ISPAC2013 plenary talk - environmental forensics and PAHs
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Plenary talk at ISPAC conference on the use of polycyclic aromatic hydrocarbons (PAHs) in environmental forensics. Covers basics of what enviromental forensics investigations (EFIs) are and how PAHs ...

Plenary talk at ISPAC conference on the use of polycyclic aromatic hydrocarbons (PAHs) in environmental forensics. Covers basics of what enviromental forensics investigations (EFIs) are and how PAHs can be used to help determine sources of releases (creosote, railway ties), oil sands development and oil spill releases (Macondo oil spill, gulf oil spill).

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ISPAC2013 plenary talk - environmental forensics and PAHs Presentation Transcript

  • 1. Use of PAHs in Environmental Forensics Presented by: Court Sandau, PhD, PChem ISPAC 2013 Corvallis, OR
  • 2. Environmental Forensics • What is it? • Analytical issues with PAHs and EFI • Expanding PAHs (beyond 16) • PAHs and EFIs – examples and case studies 2
  • 3. Environmental Forensic Investigation The systematic examination of historical and environmental information (which may be used in litigation) to allocate responsibility for contamination “The application of scientific methods used to identify the origin and timing of a contaminant release”
  • 4. Disciplines in Environmental Forensics • • • • • • • • • • • Chemistry Statistics Engineering Microbiology Hydrogeology Soil Science Toxicology Biology Ecology Litigation Experience And others….
  • 5. Birthplace of Environmental Forensics Exxon Valdez 1989 Term “Environmental Forensics” coined in Dr. Robert Morrison’s first books since it was used in a peer reviewed publication. 5
  • 6. Crime Scene Investigations 6
  • 7. Environmental Forensic Investigation
  • 8. EFI Video See link to video on slideshare: http://www.slideshare.net/csandau/environmental-forensics-spoof-of-csi-opening
  • 9. Two Categories of EFIs Academic & Research Liability Driven
  • 10. Litigation and Liability Driven EFIs • Adversarial process • Goal – make you look bad or incompetent while making themselves look good/sympathetic • They are trying to tell if you are telling the truth or not • Good science does not necessarily prevail • Unfortunately, science is complicated (scientific literacy 28% in 2007) • Need to prove it beyond a reasonable doubt 10
  • 11. Differences Between Legal and Research Date • Documentation, Documentation, Documentation Project id. Date Project id. Address Date Notes and pictures/videos
  • 12. Differences Between Legal and Research • Documentation • Sample Handling • Chain of Custody
  • 13. Differences Between Legal and Research • • • • • • Documentation Sample Handling Chain of Custody Laboratory Competence Standard Procedures Communicating Results
  • 14. Carpet Dust Sampling Designation: D 5438 – 05 • Must follow Standard Practice for Collection of Floor Dust for Chemical Analysis standardized procedures where 1. Scope larger, embedded in carpet available household vacuum cleaners 1.1 This practice covers a procedure for the collection of a 3.1.2 surface and be • Difficult to changesample offordust from carpets other bare floors that can and proximately 5-µmdust—soil equivalen analyzed lead, pesticides, or chemical compounds adhering to floor surfaces a elements. hold vacuum cleaners. 1.2 This practice is applicable to a variety of carpeted and approaches bare floor surfaces. It has been tested for level loop and plush 4. Summary of Practice pile carpets and bare wood floors, specifically. 4.1 The sampling • Validation required 1.3 Thisofpractice isthenot intended asbestos collection and from work published metho if dust for presence of for the fibers. in Rob evaluation (4). 1.4 The 4.2 Particulate methodology changesvalues stated in SI units are to be regarded as the floor by means matter is standard. of vacuu 1 This standard is issued under the fixed designation D 5438; the number immediately following the desig original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates th superscript epsilon (e) indicates an editorial change since the last revision or reapproval. 