Applied Environmental Forensics

Transcription

1 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

2 Agenda Environmental Forensics Common Applications Techniques Presenting Results Details on Several Methods Case Histories o Petroleum, Creosote, or Coal Tar? o Solvents o Stray Methane in Buildings Basic Tips for Technical/Legal Interaction

3 About Me Tom Fort Principal Forensic Scientist Apex Companies, LLC Developed & applied techniques for >30 years o Former COO of Boutique Forensics Firm - IST, Inc. o Former Corporate Environmental Director Sunoco/Chevron (20 yrs) Hydrogeologist & geological engineer Thousands of remediation sites/hundreds of claims Managed corporate remediation and 3 rd party claim reserves Risk manager and principal spill responder Environmental insurance claims expert Remedial cost estimator Expert witness

4 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

5 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

6 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 3 rd party claims (e.g. trespass, toxic tort, value diminution) Contribution claims other Responsible Parties

7 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?

8 Direct Business Applications Contaminated property cleanups ID Responsible Parties (RP)/RPs Allocate remediation cost or 3 rd party damages Insurance or 3 rd 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, other excluded conditions) Litigation as plaintiff or defendant (burden of proof) Apply technical reasoning to legal case strategy Real estate transactions - Other

9 Methods for Useful Conclusions Setting o A dispute usually exists (Symptom = Failure to Act) o Virtually guaranteed findings will be challenged o Vigorous defense of conclusions required Worthless unless defended Methods o Purposeful approach o Attention to detail o Zero reliance on speculation o High quality data collected with case objectives in mind o Prove your point AND disprove alternative explanations o Convincing and understandable presentation o Robust conclusions crafted with challenge in mind

10 Useful Tactic - Translate Conclusions Into Dollars 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.

11 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

12 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

13 Gas Chromatograph Basics CARRIER GAS A n aly s is : s a07 37, 17,1 " hy droc a rb ons,c han l_0 8. s a0 737, 17, 1, 1; " P rojec t : h y droc arbons In s t ru m ent : c han l_ 08 CG 05 Coal Tar Distillate M et hod : m a0 814 R es pons e(m V ) T im e (m inut e s ) A cquisition Tim e : 02 Oc t 1997 at 10:52.49 O TP AN D RO S TA N E A C B SAMPLE SAMPLE INJECTOR ANALYTE DETECTOR DIFFERENT TYPES OF ANALYTE DETECTORS ARE USED (FID / MS / ECD / OTHER) A B C CARRIER GAS CAPILLARY COLUMN SLOWS DOWN HEAVIER HYDROCARBON MOLECULES, ALLOWING LIGHTER ONES TO HIT THE ANALYTE DETECTOR FIRST GC OVEN/ COLUMN TEMPERATURE IS GRADUALLY RAMPED UP DATA SYSTEM LIGHT, VOLATILE COMPOUNDS ELUTE FIRST (A), FOLLOWED BY HEAVIER COMPOUNDS (B/C)

14 Different Crudes. Different GC/FID Signatures Alaska North Slope Crude Nigerian Crude After: Wang and Stout, 2007

15 Different Products. Different Signatures Injection: [SHC1996] ,30,1 Arthur D. Little Inc., EM&A Laboratory 1000 mv Gasoline mins 80 Acquired on 14-Apr-96 at 12:55:47 Reported on 18-Apr-97 at 17:34:34 Injection: [SHC1996] ,10,1 Arthur D. Little Inc., EM&A Laboratory 1000 mv Diesel Fuel UCM mins 80 Acquired on 23-Apr-96 at 00:58:38 Reported on 17-Apr-97 at 10:26:19 Injection: [SHC1996] ,3,1 Arthur D. Little Inc., EM&A Laboratory 250 mv UCM Lube Oil mins 80 Acquired on 12-Apr-96 at 20:36:42 Reported on 18-Apr-97 at 15:35:02 n-c8 n-c20 n-c30 Retention Time Minutes n-c44

16 Weathering Changes Fingerprint with Time Spilled Oil D \ F I D 1 A nc IS D \ F I D 1 A IS IS nc Weathered Oil? IS IS IS nc17 nc34 UCM Over-reliance on GC-FID can be problematic

17 Sulfur and Dyes in Distillate Fuels Distillates include heating oil, kerosene, & diesel fuel o Heating Oil #2 is similar to Diesel #2 except for sulfur restrictions, cetane no., and dye mandate. o 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. o 1920s #2 Heating Oil (Diesel) (1.5% Sulfur) o 1980s Diesel Fuel (0.18% Sulfur) o ~1998 Low Sulfur Diesel Fuel (0.04% Sulfur) o 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.

18 Gasoline Lead Content Age Dating L e a d C o n c g r a m s p e r g a l l o n Average Although Lead the Content average of lead the concentration US Gasoline Supply in gasoline Over has Time changed with time, wide regional variations are documented DATE Note: Gasoline evaporation over time in the environment concentrates lead in the remaining fuel, and must be considered in age determinations.

19 Gasoline Additives Age Dating ETHANOL Gasoline additives provide a means to date gasoline Chronology of Selected Gasoline Additives > n-propylbenzene Gasoline hydrocarbons with = n-propylbenzene 10+ carbon atoms Toluene/benzene ratio > Methyl tert-butyl ether (MtBE), eastern United States Manganese (MMT) MtBE, western United States Mixed Alkyl Leads Ethylene dibromide and ethylene dichloride Tetraethyl lead only Lead >1.1 g/gal <1.1 g/gal <0.1 g/gal Year Lead Phase Down Note: Numerous other oxygenates have been used in gasoline (not shown), principally associated with 1990 Clean Air Act compliance.

