ar3! 1882 - united states environmental protection agency · 2020. 9. 21. · ar3! 1882. mr. peter...

BRIDGESTONE/FIRESTONE, INC.LAW DEPARTMENT, " " _ _ i ^ _ _ " '- "-- - . ,5g,Ceotijry Boulevard* P.Q'. Box 14(33900 • Nashville, TN 37214-8900ENVIRONMENTAll.SECTlDKT '" . Phone: 615 872-SdOO FAX;615-872-1490

May 21, 1998 " "." ". "./.

Mr. Peter W. SchaulDirector, Superruhtf ProgramEnvironmental Protection Agency (3hs20) " " '841 Chestnut StreetPhiladelphia, PA 19107

Dear Mr. Schaul:

I am sending along the attached information, which I.received from a colleaguewho attended a seminar on remediation by monitored natural attenuation,presented by Dr. John Wilson of the USEPA Kerr research lab in Ada, Oklahoma.As the handouts from the seminar show, Dr. Wilson is using the Woodlawn site asan example of a natural attenuation remedy at an NPL landfill. Of particularinterest is the fact that Dr. Wilson has presumed that the landfill will be cappedwith a. permeable cap, not a RCRA-type barrier cap, as part of the naturalattenuation remedy, as a means to facilitate the natural, attenuation processesongoing at the site. " . - . - • .-_-_--......_-.,-_ -'- ---.-_=:—' ..-.-.-.- ..

I feel compelled to direct this information to you, as it shows that the USEPA'sown best scientific researchers believe that a permeable cap, and not themembrane cap, is the best solution for the Woodlawn site. Bridgestone/Firestoneis very concerned that, given the pressing time frame of the RA process atWoodlawn, we will be compelled to implement a remedy that is potentiallydetrimental to the beneficial natural processes that have been demonstrated to beprotecting human health and the environment Furthermore, the benefits of apermeable cap, consisting of either of our proposed ecological restoration projector engineered phyto-cover, are very important to the local human and ecologicalcommunities. These benefits include the following: , •

• Minimization of the risk of injury or death from traffic accidents, as well asnoise, dust and the inconvenience involving the many large trucks required tohaul fill materials into the site over the narrow, residential-lined roads near thesite.._Ihe_rislcof such-deaths from implementing the RCRA cap is in thesingle-digit ~percentage_ range,/far outweighing any risk from potentialexposure to .site-related chemicals.

AR3! 1882

Mr. Peter Schaul.May. 21, 1998 . ....

• Minimization of the ecological damage that would be created by a membranecap, by destroying the diverse old-field and young second-growth forestecology now thriving on the site.

• Maximization of the ecological value of "the site, through enhancement of thenatural resource base which supports the now-abundant wildlife seen on thesite. - . . " " _ . " . " . .

• Development of a community education center as proposed by the WildlifeHabitat Council (WHC), where local residents .and visitors (to this growingrecreational resource area) may learn about the ecology and waste disposalpractices, etc. to help promote responsible behavior. Bridgestone/Firestone iseager to implement these ideas in partnership with WHC and local and statestakeholders to maximize the value of this resource.

In addition to Dr. Wilson's notion that a permeable cap would be an.appropriateremedy at the Woodlawn site, we have received support for the concept from EPARegion III, includingyourself.. Bridgestone/Firestone would like to meet withyou to discuss the capping remedy, so that we can work together to create apathway through the regulatory process,~and achieve the best-suited solution forthe Woodlawn landfill site. . : . . ' . .

I will call to inquire as to when your schedule would accommodate a meeting. I ,appreciate your willingness to consider new approaches to site remediation, andlook forward to our meeting. -, . -

Sincerely,

Timothy A. BepitManager of Remediation Services

TAB:mwEnclosure,

AR:H 1883

Natural Attenuation ofChlorinated Solvents inGrounduiater

Training CourseWorkbookMarch 11-12. 1998 9King of Prussia, PR

o

www. biotreat state, pa. us

Prepared by the Industrial Members of the RTDFBioremediation Consortium

* INTERSTATE.gE-<COStua.OO Uiim

Oo

In Cooperation UUith the InterstateTechnology and RegulatoryCooperation ULJorking Group (ITRC)

PENNSTATE

Note.' This course has not been reviewed or endorsed by the U.S. Environmental Protection Agency

Tern Ridge, Governor - ...---,..——- ----- —— - - _ - - - -—; James'M. Seif, Secretory

• •• • . •.- -•• ...;:-•• — A R 3 I 188k "—————-

NATURAL ATTENUATION OFCHLORINATED SQL VENTS

Prepared by the Industrial Members of theRTDF Bioremediation Consortium

In Cooperation with ITRC

Note: This course has not been reviewed orendorsed by the USEPA

GOAL FOR THIS COURSE

Provide timely and accurate informationabout the technical aspects of

natural attenuation. .

Teach the use of screening tools forevaluating potential

natural-attenuation sites.

iA R 3 1 1885'

THE INDUSTRIAL MEMBERS OFTHE RTDF BIO CONSORTIUM

BeakDow

DuPontGEICI

NovartisZeneca

WHY WAS THIS COURSE DEVELOPED?

* A product of the RTDF/ITRC partnership* Regulators are the point in the system where

the QA/QC has to happen• Regulators need current information on NA• NA has real value as a remedy on some sites* This value could be lost if NA is permitted

on sites where it doesn't really make fit• As an information delivery method for ITRC

SR3I 1886

NATURAL ATTENUATION REMEDIES

• Natural attenuation should be evaluated withthe same-rigor as any other remedy

• Natural attenuation remedies must protecthuman health and the environment

• Natural attenuation is not a "walk-away"or do nothing remedy

* Natural attenuation is not a default or apresumptive remedy

PERFORMANCE MONITORINGPerformance monitoring is required ofall remediesAny monitoring scheme must be site specificin designFor natural-attenuation, monitoring shouldinclude key contaminants & NA parametersMonitoring can be a significant expense asit may last for a long time

flR3l 1887

WHAT YOU SHOULD LEARN - 1

• The scientific basis of natural attenuation* How to recognize natural attenuationpatterns

* What data to collect• How to interpret the data* How to present natural attenuation data• When natural attenuation is effective '

WHAT YOU SHOULD LEARN - 2

* Natural soil bacteria can biodegrade mostchlorinated solvents

* Anaerobic bacteria biodegrade highlychlorinated compounds

• Both anaerobic and aerobic bacteria canbiodegrade less chlorinated compounds

• Bacteria are responsible for most of thenatural attenuation of chlorinated solvents

A R 3 I 1888

THE THREE LINES OF EVIDENCE

-• Reduction in concentration along theflow path downgradient

* Documented loss of contaminant mass by• /chemical and geochemical data• biological decay rate data

* Microbiological laboratory datasupporting degradation and decay rates

WHY NATURAL 'ATTENUATION

• Because NA happens• Because NA is a destruction technique• Because NA happens in-situ* Because NA can be cost effective* Because NA can be a good remedy• Because NA is an important part of atreatment train

A R 3 I 1889

WHY NOT NATURAL ATTENUATION

* When a receptor is impacted• When a plume is clearly expanding• When the amount of attenuation is

insufficient• When cost/benefit ratio is HIGH

RECOMMENDED ANALYSES

• VOC's, speciate the DCE isomers• Methane, ethane, ethylene, propane• D.O.5redox• pH, conductivity, temperature* Inorganic ions: Fe, Mn, Cl, NO3,SO4, H2S, alkalinity

A R 3 I 1890

Data Interpretation Guidelines

KEY-DEFINITIONS - 1

Chlorinated solvent: A hydrocarbon inwhich one or more hydrogen atoms havebeen replaced by chlorine atoms. Thesewere commonly used for grease removal.Biodegradation: Biological conversionof one compound to another.

flR3l 189

KEY DEFINITIONS - 2

PCE - Tetrachlorotethylene C2C14TCE - Trichloroethylene C2HC13DCE - Dichloroethylene C2H2C12VC - Vinyl chloride C2R3ClCT - Carbon tetrachloride CC14CF - Chloroform CHC13DCM - Dichloromethane CH2C12TCA - 1,1,1 Trichloraethane C2H3cl3

REDUCTIVE DEHALOGENATION

PCE

TCE

cis-DCE

VC

ETH

8A R 3 I 1 8 9 2

DESCRIPTION OF ANALYTICAL PARAMETERSUSED TO ASSESS INTRINSIC BIOREMED1ATION

ParameterAlkalinity ,

p H - - - - - - - - - -

Temperature " ~

Dissolved oxygen ;

Redox potential

Sulfate '.' -..

Sulfide ' "

Methane

Ethane/ ethene

Total organic carbon(TOC) ___-•———---

Chloride . . . . . .

VOC/daughter products .

Iron (total, dissolved)

Nitrogen ' - .: , . 17.__

Nitrate

Nitrite

Phosphorus

DescriptionProvides an indication of the buffering capacity of thewater and the amount of carbon dioxide dissolved inthe water. Increases due to biodegradation of organiccompounds.Microbial activity tends to be reduced outside of a pHrange of 5 to 9, and. many anaerobic bacteria areparticularly sensitive to pH extremes.Affects rates of microbial metabolism. Slowerbiodegradation occurs at lower temperatures.Highest energy-yielding electron acceptor forbiodegradation of organic constituents. < 10 ppm.A measure "of the oxidation- reduction potential of theenvironment. Ranges from +500 mV for aerobicconditions to -3.QdmV for methanogenic conditions.Used as an electron acceptor in biodegradation oforganic constituents. Reduced to form sulfide.Microbially reduced form of suifaie. Indicates reducedconditionsIndicator of anaerobic conditions and of raethanogenicbacteria. Produced by the microbial reduction of carbondioxide. Solubility limit 25 to 40 'ppm.Metabolic end product of reductive dehaiogenation ofhalogenated ethenes and ethanes. - -A measure of the total concentration of organic materialin water that may be available for biologicaldegradation.May be useful as an. indication of biologicaldechloriroation and as a conservative tracer.Provides a measure of the type and quantity of parentand biogenic daughter products.A product of bacteria] iron reduction. Only the reducedform (ferrous) is soluble. The oxidized form (ferric) isused as an electron acceptor.An essential nutrient of microbial growth' andbiodegradation.Used as an electron acceptor. Consumed next afteroxygen.Product of nitrate reduction. Produced only underanaerobic conditions. Purely observed. .Essential nutrient for microbial growth andbiodegradation.

A R 3 I 1893

MULTIPLE DEGRADATION PATHSREDUCTIVE DIRECT

COMETABOLJSM DEHALOGENATiON OXIDATION

PCE

CO2 O^

CO2 < = cis-DCE =o CO5

CO2 <= VC => CO2

CO, <5= ETH ==> CO,

TRJCHLOROETHYLENE

H Cl\ /c = c\

ci ci

9AR3M89U

KEY DEHNmONS -

Aerobic: Environmental conditions whereoxygen i s present " ^ _ _ _ _ _ _Anaerobic; Environmental conditionswhere oxygen is absentAbiotic: A purely physical or chemicalreaction. Bacteria are not involved.

Etherx

cis-1.2-OicMoroethene

Trichloroethene

10f l R 3 J 1895

COURSE STRUCTURE8:00- 10:00 Introduction, background10:00- 11:30 Patterns and example sites

—•— 1:00 - 2:00 Evaluation & documentation2:00 - 5:00 Case studies

8:00 - 9:00 State perspectives9:00 - 10:00 Review, Rules of thumb

P. - 10:00 -12:00 Group exercise12:30 - 3:00 Independent site exercise3:00 - 4:00 State perspectives

DAY TWO EXERCISES

The exercises simulate real sitesYou will be asked to conduct naturalattenuation investigationsYou will gain site information in a waywhich simulates the normal processesWe will keep track of the time needed toreach a decision and the cost of yourinvestigations

11A R 3 I 1896

DEFINITION

The term "Natural Attenuation" refers tonaturally-occurring processes in soil and

groimdwa:ter enyironments that .act without humanintervention toTeduce the mass, toxicity, mobility,volume, or concentration of contaminants in those

media. These in-situ processes includebiodegradation, dispersion, dilution, adsorption,

volatilization, and chemical or biologicalstabilization or destruction of contaminants.

(OSWER, 1996.)

THE COST ISSUE

Some people view natural attenuationas a no action alternativeSome people view natural attenuationas very cheapThese impressions are mistaken.NaturaLattenuation remedies needlong-term ground water monitoringprograms which have a significant cost

12flR3i 1897

THE ECONOMICS OF N.A.

The incremental cost of evaluatingnatural attenuation is smallThis cost is more than offset if NAis chosen over a more costly remedyThe following estimate was done usinga template siteMethod was published in REMEDIATION

THE TEMPLATE SITE

ASSUMPTIONS:

PCE was releasedConcentrations around 10 ppm20 wells sampled twice a year for 30 yearsRI has been completedInflation rate 3%, discount rate 12%

13A R 3 I 1898

TECHNOLOGIES CONSIDERED

Pump-and-treat - air stripping withvapor-phase carbon _ _ „Natural attenuation .

ECONOMIC CONSIDERATIONS

• Investigation costs are similar regardlessof the remedy chosen

• Investigation costs are not included here• Getting natural attenuation data costs<$200 per well

• Only incremental costs are consideredin this economic analysis

14A R 3 I 1899

NATURAL ATTENUATION COSTS

CostElement

Up Front

Annual

PresentCost(30yrs)

Inv.&Long-TermMont Cost

S95.000

562,000

5800,000

N.A.RemedyCost

5135,000

568,000

5900,000

SimpleP&TCost

5650,000

5135,000

52,100,000

Incr. CostN.A. vs.Inv & Mon

$40,000

56,000

$100,000

Incr. CostP&T vs.

Inv & Mon

$555,000

573,000

$1,300,000

WHEN IS N.A. CONSIDERED?

* When it is protective* When clear proof of attenuation exists* When a source cannot be removed andlong-term treatment is needed

* When GW receptors are not affected• When alternatives pose higher risks• When the plume's future is understood

15flRSI 1900

WHAT CAN N.A. ACHIEVE?

* Aquifer restoration - ..._..... -..._.• Loss of mass• Reduction in concentration• Reduction in volume• Reduction in. toxicity•• Better-cost-effectiveness

HOW OFTEN IS KAV EFFECTIVE?

* Not enough experience yet to accuratelypredict for chlorinated solvents_L . . . . . _ . . . . . _ . . . . . . - - ' i - -- -- - - --'

• Wiedemeier and Wils'on predict 20% asa stand alone N. A, remedies

• We suggest that in a few years N.A. maybe part of a treatment train _at: another50% of sites. This is based onexisting biodegradation surveys

16AR3! 1901

TECHNICAL CHALLENGESASSOCIATED WITH SITESCONTAMINATED WITH

CHLORINATED SOLVENTS

KEY DEFINITIONS

LNAPL: LIGHT non-aqueous phaseliquid, for example gasoline. Thesefloat on waterDNAPL: DENSE non-aqueous phaseliquids, for example TCE. Thesesink through water.

17

LNAPL

Floatingif LNAPl

Groundwater Flow

DNAPL

Low Perned lrty LensGroundwater Flow

18flR3i 1903

Physical Properties Make DNAPLsDifficult to Locate, Remove or Treat

+ Denser than water

+ Almost insoluble in water

+ Can exist as vapor phase in vadoseor dissolved phase in groundwater

+ Can also exist as residuals, droplets,coatings or pools

Undesirable Properties of DNAPL4- Complex distribution controlled by geology:Where did it go??

+ Low solubility results in very long dissolutiontimes: P&T will be required for at leastthe same period of time

+ Slow desorption/diffusion out of geologicalmatrix: It takes longer to get out than ittook to get in

19A R 3 i 19014

Complications When Looking for DNAPL

Sometimes investigation (drilling) andtreatment techniques (dewatering coupled toSVE) can¥nfiahce the penetration ofDNAPLs deeper inSTthe subsurface

Example: drilling through a confining layerin a source area could allow DNAPL to draininto a deeper aquifer

How does the Presence of DNAPLAffect Site Remediation Strategy?____4 Proven technologies that can remediateDNAPL in groundwater are not available

4 Technologies such as P&T quickly reach thepoint of diminishing return for mass removal

+ A small residual mass can recontaminate alarge volume of groundwater

4 Remediation strategy should be long-term,cost-effective and protective of human healthand the environment

20A R 3 i 1905

PHYSICAL, CHEMICALAND BIOLOGICAL

ATTENUATION MECHANISMS

Physical Attenuation Mechanisms

. Dispersion

. Dilution

. Sorption• Volatilization» Barometric Pumping

flR3!I906

Dispersion

Definition: the spreading of a soluteoutward from its expected advectivepath, primarily due to mechanicalmixing.

DispersionImplications for Natural Attenuation:Chemicals will transport away from thesource area at a rate approximately equal tothe velocity of groundwater

Physical mixing and diffusion will causechemicals to spread out along the flow path(Le... plumes get wider)

79A R 3 I I 9 Q 7 z^

Dilution• Definition: A decrease in chemicalconcentration in a fluid

• Underlying process; fluid containingchemicals mixes with fluid containing lowconcentrations of chemicals or no-chemicals atall.