1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the Designation: D 422 – 63 (Reapproved 2002)e 1 user of this standard to establish approresponsibility of the priate safety and health practices and determine the applicability of regulatory limitations prior to use. 2. Referenced Documents 2.1 ASTM Standards: 2 Particle-Size Analysis of Soils1 Test Method for Particle-Size Analysis of Soils D 422 D 1356 Terminology Relating to Sampling and Analysis of This standard is issued under the fixed designation D 422; the number immediately following the designation indicates the year of Atmospheres original adoption or, in the case of revision, the year of lastE 1 Specification parentheses indicates the year of last reapproval. A revision. A number in for ASTM Thermometers superscript epsilon (e) indicates an editorial change since the last revision or reapproval. E 337 Test Method for Measuring Humidity with a Psy- Standard Test Method for through a sampling nozzle and the particles are separat cyclone is designed to effic approximately 5-µm mean However, much smaller par efficiencies. The sampling and suction adjustments to air velocity for the removal and bare floor surfaces, so be repeated. HVS-3 Vacuum Cleaner NOTE 1—Side-by-side compa upright vacuum cleaner revealed
  • 15. Commercial Laboratory PAH Analysis • Methods vary from lab to lab • Quantification – Semi-quantitative methods with surrogates – Quantitative methods with labeled internal standards • Analytes measured – Routine EPA – Routine EPA+ – Deluxe EPA compounds with substituted PAHs and then some (up to 63 compounds in an analysis)
  • 16. US EPA Priority Pollutants PAH Compounds LMW naphthalene acenaphthylene anthracene acenaphthene 2-ring chrysene 3-ring fluoranthene pyrene benzo[b]fluoranthene benzo[a]anthracene 4-ring HMW benzo[k]fluoranthene f luorene phenanthrene dibenz[a,h]anthracene benzo[a]pyrene 5-ring www.chemistry-matters.com benzo[ghi]perylene indeno[1,2,3-cd]pyrene 6-ring 16
  • 17. Relative Response Analysis of PAHs S Retention Time
  • 18. Interlaboratory Comparisons Method 8270C • Interlaboratory study conducted • Each lab measured homogeneous soil sample 4 times over a ~ week • Requested standard PAH method • Compared variability amoung labs and within each laboratory
  • 19. Naphthalene
  • 20. Fluorene
  • 21. Pyrene 0.90 0.80 0.70 mg/kg 0.60 0.50 0.40 0.30 0.20 0.10 FAL - Coarse (0.40) 0.00 All Labs Lab A Lab B Lab C Mean Value Lab D Lab E Maximum Value Lab F Lab G Minimum Value Lab H
  • 22. Results • Laboratory variability issues amoung laboratories • Sample to sample variability within the laboratories Variability can be measured and controlled with a good data validation program
  • 23. Method Comparison - PAHs Low Resolution MS Method • EPA Method 8270C • Full Scan analysis • No confirmation ions or ratios • Inappropriate surrogate standards • Many versions of method High Resolution MS Method • Modified California Method (Carb 429) • IDMS quantitation • Less likely to have interferences present • Isotopically labeled standards • More accurate and precise • Better data = better decisions
  • 24. PAH Analysis • Many interferences exist in low molecular weight range – Depends on matrix, clean up method • Specificity of HRMS allows better accuracy and precision • Comes at a cost – 4-6x Difference in measuring 252 versus 252.30928 Benzo(a)pyrene
  • 25. Internal Standards vs. Surrogates naphthalene 13 C phenanthrene * * * * * * benzo(a)pyrene * * * * * * * * * * F O N+ O-
  • 26. Isotope Dilution Quantification • Standards behave exactly like compounds being analyzed • Loss of analytes during method, included in measurement • Matrix interferences in method, can usually be seen with standards as well • THE most accurate measurement available
  • 27. Is more expensive better? Experiment: • SRM – determine accuracy • Duplicate – determine precision • Unknown duplicates to compare results Compared methods, not laboratories Lab A – ID-HRMS Lab B- LRMS, surrogates
