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Demystifying the Chain of Custody & Forensic Arson Analysis - IAAI 2017

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The results for ignitable liquid residue (ILR) analysis depend on early decisions. Sometimes, results depend on decisions made before the investigator even leaves for the arson investigation site.

How to Maintain Legal Chain of Custody
Legal chain of custody is not only about documentation. You do need to document samples and sampling procedures, but as the custodian of samples, you should also be implementing processes and procedures that prevent cross contamination.

During this course, the legal sampling and legal chain of custody process will be discussed along with implications of the sampling process on the analytical results. This will include a discussion on appropriate sampling containers and how it can impact your results.

With this course, you will learn how sampling can impact the chemistry of your results and what you can do about it as well as developing a complete understanding of chain of custody for your courtroom defense.

ILR Analysis Methods
The sampling at the investigation site provides the best opportunity to optimize the detection of ILRs. Several points will be discussed on how to accomplish the best results possible.

Once samples are submitted to the laboratory, they are processed to determine if ILRs are present and what type of ILRs are on the samples. There are different methods for analysis of ILRs and these methods will be discussed.

ILR chemical analysis requires the determination of compounds present in samples collected from the investigation. These compounds need to be present at certain concentrations (above the laboratory detection limits), in certain ratios (patterns match known ILR patterns), and have enough of the marker compounds to determine the type of ILR used on the investigation.

Not all methods and results are equal. Learning the basics of ILR analysis will allow you to ask the hard and appropriate questions about your sample results. It may also help explain apparent false positives from canine detection units.

The Importance of Reference Samples
The topic of reference samples, sometimes incorrectly referred to as 'control samples' will be discussed.

All matrices collected at fire investigations can contain marker compounds used for ILR identification but are not present on those materials because of arson. Reference samples are key samples to any arson investigation and must be collected with purpose for every investigation.

The interferences present in reference samples can help ILR analysis determine the compounds that are present in background locations. This provides further insight for the investigation.

The use of reference samples is especially important in arsonous wildfire investigations. Since ILR marker compounds can be formed in the combustion process, ILR detection in arsonous wildfire samples can be inconclusive if not considered properly.

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Demystifying the Chain of Custody & Forensic Arson Analysis - IAAI 2017

  1. 1. © 2016 Chemistry Matters Inc. Demystifying the Chain of Custody & Forensic Arson Analysis April 14, 2017 IAAI 2017, Las Vegas Court Sandau, PhD
  2. 2. © 2017 Chemistry Matters Inc. Copyright Statement 2 All rights reserved. No part of this publication may be reproduced, distributed, or transmitted in any form or by any means, including photocopying, recording, or other electronic or mechanical methods, without the prior written permission of Chemistry Matters Inc. IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  3. 3. © 2017 Chemistry Matters Inc. Introduction and Course Outline 3IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  4. 4. © 2017 Chemistry Matters Inc. Introduction 4 Court Sandau, PhD, PChem -PhD in Analytical Chemistry (2001), BSc – Chemistry/Env.Sci (1995) -Worked 5 years at Environment Canada laboratory during PhD -Worked 4 years at Centers for Disease Control and Prevention (CDC) in Atlanta (2000-2004) -Returned to Canada in 2004 – Forensic Chemistry Consultant and Expert Witness - Testifying on sampling, analysis and interpretation - Legal sampling and scientific method lectures to regulators/industry - Specialize in forensic cases (chemical, environmental, geochemical) - Have worked on arson cases since 2011 IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  5. 5. © 2017 Chemistry Matters Inc. Goal of Seminar 5IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  6. 6. © 2017 Chemistry Matters Inc. Syllabus 6 • Analytical Chemistry of Ignitable Liquids Analysis • What is legal sampling? • Legal Chain of Custody • Field Notes and Documentation • Sample Containers • Field Sampling • Future of ILR Analysis • Case Study IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  7. 7. © 2017 Chemistry Matters Inc. Starts with the Chemistry – Measurement Chemistry (Analytical) 7IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  8. 8. © 2016 Chemistry Matters Inc. What are the limits in Analytical Chemistry? 8 What are the limits? • How low can you go? IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  9. 9. © 2016 Chemistry Matters Inc. How low can we go? 9 m/z 321.8936 [M+2] Using cryo-focusing and HRMS, can achieve 540 ag 2378-TCDD, assuming 70 % recovery S/N 474 (4 Sigma) m/z 319.8965 [M] Dr. Jef Focant, Dr. Donald G. Patterson, Jr and Wayman Turner IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  10. 10. © 2016 Chemistry Matters Inc. Extreme Sensitivity – 2,3,7,8-TCDD 10 Weight Moles Parts per Molecules Microgram (10-6) 3 Nanomoles (10-9) ppm 2,000,000,000,000,000 Nanogram (10-9) 3 Picomoles (10-12) ppb 2,000,000,000,000 Picogram (10-12) 3 Femtomoles (10-15) ppt 2,000,000,000 Femtogram (10-15) 3 Attomoles (10-18) ppq 2,000,000 Attogram (10-18) 3 Zeptomoles (10-21) ppquint 2,000 Zeptogram (10-21) 3 Yaktomoles (10-24) ppsextillion (pps) 2 Yaktogram (10-24) 3 Fantomoles (10-27) ppseptillion (ppsep) 0.002 Currently at the attogram level with high resolution mass spectrometry IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  11. 11. © 2016 Chemistry Matters Inc. 11Footer Here - Edit with the "Header and Footer" option at top 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
  12. 12. © 2017 Chemistry Matters Inc. 12IAAI 2017 – Demystifying COC & Forensic Arson Analysis Detection Limits for Ignitable Liquid Residues Weight Moles Parts per Molecules Microgram (10-6) 3 Nanomoles (10-9) ppm 2,000,000,000,000,000 Nanogram (10-9) 3 Picomoles (10-12) ppb 2,000,000,000,000 Picogram (10-12) 3 Femtomoles (10-15) ppt 2,000,000,000 Femtogram (10-15) 3 Attomoles (10-18) ppq 2,000,000 Attogram (10-18) 3 Zeptomoles (10-21) ppquint 2,000 Zeptogram (10-21) 3 Yaktomoles (10-24) ppsextillion (pps) 2 Yaktogram (10-24) 3 Fantomoles (10-27) ppseptillion (ppsep) 0.002 Routine ILR analysis is at the ppb level with benchtop mass spectrometry.