Dilution

Equation: Cfinal = C tiai <Fi/[Fi+Fd])where C is concentration, F is flow rate and i Iand d are the initial and diluting solutions

23A R 3 i 1908

Dilution

Implications for Natural Attenuation:Chemical concentration decreases along theflow path in a relationship dependent onsource size and concentration, and ongroundwater velocity

Sorption

Definition: general term to define theprocess of how chemicals attach (sorb)and detach (desorb) themselves to solidparticles in solution (soils)

flR3! 1909 24

SorptionUnderlying Processes: _Chemicals sorb because they dissolve intothe organic matter on soil, diffuse into thesoil matrix or are attracted by electricalcharge .. —.

Chemicals desorb because of diffusion alonga concentration gradient or displacement bya molecule with a higher affinity for the site

Sorption, Freundlich Isotherm

* x/m = k C 1/n , where:

x/m = solute sorbed / unit weight sqrbentk = constantC = concentration of solute remaining insolution

1/n = constant

25A R 3 I I 9 I O

Sorption, Freundlich Isotherm• Or in log form:

log (x/m) = log k + 1/n log C

This equation is of the general linear formY = mx + b

where: m = slope and b is the Y-intercept;and can be plotted as follows.

Sorption, Freundlich Isotherm

A R 3 I I 9

Sorption

• Implication on Natural Attenuation:

• Slows down transport of chemicals, in somecases causing immobilization

» Can decrease the local aqueousconcentration of toxic chemicals todegrading bacteria, and;

• Increase the retention time for reactions totake place.

Volatilization

* Definition: Mass transfer of dissolvedchemicals from a liquid phase to agaseous phase.

27flR3M9!2

Volatilization

Underlying process: All chemicals havea vapor pressure. A high vaporpressure, as many chlorinated VOC'shave, indicates a tendency to exist as agas

Volatilization

Implications for Natural Attenuation:Volatilization from GW into the vadosezone, and subsequent loss to the atmosphereleads to a gradual decrease in shallow GWconcentration.

Usually minor.

f l R 3 l 1 9 1 3 28

Barometric PumpingDefinition: vertical movement of soil gasin response to atmospheric pressure-L- .... _L ' _ ! _ . - _ . . - —-

fluctuations

Underlying process: airflows into and outof.the vadose zone as the barometricpressure increases and decreases,respectively

Barometric PumpingImplication on Natural Attenuation:Combined with normal volatilization, thisprocess can remove chemical mass from thesubsurface to the atmosphere where eitherdilution or chemical reaction with light willoccurThis process can significantly influencesubsurface vapor transport

90AR3I ^

Chemical Attenuation Mechanisms

* Hydrolysis

. Elimination

• Reductive Dehalogenation


. Hydrolysis: -R-C1 + H2O => ROH + HC1

» Example: 1,1,1-TCA => acetic acidCH3CC13 + 2H2O => CH3COOH + 3HC1

* 1,1,1 TCA reaction half life is 0.5 years

A R 3 I 1 9 1 5 30


. Elimination: -CCl-CH-,=>-C-C-+HC1

. Example: 1,1,1-tCA «=> 1,1=DCE

CH3CC13 f > CC12CH2 + HCI

• 1,1,1 TCA reaction half life is 2.5 years,but others are quite high


• Reductive Dehalogenation:

. RC1 + H+ + 2e" => RH + Cl"

. Example: CT => CE

CC14 + ET + 2e" => CHC13 + Cl"Reaction half life is > 40.5 years

A R 3 I 1 9 1 6

Summarv of Chemical Degradation Ratesv O

for Chlorinated Solvents

Compound____Half life (years) ProductsPCE >1,000,000TCE >1,000,0001,2-DCE ->1,000,0001,1,1-TCA 0.5 Acetate (80%).1,1,1-TCA 2.5 1,1-DCE (20%)1,1-DCA 61.31,1-DCE >1,000,000CT 40.5Chloroform 1800 CO, formic AcidDichloromethane 700 FormaldehydeChloromethane 1.0 MethanolChloroethane 0.2 Ethanol

Biological Attenuation Mechanisms

• Reductive Dechlorination orHalorespiration (anaerobic)

• Direct Mineralization (anaerobic oraerobic)

• Cometabolic degradation (aerobic)* Biological reactions are far faster thanabiotic reactions for most compounds

A R 3 I I 9 I 7 32

Microbiology 101

Ubiquity of Microorganisms

Bacterial Growth Requirements

Electron Donors and Acceptors

Electron Acceptor Processes

Chlorinated Solvent Pathways

Ubiquity of Microorganisms

• Microorganisms (bacteria) are everywhere• There are 105 107 bacteria in every gram

of soil• Bacteria can form resting stages (spores)that are viable for thousands of years

• Bacteria can survive in extremeenvironments: from -25° to 120° C, frompH<2topH> 12

flR3f 1918

Bacterial Growth Requirements

* Like all organisms bacteria need:

• Food a carbon/energy source* Energy an electron acceptor, Water• Shelter a surface (soil particles)

DEFINITIONS

Electron donor: A compound whichloses electrons during biodegradation.Usually a food source like organic matter.Electron acceptor: A compound whichgains electrons during biodegradation. Thisis oxygen for aerobic bacteria. Can be achlorinated solvent for anaerobic bacteria.

3 R 3 1 I 9 I 9

ELECTRON DONORS & ACCEPTORS

H2° crzO " 2 H+ + 2e- Donor(oxidized)

1/2 O2° + 2e: =O O" Acceptor_____________________ (reduced)

H2 +1/2O2 =c=^ H2O

Electroji Donors and Acceptors___

* Bacteria can use (eat and breath) electrondonors and electron acceptors that higherorganisms can not use.

• Bacteria "know" which electron donors andacceptors are the best for them (mostefficient) and therefore, have a preferredorder of use for each.

3R31 1920

Preferred Electron Donors/Acceptors

* Electron Donors: small, simple moleculeslike sugars, organic acids, alcohols, alkanes,aromatics; man-made organic compounds,and natural organic carbon can be used.

. Electron Acceptors: Oxygen, nitrate,'Mn(IV), Fe(III), sulfate, CO2, andchlorinated solvents.

Processes in Groundwater - 1____

* In clean ground water there is usually enoughoxygen that electron donors (food) is thefactor which limits bacterial growth

» Most bacteria can use several electron donors

• The result is a continual "battle" over food(available electron donor)

3 1 1 9 2 1 36

Processes in Groundwater - 2_____» Most bacteria can use only one or twoelectron acceptors.

. Strictly aerobic bacteria can only use oxygen.Strictly anaerobic bacteria (methanogens)can use only use CO2. Oxygen kills them*

* Some bacteria can use both oxygen andnitrate, some can use both nitrate and iron,some use iron and sulfate, some can use CO2.

Processes in Groundwater - 3

• After a chemical release to the subsurface,there is an excess of electron donor in theimmediate vicinity and electron acceptorsbecome the limiting factor.

• The sequential nature of electron acceptor useresults in "layers" of specific electron acceptoractivity; from aerobic activity on the outside tomethanogenic activity in the center

37AR3M922

Aerobic Respiration

. C6H6 + 7.5 O2 => 6 CO2 + 3 H2O

» Electron acceptor : electron donor ratio 3.1 : 1

* Solubility of oxygen in water is ~ 10 mg/L;sufficient to degrade 3.2 mg of electron donor

Nitrate Reduction

. CH + 6 NO => 6 CO + 6 HO + 3 N66 3- 2 2 2

* Electron acceptor : electron donor ratio 4.8 : 1

» Solubility of nitrate almost unlimited in water;natural groundwater nitrate concentrationsrange from <1 to 10 mg/L, enough to degrade 1-2 mg/L of electron donor. Groundwater nitrateconcentrations are often higher due toanthropogenic inputs such as fertilizers.

U R 3 I I 9 2 3

Iron Reduction. C6H6 + 30 Fe (OH)3 + 60 H+ =>6CO2 + 30Fe+2+78 H2O

* Electron acceptor : electron donor ratio 41 : 1

• Solubility of Fe(IH) compounds is low; normalmeasured groundwater Ee(III) concentrationsare <1 mg/L, enough to degrade «1 mg/L ofelectron donor. However, an almost unlimitedsupply may be available in aquifer material.

Sulfate Reduction

C6H6 + 3.75 SO4-2 + 7.5 H+ =>6 CO2 + 3.75 H2S + 3 H2O

Electron acceptor : electron donor ratio 4.6 : 1

Solubility of sulfate usually limited to 100 ppmby CaSO4; natural groundwater sulfateconcentrations are usually > 5 mg/L, enough todegrade > 1 mg/L of electron donor. Sulfatemay be higher higher due to human inputs.

39

Methanogenesis

• Methanogenesis is a very complex processcarried out by a consortia of microorganisms

. 3H2 + CO2 => CH4 +1/2 H2O» This is the basic reaction with CO? as the

£f

electron acceptor. The reaction on the nextslide is balanced for carbon to demonstratethe stoichiometry with benzene as was donefor the previous reactions

Methanogenesis

. QH6 +4.5 H2O => 2.25 CO2 + 3.75 CH4

* Electron acceptor : electron donor ratio 1:1

. Supply of CO2 is unlimited; however, onlyspecific electron donors can supply energy forthis reaction and specific conditions arerequired. Solubility of methane is ~ 40 mg/L

A R 3 I 1925 40

Electron Acceptor Pool in Groundwater

Electron Range of Concentrations Amount of ElectronAcceptor Observed in Groundwater Donor DegradedOxygen "l'^.~"_";"? . ;'0-:iOmg/L "." " ""." " "~0-3.2mg/L

Nitrate " " """ " "1T >.5(Xmg/lT ~. : " : 0-10 mg/L

Fe(Iir)/Fe(II) 0 - > 300'mg/L":" '"" """~0"-"7".S"mg/L

Sulfate 0 -:>1000 mg/L ... 0: --200 mg/L

CO, (CHJ ' " ""15 -V>20 mg/L ;" " "0 - 20'mg/L -

TOTAL - - - 0--240 mg/L

Overview of Chlorinated SolventBiodegradation: Pathways

• Reductive dechlorination (anaerobic)

» Direct anaerobic degradation

• Direct aerobic degradation

• Cometabolic degradation (aerobic)

. Others?

f l R 3 l 1926

Chlorinated Solvent BiodegradationPROCESS PCE TCE c-DCE VC TCA DCA C"T CF DCM

Direct Aerobic N N Y&N Y S N N N Y

Cometabollc with CH. N Y Y Y YiN N* N Y NR

Cometabolic with toluene NY Y Y N N- N Y&N NR

Coraetabollc with NH." NY Y Y Y N* N Y NR

Direct Anaerobic N N N Y N S N N Y

Anaerobic/Denitrfficaticn Y&N Y&N N* N* N* N* Y Y&N NR

Anaerobic/Salfate reduction Y Y V Y Y Y Y Y NR

An*erobic/Metninogenlc Y Y Y Y Y Y Y Y NR

N: Not documented in the literatureY: Documented in the literature many times: concensus opinionY&N; Documented in the literature more tftan once of both occurrence and absenceN *; Not documented in the literature to date, but not investigated significantlyNR: Process nia> occur but Not Relevant since competing process occurs more rapidlv

Observed Laboratory and FieldBiodegradation Rates___________

A large compilation of biodegradation rateconstants with references is in Appendix C ofthe AFCEE Technical Protocol.

That table is organized by compound andindicates if data is from the field or frommicrocosms, but usually does not describe thespecific microbiological process

A R 3 I 1927 42

What is a Biodegradation Rate Constant?

* C = Coe~kt, where k is the rate constant

• Biodegradation rate constants are expressedin (day1) and look like 0.0019.............

* Biodegradation rates can also be expressedin "half-lives" in days or years

What Does a Half-Life Mean?

* Period of time required to reduce theconcentration by 50%

• Half-lives of one to two years are common;this may seem long but.....

* A one year half-life would reduce 10,000 ug/1to < 5 ug/I (MCL for PCE, TCE) in 11 years

43AR3! 1928 ^

Converting Biodegradation RateConstants to Half-lives________

* If you solve the equation C = C0e~kt, for kand t when C = 0.5C0 than t = -0.693/k wheret is half-life in days and k is the rate constant

. The k value of 0.0019 = a half-life of 365days or 1 year

Reductive Dechlorination

Bacteria substitute the chlorinatedcompound for a normal electron acceptorand replace a chlorine molecule with ahydrogen (halorespiration).Initially, it was believed that bacteria couldnot benefit from this reaction. However,more recent information shows that bacteriacan get energy for metabolism and growthby halorespiration.

44AR3M929 ^

Reductive Dechlorination

• Identical to the abiotic mechanism.

• Reductive Dechlorination:

RC1 + H+ + 2e~ => RH t Cl"

• Example: CT => CF

CC14 + H* + 2e" => CHCI3 + CI"

flR3i!930

TCE REDUCTIVE DEHALOGENATION

• TCE is reduced to cis-1,2 DCE :* Note that there are three isomers of DCE• Biological DCE is almost 100% cis-1,2 DCE• Manufactured DCE is mostly 1,1 DCE,

it contains only 10% to 20% cis-1,2 DCE* This contrast makes it easy to spot

biological production of DCE from TCE

Trichbroethane

1,1-Kdibreeftane Shaie

Q Rapid; may occur under aJ anaerobic condttons

A R 3 I I 9 3

Carbc

0 a0 si0 s0 Si

fiTetrachJoride

1

r~r (merjiyfenechfcrtle)

y A• V Triciiloromethane L—W Q^^ (chloroform) ^

r— Methane

Ttfomethane

^ipcl; occurs under aB anaerobic conditions

oisef; sffil msy occur underallanagiobic cortdftions

owest; may occur under nEthanogenic corefitionsonty.otfconipelEd by cfiiect degradation

raest; m occur under nEtfjanogeiac contSttms ortf, cuteomjjeted by diffici degradation

Range of Observed!FieldRates forBiological Reductive DechlorinationCompound ZIlFleld* half JJifeTdavs) ______sPCE 58 tp3«£ormoreTCE .., -: "-- I '--=$£ to 365 or more1 -DCE 3 to 365 or moreVC ~3S to 365 or more1,1,1-TCA NA to 300 or more1»2-DCA 300 to 365 or more1,1-DCE NA _CT ----- -- 0>5 to 365 or moreChloroform NA to 350DichJoromethane NRChloromethane NR*FieId rates are calculated from geld data and microcosms receiving no electron donorNA Not Available, usually because the process has not been investigated significantlyNR Not Relevant, direct degradation processes predominate

A R 3 I I 9 3 2

Direct Anaerobic Biodegradation

• Anaerobic bacteria "grow" on thecompound by using it as their carbon andenergy source (electron donor).

• Process may be rapid, compound usuallydegraded to CO2, other products may beformed as intermediates.

Direct Anaerobic Biodegradation___

* DCM: Rapid, leading to the production ofquantitative amounts of acetic acid (.42moles/mole of DCM) and hydrogen(1991)

» VC: Rapid, known to occur with Fe (III) asthe electron acceptor (1996); other electronacceptors not investigated but suspected

• Ethene: Suspected to occur with Fe (III) also;possibly more rapid than VC (1997)

flR3l 1933 48

Range of Observed Field Rates forDirect Anaerobic BiodegradationCompound .. _—-..Field* Half life (days)____. .PCE :~TNot DocumentedTCE --Not Documented1,2-DCE ~.~"""~ __ Not Documentedvc /:;:/-:,-,-:-— ""7 125" . '•"..........1,1,1-TCA Not Documented1,2-DCA ~ " "Not Documented1,1-DCE ______ Not DocumentedCT '~~Nbt DocumentedChloroform ot DocumentedDichloromethane 3.1-400Chloromethane NA* Reld rates are calculated from field data and microcosms receiving no additionsNA Not Available, process has not been investigated significantly?? t/pper limits often not measured

Direct Aerobic Biodegradation____

• Aerobic bacteria "grow" on the compoundby using it as their carbon and energysource (electron donor).

• Process is rapid, compound almost alwaysdegraded to CO2, degradation intermediatesmay be formed.

49AR3M93U

Direct Aerobic Biodegradation

. DCM: Very rapid, oxidized to CO2 (1981)

. VC: Very rapid, oxidized to CO2 (1985)

. 1,2-DCA: Oxidized to CO2, viachloroethanol and chloroacetic acid (1985)

* DCE: Oxidized to CO2, (1997)

Range of Observed Field Rates forDirect Aerobic Biodegradation ___...Compound_______Field* half-life fdavs)________PCE Not DocumentedTCE Not Documented1,2-DCE - 400VC 2.9-> 300UUI-TCA Not DocumentedK2-DCA 170->3651,1-DCE NACT Not DocumentedChloroform Not DocumentedDichloro methane NAChloromethaue NA*Rates calculated from field data and microcosms receiving no additionsNA Not Available, process has not been investigated significantly ID tbe field?? Upper limits often not measured

A R 3 I 1935 50

Cometabolic Degradation

• A fortuitous aerobic reaction carried out byenzymes designed to metabolize a differentcompound the bacteria normally grows on.

• Bacteria are presumed to gain nothing fromthe reaction and in fact, may be harmed byintermediates that are formed

Cometabolic BiodegradationCompounds documented in the literaturesupporting aerobic Cometabolic reactions:

- methane (1985), other short-chained alkaneslike ethane, propane (1988),

- simple aromatic ring compounds: toluene,phenol (1986)

-NH4+(1989)

flR3i 1936

Cometabolic Biodegradation

Mechanism for ethenes is epoxidation:

A-C - C- => -C - C- => CO2, other products

Example: TCE

ACI2-C=C-C1 => CI2-C-C-C1 => CO2, (smallamounts of C12-C-COOH, dichloroaceticacid)

Cometabolic DegradationCometabolic reactions vary in rate: methaneoxidizing bacteria degrade VC faster than TCE.Toluene oxidizing bacteria degrade TCE and DCEas fast or faster than VC.