  • 28. Overestimation Compound Py re ne Lab A Fl uo In de re ne no (1 ,2 .3 -c d) py 2re Me ne th yln ap ht ha len e Na ph th ale ne Ph en an th re ne Concentration (ng/g) Certified SRM Value Ch rys Di be en nz e (a .h )a nth ra ce ne Fl uo ra nt he ne An th ra ce Be ne nz o( a) an th ra ce ne Be nz o( a) py Be re ne nz o( b) flu or an th Be en nz e o( g, h, i)p er y le Be ne nz o( k) flu or an th en e Ac en ap ht he ne Ac en ap ht hy len e PAH Comparisons Standard Reference Material 1.2 1 Lab B 0.8 0.6 0.4 0.2 0
  • 29. PAH Duplicate Results Lab A 120 100 Concentration (ng/g) 3% 8% 15% 16% 18% 17% 27% 11% RPD 80 60 40 20 0 BaA BaP BbF BkF CHRY FLUOR PHEN PYR Compounds Sample 1 Lab B 120 100 Concentration (ng/g) Sample 2 100% 92% 111% 100% 86% 94% 101% 90% RPD 80 60 40 20 0 BaA BaP BbF BkF CHRY Compounds Sample 1 Sample 2 FLUOR PHEN PYR
  • 30. LRMS Method HRMS Method 500 400 300 200 100 0 IND DB(ah)A B(ghi)P BAP BKF BBF CHRY BAA PYR FLUOR PHEN ANT FLR 2-NAP IND 600 NAP 700 DB(ah)A 800 ACY 900 B(ghi)P 1000 ACE BAP BKF BBF CHRY BAA PYR FLUOR PHEN ANT FLR 2-NAP NAP ACY ACE Results of On-Site Samples (unknowns) 35000 30000 25000 20000 15000 10000 5000 0
  • 31. Causes of Overestimation • Incomplete cleanup, residue matrix in extracts • Co-elution of other PAHs not being monitored
  • 32. Data Quality for PAHs • Low resolution surrogate MS methods for PAHs can be highly variable between laboratories • Sites driven by PAH risk require IDMS – Sensitivity – for the guidelines – Specificity – for the interferences that are naturally present in samples • IDMS methods are suggested for forensics investigations – May reduce variability of diagnostic ratios
  • 33. Diagnostic Ratios Ratios Values / Sources References Phenanthrene / Anthracene < 5 = Pyrogenic; > 5 = Petrogenic Neff et al., 2005 Fluorene / Pyrene + 1 = Pyrogenic. < 1 = Petrogenic Neff et al., 2005 Indeno(1,2,3-cd)pyrene / (Indeno(1,2,3-cd)pyrene + Benzo(g,h,i)perylene > 0.1 = Combustion Motelay-Massei et al 2007; Yunker et al., 2002 Fluoranthrene/ Pyrene < 1 = Petrogenic; >1 Pyrogenic Motelay-Massei et al 2007 LMW / HMW < 1 = Combustion Zhang et al 2005; Benzo(a)pyrene / Benzo(a)pyrene + Chrysene < 0.2 = Petrogenic; > 0.35 = Combustion Zhang et al 2005; Zhang et al 2007 • Decrease analytical variability with better methods • Some good, some not as good – use what fits? • Good for bulk characterization – what about further distinction of sources
  • 34. Expanding the List of PAHs Alkylated-PAHs and Other PAHs 9 10 8 Phenanthrene 1 7 2 6 C1-Phenanthrenes 5 4 3 C2-Phenanthrenes C3-Phenanthrenes CH3 CH3 CH3 CH3 CH3 CH3 CH3 (5) CH3 H2C H3C CH2 CH3 (30) C4-Phenanthrenes… (?) CH2 (?)
  • 35. Chromatography Gets Busy C1-DBT C2-DBT C3-DBT C4-DBT
  • 36. Additional PAHs – Biogenic (transformation of natural precursors) • Yulin et al. (1996) Biogenic Polycyclic Aromatic Hydrocarbons in an Alaskan Arctic Lake Sediment, Polycyclic Aromatic Compounds, 9(1-4). Phenanthrene Retene Perylene – Petrogenic (fossil fuels) – Pyrogenic (burning of organic materials)
  • 37. Petrogenic vs. Pyrogenic
  • 38. Advanced – 2D-GC-TOF-MS • • • • • Cost – Highest Interpretation – Difficult Time – slow Can look for anything organic Advantage – separation + mass spectra id + sensitivity • Can be qualitative or semi-quantitative Diesel – Gas Station - Canada
  • 39. Middle East Crude Oil Investigation Alkyl Phenanthrenes/Anthracenes Alkyl Naphthalenes Alkyl Benzenes Alkanes
  • 40. Middle East Crude Oil Investigation Middle East Crude Oil 1 Middle East Crude Oil 2 Middle East Crude Oil 3 Saskatchewan Crude
  • 41. Stable Isotopes – CSIA “DNA” Fingerprinting • Stable isotope data gives a “signature” to samples • Samples may be linked or differentiated -15 -20 δ 13C (‰) -25 -30 -35 -40 O Compound www.chemistry-matters.com 41
  • 42. Case Study Residents have allegedly been exposed to PAHs released from a local industry. Exposure pathways include inhalation of ambient air and incidental ingestion of soil
  • 43. Investigation A number of techniques were completed including: – Chemical fingerprinting – Molecular diagnostic ratios – Statistical Analysis • Cosine Theta Analysis
  • 44. Sampling
  • 45. Chemical Fingerprint Suspected Source Unknown Human Habitation/ Background www.chemistry-matters.com 45
  • 46. Molecular Diagnostic Ratios 20 After Sicre et al 1987, Budzinski et al 1997, Tam et al 2001 and Neff et al 2005 18 16 PHEN/ANTH 14 12 Petrogenic Sources Mixed Sources 10 8 6 4 2 0 0.0 Mixed Sources 0.5 Pyrolytic Sources 1.0 Unknown 1.5 FLRN/PYR Human Habitation 2.0 Suspected Source 2.5
