14 to 47 gkg biomass(Figure 1) These emission factors are mostly higher than
previously reported from prescribed and wildfire forest burns inthe US Portugal and Mexico at 066minus16 gkg bio-mass5minus84243 but overlapping those from previous OBTFforest burns of different biomass types 11minus34 gkg biomass4
A 3-fold difference in average PM25 emission factors wasobserved between the three field values Field and correspond-ing OBTF PM25 emission factors were quite similar also
showing a 3-fold range ANOVA analyses were performed ontwenty-one OBTF and fifteen field PM25 samples from thethree field burn locations No statistical differences (α = 005)were observed between PM25 emission factors derived in thefield and the OBTF suggesting the adequacy of the laboratorysimulation A statistical difference between the OBTF-derivedemission factors was found between FL and both SC and NCThe field-derived emission factors were only statisticallydifferent between the FL and SC biomass sources Theseresults indicate that it is the biomass composition itself ratherthan the laboratory-versus field-based sampling distinctions thatdrive the PM25 emission factor levels As none of the testingafforded opportunities for both aerial and ground basedsampling future research should compare emission factorsderived from simultaneous use of both of these methods
Black and Brown Carbon The field and OBTF averageBC and BrC emission factors ranged from 12 to 21 gkgbiomass and 10 to 14 gkg biomass respectively (Figure 2)
These BC emission factors are generally higher than previouslyreported for forest burn EC and estimated BC emission factorsof 0035minus13 gkg biomass34816minus18 and 037minus066 gkgbiomass1415 respectively The BC emission factors determinedhere are in the same range as medium-and high-duty dieseltrucks 092minus2340414445 gkg fuel4041 ANOVA analysisshowed a slight difference (F = 533) in BC emission factorsbetween the SC OBTF and its corresponding field data but notfor the FL and NC field versus OBTF data There werestatistical differences in OBTF BC emission levels for the NCbiomass with those from FL and SC but no such differenceswere observed for the field dataFigures 3A and B show time-resolved BC BrC ΔCO2
ΔCO and MCE concentrations and emission factor datarespectively for a representative OBTF burn of SC biomass Alldata reach a rapid peak at the onset of combustion As theemission factor data are mass-loss-normalized (Figure 3B) theinitial peaks indicate that the early onset emissions areproportionately higher than subsequent emissions The earlypeak BC and BrC emission factors are more than 2 to 10 timeshigher respectively than their whole-run averages indicatingthat fire intensity characteristics have a significant impact onemissions The BC and BrC concentrations decline exponen-tially with the MCE and time or as the ΔCO2 concentration
Figure 1 PM25 emission factors from field and OBTF forest burns forthree different biomass sources northwestern Florida (FL) the NorthCarolina east coast (NC) and Central South Carolina (SC) Error barsdenote one standard deviation (NC SC) or range of data (FL)
Figure 2 Black and brown carbon emission factors from the threebiomass sources northwestern Florida (FL) North Carolina east coast(NC) and Central South Carolina (SC) sampled in the field and inthe OBTF Error bars denote one standard deviation (SC) or range ofdata (FL NC)
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decreases (Figure 3A) The OBTF laboratory data (Figure 3B)show an exponential decrease in BC and BrC emission factorswith a decrease in MCE and also reveal that while the BC andBrC concentrations are low at the start of a burn the MCE isthe highest (Figure 3A)Figure 4AB shows the comparable BC BrC CO2 and CO
concentrations and emission factor data respectively for thefield tests at SC The concentration data show predictably morefluctuation than the OBTF data (Figure 3A) as the former issubject to turbulent mixing while the latter is a well-stirredscenario MCE values from the Summa canister CO and CO2
grab samples were compared to the same-time BC and BrCvalues (Figure 4CD) A linear trend between BC and BrCemission factors with MCE is observed with higher values at
the start of a field burn The higher BC and BrC emissionfactors at higher MCE values suggest that more intense forestburns with higher fuel burn rates such as occur during wildfiresmay result in greater releases of BC and BrC than duringprescribed burning Additional scatter plots are available in SIFigure S4The paired BC to PM25 mass percentages for the field and
OBTF respectively were FL 18 (plusmn66) and 84 (plusmn34)NC 84 (plusmn32) and 77 (plusmn23) and SC 34(plusmn071) and 33 (plusmn12) The BrCPM25 mass fractionsat SC for the field and OBTF were 31 (plusmn20) and 23(plusmn079) respectively These BCPM25 mass percentagesfrom NC and FL are higher than the ECPM25 masspercentages found in the US EPA SPECIATE version 4346
Figure 3 A OBTF samples of continuous (10 s average) ΔCO2 ΔCO black carbon (BC) and brown carbon (BrC) concentration traces versustime and modified combustion efficiency (MCE) B OBTF time- and MCE-resolved BC and BrC emission factors with ΔCO2 and ΔCOconcentrations
Figure 4 Continuous (10 s average) ΔCO2 BC and BrC concentration traces (A) and BC and BrC emission factors with ΔCO2 (B) from arepresentative SC field emission sampling episode Scatter plots of BC and BrC concentrations vs MCE (D) and average BC and BrC emissionfactors vs MCE (C) during summa canister sampling in SC
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Table
3FieldandOBTFVOC
Emission
Factorsin
μgg
Biomassb
NCfi
eld
SCfi
eld
NCO
BTF
SCO
BTF
MCEgt095
MCElt090
MCEgt090
MCE=090
MCElt090
MCEgt095
MCElt090
MCEgt095
MCEgt0
90lt095
MCElt090
compound
average
AD
average
AD
average
AD
average
AD
average
AD
average
AD
MCE
0980
0004
0886
0011
0928
0007
0904
0004
0874
0011
0951
0889
00952
0932
0855
acroleina
627
599
697
170
385
53435
183
585
349
312
1023
154
256
381
332
propene
479
522
538
156
323
47360
80595
41
350
965
197
230
323
307
benzenea
370
369
526
262
245
23276
79441
92284
776
102
225
290
199
13-butadienea
195
222
246
6199
23114
46195
55
121
378
4797
153
108
vinylacetatea
330
455
363
82250
29256
36ND
166
830
75183
323
425
acetonitrile
165
188
172
57115
17106
16177
1054
165
013
3756
83toluenea
271
371
232
107
150
062
148
38277
51123
369
42121
171
153
2-butanone
(MEK)
128
161
124
3972
58
7354
157
4951
234
6752
8299
xylenea
6474
7817
7932
73125
131
1037
126
1557
8499
naphthalene
6468
102
6838
40
3592
6314
44116
2742
4733
styrenea
6467
8437
4042
4097
8226
102
286
2037
5341
α-pinene
6129
101
100
5632
78282
7255
26
2412
3459
40acrylonitrilea
5441
5611
2915
2450
4314
2549
91
1624
18ethylbenzenea
2729
3294
2231
2054
4217
2676
45
1926
22D-limonene
3548
4164
4319
4855
109
8397
6833
4990
114
chloromethanea
3429
4320
94
47
86
014
1133
1454
34
93
1416
124-trimethylbenzene
78
77
1027
14041
94
22
1616
37
1630
54
81
121
135-trimethylbenzene
22
26
28
55
34
028
24
072
40
062
080
33
087
13
19
30
cumenea
22
23
29
59
23
012
23
084
41
092
22
60
0079
21
29
26
methylene
chlorid
e22
34
40
36
024
042
0028
00079
0053
005
ND
0079
032
ND
ND
ND
brom
omethanea
22
23
26
53
15
034
18
012
30
14
ND
15
30
13
23
23
aIncluded
intheEP
Alistof
hazardousairpollutantsbADabsolutedifference
(twosamples)MCE
modified
combustioneffi
ciencyN
Dnot
detectedornotdetected
abovebackground
levelsN
Ceast
coastof
North
CarolinaSC
centralSouthCarolinaOBTF
open
burn
testfacility
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528449
database (source category = forest fires) of 12minus45 (ID4463minus44684) which were derived from laboratory (OBTF)tests while the SC ratios are similar to those in SPECIATE Asimilar ECPM25 percentage 39 was found from prescribedburning conducted in Georgia (USA)8 The higher ratios foundin our work seem to be due to higher BC rather than ECemission factors levels given the similar PM25 emission factorsdiscussed above This difference could be due to the differentsampling methodslight-scattering (BC) in this study versusthermaloptical transmission (EC) in Hays et al4 Thesedifferences suggest the need for a comparative investigation ofparallel BC and EC measurements from combustion sourcesVOC Ten field and six OBTF summa canister samples were
taken for VOC determination for the NC and SC campaigns(canister samples at FL could not be taken due to weightrestrictions on the aerostat) Acrolein benzene vinyl acetate(on the US EPArsquos hazardous air pollutant list) and propenehad the highest emission factors (425minus380 ugg biomass) of allVOCs analyzed (Table 3) The sixteen VOC samples weredivided according to MCE resulting in 1minus2 samples in eachMCE category (Table 3) The SC field results had no sampleswith MCE gt095 likely due more to the limitations of ground-only sampling than distinctions in the combustion character-istics of this unmanaged site No apparent differences wereobserved between field and OBTF samples for the differentMCE categories although more replicates would be needed fora robust statistical analysis A trend in decreased VOC emissionfactors with increased MCE was found when all of the collectedsamples were correlated (see SI Figure S5 for four VOCs) Theaverage field emission factor for acrolein was 350 μgg biomasswhich was in the same range as that for open burning ofmunicipal waste 310 μgg biomass47 and prescribed burning inSC 323minus472 μgg biomass48 but lower than that found fromtropical forest fires 960 μgg biomass22 The 13-butadiene hadan average emission factor from both field and OBTF of 310 plusmn182 μgg biomass higher than reported from previousprescribed and wild forest burns in the US58 and Mexico49
(67minus100 μgg biomass) and from Mexican crop residue fires(114 μgg biomass43) yet similar to open burning of municipalwaste (300 μgg biomass47) and prescribed burning of SCforest (110minus240 μgkg biomass48) Some other individualVOCs such as benzene and α-pinene were in the same rangeas emission factors from prescribed forest burning in GeorgiaUS8 All VOCs analyzed are shown in SI Tables S8minusS9PCDDPCDF Emissions The average PCDDPCDF
emission factors from the three different biomass sources andboth field (N = 5) and OBTF (N = 7) testing ranged from 006to 46 ng TEQkg biomass (ND = 0 Table 2 and SI TablesS2minusS4) Emissions exceeded the level anticipated fromvolatilization of PCDDPCDF in the raw biomass (Figure 5)which indicates that formation occurs during combustion ratherthan due to evaporation from the green biomassThese emission factors are on the lower range of similar
OBTF and field studies with US forest biomass at 040minus25 ngTEQkg biomass25minus27 (the lowest emission factor 006 ngTEQkg biomass was obtained from an OBTF sample burningNC biomass with only 6 of 17 TEF congeners detected) Therange of emission factors derived herein overlap those ofresidential wood heating appliances such as wood heaters (039ng TEQkg)50 wood stoves (025 ng TEQkg)51 andfireplaces (088 ng TEQkg)51
To discern potential emission factor differences betweenaerial- and ground-based field samples more simultaneous
aerial- and ground-based sampling is necessary The fieldsamples were of limited number and for the aerial samplesconsisted of one single composite (FL) sample from twodifferent burn days with 14 of 17 TEF congeners detected andtwo replicates (NC) with only 4 and 6 of 17 TEF congenersdetected Further none of the aerial and ground samples weretaken from the same fireThe PCDDPCDF emission factors showed similar levels
between aerial measurements in the field and OBTF samplesfor each of the biomass sources (FL and NC) except for theSC ground-based field and OBTF measurements as shown inFigure 5 The emission factors from the three SC ground fieldsamples showed an increase of up to seven times from the firstto last sample (068 22 and 46 ng TEQkg biomass)reflecting the qualitative observations of increasing smokethickness throughout the campaign (Table 3) In addition thetotal PCDD to PCDF and PCDD TEQ to PCDF TEQ massratios in these samples increased with increased emission factorlevels (SI Tables S4 and S7) A higher emission factor and agreater PCDD TEQ to PCDF TEQ ratio during smolderingversus flaming stages was found in an earlier study by Gullett etal26 burning standing trees in EPArsquos OBTF Thus the twohigher emission factors derived from the SC field study (22TEQkg biomass and 46 ng TEQkg biomass) may be due tosampling a larger portion of the smoldering stage rather thanthe flaming stage The SC OBTF emission levels (average 032ng TEQkg biomass) and PCDDPCDF ratios (12) are alsosimilar to the initial SC ground-based field sample (068 ngTEQkg biomass) which suggests the difficulty of collecting arepresentative PCDDPCDF sample from ground- rather thanaerial-based samplingThe slight emission level difference between FL and SC
biomass from the OBTF could be due to chlorine content inthe fuel 645 ppm and 111 ppm respectively (Table 2 andFigure 5) which is in agreement with a OBTF biomass studyshowing that increased chlorine content in the fuel increasesthe PCDDPCDF emissions39 The PCDDPCDF ratio wasalso higher in the FL OBTF samples (57 plusmn 17) than the SCbiomass samples (12 plusmn 02) which is in agreement with alaboratory study showing that an increased chlorine content inthe fuel enhances the formation of PCDDs over PCDFs52
More definitive conclusions regarding the effect of biomass
Figure 5 PCDDPCDF emission factors from three differentlocations on the eastern part of the USA northwestern Florida(FL) the North Carolina east coast (NC) and Central South Carolina(SC) ND not detectable congeners LOD limit of detection
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chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
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Environmental Science amp Technology Article
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of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
was performed downwind of the burn area on firebreak roadsTwo simultaneous Flyer samples were combined for two ofthree sampling days in SC to obtain detectable PCDDPCDFlevels The SC burns were presupposed to be of higherintensity than those in FL and NC since the forest had nohistory of prescribed burn treatmentOpen Burn Test Facility A 70 m3 enclosed OBTF
described in detail elsewhere39 was used for simulatingprescribed forest burns (SI Figure S1) The OBTF wasequipped with a high-volume blower that pulls ambient air intothe OBTF This blower and small fans located inside the facilityensured complete mixing and oxygen concentrations close toambient Burn tests were performed 6minus7 days after biomasscollection at the same area density as found in the field Becausethe small charge sizes used in the OBTF do not necessarilyprovide sufficient mass of PCDDPCDF emissions to avoidnondetectable congeners emissions from multiple charge burnswere composited to obtain a single measurement The biomasscharges were burned one after the other a new charge wasloaded when the CO2 concentration decreased to approx-imately 500 ppm The small burn charges were used to mimicthe field area density and keep the temperature inside thefacility below 50 degC around the sampling equipment to avoidoverheating Flyer electronics and the sampling media Theburns were performed on an aluminum-foil-covered steel plateand the aluminum foil was replaced before each burn testThe same sampling instrumentation was used in the OBTF
as in the field The Flyer was placed inside the facility near theair exit duct For the SC biomass burn tests two PCDDPCDF
samples were collected simultaneously using two Flyers Twopostburn OBTF ambient air background samples werecollected for a total of 5minus10 h inside the uncleaned OBTFover three separate days
Calculations The concentration ratios of the cosampledtarget analytes and the CO2 above ambient levels (ΔCO2)(plus Summa canister ΔCO for VOCs) were used to deriveemission factors according to the carbon mass balanceapproach40 Emission factors are expressed in terms of pollutantmass per mass of biomass where the latter indicates the mass ofbiomass consumed by the fire The carbon mass balanceassumes that all combusted carbon in the biomass is emitted tothe atmosphere as CO2 CO methane and total hydrocarbons(THCs) and that the carbon and pollutants are completelymixed in the plume Calculations from a previous forestlaboratory burn study show that 90minus996 of the total carbonemitted (sum of CO and CO2) was CO2
4 and that THCconcentration was 2minus4 times lower than the CO concentrationThus carbon concentrations from CO and THC were minimaland only CO2 measurements were needed to approximate thetotal mass of carbon emitted Neglecting CO and trace VOCscould have an approximate 10 effect on the emission factor avalue within the total error of the method and likely thereproducibility of the event The biomass composition carbonfractions (Fc) in the preburnedraw biomass (SI Table S1)were then used to calculate emission factors (EFs) bymultiplying Fc with the mass of analyte per mass of carbonThe semicontinuous CO measurements acquired from the
Table 2 Resultsa
aOBTF minus Open burn test facility FL minus North West Florida NC minus East North Carolina SC minus Central South Carolina NM minus not measured FR minusFailed recovery (recovery under method limits) bLimit of detection values within parentheses for those samples with not detected congenerscComposite sample from two field days dParallel sampling of PCDDPCDF - two PCDDPCDF samples collected during the same time eAllOBTF emission factors shown in SI Table S10
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528446
OBTF tests were used only to calculate the modifiedcombustion efficiency (MCE) (ΔCO2(ΔCO2 + ΔCO))The VOC samples were unique in that the summa canister
data provided both CO2 and measurable CO concentrationsallowing emission factors to be assigned to flaming andsmoldering modes by calculating the MCE where the flamingmode has a MCE gt 095 and the smoldering mode has a MCElt 090Custom correction factors for the continuous measured PM
were derived as by manufacture instruction to improve themeasurement accuracy from prescribed forest burns Thesecorrection factors were conducted by dividing the averagecontinuous PM25 concentration by the PM25 by filterconcentration during the same collection time (for eachcollected filter) The average correction factor for the DustTrak8520 and the Aerocet 531 was 20 plusmn 056 and 63 plusmn 22respectivelyThe black carbon data were postprocessed for noise using an
optimized noise-reduction averaging algorithm program41 Nocorrection for particle loading on the filters was made since theBC concentration did not change with an increased lightattenuation value (ATN) reported from the AE51 and AE52
RESULTS AND DISCUSSIONNine prescribed burns were sampled at three separate locationsas well as companion laboratory burns with site-gatheredbiomass At the field sites aerial ground-only or both aerial-and ground-based sampling were conducted as site constraintsallowed (Table 2)Particulate Matter The continuous PM25 and CO2
concentrations were highest for the ground-based fieldsampling in SC and lowest for the aerostat-based sampling inFL (SI Figure S3) likely due to the comparative proximity ofthe ground-based sampler to the source The average PM25emission factors from the three different field burn locationsand the OBTF derived from the ratio of the PM mass to thecarbon collected as CO2 ranged from 14 to 47 gkg biomass(Figure 1) These emission factors are mostly higher than
previously reported from prescribed and wildfire forest burns inthe US Portugal and Mexico at 066minus16 gkg bio-mass5minus84243 but overlapping those from previous OBTFforest burns of different biomass types 11minus34 gkg biomass4
A 3-fold difference in average PM25 emission factors wasobserved between the three field values Field and correspond-ing OBTF PM25 emission factors were quite similar also
showing a 3-fold range ANOVA analyses were performed ontwenty-one OBTF and fifteen field PM25 samples from thethree field burn locations No statistical differences (α = 005)were observed between PM25 emission factors derived in thefield and the OBTF suggesting the adequacy of the laboratorysimulation A statistical difference between the OBTF-derivedemission factors was found between FL and both SC and NCThe field-derived emission factors were only statisticallydifferent between the FL and SC biomass sources Theseresults indicate that it is the biomass composition itself ratherthan the laboratory-versus field-based sampling distinctions thatdrive the PM25 emission factor levels As none of the testingafforded opportunities for both aerial and ground basedsampling future research should compare emission factorsderived from simultaneous use of both of these methods
Black and Brown Carbon The field and OBTF averageBC and BrC emission factors ranged from 12 to 21 gkgbiomass and 10 to 14 gkg biomass respectively (Figure 2)
These BC emission factors are generally higher than previouslyreported for forest burn EC and estimated BC emission factorsof 0035minus13 gkg biomass34816minus18 and 037minus066 gkgbiomass1415 respectively The BC emission factors determinedhere are in the same range as medium-and high-duty dieseltrucks 092minus2340414445 gkg fuel4041 ANOVA analysisshowed a slight difference (F = 533) in BC emission factorsbetween the SC OBTF and its corresponding field data but notfor the FL and NC field versus OBTF data There werestatistical differences in OBTF BC emission levels for the NCbiomass with those from FL and SC but no such differenceswere observed for the field dataFigures 3A and B show time-resolved BC BrC ΔCO2
ΔCO and MCE concentrations and emission factor datarespectively for a representative OBTF burn of SC biomass Alldata reach a rapid peak at the onset of combustion As theemission factor data are mass-loss-normalized (Figure 3B) theinitial peaks indicate that the early onset emissions areproportionately higher than subsequent emissions The earlypeak BC and BrC emission factors are more than 2 to 10 timeshigher respectively than their whole-run averages indicatingthat fire intensity characteristics have a significant impact onemissions The BC and BrC concentrations decline exponen-tially with the MCE and time or as the ΔCO2 concentration
