Environmental Forensics - Brussels Dioxin Conference Plenary 2011

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This presentation was a plenary talk on environmental forensics delivered at the 2011 Dioxin Conference in Brussels (www.dioxin2011.org). The presentation focused on the topic of environmental forensics investigations and techniques and their application to the field of persistent organic pollutants (POPs).

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Environmental Forensics - Brussels Dioxin Conference Plenary 2011

  1. 1. Environmental Forensics and POPs – Merging Fields of Expertise Court D. Sandau, PhD Chemistry Matters Dioxin 2011 – Plenary – August 21, 2011
  2. 2. Plenary Presentation at Dioxin 2011 • Honoured to be presenting a plenary talk at Dioxin 2011 in Belgium. • Pictures from the talk below. Dioxin 2011 Plenary - August 22nd, 2011, Belgium 2
  3. 3. Environmental Forensics • What is it? • Types of Environmental Forensics investigations • Techniques used in EFIs • POPs and EFIs 3 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  4. 4. Environmental Forensic Investigation The systematic examination of environmental information, which may be used in litigation, to allocate responsibility for contamination Success relies on an understanding of a variety of disciplines and knowing which tools are best suited for a particular case “The application of scientific methods used to identify the origin and timing of a contaminant release” www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium 4
  5. 5. What do POP researchers have to offer? - Leading edge research - Finding compounds since PCBs were discovered - Knowledge of contaminants - biotransformation, air dispersion, multi-component mixtures, impurities in mixtures - Breadth of knowledge of analytical and environmental chemistry (and related sciences) After discovering PCBs because they were interfering with his DDT chromatograms…. Methyl-sulphonyl metabolites of PCBs discovered by leaving GC on, chart recorder kept reading all night, caught late eluting chemicals. Soren Jensen. 1976. 5 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  6. 6. 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. 6 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  7. 7. Crime Scene Investigations 7 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  8. 8. Environmental Forensic Investigation Heisenberg is out for a drive when he's stopped by a police officer. The cop says: " Do you know how fast you were going? Heisenberg replies: "No, but I know where I am". 8 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  9. 9. Two Categories of EFIs Academic & Research Liability Driven 9 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  10. 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 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  11. 11. Differences Between Legal and Research • Documentation, Documentation, Documentation Date Project id. Date Project id. Address Date Notes and pictures/videos 11 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  12. 12. Differences Between Legal and Research • Documentation • Sample Handling • Chain of Custody 12 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  13. 13. Differences Between Legal and Research • Documentation • Sample Handling • Chain of Custody • Laboratory Competence • Standard Procedures • Communicating Results 13 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  14. 14. Carpet Dust Sampling • Must follow standardized procedures where available • Difficult to change approaches • Validation required if methodology changes Designation: D 5438 – 05 Standard Practice for Collection of Floor Dust for Chemical Analysis1 This standard is issued under the fixed designation D 5438; the number immediately following the designation original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the superscript epsilon (e) indicates an editorial change since the last revision or reapproval. 1. Scope 1.1 This practice covers a procedure for the collection of a sample of dust from carpets and bare floors that can be analyzed for lead, pesticides, or other chemical compounds and elements. 1.2 This practice is applicable to a variety of carpeted and bare floor surfaces. It has been tested for level loop and plush pile carpets and bare wood floors, specifically. 1.3 This practice is not intended for the collection and evaluation of dust for the presence of asbestos fibers. 1.4 The values stated in SI units are to be regarded as the standard. 1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appro-priate larger, embedded in carpet household vacuum cleaners. 