The Status of Environmental Forensic Science – 2008

1. The Status of Environmental Forensic Science – 2008

2. So, What is Environmental Forensics? • A term coined by Robert Morrison around 1999. • Now there is the International Society for Environmental Forensics • And the Environmental Forensics Journal[2000-present]

3. An up and coming field • Environmental Science & Technology (Nov. 21, 2003) • ScienceDaily (Sep. 14, 2006) • Science (Aug. 03, 2007) • C&EN (Sep. 1, 2008)

4. Many new books … • Sullivan, Patrick J, Agardy, Franklin J. and Traub, Richard K., Practical Environmental Forensics: Process and Case Histories, New York: Wiley, 2000 • Morrison, Robert D., Environmental Forensics: A Glossary of Terms, Boca Raton, FL: CRC Press, 2000. • Morrison, Robert D., Environmental Forensics: Principles & Applications, Boca Raton, FL: CRC Press, 2000. [TD193.4.M67 2000] • Murphy, Brian L. and Morrison, Robert D., eds., Introduction to Environmental Forensics, 1st ed., Burlington, MA: Academic Press, 2002. [TD193.4.I58 2002] • Murphy, Brian L. and Morrison, Robert D., eds., Introduction to Environmental Forensics, 2nd ed., Burlington, MA: Academic Press, 2007. • Morrison, Robert D. and Murphy, Brian L. eds., Environmental Forensics: Contaminant Specific Guide, Burlington, MA: Academic Press, 2006. [TD193.4.M667 2006] • Wang, Zhendi and Stout, Scott, Oil Spill Environmental Forensics, Burlington, MA: Academic Press, 2006 • Pye, Kenneth, Geological and Soil Evidence: Forensic Applications, Boca Raton, FL: CRC Press, 2007. • Hester, Ron E. and Harrison, R.M., eds., Environmental Forensics, London: RSC Publishing, 2008. • Mudge, Stephen M, ed., Methods in Environmental Forensics, Boca Raton, FL: CRC Press, 2008 • Ruffell, Alastair, Geoforensics, New York: Wiley, 2008.

5. And there are academic programs … • University of Wales, Bangor University, B.S. • University of Florida, online certificate prog. • Environmental Forensics I course • Environmental Forensics II course • Queens University Belfast, M.S. • Bournemouth University, B.S.

6. And many consultants • EnviroForensics • DPRA • Integral Consulting • GTI • NewFields • Battelle • Shaw

7. Even commercial products • Carolina Biological

8. Environmental Forensics? Environmental Chemistry Toxicology Forensic Science

9. Environmental Chemistry • Study of chemicals in nature • Natural • Anthropogenic • Atmosphere • Hydrosphere • Geosphere • Biosphere

10. Toxicology • Study of poisons • Typically done on animals, tissue cultures, cells, or biochemicals • Seeks to understand target’s • Routes of exposure to chemical • Internal transport of chemical • Storage of chemical • Metabolic transformation of chemical • Elimination of chemical

11. Forensic Science • Science in the service of crime solution and prosecution (or in some instances, the settlement of civil suits) • Critical that samples (potential evidence) be collected in a legal manner • Also critical that the science be done in a manner which the court will accept • Expert witnesses must be able to communicate to juries

12. Daubert v. Merrell Dow Pharmaceutical, 1993 • The Supreme Court agreed that the trial court must play a ‘gate keeping’ function to make sure that admitted scientific evidence and expert testimony are relevant and reliable. • Five tests (applicable to federal courts only, although some states have adopted criteria which are similar and some more strict) were suggested:

13. Daubert v. Merrell Dow Pharmaceutical, 1993 • Has the scientific theory or technique been tested? • Has the scientific theory or technique been subjected to peer review and publication? • What are the known or potential error rates of the theory or technique when applied? • Do standards and controls exist and are they maintained? • Has the theory or technique been generally accepted in the relevant scientific community?