20 Diagnostic Ratios A Basic Example n-c 17 /Pristane Normal Alkane / Isoprenoid Ratio Weathering Indicator Pristane and Phytane are Isoprenoid Hydrocarbons that elute adjacent to the C 17 and C 18 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. Time, Water Contact or Microbial Degradation Note: This relationship is not recommended for precise age dating of releases without careful, site-specific calibration.

21 Weathering Trends and Source Identification Ongoing Source X n-c 17 /Pristane = High - Not Weathered n-c 17 /Pristane = Low - Weathered O Break in Weathering Trend Indicates New Source

22 Other Diagnostic Biomarkers Crude Oil Biomarkers Source Oil Indicator 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 The Biomarker Hopane The Biomarker Sterane The Biomarker Triterpane

23 Stable Carbon Isotope Ratios Source Profile d 13 C -35 Every Crude Oil Has a Diagnostic 13 C/ 12 C Ratio Depending on When/How it Formed Hydrocarbon Molecules in Fuels Refined from the Crudes Tend to Retain Diagnostic 13 C/ 12 C Ratios 13 C/ 12 C Ratios Remain Generally Stable Even in Instances of Extreme Weathering Monterey Crude Katalla Crude Cook Inlet Crude North Slope Crude Unknown Source Monterey Source NSC Source Petroleum Source Note: δ 13 C expressed relative to the PDB reference standard

24 Stable Carbon Isotope Application Impacted Domestic Well X Source Buried Utility O Source Conclusion: δ 13 C Shows Source 1 is Impacting the Domestic Well

25 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

26 Methane Identification with Isotopes Methane Isotope Analysis Is energy production at fault? o The chemical formula for Methane is CH 4 o Carbon and Hydrogen in the Methane have isotopic signatures 14 C is Radioactive with a Half Life of 5,730 Years o Methane in gas reservoirs is millions of years old, so: Only modern Methane has significant 14 C o If 14 C is abundant, Methane is not from gas production Varying Amounts of 12 C and 13 C stable isotopes indicate how the methane formed o Thermogenic (gas reservoir) or Biogenic (organic decay)

27 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?

28 Case History GC/FID Hospital Construction Internal Standard Heavy Comparison of an Unknown Soil Sample to a Gasoline Standard Light No Match The gasoline standard is much too light. It contains none of the heavier hydrocarbons found in the site pail sample.

29 Case History GC/FID Hospital Construction? Internal Standard 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.

30 Case History GC/FID Hospital Construction Internal Standard Heavy Tail 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.

31 Case History GC/FID Hospital Construction UCM 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.

32 Case History GC/MS (SIM) 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.

33 Case History PAH Source Ratio Hospital Construction Fluoranthene/Pyrene vs. Dibenzofuran/Fluorine Lab A Lab B Data Clusters Identify Like Sources Mystery Solved The sample is a Carbureted Water Gas (CWG) coal tar. Site Soil Samples and Various Hydrocarbon Standards are Shown

34 Case History Chlorinated Solvents Chlorinated solvent releases from a large filtration manufacturer o Other sources suspected up-gradient o Both sites used TCE and PCE o Multiple aquifers with natural artesian/upward flow Forensics evaluation confirmed up-gradient source impacting client s property o Highest total VOC concentration on client = 7,445ug/l o Highest total VOC Concentration up-gradient = 47,900ug/l o Contaminant flow in deeper aquifer not the shallow aquifer o 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

35 Case History Chlorinated Solvents Up-Gradient Source Client

36 Case History Chlorinated Solvents Client Property Up-Gradient Source

37 Case History Beer Warehouse with Methane A beer warehouse is located next to a Superfund Site. Extremely high concentrations of 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.

38 Case History Beer Warehouse with Methane Carbon-14 Radioactive Carbon Testing Only 11% of the carbon is modern, 89% is radiocarbon dead. Diagram After: Isotech - Coleman, Liu, Hackley, and Pelphrey, 1995

39 Case History Beer Warehouse with Methane Stable Isotope Plot Stable Carbon Isotope Domains for Common Sources of Methane Sub-Surface Microbial Gas via CO 2 Reduction. Found in Glacial Drift Deposits. Shallow Microbial Gas Typical of Swamp Gas or Landfill Gas. Gas from Energy Reservoirs. Stable isotopes show the site methane was produced by the near- surface microbial fermentation pathway. Diagram After: Isotech - Coleman, Liu, Hackley, and Pelphrey, 1995

40 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 o Poorly constructed field sampling misses critical info. o Not all data are forensics quality QA/QC critical o Collection of unnecessary new data may be risky Prepare for challenge play devil s advocate Tell a technically correct story at the 3 rd grade level Appeal to common sense of judge and jury o Like water, contamination flows downhill. Use Visuals and memorable sound bites for key points o If the Glove Doesn t Fit, You Must Acquit.

41 Wrap-Up The Need for Good Data Gas Station Known Leaks and Contaminated Wells Groundwater Flow? Historic Bulk Plant No Known Leaks, No Wells? Data Trends? Other Sources? Spatial Relationships? Migration Dynamics? Flow Divides? Neighborhood with Contaminated Wells

42 Thank you! Tom Fort, MS, PG