Figure 1 PM25 emission factors from field and OBTF forest burns forthree different biomass sources northwestern Florida (FL) the NorthCarolina east coast (NC) and Central South Carolina (SC) Error barsdenote one standard deviation (NC SC) or range of data (FL)
Figure 2 Black and brown carbon emission factors from the threebiomass sources northwestern Florida (FL) North Carolina east coast(NC) and Central South Carolina (SC) sampled in the field and inthe OBTF Error bars denote one standard deviation (SC) or range ofdata (FL NC)
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528447
decreases (Figure 3A) The OBTF laboratory data (Figure 3B)show an exponential decrease in BC and BrC emission factorswith a decrease in MCE and also reveal that while the BC andBrC concentrations are low at the start of a burn the MCE isthe highest (Figure 3A)Figure 4AB shows the comparable BC BrC CO2 and CO
concentrations and emission factor data respectively for thefield tests at SC The concentration data show predictably morefluctuation than the OBTF data (Figure 3A) as the former issubject to turbulent mixing while the latter is a well-stirredscenario MCE values from the Summa canister CO and CO2
grab samples were compared to the same-time BC and BrCvalues (Figure 4CD) A linear trend between BC and BrCemission factors with MCE is observed with higher values at
the start of a field burn The higher BC and BrC emissionfactors at higher MCE values suggest that more intense forestburns with higher fuel burn rates such as occur during wildfiresmay result in greater releases of BC and BrC than duringprescribed burning Additional scatter plots are available in SIFigure S4The paired BC to PM25 mass percentages for the field and
OBTF respectively were FL 18 (plusmn66) and 84 (plusmn34)NC 84 (plusmn32) and 77 (plusmn23) and SC 34(plusmn071) and 33 (plusmn12) The BrCPM25 mass fractionsat SC for the field and OBTF were 31 (plusmn20) and 23(plusmn079) respectively These BCPM25 mass percentagesfrom NC and FL are higher than the ECPM25 masspercentages found in the US EPA SPECIATE version 4346
Figure 3 A OBTF samples of continuous (10 s average) ΔCO2 ΔCO black carbon (BC) and brown carbon (BrC) concentration traces versustime and modified combustion efficiency (MCE) B OBTF time- and MCE-resolved BC and BrC emission factors with ΔCO2 and ΔCOconcentrations
Figure 4 Continuous (10 s average) ΔCO2 BC and BrC concentration traces (A) and BC and BrC emission factors with ΔCO2 (B) from arepresentative SC field emission sampling episode Scatter plots of BC and BrC concentrations vs MCE (D) and average BC and BrC emissionfactors vs MCE (C) during summa canister sampling in SC
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528448
Table
3FieldandOBTFVOC
Emission
Factorsin
μgg
Biomassb
NCfi
eld
SCfi
eld
NCO
BTF
SCO
BTF
MCEgt095
MCElt090
MCEgt090
MCE=090
MCElt090
MCEgt095
MCElt090
MCEgt095
MCEgt0
90lt095
MCElt090
compound
average
AD
average
AD
average
AD
average
AD
average
AD
average
AD
MCE
0980
0004
0886
0011
0928
0007
0904
0004
0874
0011
0951
0889
00952
0932
0855
acroleina
627
599
697
170
385
53435
183
585
349
312
1023
154
256
381
332
propene
479
522
538
156
323
47360
80595
41
350
965
197
230
323
307
benzenea
370
369
526
262
245
23276
79441
92284
776
102
225
290
199
13-butadienea
195
222
246
6199
23114
46195
55
121
378
4797
153
108
vinylacetatea
330
455
363
82250
29256
36ND
166
830
75183
323
425
acetonitrile
165
188
172
57115
17106
16177
1054
165
013
3756
83toluenea
271
371
232
107
150
062
148
38277
51123
369
42121
171
153
2-butanone
(MEK)
128
161
124
3972
58
7354
157
4951
234
6752
8299
xylenea
6474
7817
7932
73125
131
1037
126
1557
8499
naphthalene
6468
102
6838
40
3592
6314
44116
2742
4733
styrenea
6467
8437
4042
4097
8226
102
286
2037
5341
α-pinene
6129
101
100
5632
78282
7255
26
2412
3459
40acrylonitrilea
5441
5611
2915
2450
4314
2549
91
1624
18ethylbenzenea
2729
3294
2231
2054
4217
2676
45
1926
22D-limonene
3548
4164
4319
4855
109
8397
6833
4990
114
chloromethanea
3429
4320
94
47
86
014
1133
1454
34
93
1416
124-trimethylbenzene
78
77
1027
14041
94
22
1616
37
1630
54
81
121
135-trimethylbenzene
22
26
28
55
34
028
24
072
40
062
080
33
087
13
19
30
cumenea
22
23
29
59
23
012
23
084
41
092
22
60
0079
21
29
26
methylene
chlorid
e22
34
40
36
024
042
0028
00079
0053
005
ND
0079
032
ND
ND
ND
brom
omethanea
22
23
26
53
15
034
18
012
30
14
ND
15
30
13
23
23
aIncluded
intheEP
Alistof
hazardousairpollutantsbADabsolutedifference
(twosamples)MCE
modified
combustioneffi
ciencyN
Dnot
detectedornotdetected
abovebackground
levelsN
Ceast
coastof
North
CarolinaSC
centralSouthCarolinaOBTF
open
burn
testfacility
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528449
database (source category = forest fires) of 12minus45 (ID4463minus44684) which were derived from laboratory (OBTF)tests while the SC ratios are similar to those in SPECIATE Asimilar ECPM25 percentage 39 was found from prescribedburning conducted in Georgia (USA)8 The higher ratios foundin our work seem to be due to higher BC rather than ECemission factors levels given the similar PM25 emission factorsdiscussed above This difference could be due to the differentsampling methodslight-scattering (BC) in this study versusthermaloptical transmission (EC) in Hays et al4 Thesedifferences suggest the need for a comparative investigation ofparallel BC and EC measurements from combustion sourcesVOC Ten field and six OBTF summa canister samples were
taken for VOC determination for the NC and SC campaigns(canister samples at FL could not be taken due to weightrestrictions on the aerostat) Acrolein benzene vinyl acetate(on the US EPArsquos hazardous air pollutant list) and propenehad the highest emission factors (425minus380 ugg biomass) of allVOCs analyzed (Table 3) The sixteen VOC samples weredivided according to MCE resulting in 1minus2 samples in eachMCE category (Table 3) The SC field results had no sampleswith MCE gt095 likely due more to the limitations of ground-only sampling than distinctions in the combustion character-istics of this unmanaged site No apparent differences wereobserved between field and OBTF samples for the differentMCE categories although more replicates would be needed fora robust statistical analysis A trend in decreased VOC emissionfactors with increased MCE was found when all of the collectedsamples were correlated (see SI Figure S5 for four VOCs) Theaverage field emission factor for acrolein was 350 μgg biomasswhich was in the same range as that for open burning ofmunicipal waste 310 μgg biomass47 and prescribed burning inSC 323minus472 μgg biomass48 but lower than that found fromtropical forest fires 960 μgg biomass22 The 13-butadiene hadan average emission factor from both field and OBTF of 310 plusmn182 μgg biomass higher than reported from previousprescribed and wild forest burns in the US58 and Mexico49
(67minus100 μgg biomass) and from Mexican crop residue fires(114 μgg biomass43) yet similar to open burning of municipalwaste (300 μgg biomass47) and prescribed burning of SCforest (110minus240 μgkg biomass48) Some other individualVOCs such as benzene and α-pinene were in the same rangeas emission factors from prescribed forest burning in GeorgiaUS8 All VOCs analyzed are shown in SI Tables S8minusS9PCDDPCDF Emissions The average PCDDPCDF
emission factors from the three different biomass sources andboth field (N = 5) and OBTF (N = 7) testing ranged from 006to 46 ng TEQkg biomass (ND = 0 Table 2 and SI TablesS2minusS4) Emissions exceeded the level anticipated fromvolatilization of PCDDPCDF in the raw biomass (Figure 5)which indicates that formation occurs during combustion ratherthan due to evaporation from the green biomassThese emission factors are on the lower range of similar
OBTF and field studies with US forest biomass at 040minus25 ngTEQkg biomass25minus27 (the lowest emission factor 006 ngTEQkg biomass was obtained from an OBTF sample burningNC biomass with only 6 of 17 TEF congeners detected) Therange of emission factors derived herein overlap those ofresidential wood heating appliances such as wood heaters (039ng TEQkg)50 wood stoves (025 ng TEQkg)51 andfireplaces (088 ng TEQkg)51
To discern potential emission factor differences betweenaerial- and ground-based field samples more simultaneous
aerial- and ground-based sampling is necessary The fieldsamples were of limited number and for the aerial samplesconsisted of one single composite (FL) sample from twodifferent burn days with 14 of 17 TEF congeners detected andtwo replicates (NC) with only 4 and 6 of 17 TEF congenersdetected Further none of the aerial and ground samples weretaken from the same fireThe PCDDPCDF emission factors showed similar levels
between aerial measurements in the field and OBTF samplesfor each of the biomass sources (FL and NC) except for theSC ground-based field and OBTF measurements as shown inFigure 5 The emission factors from the three SC ground fieldsamples showed an increase of up to seven times from the firstto last sample (068 22 and 46 ng TEQkg biomass)reflecting the qualitative observations of increasing smokethickness throughout the campaign (Table 3) In addition thetotal PCDD to PCDF and PCDD TEQ to PCDF TEQ massratios in these samples increased with increased emission factorlevels (SI Tables S4 and S7) A higher emission factor and agreater PCDD TEQ to PCDF TEQ ratio during smolderingversus flaming stages was found in an earlier study by Gullett etal26 burning standing trees in EPArsquos OBTF Thus the twohigher emission factors derived from the SC field study (22TEQkg biomass and 46 ng TEQkg biomass) may be due tosampling a larger portion of the smoldering stage rather thanthe flaming stage The SC OBTF emission levels (average 032ng TEQkg biomass) and PCDDPCDF ratios (12) are alsosimilar to the initial SC ground-based field sample (068 ngTEQkg biomass) which suggests the difficulty of collecting arepresentative PCDDPCDF sample from ground- rather thanaerial-based samplingThe slight emission level difference between FL and SC
biomass from the OBTF could be due to chlorine content inthe fuel 645 ppm and 111 ppm respectively (Table 2 andFigure 5) which is in agreement with a OBTF biomass studyshowing that increased chlorine content in the fuel increasesthe PCDDPCDF emissions39 The PCDDPCDF ratio wasalso higher in the FL OBTF samples (57 plusmn 17) than the SCbiomass samples (12 plusmn 02) which is in agreement with alaboratory study showing that an increased chlorine content inthe fuel enhances the formation of PCDDs over PCDFs52
More definitive conclusions regarding the effect of biomass
Figure 5 PCDDPCDF emission factors from three differentlocations on the eastern part of the USA northwestern Florida(FL) the North Carolina east coast (NC) and Central South Carolina(SC) ND not detectable congeners LOD limit of detection
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528450
chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
REFERENCES(1) US EPA 1970minus2012 Average annual emissions all criteriapollutants httpwwwepagovttnchie1trends (accessed October17 2012)(2) Hosseini S Urbanski S P Dixit P Qi L Burling IYokelson R Shrivastava M Jung H Weise D R Miller WCocker D Laboratory characterization of PM emissions fromcombustion of wildland biomass fuels J Geophys Res 2013DOI101002jgrd50481(3) McMeeking G R Kreidenweis S M Baker S Carrico C MChow J C Collett J L Hao W M Holden A S Kirchstetter T
W Malm W C Moosmuller H Sullivan A P Wold C EEmissions of trace gases and aerosols during the open combustion ofbiomass in the laboratory J Geophys Res 2009 114(4) Hays M D Geron C D Linna K J Smith N D Schauer JJ Speciation of gas-phase and fine particle emissions from burning offoliar fuels Environ Sci Technol 2002 36 (11) 2281minus2295(5) Burling I R Yokelson R J Akagi S K Urbanski S P WoldC E Griffith D W T Johnson T J Reardon J Weise D RAirborne and ground-based measurements of the trace gases andparticles emitted by prescribed fires in the United States Atmos ChemPhys 2011 11 (23) 12197minus12216(6) Urbanski S P Hao W M Baker S Chemical composition ofwildland fire emissions In Developments in Environmental ScienceBytnerowicz A Arbaugh M Riebau A Andersen C Eds ElsevierNew York 2009 Vol 8 pp 79minus107(7) Geron C Hays M Air emissions from organic soil burning onthe coastal plain of North Carolina Atmos Environ 2013 64 192minus199(8) Lee S Baumann K Schauer J J Sheesley R J Naeher L PMeinardi S Blake D R Edgerton E S Russell A G Clements MGaseous and particulate emissions from prescribed burning in GeorgiaEnviron Sci Technol 2005 39 (23) 9049minus9056(9) Ramanathan V Carmichael G Global and regional climatechanges due to black carbon Nat Geosci 2008 1 (4) 221minus227(10) Andreae M O Gelencser A Black carbon or brown carbonThe nature of light-absorbing carbonaceous aerosols Atmos ChemPhys 2006 6 3131minus3148(11) Alexander D T L Crozier P A Anderson J R Browncarbon spheres in East Asian outflow and their optical propertiesScience 2008 321 (5890) 833minus836(12) Kirchstetter T W Novakov T Hobbs P V Evidence that thespectral dependence of light absorption by aerosols is affected byorganic carbon J Geophys Res 2004 109 (D21)(13) Kondo Y Matsui H Moteki N Sahu L Takegawa NKajino M Zhao Y Cubison M J Jimenez J L Vay S Diskin GS Anderson B Wisthaler A Mikoviny T Fuelberg H E BlakeD R Huey G Weinheimer A J Knapp D J Brune W HEmissions of black carbon organic and inorganic aerosols frombiomass burning in North America and Asia in 2008 J Geophys Res2011 116(14) Akagi S K Yokelson R J Wiedinmyer C Alvarado M JReid J S Karl T Crounse J D Wennberg P O Emission factorsfor open and domestic biomass burning for use in atmospheric modelsAtmos Chem Phys 2011 11 (9) 4039minus4072(15) Andreae M O Merlet P Emission of trace gases and aerosolsfrom biomass burning Global Biogeochem Cyc 2001 15 (4) 955minus966(16) Ferek R J Reid J S Hobbs P V Blake D R Liousse CEmission factors of hydrocarbons halocarbons trace gases andparticles from biomass burning in Brazil J Geophys Res 1998 103(D24) 32107minus32118(17) Andreae M O Andreae T W Annegarn H Beer JCachier H le Canut P Elbert W Maenhaut W Salma IWienhold F G Zenker T Airborne studies of aerosol emissionsfrom savanna fires in southern Africa 2 Aerosol chemicalcomposition J Geophys Res 1998 103 (D24) 32119minus32128(18) Alves C Vicente A Nunes T Goncalves C Fernandes AP Mirante F Tarelho L Sanchez de la Campa A M Querol XCaseiro A Monteiro C Evtyugina M Pio C Summer 2009wildfires in Portugal Emission of trace gases and aerosol compositionAtmos Environ 2011 45 (3) 641minus649(19) US EPA Hazardous Air Pollution List Clean Air Act Title 42The Public Health and Welfare US Government Printing OfficeWashington DC 2008(20) Pappas G P Herbert R J Henderson W Koenig J StoverB Barnhart S The respiratory effects of volatile organic compoundsInt J Occup Env Heal 2000 6 (1) 1minus8(21) Sinha P Hobbs P V Yokelson R J Bertschi I T Blake DR Simpson I J Gao S Kirchstetter T W Novakov T Emissions
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528451
of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
OBTF tests were used only to calculate the modifiedcombustion efficiency (MCE) (ΔCO2(ΔCO2 + ΔCO))The VOC samples were unique in that the summa canister
data provided both CO2 and measurable CO concentrationsallowing emission factors to be assigned to flaming andsmoldering modes by calculating the MCE where the flamingmode has a MCE gt 095 and the smoldering mode has a MCElt 090Custom correction factors for the continuous measured PM
were derived as by manufacture instruction to improve themeasurement accuracy from prescribed forest burns Thesecorrection factors were conducted by dividing the averagecontinuous PM25 concentration by the PM25 by filterconcentration during the same collection time (for eachcollected filter) The average correction factor for the DustTrak8520 and the Aerocet 531 was 20 plusmn 056 and 63 plusmn 22respectivelyThe black carbon data were postprocessed for noise using an
optimized noise-reduction averaging algorithm program41 Nocorrection for particle loading on the filters was made since theBC concentration did not change with an increased lightattenuation value (ATN) reported from the AE51 and AE52
RESULTS AND DISCUSSIONNine prescribed burns were sampled at three separate locationsas well as companion laboratory burns with site-gatheredbiomass At the field sites aerial ground-only or both aerial-and ground-based sampling were conducted as site constraintsallowed (Table 2)Particulate Matter The continuous PM25 and CO2
concentrations were highest for the ground-based fieldsampling in SC and lowest for the aerostat-based sampling inFL (SI Figure S3) likely due to the comparative proximity ofthe ground-based sampler to the source The average PM25emission factors from the three different field burn locationsand the OBTF derived from the ratio of the PM mass to thecarbon collected as CO2 ranged from 14 to 47 gkg biomass(Figure 1) These emission factors are mostly higher than
previously reported from prescribed and wildfire forest burns inthe US Portugal and Mexico at 066minus16 gkg bio-mass5minus84243 but overlapping those from previous OBTFforest burns of different biomass types 11minus34 gkg biomass4
A 3-fold difference in average PM25 emission factors wasobserved between the three field values Field and correspond-ing OBTF PM25 emission factors were quite similar also
showing a 3-fold range ANOVA analyses were performed ontwenty-one OBTF and fifteen field PM25 samples from thethree field burn locations No statistical differences (α = 005)were observed between PM25 emission factors derived in thefield and the OBTF suggesting the adequacy of the laboratorysimulation A statistical difference between the OBTF-derivedemission factors was found between FL and both SC and NCThe field-derived emission factors were only statisticallydifferent between the FL and SC biomass sources Theseresults indicate that it is the biomass composition itself ratherthan the laboratory-versus field-based sampling distinctions thatdrive the PM25 emission factor levels As none of the testingafforded opportunities for both aerial and ground basedsampling future research should compare emission factorsderived from simultaneous use of both of these methods
Black and Brown Carbon The field and OBTF averageBC and BrC emission factors ranged from 12 to 21 gkgbiomass and 10 to 14 gkg biomass respectively (Figure 2)
These BC emission factors are generally higher than previouslyreported for forest burn EC and estimated BC emission factorsof 0035minus13 gkg biomass34816minus18 and 037minus066 gkgbiomass1415 respectively The BC emission factors determinedhere are in the same range as medium-and high-duty dieseltrucks 092minus2340414445 gkg fuel4041 ANOVA analysisshowed a slight difference (F = 533) in BC emission factorsbetween the SC OBTF and its corresponding field data but notfor the FL and NC field versus OBTF data There werestatistical differences in OBTF BC emission levels for the NCbiomass with those from FL and SC but no such differenceswere observed for the field dataFigures 3A and B show time-resolved BC BrC ΔCO2
ΔCO and MCE concentrations and emission factor datarespectively for a representative OBTF burn of SC biomass Alldata reach a rapid peak at the onset of combustion As theemission factor data are mass-loss-normalized (Figure 3B) theinitial peaks indicate that the early onset emissions areproportionately higher than subsequent emissions The earlypeak BC and BrC emission factors are more than 2 to 10 timeshigher respectively than their whole-run averages indicatingthat fire intensity characteristics have a significant impact onemissions The BC and BrC concentrations decline exponen-tially with the MCE and time or as the ΔCO2 concentration
Figure 1 PM25 emission factors from field and OBTF forest burns forthree different biomass sources northwestern Florida (FL) the NorthCarolina east coast (NC) and Central South Carolina (SC) Error barsdenote one standard deviation (NC SC) or range of data (FL)
Figure 2 Black and brown carbon emission factors from the threebiomass sources northwestern Florida (FL) North Carolina east coast(NC) and Central South Carolina (SC) sampled in the field and inthe OBTF Error bars denote one standard deviation (SC) or range ofdata (FL NC)
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528447
decreases (Figure 3A) The OBTF laboratory data (Figure 3B)show an exponential decrease in BC and BrC emission factorswith a decrease in MCE and also reveal that while the BC andBrC concentrations are low at the start of a burn the MCE isthe highest (Figure 3A)Figure 4AB shows the comparable BC BrC CO2 and CO
concentrations and emission factor data respectively for thefield tests at SC The concentration data show predictably morefluctuation than the OBTF data (Figure 3A) as the former issubject to turbulent mixing while the latter is a well-stirredscenario MCE values from the Summa canister CO and CO2
grab samples were compared to the same-time BC and BrCvalues (Figure 4CD) A linear trend between BC and BrCemission factors with MCE is observed with higher values at
the start of a field burn The higher BC and BrC emissionfactors at higher MCE values suggest that more intense forestburns with higher fuel burn rates such as occur during wildfiresmay result in greater releases of BC and BrC than duringprescribed burning Additional scatter plots are available in SIFigure S4The paired BC to PM25 mass percentages for the field and
OBTF respectively were FL 18 (plusmn66) and 84 (plusmn34)NC 84 (plusmn32) and 77 (plusmn23) and SC 34(plusmn071) and 33 (plusmn12) The BrCPM25 mass fractionsat SC for the field and OBTF were 31 (plusmn20) and 23(plusmn079) respectively These BCPM25 mass percentagesfrom NC and FL are higher than the ECPM25 masspercentages found in the US EPA SPECIATE version 4346