  13. 13. © 2016 Chemistry Matters Inc. Sample Extraction 13IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  14. 14. © 2016 Chemistry Matters Inc. The Analytical Laboratory There is no precise regulation for the determination of accelerant in a sample. Methods provide general guidelines and approaches to how to conduct the analysis and identification. Each laboratory will have its own lab process from allowable ASTM methods AND identification process. If a laboratory is not used to dealing with arson samples there could be issues with false positives AND/OR false negatives. 14IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  15. 15. © 2016 Chemistry Matters Inc. Sample Extraction Two main analytical routines both use Passive Headspace Concentration. oASTM E1412 – …With Activated Charcoal. oASTM E2154 – …With Solid Phase Microextraction (SPME). Both use moderate heating to enhance the evaporation of ILRs from the sample onto a receiving matrix. Activated charcoal method, the matrix is extracted with a solvent, which is then analyzed for the presence of chemicals associated with ILRs. SPME fiber is exposed to headspace then directly injected onto GC-MS. 15IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  16. 16. © 2016 Chemistry Matters Inc. Sample Extraction Equipment: • Can containing fire debris (sample from field) • Carbon strip – activated and cleaned (heat treated) • Pin – heat treated • Magnet – strong lanthanide magnet 16IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  17. 17. © 2016 Chemistry Matters Inc. Heating a sample • Heating a sample transfers compounds from matrix to headspace of can • Carbon strip then adsorbs compounds • Headspace important – cans should only be ¾ full Interferences Target compounds Inc. flashpoint Heat volatilizes target compounds into headspace Carbon strip adsorbs compounds Heated Can 17IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  18. 18. © 2017 Chemistry Matters Inc. Laboratory Analysis 18 Heat volatilizes target compounds into headspace Carbon strip adsorbs compounds Heated Can IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  19. 19. © 2017 Chemistry Matters Inc. Limited Seating Available 19IAAI 2017 – Demystifying COC & Forensic Arson Analysis • Sometimes there is not enough space for target molecules to bind to either the SPME or the carbon strip due too many interferences. – Could result in false negative.
  20. 20. © 2016 Chemistry Matters Inc. Analysis of Sample Two Parts: Gas Chromatography Mass Spectrometry 20IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  21. 21. © 2016 Chemistry Matters Inc. Gasoline Chromatogram 6 7 8 9 10 11 12 13 14 Time (min) 0 Figure 1 Summed mass chromatogram for weathered diesel, k RT: 6.00 - 14.00 6 7 8 9 10 11 12 13 14 Time (min) 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 RelativeAbundance NL: 8.28E6 m/z= 90.50-91.50+ 104.50-105.50+ 118.50-119.50 + m/z= 105.50-106.50+ 119.50-120.50+ 133.50-134.50 MS 0801009 ethylbenzene m,p-xylene o-xylene n-propylbenzene 3-ethyltoluene 4-ethyltoluene 1,3,5-trimethylbenzene 2-ethyltoluene 1,2,4-trimethylbenzene trimethylbenzene C4-benzene 1,2,4,5-tetramethyl-benzene 1,2,3,5-tetramethylbenzene Three Musketeers Castle Group Gang of Four Interferences Target compounds Lower flashpoint Sample in Detector Column 21IAAI 2017 – Demystifying COC & Forensic Arson Analysis Target compounds come out at same retention time for each analysis.