Cometabolic reactions have specificity: methanesupports degradation of chlorinated ethenes,methanes, and possibly ethanes; toluene maysupport the degradation of chlorinated ethenesonly (but possibly CF as well).

A R 3 I I 9 3 7 52 _

Range of Observed. Field Rates forCometabQlic BiodegradationCompound Field* .half=life.(davs>_________PCE Not DocumentedTCE- _.;.-_: 1.1-4" ;1.2-DCE — —— 1.1-2--vc --..::: . ' ;i:i-?? ' *"~ ':'.-:."U.l-TCA NA1,2-DCA •" : "- NA""~ " •1.1-DCE - 2-??" ; . -,CT ~~ """•-——- Not DocumentedChloroform NADichforometbaoe NAChlorometbane NA*Rates calculated from field data, but all received methane or toluene additionNA Not Available, process has not been investigated?? Upper limits often not measured

Chlorinated Solvent BiodegradationPROCESS -~ _ PCE TCE c-DCE VC TCA DCA CT CF DCM

Direct Aerobic N N Y&N Y N N N N Y

Cometabolic with CH< NY Y Y Y&N N* NY NR

Cometabolic with toluene N " Y Y Y N N* " N Y&N NR

Cometabolic with NH/ NY Y Y Y N* N Y NR

Direct Anaertibic N N N Y N N N N Y

Anaerobic/Denitrification Y&N Y&N N* N* N* N* Y Y&N NR

AnaerobicySulfate reductioo Y Y Y Y. Y Y Y Y NR

Anaerobic/Methanogenic Y Y YYY Y Y Y NR

N: Not documented in the literatureY: Documented in the literature many times; concensus opinionY&N: Documented in the literature more than once of both occurrence and absenceN*: Not documented in the literature to date* but not investigated significantlyNR: Process may occur but Not Relevant since competing process occurs more rapidly

flR3M938

PATTERNS OF NATURALATTENUATION

Patterns of Natural Attenuation

• Physical Processes alone

• Anaerobic conditions

• Sequential Anaerobic.- Aerobic conditions

• Sequential Anaerobic - Anaerobic conditions

• Aerobic or Cometabolic conditions

54R3-! 1939

Natural Attenuation by PhysicalProcesses Alone

Major process: Dispersion/DilutionWhat you would observe:CVOC concentrations decline in a patternconsistent with transport processes alone

Measurements for most field and inorganicparameters do not change significantlyalong the flowpath. Minor depletion ofoxygen and ORP may occur in source area.

Physical Attenuation: Map View ofCVOCs

55flR3l

Physical Attenuation: Cross Section ofCVOCs and Redox

Physical Attenuation: Map View ofChloride, Redox

56( 3 R 3 I I 9 U I

Physical Attenuation: Cross Section ofChloride, Redox

' ll*-;WA"e& -K ££3 -ixc>i.. ^ ^ . n ^ ) , . fy--Ar :sr: Jv ^ att &• t 7 • a-rw:—r.«c»-t*~.. •;*«, «v* 3? ar«ngwe

.Av-.-S(Si1. J-iV^>«B?.'*j£aKst-Si« pM

Case Studies: Natural Attenuation duePrimarUy to Physical Processes

• EPA Region IX conducted a search of RODScompleted through mid-1994 using keywords"natural attenuation", "intrinsicbioremediation" and "intrinsic remediation".Natural Attenuation was chosen as at least aportion of the remedy for groundwater at 35sites (Hagemann and Gill, 1996).

A R 3 I 191*2

Case Studies: Natural Attenuation duePrimarily to Physical Processes

Of those 35 sites, 18 sites contained PCE,TCE, DCE, VC, TCA or DCA as at least oneof the major contaminants of concern.Natural Attenuation is occuring at those sitesthrough biological, chemical and physicalprocesses. Recurring characteristics at manyof the sites indicated physical processes arelikely the primary removal mechanism.


• Recurring site characteristics:Often course-grained sand and gravel,shallow, groundwater flow and surfacewater infiltration are probably high(dilution),

Sites were often over shallow fracturedbedrock systems where measures such asP&T might be impracticable.

58fiR3119^3


• Recurring site characteristics:

Parent compounds (PCE, TCE)predominate, indicating biological activityis low.

Sites were usually small and solventconcentrations were often low (< 200 ppb).Dilution may be a major removalmechanism.



Natural Attenuation was often part of a"treatment train" and was applied only tothe downgradient or offsite portion of theplume.

Additional remedial measures (P&T, SVEsystems) were applied in source area only.

59flR3l



Receptors were often far away.

If receptors were close by, they were oftensmall non-use streams or wetlands(dilution). Drinking water wells were dealtwith through institutional controls(supplied water).

Natural Attenuation underAnaerobic Conditions

Major process: anaerobic biodegradation

NA under anaerobic conditions will mostlikely occur at sites where a highconcentration of natural or anthropogeniccarbon (electron donor) is present

60

Natural Attenuation underAnaerobic Conditions

What you would observe:Concentration of the highly chlorinated VOCs(PCE/TCE) decline rapidly in the source area,DCE, VC and usually ethene appearTotal depletion of oxygen, nitrate, sulfate? in thesource area and downgradient; appearance ofFe+2, methane, acetate, possibly sulfide, presence ofhigh organic carbon (TOC, DOC)

Etherw

61A R 3 I I9U6

Anaerpbip Site: IS ag View ofCyOC's;Ethene/and Redox

Anaerobic Site: Cross Section ofCVQC's, Ethene, Redox

62flR3"H9U7

Anaerobic Site: Map View of Organic andInorganic Parameters

^ i ^ ^ v;^ 5( ff!fe& £ r-;

Anaerobic Site: Cross Section of Organicand Inorganic Parameters

633 R 3 I 191^8

Case Studies: Natural Attenuationunder Anaerobic Conditions

__________________________________________^- *• *S .'

St. Joseph, Michigan Superfund Site

Manufacturing Facility, Auburn, NY

Auburn, NY, Site Background

Former Electronics Manufacturing Facility

Glacial till overburden ~ 15 ft thick over veryfractured bedrock. GW shallow with largeseasonal variability, groundwater dividebeneath site; flow toward the NW and NE

TCE, acetone and methanol disposed inunlined evaporation pits and burned in theearly to mid 1960's, TCE concentrationsindicate DNAPL present

64f l R 3 l

Auburn - TCE

Auburn - Acetone

<!0 <IO

0

**»• U -lV..Z23PtrtongLot

>*> Sufefng

I

Dse ico™ • <io

PartmgLot

/rrf l R 3 I 1 9 5 0

Auburn - Cis-DCE

Auburn - Vinyl Chloride

PartangLoto 'so idem ••?!('.-

66A R 3 I 195!

Auburn - Ethene

Auburn - Acetic Acid

0 so toom

A R 3 I 1952

Auburn - Sulphate

•44.0 ,•740

Auburn - Methane

X T ^1OU

Parking Lot

) so icon

-sr-• • Veuiking ' '

i" . . ~ "n.n*

Partong- Lot.

3R3I!953

Auburn ConclusionsAnaerobic processes conducive to reductivedechlorination (methanogenesis, sulfatereduction) predominate across the site

Expected reductive dechlorination daughterproducts of TCE are present (cis-DCE, VC )as well as ethene (up to 17 mg/I)

Anaerobic processes appear to be driven byacetone and methanol

Natural Attenuation under SequentialAnaerobic - Aerobic Conditions

• Major process: Biodegradation

> Natural Attenuation under sequentialconditions is most frequently observed atsites where regional groundwater isaerobic, but a high concentration ofanthropogenic carbon (electron donor) hasbeen introduced in the source area.

694R3f195V

Natural Attenuation under SequentialAnaerobic -Aerobic Conditions___

• What you would observe:• Concentration of highly chlorinated VOCs(e.g. TCE) declines in .source area; DCE, VC,possibly ethene appear; VC and ethenedisappear downgradient

• Depletion of oxygen, nitrate in source area,presence of other COCs, appearance ofmethane, Fe4"2, acetate; oxygen reappears andmethane disappears downgradient.

Sequential Anaerobic - Aerobic Site: MapView of CVOCs, Ethene and Redox

70AR3.I 1955

Sequential Anaerobic - Aerobic Site: CrossSection of CVOCs, Ethene and Redoxi gfZ ^

Sequential Anaerobic - Aerobic Site: MapView of Inorganic and Organic Parameters

4 R 3 I 1956

Sequential Anaerobic - Aerobic Site: CrossSection of Inorganic and Organic Parameters

" ' T ' l ~ l ~ ~ ~ " ' " "

lf S f 1 8 ^ ^ 0 ?tei®l*S p

72aR3i!957

Case Studies: Natural Attenuation underSequential Anaerobic-Aerobic Conditions

Dover Air Force Base, Delaware

Manufacturing Facility, Sacramento, CA

Sacramento, CA. Site Background___

+ Former septage lagoon at industrial facility

•#• Multilayer aquifer of unconsolidated alluvialsediments and dredged materials, currentdepth to groundwater is 50 ft, but historicallyas high as 30 ft. GW flow to the NW.

+ TCE, TCA, CF disposed from 1960*s to 1979;lagoon was filled in but a septage sludge layerremains at depths of 25 - 30 ft-

73A R 3 I 1 9 5 8

Sacramento: TCE

Sacramento: cis-DCE

74flR3l I95'9

Sacramento: Vinyl Chloride

Sacramento: Ethene

75flR3M960

Sacramento: Dissolved Oxvgen" V- '-* A'' V CT

Sacramento: Redox

76flR3l 1961

Sacramento: Nitrate

Sacramento: Methane

77962

Sacramento Conclusions

+ Anaerobic process conducive to reductivedechlorination (methanogenesis)predominates in the source area

4- Expected reductive dechlorination daughterproducts of TCE, TCA and CF are present(cis-DCE, VC, 1,1-DCA, CA and DCM) aswell as ethene and ethane

Anaerobic processes are driven by septage

Sacramento Conclusions

Aerobic conditions predominate more than500 m downgradient of the source area

Chlorinated daughter products known todegrade under aerobic conditions (VC, CA,DCM, ethene, ethane) disappear

Chlorinated daughter products whichdegrade slowly under aerobic conditions(cis-DCE, 1,1-DCA) persist

78A R 3 I 1963

Natural Attenuation under SequentialAnaerobic - Anaerobic Conditions___

+ Major process: Biodegradation

+ Natural Attenuation under sequentialconditions is observed at sites where a highconcentration of anthropogenic carbon(electron donor) has been introduced in thesource area, or where groundwater isnaturally reduced.

Natural Attenuation under SequentialAnaerobic - Anaerobic Conditions____+ What you would observe:4 Concentration of highly chlorinated VOCs(e.g. TCE) declines in source area; DCE, VC,possibly ethene appear; VC and ethenedisappear downgradient

+ Depletion of oxygen, nitrate in source area,presence of other COCs, appearance ofmethane, Fe*2, acetate; reduced conditionscontinue to exist downgradient.

79A R 3 I

Sequential anaerobic-anaerobic siteIVfa vi PW

Sequential anaerobic-anaerobic siteCross-section view of CVOC's, ethene, redox

80f l R 3 i 1 9 6 5

Sequential Anaerobic - Anaerobic Site; MapView of Inorganic and Organic Parameters

Dow[nqradiCTit®

Sequential Anaerobic - Anaerobic Site: CrossSection of Inorganic and Organic Parameters

81311966

Plattsburgh" AFB

Plattsburgh AFB

82AR3-I 1967

Plattsburgh AFB

GROUNDWATERELEVATION MAP

MAY 1995

Plattsbursh AFB

83A R 3 I I968

Site Hydrogeology - Plattsburgh AFB~ 'i $ ' ~~-

i. ? ' ,.4 t • ' '• Aquifer = Well-sorted fine to mediumsand

• Hydraulic Conductivity = 12 ft/day• Gradient = 0.01 ft/ft• Effective Porosity = 0.30 (assumed)• Ground water Velocity = 145 ft/year

Plattsburg AFBHydrogeologic Section A-A'

A A*Northwest is Southeast

140 -

HORC 0 300 600 ISO)0 3MMC!

VERT 0 IS 30

84flR3H969

Plattsburg AFB

Plume ClassificationStrongly Reducing/thanogenic Conditions

Iron HI ReducingConditions

Plattsburgh AFB

Extent of Chlorinated Solvents & BTEX9.

1Q.OOO-25,000 (let1,000-10.000 pg/l.NO-1,000 iig/l

85AR3II970

PLATTSBURG AFB

Plot of TCE, DCE, VC, and Etheneversus Distance Downgradient

500 1000 1500 2000 2500 3000 3SCO

Distance From Source (feet)

Methanogenic Environment atPlattsburgh AFB

Occurs near sourceCo-mingled BTEX and chlorinated solventsStrongly reducing conditions- Oxygen = 0.1 mg/L (Background = 10 mg/L)- Nitrate = 0.1 mg/L (Background = 10 mg/L)- Iron (II) = 15 mg/L (Background < 0.05 mg/L)- Suifate < 0.05 mg/L (Background = 25 mg/L)- Methane = 3.5 mg/L (Background < 0.001 mg/L)- Hydrogen > 11 nM/L (Background < 0.01 nM)

86f l R 3 l I 9 7 I

Methanogenic Environment atPlattsburgh AFB

TCE, DCE and VC being reductively dechlorinatedVC and Ethene are accumulating(slower kinetics under reducing conditions)Biodegradation rates (as half life)

- TCE = 0.55 year- DCE = 0.87 year- VC = 3.47 year

Iron-Reducing Environment atPlattsburgh AFB

Occurs downgradient from sourceBTEX depleted (nothing to drive dechiorination)iron (III) reducing conditions- Oxygen = 0.1 mg/L (Background = 10 mg/L)- Nitrate = 10 mg/L (Background = 10 mg/L)- Iron (II) < 0.05 mg/L (Background < 0.05 mg/L)- Suifate = 15 mg/L (Background =_25 mg/L)- Methane = 0.12 mg/L (Background < 0.001 mg/L)- Hydrogen = 0.5 nM/L (Background < 0.01 nM/L)

87A R 3 I I972

Transition From Metfyanogenesis toIron Reduction "..._."...

• TCE and DCE biodegradation rates decrease

• Vinyl chloride biodegradation rate increases

• Vinyl chloride accumulation stops

• Ethene accumulation stops

• Hydrogen concentrations decrease

Iron Reduction at Plattsburgh AFB

DCE - no longer biodegrading

VC and Ethene no longer accumulating(VC likely being oxidized to CO2 + H2O)

Biodegradation rates (as half life)

- DCE = 9.9 years- VC = 1.4 years

884R'3II973

Contaminant Data - Plattsburgh AFB

Point Distance 1MB Chloride BTEX TCE DCE VC Ethene(ft) (....„..„.__.„

A 0 1757 63 16,790 25,280 52,415 0 0

B 970 491 48 3,060 2 14,930 897 35

C 1240 488 46 3,543 3 10,030 1430 182

D 2560 0 20 40 24 2,218 8 0

Geochemical Data - Plattsburgh AFB

Point Distance Oxygen Nitrate Iron (II) Sulfate Methane H2(ft) (,„„..——..——mg/L ———————) (pg/L) (nM)

A 0 0.1 0.18 4 5.51 1420 6.7

B 970 0.5 0.20 15.3 0 305. 1.7

C 1240 0.4 0.17 13.8 0 1010 11.1

D 2560 0.9 0.29 0.7 0.52 3530 0.81

89

Biodegradation Rates - Plattsburgh AFB

Compound Correction A-B B-C C - DMethod 0-970 ft 970-1240 ft 1240-2560 ft

(Half Life) (Half Life) (Haif Life)

TCE Chloride 0.55 5.33TMB 0.58 1.33 ---

DCE Chloride 11.5 1.15 9.9TMB N/A 0.77

VC Chloride N/A 4.95 1.47TMB N/A 1.61

BTEX Chloride 5.33. 2.31 1.78TMB 11.5 1.15

Plattsburg AFB Conclusions

Geochemistry in the source area is significantlydifferent from the geochemistry downgradientThe piume is methanogenic near its sourceThe plume is iron reducing downgradient fromthe sourceReductive dehalogenation of solvents near thesource with oxidation occurring downgradientNo ROD has yet been issued

90f l R 3 l I975

NATURAL ATTENUATIONUNDER AEROBIC CONDITIONS

Natural Attenuation under Aerobic Conditions

* Majorprocess: Biodegradation+ NA under aerobic conditions will occur at siteswhere regional groundwater is aerobic, solventconcentrations are low and solvents are primarilythose which degrade directly (DCE, VC, DCM,CM, CB)

+ Appropriate cometabolites are present atsufficient concentration to degrade all CVOCspresent (rare case)

91flR3i 1976

Natural Attenuation under Aerobic Conditions

4- What you would observe:+ Concentration of directly degradable CVOCs (orcometabolites) decline immediatelydowngradient of source area at a rate greaterthan predicted by transport processes alone

+ Partial depletion of oxygen in the source areaand downgradient, eventually returning to nearbackground levels, increase in chloridedowngradient

Aerobic Site: Map View of VOCs and Redox

92A R 3 I 1977

Aerobic Site: Cross Section of VOCs and Redox

- ^ > ..r*.^.....,... ., ... ..... ., .... . .