Figure 3 A OBTF samples of continuous (10 s average) ΔCO2 ΔCO black carbon (BC) and brown carbon (BrC) concentration traces versustime and modified combustion efficiency (MCE) B OBTF time- and MCE-resolved BC and BrC emission factors with ΔCO2 and ΔCOconcentrations
Figure 4 Continuous (10 s average) ΔCO2 BC and BrC concentration traces (A) and BC and BrC emission factors with ΔCO2 (B) from arepresentative SC field emission sampling episode Scatter plots of BC and BrC concentrations vs MCE (D) and average BC and BrC emissionfactors vs MCE (C) during summa canister sampling in SC
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528448
Table
3FieldandOBTFVOC
Emission
Factorsin
μgg
Biomassb
NCfi
eld
SCfi
eld
NCO
BTF
SCO
BTF
MCEgt095
MCElt090
MCEgt090
MCE=090
MCElt090
MCEgt095
MCElt090
MCEgt095
MCEgt0
90lt095
MCElt090
compound
average
AD
average
AD
average
AD
average
AD
average
AD
average
AD
MCE
0980
0004
0886
0011
0928
0007
0904
0004
0874
0011
0951
0889
00952
0932
0855
acroleina
627
599
697
170
385
53435
183
585
349
312
1023
154
256
381
332
propene
479
522
538
156
323
47360
80595
41
350
965
197
230
323
307
benzenea
370
369
526
262
245
23276
79441
92284
776
102
225
290
199
13-butadienea
195
222
246
6199
23114
46195
55
121
378
4797
153
108
vinylacetatea
330
455
363
82250
29256
36ND
166
830
75183
323
425
acetonitrile
165
188
172
57115
17106
16177
1054
165
013
3756
83toluenea
271
371
232
107
150
062
148
38277
51123
369
42121
171
153
2-butanone
(MEK)
128
161
124
3972
58
7354
157
4951
234
6752
8299
xylenea
6474
7817
7932
73125
131
1037
126
1557
8499
naphthalene
6468
102
6838
40
3592
6314
44116
2742
4733
styrenea
6467
8437
4042
4097
8226
102
286
2037
5341
α-pinene
6129
101
100
5632
78282
7255
26
2412
3459
40acrylonitrilea
5441
5611
2915
2450
4314
2549
91
1624
18ethylbenzenea
2729
3294
2231
2054
4217
2676
45
1926
22D-limonene
3548
4164
4319
4855
109
8397
6833
4990
114
chloromethanea
3429
4320
94
47
86
014
1133
1454
34
93
1416
124-trimethylbenzene
78
77
1027
14041
94
22
1616
37
1630
54
81
121
135-trimethylbenzene
22
26
28
55
34
028
24
072
40
062
080
33
087
13
19
30
cumenea
22
23
29
59
23
012
23
084
41
092
22
60
0079
21
29
26
methylene
chlorid
e22
34
40
36
024
042
0028
00079
0053
005
ND
0079
032
ND
ND
ND
brom
omethanea
22
23
26
53
15
034
18
012
30
14
ND
15
30
13
23
23
aIncluded
intheEP
Alistof
hazardousairpollutantsbADabsolutedifference
(twosamples)MCE
modified
combustioneffi
ciencyN
Dnot
detectedornotdetected
abovebackground
levelsN
Ceast
coastof
North
CarolinaSC
centralSouthCarolinaOBTF
open
burn
testfacility
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528449
database (source category = forest fires) of 12minus45 (ID4463minus44684) which were derived from laboratory (OBTF)tests while the SC ratios are similar to those in SPECIATE Asimilar ECPM25 percentage 39 was found from prescribedburning conducted in Georgia (USA)8 The higher ratios foundin our work seem to be due to higher BC rather than ECemission factors levels given the similar PM25 emission factorsdiscussed above This difference could be due to the differentsampling methodslight-scattering (BC) in this study versusthermaloptical transmission (EC) in Hays et al4 Thesedifferences suggest the need for a comparative investigation ofparallel BC and EC measurements from combustion sourcesVOC Ten field and six OBTF summa canister samples were
taken for VOC determination for the NC and SC campaigns(canister samples at FL could not be taken due to weightrestrictions on the aerostat) Acrolein benzene vinyl acetate(on the US EPArsquos hazardous air pollutant list) and propenehad the highest emission factors (425minus380 ugg biomass) of allVOCs analyzed (Table 3) The sixteen VOC samples weredivided according to MCE resulting in 1minus2 samples in eachMCE category (Table 3) The SC field results had no sampleswith MCE gt095 likely due more to the limitations of ground-only sampling than distinctions in the combustion character-istics of this unmanaged site No apparent differences wereobserved between field and OBTF samples for the differentMCE categories although more replicates would be needed fora robust statistical analysis A trend in decreased VOC emissionfactors with increased MCE was found when all of the collectedsamples were correlated (see SI Figure S5 for four VOCs) Theaverage field emission factor for acrolein was 350 μgg biomasswhich was in the same range as that for open burning ofmunicipal waste 310 μgg biomass47 and prescribed burning inSC 323minus472 μgg biomass48 but lower than that found fromtropical forest fires 960 μgg biomass22 The 13-butadiene hadan average emission factor from both field and OBTF of 310 plusmn182 μgg biomass higher than reported from previousprescribed and wild forest burns in the US58 and Mexico49
(67minus100 μgg biomass) and from Mexican crop residue fires(114 μgg biomass43) yet similar to open burning of municipalwaste (300 μgg biomass47) and prescribed burning of SCforest (110minus240 μgkg biomass48) Some other individualVOCs such as benzene and α-pinene were in the same rangeas emission factors from prescribed forest burning in GeorgiaUS8 All VOCs analyzed are shown in SI Tables S8minusS9PCDDPCDF Emissions The average PCDDPCDF
emission factors from the three different biomass sources andboth field (N = 5) and OBTF (N = 7) testing ranged from 006to 46 ng TEQkg biomass (ND = 0 Table 2 and SI TablesS2minusS4) Emissions exceeded the level anticipated fromvolatilization of PCDDPCDF in the raw biomass (Figure 5)which indicates that formation occurs during combustion ratherthan due to evaporation from the green biomassThese emission factors are on the lower range of similar
OBTF and field studies with US forest biomass at 040minus25 ngTEQkg biomass25minus27 (the lowest emission factor 006 ngTEQkg biomass was obtained from an OBTF sample burningNC biomass with only 6 of 17 TEF congeners detected) Therange of emission factors derived herein overlap those ofresidential wood heating appliances such as wood heaters (039ng TEQkg)50 wood stoves (025 ng TEQkg)51 andfireplaces (088 ng TEQkg)51
To discern potential emission factor differences betweenaerial- and ground-based field samples more simultaneous
aerial- and ground-based sampling is necessary The fieldsamples were of limited number and for the aerial samplesconsisted of one single composite (FL) sample from twodifferent burn days with 14 of 17 TEF congeners detected andtwo replicates (NC) with only 4 and 6 of 17 TEF congenersdetected Further none of the aerial and ground samples weretaken from the same fireThe PCDDPCDF emission factors showed similar levels
between aerial measurements in the field and OBTF samplesfor each of the biomass sources (FL and NC) except for theSC ground-based field and OBTF measurements as shown inFigure 5 The emission factors from the three SC ground fieldsamples showed an increase of up to seven times from the firstto last sample (068 22 and 46 ng TEQkg biomass)reflecting the qualitative observations of increasing smokethickness throughout the campaign (Table 3) In addition thetotal PCDD to PCDF and PCDD TEQ to PCDF TEQ massratios in these samples increased with increased emission factorlevels (SI Tables S4 and S7) A higher emission factor and agreater PCDD TEQ to PCDF TEQ ratio during smolderingversus flaming stages was found in an earlier study by Gullett etal26 burning standing trees in EPArsquos OBTF Thus the twohigher emission factors derived from the SC field study (22TEQkg biomass and 46 ng TEQkg biomass) may be due tosampling a larger portion of the smoldering stage rather thanthe flaming stage The SC OBTF emission levels (average 032ng TEQkg biomass) and PCDDPCDF ratios (12) are alsosimilar to the initial SC ground-based field sample (068 ngTEQkg biomass) which suggests the difficulty of collecting arepresentative PCDDPCDF sample from ground- rather thanaerial-based samplingThe slight emission level difference between FL and SC
biomass from the OBTF could be due to chlorine content inthe fuel 645 ppm and 111 ppm respectively (Table 2 andFigure 5) which is in agreement with a OBTF biomass studyshowing that increased chlorine content in the fuel increasesthe PCDDPCDF emissions39 The PCDDPCDF ratio wasalso higher in the FL OBTF samples (57 plusmn 17) than the SCbiomass samples (12 plusmn 02) which is in agreement with alaboratory study showing that an increased chlorine content inthe fuel enhances the formation of PCDDs over PCDFs52
More definitive conclusions regarding the effect of biomass
Figure 5 PCDDPCDF emission factors from three differentlocations on the eastern part of the USA northwestern Florida(FL) the North Carolina east coast (NC) and Central South Carolina(SC) ND not detectable congeners LOD limit of detection
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528450
chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
REFERENCES(1) US EPA 1970minus2012 Average annual emissions all criteriapollutants httpwwwepagovttnchie1trends (accessed October17 2012)(2) Hosseini S Urbanski S P Dixit P Qi L Burling IYokelson R Shrivastava M Jung H Weise D R Miller WCocker D Laboratory characterization of PM emissions fromcombustion of wildland biomass fuels J Geophys Res 2013DOI101002jgrd50481(3) McMeeking G R Kreidenweis S M Baker S Carrico C MChow J C Collett J L Hao W M Holden A S Kirchstetter T
W Malm W C Moosmuller H Sullivan A P Wold C EEmissions of trace gases and aerosols during the open combustion ofbiomass in the laboratory J Geophys Res 2009 114(4) Hays M D Geron C D Linna K J Smith N D Schauer JJ Speciation of gas-phase and fine particle emissions from burning offoliar fuels Environ Sci Technol 2002 36 (11) 2281minus2295(5) Burling I R Yokelson R J Akagi S K Urbanski S P WoldC E Griffith D W T Johnson T J Reardon J Weise D RAirborne and ground-based measurements of the trace gases andparticles emitted by prescribed fires in the United States Atmos ChemPhys 2011 11 (23) 12197minus12216(6) Urbanski S P Hao W M Baker S Chemical composition ofwildland fire emissions In Developments in Environmental ScienceBytnerowicz A Arbaugh M Riebau A Andersen C Eds ElsevierNew York 2009 Vol 8 pp 79minus107(7) Geron C Hays M Air emissions from organic soil burning onthe coastal plain of North Carolina Atmos Environ 2013 64 192minus199(8) Lee S Baumann K Schauer J J Sheesley R J Naeher L PMeinardi S Blake D R Edgerton E S Russell A G Clements MGaseous and particulate emissions from prescribed burning in GeorgiaEnviron Sci Technol 2005 39 (23) 9049minus9056(9) Ramanathan V Carmichael G Global and regional climatechanges due to black carbon Nat Geosci 2008 1 (4) 221minus227(10) Andreae M O Gelencser A Black carbon or brown carbonThe nature of light-absorbing carbonaceous aerosols Atmos ChemPhys 2006 6 3131minus3148(11) Alexander D T L Crozier P A Anderson J R Browncarbon spheres in East Asian outflow and their optical propertiesScience 2008 321 (5890) 833minus836(12) Kirchstetter T W Novakov T Hobbs P V Evidence that thespectral dependence of light absorption by aerosols is affected byorganic carbon J Geophys Res 2004 109 (D21)(13) Kondo Y Matsui H Moteki N Sahu L Takegawa NKajino M Zhao Y Cubison M J Jimenez J L Vay S Diskin GS Anderson B Wisthaler A Mikoviny T Fuelberg H E BlakeD R Huey G Weinheimer A J Knapp D J Brune W HEmissions of black carbon organic and inorganic aerosols frombiomass burning in North America and Asia in 2008 J Geophys Res2011 116(14) Akagi S K Yokelson R J Wiedinmyer C Alvarado M JReid J S Karl T Crounse J D Wennberg P O Emission factorsfor open and domestic biomass burning for use in atmospheric modelsAtmos Chem Phys 2011 11 (9) 4039minus4072(15) Andreae M O Merlet P Emission of trace gases and aerosolsfrom biomass burning Global Biogeochem Cyc 2001 15 (4) 955minus966(16) Ferek R J Reid J S Hobbs P V Blake D R Liousse CEmission factors of hydrocarbons halocarbons trace gases andparticles from biomass burning in Brazil J Geophys Res 1998 103(D24) 32107minus32118(17) Andreae M O Andreae T W Annegarn H Beer JCachier H le Canut P Elbert W Maenhaut W Salma IWienhold F G Zenker T Airborne studies of aerosol emissionsfrom savanna fires in southern Africa 2 Aerosol chemicalcomposition J Geophys Res 1998 103 (D24) 32119minus32128(18) Alves C Vicente A Nunes T Goncalves C Fernandes AP Mirante F Tarelho L Sanchez de la Campa A M Querol XCaseiro A Monteiro C Evtyugina M Pio C Summer 2009wildfires in Portugal Emission of trace gases and aerosol compositionAtmos Environ 2011 45 (3) 641minus649(19) US EPA Hazardous Air Pollution List Clean Air Act Title 42The Public Health and Welfare US Government Printing OfficeWashington DC 2008(20) Pappas G P Herbert R J Henderson W Koenig J StoverB Barnhart S The respiratory effects of volatile organic compoundsInt J Occup Env Heal 2000 6 (1) 1minus8(21) Sinha P Hobbs P V Yokelson R J Bertschi I T Blake DR Simpson I J Gao S Kirchstetter T W Novakov T Emissions
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528451
of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
decreases (Figure 3A) The OBTF laboratory data (Figure 3B)show an exponential decrease in BC and BrC emission factorswith a decrease in MCE and also reveal that while the BC andBrC concentrations are low at the start of a burn the MCE isthe highest (Figure 3A)Figure 4AB shows the comparable BC BrC CO2 and CO
concentrations and emission factor data respectively for thefield tests at SC The concentration data show predictably morefluctuation than the OBTF data (Figure 3A) as the former issubject to turbulent mixing while the latter is a well-stirredscenario MCE values from the Summa canister CO and CO2
grab samples were compared to the same-time BC and BrCvalues (Figure 4CD) A linear trend between BC and BrCemission factors with MCE is observed with higher values at
the start of a field burn The higher BC and BrC emissionfactors at higher MCE values suggest that more intense forestburns with higher fuel burn rates such as occur during wildfiresmay result in greater releases of BC and BrC than duringprescribed burning Additional scatter plots are available in SIFigure S4The paired BC to PM25 mass percentages for the field and
OBTF respectively were FL 18 (plusmn66) and 84 (plusmn34)NC 84 (plusmn32) and 77 (plusmn23) and SC 34(plusmn071) and 33 (plusmn12) The BrCPM25 mass fractionsat SC for the field and OBTF were 31 (plusmn20) and 23(plusmn079) respectively These BCPM25 mass percentagesfrom NC and FL are higher than the ECPM25 masspercentages found in the US EPA SPECIATE version 4346
Figure 3 A OBTF samples of continuous (10 s average) ΔCO2 ΔCO black carbon (BC) and brown carbon (BrC) concentration traces versustime and modified combustion efficiency (MCE) B OBTF time- and MCE-resolved BC and BrC emission factors with ΔCO2 and ΔCOconcentrations
Figure 4 Continuous (10 s average) ΔCO2 BC and BrC concentration traces (A) and BC and BrC emission factors with ΔCO2 (B) from arepresentative SC field emission sampling episode Scatter plots of BC and BrC concentrations vs MCE (D) and average BC and BrC emissionfactors vs MCE (C) during summa canister sampling in SC
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528448
Table
3FieldandOBTFVOC
Emission
Factorsin
μgg
Biomassb
NCfi
eld
SCfi
eld
NCO
BTF
SCO
BTF
MCEgt095
MCElt090
MCEgt090
MCE=090
MCElt090
MCEgt095
MCElt090
MCEgt095
MCEgt0
90lt095
MCElt090
compound
average
AD
average
AD
average
AD
average
AD
average
AD
average
AD
MCE
0980
0004
0886
0011
0928
0007
0904
0004
0874
0011
0951
0889
00952
0932
0855
acroleina
627
599
697
170
385
53435
183
585
349
312
1023
154
256
381
332
propene
479
522
538
156
323
47360
80595
41
350
965
197
230
323
307
benzenea
370
369
526
262
245
23276
79441
92284
776
102
225
290
199
13-butadienea
195
222
246
6199
23114
46195
55
121
378
4797
153
108
vinylacetatea
330
455
363
82250
29256
36ND
166
830
75183
323
425
acetonitrile
165
188
172
57115
17106
16177
1054
165
013
3756
83toluenea
271
371
232
107
150
062
148
38277
51123
369
42121
171
153
2-butanone
(MEK)
128
161
124
3972
58
7354
157
4951
234
6752
8299
xylenea
6474
7817
7932
73125
131
1037
126
1557
8499
naphthalene
6468
102
6838
40
3592
6314
44116
2742
4733
styrenea
6467
8437
4042
4097
8226
102
286
2037
5341
α-pinene
6129
101
100
5632
78282
7255
26
2412
3459
40acrylonitrilea
5441
5611
2915
2450
4314
2549
91
1624
18ethylbenzenea
2729
3294
2231
2054
4217
2676
45
1926
22D-limonene
3548
4164
4319
4855
109
8397
6833
4990
114
chloromethanea
3429
4320
94
47
86
014
1133
1454
34
93
1416
124-trimethylbenzene
78
77
1027
14041
94
22
1616
37
1630
54
81
121
135-trimethylbenzene
22
26
28
55
34
028
24
072
40
062
080
33
087
13
19
30
cumenea
22
23
29
59
23
012
23
084
41
092
22
60
0079
21
29
26
methylene
chlorid
e22
34
40
36
024
042
0028
00079
0053
005
ND
0079
032
ND
ND
ND
brom
omethanea
22
23
26
53
15
034
18
012
30
14
ND
15
30
13
23
23
aIncluded
intheEP
Alistof
hazardousairpollutantsbADabsolutedifference
(twosamples)MCE
modified
combustioneffi
ciencyN
Dnot
detectedornotdetected
abovebackground
levelsN
Ceast
coastof
North
CarolinaSC
centralSouthCarolinaOBTF
open
burn
testfacility
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528449
database (source category = forest fires) of 12minus45 (ID4463minus44684) which were derived from laboratory (OBTF)tests while the SC ratios are similar to those in SPECIATE Asimilar ECPM25 percentage 39 was found from prescribedburning conducted in Georgia (USA)8 The higher ratios foundin our work seem to be due to higher BC rather than ECemission factors levels given the similar PM25 emission factorsdiscussed above This difference could be due to the differentsampling methodslight-scattering (BC) in this study versusthermaloptical transmission (EC) in Hays et al4 Thesedifferences suggest the need for a comparative investigation ofparallel BC and EC measurements from combustion sourcesVOC Ten field and six OBTF summa canister samples were
taken for VOC determination for the NC and SC campaigns(canister samples at FL could not be taken due to weightrestrictions on the aerostat) Acrolein benzene vinyl acetate(on the US EPArsquos hazardous air pollutant list) and propenehad the highest emission factors (425minus380 ugg biomass) of allVOCs analyzed (Table 3) The sixteen VOC samples weredivided according to MCE resulting in 1minus2 samples in eachMCE category (Table 3) The SC field results had no sampleswith MCE gt095 likely due more to the limitations of ground-only sampling than distinctions in the combustion character-istics of this unmanaged site No apparent differences wereobserved between field and OBTF samples for the differentMCE categories although more replicates would be needed fora robust statistical analysis A trend in decreased VOC emissionfactors with increased MCE was found when all of the collectedsamples were correlated (see SI Figure S5 for four VOCs) Theaverage field emission factor for acrolein was 350 μgg biomasswhich was in the same range as that for open burning ofmunicipal waste 310 μgg biomass47 and prescribed burning inSC 323minus472 μgg biomass48 but lower than that found fromtropical forest fires 960 μgg biomass22 The 13-butadiene hadan average emission factor from both field and OBTF of 310 plusmn182 μgg biomass higher than reported from previousprescribed and wild forest burns in the US58 and Mexico49
(67minus100 μgg biomass) and from Mexican crop residue fires(114 μgg biomass43) yet similar to open burning of municipalwaste (300 μgg biomass47) and prescribed burning of SCforest (110minus240 μgkg biomass48) Some other individualVOCs such as benzene and α-pinene were in the same rangeas emission factors from prescribed forest burning in GeorgiaUS8 All VOCs analyzed are shown in SI Tables S8minusS9PCDDPCDF Emissions The average PCDDPCDF
emission factors from the three different biomass sources andboth field (N = 5) and OBTF (N = 7) testing ranged from 006to 46 ng TEQkg biomass (ND = 0 Table 2 and SI TablesS2minusS4) Emissions exceeded the level anticipated fromvolatilization of PCDDPCDF in the raw biomass (Figure 5)which indicates that formation occurs during combustion ratherthan due to evaporation from the green biomassThese emission factors are on the lower range of similar
OBTF and field studies with US forest biomass at 040minus25 ngTEQkg biomass25minus27 (the lowest emission factor 006 ngTEQkg biomass was obtained from an OBTF sample burningNC biomass with only 6 of 17 TEF congeners detected) Therange of emission factors derived herein overlap those ofresidential wood heating appliances such as wood heaters (039ng TEQkg)50 wood stoves (025 ng TEQkg)51 andfireplaces (088 ng TEQkg)51
To discern potential emission factor differences betweenaerial- and ground-based field samples more simultaneous
aerial- and ground-based sampling is necessary The fieldsamples were of limited number and for the aerial samplesconsisted of one single composite (FL) sample from twodifferent burn days with 14 of 17 TEF congeners detected andtwo replicates (NC) with only 4 and 6 of 17 TEF congenersdetected Further none of the aerial and ground samples weretaken from the same fireThe PCDDPCDF emission factors showed similar levels
between aerial measurements in the field and OBTF samplesfor each of the biomass sources (FL and NC) except for theSC ground-based field and OBTF measurements as shown inFigure 5 The emission factors from the three SC ground fieldsamples showed an increase of up to seven times from the firstto last sample (068 22 and 46 ng TEQkg biomass)reflecting the qualitative observations of increasing smokethickness throughout the campaign (Table 3) In addition thetotal PCDD to PCDF and PCDD TEQ to PCDF TEQ massratios in these samples increased with increased emission factorlevels (SI Tables S4 and S7) A higher emission factor and agreater PCDD TEQ to PCDF TEQ ratio during smolderingversus flaming stages was found in an earlier study by Gullett etal26 burning standing trees in EPArsquos OBTF Thus the twohigher emission factors derived from the SC field study (22TEQkg biomass and 46 ng TEQkg biomass) may be due tosampling a larger portion of the smoldering stage rather thanthe flaming stage The SC OBTF emission levels (average 032ng TEQkg biomass) and PCDDPCDF ratios (12) are alsosimilar to the initial SC ground-based field sample (068 ngTEQkg biomass) which suggests the difficulty of collecting arepresentative PCDDPCDF sample from ground- rather thanaerial-based samplingThe slight emission level difference between FL and SC