  22. 22. © 2016 Chemistry Matters Inc. Mass Spectrometry Figure 1 Summed mass chromatogram for weathered diesel, kerosene and gasoline RT: 6.00 - 14.00 6 7 8 9 10 11 12 13 14 Time (min) 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 RelativeAbundance NL: 8.28E6 m/z= 90.50-91.50+ 104.50-105.50+ 118.50-119.50 + m/z= 105.50-106.50+ 119.50-120.50+ 133.50-134.50 MS 0801009 ethylbenzene m,p-xylene o-xylene n-propylbenzene 3-ethyltoluene 4-ethyltoluene 1,3,5-trimethylbenzene 2-ethyltoluene 1,2,4-trimethylbenzene trimethylbenzene C4-benzene 1,2,4,5-tetramethyl-benzene 1,2,3,5-tetramethylbenzene Three Musketeers Castle Group Gang of Four Figure 2 Summed mass chromatogram for regular gasoline Provides highly specific identification of each chemical. 22IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  23. 23. © 2017 Chemistry Matters Inc. Chemical identification 23IAAI 2017 – Demystifying COC & Forensic Arson Analysis • We know where each of our marker compounds elute from GC • Each compound has distinctive mass spectrometry fingerprint which can be matched to library 78% match Library Sample
  24. 24. © 2016 Chemistry Matters Inc. Data Analysis 24IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  25. 25. © 2017 Chemistry Matters Inc. Look for Distinctive Patterns 25 Three Musketeers C2-benzenes Castle Group C3-benzenes Gang of Four C4-benzenes Twin Towers C1-naphthalenes Five Fingers C2-naphthalenes IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  26. 26. © 2016 Chemistry Matters Inc. Ignitable Liquid Types 26IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  27. 27. © 2016 Chemistry Matters Inc. Example profile - alkylbenzenes Gasoline Kerosene Diesel 27IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  28. 28. © 2016 Chemistry Matters Inc. Matrix Effects 28IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  29. 29. © 2016 Chemistry Matters Inc. Burnt baseboardsChar debris Burnt Flooring Control Flooring Soil and humusForest debris ILRs are readily extracted from all types of material. Analysis patterns can be compared regardless of sample type. 29IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  30. 30. © 2016 Chemistry Matters Inc. Gasoline - No Matrix 30 Three Musketeers Castle Group Gang of Four Twin Towers IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  31. 31. © 2016 Chemistry Matters Inc. Gravel 31IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  32. 32. © 2016 Chemistry Matters Inc. Burnt flooring 32IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  33. 33. © 2016 Chemistry Matters Inc. Burnt wood and glass 33IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  34. 34. © 2016 Chemistry Matters Inc. Burnt carpet and flooring 34IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  35. 35. © 2016 Chemistry Matters Inc. Partly burnt flooring 35IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  36. 36. © 2016 Chemistry Matters Inc. Fresh Vegetation Pinene Limonene p-cymene secbutyl benzene Lots of natural chemicals, but can still see pattern of gasoline 36IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  37. 37. © 2017 Chemistry Matters Inc. How complicated can it get? 37 ++ = ? IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  38. 38. © 2017 Chemistry Matters Inc. How complicated can it be? 38 How many compounds are in…. • The atmospheric aerosol from a coniferous forest? • The volatile fraction of roasted coffee beans? • Cigarette smoke? • Gasoline? • 50 compounds (Kallio, 2006) • 1,000 compounds (Mondello, 2004) • 6,000 compounds (van Mispelaar, 2005) A. < 50 B. 50-100 C. 300-500 D. 500-1000 IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  39. 39. © 2017 Chemistry Matters Inc. Implications on Analysis 39IAAI 2017 – Demystifying COC & Forensic Arson Analysis • For wildfires (especially), sampling natural areas (bark, pine needles, forest ‘debris’, mossy soil – Large concentration of natural compounds that are structurally similar to target compounds – Natural compounds present in % quantities • All compounds (natural and ILR) are competing for “limited seating” on SPME fiber or carbon strip. – High potential for false negatives
  40. 40. © 2017 Chemistry Matters Inc. How complicated can it get? 40 ++ = Thousands of Compounds IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  41. 41. © 2016 Chemistry Matters Inc. Overall Laboratory Output 41IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  42. 42. © 2016 Chemistry Matters Inc. Chemical identification Figure 1 Summed mass chromatogram for weathered diesel, kerosene and gasoline RT: 6.00 - 14.00 6 7 8 9 10 11 12 13 14 Time (min) 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 RelativeAbundance NL: 8.28E6 m/z= 90.50-91.50+ 104.50-105.50+ 118.50-119.50 + m/z= 105.50-106.50+ 119.50-120.50+ 133.50-134.50 MS 0801009 ethylbenzene m,p-xylene o-xylene n-propylbenzene 3-ethyltoluene 4-ethyltoluene 1,3,5-trimethylbenzene 2-ethyltoluene 1,2,4-trimethylbenzene trimethylbenzene C4-benzene 1,2,4,5-tetramethyl-benzene 1,2,3,5-tetramethylbenzene Three Musketeers Castle Group Gang of Four Figure 2 Summed mass chromatogram for regular gasoline Provides highly specific identification of each chemical. 42IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  43. 43. © 2016 Chemistry Matters Inc. Target group of key chemicals We use 58 specific chemicals for analysis, plus visual inspection of hundreds of other chemicals. Partial data output 43IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  44. 44. © 2016 Chemistry Matters Inc. Target group of key chemicals Examine patterns of targeted groups for compounds. In addition, we use 63 specific chemicals for analysis, plus visual inspection of hundreds of other chemicals. Partial data output Good match Poor match Not present 44IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  45. 45. © 2016 Chemistry Matters Inc. Report of ILRs – Presence or Absence • All this to say presence or absence of ILR 45IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  46. 46. © 2016 Chemistry Matters Inc. How much gasoline can be detected in a sample? 46IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  47. 47. © 2016 Chemistry Matters Inc. 47 Burn Tests • Develop a test to see how much gasoline can be detected during a burn test • Spike with gasoline so it can be detected and within linear range of instrumentation • Spiked to 70 grams woodchips (~2.5 ounces) • Burn to varying degrees (0.5 min, 1 min, 2 min, 4 min) • Determine where gasoline can no longer be measured 30 sec 60 sec 120 sec 240 sec IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  48. 48. © 2017 Chemistry Matters Inc. Comfortable with Volumes? 48 What is 100 µL of fluid (0.003 ounces)? A B C D 250 µL 100 µL 50 µL 25 µL IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  49. 49. © 2016 Chemistry Matters Inc. Burn Test Results 49 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% 0 50 100 150 200 250 300 Percent Gasoline Remaining Seconds of Burn Time Amount of gasoline remaining following ILR burn trials Burn Tests show ILR residue after relatively short exposure to intense fire is 5% or less. Linear extrapolation of the line will show less than 0.1% after 6 minutes. Can still detect 0.5 µL gasoline after 4 minute burn time! IAAI 2017 – Demystifying COC & Forensic Arson Analysis What happens to the pattern of ILR?