3.1.2 surface dust—soil 5-μm equivalent adhering to floor surfaces and vacuum cleaners. 4. Summary of Practice 4.1 The sampling method from work published in Roberts, (4). 4.2 Particulate matter is floor by means of vacuum-through a sampling nozzle Designation: D 422 – 63 (Reapproved 2002)e 1 and the particles are separated safety and health practices and determine the applica-bility cyclone is designed to efficiently of regulatory limitations prior to use. approximately 5-μm mean However, much smaller particles 2. Referenced Documents efficiencies. The sampling 2.1 ASTM Standards: 2 and suction adjustments to D 422 Test Method for Particle-HVS-Size Analysis 3 Vacuum of Soils air velocity Cleaner for the removal D 1356 Terminology Relating to Sampling and Analysis of and bare floor surfaces, so Atmospheres be repeated. E 1 Specification for ASTM Thermometers NOTE 1—Side-by-side comparison E 337 Test Method for Measuring Humidity with a Psy-chrometer upright vacuum cleaner revealed (the Measurement of Wet- and Dry-Bulb Tem-peratures) least 0.2 μm and that the HVS3 smaller than 20 μm than conventional Standard Test Method for Particle-Size Analysis of Soils1 This standard is issued under the fixed designation D 422; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon (e) indicates an editorial change since the last revision or reapproval. e1 NOTE—Adjunct references were corrected editorially in July 2006. 14 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  15. 15. Contaminants where Environmental Forensics has been used • Petroleum Hydrocarbons (refined/unrefined)… • PAHs • Chlorinated solvents (PERC) • PCBs/PCDDs/PCDFs • Metals (selected) • VOCs • Methane (coal bed methane) • Pesticides (persistent/non-persistent) • Other persistent organic pollutants – soon… 15 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  16. 16. Chemical Fingerprinting Molecular fingerprint Retention Time Relative Response S S = Chemical Signature DNA = Isotope Profiling 15 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  17. 17. Chemical Fingerprinting Molecular fingerprint Retention Time Relative Response S S = Chemical Signature Chemical Profiles Marker compounds - additives, indicator compounds, impurities 16 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  18. 18. Marker Compounds in Petroleum Hydrocarbons Note that the sample is severely weathered. Biomarkers have become the predominant peaks Site Sample Isoprenoid / Hopane Petroleum Biomarker Standard Soil samples from boggy areas have phytogenic hydrocarbons 18 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  19. 19. Additives to Gasolines • Proprietary additives are compounds added to hydrocarbon products for specific purposes. Type of Additive Examples 62% 1980s Antiknock Alkyl Leads Antioxidants p-phenylenediamine; alkyl-substituted phenols 2% Metal Deactivators Disalicylpropanediamine Corrosion Inhibitors Carboxylic acids and diimides Anti-icers Short-chained n-alcohols (freeze point depressants); amines and ethoxylated alcohols with long hydrocarbon chains. Oxygenates Methanol, methyl-tertiary butyl ether (MTBE) 18% Lead Scavengers Ethylene dibromide, Ethylene dichloride • Additives often have discrete time intervals during which they were introduced into a formulation. 18 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  20. 20. Dating with Additives Historical trend in lead usage in gasoline Phased out 20 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  21. 21. Formulations of Aroclor 1254 - Dated Aroclor production changes - Late production Aroclor - 1972 - Gives potential dating mechanism of PCB sources (unweathered) Dr. Glenn Johnson, Energy & Geoscience Institute University of Utah G. Frame (1999) Improved Procedure for Single DB-XLB Column GC-MS-SIM Quantitation of PCB Congener Distributions and Characterization of Two Different Preparations Sold as “Aroclor 1254”Journal of High Resolution Chromatography 22:10, 533–540. Johnson, G.W. et al (2007). Chapter 6: Principal components analysis and receptor models in environmental forensics. In: An Introduction to Environmental Forensics. 2nd Edition. (R. Morrison and B. Murphy, eds.). Elsevier. Amsterdam. pp. 207-272. 21 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  22. 22. Chemical Fingerprinting Molecular fingerprint Retention Time Relative Response S S = Chemical Signature Chemical Profiles 21 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  23. 