Applied Environmental Forensics Technical Considerations For Legal, - - PowerPoint PPT Presentation

Applied Environmental Forensics

Technical Considerations For Legal, Insurance, and Real Estate Decisions

Environmental Federation of Oklahoma 26th Annual Meeting October 2017

Contact: Tom Fort, MS, PG tfort@apexcos.com • 610-722-9050

Agenda – Environmental Forensics

▪ Common Applications ▪ Techniques ▪ Presenting Results ▪ Details on Several Methods ▪ Case Histories

• Petroleum, Creosote, or Coal Tar?
• Solvents
• Stray Methane in Buildings

▪ Basic Tips for Technical/Legal Interaction

About Me – Tom Fort

▪ Principal Forensic Scientist – Apex Companies, LLC ▪ Developed & applied techniques for >30 years

• Former COO of Boutique Forensics Firm - IST , Inc.
• Former Corporate Environmental Director – Sunoco/Chevron (20 yrs)

▪ Hydrogeologist & geological engineer ▪ Thousands of remediation sites/Hundreds of claims ▪ Managed corporate remediation and 3rd party claim reserves ▪ Risk manager and principal spill responder ▪ Environmental insurance claims expert ▪ Remedial cost estimator ▪ Expert witness

Apex Quick Facts

• Privately-held company with nearly three decades of

customer satisfaction

• 700+ employees in 60+ offices nationwide
• Full suite of professional and field environmental services

serving over 2,000 clients across the US each year

Forensics and Environmental Forensics Forensics: Using science to establish facts

▪ Who? What? When? Where? How? ▪ “A technical investigation that produces hard evidence useful in crafting a theory or in supporting or refuting a position”

Environmental Forensics

▪ Highly site-specific ▪ Multidisciplinary approach ▪ Data sources ▪ Lines of evidence

Typical Applications

▪ Contaminated industrial and commercial properties ▪ Cleanups, refinancing, or real estate transactions ▪ Post-closing responsibility for discovered contamination ▪ Applying buyer/seller indemnities ▪ Source ID / Cost allocation ▪ Insurance claims ▪ 3rd party claims (e.g. trespass, toxic tort, value diminution) ▪ Contribution claims – other Responsible Parties

Common Questions

▪ Source of the release? ▪ When did the release happen? ▪ How did the release happen? ▪ Single release or more than one? ▪ Contribution from neighbors? Prior owners? Tenants? ▪ Cost of cleanup? ▪ Will insurance pay? ▪ If I have to sue for damages, what do I have to prove? ▪ How to prepare in case I am sued?

Direct Business Applications

Contaminated property cleanups

▪ ID Responsible Parties (RP)/RPs ▪ Allocate remediation cost or 3rd party damages

Insurance or 3rd Party Funding – Environmental policies

▪ Covered or not covered?

• Release source and timing
• Sudden and accidental vs. intentional or operational
• Consistency with policy terms
• Policy exclusions (possible pre-policy,
• ther excluded conditions)

Litigation – as plaintiff or defendant (burden of proof)

▪ Apply technical reasoning to legal case strategy

Real estate transactions - Other

Methods for Useful Conclusions

▪ Setting

• A dispute usually exists (Symptom = Failure to Act)
• Virtually guaranteed findings will be challenged
• Vigorous defense of conclusions required
• Worthless unless defended

▪ Methods

• Purposeful approach
• Attention to detail
• Zero reliance on speculation
• High quality data – collected with case objectives in mind
• Prove your point AND disprove alternative explanations
• Convincing and understandable presentation
• Robust conclusions crafted with challenge in mind

Cost = Where “Data Impact the Deal” Always: find ways to express technical answers in dollars. Remember: You may need to close data gaps and retain a testifying expert to defend claimed costs. Approach: Closely target any new data collection, build a defensible technical basis for cost or allocation, and prepare for rigorous challenge. The most useful forensics practitioner is not just a scientist, but also a remedial cost estimator and potential testifying expert to defend the results.

