Oil Spill Chemistry, Laboratory Analysis, and Field Screeningp y y y g

D A th B dDr. Anthony BednarResearch Chemist

USACE ERDC-EL

11 A t 201011 August 2010

US Army Corps of EngineersBUILDING STRONG®

Outline ‘Historical’ efforts

► Initial work dates back to 2008• MVN SPN Both started as DOTS responses• MVN, SPN – Both started as DOTS responses• Decades of experience with PAHs

More recently Alkylated-PAHs

Laboratory Analysis► Methods► Characterization of source and weathered oil

• PAHs and Alkylated PAHs• GRO/DRO/ORO• Degradation/Photolysis• Degradation/Photolysis

Field Analysis► Portable GC-MS instruments

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► Screening test kit / Demonstration

2008 Efforts 2008 Events

► Oil spill in San Francisco Bay (December, 2007)• Initial ERDC response options included field portable GC-MS• Slow startup due to holidays and shipping instrument to CA• SPN used Pom-Poms

► Lower MS River Barge Sinking• Same Field Instrumentation Response Option

Co pled to laborator anal sis of samples Coupled to laboratory analysis of samples• Faster Deployment • In-Field ‘discovery’ of colorimetric oil determination

Subsequent laboratory optimization Later developed into current fluorescence based method

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Techniques GC-MS

► Polycyclic Aromatic Hydrocarbons – 8270► Alkylated PAHs – 8272 / Modified 8270► Alkanes (C8 to 40) – Modified 8015 ► Volatiles (GRO BTEX) 8260► Volatiles (GRO, BTEX) – 8260

GC-FID► Alkanes – 8015► Alkanes 8015

Other► Oil and Grease – 1664 ► Metals – 6020

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Sample Analysis Background

► Five Soil and Five water samples collected by ERDC/USGS• Very Low Levels or non-detects• <0.02 g/L in water, 4.1-74 g/kg Benzo (a) pyrene,

Chrysene/Fluorene in 2 samplesChrysene/Fluorene in 2 samples► Surface Oil Samples provided by MVN► Source Oil and weathered sample provided by MVN from BPp p y► Alabama Geological Survey shoreline groundwater samples

Standard Analyte List► GRO/DRO/ORO► PAHs, Alkylated-PAHs

Oil d GBUILDING STRONG®

► Oil and Grease

Characterization South Louisiana Crude

► Commercially available standard from Fisher Scientific► Compared to field collected samples provided by MVN► Compared to field collected samples provided by MVN

12000

14000

16000

18000

20000 ALKANESMSRC570 A1 SKIMMER OIL

(WEATHEREDOIL)

SOUTH LA REFERENCEOIL12000

14000

16000

18000

20000 ALKANESMSC252 SURFACE OIL S2

SOUTH LAREFERENCEOIL12000

14000

16000

18000

20000 ALKANESMSC252 SURFACE OIL S3

SOUTH LAREFERENCEOIL

0

2000

4000

6000

8000

10000

12000

8 9 101112131415161718192021222324252627282930Concentration  ug/g

SOUTH LA REFERENCEOIL

0

2000

4000

6000

8000

10000

12000

8 9 101112131415161718192021222324252627282930Concentration  ug/g

0

2000

4000

6000

8000

10000

12000Concentration  ug/g

8 9 101112131415161718192021222324252627282930C

Number of C

8 9 101112131415161718192021222324252627282930C

Number of C

1500

2000

2500

tion ug/g

PAHsmsc 252 surface oil s2

south LA reference oil

8 9 101112131415161718192021222324252627282930C

Number of C

1500

2000

2500

tion ug/g

PAHsmsc 252 surface oil s3

south LA reference oil 1500

2000

2500

tion ug/g PAHs

msrc 570 a1 Skimmer Oil (Weathered Oil)

south LA reference oil

0

500

1000

Concentrat

0

500

1000

Concentrat

0

500

1000

Concentrat south LA reference oil

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Fingerprinting Analysis Specific organic compounds/patterns

