surface water sheen chracterization sampling and analysis
TRANSCRIPT
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Surface Water Sheens
Characterization, Sampling and Analysis
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• Safety Moment
• Purpose and Scope
• Sheen Evaluation Hierarchy
• Marine Sheen Case Study
• Inland Sheen Case Study
• Laboratory Coordination
• Open Discussion
Agenda
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Purpose and Scope
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• Environmental Stewardship
Pollution Prevention
Spill Response
• Regulatory Environment
Oil Pollution Act
NRDA Claims
State/Federal NOVs
• Fiscal Implications
Sheen Evaluation –
Importance to our Clients
Example:
• $500,000 fine
• $7.5 million “Donation”
• Why . . . poor field
notes
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• Expand program awareness
- PICs, PMs, Program Managers
• Improve knowledge base
- Ongoing training
- Better staff work
• Identify appropriate resources
- Key technical resources
- SOPs, Best Practices
- Laboratory contacts
Sheen Evaluation –
Importance to our Clients
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• Sheen Overview
- Nature and classification
- Marine vs. Inland
• Field Observations
- Structure, color, distribution
- Surrounding land/water
• Laboratory Analysis
- Basic laboratory analyses
- Forensic and Isotope methods
Sheen Evaluation –
Methods and Resources
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Sheen Classification (S,R, st)
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• Very thin layer of non-miscible phase resting on surface water
• May be liquid, waxy semi-solid or solid material
• Less dense than water
• Biogenic sheens derived from the breakdown of natural organic material
• “Petroleum” sheens derived from crude or refined petroleum
What is a Sheen?
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Sheen ClassificationMarine/Harbor vs. Inland
• Sources- Leaks/Spills- Vessels- Fixed Facilities- Seeps
• Types
- Biogenic- Petrogenic- Pyrogenic
• Can Differ in Scale and Magnitude
Emulsified Oil (USCG)Algal Bloom (NOAA)
Wetland Biogenic (?????) Fuel in Lake ()
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Sheen Classification Visual Inspection
Things to consider:
Color
Structure
Break-up and recovery using the “stick test”
Behavior under polarized light
Presence of bubbles or foam
“What else” is in the area (e.g. pipes, wetlands, parking lots)
Odors
Be very careful in describing!!
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Sheen Classification
Visual Inspection - Biogenic
Polarized parallelPolarized normal
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Sheen Classification
Visual Inspection - Petroleum
Gasoline, Vegetable Oil, Kerosene, Brake Fluid, Lube Oil, Waste Oil
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Sheen Classification
Visual Inspection - Petroleum
Vegetable OilWaste Oil80W-90 Gear Oil
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Sheen Classification
Petrogenic vs. Pyrogenic
Petrogenic Sheen Rainbow Pyrogenic Sheen Rainbow
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Sheen Classification
Rock and Stick Test
Rock Test with Pyrogenic Sheen
Stick Test with Biogenic Sheen
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Location/Size Mapping
1 - Location/Size • Delineate Monitoring Zones• Tide level?• Orientation• Parallel to shore?• Dimensions • Size (1x1’ or 300 x 5’)• Percent Coverage
2 - Color/Appearance
3 - Structure
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Color and Appearance
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Color Example
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Structure
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STREAMER
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Convergence
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Windrows
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Patches
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Tarballs
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Sheen Thickness Estimates
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Sheen Sampling
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Sheen Sampling
Grab
Net Preferred Method
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Net Source
http://www.generaloceanics.com/product.php?productid=1179&cat=36&page=1
General Oceanics1295 N.W. 163rd Street Miami, Florida 33169 Phone: (305) 621-2882Fax: (305) 621- 1710 E-mail: [email protected]
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Sheen Analysis and
Evaluation
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• Hierarchical Approach
- Simple analytical methods may be sufficient
- Advanced analysis and a good argument is far cheaper than fines or litigation
• Focus on Specific Regulatory, Responsibility and Scientific Issues
- Regulatory Program
- Dispute Resolution
- Identification of source(s)
- Differentiation between natural and anthropogenic
Sheen Analytical Methods
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• Standard Analysis
- Total Petroleum Hydrocarbons
- PAHs, VOCs
• Advanced Methods
- PIANO analysis
- Full Scan Petroleum Hydrocarbons
- Alkylated PAHs
- Biomarkers
• Special Applications
- Isotope Analysis
- GCxGC TOF/MS
Sheen Analytical Methods
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• Statistical Evaluation
- Comparison between sample locations
- Comparison against standard materials
• Degradation Analysis
- Evaluation of evaporation, biodegradation, water washing, other weathering
• Mixing Models
- Comparison of known samples from different sources
- Estimation of relative contribution
Sheen Evaluation Methods
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• Present Data not Numbers