  50. 50. © 2016 Chemistry Matters Inc. 50 Added to woodchips IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  51. 51. © 2016 Chemistry Matters Inc. 51 30s burn time Approximately 50% of signal is gone IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  52. 52. © 2016 Chemistry Matters Inc. 52 60s burn time Approximately 70% of signal is gone IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  53. 53. © 2016 Chemistry Matters Inc. 53 90s burn time Approximately 80% of signal is gone IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  54. 54. © 2016 Chemistry Matters Inc. 54 120s burn time Approximately 85% of signal is gone IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  55. 55. © 2016 Chemistry Matters Inc. 55 180s burn time Approximately 90% of signal is gone IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  56. 56. © 2016 Chemistry Matters Inc. 56 240s burn time Approximately 95% of signal is gone IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  57. 57. © 2016 Chemistry Matters Inc. Loss of Distinctive Castle Pattern 57 Fresh 90% weathered Even if we can quantify these chemicals without interferences – ratios of chemicals do not appear to be stable. IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  58. 58. © 2016 Chemistry Matters Inc. Overall Output • Recoveries of surrogate standards are examined to ensure sufficient extraction efficiency • Each of 63 target chemicals are quantitatively identified, with a ‘similarity match’ to a library example of the chemical measured • The concentrations of the 63 chemicals are measured • Patterns of these chemicals and hundreds of other chemicals are inspected • Chromatograms assessed to determine the type of ILRs present in the sample • All to the ppb to ppt level 58IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  59. 59. © 2016 Chemistry Matters Inc. Analytical Chemistry Summary • Can detect multiple ILRs to the ppb and ppt levels – Very sensitive methods • Can distinguish between different ILRs at these levels • Methods used by laboratories to determine potential ILRs are not all equal • When concentrations of ILRs are high on samples and matrix effects are minimal, ILR determination is relatively easy… 59IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  60. 60. © 2017 Chemistry Matters Inc. Questions? 60IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  61. 61. © 2017 Chemistry Matters Inc. What differentiates a legal case from a normal investigation? 61 Best practice should be the same for any investigation regardless of what the ultimate conclusions are used for. IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  62. 62. © 2017 Chemistry Matters Inc. What differentiates a legal case from a normal investigation? 62 Increasing pressure for complete documentation of activities to acquire and submit a sample to meet legal scrutiny: • Note taking (dedicated scribe recommended) • Photography Documentation of the scene • Videography Especially as demonstration for sampling techniques or deviations from normal techniques • GPS – sub-centimeter preferred • Chain of custody maintained Anything that could be questioned, provide proof /documentation on what was done and where IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  63. 63. © 2016 Chemistry Matters Inc. Science in the Courtroom • Collection of samples and chemical analyses to support prosecution must follow good science – Good laboratory practice – Solid field sample procedures – Sound scientific process • Science is often misunderstood by the legal profession • Scientists, lawyers and judges operate in different worlds 63IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  64. 64. © 2017 Chemistry Matters Inc. What differentiates a legal case from a normal investigation? 64 Demonstration of correct procedures (sample collection, sample transport) • How was sample taken? • Who took the sample? Qualified? • Where was sample taken? Documented? • Integrity of sample – preservation and chain of custody • Chain of custody must be maintained Must stand up to legal scrutiny! IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  65. 65. © 2017 Chemistry Matters Inc. Legal Chain of Custody 65IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  66. 66. © 2017 Chemistry Matters Inc. What is Legal Chain of Custody? 66 Legal samples require that the physical control or continuity of a sample be documented from the time it is taken until the time it is destroyed. IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  67. 67. © 2017 Chemistry Matters Inc. Maintaining Legal Chain of Custody 67 Sample is under custody if: • the sample is in a person’s possession • the sample is in a person’s view after being in possession • the sample was in the person’s possession and then was locked up to prevent tampering • the sample is in a designated secure area Also includes: • Taking precautions to prevent sample mix-up • Providing clear information to laboratory • Contents in controlled and “monitored” environment IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  68. 68. © 2017 Chemistry Matters Inc. Sampling 68 Fundamental sampling techniques and unique sampling techniques beyond scope of this talk. Assume: - Proper training for how to acquire samples - Proper sample containers are available - Proper techniques are used to acquire samples Proper = the right tool for the job IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  69. 69. © 2016 Chemistry Matters Inc. Sample Label • Project Name / Case Number / File Number • Unique Sample Identifier • Sample Type / Description of material • Date/Time of Collection • Location of the sample • Sampler Name or Initials 69IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  70. 