Aerobic Site: Map View of Inorganic Parameters

Cnionoe£ll ~>i'- -t. "'• T SS f— Tnr •*•„

93flR3i)978

Aerobic Site: Cross Section ofInorganic Parameters

Background Source • ;.<•; Downgradient;—— Distances"Direction of Groundwater Flow

IntroductionKey aspects of a successful case study arepresented for a chemical manufacturing sitein Mississippi with a vinyl chloride (VC)ground water plume.

94A R 3 I 1979

HydrogeologyThe aquifer is composed of fine and very fine-grained sands and clay of fluvial origin.The base of aquifer is defined by clay layer thatlies approximately 20 feet below ground surface.The aquifer is semi-confined.Local ground water flow is radial. Velocity isestimated to be 90 feet per year.

Eotentiometric Surface Map

95R3J 1980

VC Concentrations through time

Six years of ground water data wereavailable to characterize the site.Maximum VC concentration in ground..water decreased by 98% from 1990 to 1995Maximum concentration declined from3,250 ppb in 1990 to 76 ppb in 1996The plume is detached from its source area.

1992 VC Isoconcentration Map

Based on Wells and CPTData

VC Concentrations in ppb

96A R 3 I I 9 8 I

1995 VC Isoconcentration Map

VC Concentrationsin ppb

VC Concentration in MW-7

3250 * 3250

Time

97T'fiR3J 1982

MW-7 Half Life PlotiQOOO

, 1, = -,«.. ,t-1 6247x1000

' 0.8057

tool \ \ : : , : , Half Life --0.693/K

0.00 1.00 2.00. 3,00 4.00 5.00 6.00

S '° '\7sA -0.693/-I.625\ /\\ 0.426 year -

or 156 days

Biodegradation Rate Estimation

A half life of 156 days fits the wellMW-7 data best.

A conservative VC biodegradation half lifeof 400 days (1.1 years) was used forground water modeling purposes.

98f l R 3 l l 9 8 3

Year 2000 Modeled VC Concentrations

VC Concentrationsin ppb

Geochemical AnalysesGround water: samples were collected in1994 and 1995 and analyzed for thefollowing.* Nitrate * Ammonia* Sulfate * Sulfide* Total iron * D.O.* Redox * pH* Temperature * Conductivity* Metabolic gasses

99

Schematic Cross-Section

Geochemistry Summary

Dissolved oxygen is present but lowDissolved iron is absentSulfate is present at backgroundconcentrations throughout the siteRedox does not go low enough toallow reductive dechlorination of VC

100flR3l 1985

Conclusions

A maximum VC biodegradation rate of 400days (1.1 years) was estimated. (200 daysis more probable) .Biodegradation appears to be aerobic.VC biodegradation should increase withoxygen replenishment.Intrinsic degradation is shrinking the plume.

Site SummaryMaximum VC concentrations in groundwater have decreased by over 99%Modeling indicates attainment of 2.0 ug/Lobjective by the year 2006.Natural attenuation was proposed by the RP.Regulatory approval has been given andlong term monitoring has begun.

101flR3l 1986

Case Study: Natural Attenuation underAerobic Conditions

Woodlawn Landfill, Cecil County Maryland

Woodlawn Landfill Cecil County, Maryland

VC degradation:WHY IS IT HAPPENING?

* Aerobic Oxidation (most rapid)» 2O2 + CH2 = CHC1 » 2CO2 + 3H+ + Cl~

• Anoxic Oxidation10Fe3+ + CH2 = CHCI «• 4H2O »

2CO2 + 11H* + Cl- * 10Fe2*

* Volatilization• Sorption (very low for vinyl chloride)

102f l R 3 l 1 9 8 7

Woodlawn Landfill, Geologic Cross SectionDecomposed rock (saprolite)ff ' :--> -:- -j————Watertable

Fracturedcry'stallinerock - __ .

Not to scale

Occurrence of ground water in the Piedmont

Woodlawn Landfill, Geologic Cross Section

souro _ Fill

fSand*Gravel RH

Saprolite

^ Granitic m._ .. „Gneiss Metadionte Granitic

Gneiss0 ISO 2«OfT. i

103A R 3 I I 9 8 8

Woodlawn Landfill, Water Levels

Observed Water LevelsMarch 1996

Woodlawn Landfill, VC in Saprolite, 1987

• > 500 ppbD> 100 ppb• >20ppb• >1 ppb

Observed Vinyl Chloride Concentrationo 2so «oo /y in the Saprolite

November 1987

104f l R 3 l 1 9 8 9

Woodlawn Landfill, VC in Saprolite, 1996

• > 500 ppbn> 100 ppbB > 20 ppba > 1 ppb

Observed Vinyl Chloride Concentrationin the SaproliteMarch 1996

Woodlawn Landfill, VC in Bedrock, 1990

• > 500 ppbD > 100 ppb• > 20 ppbB > 1 ppb

Observed Vinyl Chloride Concentrationin the BedrockNovember 1990

105AR3N990

Woodlawn Landfill, VC in Bedrock, 1996

Approximate Property/ ""Boundwy

' V Sr- \m > 500 ppbn > 100 ppb• > 20 ppbD > 1 ppb

Observed Vinyl Chloride Concentrationin the BedrockMarch 1996

Woodlawn Landfill Conclusions

VC plumes are getting smallerVC is biodegradingMaintaining aerobic conditions is keyA permeable cap was installed to allowcontinued infiltration of oxygenatedwater

106f l R 3 1 1 9 9 !

EVALUATINGAND

DOCUMENTINGNATURAL ATTENUATION

Evaluating and Documenting NaturalAttenuation________________Natural Attenuation is evaluated using a"lines of evidence" approach. All currentprotocols and guidance documents use thisapproach. The suggested lines of evidence are:1) Documented loss of contaminants at thefield scale2) Presence and distribution of geochemical/biochemical indicators of Natural Attenuation3) Direct microbiological evidence

107A R 3 I 1992

Document Loss of Mass

* How are the lines of evidence documented?

1) Loss of contaminants at the field scale isdocumented through reviewing historicaltrends in contaminant concentration to showmass loss over time in the source area and/oralong the flowpath

This mass loss must exceed losses predictedthrough transport processes alone.

Document Loss of Mass - 2

* How are the lines of evidence documented?

1) Because chlorinated solvents usually do notbiodegrade on their own like BETX,biodegradation rates are very site specific.

Estimating site specific biodegradation rates asadditional proof of loss of contaminants canusually be done from field data.

108A R 3 I 1993

Geochemical and Biochemical Indicators* How are the lines of evidence documented?

2) Presence and distribution of geochemicaland biochemical indicators are documentedthrough a correlation of the changes inconcentration and distribution of indicatorparameters of specific natural attenuationprocesses. These specific parameters vary forthe different site types (patterns)

Direct Microbial Evidence

How are the lines of evidence documented?

3) Direct microbiological evidence is obtainedthrough microcosm studies which candocument specific biodegradation processes orestimate site-specific rates of biodegradationMicrocosm studies are costly. However,studies using 14C labeled contaminants canprovide incontrovertible proof ofbiodegradation.

109ARTII99I*

Evaluating and DocumentingNatural Attenuation______

Step 1: Review available site dataStep 2: Review/develop site conceptual modelStep 3: Screen data for evidence of natural

attenuationStep 4: Identify additional data requirementsStep 5: Collect additional site data

Evaluating and Documenting___Natural Attenuation______

• Step 6: Refine site conceptual model* Step 7: Interpret data and test fit to

conceptual model• Step 8: Conduct an exposure pathway

analysis* Step 9: If accepted, integrate NA into long-

term site management strategy

noA R 3 I 1995

Step 1: Review Available Site Data

Data you usually have: Site use; history,geology, hydrogeology, historical andcurrent CVOC and non-VOC data, someidea of relevant regulatory criteria, locationof potential receptors of concern.

Step 1: Review Available Site Data

Data you might have: DO (dissolvedoxygen), some inorganic parameters (i.e.nitrate)

Data you usually do not have: Redox, mostinorganic parameters (i.e. sulfate, chloride,Fe+2), dissolved hydrocarbon gases (i.e.methane, ethene), volatile fatty acids (i.e.acetic), other compound specific degradationproducts

inflR3U996

Step 2: Review Site Conceptual Model

A Conceptual Model for Natural Attenuation isa hypothesis about how releases occurred,current plume characteristics (plume stability),the idealized site type, and whether or notNatural Attenuation can meet regulatorycriteria for the specific siteMost site reports do not have a conceptualmodel as it pertains to Natural Attenuation

Step 2: Develop Site Conceptual Model

The available data is often sufficient todevelop a preliminary conceptual model

Data gaps will be filled in during the fieldinvestigations in support of NaturalAttenuation, and will modify or refine theidealized site type and plume status for thefinal conceptual model.

112flRJI1997

Step 2: Develop Site Conceptual Model

» How release(s) occurred (usually have)

» Current plume characteristics (See step 3)

» Idealized Site Type (See step 3)

» Receptors/Regulatory Considerations (input)

Step 2: Completing Site Conceptual Model

» Regulatory considerations:

Plume distance to nearest receptorsGuesstimate of future plume stability (i.e.steady state, shrinking), and time to reachstability, sustainability of those conditionsOther Regulatory considerations?

113R3II998

Step 2: Completing Site Conceptual Model

. Completing first Conceptual Model:Requires an integration of site type, plumestability and sustainability of NaturalAttenuation processes with regulatorycriteria to determine if Natural Attenuationhas a chance of meeting the criteria

. Usually not possible at this point; more datacollection needed

Step 3: Screen Data for Evidence of_____Natural Attenuation______

Current plume characteristics are almostalways available in reports, historical plumecharacteristics are often available as well.Mass loss in source area and along flowpathas well as plume stability can be determinedfrom this data if it is fairly complete.Preliminary "loss rates" can be calculatedfrom historical data.

114A R 3 I 1999

Step 3: Screen Data for Evidence ofNatural Attenuation______

Identifying Site Type (pattern)

A preliminary site type can usually beidentified with the data currently available:

Presence and trend of daughter compounds,

Distribution of DO, other indicators

Step 4: Identify Additional Data Requirements

• Reminder: Sites that gave little or noindication of biological processes in Step 3may still be candidates for NaturalAttenuation via physical processes ifreceptors of concern are not close and/orcontaminant concentrations are low.

115fl.R3!2000


• For sites with biodegradation, compare theavailable data used to develop ConceptualModel, to the proper data "tier" needed for arefined Conceptual Model for the specificsite pattern identified.


* Select appropriate Data Collection Tier andidentify data gaps

• Select locations for additional data collection;upgradient, source, lateral, downgradient.Avoid additional wells unless necessary; it isusually possible to interpret around imperfectwell locations or well screens

116flR31200i

RECOMMENDED ANALYSES

• VOC's, speciate the DCE isomers9 Methane, ethane, ethylene, propane• D.O., redox• p_H9 conductivity, temperature• Inorganic ions: "Fe, Mn, Cl, N03,SO4,H2S? alkalinity "'

Data Interpretation Guidelines

1173R3I2002

DESCRIPTION OF ANALYTICAL PARAMETERSUSED TO ASSESS INTRINSIC BIOREMEDIATION

ParameterAlkalinity

pH

Temperarure

Dissolved oxygen

Redox potential

Sulfate

Sulfide

Methane

Ethane/eihene

Total organic carbon(TOC)

Chlonde

VOC/daughter products

iron (total, dissolved)

Nitrogen

Nitrate

Nitrite

Phosphorus

DescriptionProvides an indication of the buffering capacity of thewater and the amount of carbon dioxide dissolved indie water. Increases due to biodegradation of organiccompounds. -Microbial activity tends to be reduced outside of a pHrange of 5 to 9, and many anaerobic bacteria areparticularly sensitive lo pH extremes. :Affects rates of microbial metabolism. Slowerbiodegradation occurs at lower temperatures.Highest energy-yielding electron acceptor forbiodegradation of organic constituents. < 10 ppm.A measure of the oxidation-reduction potential of theenvironment. Ranges from -**5QO mV for aerobicconditions to -300 mV for methanogenic conditions.Used as an electron acceptor in biodegradation oforganic constituents. Reduced to form sulfide.Microbially reduced form of sulfate. Indicates reducedconditions "Indicator of anaerobic conditions and of methanogenicbacteria. Produced by the microbia! reduction of carbondioxide. Solubility limit 25 to 40 ppm.Metabolic end product of reductive dehalogenation ofhalogenated ethenes and ethanes. . - — - -A measure of the total concentration of organic materialin water that may be available for biologicaldegradation.May be useful as an indication of biologicaldechlorination and as a conservative tracer.Provides a measure of the type and quantity of parentand biogenic daughter products.A product of bacterial iron reduction. Only the reducedform (ferrous) is soluble. The oxidized form (ferric) isused as an electron acceptor.An essential nutrient of microbial growth andbiodegradation.Used as an electron acceptor. Consumed next afteroxygen.Product of nitrate reduction. Produced only underanaerobic conditions. Rarely observed.Essential nutrient for microbial growth andbiodegradation.

AR3I2003

j5_, H± r - ,——- . -T--- - - '

Step 4: Additional Data Requirements

Evaluate need for microcosm studies

Recommendation: Microcosm studies areneeded when clear evidence of biodegradationevidence can not be obtained from field data .

Microcosm studies which 14C labeledcontaminants can be an excellent way to showdegradation by indigenous bacteria.

Step 5: Collect Additional Data

Recommendations:

• Coordinate additional data collection withregular groundwater monitoring events: sitefamiliarity of regular field staff is invaluable

* Make sure field staff are familiar withprocedures and QA/QC of "new" parametersthey have never collected before.

118AR3I200!*

Steps 6 & 7: Interpret New Data,refine and test Site Conceptual Model

Interpret the new data and add to preliminarysite Conceptual Model

BEWARE: Bad Data or Bad Interpretation

Estimate mass balance and flux,biodegradation kinetics and sustainability

Conduct preliminary fate/transport modelingif needed

Steps 6 & 7: Interpret New Data,refine and test Site Conceptual Model

* Refine conceptual model to accomodate all data

» Test original hypothesis to see if ConceptualModel still fits

• Determine if refined Conceptual Model canmeet regulatory requirements

* Reiterate steps 4-7 if necessary to refineConceptual Model until it fits observed data

119flR3!2005

Step 8: Conduct an ExposurePathway Analysis

This step can be done at any time

Are the rates of natural attenuation sufficientto reduce risk?

Make sure to incorporate all stakeholderconcerns!!!!

Step 9: Integrate NA into Long-Term___Site Management Strategy____

Assess the long-term prognosis of the site-specific natural attenuation processes

Select a "conceptual" backup remedialalternative to natural attenuation for all sites

120«R3i2006

Step 9: Integrate NA into Long-TermSite Management Strategy

• Develop strategy for process validationincluding a long-term monitoring plan

» Do a cost-benefit analysis of NA vs othertechnologies including an analysis of thepotential indirect costs (e.g. legal) of NA

• Pursue acceptance by regulators andstakeholders

121flR3!2007

DATA QA/QC

DATA QA/QC

Problems occur on many projects

Data problems fall into categories

They can be simple to recognize

The data may NOT BE bad after all.

122flR3'l2008

WHAT ARE QA TRIGGERS?

Data which is physically impossible• 75 ppm dissolved oxygen• VOC levels over solubility limitsData sets without proper trends* D.O. vs. redox is random (try plotting it)* Redox doesn't correlate to SO4, NO3Data which is out of place* i.e.. well or sample numbers mixed

SOURCES OF QA PROBLEMS• Field instruments not calibrated• Field crews not properly trained• Improperly screened/surveyed wells• Over purging - it dries out wells• Wells not stabilized before reading• Faulty field lab procedure• Faulty conceptual models - samplingthe right thing in the wrong place

1234R3I2009

GOOD D.O. & REDOX DATA

D.O. REDOX

MW-1 5.0 300MS-2 2.0 200MW-3 1.0 100MW-4 0.1 -150MW-5 0.0 -200

D.O. VS. REDOX - GOOD

gpstf

500-p———— — — ' . . . . . - - - - — — --

400-

300-

200-

100-

0--100-

oo

*[ - • 0 . . . . . . .

•o-200< - ————— , ——————— | ——————— | ——————— j

0 2 4 6 b

0-O.

124R 3 I 2 0 I O

GOOD ORP FIELD DATA

-200

1:15 1:30 1:45 2:00 2:15Time

BAD D.O. AND REDOX DATA

D.O. REDOX

MW-1 65.0 600MW-2 2.0 0MW-3 1.0 -200MW-4 45.0 -250MW-5 15.0 -100

125A R 3 I 2 0 I I

D.O. VS REDOX - BAD

vbQ«

'200-j

100

0-

-100-

-200-

-300-————— c

O0 0

o . . . . . . . . . . . . . . . -...

oo

0 0

t i l li ——————— 4 n ..... ——— on ——— .,. — o/w ———— ., -4A —— ., ———— rrA —

D.O.