Useful Tactic - Translate Conclusions Into Dollars

Petroleum Chemistry – Three Controls

1) Crude oil genesis

▪ Crudes are vastly different mixtures with unique attributes, some of which are conserved through refining

2) Refining processes

▪ Refining processes used at different facilities for different periods leave recognizable signatures on fuel products

3) Environmental weathering

▪ The environment alters petroleum in predictable ways allowing trend recognition and comparisons ▪ Preferential loss of light ends and easily biodegraded alkanes

Chemistry Approach and Types of Comparison

For Unknowns – Follow a Tiered Analytical Approach ▪ Direct comparison – field sample with a tank sample ▪ Quantitative comparison – field samples from the same site to each other ▪ Reference comparison – field sample to a lab standard reference ▪ Fuel type ID – Fuel ID (e.g. diesel, gasoline) with history of products handled or stored

▪ Changing tank contents over time

Gas Chromatograph Basics

SAMPLE

B C A

SAMPLE INJECTOR ANALYTE DETECTOR

CARRIER GAS GC OVEN/ COLUMN DATA SYSTEM

A C B

CARRIER GAS TEMPERATURE IS GRADUALLY RAMPED UP LIGHT, VOLATILE COMPOUNDS ELUTE FIRST (A), FOLLOWED BY HEAVIER COMPOUNDS (B/C) CAPILLARY COLUMN SLOWS DOWN HEAVIER HYDROCARBON MOLECULES, ALLOWING LIGHTER ONES TO HIT THE ANALYTE DETECTOR FIRST DIFFERENT TYPES OF ANALYTE DETECTORS ARE USED (FID / MS / ECD / OTHER)

Different Crudes. Different GC/FID Signatures

Alaska North Slope Crude After: Wang and Stout, 2007 Nigerian Crude

Different Products. Different Signatures

Arthur D. Little Inc., EM&A Laboratory

Injection: [SHC1996] 1 0412961,30,1

A cquired on 14-A pr-96 at 12:55:47 Reported on 18-A pr-97 at 17:34:34

10 20 30 40 50 60 70 80 mins 200 400 600 800 1000 mV

Arthur D. Little Inc., EM&A Laboratory

Injection: [SHC1996] 4 0422964,10,1

A cquired on 23-A pr-96 at 00:58:38 Reported on 17-A pr-97 at 10:26:19

10 20 30 40 50 60 70 80 mins 200 400 600 800 1000 mV

Arthur D. Little Inc., EM&A Laboratory

Injection: [SHC1996] 1 0412961,3,1

A cquired on 12-A pr-96 at 20:36:42 Reported on 18-A pr-97 at 15:35:02

10 20 30 40 50 60 70 80 mins 50 100 150 200 250 mV

Gasoline Diesel Fuel Lube Oil

UCM UCM n-C8 n-C20 n-C30 n-C44

Retention Time Minutes

2 1 9 8 1 . D \ F I D 1 A

0 2 1 0 9 8 3 1 . D \ F I D 1 A

Spilled Oil Weathered Oil

IS IS IS nC17 nC34 IS IS IS nC17 nC34

Over-reliance on GC-FID can be problematic

?

UCM

Weathering Changes Fingerprint with Time

Sulfur and Dyes in Distillate Fuels

▪ Distillates include heating oil, kerosene, & diesel fuel

• Heating Oil #2 is similar to Diesel #2 except for sulfur

restrictions, cetane no., and dye mandate.

• Jet Fuel (Jet A), kerosene, and Diesel #1 are also similar.

▪ Sulfur content has been regulated over time and provides useful criteria to date distillate releases.

• 1920s #2 Heating Oil (Diesel) (1.5% Sulfur)
• 1980s Diesel Fuel (0.18% Sulfur)
• ~1998 Low Sulfur Diesel Fuel (0.04% Sulfur)
• 2006 Ultra Low Sulfur Diesel Fuel (0.0015% or 15ppm)

▪ Dyes added to heating oil and aviation fuels over time (tax and safety reasons) can be useful.

Although the average lead concentration in gasoline has changed with time, wide regional variations are documented

0.5 1 1.5 2 2.5

L e a d C o n c g r a m s p e r g a

1920 1925 1930 1935 1940 1945 1950 1955 1960 1965 1970 1975 1980 1985 1990 1993

DATE

Gasoline Lead Content – Age Dating

Average Lead Content of the US Gasoline Supply Over Time

Note: Gasoline evaporation over time in the environment concentrates lead in the remaining fuel, and must be considered in age determinations.