70. © 2016 Chemistry Matters Inc. Labeling Samples • Waterproof ink / Sharpie – Sharpie still smears if solvents/free product present • Secondary containment is good practice – Especially for high concentration samples – Reduces cross contamination – Second barrier for ice/water wetting sample • Two labels required – one for sample, one for bag 70IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  71. 71. © 2017 Chemistry Matters Inc. Field notes and documentation 71IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  72. 72. © 2017 Chemistry Matters Inc. Field Notebooks 72 • Waterproof notebooks and pens highly recommended • Only use legally defensible notebooks – Bound, no ripped out pages, pages numbered • www.riteintherain.com IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  73. 73. © 2017 Chemistry Matters Inc. Notes about Notebooks 73 • Waterproof • Bound with numbered pages – Hard spine only • Each project should have dedicated notebook (can be subpoenaed as evidence) • Field data and observations recorded in log books IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  74. 74. © 2017 Chemistry Matters Inc. The Art of Note Taking 74 • Record observations • No emotions or opinions • Be very thorough • Use consistent terminology • Have standardized points/definitions to include for each investigation • Try to remain unbiased with everything being documented – e.g. • “visible burn marks near baseboard consistent with pour pattern” • “burn marks near baseboards demonstrate obvious pour pattern from gasoline found on site ” IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  75. 75. © 2017 Chemistry Matters Inc. The Art of Note Taking 75 • Each page dated and signed • All lines are filled (no blank spaces) • When page finished, jagged line through remainder of space with note takers initials – Cannot leave space for later notes to be added • Errors are crossed out with a single line and initialed by note taker – Must be able to read the error, no covering up of evidence IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  76. 76. © 2016 Chemistry Matters Inc. Sampling Forms • No empty fields to be filled in • Data used months to years after the fact • Completeness/thoroughness is key • Data blanks make it look incomplete or careless • Questioning whether procedures were followed 76 Name Date Location IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  77. 77. © 2017 Chemistry Matters Inc. Digital Notebooks Becoming Popular 77 • Standardized programs or customized programs can be developed and used for consistency • Advantages: – Reports essentially completed in field – Forced to fill in fields, if standardized – GPS coordinates (not sub-cm), pictures all linked – Can be synced to server while in field – Looks neat and tidy, no handwriting issues – Can be weather proofed • https://www.lifeproof.com/ IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  78. 78. © 2017 Chemistry Matters Inc. Digital Notebooks Becoming Popular 78 • Disadvantages: – Battery life – Cold weather can drain battery quickly – Limitations with annotations, drawings, sketches IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  79. 79. © 2017 Chemistry Matters Inc. Photography 79 • Essential for any litigious/adversarial sampling • Provides visual for site conditions, site layout, sampling and sample integrity • Can be done easily, everyone has cellphone cameras – No excuse not to take pictures • Document anything that can be questioned • Photographs taken as soon as possible during investigation before any alterations of the scene IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  80. 80. © 2017 Chemistry Matters Inc. Photography 80 • Camera can be phone, tablet, SLR, or custom digital GPS camera – High resolution SLR is preferred • Pictures can be uploaded later (renaming, organized) • Must keep a photolog • Tablet/iPhone can be used with software for automatic photolog/reporting IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  81. 81. © 2017 Chemistry Matters Inc. Photography 81 • How many photographs to take? • What to take pictures of? • Can you take too many pictures? IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  82. 82. © 2016 Chemistry Matters Inc. Photographic evidence 82 Story board of sample collection. Visual prompts for litigation. Demonstration of techniques. Sample collection from a failed pipeline for litigation Document how sampling location was exposed IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  83. 83. © 2017 Chemistry Matters Inc. Photography – Story Board 83IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  84. 84. © 2016 Chemistry Matters Inc. Photographic evidence 84 • Document how samples were collected • Pre- and post-disturbance sampling locations – White board serves as good method to document sample ID and basic information in picture – Signage kept in same location and picture taken from same location – Pre-disturbance picture with cans/sampling supplies – Post-disturbance with samples in sampling vessels IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  85. 85. © 2017 Chemistry Matters Inc. Photography – Must Haves 85 • Location/site should be documented – North, East, South, West – GPS location should be recorded for each picture • Pictures approaching sampling location • Pictures of sampling location – before and after sampling • Scale in picture is good practice • Pictures of samples – sealed for shipment • Pictures of coolers – documenting sealed cooler with initials • Complete documentation of removes doubt of how samples were taken. IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  86. 86. © 2017 Chemistry Matters Inc. Videography 86 • Used in addition to photography • Video sampling procedure once for demonstration of what was done on-site • Any deviations of standard sampling procedures should be recorded • Contentious sites/issues should be completely recorded http://www.movensee.com/store.html IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  87. 