BAD ORP FIELD DATA

200 —

100 —

1 OH

o-100 —

-200

1:00 1:15 1:30 1:45 x 2KM) 2:15Time

126AR3I20I2

DATA THAT ONLY LOOKS BAD

• Data from transition zones• Data from layered systems• Inhoniogeneous sites• Characteristics:• No physically impossible numbers* Consistent between sampling events• Consistent with other internal parameters• Fits a reasonable conceptual model

DATA THAT ONLY LOOKS BAD

• Dover AFB transition zone wells• D.O., CH4, H2S, VC, ETH together* All values are within possible range• Values consistent between samplings• Fits conceptual model

127f l R 3 l 2 Q I 3

DOVER AFB EXAMPLE

XCE 390 ppbDCE 2000 ppbVC 320 ppbD.O. 1.7 ppmRedox 242 mvCH4 170 ppbH2S 400 ppbEthylene 20 ppb

DOVER AFB INTERPRETATION

v

REDUCED o —————-> OXIDIZED

128AR3 120114

DOVER AIR FORCE BASE

OBJECTIVES:

* Understand the development andapplication of a conceptual model

• Examine the three lines of evidence• Hands-on practice using NA tools


Wilmington

Dover AFB

129A R 3 I 2 0 I 5


THE C-5 GALAXY

130flR3!2016

DRILLING AT DOVER AFB

SAMPLING AT DOVER AFB

131flR3i20!7

THE ST. JONES RIVER

DOVER LOCATION MAP

132A R 3 1 2 0 I 8

LINES OF EVffiENCF

Reduction in concentration along theflow path -down gradientDocumented loss of contaminant mass by* chemical and geochemical data• biological, decay rate dataMicrobiological laboratory datasupporting degradation and decay rates

ORIGINAL DOVER TCE MAP

133A R - 3 I 2 0 I 9

DOVER AFB SOURCE AREAS

^t- X- vx

^

DOVER AFB EXPOSURES

No-one drinks or uses the waterNo physical contact with contaminatedwater or soilPlume does not discharge

134AR312020

SITE HYDROLOGY

Water-bearing unit— Fine-to-coarse grained sand— 30 to 60 feet thick— Three zones— Deep zone carries most contaminantsGroundwater velocity 150 to 200 ft/yr.Groundwater moves north to southConductivity 10"3 cm/sec

TYPICAL CROSS-SECTION

-s — - UPPER ZONE

-tt — r~ i. . —— — ....•>••:•- t-- • ——— * """•- —— "~™ '

160 ' 1360 * soo * TOO aoo TOO 000HORIZONTAL DISTANCE {FTJ

135AR3I202!

INDICATOR PARAMETERS MW-236DPCE 190TCE 500cDCE 4,400VC 310CH4 170ETHANE NDETHYLENE 11D.O. 1.7Eh +242H2S 0.4

FIRST CONCEPTUAL MODEL

• Simple TCE spill• Horizontal transport through 2 layers• Well data a little complex• Degradation by reductive dehalogenation• No exposure

136AR3I2022.

DOVER CONCEPTUAL MODEL #1

. V'vN " 'V x"• - *> s& • ~ *S*S »— . ". ...*& - fff

:-'.VN*>TV'V'V..OUncontaminated

REDUCTIVE DEHALOGENATION

PCE4TCE^

cis-DCE• £

VC^ETH

1374R3I2023

CRT AND HYDROPROBE SITES

PLUME PROFILE

V!\

138

TCE

Concentration = ug/L

CIS-DCE

Concentration = ug/L

139flR3!2025

VINYL CHLORIDE

'-jW* - * \ ^ V* • -^ -Concentration s ug/L

ETHYLENE - DEEP ZONE

140flR3!2026

SECOND CONCEPTUAL MODEL

• Sources the same f~ - - - - - - ——• Hydrogeology more complex .• Plume distribution unusual• Sequential anaerobic - aerobic biodegradation• New cis-DCE-hiodegradation pathway• No current exposure' -

DOVER CONCEPTUAL MODEL #2

Uncontaminated

141A R 3 I 2027

BIODEGRADATION PATHWAYSREDUCTIVE DIRECT

COMET ABO L1SM DEHALQGENATION OXIDATIONPCE$

C02 <= TCE£

CO2 <*= cis-DCE => CO2$

C02 <=• VC =i> CO2£

CO2 <=» ETH =o CO2

APPROACH TO THE SITE

• Plume length• Retardation factors• Relative distributions* Mass losses• Apparent half lives• Indicator parameters• Biological information• Conclusions

f\

f\*O*

9*9ty

f\

f\

142AR3I2028

GROUNDWATER VELOCITY

V = (k*i)/n

V = (60*0.0019)7 0.30V = velocity

V- 1/tnffAr^ k= PermeabilityV - 140ft/yr 5 = gradlentn = porosity

MAXIMUM PLUME LENGTH

L = -V * (Age of Release)L = 140Vyr * (50 years) = 7,000'

FROM THE MOST DOWN GRADIENTPOINT OF RELEASE!

Where:

L = length in feet, V = GW velocity

143/5R3S2Q29

PLUME PROFILE

CONCLUSION

The plume has traveled 4,500% not 7,000',from the most down gradient point of release.

144AR3I2030

RETARDATION

Rl= l+;((Pb/n)*Kd)

Pb^n =

• *oc ~"Kd =

1.8 gm/cc0.300.00025k * foc *~oc

koc values

TCE = 126ml/gc-DCE= 49ml/gVC = 2.5 ml/g

RETARDATION FACTORSRETARDATION FACTOR

* WORKSHEETRf-l-Kpfc/n)*K«

RfWhere: . . " _. ... .--- .. - - - - - - - - - - - - -—^-—

p_ = buikdmsiry - Table of Ws " (Uoiis irer. = porosjiy; as voW fraction (NOT percent!) " ~ / • ~-x_. ' r*" ""' ' i;n

f^ = fracticn of organic carbon (N'OT perccntl) 11 DCE 65 "M«O ^Sk« = panltioning coeffTcTeiif " ~ t-DCE 39 CM 35

e-DCE 49 1J.ITCA IKVC 15 UDCA 62

________________-— r-—- •..——— - _-..-- ,.,.- - "-=- ,;-••— . ..*•-« CA . .3,Calculate retardation factors for Dover AFB using: , .

SOURCE M.D JjOuji lW.

n = Q.30 Toe = O.OOSS p. =T.iSgm/cc" """-. .- Rf = i -V "/ '

and f_-'s from Tible'lA__. ... .-

Rf = 1

145«R3I'203'I I

RETARDATION

Rf= l + (Pb/n)*Kd

RfTCE = l + (1.8/0.30)*(126*0.00025)RfTCE = 1.19

Rfvc = 1 + (1.8/0.30)*2.5*0.00025)Rfvc= 1.004

RETARDED CONTAMINANT VELOCITY

Rvc ~

V -

Vvc =

V SBvvc

1.004

140 ft/yr

140/1.004

139 ft/yr

R = 1 2Tf p1 JL«A*

V = 140 ft/yr

VTCE = 140/1.2

VTCE = 117 ft/yr

146AR3I2032

MAXIMUM RETARDED LENGTH

L = (V*Age)/Rf

(or for Dover)Lx= (7,000')/Rfx

LTCE = (7,000')/1.2 = 5,833'

Lvc = (7,000'/1.004 = 6,970'

PLUME PROFILE

147SR3I2033

CONCLUSION

The plume has not traveled 7,000' fromthe down gradient point of releaseRetardation is low for all compoundsEven with retardation the plume is too shortDistribution not as expected, VC has notgone farther than TCE

HALF LIFE ESTIMATION

In(C/C0) = -KAt C0 = Upgradientconcentration

InfC/Co) - -K C = Downgradient,, concentration

At = Travel time

T = - fl 6Q11 1/2 u.oyj constant-K= Degradation

constan= Half life

148AR3I203U

HALF LIFE ESTIMATION

• Two similar methods

• Graphical estimation• Buschek method - well data

GRAPHICAL EXTRAPOLATION

50% concentration loss is one half life75% is two half lives90% is about three half livesMeasure distances from the source areaand divide each by GW velocityAdd the results and divide by 6 for H.L.This is the method on your worksheets

149AR3I2035

GRAPHICAL EXTRAPOLATIONWORKSHEET for

HALF PRECALCULATIONBY GRAPHICAL EXTRAPOLATION

r 4>gifig*t fmm rbf m-m rtrmTT gylgre tfaur?

The compcMi) wbocc Wlf life a being

Sunaif eoncoKnuon _________ ppm

D • Dutmre 10 JWldcCluc

Di * Dutuxe lo 90W OKtm «

BUSCHEK HALF LIFE METHOD

Based on data from wellsMust be along a single flow pathPlot In concentration vs. distanceSlope of the best fit line is K/VSlope * V = KT 1/2 = -0.693/K

150AR3I2036

BUSCHEK HALF LIFE - CONTOURS I

Similar to previous methodInstead of data from wells, useconcentrations from contour linesSlope of best fit line is K/VAgain, T 1/2 = -0.693/(slope*V)

BUSCHEK HALF LIFE FROM WELLS

EAST PLUME

Well distance TCE ppb

316D 0 3,700354D 1,812 770355D 2,688 210IR2D 4,125 65IR3D 5,000 1

151flR3!2037

Buschek Half Life by Microsoft Excel

1. List data in two columns2. Distance of time in the first,

concentrations in the second3. Highlight the block of numbers4. Select ChartWizard5. Click it onto the selected block6. Select XY (Scatter)7. Select Semilog, data in columns

TCE tl/2: East Plume

TCCCD

316D 0 SCOSO 1812 W 13SD S6B3 2K) w XDFSD 4IS © "FED aro 1 10

TCCO am aro 4DD

>€BS

152flR312038

Buschek Half Life by Microsoft Excel

8. Select "Insert"9. Select "Trendline" I10. Select "Exponential"11. Select "Options"12. Display "Equation" and "R2"13. If column one is time, HL = (-0.693/K)

If column one is in distance,then HE = -0.693/(K* V)

TCE tl/2: East Plume-answer

SstfiUTB ' , - 1CDDD! Dsa3.eS TCEigl :

316D ~ ~" 7T~0~ 5xD ._ ./1CCD'ran 1817 TTi ~3SD -• V- - --.-3938 •" 2» 5 tD-1KD • 4l>> , fe. .'. -HIR3D - 3iCD -"..'A "0

\ .. . -:— idn*A»- 1

j ".-a-.r —— '^— —— . , —— . — ss.r - =

- , , ^ S ^ . . . - - • •• — " ^ ——— ™__ —— __ — , — - —— p.

. 7T* *

^ •W

———————————— = ———————— : ———— - ----.- • ——— .. —————— __.

0 tHJ 2TJJ-,,- 33D" 4TD 3TD

1534R312039

TCE k: East Plume

CONCLUSIONS

The plume has not traveled 7,000' fromthe point of releaseRetardation is low for all compoundsDistribution not as expected, VC has notgone farther than TCEHalf lives are similar to literature values

154

ESTIMATING MASS LOSS

The approximation method used here isbased on having good isoconcentration maps

This can be used much more quickly thantransect analyses. The relative accuracy ofthe two methods is being tested by severalfield studies.

ESTIMATING MASS LOSS%

1. Draw a line perpendicular to flow2. Using thickness of aquifer and GW velocity

estimate mass of GW/yr which passesthough each line.

155A R 3 I 2 0 U I

TOTAL CHLORINATED SOLVENTS

-j ' \ v * A

Cooctniriiton = mg/1

MASS OF WATER PER YEAR

Water Volume = L x H x V x n

Water Volume = LxHxVxO.30 =250' x 10' x 140'/yr x 0.30 = 105,000 ft3/yr

Water Mass = 105,000 ft3/yr x 62.5 Ib/ft3= 6,562,500 Ib/yr

156




3. Take that mass times the mass fraction ineach contaminant concentration interval.


Concentration = mg/L

157




3. Take that mass times the mass fraction ineach contaminant concentration interval.

MASS OF SOLVENT PER YEAR

Mass of Water = 6,562,500 Ib/year

TCE Mass/year = 6,562,500 Ib/year x 1.5 ppm

6,562,500 x 1.5/1,000,000 = 9.84 Ib/year

1583I20M*

MASS LOSS WORK SHEETMASS LOSS CALCULATION

Length ofQ- I ppm = ______ ft iLength of I . : ppm * ______ ft _... ....Loifih of! - 5 ppro = , _____ ftLengtti of 5 - 10 ppm = _____ ft _. _ .LenjihoflO- lippm = _____ A -- -TOTAL = _____ ftPLUME WIDTH = _____ ft .;"..•.

Hint EkmrcnraejHirelxJUiIMJelol'SiepSirn: JQd Ihouod iiuo (onceraraoon tcpncn IcnjUu.

Man, =(M*n,,,*OJVl-000.000 = , _______ lbMo to =(MMy.:,' I , .5 U. 000.000. = _____ lb.MQMI =(M*,..),* 3,. V l'.000.000 = _____ IhMet}.,* = {M»,w« • T.SVr.OOOJX» = ______ |bMaim. =(Mwt*.i»i* HSX1JXO.OOO= _____ .lb=

MASS LOSS WORK SHEET

MAS.S_LQSSgALCOLAT!ONWQRKSHEET.- Linf *1 _

LcngibofO. I ppm= ___600_-fl-Lcngih of 1 - 2 ppm « __ 250 _ ft

ofS- I0pf«n= __ 590 _ "ft _ . .. - .. .-._of 10- L5pp»=" __ 200 _ ft

TOTAL = __L670_ft- ._ _ _ . .PLUME ftTDTHs _L670_ ft ."..-."." .....

Hid: Be sure to sxaarc boUi nda of UK ptiaoe ami Sun Md in- nre jonoca DoQ JC BXW Kagttii

M«»t,= (600)-{10)'(140)-(DJO)-S15- JS.750.000 ibMw,.;»= aSD)'(IOr(l«3r(0.30)*62.S= 6J62JW ibMwn.» = 03DH I0)'( I4flr(0.30)'62J = 3.M2JQO IbM*a.,.,= {I90J*[IO)-(l40ri0.30)-Si5= 15,437 JOO to 'Mv.a-.Ji »{200.-UOr{140>-(QJOJ*«._r= 5,350.000ib

MQ»,, =(M«.t) •0,5X1.000.000 = __ 7,3 _ lbMOM, =(Mw,|.., •i.SVi.000.000 = 93 _ lb 'MQ:.,, ={MMj.» • 3.5Vi,000.000 » __30J_lb. .MCD.H, =CM*i!-i0i •T.5VI.OOOJXKJ = _H62_Ib

= _ &5J Ib

Mm.), * Mas.i» » Man..,

159A.R3I20U5

CONCLUSIONS

The plume has not traveled 7,000' fromthe point of releaseRetardation is low for all compoundsDistribution not as expected, VC has notgone farther than TCEHalf lives similar to literature values220 (97%) pounds are being lost per year

GEOCHEMICAL DATA

D.O.What can geochemical Ehdata tell us in support H2about the loss of solvents? CH4

Cl2 RCL's

160AR3I20U6

DISSOLVED OXYGEN

REDOX STATE

161/IR3I20U7

METHANE

Conaniration « og/L

HYDROGEN

Concentration in nano moles/liter

162

CONCLUSIONS

The plume has not traveled 7,000'.fromthe point of releaseRetardation is low for all compoundsDistribution not as expected, VC has notgone fartherjhan TCEHalf lives similar to literature values220+ pounds are being lost per yearGeochemistry favorable


Concentration = mg/L

163/3R3-I201.9

SOLUBLE CHLORIDE ION

Conotntratlon =

CHLORIDE VS. TOTAL SOLVENTS

164flR3l2050

MASS OE SOLVENTS DEGRADED

• Chloride ion above background is 33,000 Ibs• Multiply 33,000 Ibs by 131.5/106.5(TCE/3 chlorides)

• Dover AFB bacteria have degraded morethan 40,000 Ibs TCE

• Solvents in solution at Dover AFB totalabout 4,000 Ibs. There is little sorbed solvent,

• What proportion of the TCE spilled hasbeen biodegraded? This da_tg doesn't tell us!

CONCLUSIONS

The plume has not traveled 7,000' fromthe point of releaseRetardation is low for all compoundsDistribution not as expected, VC has notgone farther than TCEHalf lives similar to literature values220+ pounds are being lost per yearGeochemistry favorableChloride accumulates as solvents disappear

165ARJI205I

MICROCOSM EVIDENCE

• Soils collected aseptically* Most 28 ml sealed vials* Aerobic and anaerobic• Work split among many labs• Thousands of individual tests

REDUCTIVE DEHALOGENATION14000

12000 -CO

10000

3 6000oS 4000O

2000

•BENZOATEDCE•BENZOATETCE

|___• BENZOATE VC«

8000 has

10 20 30 40 50Days

166R312052

AEROBIC DCE DEGRADATION120

QO "WO

§ *CCa 60

£8

Duplicates

2D 40 60 80 K30

AEROBIC VC BIODEGRADATIONDOVER 1-SUE 56 AEROBICEXP. LIVE VSKILLED

DAYS

167flR312053

UPGRADIENT PATHWAYS

REDUCTLVE DIBECTCQMETABOL1SM DEHALOGENATION . .. OXIDATION

PCE0

C02 <*= TCE£

C02 <*=> cis-DCE = > C020

CO2 <=• VC => C02^

CO, < ETH =f> CO,

DOWNGRADIENT PATHWAYSREDUCTIVE DIRECT .

COMETASOL1SM DEHALQGENATIQN OXIDATIONPCE

Cis-DCE c > CO2

C02 <=• VC =o C02

CO, < ETH > CO.