Gasoline Additives – Age Dating

Chronology of Selected Gasoline Additives

Gasoline hydrocarbons with 10+ carbon atoms Mixed Alkyl Leads Lead

1960 1965 1970 1975 1980 1985 1990 1995 2000 Y ear

>1.1 g/gal <1.1 g/gal

<0.1 g/gal > n-Propylbenzene

= n-Propylbenzene MtBE, western United States Methyl tert-butyl ether (MtBE), eastern United Stat es T etraethyl lead only Ethylene dibromide and ethylene dichloride T

• luene/benzene rat

io > 2.5 - 4 Manganese (MMT) Lead Phase Down

ETHANOL

Gasoline additives provide a means to date gasoline

Note: Numerous other oxygenates have been used in gasoline (not shown), principally associated with 1990 Clean Air Act compliance.

Diagnostic Ratios – A Basic Example

Time, Water Contact or Microbial Degradation n-C17/Pristane

Weathering Indicator

Pristane and Phytane are Isoprenoid Hydrocarbons that elute adjacent to the C17 and C18 normal alkanes. Isoprenoids are branched chain unsaturated hydrocarbons Isoprenoids are resistant to weathering; normal alkanes degrade more quickly. As normal alkanes degrade over time, Isoprenoids become more dominant in the petroleum mixture.

Note: This relationship is not recommended for precise age dating of releases without careful, site-specific calibration.

Normal Alkane / Isoprenoid Ratio

Weathering Trends and Source Identification

X O n-C17 /Pristane = High - Not Weathered n-C17/Pristane = Low - Weathered Break in Weathering Trend Indicates New Source Ongoing Source

Other Diagnostic Biomarkers

▪ Biomarker presence and relative quantities are unique to particular crude oils ▪ Some biomarkers are conserved in the refining process ▪ Some biomarkers persist in the environment making them useful in forensics Crude Oil Biomarkers – Source Oil Indicator

The Biomarker Triterpane The Biomarker Hopane The Biomarker Sterane

Stable Carbon Isotope Ratios – Source Profile

• 20
• 25
• 30
• 35
• 23.27
• 25.66
• 30.06
• 29.52
• 29.50
• 23.45
• 29.68

Monterey Crude Katalla Crude Cook Inlet Crude North Slope Crude Unknown Source Monterey Source NSC Source Petroleum Source d13C

Every Crude Oil Has a Diagnostic 13C/12C Ratio Depending on When/How it Formed Hydrocarbon Molecules in Fuels Refined from the Crudes Tend to Retain Diagnostic 13C/12C Ratios

13C/12C Ratios Remain Generally Stable Even in Instances of

Extreme Weathering

Note: δ13C expressed relative to the PDB reference standard

Stable Carbon Isotope Application

X O

• 29.60
• 25.66

Source 1 Source 2 Impacted Domestic Well

• 29.52

Buried Utility Conclusion: δ13C Shows Source 1 is Impacting the Domestic Well

Methane Identification with Isotopes

▪ Methane can seep into structures or water wells ▪ Creates aesthetic problems and at high concentrations (>5%) may be a safety concern ▪ A natural condition in many areas of the U.S. ▪ Often blamed on energy production or ”fracking”

Methane Identification with Isotopes

▪ Methane Isotope Analysis – Is energy production at fault?

• The chemical formula for Methane is CH4
• Carbon and Hydrogen in the Methane have isotopic signatures

▪

14C is Radioactive with a Half Life of 5,730 Years

• Methane in gas reservoirs is millions of years old, so: Only

modern Methane has significant 14C

• If 14C is abundant, Methane is not from gas production

▪ Varying Amounts of 12C and 13C stable isotopes indicate how the methane formed

• Thermogenic (gas reservoir) or Biogenic (organic decay)

Case History – Hospital Construction

▪ During construction of a new hospital wing in New York City, black sticky soil contamination was encountered. ▪ The site’s 150-year-old history included fuel storage, wood preserving, steam ship fueling, and manufactured gas production. ▪ The developer was facing $1.2M in remedial cost. ▪ Historic site industries had successors with insurance. ▪ How to get responsible parties to pay?

Comparison of an Unknown Soil Sample to a Gasoline Standard

No Match – The gasoline standard is much too

• light. It contains none of

the heavier hydrocarbons found in the site pail sample. Light Heavy Internal Standard

Case History – GC/FID – Hospital Construction

Comparison of an Unknown Soil Sample to a Fuel Oil #6 Standard (Bunker Fuel)

No Match – The hydrocarbon range is close, but the normal alkane profiles are different. ? Internal Standard ?