14. Some Applications of Environmental Forensics • Environmental site assessment • Liability allocation at Superfund sites • Insurance litigation • Toxic torts • Natural resource damage assessment • Marine oil pollution

15. Some target chemicals • Heavy metals • Mercury, lead, chromium • Arsenic • Perchlorate • Asbestos • Organics • Hydrocarbons • Crude oil • Fuels – gasoline, diesel, etc. and their additives • PAHs • Chlorinated organics • Pesticides • PCBs • Dioxins and furans

16. Who’s responsible?Site History – The first step • Documentary records • Who owned the property and when? • What processes, products and wastes did they produce? • Some situations • Single-party industrial site • Sequential multi-party industrial site • Landfill site with commingled wastes from multiple sources

17. What is that stuff?Chemical Fingerprinting • Spectrometry • IR • Atomic Absorption • ICP • X-ray Diffraction • Radiochemistry • Chromatography • Flame ionization GC (ASTM D3328) • HPLC • Ion • Mass spectrometry • GC/MS • GC/MS-SIM (ASTM D5739) • Thermal ionization (TIMS) • IRMS • ICP-MS

18. Case Study – Katrina Oil Spill* Hurricane Katrina’s 17 foot storm surge on Aug. 29, 2005 just a few miles east of New Orleans moved an oil storage tank causing it to rupture. ___________________ *Based on a paper by Scott A. Stout, et al., “Use of Chemical Fingerprinting to Establish the Presence of Spilled Crude Oil in a Residential Area Following Hurricane Katrina, St. Bernard Parish, Louisiana,” E.S.&T., 41(21), 7242-7251 (2007)

19. Case Study – Katrina Oil Spill X The tank leaked 25,000 gallons of its 40,000 gallons of Nigerian light crude. Some of the oil floated over a retaining wall into a residential area of Chalmette, La.

20. Case Study – Katrina Oil Spill • Floating oil contaminated many structures in the area. • Large quantities of particulate matter from nearby bayous and lakes mixed with the oil leading to sedimentation of oil onto the ground. • NewFields Environmental Forensics Practice of Rockland, MA was hired by Murphy Oil, Inc., owners of the ruptured tank, to assess the impact of the oil on the community (which eventually resulted in a class action suit).

21. Case Study – Katrina Oil Spill • Forensic work began on Sept. 5, eight days after the storm and lasted for nine months. • Initial investigation revealed hydrocarbons and organic materials which did not appear to come from the crude oil spill. • Over 14,500 samples were taken for examination to characterize the source of the organic materials. • Samples were taken from inside the oil tank, the diked area around the tank as well as the neighborhood. • Some of the material was shown to have come from abandoned vehicles, garages, and service stations in the area.

22. Case Study – Katrina Oil Spill • GC/FID chromatograms • Soil sample – weathered Murphy crude • Wipe sample – weathered Murphy crude • Soil sample – weathered Murphy crude + natural organic matter • Negative sample – lube oil • Negative sample – natural organic matter

23. Emerging Techniques • Dendroecology • Age dating of soil contaminants by air analysis • Tritium • CFC’s • DNA fingerprints

24. Forensic Dendroecology* • Age dating • Contaminant assessment using energy dispersive x-ray fluorescence (EDXRF) – Pb, Cl, S • Characterization of chemical releases • Mapping extent of contaminant plumes ________________________________ Balouet, J.-C. et al., “Applied Dendroecology and Environmental Forensics. Characterizing and Age Dating Environmental Releases: Fundamentals and Case Studies.” Environmental Forensics, 8, 1-17 (2007)

25. Forensic Dendroecology

26. Aging Soil Contaminants • 3H, tritium, 85Kr, CFC’s, SF6 can be used estimate the age of groundwater. • In some cases, non-atmospheric contaminants such as detergents and pharmaceuticals might be used. • Groundwater age is defined as the time elapsed since the water entered the saturated zone and was isolated. • The age determined by these techniques is truly the date of introduction of contaminant and not the age of the water.

27. Aging Soil Contaminants • It is assumed that the age of release can be estimated if a groundwater sample is collected from the horizontal and vertical leading edges of a contaminant plume. • The recharge water must pass through the unsaturated zone picking up contaminants from any release and that water will have an age signature of tritium, CFC’s, etc.

28. Aging Soil Contaminants • Tritium was introduced into the groundwater cycle by the explosion of H-bombs in the late 1950s, peaking around 1964. Ottawa, Oudjik, 2005.

29. Aging Soil Contaminants • Tritium decays into 3He with a half-life of 12.43 yrs. • To determine the tritium concentration in rainwater, the 3H/3He ration must be determined. • Both 3H and 3He are present from decay of uranium in rocks. • Determination of 3He/Ne ratios are used to quantify 3He from tritium vs. rocks.