168AR3I2051+

LUO

APPROACH

Plume length TOO SHORTRetardation factors SMALLRelative distributions UNUSUALMass losses SUBSTANTIALApparent half lives TYPICALIndicator parameters EVIDENTBiological information FAVORABLEConclusions N.A. POSSIBLE

LINES OF EVIDENCE

Reduction in concentration along theflow path down gradientDocumented loss of contaminant mass by• chemical and geochemical data• biological decay rate dataMicrobiological laboratory datasupporting degradation and decay rates

169flR3!2055

DOVER AFB CONCLUSIONS

• The plume has not traveled 7,000' fromthe point of release

• Retardation is low for all compounds• Distribution not as expected, VC has notgone farther than TCE

* Half lives similar to literature values• 220* pounds are being lost per year* Geochemistry favorable* Chloride accumulates as solvents disappear• Microcosm studies show clear biodegradation

CURRENT CONCEPTUAL MODEL

• Source areas the same* Reduction followed by oxidation* Two plumes which act differently* Source areas of different nature -one may have more BTEX

* No current exposures

1704R312Q56

DOVER LOCATION MAP

. 3$&%f ..y/e

.M &Uhcontaminated

171flR3!2057

St. Joseph, Michigan

Natural Attenuation of TCE

St. Joseph Site

Scale; 500 Meters

172AR3I2058

St. Joseph Site

St. Joseph Site

JSMIIHr ••-..

173flR3!2059

St. Joseph Site

St. Joseph Site

Scale: 500 Meters

174SR3I2060

St. Joseph Site

St. Joseph Site

175f l R 3 i 2 0 6 l

si. Joseph Site

Vertical Transects(TRANSECTOR)

Transects form logical units for studying sitesData in this form can be displayed intwo-dimensions:By representing the data as rectangles aroundeach measurement point(chemical mass per unit thickness =porosity x concentration x length x width)

1769R3J2062

St. Joseph Site

St. Joseph Site

177AR3I2063

St. Joseph Site

St. Joseph Site

CHEMICAL: Trichloroethene ConcentrationTRANSECT: 4MASS(kg/m): 1,397

0-2500E+05

Ground Surface

10ft.J __________ _____" ~ ™ 0.2SOO I

2500.

250.0j

25.00

2 00

approx.N 100ft

178flR3!206U

St. Joseph Site

CHEMICAL; Vinyl Chloride uoncenuananTRANSECT: 4 tJQ/LMASS(kaym): 0.4868 0.2500E+06

0.2SOOE+ OS I

Ground Surface __..

r— —— I —— ——— | —— —— i —— ——— I 25.00 Hi ^^Hr ^^H

_j —— , —— , ——— —————— —— i ——— 2.500 •

I —— • —— —— i ——— —— —— 0.2500 J

Transect-Averaged Concentrations (Mg/L)Dissolved Oxygen below 2.0 mg/L

Chemical Transect 2 Transect 4 Transect 5 Lake Transect

TCE 7411 864 30.1 1.4

c-DCE 9117 1453 281 (0.80)

Vinyl 998 473 97.7 (0.16)Chloride

179AR312065

Transect-Averaged ConcentrationsDissolved Oxygen below 2.0 mg/L

Chemical Transect 2 Transect 4 Transect 5 Lake Transect

Ethene 480 297 24.2 no data

Sum of the 19100 3150 442 3.5Ethenes

Chloride 65073 78505 92023 44418

Apparent Loss Coefficients

CJ+1

cj+1 = average concentration at the down gradient transect

Cj = average concentration at the up gradient transect

X = apparent loss coefficient from transect j to j+1

A t = travel time, determined from the seepage velocity,retardation factor and the distance

180flR'31'2066

St. Joseph Site

For TCE from transect 2 to 4

At = 340 weeks

cj+1 = 5.04 x 10'4 kg/m;

Cj = 6.70 x 10-3 kg/m3

= -0.38/year

181flR3!2067 - - - -

TransectPair

•

2 to 4

4 to 5

5 to Lake

TCE c-DCE VinylChloride

Apparent change (per year)

-0.38

-1.3

-0.94

-0.50

-0.83

-3.1

-0.18

-0.88

-2.2

Methods to Calculate Rate Constants

1) Method of Buscheck and Alcantar(1995)

2) Normalize to a conservative tracer

3) Calibrate a mathematical model

182AR3I2068

Sampling Locations Along Centerlineof Plume - St. Joseph

T-2-5 T-1-4 T-4-2 T-5-3 55AEOft 200ft 1000ft 1500ft 2000ft

——————————— mg/L —-————————TCE 12.1 3.4 1.3 0.035 0.022

Cis-DCE 33.7 11.2 2.3 0.22 0.42

Vinyl 2.3 3.7 0.51 0.063 0.070chlorideOraanic 35.8 11.2 3.0 0.23 0.37chlorine

Method of Buscheck and Alcantar_________(1995)________

Distance TCE Log cone. TCE(ft)______(mg/L)_____________0 12.1 1.0827

200 3.4 0.53151000 1.3 0.11391500 . 0.035 -1.4562000 0.022 -1.6576

183AR3J2069

St. Joseph Sitey =-0.0014x +1.0244

R2 = 0.92521.51

0.5Log [TCE] o(mg/L) -0-5-1

-1.5-1-20 500 1000 1500 2000

Distance from Source (feet)

Method of Buscheck and Alcantar_________(1995)_______

R = 1 + Koc foe p / 0

Koc =120 mL/gfoe = 0.001Porosity = 0.3Bulk Density = 1.7 g/cm3

Retardation = 1.7

184flR3!2070

Method of Buscheck and Alcantar(1995)

WhenVc = 0.76 ft per day<xv = 100 feetA

k/Vx = -0.0014

ThenA, = - 0.000915 per day

= - 0.33 per year

Normalize to a Conservative Tracer

Use the sum of chloride ion andorganic chlorine as a tracer

185SR31207I

Sampling Locations Along Centerlineof Plume - St. Joseph

T-2-5 T-1-4 T-4-2 T-5-3 55 AEOft 200ft 1000ft 1500ft 2000ft

.——————————— mg/L ———————————-

Chloride 89.7 78.6 98.9 63.6 54.7

Organic 35.8 11.2 3.0 0.23 0.37ChlorineTotal 125.5 89.8 101.9 63.8 55.1Chlorine& Chloride

Normalize to a Conservative Tracer

k = - 5.49 / 2,631 days= -0.00208/day

= - 0.76 / year

*186

.4R;ii2072'

31QSCR5EN Natural At»nu*bon Decision Support System *, ...

^iEH^UNE RUNARRAY

- VKW Culput V»w Output

*9><Iun»Caa

a*B« mJM tv t

DBSOLVEO HY&RCKHMON CONCZNTXATTOIS ALO.SC «JJME ON TCRUNE <n«A. it Z-*)

__________________________&H*~rf**Simm&l_________________________________

_______ 3 ___XQ <oo <oo »o |ooo i»o 1*00 i«oo aoo aaoo• . e.t <.»-» atTf ««< i.»i a.pa '<CB t«ii &<» S.IM 1793 isoc 1311iH««4>t>iiv u«7M rm *,*» tsis iw aaes aco7 O.K7 aju o)» a ica

1..V •...». nr-i M«M *.ai taa T*M am na siot i?aa HM iailinn aioo i aoo oca 0.022

i,Annul ^ .WOnin»»ji | fl*uCim™m5*

187AR312073

DISSOLVED H.7>ROCARBON COPJCENTRAT1QVS IS FU;ME inert,« Z-0)

O("neeffl ._..,.,-_„ ,. - .. jmB-jniJi'JL 'SK3r-_a -SSJr9?J1t!. j... j ..-»,: _tJf.-.-at'iiJJa':' -• - --". -"t -" •u*"c(» Dafbn+ 0 300 400 S(JO._ .. SCO .. _jjX».- ilDC--

i2J~ af j.pog,.. t. 0.952_.....gig..._ .q.saz Vjj .„ _9fg« ..--.-pazp. . o.!P3 Q_ -_ 0.03* .Q-. 2_-~br i- . O Oifi Afcod^.

o 13.974 • -rzn'US OS9S 1CCG

Al^O. ..«{&«• Quay

-;»_-aoco ao«

^ . n*i-

hta»»«j> kian • M^*t Ffe-ucain

Calculated Rate Constants

Transect Method: - 0,38 to -1.3 / year

Buschek and Alcantar Method: -0.33 / year

Conservative Tracer Method: -0-76 / year

188

ST. JOSEPH SUMMARY

Currently there is an informal agreementbetween ERA Region V and the RP thatnatural attenuation with monitoring is theaccepted remedy for the West Plume

There are other risks at this site that thelocal residents are more concerned about,

St. Joseph Site

189AR312075

PTOWRTDF INDUSTRIALMEMBERS WOULD

EVALUATEAN UNKNOWN SITE""

EVALUATING A NEW SITE

• First cut evaluation of-data• The example has a typical RJ. data

• Data QA/QC. ."'". ",'_ , _ ".:."• What questions tcrask first?'• What data to focus upon?

190AR3 12076

LINES OF EVIDENCE

Reduction in concentration along theflow path down gradientLoss of contaminant mass by:* geochemical data• biological decay rateMicrobiological laboratory datasupporting biodegradation and rate

CHECK INFORMATION QUALITY!

• Contaminants vs. solubility limits?* IsD.O.<10?* Does the plume go down gradient?• Are the hydrogeo numbers consistent?• What is the range of GW velocity?• Do the maps "look right" ?* How long are the well screens?

1913R3I2077

WHAT TO DO FIRST

Find out if receptors are impactedUnderstand" the source area ';Identify pattern of VOC distributionCons.trucf a draft conceptual modelEvaluate lines .of evidence one and two

SITE CONCEPTUAL MODEL

• A theory which considers:• hydrogeology

* source area• degradatiion mechanisms \ ...;.• VOC "degradation pattern* Potential exposuresIt is revised whenever necessary

192flR3!2078

LOSS OF MASS

Are biodegradation productsreported? Look for DCE, VC,CF, DCMIsoconcentration mapsCompare plume size to age*velqcityIs there excess chloride?Are there trends in concentrationin individual wells?

GEOCHEMICAL EVIDENCE

Can bacteria survive? pH, As, PbIs the proportion of cis-DCE high?Electron donors? TOC7 BOD, BTEXIs dissolved iron high?Are nitrate or sulfate depleted?Which VOC pattern matches best?Are D.O. & redox high or low?Metabolic gasses? CH4, ETH

1934R3I2079

POTENTIAL FOLLOW UPS

ONLY DO THE ONES YOU NEED!

• Tiered evaluation based on complexity• Calculate degradation rates• Resample wells, resurvey?• Reinterpret geology _ .;• Gather additional field data• Microcosm studies

194flR3l'2'080

NATURAL ATTENUATIONRULES OF THUMB

RULES OF THUMB FOR N.A.

• These are range finding tools ONLY• They do not work everywhere or .

every time!!!• All conclusions must be backed up byhard data '. *'

• This is a first cut only, still need to havesite-specific evidence _ _ _ :

195AR3I208I

BIODEGRADATION RULES OF THUMB

• All chlorinated solvents can be biodegraded• Old plumes biodegrade more often* Reductive dehalogenation is easy to prove* Oxidative degradation is.harder to prove* Co-oxidation is nearly impossible to prove• VC is always biodegradable* DCE degradation is the key to NA of TCE

GEOCHEMISTRY RULES OF THUMB

• Dissolved oxygen is always below 10 ppm• Methane is always below 25 ppm• Biological DCE is at least 80% cis-1,2 DCE• Dissolved iron over 5 ppm is important* Coastal aquifers are normally oxidized• Coastal aquifers often show low retardation* Many glacial aquifers are naturally reduced

196flK3l2082

SITRASSESSMENT RULES OF THUMB

• You've got to.have a conceptual model• You will usually find fluvial systems• Divide length by spill age for SWAG velocity• The older the well screen the longer it is• So_urce~areas are either easy to find or.are

a wild goose chases,.... . ". .* The shorter the screen interval, the more

extreme the concentrations you may find

CONTAMINANT RULES OF THUMB>

• Products are never "pure" - e.g. PCE "'contains TCE .

•' DNAPL's often "contain other things -especially oils from degreasing!._

* What is in solution reflects'what's sorbed(though proportions differ) ......

• Nbtfall hydrocarbons float! - napthalene* DNAPL?s viscosity is less than water's• DNAPL saturated areas are over 50% water

1974R312083

SOURCE AREA RULES OF THUMB

• If there's lots of DNAPL it's easy to find* If you can't find it, it's not very big* Small source areas will often attenuate inacceptable periods of time

• Big sources can attenuate if the disposedmaterials mixture is favorable - contain :lots of biodegradable organic carbon

HALF LIFE RULES OF THUMB

• BTEX is weeks* Cl-HC's are'months to years• DCE is the slowest• VC degrades fast - months• CT degrades easily• TCA is about a year* Chlorobenzene degrades, but the

rate is not defined

198AR3I2081*

PRACTICAL

EXERCISES

PRACTICAL EXERCISES

• The instructors have created twonatural attenuation site exercises

• The exercises give you experience inusing the natural attenuation tool set^ y - - - , . - • - -

• The simulations are based on real sites

199fiR3i2Q85

HOW EXERCISE #1 WORKS

• This exercise is done in one large group• Examine your set of RJ. data• The group evaluates the site for N.A.• If attenuation is technically acceptable,document the lines of evidence

• If attenuation is not acceptable, showwhy not

HOW EXERCISE #2 WORKS

Break out into small teamsThe RJ. contains base maps,groundwater data, and a site historyTo get new data use the Work Plan FormA data base will provide the informationYou get both chemistry and geologyThe time and cost of your study istracked by the1 data base

200flR3 12086

THE Rj; DATA PACKAGE

Base mapsSite historyPiezometric surface mapIsoconcentration mapsCross sectionData table

EXERCISE TRACKING

Time and cost is tied to each work planThe data base keeps a running totalTotals will.be reported to you eachtime new information is deliveredWhen you reach your conclusions we'llstop your clock, then add the cost ofcompleting negotiations

201/IR3I2087

EXERCISE COMPLETION

• Define your conceptual model

• Share your model with the group

• Define critical NA parameters

• We will show you the real site afterward

Evaluating and DocumentingNatural Attenuation_______

+ Step 1: Review available site data+ Step 2: Review/develop site conceptual model4- Step 3: Screen data for evidence of natural

attenuation4- Step 4: Identify additional data requirements

4 Step 5: Collect additional site data

202AR3S2.088

Evaluating and Documenting___Natural Attenuation_____

4 Step 6: Refine site conceptual model4 Step 7: Interpret data and test fit to

conceptual model4 Step 8: Conduct an exposure pathway

analysis4 Step 9: If accepted, integrate NA into long-

term site management strategy

TIMING GUIDE EXAMPLE

* Install new wells• Plan, approval, mobilize 8 weeks• Install wells 3 weeks• Sampling & analysis 8 weeks• Report & approval 10 weeks• Total 29 weeks

• Sampling existing wells•"Total 18 weeks

• Geoprobes• Total 21 weeks

203AR3I208.9

ANALYTICAL COSTS

• VOC'S- TOC/BOD• Inorganics• Metabolic gasses• TPH• Acetate• Total oxygenates

$175$ 32 ..$110$100$ 40$ 30$ 30

FIELD & REPORT COSTS

New Wells Sampling Geoprobes

Plan $10,000 $ 1,000 $ 5,000Mobilize $4,000 $1,000Sample $10,000 $ 9,000Report $25,000 $10,000 $15,000

Totals $45,000 $20,000 $21,000

+ $4,000/well + $400/point

204AR3I2090

MICROCOSMS GUIDE

Low information level12 weeks & $25,000(Adds 6 weeks to project)

High information level^y. _ - .-= - - - * --=--'--- - ----- =-- -' - -

24 weeks & $75,000(Adds 18 weeks to project)

NA STUDY COMPLETION

• NA report 16 weeks $30,000\

• Negotiations 26 weeks $20,000

• These total ten months and $50,000.These occur after you finish theexercise. They are always the same.

205ftR3i209l

ACKNOWLEDGEMENTS

Data base tools - Craig BartlettData base creation- Tom GrossoSite creation - Dave Ellis

Leo LehmickeDave MajorRichard SydorDan Acton

206.4R3I2092

REFERENCES1""' ."". ' V"..."

Acree,S..D:,M.HightoWr 1997 SiteCharacterization methodsJbrjhe design pfIn-Situ£leatr_o^ Donor Delivery Systems In-In Situ and On-Site BiofeniediHofi;' 261-255.

Barcelona, M. J. 1996. ase Study: Wurtsmith Air Force Base, Michigan. Symposium onNatural Attenuation of Chlorinated Organics in Ground. Water, Dallas September 11-13.EPA/540/R-96/509,pp98-r63;; ' " --——--—————— -

Beeman, R. E. rl Rodriguez. Fotiades, S. H. Shoemaker, andD. Ellis. 1997. AnaerobicBiodegradktiQii;of _Tetrapliloroethene in the Unsaturated Zone using BioventingTechnology. In: In SituaniOn-SiteBiorernediaHonrvSri^ 393.

BEAK Report, I996a; Site-Wide Reconnaissance Study of Intrinsic Biodegradation ofChlorinated Volatile Organic CqsSgoiiacis in Cjroundwater, Aerojet Propulsion Systems.Plant, Sacramento, CalifofniarExecutive Suniinaiy Available upon request.