Case History – GC/FID – Hospital Construction

Comparison of an Unknown Soil Sample to a Creosote Standard

No Match - Light ends in the field sample are missing; the field sample also extends into heavier compounds than the creosote standard – “tail”. The normal alkane profile is also different. Internal Standard Heavy Tail

Case History – GC/FID – Hospital Construction

Comparison of an Unknown Soil Sample to a Coal Tar Standard

A Match – After accounting for weathering Letters help connect compound peaks between chromatograms. “a” is Naphthalene and relatively weathered in the pail excavation sample (Expected). Note also the Unresolved Complex Mixture (UCM) “Hump” in the pail sample indicative of weathering. UCM

Case History – GC/FID – Hospital Construction

GC/MS With Selected Ion Monitoring (SIM)

Parent and Alkylated PAH Distribution Histograms

Note the patterns of substituted vs. parent PAHs (Red Envelopes). This is a classic Petrogenic

• vs. Pyrogenic PAH pattern

comparison.

Case History – GC/MS (SIM) – Hospital Construction

Site Soil Samples and Various Hydrocarbon Standards are Shown

Fluoranthene/Pyrene vs. Dibenzofuran/Fluorine

Data Clusters Identify Like Sources

Mystery Solved– The sample is a Carbureted Water Gas (CWG) coal tar.

Case History– PAH Source Ratio– Hospital Construction

Lab A

Lab B

Lab B

Case History – Chlorinated Solvents

▪ Chlorinated solvent releases from a large filtration manufacturer

• Other sources suspected up-gradient
• Both sites used TCE and PCE
• Multiple aquifers with natural artesian/upward flow

▪ Forensics evaluation confirmed up-gradient source impacting client’s property

• Highest total VOC concentration on client = 7,445ug/l
• Highest total VOC Concentration up-gradient = 47,900ug/l
• Contaminant flow in deeper aquifer not the shallow aquifer
• Local pumping of groundwater from production wells pulled

contamination down ▪ Conclusion: site should be remediated on a regional basis vs. site basis ▪ Up-gradient property owner required to cooperate & remediate

Case History – Chlorinated Solvents

Client Up-Gradient Source

Case History – Chlorinated Solvents

Client Property Up-Gradient Source

Case History – Beer Warehouse with Methane

▪ A beer warehouse is located next to a Superfund Site. ▪ Extremely high concentrations

• f Methane beneath the

warehouse floor (Methane >50%, ~10x the LEL). ▪ A 6-foot thick oil plume from Superfund Site was floating on water table beneath the building. ▪ PRPs took responsibility for oil plume, but not for Methane, stating it was naturally-occurring. ▪ Methane abatement estimated to cost >$1M. ▪ Isotope testing of the Methane determined its source.

Case History – Beer Warehouse with Methane

Diagram After: Isotech - Coleman, Liu, Hackley, and Pelphrey, 1995

Carbon-14 – Radioactive Carbon Testing

Only 11% of the carbon is modern, 89% is radiocarbon “dead.”

Case History – Beer Warehouse with Methane

Diagram After: Isotech - Coleman, Liu, Hackley, and Pelphrey, 1995

Stable Isotope Plot

Stable isotopes show the site methane was produced by the near- surface microbial fermentation pathway.

Stable Carbon Isotope Domains for Common Sources of Methane

Sub-Surface Microbial Gas via CO2 Reduction. Found in Glacial Drift Deposits. Shallow Microbial Gas Typical of Swamp Gas

• r Landfill Gas.

Gas from Energy Reservoirs.

Technical / Legal Interaction to Win

▪ Lawyers: “Involve your technical expert EARLY” ▪ Scientists: “Understand and CONTRIBUTE to the legal case strategy” ▪ Develop sampling plans to close data gaps

• Poorly constructed field sampling misses critical info.
• Not all data are forensics quality – QA/QC critical
• Collection of unnecessary “new” data may be risky

▪ Prepare for challenge – play “devil’s advocate” ▪ Tell a technically correct story at the 3rd grade level ▪ Appeal to common sense of judge and jury

• “Like water, contamination flows downhill.”

▪ Use Visuals and memorable sound bites for key points

• “If the Glove Doesn’t Fit, You Must Acquit.”

Wrap-Up – The Need for Good Data

Groundwater Flow Gas Station Known Leaks and Contaminated Wells Neighborhood with Contaminated Wells

?

Historic Bulk Plant – No Known Leaks, No Wells

?

• Data Trends?
• Other Sources?
• Spatial Relationships?
• Migration Dynamics?
• Flow Divides?

Thank you!

Tom Fort, MS, PG tfort@apexcos.com 610-722-9050