30. Case Study – New Jersey Solvent Contamination* • An industrial site in NJ near the GW Bridge was to be sold. • An environmental investigation showed contamination of underlying groundwater by chlorinated solvents, TCE and PCE. • The company claimed those solvents had never been used by them at that site. • Environmental forensic investigation ensued to determine the age of the contamination source.___________ *Oudjik, Gil, “The Use of Atmospheric Contaminants to Estimate the Minimum Age of Environmental Releases Impacting Groundwater,” Environmental Forensics, 6 (4), 345-354 (2005).

31. Case Study – New Jersey Solvent Contamination • Several monitoring wells were installed and the extent of the solvent plume delineated. • Based on the results it was assumed the leak came from a catch basin beneath a paint storage room. • Because very low VOC levels were found at MW-1, it was assumed that location was in the oldest portion of the plume. • Samples from MW-1 were analyzed for 3H, He isotopes, Ne, and CFC’s. • Based on tritium, groundwater age was estimated to be 31-32 years. • Based on tritium, groundwater age was estimated to be 31-32 years. CFC levels indicated 32-35 years. • When this data was presented to the previous property owner, a cleanup settlement was negotiated.

32. Case Study – New Jersey Solvent Contamination • The investigators noted that this contamination came from beneath an impervious surface, a concrete floor. • If the leak had come from an underground storage tank, the methods used might not have worked because water would not have been released with the solvent. • In this case, the leak was from a catchment basin and solvent most likely mixed with runnoff from periodic floor washings. • The runnoff retained the tritium and CFC signature of the time of the release to groundwater because of equilibration with the atmosphere. • Total cost of the investigation was $12,000 including well installation.

33. Case Study – Shaker Village Catchment, ME* • Trace Pb concentrations in groundwater within glacial deposits across Maine fluctuate considerably. • Deciphering the distribution and sources of naturally occurring Pb in groundwater with only the use of conventional anomaly identification techniques presents a challenge. ________________________________ * W. C. Sidle & Derrick Allen, “Deciphering Naturally Occurring Pb Contamination Impacting Drinking Water Wells: Shaker Village Catchment, Maine,”Environmental Forensics, 9, Issue 2 & 3 April 2008 ,197 – 204.

34. Case Study – Shaker Village Catchment, ME • This area contains braided Pleistocene channel deposits up to 45 m in depth. • 144 samples were collected from 46 wells and 2 springs over a 3 year period. • Samples, filtered and unfiltered, were spiked with 204Pb and isotope dilution analysis employed to determine Pb conc. and stable Pb isotope ratios.

35. Case Study – Shaker Village Catchment, ME • The isotopic compositions of the filtered samples exhibited two distinct groups. • One group plotted in the north-central area (I) and the other group (II) was scattered throughout the watershed. • There was no evidence for an anthropogenic Pb source for group I. • It was suggested that the source was rock dissolution from U- and Th-rich minerals.

36. Case Study – Shaker Village Catchment, ME • Recent identification of elevated excess 210Pb (≤302.6 mBq/L) and 137Cs (≤ 111.3 mBq/L) activity in drinking water wells up to 20 m depth indicates some transport of airborne radionuclide fallout beyond soils in the Shaker Village catchment, Maine. • Estimated airborne mass loading excess 210Pb fluxes of about 0.9 mBq m-3 in this headwater catchment may be sufficient to pose risks to unprotected shallow wells. • Inventories of excess 210Pb and 137Cs in pond sediments indicate maximum median activities of 94.3 mBq/g and 40.0 mBq/g, respectively. • Calculated excess 210Pb fluxes in the catchment soils range from 0.62-0.78 Bq/cm2/yr and yield a mean residence time of near 140 yr. • Measured 137Cs activity up to 51.1 mBq/g occurs in sediments at least to 5 m depth. • Assumed particle transport in groundwater with apparent 85Kr ages less than 5 years BP (2005) may explain the correlation between these particle-reactive radionuclides and elevated activity in some drinking water wells. _______________________________________________________________________ Sidle, W.C., “Vulnerability of Headwater Catchment Resources to Incidences of 210Pb Excess and 137Cs Radionuclide Fallout.” in P. E. LaMoreaux (ed.), Environmental Geology. Springer-Verlag, Berlin, Germany, 10.1007/s00254-0:1, (2008).