BEAK Report, 199<5b. Evaluation of Cbmetabolic Bioyenting at the Old Septage Laaoon,ASite 4 ID, Aerojet Propulsion Systems Plant, Sacramento, C A. Executive Summary ~^ Available upon request; """" " - - - -.-..--..

BEAK Report, 1997a. Evaluation ( Infin Biodegmdation of Chlorinated VOCs inGroundwater at the Environmental Chemistry Laboratory, Canoga Park, California. .Executive Summary Available upon request.

BEAK Report, I997b. Evaluaffon" ofEtrinsic Biodegradati^i of Chlorinated VOCs inGroundwater- at Chemical Plant 1, Aerojet Propulsion Systems Plant, Sacramento, CA.Executive Summary1 Available upon request.

Bosma, T. N.B.,M. Van Aal lK.11Intrinsic De"clilorinafa'on"blT,2-Dichloroethiane at an Industrial Site. In: In Situ andOn-SiteBioremediation: Vol. 3. Battelle Press, pp. 155 - 160.

Bradley, P. M. and F. H: CHapelle. 1996. Anaerobic Mineralization of Vinyl Chloride inFe(III)- Reducing, Aquifer Sediments. Env. Sci & f echn. 40:2084-2086.

uchanan, R. J., Jr., K E; Ellis, J™ ML"Odom, P.F. Mazierski, and M. D.Lee. 1995.

AR3I2093

Intrinsic and Accelerated Anaerobic Biodegradation of Perchloroethylene in Grouridwa^tIn :Intrinsic Bioremediation, R.E. Hinchee, J.T. Wilson, and D.C."Downey (eds).Battel BPress, Columbus, OH, pp 245-252. . ^^

Buchanan. R, J. Jr., E. J. Lutz, D. E. Ellis, C, L. Bartlett, G. J. Hanson, M. D. Lee, M.A.Heitkamp, M. A. Harkness, K. A. DeWeerd, J. L. Spivak, J. W. Davis. G_M.Klecka,andD, L. Pardieck. 1996. Anaerobic Reductive Dehalogenation Pilot Design for DoverAirForce Base. In: In Situ and On-Site Bioremediation: Vol. 3. Battelle Press, p. 289

Buscheck, T. And C. M. Alcantar. 1995. Regression Techniques and Analytical Solutions 'to Demonstrate Intrinsic Bioremediation. In : Intrinsic Bioremediation, R.E."Hinchee,J.T.Wilson, and D.C. Downey (eds). Battelle Press, Columbus, OH.

Buscheck, T., K. T. OiReilly, and G. Hickman. 1997. Intrinsic Anaerobic Biodegradationof Chlorinated Solvents at a Manufacturing Plant. In: In Situ and On-Site " .BioremediatiomVol. 3. Battelle Press, pp. 149-154.

Braus-Stromeyer, S. A., R. Hermann, A. M. Coo and T. Leisinger.. 1993. Dichloromethaneas the Sole Carbon Source for an Acetogenic Mixed Culture and Isolation of afermentative, Dichloromethane-Degrading bacterium. Appl. Environ. Microbiol. 59:37)3797.

Cline, P,V, and JJL Delfino. 1989. Transformation kinetics of 1,1,1-trichloroethane to thestable product 1,1-dichloroethene. In: Biohazards of Drinking Water Treatment,R.A.Larson(Ed). Lewis Publishers, Boca Raton, FL. . _

Cox, E.E., E Edwards, L. Lehmicke, and D.W. Major. 1995. Intrinsic biodegradation oftrichloroethene and trichloroethane in a sequential anaerobic-aerobicaquifer. In : IntrinsicBioremediation, R.E. Hinchee, J.T. Wilson, and D.C. Downey (eds). BattellePress9CoIumbus, OH.

Cox, E.E., L. Lehmicke, E. Edwards, R. Mechaber, B. Su'and D.W. Major. 1996."Intrinsicbiodegradation of chlorinated aliphatics under sequential anaerobic-cometabolicconditions.In : Symposium on Natural Attenuation of Chlorinated Organics in GroundWater.EPA/5407R-96/509.

Cox, E.E., L. Lehmicke, E. Edwards, R. Mechaber, B. Su and D.W. Major. 1997. Field andLaboratory Evidence of Sequential Anaerobic-Cometabolic Biodegradation ofChlorinatedSolvents. In: In Situ and On-Site Bioremediation: Vol. 3. Battelle Press,p.

Davis, J. W. And C L, Carpenter. -1990. Aerobic Biodesradation of Vinyl Chloride in......... _ _ . _ . . - - - -X - - . - . ^-^ . r • -

Groundwater Samples. Appl. Environ. Microbiol. 56:3878-3880. -_

Distefano;iVD,, M. Gos.sej±'] Dechlorination of HighConcentrations of Tetrachloroethene to Ethene by an. Anaerobic Enrichment Culture in theAbsence of Methanogenesis. Appl. Environ. Microbiol. 57:2287-2292. ..

Dolan, ME., and P. L.McCarty. 1994 Factors" Affecting Transformation of ChlorinatedAliphatic Hydrocarbons by Methanotrophs. In: Bioremediation of Chlorinated andPolycyclic AromaticJHydrocarboaCompounds, R. Hinchee,- A. Leeson, L.Semprini, and .S.K. Ong (Eds.)rLewis Publishers, Boca Raton, FL., pp 303-308; .

Dupont, R. R., K. Gorder, D. L,_Sorensen, M. W. Kemblowski, and P. Haas. 1996. CaseStudy: Eielson Air Force Base, Alaska. Symposium on Natural Attenuation ofChlorinatedOrga cs'in Qround""WatCT..J3gyfe,.September" 11-13. EPA/540/R-96/509,PP 104-109.:....".: :./,_:::_:-::;:''r~: r.~r--- - - - .---.,-r-Edwards, E; A., and E. E. Cox.' 1997. Field and Laboratory Studies of Sequential

aerobic- Aerobic Chlorinated Solvent Biodegradation. In: InSitu and On-SiteBioremediation: Vol.3. Battelle Press, p. 261 - .

Egli, C., R. Schoitz, A; Cook and T. Leisinger. 1987. Anaerobic dechlorination of -tetrachloromethane and l,2-dichloroethane_to degradable products by pure cultures ofDesulfobacterium sp." arid Methanobacterium sp. FEMS Microbiol. Lett.43:257-261.

Ellis, D.E., 1996. Intrinsic Remediation in the Industrial Marketplace. Symposium onNatural Attenuation of Chlorinated Organics iri Groiiiid,Water. Dallas, September 11-

Ellis, D. E., E. J. Lutz, G /MTKlecka. D-.L ardieck, J. J.,SaJvo, M. A.Heitkamp, D.J.Gannon, C. Cl'Klikula, C. M. Vogel, G. D. 'Sayles, D. H. Kampbeil. J.T.Wilson and D.T.'

J - ? ___ _ _ _ _ f^ - ' . ., . . - -J- - - - 7 - - - - - - - - ^ t

Maiers. 1996rRemeffiation Technology Development Forum Intrinsic RemediationProject at Dover Air Force Base, Delaware, Syrnposium on Natural Attenuation ofChlorinated Organics in Ground Water. Dallas,'September 11-13.EPA/540/R-967509, 'pp93-97. •" ^ ^ :

'1R3I2095

Fennell, D. E., J. M. Gossett and S. H. Zinder. 1997. Comparison of BiityricAcid,Ethanol, Lactic Acid and Propionic Acid as Hydrogen Donors for the ReductiveDechlorination of Tetrachloroethene. Environ. ScL Technol. 31:918-926.

Fiorenza, S., EX. Hockman Jr., S..Szojka, R.M. Woeller, and J.W. Wigger. 1994. Naturalanaerobic degradation of chlorinated solvents at a Canadian manufacturing'plant. In:Bioremediation of Chlorinated and Polycyclic Aromatic Hydrocarbon Compounds,R.Hinchee, A. Leeson, L. Semprini, and S.K. Ong (Eds.). Lewis Publishers, BocaRaton,FL.

Freedman, D.L. and J.M. Gossett. 1991. Biodegradation of Dichloromethane in a Fixed-film reactor under methanogenic conditions. In: In Situ and On Site Bioreclamation,R.Hinchee and R. Olfenbuttel (Eds.). Buttersworth-Heineman, Stoneham, MA.

Freedman, D.L. 1990. Biodegradation of Dichloromethane, Trichloroethylene andTetrachloroethylene Under methanogenic Conditions. Ph.D Dissertation, Cornell"University, Ithaca, NY.

Galli, R. and T. Leisinger. 1985. Specialized bacterial strains for the removal ofdichloromethane from industrial waste. Conserv. Recycl. 8: 91-100.

Goltz, M.N., G. D, Hopkins, J. P. Allan, M.E. Dolan, and P.L. McCarty. 1997. .Full-ScaleDemonstration of In Situ Aerobic Cometabolism of Trichloroethylene-ContaminatedGroundwater. In: In Situ and On-Site Bioremediation: Vol. 3. Battelle Press, p. 71.

Graves, R. W. R. E. Hinchee, T. M. Jensen, A. E. Graves, T. Wiedemeier, M.Wheeler, andR-EIliott. 1997. Natural Attenuation of Chlorinated Solvents in Six Plumes at Hill AFB.In: In Situ and On-Site Bioremediation: Vol. 3. Battelle Press, pp. 141-146.

Hagemann, M. And M. Gill. 1996. Impediments to Intrinsic Remediation. Conference onIntrinsic Remediation of Chlorinated Solvents. April 2, 1996. Salt LakeCity, UT,

Henschler, D., W. R. Hoos, H. Fetz, E. Dallmeier and M. Metzler. 1979. Reactions ofTCE epoxide in aqueous systems. Biochemical Pharmacology 28: 543-548.

Harkness, M. R, A. A. Bracco, K. A. DeWeerd, and J. L. Spivack. 1997. Evaluation ofAccelerated TCE Biotransformation in Dover Soil Columns. In: In Situ and On-SiteBioremediation: Vol. 3. Battelle Press, p 297.

QR3I2096

Hartmans, S., JA.M."de"B.ont,"J."Tramper aridK.Ch.A. M. Luyben. 1985. Bacterialdegradationof vinyl chloride. Biotechn. Lett. 7:383-386. r- -

Hinchee, R/E. 1996.VKa'tural Attenuation of Chlorinated Compounds in Matrices otherthanGroundwater: The Future of Natural Attenuation. In /Symposium on NaturalAttenuation of Chlorinated Organics in Ground Water. EPA>540/R-96/509.

Imbrigio.lta,T/E?,;T; A,.EKlke;B,H, Wilson, and"j.Y.;.\Vilspn. l9%. .Case Study: NaturalAttenuation of a Trichloroethene Plume .at Picatinny Arsenal, New Jersey, Symposium on-Natural Attenuation of Chlorinated Organics in "Qiroiind" Water.' Dallas "September 11 -13.EPA/540/R-9S/5Q§ '^ " '

Janssen, D.B., A.,S_cheper,I. Dijkhuizen and B. Witholt. 1985 Degradation ofhalogenated aliphatic compounds by Xanthobacter autotrophicus GJ10 Appl EnvironMicrobiol. 49:673-677. . .. ......:;".. :...... •:'.'.''"'" .:.' ~~'".."..'. - .-

Kitanidis, P.K1, L. Semprini, D. H~~ JC gbelljmd J.T. Wilson. 1993. Natural anaerobicbioremediation of TCE' at tEe "St! JosepK," ghlgan. Siipei ind site. In: .U.S. EPA,Symposium on Bioremediation ofhazardous wastes. IPA76DO/R-92/126. pp. 47-50. "

•Klecka, G.M., E. J. Lutz, N. J. Klier, RJ. West, J. W." D vis, D.E. Ellis, J.M. Odom, T.A.Ei, F.H.:Chapelle, D. W. Major, and J. J. Salvo. 1997. Intrinsic Bioremediation ofChlorinated Ethenes at Dover Air Force Base. In: In Situ and On-Site Bioremediation'Vol.3. Battelle Press, p 287. .

Lee^M. D.,P.F.-Ma2iersH;R.l.'Siichanan,Jr. 1995,Intrinsic In Situ Anaerobic Biodegradation of Chlorinated Solvents.at an IndustrialLandfill. In :Intrinsic.BioremediatiQn, R.E.Jlinchee," J.T. Wilson, and D.C. Downey

--—-————fpp'255-222. ""':' "~T""

Lee, M. D., L. S/Sehayek and f."D. Vandell. 1996! Intrinsic Bioremediation of 1,2- '.dichloroethane. Symposium on Natural Attenuation of Chlorinated Organics inGroundWater; Dallas, September 11-13. EPA/546/R-96/509. .

Leethem, J. T., and J. R. Larson. 1997. Intrinsic Bioremediation of Vinyl Chloride inGroundwater at an Industrial Site. In: In Situ and On-Site Bioremediation:Vol. 3.BattellePress,pp 167-172: . . . . . . . ... . .. ....:. .... . . l._

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Major, D.W., and E.E, Cox, 1992 Field and laboratory evidence of in situbiotransformationof chlorinated ethenes at two district sites: Implications forbioremediation. In: In Situ Bioremediation Symposium '92. S. Lesage (Ed.),EnvironmentCanada, Niagara-on-the-Lake, Canada.

Major, D.W., and E.E. Cox, 1993. A field and laboratory study to assess thebiotrans formation of tetrachloroethene at a chemical transfer facility inToronto. In: FinProgram and Proceedings of the Ministry of Environment and Energy TechnologyTransfer Conference, November 22 and 23, 1991. Toronto, Ontario.

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Major, D.W., E.E. Cox, E. Edwards, and P.W. Hare. 1995. Intrinsfe dechlorination oftrichloroethene to ethene in a bedrock aquifer. In : Intrinsic Bioremediation, R.E. Hinchee.J.T. Wilson, and D.C. Downey (eds). Battelle Press, Columbus, OH. pp 197-203.

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-& ftemon, C Tiedeman, S. M.Gorelick.1991. In Situ MethanoSophi Biormediation for Contaminated Groundwater at St.Joseph, Michigan. In: Iri.Situ and On Site reclamation, R. Hinchee and R.Olfenbuttel(Eds.)- Buttersworth-Heineman, Stoneham, MA.

Mqser, L. E., G. P 'Say es and CM.Vogel. l_ 7,_;Conij5a:r ^ Bioventing TreatabilityStudies. In:In Situ and On-Bite "Bioremediation: Vol. 3. Battelle Press, p 299. .

Newell, C. J., R. K. McLeod andJL R. Gorizales. 1996. The'BIOSCREEN Computer ToolSymposium on Natural Attenuation of Chlonnated Qrganics in Ground Water DallasSeptember 11-13..EPA/540/R-96/5Q9.' ":;;: ' , ;." . ,

Pankow, J. F. And J. A7 Cherry. _199_6. Dense Chlorinated Solvents and other DNAPLs inGroundwater. Waterloo Press, Portland, Oregon. 522 pages) . . . . . ....... ..._...,.. . .I...... - - - -Quinton,, G .,Buchanan, R.H., Ellis, D.E., and Shoemaker, S.E., 1997. A method tocompare gourndwater cleanup technologies. Remediation, Autumn 1997, pp. 7 - 16.

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Wiedemeier, T. H., M. A. Swanson, D.E. Moutoux, J. T. Wilson, D", H. Kampbell, J.E.Hansen and P. Haas, 1996a. Overview of Technical Protocol for Natural Attenuation ofChlorinated Aliphatic Hydrocarbons in Groundwater Under Development for the U.S. AirForce Center for Environmental Excellence. Symposium on Natural Attenuation ofChlorinated Organics in Ground Water. Dallas, September 11-13.EPA/540/R-96.:'5.09.

\Viedemeier_ T. H., J, T. Wilson, and D. H. Kampbell. 1996b. Natural Attenuation ofChlorinated Aliphatic Hydrocarbons at Plattsburgh Air Force Base, New York,Symposium on Natural Attenuation of Chlorinated Organics in Ground Water. Dallas,September 11-13. EPA/540/R-96/509, pp 74-82.

Wilson, J.T., J.W. Weaver, and D.H. Kampbell. 1994. Intrinsic bioremediation of TCE inground water at an NPL site in St. Joseph, Michigan, In : Symposium .on IntrinsicBioremediation of Groundwater, United States Environmental Protection AgencyEPA/540/R-94/515, August 1994, Denver, CO. ~~ ;

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Witt, M. E., D, t" Wiggert, M,J. Dybas, K. C. Kelly, and C- S. Griddle..1997. Bioaugrneiitation d..numerical simulation of carbon tetrachloridetransformation in groundwater. In In Situ and On Site Bioremediation: Vol.4.' Papers'from, the Fourth hitenialional In Situ_and_On Site. Bioremediation .Symposium'. Ne\v Orleans,'LA, April2S-May I, 1997. Battelle Press,Columbus;OH,:pp.573^5S077V.-7"""~7!^""^^"7 7. """ " . " . . .

Workman, D. J;,"S,L; Woods, Y. A. Gorby, J. K. Fredrickson, and M. J. Truex. 1997.Microbial reduction of vitamin B"i"2 by Shewanella alga Strain BrY with subsequenttransformation of carbon tetrachloride. Environ. Set, Technol. 31(8):2292-2297.