biomass from the OBTF could be due to chlorine content inthe fuel 645 ppm and 111 ppm respectively (Table 2 andFigure 5) which is in agreement with a OBTF biomass studyshowing that increased chlorine content in the fuel increasesthe PCDDPCDF emissions39 The PCDDPCDF ratio wasalso higher in the FL OBTF samples (57 plusmn 17) than the SCbiomass samples (12 plusmn 02) which is in agreement with alaboratory study showing that an increased chlorine content inthe fuel enhances the formation of PCDDs over PCDFs52
More definitive conclusions regarding the effect of biomass
Figure 5 PCDDPCDF emission factors from three differentlocations on the eastern part of the USA northwestern Florida(FL) the North Carolina east coast (NC) and Central South Carolina(SC) ND not detectable congeners LOD limit of detection
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528450
chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
REFERENCES(1) US EPA 1970minus2012 Average annual emissions all criteriapollutants httpwwwepagovttnchie1trends (accessed October17 2012)(2) Hosseini S Urbanski S P Dixit P Qi L Burling IYokelson R Shrivastava M Jung H Weise D R Miller WCocker D Laboratory characterization of PM emissions fromcombustion of wildland biomass fuels J Geophys Res 2013DOI101002jgrd50481(3) McMeeking G R Kreidenweis S M Baker S Carrico C MChow J C Collett J L Hao W M Holden A S Kirchstetter T
W Malm W C Moosmuller H Sullivan A P Wold C EEmissions of trace gases and aerosols during the open combustion ofbiomass in the laboratory J Geophys Res 2009 114(4) Hays M D Geron C D Linna K J Smith N D Schauer JJ Speciation of gas-phase and fine particle emissions from burning offoliar fuels Environ Sci Technol 2002 36 (11) 2281minus2295(5) Burling I R Yokelson R J Akagi S K Urbanski S P WoldC E Griffith D W T Johnson T J Reardon J Weise D RAirborne and ground-based measurements of the trace gases andparticles emitted by prescribed fires in the United States Atmos ChemPhys 2011 11 (23) 12197minus12216(6) Urbanski S P Hao W M Baker S Chemical composition ofwildland fire emissions In Developments in Environmental ScienceBytnerowicz A Arbaugh M Riebau A Andersen C Eds ElsevierNew York 2009 Vol 8 pp 79minus107(7) Geron C Hays M Air emissions from organic soil burning onthe coastal plain of North Carolina Atmos Environ 2013 64 192minus199(8) Lee S Baumann K Schauer J J Sheesley R J Naeher L PMeinardi S Blake D R Edgerton E S Russell A G Clements MGaseous and particulate emissions from prescribed burning in GeorgiaEnviron Sci Technol 2005 39 (23) 9049minus9056(9) Ramanathan V Carmichael G Global and regional climatechanges due to black carbon Nat Geosci 2008 1 (4) 221minus227(10) Andreae M O Gelencser A Black carbon or brown carbonThe nature of light-absorbing carbonaceous aerosols Atmos ChemPhys 2006 6 3131minus3148(11) Alexander D T L Crozier P A Anderson J R Browncarbon spheres in East Asian outflow and their optical propertiesScience 2008 321 (5890) 833minus836(12) Kirchstetter T W Novakov T Hobbs P V Evidence that thespectral dependence of light absorption by aerosols is affected byorganic carbon J Geophys Res 2004 109 (D21)(13) Kondo Y Matsui H Moteki N Sahu L Takegawa NKajino M Zhao Y Cubison M J Jimenez J L Vay S Diskin GS Anderson B Wisthaler A Mikoviny T Fuelberg H E BlakeD R Huey G Weinheimer A J Knapp D J Brune W HEmissions of black carbon organic and inorganic aerosols frombiomass burning in North America and Asia in 2008 J Geophys Res2011 116(14) Akagi S K Yokelson R J Wiedinmyer C Alvarado M JReid J S Karl T Crounse J D Wennberg P O Emission factorsfor open and domestic biomass burning for use in atmospheric modelsAtmos Chem Phys 2011 11 (9) 4039minus4072(15) Andreae M O Merlet P Emission of trace gases and aerosolsfrom biomass burning Global Biogeochem Cyc 2001 15 (4) 955minus966(16) Ferek R J Reid J S Hobbs P V Blake D R Liousse CEmission factors of hydrocarbons halocarbons trace gases andparticles from biomass burning in Brazil J Geophys Res 1998 103(D24) 32107minus32118(17) Andreae M O Andreae T W Annegarn H Beer JCachier H le Canut P Elbert W Maenhaut W Salma IWienhold F G Zenker T Airborne studies of aerosol emissionsfrom savanna fires in southern Africa 2 Aerosol chemicalcomposition J Geophys Res 1998 103 (D24) 32119minus32128(18) Alves C Vicente A Nunes T Goncalves C Fernandes AP Mirante F Tarelho L Sanchez de la Campa A M Querol XCaseiro A Monteiro C Evtyugina M Pio C Summer 2009wildfires in Portugal Emission of trace gases and aerosol compositionAtmos Environ 2011 45 (3) 641minus649(19) US EPA Hazardous Air Pollution List Clean Air Act Title 42The Public Health and Welfare US Government Printing OfficeWashington DC 2008(20) Pappas G P Herbert R J Henderson W Koenig J StoverB Barnhart S The respiratory effects of volatile organic compoundsInt J Occup Env Heal 2000 6 (1) 1minus8(21) Sinha P Hobbs P V Yokelson R J Bertschi I T Blake DR Simpson I J Gao S Kirchstetter T W Novakov T Emissions
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528451
of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
Table
3FieldandOBTFVOC
Emission
Factorsin
μgg
Biomassb
NCfi
eld
SCfi
eld
NCO
BTF
SCO
BTF
MCEgt095
MCElt090
MCEgt090
MCE=090
MCElt090
MCEgt095
MCElt090
MCEgt095
MCEgt0
90lt095
MCElt090
compound
average
AD
average
AD
average
AD
average
AD
average
AD
average
AD
MCE
0980
0004
0886
0011
0928
0007
0904
0004
0874
0011
0951
0889
00952
0932
0855
acroleina
627
599
697
170
385
53435
183
585
349
312
1023
154
256
381
332
propene
479
522
538
156
323
47360
80595
41
350
965
197
230
323
307
benzenea
370
369
526
262
245
23276
79441
92284
776
102
225
290
199
13-butadienea
195
222
246
6199
23114
46195
55
121
378
4797
153
108
vinylacetatea
330
455
363
82250
29256
36ND
166
830
75183
323
425
acetonitrile
165
188
172
57115
17106
16177
1054
165
013
3756
83toluenea
271
371
232
107
150
062
148
38277
51123
369
42121
171
153
2-butanone
(MEK)
128
161
124
3972
58
7354
157
4951
234
6752
8299
xylenea
6474
7817
7932
73125
131
1037
126
1557
8499
naphthalene
6468
102
6838
40
3592
6314
44116
2742
4733
styrenea
6467
8437
4042
4097
8226
102
286
2037
5341
α-pinene
6129
101
100
5632
78282
7255
26
2412
3459
40acrylonitrilea
5441
5611
2915
2450
4314
2549
91
1624
18ethylbenzenea
2729
3294
2231
2054
4217
2676
45
1926
22D-limonene
3548
4164
4319
4855
109
8397
6833
4990
114
chloromethanea
3429
4320
94
47
86
014
1133
1454
34
93
1416
124-trimethylbenzene
78
77
1027
14041
94
22
1616
37
1630
54
81
121
135-trimethylbenzene
22
26
28
55
34
028
24
072
40
062
080
33
087
13
19
30
cumenea
22
23
29
59
23
012
23
084
41
092
22
60
0079
21
29
26
methylene
chlorid
e22
34
40
36
024
042
0028
00079
0053
005
ND
0079
032
ND
ND
ND
brom
omethanea
22
23
26
53
15
034
18
012
30
14
ND
15
30
13
23
23
aIncluded
intheEP
Alistof
hazardousairpollutantsbADabsolutedifference
(twosamples)MCE
modified
combustioneffi
ciencyN
Dnot
detectedornotdetected
abovebackground
levelsN
Ceast
coastof
North
CarolinaSC
centralSouthCarolinaOBTF
open
burn
testfacility
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528449
database (source category = forest fires) of 12minus45 (ID4463minus44684) which were derived from laboratory (OBTF)tests while the SC ratios are similar to those in SPECIATE Asimilar ECPM25 percentage 39 was found from prescribedburning conducted in Georgia (USA)8 The higher ratios foundin our work seem to be due to higher BC rather than ECemission factors levels given the similar PM25 emission factorsdiscussed above This difference could be due to the differentsampling methodslight-scattering (BC) in this study versusthermaloptical transmission (EC) in Hays et al4 Thesedifferences suggest the need for a comparative investigation ofparallel BC and EC measurements from combustion sourcesVOC Ten field and six OBTF summa canister samples were
taken for VOC determination for the NC and SC campaigns(canister samples at FL could not be taken due to weightrestrictions on the aerostat) Acrolein benzene vinyl acetate(on the US EPArsquos hazardous air pollutant list) and propenehad the highest emission factors (425minus380 ugg biomass) of allVOCs analyzed (Table 3) The sixteen VOC samples weredivided according to MCE resulting in 1minus2 samples in eachMCE category (Table 3) The SC field results had no sampleswith MCE gt095 likely due more to the limitations of ground-only sampling than distinctions in the combustion character-istics of this unmanaged site No apparent differences wereobserved between field and OBTF samples for the differentMCE categories although more replicates would be needed fora robust statistical analysis A trend in decreased VOC emissionfactors with increased MCE was found when all of the collectedsamples were correlated (see SI Figure S5 for four VOCs) Theaverage field emission factor for acrolein was 350 μgg biomasswhich was in the same range as that for open burning ofmunicipal waste 310 μgg biomass47 and prescribed burning inSC 323minus472 μgg biomass48 but lower than that found fromtropical forest fires 960 μgg biomass22 The 13-butadiene hadan average emission factor from both field and OBTF of 310 plusmn182 μgg biomass higher than reported from previousprescribed and wild forest burns in the US58 and Mexico49
(67minus100 μgg biomass) and from Mexican crop residue fires(114 μgg biomass43) yet similar to open burning of municipalwaste (300 μgg biomass47) and prescribed burning of SCforest (110minus240 μgkg biomass48) Some other individualVOCs such as benzene and α-pinene were in the same rangeas emission factors from prescribed forest burning in GeorgiaUS8 All VOCs analyzed are shown in SI Tables S8minusS9PCDDPCDF Emissions The average PCDDPCDF
emission factors from the three different biomass sources andboth field (N = 5) and OBTF (N = 7) testing ranged from 006to 46 ng TEQkg biomass (ND = 0 Table 2 and SI TablesS2minusS4) Emissions exceeded the level anticipated fromvolatilization of PCDDPCDF in the raw biomass (Figure 5)which indicates that formation occurs during combustion ratherthan due to evaporation from the green biomassThese emission factors are on the lower range of similar
OBTF and field studies with US forest biomass at 040minus25 ngTEQkg biomass25minus27 (the lowest emission factor 006 ngTEQkg biomass was obtained from an OBTF sample burningNC biomass with only 6 of 17 TEF congeners detected) Therange of emission factors derived herein overlap those ofresidential wood heating appliances such as wood heaters (039ng TEQkg)50 wood stoves (025 ng TEQkg)51 andfireplaces (088 ng TEQkg)51
To discern potential emission factor differences betweenaerial- and ground-based field samples more simultaneous
aerial- and ground-based sampling is necessary The fieldsamples were of limited number and for the aerial samplesconsisted of one single composite (FL) sample from twodifferent burn days with 14 of 17 TEF congeners detected andtwo replicates (NC) with only 4 and 6 of 17 TEF congenersdetected Further none of the aerial and ground samples weretaken from the same fireThe PCDDPCDF emission factors showed similar levels
between aerial measurements in the field and OBTF samplesfor each of the biomass sources (FL and NC) except for theSC ground-based field and OBTF measurements as shown inFigure 5 The emission factors from the three SC ground fieldsamples showed an increase of up to seven times from the firstto last sample (068 22 and 46 ng TEQkg biomass)reflecting the qualitative observations of increasing smokethickness throughout the campaign (Table 3) In addition thetotal PCDD to PCDF and PCDD TEQ to PCDF TEQ massratios in these samples increased with increased emission factorlevels (SI Tables S4 and S7) A higher emission factor and agreater PCDD TEQ to PCDF TEQ ratio during smolderingversus flaming stages was found in an earlier study by Gullett etal26 burning standing trees in EPArsquos OBTF Thus the twohigher emission factors derived from the SC field study (22TEQkg biomass and 46 ng TEQkg biomass) may be due tosampling a larger portion of the smoldering stage rather thanthe flaming stage The SC OBTF emission levels (average 032ng TEQkg biomass) and PCDDPCDF ratios (12) are alsosimilar to the initial SC ground-based field sample (068 ngTEQkg biomass) which suggests the difficulty of collecting arepresentative PCDDPCDF sample from ground- rather thanaerial-based samplingThe slight emission level difference between FL and SC
biomass from the OBTF could be due to chlorine content inthe fuel 645 ppm and 111 ppm respectively (Table 2 andFigure 5) which is in agreement with a OBTF biomass studyshowing that increased chlorine content in the fuel increasesthe PCDDPCDF emissions39 The PCDDPCDF ratio wasalso higher in the FL OBTF samples (57 plusmn 17) than the SCbiomass samples (12 plusmn 02) which is in agreement with alaboratory study showing that an increased chlorine content inthe fuel enhances the formation of PCDDs over PCDFs52
More definitive conclusions regarding the effect of biomass
Figure 5 PCDDPCDF emission factors from three differentlocations on the eastern part of the USA northwestern Florida(FL) the North Carolina east coast (NC) and Central South Carolina(SC) ND not detectable congeners LOD limit of detection
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528450
chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
REFERENCES(1) US EPA 1970minus2012 Average annual emissions all criteriapollutants httpwwwepagovttnchie1trends (accessed October17 2012)(2) Hosseini S Urbanski S P Dixit P Qi L Burling IYokelson R Shrivastava M Jung H Weise D R Miller WCocker D Laboratory characterization of PM emissions fromcombustion of wildland biomass fuels J Geophys Res 2013DOI101002jgrd50481(3) McMeeking G R Kreidenweis S M Baker S Carrico C MChow J C Collett J L Hao W M Holden A S Kirchstetter T
W Malm W C Moosmuller H Sullivan A P Wold C EEmissions of trace gases and aerosols during the open combustion ofbiomass in the laboratory J Geophys Res 2009 114(4) Hays M D Geron C D Linna K J Smith N D Schauer JJ Speciation of gas-phase and fine particle emissions from burning offoliar fuels Environ Sci Technol 2002 36 (11) 2281minus2295(5) Burling I R Yokelson R J Akagi S K Urbanski S P WoldC E Griffith D W T Johnson T J Reardon J Weise D RAirborne and ground-based measurements of the trace gases andparticles emitted by prescribed fires in the United States Atmos ChemPhys 2011 11 (23) 12197minus12216(6) Urbanski S P Hao W M Baker S Chemical composition ofwildland fire emissions In Developments in Environmental ScienceBytnerowicz A Arbaugh M Riebau A Andersen C Eds ElsevierNew York 2009 Vol 8 pp 79minus107(7) Geron C Hays M Air emissions from organic soil burning onthe coastal plain of North Carolina Atmos Environ 2013 64 192minus199(8) Lee S Baumann K Schauer J J Sheesley R J Naeher L PMeinardi S Blake D R Edgerton E S Russell A G Clements MGaseous and particulate emissions from prescribed burning in GeorgiaEnviron Sci Technol 2005 39 (23) 9049minus9056(9) Ramanathan V Carmichael G Global and regional climatechanges due to black carbon Nat Geosci 2008 1 (4) 221minus227(10) Andreae M O Gelencser A Black carbon or brown carbonThe nature of light-absorbing carbonaceous aerosols Atmos ChemPhys 2006 6 3131minus3148(11) Alexander D T L Crozier P A Anderson J R Browncarbon spheres in East Asian outflow and their optical propertiesScience 2008 321 (5890) 833minus836(12) Kirchstetter T W Novakov T Hobbs P V Evidence that thespectral dependence of light absorption by aerosols is affected byorganic carbon J Geophys Res 2004 109 (D21)(13) Kondo Y Matsui H Moteki N Sahu L Takegawa NKajino M Zhao Y Cubison M J Jimenez J L Vay S Diskin GS Anderson B Wisthaler A Mikoviny T Fuelberg H E BlakeD R Huey G Weinheimer A J Knapp D J Brune W HEmissions of black carbon organic and inorganic aerosols frombiomass burning in North America and Asia in 2008 J Geophys Res2011 116(14) Akagi S K Yokelson R J Wiedinmyer C Alvarado M JReid J S Karl T Crounse J D Wennberg P O Emission factorsfor open and domestic biomass burning for use in atmospheric modelsAtmos Chem Phys 2011 11 (9) 4039minus4072(15) Andreae M O Merlet P Emission of trace gases and aerosolsfrom biomass burning Global Biogeochem Cyc 2001 15 (4) 955minus966(16) Ferek R J Reid J S Hobbs P V Blake D R Liousse CEmission factors of hydrocarbons halocarbons trace gases andparticles from biomass burning in Brazil J Geophys Res 1998 103(D24) 32107minus32118(17) Andreae M O Andreae T W Annegarn H Beer JCachier H le Canut P Elbert W Maenhaut W Salma IWienhold F G Zenker T Airborne studies of aerosol emissionsfrom savanna fires in southern Africa 2 Aerosol chemicalcomposition J Geophys Res 1998 103 (D24) 32119minus32128(18) Alves C Vicente A Nunes T Goncalves C Fernandes AP Mirante F Tarelho L Sanchez de la Campa A M Querol XCaseiro A Monteiro C Evtyugina M Pio C Summer 2009wildfires in Portugal Emission of trace gases and aerosol compositionAtmos Environ 2011 45 (3) 641minus649(19) US EPA Hazardous Air Pollution List Clean Air Act Title 42The Public Health and Welfare US Government Printing OfficeWashington DC 2008(20) Pappas G P Herbert R J Henderson W Koenig J StoverB Barnhart S The respiratory effects of volatile organic compoundsInt J Occup Env Heal 2000 6 (1) 1minus8(21) Sinha P Hobbs P V Yokelson R J Bertschi I T Blake DR Simpson I J Gao S Kirchstetter T W Novakov T Emissions
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528451
of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
database (source category = forest fires) of 12minus45 (ID4463minus44684) which were derived from laboratory (OBTF)tests while the SC ratios are similar to those in SPECIATE Asimilar ECPM25 percentage 39 was found from prescribedburning conducted in Georgia (USA)8 The higher ratios foundin our work seem to be due to higher BC rather than ECemission factors levels given the similar PM25 emission factorsdiscussed above This difference could be due to the differentsampling methodslight-scattering (BC) in this study versusthermaloptical transmission (EC) in Hays et al4 Thesedifferences suggest the need for a comparative investigation ofparallel BC and EC measurements from combustion sourcesVOC Ten field and six OBTF summa canister samples were
taken for VOC determination for the NC and SC campaigns(canister samples at FL could not be taken due to weightrestrictions on the aerostat) Acrolein benzene vinyl acetate(on the US EPArsquos hazardous air pollutant list) and propenehad the highest emission factors (425minus380 ugg biomass) of allVOCs analyzed (Table 3) The sixteen VOC samples weredivided according to MCE resulting in 1minus2 samples in eachMCE category (Table 3) The SC field results had no sampleswith MCE gt095 likely due more to the limitations of ground-only sampling than distinctions in the combustion character-istics of this unmanaged site No apparent differences wereobserved between field and OBTF samples for the differentMCE categories although more replicates would be needed fora robust statistical analysis A trend in decreased VOC emissionfactors with increased MCE was found when all of the collectedsamples were correlated (see SI Figure S5 for four VOCs) Theaverage field emission factor for acrolein was 350 μgg biomasswhich was in the same range as that for open burning ofmunicipal waste 310 μgg biomass47 and prescribed burning inSC 323minus472 μgg biomass48 but lower than that found fromtropical forest fires 960 μgg biomass22 The 13-butadiene hadan average emission factor from both field and OBTF of 310 plusmn182 μgg biomass higher than reported from previousprescribed and wild forest burns in the US58 and Mexico49
(67minus100 μgg biomass) and from Mexican crop residue fires(114 μgg biomass43) yet similar to open burning of municipalwaste (300 μgg biomass47) and prescribed burning of SCforest (110minus240 μgkg biomass48) Some other individualVOCs such as benzene and α-pinene were in the same rangeas emission factors from prescribed forest burning in GeorgiaUS8 All VOCs analyzed are shown in SI Tables S8minusS9PCDDPCDF Emissions The average PCDDPCDF
emission factors from the three different biomass sources andboth field (N = 5) and OBTF (N = 7) testing ranged from 006to 46 ng TEQkg biomass (ND = 0 Table 2 and SI TablesS2minusS4) Emissions exceeded the level anticipated fromvolatilization of PCDDPCDF in the raw biomass (Figure 5)which indicates that formation occurs during combustion ratherthan due to evaporation from the green biomassThese emission factors are on the lower range of similar
OBTF and field studies with US forest biomass at 040minus25 ngTEQkg biomass25minus27 (the lowest emission factor 006 ngTEQkg biomass was obtained from an OBTF sample burningNC biomass with only 6 of 17 TEF congeners detected) Therange of emission factors derived herein overlap those ofresidential wood heating appliances such as wood heaters (039ng TEQkg)50 wood stoves (025 ng TEQkg)51 andfireplaces (088 ng TEQkg)51
To discern potential emission factor differences betweenaerial- and ground-based field samples more simultaneous
aerial- and ground-based sampling is necessary The fieldsamples were of limited number and for the aerial samplesconsisted of one single composite (FL) sample from twodifferent burn days with 14 of 17 TEF congeners detected andtwo replicates (NC) with only 4 and 6 of 17 TEF congenersdetected Further none of the aerial and ground samples weretaken from the same fireThe PCDDPCDF emission factors showed similar levels