  • 47. Cosine Theta Analysis An analysis of the matrix of similarity coefficients between several different samples Theoretical Vector 0.00, 90o Orthogonal Dissimilar Suspected Source 0.586 Human Habitation/Background 0.995 Unknown Co-linear, similar compositions Theoretical Vector 1.00, 0o
  • 48. Results of Study – Independent lines of evidence were developed to indicate the potential source of PAHs in soils – Multiple forensic techniques supported these lines of evidence – Conclusion: PAHs found at residence shared similar properties to those of human habitation or background – Not similar to the suspected source
  • 49. Environmental Forensics in the Gulf Oil Spill • Reddy et al. sampled oil directly above well to conduct comprehensive characterization – Gas isotopes, GOR, fluid characteristics, API etc. – Fingerprinted with 2D-GC-TOF – Could distinguish between crudes Reddy et al. 2011, PNAS Early Edition, p.1-6
  • 50. Environmental Forensics in the Gulf Oil Spill • • • Hall et al. took 41 samples (slicks, scrapings off rocks, grasses and debris, sand patties etc) Oxidized hydrocarbons comprised of more than 50% of extractable hydrocarbons Used 2D-GC-TOF of samples compared to oil to assess weathering of oil spill using chemometric techniques Hall et al. 2013, Marine Pollution Bulletin, in press
  • 51. Environmental Forensics in the Oil Sands
  • 52. Environmental Forensics in the Oil Sands
  • 53. Alberta Oil Sands • Discovered by aboriginals and used to waterproof canoes – “tar sands” – “Tar sands” is a dirty term • In 1719, European fur traders received sample at Hudson’s Bay Company • In 1783, first European saw them personally • Development began in 1967 by (now known as) Suncor
  • 54. Environmental Forensics in the Oil Sands • 2009 Kelly et al. (Schindler) examined water and snow PAHs near oil sands development • Upstream [PAC] < downstream [PAC] (p<0.05) • Study was generally ignored by industry but is cited as the first attempt to assess environmental impacts from oil sands development Kelly et al. 2009, PNAS, 106, 52, p.22346
  • 55. Environmental Forensics in the Oil Sands • Kurek et al. sampled local lake sediments (no flow) • Sediment dating (Pb/Cs) combined with PAH analysis • PAHs sharply increased in lake sediments in ~1970 (but are still well below guidelines) • Important study: – Demonstrated that inputs were occurring – Established historical baseline (hadn’t been done previously) • No longer a question of if, now it is question of how much Kurek et al. 2013, PNAS, 110, 5, p.1761
  • 56. Environmental Forensics in the Oil Sands • • • • Jautzy et al. sampled local lake sediments (no flow) Sediment dating (Pb/Cs) combined with PAH analysis & compound specific isotopic analysis Additional line of evidence showing isotope shift in DBT Increase due to deposition of bitumen in dust particles with erosion of open pit mines Jautzy et al. 2013, ES&T, 47, p.6155
  • 57. Environmental Forensics in the Oil Sands • • • • Lundin et al. sampled scat from wolf, moose and caribou around SAGD facilities DNA testing, hormone testing, scat detection dogs, etc. Higher concentrations of PAHs (NAP and alkyl-NAP) in moose scat near SAGD compared to control locations Suggests that SAGD facilities may still be implicated Lundin et al. 2013, ISPAC 2013, Tues,11:00 AM
  • 58. Environmental Forensics Resources
  • 59. Societies and Organizations • • International Network of Environmental Forensics (INEF) Association for Environmental Health & Sciences (AEHS) Foundation • International Society of Environmental Forensics (ISEF)
  • 60. University Degrees and Training • Masters degree – University of Strathclyde • Bachelor Degree – Bangor University • University of Florida – Certificate program • Many courses on Environmental Forensics offered at Universities • Environmental Forensics certification (AEHS Foundation and others)
  • 61. Questions? Contact Info: Chemistry Matters Court Sandau Email: csandau@chemistry-matters.com URL: chemistry-matters.com Twitter: @EnviroCertainty Slideshare: www.slideshare.net/csandau