87. © 2017 Chemistry Matters Inc. Video Log Unique or Demonstrative Sampling Techniques 87IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  88. 88. © 2017 Chemistry Matters Inc. GPS 88 • GPS cameras available (can triangulate objects visible in the distance) • Handheld GPS work • Phones have GPS available as well • GPS – use best technique available – Many people associate precision = accuracy • Handheld GPS +/- 3-5 m vs. sub-cm IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  89. 89. © 2016 Chemistry Matters Inc. Transfer of Custody to the Laboratory 89IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  90. 90. © 2016 Chemistry Matters Inc. Transfer of Custody The CoC is the important document. The receiving person at the lab will check the contents against the CoC. The outer vessel (cooler) will be inspected for integrity, and photographed. Each sample is photographed. Sign-off and formal transfer of custody. 90IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  91. 91. © 2016 Chemistry Matters Inc. Chain of Custody Documentation A document that lists important information for the fire debris samples. • Demonstration of sample control. • Can be filled out electronically or by hand. • Often misused and represents a weakness in a legal case. • Lawyers love to pick through deficiencies in CoCs. 91IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  92. 92. © 2016 Chemistry Matters Inc. Chain of Custody Documentation Signature Signature Filled out to completion - No blanks Arrows look sloppy – fill out form Do not skip lines for sample list Signatures present from sampler, person dropping off samples, and laboratory Date and time on signature line Samples on COC match samples in cooler No empty fields – can be construed as careless 92IAAI 2017 – Demystifying COC & Forensic Arson Analysis LAB ABC
  93. 93. © 2016 Chemistry Matters Inc. Chain of Custody Documentation Common issues with COCs • Incomplete fields • No signatures • Arrows instead of filling in • Missing samples/extra samples COCs are a legal document showing transition of samples from field to laboratory Forms need to be filled out properly and completely to demonstrate proficiency and thoroughness. 93IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  94. 94. © 2016 Chemistry Matters Inc. Photographic evidence 94 Document sample containment securing IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  95. 95. © 2017 Chemistry Matters Inc. Laboratory Custody 95 • Laboratory should document and handle samples with similar chain of custody procedures. • Samples and extracts should be properly documented and labeled • Samples should be stored in freezers until client allows them to be destroyed which is also documented. IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  96. 96. © 2017 Chemistry Matters Inc. Documentation Summary 96 • There is no single method to document a site • Each organization should develop a standard procedure followed by all personnel • Exceptions to the rules may apply – Only experience can help in these instances • When in doubt, ASK! It needs to be done right. IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  97. 97. © 2016 Chemistry Matters Inc. What Not To Do 97IAAI 2017 – Demystifying COC & Forensic Arson Analysis Potentially litigious samples submitted for forensic analysis.
  98. 98. © 2017 Chemistry Matters Inc. Questions? 98IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  99. 99. © 2016 Chemistry Matters Inc. Where to sample? • Wildfire pattern experts determine if source of fire is suspicious – ‘read the grass’ to determine origin • Look for tell tale ‘burn patterns’ that indicate arson may have occurred 99IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  100. 100. © 2016 Chemistry Matters Inc. A little help is still required 100IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  101. 101. © 2016 Chemistry Matters Inc. Sense of Smell o As we breathe, air passes over olfactory receptor neurons that bind to these small molecules to interpret smell o Small area on top of nasal cavity o Humans have large range of odour detection capabilities 101 Propyl Acetate Butyl Acetate IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  102. 102. © 2016 Chemistry Matters Inc. How does a dog’s nose work? • Possess up to 300 million olefactory receptors (6 million in humans) • Dedicated olefactory region which is very large and takes 12% of air breathed in for scent detection • Receptors are trained for specific target compounds 102 www.pbs.org/wgbh/nova/nature/dogs-sense-of-smell.html IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  103. 103. © 2016 Chemistry Matters Inc. The use of Accelerant Detection Canines (ADCs) o ADCs possess excellent capability to detect chemicals commonly associated with ILRs. o ADCs exceed field equipment currently available for the detection of chemicals commonly associated with ILRs. 103 Generalized sensitivity comparisons: K-9 – ppt Human – ppm/ppb Lab – ppb (but getting to ppt) IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  104. 104. © 2016 Chemistry Matters Inc. Sample Containers 104IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  105. 105. © 2016 Chemistry Matters Inc. Sampling Vessels Taken from: E. Stauffer et al, Handbook of Fire Debris Analysis, 2007. 105IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  106. 106. © 2016 Chemistry Matters Inc. Choosing a Sample Vessel • Need to be durable and have easy availability • Need to fit the material being sampled • Fit for purpose • Needs to be guaranteed clean 106 Environmental Sampling Story IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  107. 107. © 2016 Chemistry Matters Inc. Sample Vessels for Fire Debris • Stainless steel cans – Lined or unlined • Glass laboratory jars • Nylon bags/Kapak bags 107IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  108. 108. © 2016 Chemistry Matters Inc. Paint Cans for Evidence Collection • Paint cans were designed to hold paint • No where are they checking for QA-QC for cleanliness for ILR analysis • Process to manufacture and line paint cans meet paint container requirements, not forensic evidence collection • Lubricants are petrochemicals 108IAAI 2017 – Demystifying COC & Forensic Arson Analysis https://www.alibaba.com/showroom/paint-can-manufacturing-equipment.html