between aerial measurements in the field and OBTF samplesfor each of the biomass sources (FL and NC) except for theSC ground-based field and OBTF measurements as shown inFigure 5 The emission factors from the three SC ground fieldsamples showed an increase of up to seven times from the firstto last sample (068 22 and 46 ng TEQkg biomass)reflecting the qualitative observations of increasing smokethickness throughout the campaign (Table 3) In addition thetotal PCDD to PCDF and PCDD TEQ to PCDF TEQ massratios in these samples increased with increased emission factorlevels (SI Tables S4 and S7) A higher emission factor and agreater PCDD TEQ to PCDF TEQ ratio during smolderingversus flaming stages was found in an earlier study by Gullett etal26 burning standing trees in EPArsquos OBTF Thus the twohigher emission factors derived from the SC field study (22TEQkg biomass and 46 ng TEQkg biomass) may be due tosampling a larger portion of the smoldering stage rather thanthe flaming stage The SC OBTF emission levels (average 032ng TEQkg biomass) and PCDDPCDF ratios (12) are alsosimilar to the initial SC ground-based field sample (068 ngTEQkg biomass) which suggests the difficulty of collecting arepresentative PCDDPCDF sample from ground- rather thanaerial-based samplingThe slight emission level difference between FL and SC
biomass from the OBTF could be due to chlorine content inthe fuel 645 ppm and 111 ppm respectively (Table 2 andFigure 5) which is in agreement with a OBTF biomass studyshowing that increased chlorine content in the fuel increasesthe PCDDPCDF emissions39 The PCDDPCDF ratio wasalso higher in the FL OBTF samples (57 plusmn 17) than the SCbiomass samples (12 plusmn 02) which is in agreement with alaboratory study showing that an increased chlorine content inthe fuel enhances the formation of PCDDs over PCDFs52
More definitive conclusions regarding the effect of biomass
Figure 5 PCDDPCDF emission factors from three differentlocations on the eastern part of the USA northwestern Florida(FL) the North Carolina east coast (NC) and Central South Carolina(SC) ND not detectable congeners LOD limit of detection
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528450
chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
REFERENCES(1) US EPA 1970minus2012 Average annual emissions all criteriapollutants httpwwwepagovttnchie1trends (accessed October17 2012)(2) Hosseini S Urbanski S P Dixit P Qi L Burling IYokelson R Shrivastava M Jung H Weise D R Miller WCocker D Laboratory characterization of PM emissions fromcombustion of wildland biomass fuels J Geophys Res 2013DOI101002jgrd50481(3) McMeeking G R Kreidenweis S M Baker S Carrico C MChow J C Collett J L Hao W M Holden A S Kirchstetter T
W Malm W C Moosmuller H Sullivan A P Wold C EEmissions of trace gases and aerosols during the open combustion ofbiomass in the laboratory J Geophys Res 2009 114(4) Hays M D Geron C D Linna K J Smith N D Schauer JJ Speciation of gas-phase and fine particle emissions from burning offoliar fuels Environ Sci Technol 2002 36 (11) 2281minus2295(5) Burling I R Yokelson R J Akagi S K Urbanski S P WoldC E Griffith D W T Johnson T J Reardon J Weise D RAirborne and ground-based measurements of the trace gases andparticles emitted by prescribed fires in the United States Atmos ChemPhys 2011 11 (23) 12197minus12216(6) Urbanski S P Hao W M Baker S Chemical composition ofwildland fire emissions In Developments in Environmental ScienceBytnerowicz A Arbaugh M Riebau A Andersen C Eds ElsevierNew York 2009 Vol 8 pp 79minus107(7) Geron C Hays M Air emissions from organic soil burning onthe coastal plain of North Carolina Atmos Environ 2013 64 192minus199(8) Lee S Baumann K Schauer J J Sheesley R J Naeher L PMeinardi S Blake D R Edgerton E S Russell A G Clements MGaseous and particulate emissions from prescribed burning in GeorgiaEnviron Sci Technol 2005 39 (23) 9049minus9056(9) Ramanathan V Carmichael G Global and regional climatechanges due to black carbon Nat Geosci 2008 1 (4) 221minus227(10) Andreae M O Gelencser A Black carbon or brown carbonThe nature of light-absorbing carbonaceous aerosols Atmos ChemPhys 2006 6 3131minus3148(11) Alexander D T L Crozier P A Anderson J R Browncarbon spheres in East Asian outflow and their optical propertiesScience 2008 321 (5890) 833minus836(12) Kirchstetter T W Novakov T Hobbs P V Evidence that thespectral dependence of light absorption by aerosols is affected byorganic carbon J Geophys Res 2004 109 (D21)(13) Kondo Y Matsui H Moteki N Sahu L Takegawa NKajino M Zhao Y Cubison M J Jimenez J L Vay S Diskin GS Anderson B Wisthaler A Mikoviny T Fuelberg H E BlakeD R Huey G Weinheimer A J Knapp D J Brune W HEmissions of black carbon organic and inorganic aerosols frombiomass burning in North America and Asia in 2008 J Geophys Res2011 116(14) Akagi S K Yokelson R J Wiedinmyer C Alvarado M JReid J S Karl T Crounse J D Wennberg P O Emission factorsfor open and domestic biomass burning for use in atmospheric modelsAtmos Chem Phys 2011 11 (9) 4039minus4072(15) Andreae M O Merlet P Emission of trace gases and aerosolsfrom biomass burning Global Biogeochem Cyc 2001 15 (4) 955minus966(16) Ferek R J Reid J S Hobbs P V Blake D R Liousse CEmission factors of hydrocarbons halocarbons trace gases andparticles from biomass burning in Brazil J Geophys Res 1998 103(D24) 32107minus32118(17) Andreae M O Andreae T W Annegarn H Beer JCachier H le Canut P Elbert W Maenhaut W Salma IWienhold F G Zenker T Airborne studies of aerosol emissionsfrom savanna fires in southern Africa 2 Aerosol chemicalcomposition J Geophys Res 1998 103 (D24) 32119minus32128(18) Alves C Vicente A Nunes T Goncalves C Fernandes AP Mirante F Tarelho L Sanchez de la Campa A M Querol XCaseiro A Monteiro C Evtyugina M Pio C Summer 2009wildfires in Portugal Emission of trace gases and aerosol compositionAtmos Environ 2011 45 (3) 641minus649(19) US EPA Hazardous Air Pollution List Clean Air Act Title 42The Public Health and Welfare US Government Printing OfficeWashington DC 2008(20) Pappas G P Herbert R J Henderson W Koenig J StoverB Barnhart S The respiratory effects of volatile organic compoundsInt J Occup Env Heal 2000 6 (1) 1minus8(21) Sinha P Hobbs P V Yokelson R J Bertschi I T Blake DR Simpson I J Gao S Kirchstetter T W Novakov T Emissions
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528451
of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
chlorine content versus combustion quality on PCDDPCDFemission levels and ratios requires further studyOcta-CDD was the most prevalent homologue of the PCDD
homologues in all the collected samples with the exception ofthe OBTF test of the NC biomass that had several nondetectcongeners (SI Tables S5minusS7) The PCDD homologue profilesexhibit higher homologue concentrations with increasingchlorination level similar to previous OBTF results26 fromburning standing pine trees The PCDF homologue profilesfollowed the opposite trend (SI Tables S5minusS7) lowerhomologue concentrations with increasing chlorination levelconsistent with earlier results26 (except for SC day 3 fieldsample which had Hepta-CDF as the most prevalent congener)
ASSOCIATED CONTENTS Supporting InformationAdditional material noted in the text This material is availablefree of charge via the Internet at httppubsacsorg
AUTHOR INFORMATIONCorresponding AuthorPhone (919) 541minus1534 e-mail gullettbrianepagovPresent AddressdaggerUniversity of Dayton Research InstituteNotesThe authors declare no competing financial interest
ACKNOWLEDGMENTSThis work was funded by the Strategic Environmental Researchand Development Program and the US EPA Special thanksto John Hall (SERDP) Susan Cohen Danny Becker andpersonnel at Marine Corps Base Camp Lejeune (NC) KevinHiers and Brett Williams at Eglin Air Force Base (FL) andJohn Maitland and Thomas Clawson at Fort Jackson (SC) Weare grateful to Roger Ottmar and David Weiss (US ForestService) Karsten Baumann (Atmospheric Research andAnalysis Inc) and Tim Johnson (PNNL) for researchcoordination and helpful assistance Contributing EPA person-nel included Chris Pressley Dennis Tabor Bill Squier BillMitchell and William Stevens (ORISE postdoctoral fellow)Aerostat operations were handled by Rob Gribble (ISSI Inc)with field assistance by Steve Terll (ARCADIS-US Inc) JeffBlair of AethLabs donated use of the AE-52 Special thanks toDahman Touati and Barbara Wyrzykowska (ARCADIS-USInc) for analyses and Tiffany Yelverton and Amara Holder(US EPA) for helpful BCBrC discussions This research wasperformed while JA held a National Research CouncilResearch Associateship Award at the US EPANRMRLThis publication has been subjected to the US EPArsquos peer andadministrative review and has been approved for publication asa US EPA document
REFERENCES(1) US EPA 1970minus2012 Average annual emissions all criteriapollutants httpwwwepagovttnchie1trends (accessed October17 2012)(2) Hosseini S Urbanski S P Dixit P Qi L Burling IYokelson R Shrivastava M Jung H Weise D R Miller WCocker D Laboratory characterization of PM emissions fromcombustion of wildland biomass fuels J Geophys Res 2013DOI101002jgrd50481(3) McMeeking G R Kreidenweis S M Baker S Carrico C MChow J C Collett J L Hao W M Holden A S Kirchstetter T
W Malm W C Moosmuller H Sullivan A P Wold C EEmissions of trace gases and aerosols during the open combustion ofbiomass in the laboratory J Geophys Res 2009 114(4) Hays M D Geron C D Linna K J Smith N D Schauer JJ Speciation of gas-phase and fine particle emissions from burning offoliar fuels Environ Sci Technol 2002 36 (11) 2281minus2295(5) Burling I R Yokelson R J Akagi S K Urbanski S P WoldC E Griffith D W T Johnson T J Reardon J Weise D RAirborne and ground-based measurements of the trace gases andparticles emitted by prescribed fires in the United States Atmos ChemPhys 2011 11 (23) 12197minus12216(6) Urbanski S P Hao W M Baker S Chemical composition ofwildland fire emissions In Developments in Environmental ScienceBytnerowicz A Arbaugh M Riebau A Andersen C Eds ElsevierNew York 2009 Vol 8 pp 79minus107(7) Geron C Hays M Air emissions from organic soil burning onthe coastal plain of North Carolina Atmos Environ 2013 64 192minus199(8) Lee S Baumann K Schauer J J Sheesley R J Naeher L PMeinardi S Blake D R Edgerton E S Russell A G Clements MGaseous and particulate emissions from prescribed burning in GeorgiaEnviron Sci Technol 2005 39 (23) 9049minus9056(9) Ramanathan V Carmichael G Global and regional climatechanges due to black carbon Nat Geosci 2008 1 (4) 221minus227(10) Andreae M O Gelencser A Black carbon or brown carbonThe nature of light-absorbing carbonaceous aerosols Atmos ChemPhys 2006 6 3131minus3148(11) Alexander D T L Crozier P A Anderson J R Browncarbon spheres in East Asian outflow and their optical propertiesScience 2008 321 (5890) 833minus836(12) Kirchstetter T W Novakov T Hobbs P V Evidence that thespectral dependence of light absorption by aerosols is affected byorganic carbon J Geophys Res 2004 109 (D21)(13) Kondo Y Matsui H Moteki N Sahu L Takegawa NKajino M Zhao Y Cubison M J Jimenez J L Vay S Diskin GS Anderson B Wisthaler A Mikoviny T Fuelberg H E BlakeD R Huey G Weinheimer A J Knapp D J Brune W HEmissions of black carbon organic and inorganic aerosols frombiomass burning in North America and Asia in 2008 J Geophys Res2011 116(14) Akagi S K Yokelson R J Wiedinmyer C Alvarado M JReid J S Karl T Crounse J D Wennberg P O Emission factorsfor open and domestic biomass burning for use in atmospheric modelsAtmos Chem Phys 2011 11 (9) 4039minus4072(15) Andreae M O Merlet P Emission of trace gases and aerosolsfrom biomass burning Global Biogeochem Cyc 2001 15 (4) 955minus966(16) Ferek R J Reid J S Hobbs P V Blake D R Liousse CEmission factors of hydrocarbons halocarbons trace gases andparticles from biomass burning in Brazil J Geophys Res 1998 103(D24) 32107minus32118(17) Andreae M O Andreae T W Annegarn H Beer JCachier H le Canut P Elbert W Maenhaut W Salma IWienhold F G Zenker T Airborne studies of aerosol emissionsfrom savanna fires in southern Africa 2 Aerosol chemicalcomposition J Geophys Res 1998 103 (D24) 32119minus32128(18) Alves C Vicente A Nunes T Goncalves C Fernandes AP Mirante F Tarelho L Sanchez de la Campa A M Querol XCaseiro A Monteiro C Evtyugina M Pio C Summer 2009wildfires in Portugal Emission of trace gases and aerosol compositionAtmos Environ 2011 45 (3) 641minus649(19) US EPA Hazardous Air Pollution List Clean Air Act Title 42The Public Health and Welfare US Government Printing OfficeWashington DC 2008(20) Pappas G P Herbert R J Henderson W Koenig J StoverB Barnhart S The respiratory effects of volatile organic compoundsInt J Occup Env Heal 2000 6 (1) 1minus8(21) Sinha P Hobbs P V Yokelson R J Bertschi I T Blake DR Simpson I J Gao S Kirchstetter T W Novakov T Emissions
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dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528451
of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
of trace gases and particles from savanna fires in southern Africa JGeophys Res 2003 108 (D13)(22) Yokelson R J Christian T J Karl T G Guenther A Thetropical forest and fire emissions experiment laboratory firemeasurements and synthesis of campaign data Atmos Chem Phys2008 8 (13) 3509minus3527(23) Yokelson R J Karl T Artaxo P Blake D R Christian T JGriffith D W T Guenther A Hao W M The tropical forest andfire emissions experiment Overview and airborne fire emission factormeasurements Atmos Chem Phys 2007 7 (19) 5175minus5196(24) Fiedler H National PCDDPCDF release inventories underthe Stockholm Convention on persistent organic pollutants Chemo-sphere 2007 67 (9) S96minusS108(25) Gullett B K Touati A PCDDF emissions from forest firesimulations Atmos Environ 2003 37 (6) 803minus813(26) Gullett B Touati A Oudejans L PCDDF and aromaticemissions from simulated forest and grassland fires Atmos Environ2008 42 (34) 7997minus8006(27) Black R R Meyer C P Touati A Gullett B K Fiedler HMueller J F Emissions of PCDD and PCDF from combustion offorest fuels and sugarcane A comparison between field measurementsand simulations in a laboratory burn facility Chemosphere 2011 83(10) 1331minus1338(28) Aurell J Gullett B K Aerostat sampling of PCDDPCDFemissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(29) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure) 1989(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Method TO-13A Determination of polycyclic aromatichydrocarbons (PAHs) in ambient air using gas chromatographymassspectrometry (GCMS) 1999(33) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(34) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(35) US EPA Compendium Method TO-9A Determination ofpolychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(36) US EPA Method 8290A Polychlorinated dibenzo-p-dioxins(PCDDs) and polychlorinated dibenzofurans (PCDFs) by high-resolutiongas chromatographyhigh-resolution mass spectrometry (HRGCHRMS)2007(37) US EPA Method 3540C Soxhlet extraction 1996(38) Van den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(39) Grandesso E Gullett B Touati A Tabor D Effect ofmoisture charge size and chlorine concentration on PCDDFemissions from simulated open burning of forest biomass EnvironSci Technol 2011 45 (9) 3887minus3894(40) Laursen K K Ferek R Hobbs P Rasmussen R A Emissionfactors for particles elemental carbon and trace gases from the Kuwaitoil fires J Geophys Res 1992 97 (D13) 14491minus14497(41) Hagler G S W Yelverton T L B Vedantham R Hansen AD A Turner J R Post-processing method to reduce noise whilepreserving high time resolution in aethalometer real-time black carbondata Aerosol Air Qual Res 2011 11 (5) 539minus546
(42) Alves C A Vicente A Monteiro C Goncalves CEvtyugina M Pio C Emission of trace gases and organic componentsin smoke particles from a wildfire in a mixed-evergreen forest inPortugal Sci Total Environ 2011 409 (8) 1466minus1475(43) Yokelson R J Burling I R Urbanski S P Atlas E LAdachi K Buseck P R Wiedinmyer C Akagi S K Toohey DW Wold C E Trace gas and particle emissions from open biomassburning in Mexico Atmos Chem Phys 2011 11 (14) 6787minus6808(44) Ban-Weiss G A Lunden M M Kirchstetter T W HarleyR A Measurement of black carbon and particle number emissionfactors from individual heavy-duty trucks Environ Sci Technol 200943 (5) 1419minus1424(45) Ban-Weiss G A McLaughlin J P Harley R A Lunden MM Kirchstetter T W Kean A J Strawa A W Stevenson E DKendall G R Long-term changes in emissions of nitrogen oxides andparticulate matter from on-road gasoline and diesel vehicles AtmosEnviron 2008 42 (2) 220minus232(46) US EPA SPECIATE Version 43 httpwwwepagovttnchiefsoftwarespeciateindexhtml (accessed May 2 2013)(47) Aurell J Gullett B K Yamamoto D Emissions from openburning of simulated military waste from forward operating basesEnviron Sci Technol 2012 46 11004minus11012(48) Akagi S K Yokelson R J Burling I R Meinardi SSimpson I Blake D R McMeeking G R Sullivan A Lee TKreidenweis S Urbanski S Reardon J Griffith D W T JohnsonT J Weise D R Measurements of reactive trace gases and variableO-3 formation rates in some South Carolina biomass burning plumesAtmos Chem Phys 2013 13 (3) 1141minus1165(49) Yokelson R J Urbanski S P Atlas E L Toohey D WAlvarado E C Crounse J D Wennberg P O Fisher M E WoldC E Campos T L Adachi K Buseck P R Hao W M Emissionsfrom forest fires near Mexico City Atmos Chem Phys 2007 7 (21)5569minus5584(50) Aurell J Gullett B K Tabor D Touati A Oudejans LSemivolatile and volatile organic compound emissions from wood-fired hydronic heaters Environ Sci Technol 2012 46 (14) 7898minus7904(51) Gullett B K Touati A Hays M D PCDDF PCB HxCBzPAH and PM emission factors for fireplace and woodstovecombustion in the San Francisco Bay region Environ Sci Technol2003 37 (9) 1758minus1765(52) Aurell J Marklund S Effects of varying combustion conditionson PCDDF emissions and formation during MSW incinerationChemosphere 2009 75 (5) 667minus673
Environmental Science amp Technology Article
dxdoiorg101021es402101k | Environ Sci Technol 2013 47 8443minus84528452
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
Emissions from Open Burning of Simulated Military Waste fromForward Operating BasesJohanna Aurelldagger Brian K GullettDagger and Dirk Yamamotosect
daggerNational Research Council Post Doctoral Fellow to the US Environmental Protection AgencyDaggerUS Environmental Protection Agency Office of Research and Development National Risk Management Research LaboratoryResearch Triangle Park North Carolina 27711 United StatessectUS Air Force Institute of Technology 2950 Hobson Way Wright-Patterson Air Force Base Ohio 45433 United States
S Supporting Information
ABSTRACT Emissions from open burning of simulated military waste from forwardoperating bases (FOBs) were extensively characterized as an initial step in assessingpotential inhalation exposure of FOB personnel and future disposal alternativesEmissions from two different burning scenarios so-called ldquoburn pilespitsrdquo and an aircurtain burnerldquoburn boxrdquo were compared using simulated FOB waste from municipaland commercial sources A comprehensive array of emissions was quantified includingCO2 PM25 volatile organic compounds (VOCs) polyaromatic hydrocarbons (PAHs)polychlorinated dibenzodioxins and -furans (PCDDsPCDFs) polybrominateddibenzodioxins and -furans (PBDDsPBDFs) and metals In general smolderingconditions in the burn box and the burn pile led to similar emissions However whenthe burn box underwent periodic waste charging to maintain sustained combustionPM25 VOCs and PAH emissions dropped considerably compared to smolderingconditions and the overall burn pile results The PCDDPCDF and PBDDPBDFemission factors for the burn piles were 50 times higher than those from the burn box likely due to the dominance of smolderingcombustion in the burn piles
INTRODUCTION
Military operations at forward operating bases (FOBs) generatesignificant amounts of solid waste requiring field-expedientmethods to dispose of the waste with minimal risk to personneland the environment The US Department of Defense (DOD)estimated that 36minus45 kg of waste is generated per day per USsoldier deployed at FOBs or about 90 000minus180 000 kg ofwaste per day for an FOB such as at the previously used BaladAir Base Iraq1 A common solution has been the use of openburning on site to reduce the waste volume Typically this hasinvolved open burning in piles rows or holes in the ground(so-called ldquoburn pitsrdquo) While eliminating the risk of traveloutside of the FOB for disposal operations (ie backhauling)personnel near the burn site may be exposed to the emissionsfrom the burning pilespits Concern has been raised that theseemissions contain toxics which may present airborne inhalationhazards and result in an adverse effect on personnel health2 Arecent study indicated that military deployers have increasedrates of reported respiratory symptoms with ldquosignificantassociations with deployment location that were more stronglynoted among persons deployed exclusively to Iraqrdquo and thatldquoinconsistency in risk for new-onset respiratory conditions andcumulative exposure time by service branch strongly suggestsspecific exposures rather than deployment in general asdeterminants of post-deployment respiratory illnessrdquo3 Furtherthe 2008 Enhanced Particulate Matter Surveillance ProgramFinal Report lists burn pit smoke as one of the three primary air
pollutant types4 Also the 2008 health risk screening reportfrom US Army Center for Health Promotion and PreventiveMedicine (now the US Army Institute for Public Health) andAir Force Institute for Operational Health (now the US AirForce School of Aerospace Medicine) includes Defense HealthBoard comments indicating strong interest in multivariatecorrelations between exposures and health effects andrelationships between personnel location and exposure5
More recently the National Academies of Science Institute ofMedicine (IOM) at the request of the Veteranrsquos Admin-istration formed a committee to investigate long-term healtheffects of burn pit emissions exposure Their report concludedthat insufficient exposure data prevented a determination ofwhether long-term health effects are attributable to burn pitsand that additional research to characterize exposures isnecessary1
Emissions of concern from waste burning typically includeparticulate matter (PM) volatile organic compounds (VOCs)polyaromatic hydrocarbons (PAHs) and polychlorinateddibenzodioxins and -furans (PCDDsPCDFs) PM is ofparticular interest due to the high levels from open burningthe predominance of the inhalable size fraction and the ability