- Organic chemistry is complex
- Data illustrates relationships
• Provide Clear Graphics
- Show process
- Illustrate relationships
• Tell the Story
- Begin with fundamental problem
- Show what is, what isn’t and why
- Provide conclusions and limitations
Evaluation for Clients and
Regulators
So
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So
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e B
So
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So
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Sh
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n 1
Sh
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n 2
<0.01 <0.01 <0.01 <0.01 <0.01 <0.01
6.46 1.17 <0.01 <0.01 <0.01 <0.01
9.50 7.14 <0.01 <0.01 0.04 0.13
3.12 6.13 0.04 0.04 0.88 2.19
1.75 6.67 0.14 0.12 1.69 5.96
0.88 6.13 0.47 0.26 1.88 6.27
0.25 2.87 3.09 0.52 2.28 1.85
<0.01 0.03 6.21 0.94 2.67 1.68
<0.01 <0.01 5.48 1.60 2.55 1.61
<0.01 <0.01 4.40 2.19 2.39 1.50
<0.01 <0.01 3.80 3.26 2.20 1.39
<0.01 <0.01 2.80 4.46 1.85 1.15
<0.01 <0.01 2.23 6.84 1.54 0.92
So
urc
e A
So
urc
e C
So
urc
e D
So
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e E
Sh
ee
n 1
Sh
ee
n 2
0.50 0.59 <0.01 <0.01 0.05 0.19
1.73 3.21 0.04 0.04 0.72 1.44
1.41 3.36 0.07 0.07 0.94 1.85
0.13 0.31 0.01 <0.01 0.11 0.23
0.28 0.79 0.03 0.02 0.28 0.69
0.46 1.44 0.04 0.04 0.51 1.26
2.26 7.58 0.26 0.23 2.15 6.75
0.22 0.61 0.03 0.02 0.30 0.72
0.15 0.58 0.03 0.04 0.23 0.68
0.14 0.58 0.04 0.03 0.27 0.71
0.02 0.16 0.01 0.01 0.07 0.19
0.46 2.39 0.21 0.14 0.88 2.47
0.11 0.48 0.05 0.04 0.12 0.67
0.22 0.97 0.13 0.07 0.42 0.98
0.01 0.08 0.01 <0.01 0.04 0.09
0.07 0.32 0.06 0.04 0.20 0.37
<0.01 0.05 0.03 0.04 0.15 0.06
<0.01 0.09 0.17 0.04 0.16 0.13
<0.01 <0.01 <0.01 <0.01 <0.01 <0.01
<0.01 <0.01 <0.01 <0.01 <0.01 <0.01
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Marine Sheen Case Study
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• Occurred near to known source in subsurface
• Occurred near to loading dock
• Trace intermittent sheens observed historically
• Bulkhead has holes
• Tidally influence
• Saline conditions
• Sources – sea or land or subsurface?
- Sea o vessel cargo or fuel supply during loading
- Land o operation surface spills
o nonpoint source - storm drains, parking lots, roads
o seeps from LNAPL in subsurface
Conditions and Source
Considerations
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Initial Assessment
0’ 30’ 60’
B513
B501
B502
B503
B504
B505
B506
B507
B508
B509
B510B511
B512
MW-24
Sheens
ISBIO Pilot
Study Area
River
Groundwater
flow direction
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• Tiered investigation approach providing multiple lines of evidence
• Fuel Fluorescence Detector (FFD) field screening
• TPH chromatograms (GC-FID)
• PAH fingerprinting (GC-MS)
• Bulk C & H isotopes (IRMS)
• Laboratory-generated sheen study
• Compound-specific C isotopes (GC-IRMS)
• Biomarker Fingerprints (GC-MS)
Initial Assessment
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Initial Assessment
OTP
OTP
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Initial Assessment
-29
-28
-27
-26
-25
-24
-23
-22
-21
-20
-29.00 -28.50 -28.00 -27.50 -27.00 -26.50 -26.00
Phyta
ne
d1
3C
(pe
r m
il)
Pristane d13C (per mil)
B501
B508
MW-24 LNAPL
B502
B504
B513
Sheen
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• Multiple Lines of Evidence
1) Forensic analysis of surface water sheen
2) Forensic analysis of suspected sources
3) Historic monthly sheen monitoring records
4) Physical observations
Recent Event
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Forensic Analysis of Surface Water Sheen and Suspected Sources
Forensics
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Forensics
OTP
2011 Sheen
2002 River Sheen
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1) Client avoided a reportable incident – liability retracted and transferred
2) Owner offered to reimburse client cost of remediation ~ $250,000
Lesson # 1Have sheen test kits readily available
Lesson # 2Sheen grab sample is a waste of $s (unless dark/tarball)
Lesson # 3Use multiple lines of evidence, historical records
Lesson # 4Treat data as if it were for litigation
Results and Lessons
Learned
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Inland Sheen Case Study
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• Situation
Sheen identified on surface water near known facility with petroleum USTs
State Regulators presume sheen associated with USTs
• Initial Response Actions
Contain surface water release
Investigate UST area
UST release confirmed for gasoline
• Sheen Evaluation Approach
Complete GC/FID Fingerprint analysis of recovered materials including surface water sheen and Frac-Tank product
Conditions and Source
Considerations
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Fingerprint Evaluation
Chromatogram of free product in frac tank recovered during active release investigation
Chromatogram of sheen from ditch recovered during active release investigation
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Comparison with Other
Sources
Chromatogram of free product from ditch recovered during active release investigation
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Sheen Evaluation – Take
Home
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• Important to our clients Good Stewardship
Costly fines
• Sheens have multiple sources including Biogenic, Petrogenic and Pyrogenic Sheen Marine and inland sheens have both significant differences and important
similarities
Field observations critical
Sampling protocols available
• Use the proper analytical and evaluation methods GC/FID Fingerprint
Standard analytical methods (8015, 8260, 8270, TICs)
Advanced Forensic and Isotope Analytical Methods
Sheen Evaluation –Take Home