  109. 109. © 2016 Chemistry Matters Inc. Stainless Steel Cans • If using stainless steel cans: – Get supply from laboratory which pre-cleans cans (heats them to remove contamination) – Get enough for investigation only, do not transport around until needed – If purchasing from paint store: • Each batch of cans must be checked for cleanliness, submit to laboratory for analysis • May invalidate your ILR results if found to have contamination 109IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  110. 110. © 2016 Chemistry Matters Inc. Sampling Vessels Preference for unlined heat treated sampling cans. •Ensures highest degree of cleanliness •Ensures consistency • Also heat treated carbon strips used for extraction Interferences Target compounds Inc. flashpoint Pre-Treatment Post-Treatment Heat above extraction temperature 110IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  111. 111. © 2016 Chemistry Matters Inc. Lined vs. Unlined • No guarantees that epoxy coatings are clean • They are made for paint, not for forensic samples • "A light to medium aromatic product was detected in the empty half-gallon gold lined cans. This product is classified as an ignitable liquid, and its presence would affect the laboratory analysis of any debris contained in such can." 111 https://www.firearson.com/About-IAAI/News/Contamination-Of-Evidence-Cans-Lined-With-Gold-Epoxy-Coating.aspx IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  112. 112. © 2016 Chemistry Matters Inc. Sample Integrity Clips and security tabs 112IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  113. 113. © 2016 Chemistry Matters Inc. Sample Integrity Secondary containment in evidence bags - Prevents moisture contacting outside of can - Provides secondary barrier to prevent high ILR containing evidence from contaminating low ILR evidence - Unfortunately, evidence bags have glue that contains interferences with ILR analysis 113IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  114. 114. © 2016 Chemistry Matters Inc. Sample Integrity Trip Blanks • Pre-cleaned sampling cans are taken to the investigation site, and returned to the lab, unopened. • The cans travel with the other samples. • Allows proof that potential cross- contamination during transport did not occur. 114IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  115. 115. © 2016 Chemistry Matters Inc. Trip Blank Issues • Trip blanks provide method to look for cross contamination during field deployment – Very common practice in environmental forensics/sampling • Empty can with suspended carbon strip sent into the field with each of sample coolers • Passively collects volatile compounds from when cooler picked up until samples submitted to laboratory (and analyzed) 115IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  116. 116. © 2016 Chemistry Matters Inc. Sampling Vessels May Leak 116 Bagged Non-Bagged • Trip blanks were sent to the field with samples for evidence collection. • Measured amount of marker compounds present on carbon strip once returned to laboratory. Concentration IAAI 2017 – Demystifying COC & Forensic Arson Analysis Days in Field Days in Field
  117. 117. © 2016 Chemistry Matters Inc. Sampling Vessels May Leak 117 • In general, bagged cans better than non-bagged • Secondary containment helps, but doesn’t eliminate the problem • Lighter compounds worse than heavier compounds IAAI 2017 – Demystifying COC & Forensic Arson Analysis C2-benzene C3-benzene
  118. 118. © 2016 Chemistry Matters Inc. Contamination can Wreck an Investigation • Cannot make a conclusive statement about the presence of ILRs 118IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  119. 119. © 2017 Chemistry Matters Inc. Preventing Contamination 119 • Stainless steel cans leak • Double-containment helps, but does not prevent/guarantee clean samples • Only take sample canisters out for investigation, then return unused to laboratory • Submit samples as soon as they are collected IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  120. 120. © 2017 Chemistry Matters Inc. Field Sampling and Choices to be Made 120IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  121. 121. © 2016 Chemistry Matters Inc. Sampling Taken from: E. Stauffer et al, Handbook of Fire Debris Analysis, 2007. From Stauffer: “Samples that are protected from the fire can better retain ILR than those that are exposed to the fire.” “When considering the origin of the fire, the investigator should not take the most burned part as a sample. If the substrate is charred completely beyond recognition, there is little chance that any ignitable liquid has survived.” 121IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  122. 122. © 2016 Chemistry Matters Inc. Acquiring a Sample • All samples should be acquired in triplicate: – One for analysis – One for counter valuation – One for storage • Should be collected by duly authorized and trained personnel – Is their training documented? – Sampling SOPs available on site • Good practice to have witness (2nd party) present during sampling (dedicated scribe) 122IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  123. 123. © 2016 Chemistry Matters Inc. Sampling Strategy • Most of arson debris sampling for ILRs is judgmental sampling – Is the person qualified to make the judgments? – Are the judgments being documented – reasons why? • Used years later – Remember that one person’s judgment may be different than another • Must be able to defend choices 123IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  124. 