Received August 1 2012Revised August 31 2012Accepted September 4 2012Published September 19 2012
Article
pubsacsorgest
copy 2012 American Chemical Society 11004 dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus11012
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
to bear metals and other pollutants with toxic potentialPCDDsPCDFs are considered more of an ingestion risk thanan inhalation risk for the general populace6 but the FOB wasteburns present a short source to-receptor path that may increasethe risk of inhalation exposure Polybrominated dibenzodioxinsand -furans (PBDDsPBDFs) are likely combustion byproductsof common items containing brominated flame retardants andhave been highlighted for concern7 and potential dioxin-liketoxicity89 VOCs include a range of compounds that can causeshort or long-term health effects The majority of thecompounds on the US EPArsquos list of hazardous air pollutants(HAPs) are VOCs10
In recent years the US DOD has relied more heavily onincinerator and similar technologies to improve combustionquality An incinerator consists typically of a two-stage burnerwhile ldquoburn boxesrdquo that are more commonly found at FOB donot have secondary combustion systems to promote pollutantburnout11 A comparison of emissions from open pilepit burnsversus those from either burn boxes or incinerators has to ourknowledge not been undertakenHistorically emissions from open burning of waste have been
minimally characterized due to a lack of relevance to modernsocieties and the hazard imposed to safely and representativelysample the emissions Recent research has sampled emissionplumes from various open burns developing methods todescribe emissions and determine emission factors for some ofthe greatest toxics of concern such as PCDDsPCDFs12minus18
The differences in waste types and the single analyte focus ofthese studies however limit their relevance to our studyThis work comprehensively characterizes FOB burn pitpile
and burn box emissions using a simulated FOB waste andunique methods of open area emission sampling Emissionfactors are calculated as mass of pollutant per unit mass ofburned waste as a first step toward characterizing potentialinhalation risk Results from the burn pitpile and burn box arecompared and where possible separated into flaming andsmoldering phases to understand best operational practices tominimize emissions
EXPERIMENTAL METHODSix emission tests were conducted over six days with burn pilesand a burn box using two types of waste The tests wereperformed at the US Armyrsquos Tooele Army Depot (TEAD)Test Range (Utah)
Waste FOB waste was simulated using both municipal anddepot waste separately FOB waste composition is highlyvariable but often includes greater percentages of food wasteand packing material than civilian sources19 Howevercomparison of FOB waste surveys19 with published USmunicipal waste surveys20 did not show outstanding composi-tional differences resulting in use of local waste sources as anecessary and reasonable compromise to use of actual FOBwaste On-site characterizations of the waste were conducted atthe TEAD confirming the appropriateness of the wastecomposition as a simulant for FOB waste (Supporting
Table 1 Experimental Matrix and Sampling Times
number of samplessamplingperiod (min)
burn no waste waste weight (kg) sampling platform sampling starta (min) SVOC VOCb PM25c
burn box batch- 1 municipal 3 times 290 crane 10 143 1 145feed 1 4 times 290 crane 80 1103 1 132
1 5 times 290 crane 170 184 1 1911 4 times 290 crane 300 181 1 181
burn box single-charge 2 municipal 1 times 290 crane 60 155 2 216 9aDuration after waste ignition when the sampling platform was moved into the plume bThe sampling period was the duration of the Summa canpressure equilibration ranging from 1 to 15 min cPM25 by filter samples
Figure 1 Sampling at burn pile (A) and air curtain burnerburn box (B) using a battery operated instrument package (C) termed the ldquoFlyerrdquo
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211005
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
Information (SI) Table S1) The municipal waste containedapproximately 10 less cardboardpaper and 10 more fooddiapers than the depot waste Near-daily deliveries of municipalwaste with all hazardous materials removed were combustedwithin two days two deliveries of the depot waste over the testperiod were similarly promptly combusted but separately fromthe municipal wasteBurn Pile Emissions from four different waste burn piles
were collected over four days Each burn pile consisted of aboutapproximately 50 m3 (25 times 25 times 08 m) of waste with a weightof approximately 6500 kg (Table 1) based on an assumed bulkdensity of 130 kgm321 The waste was piled into rows directlyon the sandy ground (Figure 1) Approximately 8 L of dieselfuel was applied with a pump sprayer to initiate combustion ofeach burn pile mimicking historical procedures at FOBs About5 min after ignition sampling was conducted for an average of 2h (Table 1) at which point active flaming combustion had longsince ceasedBurn Box The burn box was a McPherson unit (model
M10E) with inside dimensions of 30 times 27 times 30 m and astated maximum burn rate of 1200 kgh The burn box wasequipped with a diesel driven fan that blows high speed airthrough a plenum and nozzle down to the topsurface of theburning waste creating temperatures between 980 and 1370 degCThe burn box was ignited following the manufacturerrsquosrecommended procedures that is limited diesel fuel was usedas an igniter on a charge of wood Emissions from two burndays were collected while running the burn box in a wastebatch-feed mode to promote sustained flaming combustion anda single-charge mode to simulate conditions during discontin-uous waste charging In the batch-feed mode the burn box wasstarted with one charge of wood (only) lasting for 30 min thenwaste (approximately 290 kg per charge) was added every 30minus45 min for 35 h and for every 10minus20 min for the last 4 h of the75 h run Sampling commenced within 10 min after wastecharging The single-charge mode run followed the start upprocedures from the first run but was only charged with wasteonce for the entire 2 h run Emission sampling started 1 h afterthe waste charge in order to only characterize smolderingemissions Table 1 shows the experimental matrixSampling Emissions were representatively characterized by
sampling the full extent of the burns from flaming modethrough smoldering mode Emission sampling from burn pilesand the burn box was performed using two battery-operatedinstrument packages called the ldquoFlyersrdquo (Figure 1) One Flyerwas lofted by a 49 m times 39 m diameter aerostat and the otherby a 32 m crane Each method was employed to ensure arepresentative sample of the emissions with minimal risk topersonnel and equipment The burn box was sampled only withthe crane collecting sequential samples during the burn withthe Flyer positioned in the combustion gas flow above the opentop of the burn box Parallel sampling of the burn piles wasaccomplished with simultaneous use of both the aerostat- andcrane-lofted Flyers (Figure 1) The aerostat lofted samplingmethod and Flyer has been described earlier by Aurell et al22
Briefly the aerostat based sampling method consists of ahelium-filled aerostat which is tethered to one or two groundbased vehicles each equipped with an electrically powered andremotely controlled winch The Flyer included an on-boardcomputer running a data acquisition (DAQ) program and awireless transmitter allowing the sampling to be controlledfrom the ground The DAQ program includes ldquotriggersrdquo whichenable emission samplers to be turned on and off at different
carbon dioxide (CO2) levels The Flyer includes a blower forsampling of semivolatile compounds and 48 V rechargeable Li-ion batteries In this study the Flyer was equipped for samplingof CO2 with a continuous gas analyzer (CGA) volatile organiccompounds (VOCs) sampler using a Summa canister (6 L) viaUS EPA Method TO-1523 SVOCs (PCDDPCDF PBDDPBDF and PAH) sampler using a polyurethane foam (PUF)XAD-2PUF sorbent PM25 filter sampler and a PM25continuous real-time sampler (DustTrak 8520) The PM25was sampled using an impactor with 47 mm tared Teflonfilters (2 μm pore size) connected to a pump (Leland LegacySKC) with a constant airflow of 10 Lmin PM25 by filter wassampled as long as the back pressure compensating pump wasable to provide constant air flow and PM25 by real-time wasmeasured during the entire sampling period The Summacanisters were equipped with an electronic solenoid valve with a05 μm metal filter enabling sampling for approximately 1minus15min over a 7minus30 min sampling period The SVOC samplingwas performed based on US EPA Method TO-13A24 using asampler consisting of a cartridge and filter holder mounted on aWindjammer brushless direct low current blower (AMTEKInc) The sampling rate was approximately 065 m3min andwas measured by differential pressure across a calibratedVenturi mounted on the outlet of the blower In addition theFlyer also had a global positioning system (GPS) on board forposition altitude and atmospheric pressure and a T-typethermocouple (Super MCJ Omega Engineering Inc) forambient temperature mounted at the sampler inlets All sensordata and flow rates were logged continuously to the on-boardcomputer All sampling equipment was time synchronizedbefore each test day The sampling periods were approximately2 and 1minus15 h long for burn piles and burn box respectivelySampling was continued until the pressure drop on the SVOCfan became excessive or until sufficient carbon (as CO2) wascollected to minimize the chance of nondetects on the targetanalytes The plume collection temperature during samplingwas kept below 50 degC for the safety of the electronics on theFlyers
Analytical Methods The PCDDsPCDFs PBDDsPBDFs and PAHs extraction clean up and analyses wereperformed using modified methods of US EPA Method TO-13A24 and TO-9A25 The PCDDsPCDFs and PBDDsPBDFswere analyzed by high resolution gas chromatographyhighresolution mass spectrometry (HRGCHRMS) using aHewlett-Packard gas chromatograph 6890 Series coupled to aAutoSpec Premier mass spectrometer (Waters Inc UK) ADB-Dioxin 60-m times 025 mm times015 μm column (AgilentJampWScientific) and a DB-5 15 m times 025 mm times 025 μm column(AgilentJampW Scientific) was used for the PCDDsPCDFs andPBDDsPBDFs respectively A Hewlett-Packard gas chromato-graph 5890 5972 ms with a 60 m times 025 mm times 015 μmcolumn (AgilentJampW Scientific) was used to analyze the 16US EPA PAHs according to US EPA Method 8270D26
PCDDPCDF and PBDDPBDF concentrations were deter-mined by using the isotope dilution method The PCDDPCDF toxic equivalent (TEQ) emission factors weredetermined using the World Health Organization (WHO)2005 toxic equivalent factors (TEFs)27 All PCDDPCDF TEFcongeners were detected in all samples The PCDDPCDFTEFs were used to calculate the PBDDPBDF TEQ based onthe International Programme on Chemical Safety (IPCS) thatsuggest using the same TEF analogs for the PBDDPBDF asthe PCDDPCDF28 Almost all 13 PBDDPBDF congeners
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211006
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
were detected in all samples (10minus13) the congeners that werenot detected (ND) were set to zero (SI Table 6 shows bothND = 0 and ND = limit of detection) The PAH samples werespiked preanalysis according to US EPA Method 8270D26
VOCs were analyzed using US EPA Method TO-1523 by gaschromatographymass spectrometry (GCMS) In additioneach Summa canister sample was also analyzed for CO2 andcarbon monoxide (CO) by GC according to US EPA Method25C29 The PCDDsPCDFs PBDDsPBDFs PAHs andVOCs were normalized to 1 atm 211 degC The CGA CO2(LI-COR 820) measurements were performed and theinstrument was calibrated according to US EPA Method3A30 The gravimetric weighing of the PM25 filters wasperformed according to 40 CFR Part 5031 Metals wereanalyzed from the PM25 filters using inductively coupledplasma spectroscopy following the procedures described inUS EPA Compendium Method IO 3432 The data werebackground-corrected by subtracting the ambient air contribu-tion to the sample although the effect on the concentrationvalues was minimalCalculations The modified combustion efficiency (MCE)
(ΔCO2(ΔCO2+ΔCO)) was calculated for each of the VOCSumma canister samples after correcting for background COand CO2 Flaming modes were assumed to be represented byconditions in which the MCE gt 090 and smoldering modes forMCE lt 090The continuous PM25 concentration used a correction factor
determined by simultaneous collection of PM25 mass on a filter(averaged continuous PM25 concentration divided by PM25 byfilter mass) For those runs where no PM25 by filter wascollected an average correction factor from all of the other runswas appliedThe carbon mass balance approach was used for calculating
emission factors (EFs) This method assumes that all carbon inthe waste is emitted to the atmosphere as CO2 CO methane
(CH4) and total hydrocarbons (THC) and that the carbon andpollutants emitted where evenly distributed throughout theplume The carbon from CH4 has been shown to amount to06 of the total carbon from CO2 CO and CH4 during poorcombustion conditions of municipal solid waste incineration33
In addition previous waste dump burn studies have shown that89 of the total carbon (sum of CO2 and CO) was CO2
121516
In this study only carbon from CO2 was used for calculating thetotal mass of carbon sampled Anticipated minor contributionsfrom CH4 and THC would not have a significant effect on theaverage emission factor Likewise CO was expected to have arelatively minor impact and its measurement was precluded bythe lack of a portable CO monitor that can quickly respond tothe rapid fluctuations in the plume concentrations Theexception to this CO measurement was the determination ofVOC emission factors where both CO2 and CO could bequantitatively sampled and measured from the Summa canisterAll emission factors were expressed as pollutant concentrationper cocollected concentration of carbon burned Theseemission factors can be calculated to pollutant per unit massof burned waste by multiplying with an estimated carbonfraction of 050 and 042 for the municipal and depot wastecomposition (SI Table S1) respectively using carbon fractionestimations for each component from Liu and Liptak34
RESULTS AND DISCUSSION
Emissions were collected from four different burn piles (eachburn pile having parallel samplers) and two different burn boxburns (sequential samplers) Forty-one SVOC PM25 by filterand VOC samples were collected Results are presented bypollutant type comparing burn pile and burn box emissionfactors and further distinguished by combustion efficiency
VOCs The VOCs were dominated by styrene propene andbenzene but the emissions also included the toxic compoundsvinyl chloride and 13-butadiene (Table 2) The VOC emission
aIncluded in EPAs list of hazardous air pollutants10 MCE= Modified combustion efficiency
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211007
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
factors were in the same range as found in laboratoryexperiments burning simulated FOB waste35 Burning ofdepot waste showed similar VOC emission factor levels asthe municipal waste No difference between burn pile and burnbox VOC emission levels could be found The VOC samplescollected from the burn box running in a continuous batch-feeding mode were associated with a higher MCE 097 plusmn 0019(1 STDV) than samples collected in the single-charge mode089 plusmn 0018 indicating that a higher level of smolderingoccurred in the single-charge mode36 The municipal burn pileVOC samples fell into two classes based on the MCE flaming097 plusmn 0025 and smoldering 088 plusmn 0020 A significantdifference in VOC emission factors between the two phases wasfound for both ACI and burn pile for example the benzeneemission factor was 6- and 10 fold higher during smolderingconditions in both burn scenarios respectively (Figure 2) AllEPA method TO-15 compounds are shown in SI Table S2
PAHs Of the 16 EPA PAHs approximately 50 of thesampled mass consisted of phenanthrene and naphthalene forboth burn pile and burn box tests A higher emission factor forTotal PAH was found for each burn pile sample with a delayedsampling start (Figure 3) suggesting better combustion qualityat the beginning of the burn The total PAH emission factor forburn piles (257 plusmn 101 μgg Carbonburned) was lower than foundin laboratory tests of simulated FOB waste (803 plusmn 207 μggCarbonburned)
35 Running the burn box in a continuous batch-feed mode (42 plusmn 33 μgg Carbonburned) resulted in significantlylower PAH emissions than running the burn box in a single-charge mode (259 μgg carbonburned) indicating that moresmoldering occurred during the single-charge mode During thecontinuous batch-feed mode the PAH emission factors alsodecreased with time from 73 to 95 μgg Carbonburned (Table 3)suggesting an increased combustion quality with burn timeRunning the burn box in a continuous mode (BB 1A-D)
Figure 2 BTEX emission factors for burn box and burn piles during smoldering (MCE lt 090) and flaming (MCE gt 095) conditions
Figure 3 Emission factors for Total PAH (16 EPA PAHs)
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211008
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
reduced the PAH emissions up to 38 times compared toburning waste in piles The individual 16 PAH compoundsresults are shown in SI Table S3PCDDsPCDFs and PBDDsPBDFs The PCDDPCDF
emissions from the burn box were about 50 times lower thanemissions from burn piles 0071 plusmn 0048 ng TEQgCarbonburned and 34 plusmn 25 ng TEQg Carbonburned respectively(Figure 4) The burn pile emission factors were four timeshigher than reported from a Mexican waste dump burn12 Nodifferences in emission levels were found burning municipal ordepot waste in the burn piles 35 plusmn 30 ng TEQg Carbonburnedand 30 plusmn 12 ng TEQg Carbonburned respectively The burnpile emission factors for both municipal and depot waste hadhigher emission factor levels than reported in a laboratory studyburning a 10 kg pile of a simulated FOB waste withoutpolyethylene terephthalate (PET) plastic bottles (042 plusmn 030ng TEQg Carbonburned) and with PET bottles (0056 plusmn 0023ng TEQg Carbonburned)
35 Samples collected at the onset ofburning had a 33minus61 lower PCDDPCDF value than thosewith delayed collection implying that the elevated emissionfactors could be due to increased smoldering later in the burnas shown elsewhere12 A 46 higher emission factor (sample
BP1B compared to BP1C) was also found when one of twoparallel samplers was continued for an additional 90 min (170min totally) presumably sampling more of the smolderingphase Similar trends were found for tests in which the burn boxwas operated in a continuous batch-feed mode limitingsmoldering and resulting in a 3 times lower PCDDPCDFemission factor than the single-charge mode (Figure 4)The PBDDPBDF emission factor for the burn box was also
lower than for the burn piles 0083 plusmn 012 ng TEQgCarbonburned versus 35 plusmn 56 ng TEQg Carbonburned (Figure4) The burn pile emission factors for municipal waste rangedalmost 2 orders of magnitude from 026 to 17 ng TEQgCarbonburned The lower values are within the range (0033minus061 ng TEQg Carbonburned) obtained at a Mexican wastedump burn12 However in our study 10minus13 PBDDF TEFcongeners were detected compared to 2minus6 in the Mexicanwaste dump burn study which may be at least in part thereason for the higher values found in this study An almost 10-fold lower emission factor was found for the depot waste burnpile than from the lowest emission factor from a municipal burnpile (Table 3) Furthermore the depot burn pile emissionfactor was in the same range as burning simulated FOB waste in
Table 3 Emission Factors for PM25 by filter PM25 by CEM PCDDPCDF PBDDPBDF and Total PAHa
aTotal PAH = 16 EPA PAH NS not sampled SO sample overloaded bContinuous PM25 sampled for the entire sampling period
Figure 4 PCDDPCDF and PBDDPBDF emission factors in ng WHO-TEQg Carbonburned
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211009
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
laboratory tests35 The highest PBDDPBDF TEQ emissionfactor from burn pile 2 (BP2B) consisted of 95 of 123478-HpBDF 23478-PeBDF 2378-TBDF and 1234678-HpBDF The other elevated PBDDPBDF emission factorfrom burn pile number 4 (sample BP4B) consisted of 67 of2378-TBDF A 10-fold decrease was found in the PBDDPBDF emission factor running the burn box in a continuousbatch-feed mode compare to running the burn box in a single-
charge mode However only one sample was collected in thesingle-charge mode in which 82 of the emission factorconsisted of the 2378-TBDD congener The TEQ emissionfactors for each PCDDPCDF and PBDDPBDF congener areshown in SI Tables S4minusS6
PM25 and Metals An ANOVA analysis of eight PM25
samples found a statistical difference in PM25 emission factorsbetween burn piles and the burn box (in batch-feed mode) A
Figure 5 Emission factors for PM25 sampled continuously
Figure 6 Continuous sampling (20 s average) of CO2 and PM25 from burning of depot waste in a pile using the aerostat-based sampling method(Burn No 4)
Figure 7 Metal emission factors from PM25 by filter Included in EPArsquos list of hazardous air pollutions10 Numbers represent values ND notdetected
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211010
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
higher emission factor was found between the five municipaland one depot waste tests however only one burn with depotwaste was conducted so this conclusion remains tentative(Figure 5) The burn pile emission factors were also shown toincrease with burn time (Table 3 Burn pile 4) as shown byincreased PM25 with decreased CO2 concentration with time(Figure 6) likely due to increased smoldering Running theburn box in continuous batch-feed mode showed a loweremission factor than in single-charge mode Furthermore theemission factors in the continuous batch-feed mode decreasedwith burn time (Table 3) which may be due to increasedcombustion qualityThere was no distinction in metal emissions between burn