23. Limitations of Standard Practices • Dioxin analyses focus on the dirty 17 congeners – Health driven, not forensically driven – PCBs went differently • 193 other congeners to elucidate patterns of contamination • More data is better for fingerprinting • Not limited to 2378 congeners • The other peaks are integrated for total homologues Dr. Walt Shields (Exponent) and Dr. Yves Tondeur (Analytical Perspectives) have presented on patterns of dioxins (all congeners). Dioxin 2010. - QA-QC of other congeners (standards!) 23 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  24. 24. Dioxin Fingerprinting Unstandardized Fingerprint 24 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  25. 25. Normalizing Data 2378-Sum Relative Homologue Relative TEQ Total Homologue 25 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  26. 26. From Literature Barrel Burning Diesel Fueled Crematorium Truck 2,3,7,8 Sum Relative Homologue Relative TEQ Total Homologue 26 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  27. 27. Case Studies Creosote Unknown Incinerator 2,3,7,8 Sum Relative Homologue Relative TEQ Total Homologue 27 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  28. 28. Interpretation and Visualization Stout et al. 2002, Intro to Enviro Forensics Courtesy of ALS Laboratories, Edmonton 28 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  29. 29. PCB Case Study • PCBs measured in sediments from a man-made lake in USA • Local authorities insisted that source was from my client *13 sediments samples were analyzed for PCBs (congener specific analysis) 29 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  30. 30. Measuring PCBs • First measured on packed GC columns – Aroclor pattern analysis – Limited or no standards • High resolution GC coupled with mass spectrometry (low / high resolution) – surrogates / isotope labels 30 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  31. 31. Aroclor Differences • Degree of chlorination shifts chromatogram to the right • Most extensively used mixture was 1254 – Two different formulations • Weathering will also shift chromatogram to right • Less time in environment = looks more like the source pattern and closer to the source 1242 1254 1260 31 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  32. 32. Cosine Theta Analysis • An analysis of the matrix of similarity coefficients between two different samples • Compared each lake sediment sample congener pattern to each of the Aroclor patterns 32 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  33. 33. Cosine Theta Analysis Aroclor 1242 0.08, 85o Aroclor 1254 Sample X Aroclor 1248 0.20, 78o Aroclor 1262 0.68, 47o Aroclor 1260 0.75, 41o 0.91, 25o Orthogonal Dissimilar Co-linear, similar compositions Theoretical Vector 1.00, 0o Theoretical Vector 0.00, 90o • Normalize data into vectors • Angles between the vectors are calculated • Cosines of these angles represent the proportional similarity between the samples • Nearest to one is closest resemblance 33 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  34. 34. Sediment Pattern Similarity to Aroclor 1254 0.63 0.64 0.67 0.67 • Sediments were most similar to Aroclor 1254• Aroclor 1254 most likely source 0.75 0.78 0.77 0.76 0.89 0.86 0.85 0.79 • Very little difference between early and late production Aroclor 1254 for cosine theta 0.67 • Closest to one is more resemblance to 0.74 Dam Aroclor 1254 Outfall 34 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  35. 35. Chemical Fingerprinting DNA = Isotope Profiling 34 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  36. 36. Isotopes What is an isotope? - has same number of protons and electrons, but different number of neutrons. Protium Deuterium Tritium Electron Proton Neutron Stable Unstable 3He Radioactive 1H (99.98%) 2H (0.015%) 3H T1/2 = 12.32 years 36 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  37. 37. Common Stable Isotopes Used in EFIs Hydrogen 1H, 2H Carbon 12C, 13C Nitrogen 14N, 15N Oxygen 16O, 17O, 18O Sulfur 32S, 34S Chlorine 35Cl, 37Cl 37 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  38. 38. Stable Isotope Analysis Clarke Diagram for 2D Fingerprinting after Whiticar, M.J., 1999 Organic matter Bacterial MF d2H-CH4 (‰) d13C-CH4 (‰) Bacterial Carbonate Reduction Bacterial Mix and Transition Early Mature Thermogenic 38 O’Sullivan, G, et al. (2010) Methane forensic geo-gas investigation: building an urban reference library. Environmental Forensics 11:1, 1-9. www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  39. 39. Stable Isotopes -15 -20 -25 -30 -35 -40 δ 13C (‰) • Stable isotope data gives a “signature” to samples • Samples may be linked or differentiated O Compound AWMA – Vapour Intrusion 2007 38 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  40. 