► Aliphatic Hydrocarbons► PAHs and Alkylated-PAHs► Large Aromatics/Biomarkers

• Dibenzothiophene• Hopanes

St• Steranes► LSU GC-MS analysis of South Louisiana Crude

• Initial samples were a slightly weathered surface oil

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Degradation Losses due to volatilization

► Biological Degradation► Photolysis

Hexane Insoluble ► Photolysis Residue

After Photolysis

BP Source OilAfter PhotolysisAfter Photolysis

South La OilAfter Photolysis

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Characterization/Degradation BP Crude

► Source Oil► UV Weathering 800

1000

1200

n ug/g

PAHsSouth LA Crude ‐ Photodegradation

Control

Ph D d d

4000

5000ALKANES

South LA Crude ‐ PhotodegradationControl

► UV Weathering• 6 hours, 300nm

0

200

400

600

Concentration Photo Degraded

1000

2000

3000

Concentration ug/g

Photo Degraded

PAHs

1200

g

PAHsSourceOil Photodegradation

0C8 C10 C12 C14 C16 PRI PHY C20 C22 C24 C26 C28 C30 C32 C34 C36 C38 C40

Alkanes

6000ALKANES

Source Oil ‐ Photodegradation

200

400

600

800

1000

Concentration ug/g Source Oil ‐ Photodegradation

ControlPhoto Degraded

2000

3000

4000

5000

oncentration ug/g

Control

Photo Degraded

0

PAHs

0

1000

C8 C10 C12 C14 C16 PRI PHY C20 C22 C24 C26 C28 C30 C32 C34 C36 C38 C40

Co

Alkanes

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Field-Portable GC-MS Originally Developed for Explosives

Analysis of 10 g/L TNT in well water

10 g/L TNT x 100x Concentration = 1000 g/L TNT

Direct Push Well

500 mL sampleof well water

1

Extracted usingSPE Cartridge

1

Eluted off ofSPE Cartridge

using 5 mL solvent

10 g/L TNT x 100x Concentration = 1000 g/L TNT

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for analysis

2008 MS River Deployment Analysis of PAHs in Dredged Material

► Laboratory based GC-MS is standard PAH analysis method• Samples taken during active dredging operations

► Field instrument provides near real time analysis

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2008 MS River Deployment Similar ‘laboratory’ set-up as field explosives analysis

► Solids extraction by hexane using sonication► Liquid extraction by methylene chloride using separatory funnel► Liquid extraction by methylene chloride using separatory funnel

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In-Field Analysis Comparison PAHs in Dredged Material

• PAHs below action limits, allowed dredging to continue

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Field Screening Test Kit Hexane extraction of oil produces colored liquid solution

► Colorimetric screening for heavy oil► Extraction based on Method 1664, Oil and Grease (HEM)

ERDC Field Fuel Oil Screening Kit – 2008 g

Test vials containing hexane extraction solvent and drying agent, and example extract solution

Blank to 100 mg/L

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Calibration SolutionsScoop and Spatula for measuring and mixing

Blank to 100 mg/L

Test Kit Modifications Modifications for ‘Light Sweet’ Crude – 2010

► Fluorescence DetectionField Fl orometer► Field Fluorometer

• 5 mg/L compared to 10 mg/L with heavy oil colored solution► Deployed by MVN and SAM in 2010

Comparison Sol tions

UV Fluorometer

SolutionsVials for Tests

Sample with Fluorescence

Hexane Blank

Fluorescence

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Hexane Blank, No Fluorescence

Test Kit Demonstration Standards from 5 to 1000 mg/L (and Blank)

► Below 100 mg/L, Light Sweet Crude is not visible without fluorescence► Fluorescence is clear, particularly with little ambient light

“Natural” Samples► Pond water and Indiana Harbor Sediment► Pond water and Indiana Harbor Sediment

Pond Water Indiana Harbor- x2- x40

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QuestionsQuestions

Thanks

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