piles and the burn box (Figure 7) Lead iron and copper weredetected in all samples collected Mercury was not detected inany of the samples while chromium arsenic nickel andcadmium were detected in some of the samples (SI Table S7)Lead emission factors (037 μgg Carbonburned) were more then10-fold lower than found in a Mexican municipal landfill burnstudy (14 μgg Carbon)37 and a simulated FOB wastelaboratory burn study (24 μgg Carbon)35
Running the burn box in a continuous batch-feed modeshowed lower emission factors than burning waste in piles forall compounds studied PCDDPCDF and PBDDPBDFemission factors were always lower in the burn box than theburn piles In general smoldering conditions in the burn boxand the burn pile led to similar emissions However when theburn box underwent periodic waste charging to maintainsustained combustion PM25 VOCs and PAH emissionsdropped considerably compared to smoldering conditions andthe overall burn pile results Running the burn box in acontinuous batch-feed mode reduced the PM25 and PAHemissions with time
ASSOCIATED CONTENTS Supporting InformationAs noted in the text This material is available free of charge viathe Internet at httppubsacsorg
ACKNOWLEDGMENTSThis research was supported by the US Air Force SurgeonGeneral AFSG9S Force Health Protection office andconducted under the auspices of an IntergovernmentalAgreement with the US Environmental Protection AgencySpecial thanks to personnel at the US Armyrsquos Tooele Depotwho were critical to the success of this mission Don FanningRoger Hale Darwin Jones Coy Christensen Jacinta Williamsand Dave Woodworth Contributing EPA personnel includedChris Pressley Dennis Tabor and William Stevens (ORISEpostdoc) Aerostat operations were handled by Rob Gribbleand Larry Plush of ISSI Inc Assisting AFIT personnel includedMike Schmidt and Val Oppenheimer This research wasperformed while Johanna Aurell held a National ResearchCouncil Research Associateship Award at the US EPANRMRL This publication has been subjected to the US EPArsquos
peer and administrative review and has been approved forpublication as an US EPA document
REFERENCES(1) Long-Term Health Consequences of Exposure to Burn Pits in Iraqand Afghanistan Institute of Medicine National Academies PressWashington DC 2011(2) Mulrine A Military Veterans worry about exposure to toxic waste2010 US News amp World Report LP httpwwwusnewscomnewsarticles20100621military-veterans-worry-about-exposure-to-toxic-waste (accessed May 1 2012)(3) Smith B Wong C A Smith T C Boyko E J Gackstetter GD Ryan M A K Millennium cohort study T Newly reportedrespiratory symptoms and conditions among military personneldeployed to Iraq and Afghanistan A prospective population-basedstudy Am J Epidemiol 2009 170 (11) 1433minus1442(4) Engelbrecht J P McDonald E V Gillies J A Gertler A WEnhanced particulate matter surveillance program A multidisciplinaryapproach to understanding mineral dusts from the Middle EastGeochim Cosmochim Acta 2008 72 (12) A243minusA243(5) Jay A V Gregory T Vivian R Adam D Screening Health RiskAssessment Burn Pit Exposures Balad Air Base Iraq and AddendumReport Air Force Institute for Operational Health 2008(6) Schecter A Birnbaum L Ryan J J Constable J D DioxinsAn overview Environ Res 2006 101 (3) 419minus428(7) Birnbaum L S Staskal D F Brominated flame retardantsCause for concern Environ Health Perspect 2004 112 (1) 9minus17(8) Behnisch P A Hosoe K Sakai S-i Brominated dioxin-likecompounds in vitro assessment in comparison to classical dioxin-likecompounds and other polyaromatic compounds Environ Int 2003 29(6) 861minus877(9) Samara F Gullett B K Harrison R O Chu A Clark G CDetermination of relative assay response factors for toxic chlorinatedand brominated dioxinsfurans using an enzyme immunoassay (EIA)and a chemically-activated luciferase gene expression cell bioassay(CALUX) Environ Int 2009 35 (3) 588minus593(10) US EPA Hazardous Air Pollution List Clean Air Act Title 42The public Health and Welfare US Government Printing OfficeWashington DC 2008(11) Government Accountabilility Office Afghanistan and Iraq DODShould Improve Adherence to Its Guidance on Open Pit Burning and SolidWaste Management 2010(12) Gullett B K Wyrzykowska B Grandesso E Touati ATabor D G Ochoa G S PCDDF PBDDF and PBDE emissionsfrom open burning of a residential waste dump Environ Sci Technol2010 44 (1) 394minus399(13) Aurell J Gullett B K Aerostat Sampling of PCDDPCDFEmissions from the Gulf Oil Spill in situ burns Environ Sci Technol2010 44 (24) 9431minus9437(14) Gullett B K Lemieux P M Lutes C C Winterrowd C KWinters D L Emissions of PCDDF from uncontrolled domesticwaste burning Chemosphere 2001 43 (4minus7) 721minus725(15) Solorzano-Ochoa G de la Rosa D A Maiz-Larralde PGullett B K Tabor D G Touati A Wyrzykowska-Ceradini BFiedler H Abel T Carroll W F Jr Open burning of householdwaste Effect of experimental condition on combustion quality andemission of PCDD PCDF and PCB Chemosphere 2012 87 (9)1003minus1008(16) Zhang T Fiedler H Yu G Ochoa G S Carroll W F JrGullett B K Marklund S Touati A Emissions of unintentionalpersistent organic pollutants from open burning of municipal solidwaste from developing countries Chemosphere 2011 84 (7) 994minus1001(17) Lemieux P M Gullett B K Lutes C C Winterrowd C KWinters D L Variables affecting emissions of PCDDFs fromuncontrolled combustion of household waste in barrels J Air WasteManage 2003 53 (5) 523minus531(18) Hedman B Naslund M Nilsson C Marklund S Emissionsof polychlorinated dibenzodioxins and dibenzofurans and polychlori-
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211011
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
nated biphenyls from uncontrolled burning of garden and domesticwaste (backyard burning) Environ Sci Technol 2005 39 (22) 8790minus8796(19) Rupert W H Bush T A Verdonik D P Geiman J AHarrison M A Force Provider Solid Waste Characterization Study USArmy Research Development and Engineering Command NatickSoldier Center MA 2004(20) Lemieux P M Lutes C C Abbott J A Aldous K MEmissions of polychlorinated dibenzo-p-dioxins and polychlorinateddibenzofurans from the open burning of houshold waste in barrelsEnviron Sci Technol 2000 34 377minus384(21) George T Hilary T Eliassen R Solid Wastes EngineeringPrinciples and Management Issues McGraw-Hill Book Company NewYork 1977 p 621(22) Aurell J Gullett B K Pressley C Tabor D Gribble RAerostat-lofted instrument and sampling method for determination ofemissions from open area sources Chemosphere 2011 85 806minus811(23) US EPA Compendium Method TO-15 Determination ofvolatile organic compounds (VOCs) in air collected in specially-preparedcanisters and analyzed by gas chromatographymass spectrometry (GCMS) 1999(24) US EPA Compendium Method TO-13A Determination ofpolycyclic aromatic hydrocarbons (PAHs) in ambient air using gaschromatographicmass spectrometry (GCMS) 1999(25) US EPA Compendium Method TO-9A EPA U SDetermination of polychlorinated polybrominated and brominatedchlorinated dibenzo-p-dioxins and dibenzofurans in ambient air 1999(26) US EPA Method 8270D Semivolatile organic compounds by gaschromatographymass spectrometry (GCMS) 2007(27) V an den Berg M Birnbaum L S Denison M De Vito MFarland W Feeley M Fiedler H Hakansson H Hanberg AHaws L Rose M Safe S Schrenk D Tohyama C Tritscher ATuomisto J Tysklind M Walker N Peterson R E The 2005World Health Organization reevaluation of human and mammaliantoxic equivalency factors for dioxins and dioxin-like compoundsToxicol Sci 2006 93 (2) 223minus241(28) IPCS-WHO Polybrominated Dibenzo-p-Dioxins and Dibenzofur-ans Environmental Health Criteria 205(29) US EPA Method 25C Determination of nonmethane organiccompounds (NMOC) in landfill gases(30) US EPA Method 3A Determination of oxygen and carbondioxide concentrations in emissions from stationary sources (instrumentalanalyzer procedure)(31) 40 CFR Part 50 Appendix J Reference method for thedetermination of particulate matter as PM10 in the Atmosphere 1987(32) US EPA Compendium Method IO 34 Determination of metalsin ambient particulate matter using inductively coupled plasma (ICP)spectroscopy 1999(33) Aurell J Fick J Haglund P Marklund S Effects of sulfur onPCDDF formation under stable and transient combustion conditionsduring MSW incineration Chemosphere 2009 76 (6) 767minus773(34) Liu D H F Liptak B G Hazardous Waste and Solid WasteLewis Publishers Boca Raton FL 1999 p 288(35) Woodall B D Yamamoto D P Touati A Gullett B KCharacterization of Emissions from Simulated Deployed US MilitaryWasteEnviron Sci Technol 2012 DOI 101021es3021556 (36) Ward D E Hardy C C Smoke emissions from wildland firesEnviron Int 1991 17 (2minus3) 117minus134(37) Christian T J Yokelson R J Cardenas B Molina L TEngling G Hsu S C Trace gas and particle emissions from domesticand industrial biofuel use and garbage burning in central MexicoAtmos Chem Phys 2010 10 (2) 565minus584
Environmental Science amp Technology Article
dxdoiorg101021es303131k | Environ Sci Technol 2012 46 11004minus1101211012
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
Aerostat-lofted instrument and sampling method for determinationof emissions from open area sources
Johanna Aurell a1 Brian K Gullett buArr Christopher Pressley b Dennis G Tabor b Robert D Gribble c
a National Research Council US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle ParkNC 27711 USAb US Environmental Protection Agency Office of Research and Development National Risk Management Research Laboratory Research Triangle Park NC 27711 USAc Integrated Systems Solutions Incorporated 22685 Three Notch Road California MD 20619 USA
a r t i c l e i n f o a b s t r a c t
Article historyReceived 13 April 2011Received in revised form 16 June 2011Accepted 17 June 2011Available online 15 August 2011
An aerostat-borne instrument and sampling method was developed to characterize air samples from areasources such as emissions from open burning The 10 kg battery-powered instrument system termedlsquolsquothe Flyerrsquorsquo is lofted with a helium-filled aerostat of 4 m nominal diameter and maneuvered by meansof one or two tethers The Flyer can be configured variously for continuous CO2 monitoring batch sam-pling of semi-volatile organic compounds (SVOCs) volatile organic compounds (VOCs) black carbonmetals and PM by size The samplers are controlled by a trigger circuit to avoid unnecessary dilutionfrom background sampling when not within the source plume The aerostatFlyer method was demon-strated by sampling emissions from open burning (OB) and open detonation (OD) of military ordnanceA carbon balance approach was used to derive emission factors that showed excellent agreement withpublished values
Published by Elsevier Ltd
1 Introduction
Air sampling from open area sources can be used to determineemission factors which allow calculation of source strength atmo-spheric pollutant loading and with dispersion modeling down-wind exposures to assess possible harm to human health and theenvironment Emission factors are significant for developing emis-sion control strategies permit applications and for use in emissioninventories Open area sources include sources such as industrialplants animal feed operations and open burning Typical sourcesof open burning include landfill or dump fires structural fires agri-cultural burns and prescribed forest and grassland burns Sam-pling emissions from open burning sources is particularlydifficult due to the challenge of balancing the need for proximityto the undiluted source with safety issues for personnel Further-more flame or explosion conditions which preclude sampling untilonset of smoldering conditions may limit the representativeness ofthe emission sample
Various methodologies and instrumentation have been used foropen area sampling depending on the source characteristics andtarget analytes Varying meteorological conditions such as windspeed and direction may pose location challenges for ground-based
Ltd
+1 919 541 0554)
point samplers In addition although ground-based samplers areoften positioned on towers to improve their possibility for sam-pling higher plumes and wind shifts may result in insufficientsample size to exceed detection limits Optical remote sensingmethods using lsquolsquoline of sightrsquorsquo measurements offer the benefit ofpath-integrated rather than single point measurements Thesesample methods are also ground-based and may be limited bytheir maneuverability as well as their applicability for some ana-lytes such as polycyclic aromatic hydrocarbons (PAHs) Aerialsampling methods with capabilities for vertical and horizontalmaneuverability overcome concerns in sampling lofted plumesThese methods can employ airplanes helicopters miniature re-mote control helicopters and unmanned airshipsaerostats (Lundand Starkey 1990 Laursen et al 1992 Frick and Hoppel 1993Li et al 1995 Imhoff et al 1995 Fingas et al 1996) While air-planes and helicopters can carry heavy payloads pilots are oftenquite reticent to fly through combustion plumes due to visibilityand turbulence concerns The use of airplanes and helicopters oftenhas high operating costs and especially for airplanes short timesin the near-source plume limiting the amount of sample thatcan be collected Remote-controlled helicopters and airshipsaero-stats are slower making it possible to achieve a long residencetime in the plume minimizing concerns of limited sample size Re-motely-controlled helicopters are generally limited in payloadcapacity and may not be suitable for use in turbulent or opaqueplumes It has also been found that larger remote helicopters are
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
J Aurell et al Chemosphere 85 (2011) 806ndash811 807
more difficult to operate than smaller (Li et al 1995) which hasthe consequence of reduced payload weight Tethered aerostatscan be used to address many of these limitations by providingmaneuverability loft capacity plume residence time and safetyAerostat-lofted instruments have been used for emission samplingwith open detonation of military ordnance (Lindsay et al 2000)and in situ burning of crude oil at sea (Fingas et al 1996 Aurelland Gullett 2010) Lindsay et al (2000) sampled gas via summacanister and particulate matter collection by filter They had partialsuccess but experienced some difficulties with failure to trigger thesampling instruments and damage to the sampling equipmentTethered blimp sampling of PAHs from oil burn plumes was con-ducted by Fingas et al (1996) but was of insufficient sampling vol-ume (30 L) to reach detectable levels of the analyzed PAHs Recentadvances in aerostat materials and miniaturization of samplers andbatteries have improved the possibilities for lofted sampling Useof continuous carbon dioxide (CO2) measurements with wirelesstelemetry systems has allowed optimization sampler position toachieve the highest plume concentration
This paper describes the development and demonstration of amethod using an instrumented tethered aerostat to characterizeair emissions from open area sources The method was demon-strated by sampling emissions from open burning (OB) and opendetonation (OD) plumes during disposal of military ordnanceThe resulting emission factors are used in dispersion models bythe military to ensure that the emissions are not adversely affect-ing human and environmental health The sampled emission fac-tors were compared to literature values obtained from fieldmeasurements
2 Material and methods
21 The aerostat-borne sampling method
The sampling instruments were lofted by a 40 m 31 m semi-spherical helium-filled two layer aerostat (Kingfisher Model Aer-ial Products Inc USA) The inner layer is made of polyurethanewith additional ultraviolet and hydrolysis inhibitors and the outerlayer consists of rip-stop nylon The aerostat uses a tether attach-ment over the whole sphere that results in tension around thewhole aerostat rather than at a single point of connection therebyeliminating concerns regarding tether breakage The maximum loftcapacity is approximately 19 kg at sea level but was 118 kg at1500 m elevation during this test study The aerostat was tetheredand maneuvered by using two 300 m long 25 mm diameter Spec-tra lines (Cortland Cable Company USA) attached to a pair of all-terrain vehicles (ATVs) equipped with electrically poweredwinches
HOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
HOBOHOBO
PM10 PM10 Pump Ba
Semi-volatile sampler
CEM CO2VenturiData logginCEM particle
filter
GPS
Fig 1 Schematic illustration of the sampling
The aerostat carries a lightweight instrument sampling packagetermed lsquolsquothe Flyerrsquorsquo Fig 1 The Flyer consists of multiple samplinginstruments which can be added or removed to match the sourcepollutants or measurements of interest In addition the Flyer sam-pling method can be optimized to the source characteristics to ef-fect sampling onset duration and volume The Flyer is comprisedof interchangeable instruments including total PM PM10 PM25CO CO2 semi-volatile organic compounds (SVOCs) such as PAHsand polychlorinated dibenzodioxins and dibenzofurans (PCDDsPCDFs) black carbon volatile organic compounds (VOCs) andHCl In addition filter analysis can be done for PM-borne metalsAdditional measurements include temperature humidity GPScoordinates wind velocity and altitude
This paper will describe the Flyer performance while measuringemissions from OB and OD Sampling emissions from OB and OD ofmilitary ordnance is challenging as safety considerations limitsource proximity In addition plume generation is very quick(lt15 s) and transport by winds past the relatively stationary Flyerlimits the available sampling time and hence the sample suffi-ciency In order to determine emission factors for the target com-pounds of this test campaign the Flyer was configured with acontinuous emission monitor (CEM) for CO2 measurements aSumma canister for sampling of benzene (a VOC) a polyurethanefoamXAD-2polyurethane foam (PUF) sorbent sampler for collec-tion of PAHs and a single stage PM10 impact sampler by filter(Fig 1) CEM data and flow rate were logged every second to anon-board data acquisition system (HOBO U12-013 Onset Com-puter Corporation USA) which also measured temperature Fur-thermore the Flyer also had a Geko 301 (Garmin USA) globalposition system (GPS) and a Lead Acid 12 V 5 Ah rechargeable bat-tery (BatteriesPlus USA) on board all resulting in a total weight ofabout 11 kg (Table 1) just below the 118 kg payload capacity at anelevation of 1500 m
The carbon mass balance approach was used to derive emissionfactors as is common for sources of open burning (Laursen et al1992 Gullett et al 2006) It was assumed that all the carbon fromthe material burned was emitted to the atmosphere (Laursen et al1992) and that the plume was completely mixed (ie the pollutantsand the carbon emitted were assumed to be proportionally distrib-uted throughout the plume) Emission factors derived from the car-bon mass balance have been shown to be in good agreement withemission factors derived from direct mass loss measurementmethods (Gullett et al 2006 Dhammapala et al 2006) The majorcarbon product has been shown to be CO2 in OB and OD combus-tion plumes 99 and 97 respectively (Johnson 1992a) Otherminor carbon products were CO CH4 total hydrocarbons and par-ticle-bound carbon The relative concentration of the carbon spe-cies and the power and weight cost of its measurement method
ttery
Volatile sampler
g
ttery
Volatile sampler
g
package termed the lsquolsquoFlyerrsquorsquo not to scale
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
Table 1Sampling components
Sampling component Manufacturer Analyte Range Sensitivityaccuracy
Flow rate Powerrequirement
Weight(kg)
Dimensions
CEM ndash NDIR LI-CORBiosciencesUSA
CO2 0ndash2000 ppm 1 ppm25 ofreading
lt1 L min1 12 V 10 222 153 76
6 L Summa canister VOCbenzene 295 330 203 203Semi-volatile
samplerMinijammerblower
Amtek USA PAH 25ndash220 L min1
plusmn1 L min1 220 L min1 12 V 173 280 101 101
Glasscartridge
TISCHScientific USA
NA NA NA 76 76
PM Leland Legacypump
SKC Inc USA PM10 5ndash15 L min1 plusmn5 ofset-point
10 L min1 74 V Li-Ion 023 7 5 10
Atmosphericpressure LelandLegacy pump
SKC Inc USA AtmosphericPressure
plusmn03 Hg NA 74 V Li-Ion 1 20 10 7
GPS ndash Garmin Geko301
Garmin USA AltitudeLocation
610ndash144 m 1 mlt15 m Update rate 1readingsecond
2 15 V 0096 48 99 24
Lead acid battery Battery PlusUSA
NA NA NA NA 12 V 5 Ah 095 101 89 76
HOBO U12-013 OnsetComputerCorporationUSA
Temperature 20ndash70 C 003 Cplusmn035 C
NA 3 Volt 0046 58 74 22
Relativehumidity
5ndash95 003plusmn25 NA
Data logging 64 KBmemory
Time accuracyplusmn1 min permonth
Readingeverysecond
Frame andelectronic parts
195 457 305 305
808 J Aurell et al Chemosphere 85 (2011) 806ndash811
has to be considered with the overall data quality objectives whenmaking a decision as to which carbon species should measuredThis work assumed complete oxidation of the carbon in the ord-nance such that all of the carbon was emitted to the atmosphereas CO2 or as particulate carbon
22 Emission sampling and analysis methods
Successful sampling in which the target analyte exceeds themethod detection limit is predicated upon sufficient plume con-centration and duration as well as instrument performance andanalytical constraints Analytical instruments need to be light-weight portable and rugged with a short response time and lowlimits of detection The sampling duration required for each targetanalyte to exceed the method detection limits was estimated usingthe volumetric sampling rate analytical detection limits publishedemission factors and the predictive open burnopen detonationdispersion model (OBODM) (Bjorklund et al 1998) Due to theshort sampling duration available for each burn and detonationcomposite samples for both SVOCs and PM10 were created by reus-ing their respective sampling media during multiple events TwoSVOC composite samples were collected for both OB and OD Inaddition one and two PM10 samples were collected for the burnand detonation tests respectively