40. Radiocarbon Isotope 14C Naturally occurring isotope with a half life of 5730 yrs Measure in Percent Modern Carbon (pMC) 40 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  41. 41. Radiocarbon Dating Relies on the radioactive nature and influence of events such as nuclear testing and fossil fuel burning 41 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  42. 42. Carbon 14 and Natural Brominated Compounds Compound Δ14C (pMC) MeO-BDE47 +103 MeO-BDE68 +119 Bromkal 70 -998 Aroclor 1260 -999 Can use natural abundance 14C measurements to uncover the relative contribution of industrial and natural sources of halogenated organic compounds to a variety of environ- mental media Teuten et al (2005) Two Abundant Bioaccumulated Halogenated Compounds Are Natural Products, Science, 307 (5711) p.917-920. 42 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  43. 43. Pushing Environmental Forensics Forward What are the limits? • How low can you go? • Complex mixtures? 43 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  44. 44. How Low Can We Go? Using cryo-focusing and HRMS, can achieve 540 ag 2378-TCDD, assuming 70 % recovery S/N 474 (4 Sigma) m/z 321.8936 [M+2] 12C-2378- TCDD in Serum m/z 319.8965 [M] Dr. Donald G. Patterson, Jr and Wayman Turner Zoex - loop modulator 44 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  45. 45. Extreme Sensitivity (2,3,7,8-TCDD) Weight Moles Molecules Microgram (10-6) 3 Nanomoles (10-9) 2,000,000,000,000,000 Nanogram (10-9) 3 Picomoles (10-12) 2,000,000,000,000 Picogram (10-12) 3 Femtomoles (10-15) 2,000,000,000 Femtogram (10-15) 3 Attomoles (10-18) 2,000,000 Attogram (10-18) 3 Zeptomoles (10-21) 2,000 Zeptogram (10-21) 3 Yaktomoles (10-24) 2 Yaktogram (10-24) 3 Fantomoles (10-27) 0.002 Currently at the attogram level with high resolution mass spectrometry Dr. Donald G. Patterson, Jr. 44 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  46. 46. One part-per-quadrillion (ppq or ag/μL) is like measuring 1 second in 1 x 1015 seconds … or 1 second in 32,000,000 years www.chemistry-matters.com Wayman Turner Dioxin 2011 Plenary - August 22nd, 2011, Belgium 46
  47. 47. Complexity? Conventional GC Analysis Unresolved Complex Matter Nelson et al. Environmental Forensics, 7:33–44, 2006 47 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  48. 48. Two-Dimensional Gas Chromatography Nelson et al. Environmental Forensics, 7:33–44, 2006 48 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  49. 49. Separation Power of GCxGC – POPs β-HCCH γ-HCCH PCB-74 + Heptachlor Epoxide PCB-44 PCB-28 HCB PCB-18 PCB-87 PCB-66 PCB-49 PCB-52 PCB-101 Oxychlordane PCB-158 PCB-138 DDE PCB-99 t-Nonachlor Dieldrin PCB-110 PCB-151 PCB-156 PCB-167 o,pDDT PCB-149 PCB-177 PCB-153 PCB-146 p,pDDT PCB-118 BDE-28 PCB-105 PCB-178 BDE-66 BDE-85 BB-153 PCB-189 PCB-172 BDE-100 PCB-194 PCB-183 PCB-187 PCB-180 PCB-128 PCB-157 BDE-47 Mirex PCB-201 PCB-196 + PCB-203 PCB-170 PCB-195 PCB-206 PCB-209 BDE-99 BDE-153 BDE-154 59 Analytes Dr. Jef Focant 49 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  50. 50. Dust Extract D/F Fraction by GCxGC-TOFMS TIC Dr. Donald G. Patterson, Jr and Dr. Jef Focant 50 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  51. 51. Local Supply of Diesel Fuel Dr. Ralph Ruffolo 51 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  52. 52. Comparison of Gasolines Gas Station 1 Gas Station 2 Dr. Ralph Ruffolo 52 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  53. 53. Concluding an EFI *Communicating the results becomes the focus of most EFIs *Complicated methodologies, analytical techniques and results of the data interpretation must be easy to understand 53 3D-GIS Movie Removed for smaller file size www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  54. 54. Environmental Forensics Resources 54 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  55. 55. Societies and Organizations • International Network of Environmental Forensics (INEF) • Association for Environmental Health & Sciences (AEHS) Foundation • International Society of Environmental Forensics (ISEF) 55 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  56. 56. 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 coming soon (AEHS Foundation) 56 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium
  57. 57. Acknowledgements Contact Info: Chemistry Matters Inc. Court Sandau csandau@chemistry-matters.com www.chemistry-matters.com Twitter – Chem_Matters 57 www.chemistry-matters.com Dioxin 2011 Plenary - August 22nd, 2011, Belgium

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