Surface Water Sheens

Characterization, Sampling and Analysis

• Safety Moment

• Purpose and Scope

• Sheen Evaluation Hierarchy

• Marine Sheen Case Study

• Inland Sheen Case Study

• Laboratory Coordination

• Open Discussion

Agenda

Purpose and Scope

• 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

• 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

• 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

Sheen Classification (S,R, st)

• 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?

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 ()

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!!

Sheen Classification

Visual Inspection - Biogenic

Polarized parallelPolarized normal

Sheen Classification

Visual Inspection - Petroleum

Gasoline, Vegetable Oil, Kerosene, Brake Fluid, Lube Oil, Waste Oil

Sheen Classification

Visual Inspection - Petroleum

Vegetable OilWaste Oil80W-90 Gear Oil

Sheen Classification

Petrogenic vs. Pyrogenic

Petrogenic Sheen Rainbow Pyrogenic Sheen Rainbow

Sheen Classification

Rock and Stick Test

Rock Test with Pyrogenic Sheen

Stick Test with Biogenic Sheen

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

Color and Appearance

Color Example

Structure

STREAMER

Convergence

Windrows

Patches

Tarballs

Sheen Thickness Estimates

Sheen Sampling

Sheen Sampling

Grab

Net Preferred Method

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: sales@generaloceanics.com

Sheen Analysis and

Evaluation

• 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

• 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

• 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

• 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

urc

e A

So

urc

e B

So

urc

e C

So

urc

e D

Sh

ee

n 1

Sh

ee

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

urc

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

Marine Sheen Case Study

• 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

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

• 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

Initial Assessment

OTP

OTP

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

• 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

Forensic Analysis of Surface Water Sheen and Suspected Sources

Forensics

Forensics

OTP

2011 Sheen

2002 River Sheen

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

Inland Sheen Case Study

• 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

Fingerprint Evaluation

Chromatogram of free product in frac tank recovered during active release investigation

Chromatogram of sheen from ditch recovered during active release investigation

Comparison with Other

Sources

Chromatogram of free product from ditch recovered during active release investigation

Sheen Evaluation – Take

Home

• 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