Continuous measurements of CO2 were performed using a LI-820 (LI-COR Biosciences USA) non-dispersive infrared (NDIR)-based CEM using a 14 cm optical bench with an analytical rangeof 0ndash2000 ppm with an accuracy specification of less than 25 ofreading The LI-820 was equipped with a programmable alarm out-put (trigger circuit) which turned on the semi-volatile blower andthe PM10 pump and opened the solenoid valve on the summa can-ister This trigger circuit was programmed to turn on at a CO2 con-centration of 410 ppm for the OB tests and 400 ppm for the ODtests which was about 30ndash20 ppm above the ambient levels(390 ppm) of CO2 at the test site The LI-820 voltage equivalent
CO2 concentration was recorded on the HOBO external data loggerThe LI-820 and the HOBO were calibrated for CO2 on a daily basisaccording to US EPA Method 3A (2008)
Summa canisters (6 L capacity) with an electronic solenoidvalve sampling system were used for collection of benzene viaUS EPA Method TO-15 (1999) The electronic solenoid valve sam-pling system was opened and closed by the CO2 concentration trig-ger circuit The valve was followed by a frit filter in the stem of thesumma canister Canister fill times of 120ndash180 s were observedduring pre-tests The VOCs were analyzed using US EPA MethodTO-15 (1999) using selective ion monitoring (SIM) mode gas chro-matograph-low resolution mass spectrometer (GCLRMS) EachSumma canister sample was also analyzed for CO2 by GC utilizingUS EPA Method 25C using a GC-flame ionization detector (FID)
SVOCs were sampled via US EPA Method TO-13 (1999) using aPUFXAD-2PUF sorbent The pre-cleaned XAD-sorbent (SUPELCOUSA) was further cleaned by solvent extraction with dichlorometh-ane and dried with flowing helium to minimize contamination ofthe media with the target analytes The pre-sampling tests of theXAD sorbent showed contamination of naphthalene (32 ng g1
XAD) fluorine (065 ng g1 XAD) phenanthrene (55 ng g1 XAD)anthracene (065 ng g1 XAD) fluoranthene (065 ng g1 XAD)and pyrene (070 ng g1 XAD) despite these extra solvent extrac-tions The XAD-2 resin was prespiked with naphthalene-d8 ace-naphthene-d10 phenanthrene-d10 chrysene-d12 and perylene-d12 allowing PAH emission factors other than naphthalene to bequantitated The PUFXAD-2PUF sorbent was mounted in a glasscartridge (TISCH Scientific USA) and inserted in a cartridge holdermounted on a MINIjammer brushless direct current blower (AME-TEK Inc USA) SVOC sampling was performed with a nominal sam-pling rate of 022 m3 min1 The blower was controlled by the CEMCO2 trigger circuit Flow rate was measured by a 0ndash622 Pa pressuredifferential transducer (Setra Model 265 USA) across a HerschelStandard Venturi tube The Venturi tube was specially designedto meet the desired sampling rate in this sampling campaign and
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
J Aurell et al Chemosphere 85 (2011) 806ndash811 809
had a throat and upstream diameter of 96 and 18 mm respec-tively The Venturi tube was mounted on the outlet of the MINI-jammer blower The voltage equivalent to this pressuredifferential was recorded on the HOBO external event loggerwhich was calibrated with a Roots meter (Model 5M Dresser Mea-surement USA) The Flyer had battery capacity for about 1 h ofSVOC sampling The samples were cleaned up according to USEPA Method TO-13 (1999) and analyzed using GCLRMS Trip andfield blanks were collected and analyzed The flow rate was cor-rected to standard conditions 211 C and 101325 hPa
The two last target compounds were PM10 and lead (Pb) whichwere sampled using a 47 mm tared Teflon filter with a pore size of20 lm via a Leland Legacy Sample pump (SKC Inc USA) with aconstant airflow of 10 L min1 The pump was controlled by theCEM CO2 trigger circuit The Leland Legacy Sample pump was cal-ibrated with a Gilibrator Air Flow Calibration System (SensidyneLP USA) PM10 was measured gravimetrically and followed theprocedures described in 40 CFR Part 50 (1987) The particulatematter collected on Teflon filters was also used to determine thePb concentration from the OB analyzed by energy dispersive X-ray fluorescence spectrometry (ED-XRF) according to US EPA Com-pendium Method IO-33 (1999)
23 Testing and sampling procedures Open burning
The open burns were conducted by sequentially igniting 45 kgof M1 propellant (Johnson 1992b) in each of six iron pans on aconcrete burn pad (20 m 25 m) The aerostatFlyer was prepo-sitioned downwind of the burn site using two tethers each spooledon an ATV-mounted winch Fig 2 The combination of two ATVsand two tethers positioned the aerostatFlyer at a specific down-wind location and height typically 20ndash60 m The ATVs as well asall personnel were located outside the 64 m safety stand-off dis-tance for humans When necessary and possible the aerostat wasmaneuvered into the thicker parts of the plume by reeling in thetether or by manually running the tethers down as guided by vi-sual observations
24 Testing and sampling procedures Open detonations
The open detonation test range consisted of a gravelsand area(100 m 100 m) upon which the wooden crates of explosiveswere placed The charge sizes of the TNT detonations were either23 kg or 45 kg Detonations were initiated with a 1 kg block ofC4 Based on several pre-sampling detonations it was estimatedthat the hazardous shrapnel zones for the ATVs and the aerostat
ATV
Winch
Tether line
Aerostat with the Flyer
ATV
Winch
Tether line
Aerostat with the Flyer
Fig 2 Schematic illustration of the aerostat-borne plume sampling method not toscale
were within approximately 90 m from the detonation The shock-wave created from the detonation was observed to have only min-or movement effects if any on the aerostat The aerostat and Flyerwere pre-positioned downwind of the detonation site at a height ofabout 30ndash70 m above ground level The two ATVs and their tetherwinches were located inside the 464 m safety stand-off distancefor humans All personnel were located outside of the safetystand-off distance and behind a protective wall
3 Calculations
The CEM and Summa canister CO2 data were used to calculatethe carbon concentration associated with the co-sampled targetanalyte permitting conversion of the pollutant concentration toemission factors by the carbon mass balance method (mass of pol-lutant per mass of carbon in the material burned) Fig 3 shows thecumulative carbon content sampled (038 g) for one SVOC samplebased on the CO2 CEM concentration (corrected for backgroundCO2) versus sampling time for multiple burns (22) Emission fac-tors were calculated according to
Emission Factor frac14 mfc Pollutant
C
where the Emission Factor is in g g1 net explosive weight (NEW)mfc is the mass fraction of carbon in the material burned (37and 33 in the TNT flakes and M1 propellant respectively) Pollutantis the background-corrected mass in lg analyte of the pollutant col-lected C is the background-corrected mass of carbon collected in lgcarbon The PUFXADPUF-derived emissions and emission factorswere calculated with corrections for ambient air background levelsas well as for contamination of the sorbent media itself by the targetanalyte Emission factors were calculated using both Summa canis-ters values for CO2 (for benzene) and the CEM CO2 values (for PAHPM10 and Pb)
4 Results and discussion
41 Ambient air and plume concentrations
The Flyeraerostat successfully sampled emissions in 85 of 66open burns and 76 of 37 open detonations as determined by thenumber of times that the CO2 concentration exceeded the triggerpoint of 410 ppm (OB) and 400 ppm (OD) Unsuccessful samplingwas due to wind shifts or variation in the plume path resulting inthe Flyer missing the plume Fig 4 shows the CO2 trace of six OBsas well as the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point of 410 ppm The CO2 ambient
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
000
005
010
015
020
025
030
035
040
00 05 10 15 20 25 30 35 40 45 50 55 60 65
Sampling time (min)
Cum
ulat
ive
carb
on c
onte
nt (g
)
0
400
800
1200
1600
2000
0 4 8 12 16 20
Sampling time (second)
CO
2 Con
cent
ratio
n (p
pm)
135137139141143145147149
Am
bien
t Tem
pertu
re
(degC
)
CO2
Temperature
Fig 3 Background-corrected cumulative carbon content sampled from 22 openburns of M1 propellant
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
Fig 4 Typical CO2 trace through six OB plumes Showing the CO2 triggering function turning on and off the semi-volatile sampler at the trigger point 410 ppm
810 J Aurell et al Chemosphere 85 (2011) 806ndash811
air concentrations were measured as 390 ppm The average deltaCO2 concentration over ambient was approximately 420 and125 ppm for OB and OD respectively The ambient air concentra-tions and background corrected plume concentrations of PAH ben-zene PM and Pb are shown in Table 2 The average background-corrected naphthalene concentrations in the OB and OD plumeswere 0068 and 16 lg m3 respectively which are greater thanfourfold higher than the ambient air background values (Table 2)PAH species other than naphthalene were primarily detected forthe OD events The contaminant-corrected concentration of targetanalytes in each of PUFXADPUF sorbents after OB OD and ambientair sampling was over three times higher than the media contamina-tion level All surrogate standard recoveries for analyses of CO2 fromsumma canisters were between 102 and 115 which was withinthe standard method criteria (94 and 137)
42 Emission factors
421 PAHTable 2 lists this projectrsquos emission factors alongside those from
previous field (Johnson 1992b) sampling of M1 propellant and
Table 2Plume concentration and emission factors derived from this study (Flyer) and previous op
A ND ndash no data BDL ndash below detection limit either never detected or if detected nevergram per gram net explosive weight
a Method reporting limit for PM10 was 1 lg filter1 and all PM10 results were above 5b Method reporting limit for lead was 000014 lg m3c Emission factor from laboratory scale (BangBox) (Mitchell and Suggs 1998)
TNT The sampled PAH values are within factors of 25ndash45 of thepublished value These differences may be due to variation in theOB and OD process or in the sampling methods used The publishedvalues were based solely on a PAH analysis of the filter catchwhich may result in significant loss of lighter semi-volatile com-pounds such as naphthalene (US EPA Method TO-13 1999) In thisstudy we used XAD-2 resin as the primary sorbent media of semi-volatile compounds to minimize compound loss an approach con-firmed by good recoveries for isotopically-labeled presamplingstandards on the XAD-2 sorbent The relative percent differenceof 48 and 31 for OB and OD samples respectively implies a goodmethod reproducibility All surrogate standard recoveries for thePAHs were between 59 and 112 which was within the standardmethod criteria (25 and 130)
422 BenzeneThe sampled benzene emission factor value for OB agrees very
well with the published emission factor value (Table 2) The coef-ficient of variance was 54 indicating a good reproducibility for themethod For OD the sampled benzene emission factor value isabout two times higher than the existing data but this is within
en test range sampling (existing) (Johnson 1992b) of M1 propellant and TNTA
detected above the backgroundcontamination level NS ndash not sampled g g1 NEW ndash
0 lg filter1
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
J Aurell et al Chemosphere 85 (2011) 806ndash811 811
the expected variation given the limited number of trials con-ducted The published emission factor was derived from 35 sam-ples while the emission factor in this study was calculated fromonly one OD Summa canister sample All surrogate standard recov-eries for this project were between 82 and 127 which was with-in the standard method criteria (70 and 130)
423 PM10 and PbEmission factors for PM10 and Pb are also listed in Table 2 The
PM10 value from OB was in good agreement with the published va-lue No emission factor for PM10 from open test range of OD of TNTexists The derived emission factor for PM10 in this study wastherefore compared to a value determined in a laboratory-scaledlsquolsquoBangBoxrsquorsquo (Mitchell and Suggs 1998) The emission factor in thisstudy was 2 times higher than the published BangBox emissionfactor this higher value is possibly due to the differences in thedetonation surface concrete versus soil This study derived afirst-ever emission factor for Pb from OB of M1 propellant (Table 2)which has not yet been accomplished In addition the relative per-cent difference was 54 which puts the literature value within therange of the derived EF This emission factor and the other derivedemission factors in this study confirms a great sampling potentialfor a wide range of analytes by this aerostat-borne samplingmethod
5 Conclusions
An aerostatFlyer successfully sampled an elevated plume for avariety of pollutants from open burning and open detonation ofmilitary ordnance The system achieved a high plume samplingsuccess of 85 and 76 from OB and OD plumes respectively Inaddition the Flyer achieved these high success rates in both lowand high winds due to quick maneuverability and high mobilityof the aerostat using adjustable tethers mounted on ATVs TheCO2 trigger initiated sampling instruments on the Flyer allowingfor successful determination of emission factors for a wide rangeof target emissions PAHs (SVOC) benzene (VOC) PM10 (particu-late matter) and Pb (metal) Further these emission factors werein good agreement with the few published data available using dif-ferent sampling approaches and comparable ordnance Improve-ments in instrumentation and aerostat flight operations areunder consideration or in-process These include different Summacanister valves in-flight transmission of CO2 and video data re-mote control of Flyer position via radio-controlled tether winchespowered tethers and use of light Li-ion batteries
Acknowledgments
This work was funded in part by the Strategic EnvironmentalResearch and Development Program (SERDP) under a project co-led by Byung Kim and Michael Kemme of the US Army Corps ofEngineers This research was performed while Johanna Aurell helda National Research Council Research Associateship Award at Na-tional Risk Management Research Laboratory US EPA Aerostatfield crew support by Brad Campbell (ISSI Inc) Donnie Gillis andSteve Terll (Arcadis-US Inc) and field assistance by Roger HaleDarwin Jones and Cody Spencer (Tooele Army Depot Test Range)is much appreciated The authors acknowledge special expertiseprovided by Bill Squire (US EPAORDNRMRL) Mike Tufts (Arca-
dis-US Inc) and Kevin Hess (Aerial Products FL) Technical advis-ors included Ryan Williams and Tyrone Nordquist US ArmyDefense Ammunition Center (DAC) Randy Cramer Naval Ord-nance Safety and Security Activity Eric Erickson Naval Air WarfareCenter-Weapons Division China Lake Tony Livingston Joint Muni-tions Command Bill Mitchell of Mitchell and Associates GeorgeThomson Chemical Compliance System Inc
References
40 CFR Part 50 1987 Appendix J Reference Method for the Determination ofParticulate Matter as PM10 in the Atmosphere 52 FR 24664 July 1 1987 52 FR29467
Aurell J Gullett BK 2010 Aerostat sampling of PCDDPCDF emissions from theGulf oil spill in situ burns Environ Sci Technol 44 9431ndash9437
Bjorklund J Bowers J Dodd G White J 1998 Open BurningOpen Detonation(OBODM) Userrsquos Guide Volume II Technical Description DPG Document NoDPG-TR-96-008b US Army Dugway Proving Ground Dugway UT lthttpwwwepagovttnscramusergnonepaobodmvol2pdfgt (accessed Mars 0811)
Dhammapala R Claiborn C Corkill J Gullett B 2006 Particulate emissions fromwheat and Kentucky bluegrass stubble burning in eastern Washington andnorthern Idaho Atmos Environ 40 1007ndash1015
Fingas M Li K Ackerman F Campagna P Turpin R Getty S Soleki MTrespalacios M Wang Z Pareacute J Beacutelanger J Bissonnette M Mullin JTennyson E 1996 Emissions from mesoscale in situ oil fires the mobile 1991experiments Spill Sci Technol Bull 3 (3) 123ndash137
Frick GM Hoppel WA 1993 Airship measurements of aerosol-size distributionscloud droplet spectra and trace gas concentrations in the marine-boundary-layer Bull Am Meteorol Soc 74 (11) 2195ndash2202
Gullett BK Touati A Huwe J Hakk H 2006 PCDD and PCDF Emissions fromsimulated sugarcane field burning Environ Sci Technol 40 6228ndash6234
Imhoff RE Valente R Meagher JF 1995 The production of O3 in an urbanplume airborne sampling of the Atlanta urban plume Atmos Environ 292349ndash2358
Johnson M 1992a Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Bangbox Test Series Volume 1 Test Summary ndashFinal Report US Army Armament Munitions and Chemical Command ReportNo AD-A250733
Johnson M 1992b Development of Methodology and Technology for Identifyingand Quantifying Emission Products from Open Burning and Open DetonationThermal Treatment Methods Field Test Series A B and C Volume 1 TestSummary ndash Final report US Army Armament Munitions and ChemicalCommand Report No AD-A250735
Laursen KK Ferek R Hobbs P Rasmussen RA 1992 Emission factors forparticles elemental carbon and trace gases from the Kuwait oil fires JGeophys Res 97 (D13) 14491ndash14497
Li K Dainty E Fingas MF Belanger JMR Pare JRJ 1995 Remote controlledhelicopters a tool for air sampling in difficult situations J Hazard Mater 43117ndash127
Lindsay ML McMorris R Baroody EE Watkins JW Olsen T 2000 Use ofBlimps to Collect in-situ Reaction Products from Detonation Plumes US NavalSurface Warfare Center Indian Head MD
Lund WW Starkey R 1990 Applications of miniature remotely guided aircraft tomonitoring ans sampling atmospheric pollutants and toxichazardousmaterials Journal of Air Waste Management Association 40 (6) 896ndash897
Mitchell J Suggs JC 1998 Emission Factors for the Disposal of Energetic Materialsby Open Burning and Open Detonation (OBOD) EPA600R-98103
US EPA Compendium Method IO-33 1999 Determination of Metals in AmbientParticulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy
US EPA Compendium Method TO-13A 1999 Determination of Polycyclic AromaticHydrocarbons (PAHs) in Ambient Air Using Gas ChromatographicMassSpectrometry (GCMS) second ed
US EPA Compendium Method TO-15 1999 Determination of Volatile OrganicCompounds (VOCs) in Air collected in Specially-Prepared Canisters andAnalyzed by Gas ChromatographyMass Spectrometry (GCMS) second ed
US EPA Method 25C xxxx Determination of Nonmethane Organic Compounds(NMOC) in Landfill Gases US Environmental Protection Agency lthttpwwwepagovttnemcpromgatem-25cpdfgt (accessed Mars 0811)
US EPA Method 3A 2008 Determination of Oxygen and Carbon DioxideConcentrations in Emissions from Stationary Sources (Instrumental AnalyzerProcedure) 1162008 US Environmental Protection Agency lthttpwwwepagovttnemc01methodsmethod3ahtmlgt (accessed Mars 0811)
Aerostat-lofted instrument and sampling method for determination of emissions from open area sources
1 Introduction
2 Material and methods
21 The aerostat-borne sampling method
22 Emission sampling and analysis methods
23 Testing and sampling procedures Open burning
24 Testing and sampling procedures Open detonations
3 Calculations
4 Results and discussion
41 Ambient air and plume concentrations
42 Emission factors
421 PAH
422 Benzene
423 PM10 and Pb
5 Conclusions
Acknowledgments
References
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
research papers Mr Gullett has published on the subject matter
4 I have spoken with our air modeling group at DEQ regarding the models currentlyin use for OBOD units Previously the Open Burn-Open Detonation Model (ODODM)was used in the risk assessment of the open burning grounds This model and thescience behind it have not substantially changed since the previous risk assessmentand the OBODM should be used in the current risk assessment The modeling groupdid suggest that if your facility participates in the EPA study to monitor emissions fromthe open burning ground to use those emission factors developed from the monitoringas the input for the OBODM For the previous risk assessment the modeling usedmonitored emissions from a bang box for small caliber ammunition As these are notquite comparable to the open burning grounds it is highly suggested the emissions bedirectly monitored and these values be input into the model to ensure the most accurateresults
Please let me know if you have any additional questions I can be reached using thecontact information in my signature line and I maintain regular office hours Mondaythrough Friday
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov
wwwdeqvirginiagov
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
Archived Thursday March 12 2015 104845 AMFrom Davie Robert N III CIV (US)Sent Thursday December 18 2014 124022 PMTo Scott Ashby (DEQ)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ) Jennings Ross BCIV (US) Saks Charles E Jr CIV USARMY JMC (US) Diioia Leonard L Jr CIV (US)Subject RE Contact Information for AerojetImportance NormalDigitally Signed Yes
___________________________________Ashby
It was good to meet you as well and thanks for the info Ill pass it alongto the right folks so they can make contact
Enjoy your holidays
Rob
-----Original Message-----From Scott Ashby (DEQ) [mailtoAshbyScottdeqvirginiagov]Sent Thursday December 11 2014 249 PMTo Davie Robert N III CIV (US)Cc Romanchik Leslie (DEQ) Williams Justin (DEQ) Regn Ann (DEQ)Subject Contact Information for Aerojet
Rob
It was good to meet you during our site visit below is the contactinformation for the environmental manager at the Aerojet facility which hasstarted shipping their previously open burned hazardous waste offsite to betreated
Tim Holden
Environmental and Safety Manager
Aerojet - Virginia Operations
540-854-2037
timholdenaerojetcom
Please let me know if you need any additional information
Thanks
Ashby
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
wwwdeqvirginiagov lthttpwwwdeqvirginiagovgt
Ashby R ScottTitle V Coordinator
Department of Environmental Quality
629 East Main Street
Richmond VA 23218Phone 804-698-4467Fax 804-698-4234AshbyScottdeqvirginiagov ltmailtoarscottdeqvirginiagovgt