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SAMPLING PROTOCOL _Remediation Technologies Development Forum

Chlorinated Solvents Subgroup

1.0 Introduction

This document provides the objectives and procedures for sampling groundwater duringthe Remediation Technologies Development Forum (RTDF) Chlorinated SolventsSubgroup pilot program.7 A statement, of work, for "this subgroup-defining theanticipated contributions of participants in. the study of co-metabolic bioventing,accelerated anaerobic, and intrinsic bioremediation of ..chlorinated solvents at twodifferent geographic ioeatip.ns -has been established. - The statement of work discussesthe need for groundwater sampling in connection " with the intrinsic "and acceleratedanaerobic remediation studies, the. specific requirements !of which are detailed inSection

This document is intended to.serve as ••-•_-

Q A guide for conducting grounoVwater sampling during the program.Of Documentation for the subgroup laboratory personnel to understand the source of

water used in their experiments.Q "Reference for reviewers and ruture practitioners, of these technologies.

This protocol has been developed because of the potential adverse effects of commonlyemployed groundwater sampling methodology on the quality of bioremediation data.Naturally occurring contaminant biodegradation can result in dramatic non-equilibriumwith the atmosphere. The intent of this document is to describe a sampling methodologyfor use in the RTDF program to minimize the effects" of sampling ,on groundwatercollection and characterization.' This "protocol has drawn heavily from a proposed"minimal, aeration method" prepared for the American Petroleum Institute and theNew Jersey . Department of Environmental Protection "(NJDEP) Field SamplingProcedures Manual (19.9.2). . . .

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2.0 Objectives

In gathering groundwater samples for the bioremediation subgroup's work, the followingobjectives should be met:

Q Regularly and consistently collect representative groundwater samples foranalysis of contaminant levels, geochemical,conditions, biological, and water-quality parameters to characterize subsurface conditions in the saturated zone,

Q Assess the presence of and potential for bioremediation of chlorinated solvents.Q Gather representative bulk groundwater samples for laboratory experimentation

(e.g., microcosms and column studies, adsorption-desorptkm testing, andmicrobial counts).

Q Provide consistent data of the highest quality appropriate for the program'sresearch and development activities.

Q Provide a template for future sampling effortsTh bioremediation work.

3.0 Sampling Procedure3,1 P resampling Review

Prior to sampling, the following items must be addressed: :Q Review the well list to verify sampling sequence, number of samples from each

well, and quantity of water for each sample.D Review container, labeling, and preservative requirements for each sample.Q Review the packaging material and container requirements.Q Ensure that shipping arrangements have been made in advance.Q Review the location map for each well and check each well's construction details

(i.e., diameter, total depth, depth to screen, screen length).Q Have prepared field sampling logs with well details in advance.

Q Review decontamination procedures, materials, and containers,Q Review the requirements for field and trip blanks.Q Review the equipment checklist (see Appendix A).

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3.2 Prep urging Procedures

Prior to. purging1 st g;;]wlter;"5om_A_j U _j ..fc .wing procedures should beconducted: . . . _ . . . . . . . — - -- -

Q Review the.specific well log and prepare the field sarnpiing log in advance of thepursing activities. " ; " : " """: ~"~ ; -f i ^J U — - -- -- - - - -- - - - .--..-....- ——-- ._....._. ._ _ _... . .... .... - -— ——:- — - - -

• Decontaminate .bladder pump.--• Replace discharge tubing.

• Calibrate field parameters (e.g., pH, Eh, specific conductance, dissolvedoxygen, Hnu).

• Decontaminate water-level indicator probe and tape,i

• Unlock the monitoring well and measure vapor concentrations in accordancewith the site-specific Health and Safety Plan.

. * Measure depth to water.

• Evaluate whether the water table surface is "above or within the screenedinterval. . . •

• Calculate the volume of well water and borehole filter sand pack pore space(borehole volume).

• Install pump into the well slowly to minimize aeration, placing the pumpintake midway in the screened interval or .at least 1 foot below the water level

• Take precautions to prevent the exhaust from contaminating the samples ifgasoline- or diesel-powered generators or compressors are used to operate thepump.

• • Configure the discharge tubing with a-gate valve and three-way valve, withdischarge directed through the three-way valve and flow cell and into acalibrated decontaminated bucket (see Figure 1)

The following information should be recorded on the sampling log for each monitoringwell before purging: . . ... _ _ . . ; . ..._V '-.'-.

Q Date, time~aiid weather conditions

Q Well number and well permit numberQ Photoionization detector (PID) or flame ionization detector (FID) reading taken

from the well immediately.after cap removalQ pH, Eh, dissolved oxygen, temperature, and specific conductivity

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Q Total depth of well from the top of inner casing or surveyor's mark, if presentQ Depth from the top of inner casing to the top of screenQ Depth from the top of inner casing to waterQ Estimated water volume in well

The following information should be recorded on the sampling log for each monitoringwell after purging:

Q Start and end time for purgingQ Purge methodQ Purge rate(s)Q Total volume purgedQ pH, EhT dissolved oxygen, temperature, and specific conductivity (during and

after purging)Q Sampling method

Any comments concerning field observations during the groundwater sampling event(i.e., slow recharge, turbidity, odor, sheen, PID or FID readings) should also be reported.

3.3 Monitoring Well Purging Procedure

The monitoring well is purged to remove the standing water column and inducegroundwater flow from the surrounding formation into the well. With the minimaldrawdown low-flow aeration method, the objective is to accomplish this withoutintroducing air into the groundwater that flows into the well. Pumping at a rate (less than1 liter per minute) that does not lower the level in the well more than'10 percent of thescreen length will prevent air from being introduced into the groundwater. The purgingrate should be controlled, as needed, using the pump's variable speed flow controllerand/or the gate valve in the discharge line. Water-level measurements should becollected frequently during purging to ensure that the water level has not dropped lowerthan desired. The pump rate for purging will be determined by the drawdown in waterlevel. Wells can be pumped at a rate in excess of 1 liter per minute as long as thedrawdown does not exceed 10 percent of the screen length in the water level. Monitoring

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wells should be purged .until.the...field.parameters have stabilized .to within the rangespresented in Table 1. . -

The minimal drawd6wn~low-flow aeration method is specified as. an alternative to theconventional "three well volume" purging protocol. Purging until the parameters inTable 1 have stabilized is a technically sound method for obtaining groundwater samplesthat are representative of formation groundwater.' While sampling under this protocol, theremoval of three well volumes prior to sampling may be unnecessary. If the indicatorparameters stabilize before that volume has been purged, it is acceptable to beginsampling. If the indicator parameters fail to stabilize in accordance with Table 1,sampling should commence after, three well volumes are removed. At least one wellvolume must be. purged before sampling can begin. During purging it is permissible toby-pass the flow cell until the groundwater has cleared. . . -:..,- _ ..-

3.4 Field Indicator Parameter Measurement

During purgingVdissolved oxygen, electrical conductance, pH, Eh, and temperatureshould be measured continuously using the flow cell.

Indicator parameters and water-level measurements should .be recorded in a fieldnotebook or on sampling logs at approximately 1A well volume increments. Purging iscomplete after the parameters have stabilized to within the ranges presented in Table 1,, orwhen a minimum of one well volume has been removed.

5.5 Groundwater Sample Collection

When purging is complete, aliquots should be collected for the analytical parameterslisted in Table 2. To ensure the most consistent, comparable results, individualsamples/measurements from all wells should be collected in the same order. The orderused under this protocol is based on the approximate order of susceptibility to artificialaeration and is as follows: .volatile organic constituents, total organic carbon (TOC),methane, iron, sulfide, alkalinity, and sulfate.

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The pumping rale should be reduced to 100 milUUters per minute (ml/min) during samplecollection. The flow cell may be disconnected during sampling. The discharge should bedirected toward the inside wall of the jar to minimize volatilization and should be rilled tooverflowing. The discharge should be filtered before the ferrous iron sample jar is filledusing an in-line 0.45-micron filter. (Filtration is recommended to eliminate biasintroduced with particulates; in-line filtration is recommended to prevent artificialaeration of the sample.)

If additional samples are collected for dissolved oxygen analysis using field kits(i.e., Hach or Winkler), the sample jar should be submerged into the bottom of the largecontainer. The container should be filled to overflowing and the sample jar should beallowed to fill without aeration,

The samples should be preserved and analyzed as described hi the Project Sampling andAnalysis Plan.

3.6 Pump Decontamination

The submersible pumps used to evacuate and sample groundwater in the well casing mustbe cleaned and flushed prior to and between each use. This cleaning process consists ofan external laboratory-grade glassware detergent wash and tap-water rinse, or steamcleaning of pump casing, hose and cables, followed by a ID-gallon flush of potable waterthrough the pump. Flushing can be accomplished using a clean plastic overpack drum ora plastic garbage can filled with potable water. Flushing must be followed by a distilledand deionized rinse of the outside of the pump.

4.0 Calibration Procedures

The following is a description of the calibration procedures developed after the firstround of sampling at Dover AFB, Dover, DE. These procedures are to be followedduring all subsequent groundwater sampling events. . .

1, The Purge Saver Meter will be calibrated before operations begin in the morningand checked for accuracy in the middle of the day and again at the end of the day.If the meter does not display the desired results during the check, it will then be

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recalibrated. Calibration will be done in accordance with the Purge Saver user'sguide.. _ ^+. ,,v.,.L_ -;rr-_-_._ : _;.. _;_._. _.-._.. _____ ._ ,.:, :....,.__.-.... T._-._-._ .._

2-. The dissolved oxygen probe will be calibrated in the following manner. Dissolvedoxygen (DO) will be checked under conditions _ of _1QO percent, humidity asdescribed, in the user's guide. This will be considered, the high end check. DO willalso be checked under conditions of 0 percent oxygen:—low end check. An air-tight sample "bag will be attached _to7 the"probe and then filled with nitrogen gas.The nitrogen will displace the oxygen arid.the meter.should display zero percentoxygen." If the instrument.. fallsto display the appropriate response for eitherprocedure, it will then be recalibrated and rechecked,

3. Redox probe will be calibrated in accordance with the user's guide. Followingcalibration the redox will be checked with a reference solution to ensure the meteris functioning projJerly..

4. The pH probe will be calibrated to buffer solutions of 4, 7, and 10 in accordance tothe user guide....... .......V- - _. --___:-.L..,--._. -.. . . r

5.. The conductivity probe will be calibrated with four conductivity standards asspecified in the user's guide. . . . ;;._-..:./.; ........ .

6. If the instrument displays unreasonable results for any of the parameters duringoperations, the purging process will stop and the meter will be recalibrated.

5.0 References J

CH2M Hill. April 3, 1995. Standard Operating Procedure—Ground-water Sampling forIntrinsic'Bioremediation Characterizations.

tyew Jersey Department of Environmental Protection. May 1992. Field SamplingProcedures Manual.

Remediation Technologies Development Forum. Statement of Work for Joint R&DAgreement^ Concerning'"Bioremediation of Qhlorinated Solvents. TheRemediation " Technologies Development Forum Chlorinated SolventsBioremediation'Subgroup.

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Table 1

CRITERIA FOR STABILIZATION OF INDICATORPARAMETERS DURING PURGING

' ., , = ? i. & ,;„ Fie&i'Paraiaeter : :/;-_. £ :.y : •_ :Dissolved oxygenElectrical conductivitypHTemperature - - - - - - - - - - -Eh

^ V/'Sl lbatioo'CHIeiiaK1"1'.'"Not applicable

3% full scale range .O.IOpH unit

0.2°CNot applicable

mg/l = Milligrams per liter

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Table 2

GROUTSTDWATER SAMPI-ING PARAMETERS

;;::;:-:f^Priority Pollutant Volatile Compounds

Benzene .'",'-' .Carbon tetrachloride .Chlorobenzene . . - - -Chloroe thaneChloroformChlorornethane . . .1,1-dichloroethancl,2-<iichloroethene1, 1 -dichloroethenecis-l,2-dichloroelhenetrans-i,2-dichloroelhene1,2-dichloroethene (total)EthylbenzeneMethylene chloride ... . ., , .........Naphthalene1 , 1 , 1 ,2-tetrachIoroethane1, 1,2.2-tetrachloroeihaneTetrachloroethene . .. . .._- - -- —Toluene1,1,1 -trichloroethane1 , 1 ,2-irichJ.oroethaneTrichloroetheneVinyl chlorideXylenes (total)

SW-846 Method 8240ASW-846 Method 8240ASW-846 Method 8240ASW-8,46 Method 8240ASW-846 Method 8240ASW-846 Method 8240ASW-846 Method 8240ASW-846 Method 8240ASW-846 Method 8240ASW-S46 Method 8160SW-846 Method 8260SW-846 Method 8240ASW-846 Method 8240ASW-846 Method .8240ASW-S46 Method 8260 .SW-846 Method 8240ASW-846 Method 8240A -SW-846 Method 8240ASW-846 Method 8240ASW-846 Method S240ASW-846 Method 8240ASW-846 Method 8240ASW-846 Method 8240ASW-846 Method 8240A ,

Metabolic End Products \EthaneEtheneMethane

SW-846 Method 80 1 5 (modified) iSW-846 Method 80 1 5 (modified) JSW-846 Method 80 1 5 (modified) |

Propane - I SW-846 Method 8015 (modified) 1Water-Quality Parameters \

Sodium " ~ ' ""T:Calcium . ~ ' . - - . - - . •Magnesium •ChlorideConductivitySulfateNitrate nitrogenp H - . . - - . . .CarbonateBiocarbonatePhosphorus - - - -'-- -----PotassiumBoron

Method 200.7 1Method 200.7 IMethod 200.7 JMethod 300.0 J

- Method 12.01 JMethod 300.0 J

Method 353.2/300 jMethod 1501 . JMethod 310.1 jMethod 3 10.1 JMethod. 365,3 . jMethod 200. 7 ' IMcihod,200.7 .

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Table 2

GROUNDWATER SAMPLING PARAMETERS

*.' r- • —— " rf*-vf*S - •*---_.*_a£*-*v —— f -f- .-f ffyKM-.i i.- -.- Jf-v r.fy.-.-- vw •-Z > ^ ~ vr*xatt<?rW$r' & ^Total dissolved solidsSARBODCODAmmonia nitrogenAlkalinity

^ ^ ; C-Ibdriaiory • Aal!yit.Hal iMS oH '^^Method 160.3

calc.Method 405.1Method 4 10.4.

350.2310.1

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EQUIPMENT CHECKLIST

The" following equipment is necessary for samplingf"

Q Monitoring well construction details (e.g., geologic log,, screened interval, welldepth, borehole diameter)

Q Water-level indicator "

' Q "Submersible positive,displacement pump and controller or bladder pump

Q PTFE-lined polyethylene tube in sufficient quantity to use new" tubing for eachwell (Teflon® is quite permeable to certain gasses)

Q Throttling valves and .three-way flow-tee sampling valve (see Figure 1)Q Field measurement devices for pH, Eh, dissolved oxygen, temperature, electrical

, conductance (including instrument manuals and calibrate materials)Q" Calibrated bucket or beaker

Q 'Flow cell with ports for each of the field meter probes (optional)Q Field notebook and/or well purging log forms

Q Sample containers, preservatives, ice and cooler(s)Q Decontamination supplies '•" '" " '"

Equipment necessary-fora sampling episode may also include the following:Q Field instrumentation (i.e., PID and FID) T _Q Field and trip blanks - - - -

Q Sample analysis request forms

Q Chain-of-custody forms

Q Chain-of-custody seals

Q Sample labels , -

Q AppropriatT-persorial safety equipment (e.g., disposable gloves)Q "Appropriate hand tools

Q . "Keys t o locked wells . . .Q "Metal filtering devices . . - . " • ." ." , .

Q Plastic sheeting, ties, and bags . . - '

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Q Calculator, wristwatch, timerQ Sample shuttle (cooler)Cl Indelible markerQ Distilled and deionized waterQ Laboratory-grade glassware detergentQ Paper towelsQ Stainless-steel clamps

DttPont Environmental Remediation Services

Appendix B

OUTLINE OF GROUNDWATER SAMPLING PROCEDUREFOR RTDF PILOT STUDIES AT DOVER AFB

A R 3 I 2 I 3 . 5

OUTLINE OF GROUNDWATER SAMPLING PROCEDUREFOR RTDF PILOT STUDIES AT DOVER AFB

The following is an outline of the procedures to be used during the second round of sampling.1, Open the well cap and measure the presence of volatile constituents with a PID meter.2, Record the water level in the well.3, Slowly lower the DO meter down the well to the top of screened interval and record the

percent oxygen. Measure DO at the middle and bottom of the screened interval, if"possible. DO measurements can only be obtained from the top of the screened interval inmonitoring wells with dedicated.pumps.

4, Begin purging the well at a rate that will not drop the water level in the well by more than1 foot

5, Record pH, temperature, conductance, DO, and redox every V* well volume.6. After one well volume has been purged and pH, temperature, and conductance have

stabilized, the sample can be collected. Prior to collecting the sample field measurementsof soluble iron, total iron, manganese, sulfide, and DO using ChemMetric kits.The range of the ChemMetric Kits are: - •

iron 0-0.9& 1 - lOppmsulfide 0 - 0.9 & 1 -10 ppmmanganese 0-2 ppmDO "" 0- 10 ppm

7. Samples will be stored on ice and shipped daily to the appropriate laboratory.

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