124. © 2016 Chemistry Matters Inc. Sampling Strategy • Composite (forest debris in area) or discrete (soil core samples) • Statistical / Judgmental / Opportunistic Systematic grid 124IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  125. 125. © 2016 Chemistry Matters Inc. Sampling Strategy • Multiple samples at each flag? • Sample across potential ‘pour’ pattern (left, center, right)? • Just at the flag? 125IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  126. 126. © 2017 Chemistry Matters Inc. Sampling 126 Fundamental sampling techniques and unique sampling techniques beyond scope of this seminar. Assume: -Proper training for how to acquire samples -Proper sample containers are available -Proper techniques are used to acquire samples Proper = the right tool for the job IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  127. 127. © 2017 Chemistry Matters Inc. Sampling Fundamentals 127IAAI 2017 – Demystifying COC & Forensic Arson Analysis • Be cognizant of cross-contamination and spoiling of evidence • Wear latex/nitrile gloves for evidence collection. New pair for each sample • Use clean, previously unused containers for evidence • Label properly, completely, and consistently • Tools used for sampling must be cleaned in between each use • Identify and collect appropriate ‘comparison’ sample for each location. Helps laboratory to identify potential interferences
  128. 128. © 2017 Chemistry Matters Inc. Cleaning Procedures 128IAAI 2017 – Demystifying COC & Forensic Arson Analysis • Dry brush to remove particulates • Wash sampling device with soapy water • Soap can be checked for interferences by laboratory • Use a wet brush to remove any stuck on debris • Rinse thoroughly with water to remove soap • Rinse with clean water (double rinse) – lab supplied • Solvent rinse is effective to remove any trace organics remaining • Acetone, methanol, isopropanol (laboratory grade) • Allow to dry • The higher the amount of ILR, the more important the cleaning procedures are
  129. 129. © 2017 Chemistry Matters Inc. Where to collect samples? 129IAAI 2017 – Demystifying COC & Forensic Arson Analysis • Select areas that are protected from thermal impact of fire • Thermal impact includes pyrolysis, evaporation or both • ILRs can absorb into substrates included carpet, fabrics and soil • Avoid heavily burnt areas (heavily charred) • Likelihood of ILR survival is low • Carbon from heavily burnt areas ‘competes’ with analytical extraction method
  130. 130. © 2016 Chemistry Matters Inc. Sampling Loss of ILRs: 1. Consumed in the fire as fuel. 2. Lost by evaporation due to heat. High char samples often do not represent good samples. An example of charred wood sample. 130IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  131. 131. © 2016 Chemistry Matters Inc. 131 Burn Tests • Develop a test to see how extraction is impacted by char • Burn to varying degrees (0.5 min, 1 min, 2 min, 4 min) • Added internal standards to cans prior to extraction to monitor extraction efficiency – Compounds with same structures as marker compounds but have been isotopically labeled – Therefore, they behave the same as the marker compounds 30 sec 60 sec 120 sec 240 sec IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  132. 132. © 2016 Chemistry Matters Inc. Burn Tests 132IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  133. 133. © 2017 Chemistry Matters Inc. High Char Samples 133 • High char samples can compete with carbon strip • Burnt wood is essentially carbon, thus attracts compounds similar to carbon strips • More charred samples, results in less of target compounds transferring to carbon strip IAAI 2017 – Demystifying COC & Forensic Arson Analysis 0 20 40 60 80 100 120 0 30 60 120 240 360 Percent Recovery Burn Time (seconds) Percent Recovery versus Burn Time Ethylbenzene-d10 Benzene, 1,3,5-trimethyl-d12 Benzene, 1,2,4,5,-tetramethyl-d14 Naphthalene-d8
  134. 134. © 2016 Chemistry Matters Inc. Sampling Best sampling: 1. ILRs often soak into materials and are preserved. 2. Low char material option presents best opportunity to present ILRs if used. A good example is a baseboard. 134IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  135. 135. © 2016 Chemistry Matters Inc. Stability of ILRs 135IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  136. 136. © 2016 Chemistry Matters Inc. Sample Stability ILR can degrade with time. Regulated time between collection of sample and analysis of sample to ensure the sample is representative of the place and time it was collected. Termed “Hold Time” Low concentrations of ILRs allowed to degrade may be undetected in analysis = false negative. 136IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  137. 137. © 2016 Chemistry Matters Inc. Sample Stability Samples require specific preservation activities. Examples include… Store samples between 2 and 8oC - Inhibits bacterial degradation Get to the laboratory - Get samples to laboratory as soon as possible Store samples in correct sample vessel material - Should be inert to the chemicals of interest - Should be free of any potential interferences ”proofed” - Should be sealed/not leak 137IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  138. 138. © 2016 Chemistry Matters Inc. Thermochron !30$ !20$ !10$ 0$ 10$ 20$ 30$ 40$ 24!Nov!08$ 25!Nov!08$ 26!Nov!08$ 27!Nov!08$ 28!Nov!08$ 29!Nov!08$ 30!Nov!08$ 1!Dec!08$ 2!Dec!08$ 3!Dec!08$ Date% Temperature(°C) Samples collected Samples moved to freezer Samples moved to shipping cooler Samples received 138138IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  139. 139. © 2016 Chemistry Matters Inc. Tamper Proof Seals • Samples should be sealed – Can be tamper-proof seal if needed • Demonstrates integrity of samples • Shows intent and professionalism 139IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  140. 140. © 2017 Chemistry Matters Inc. Transition – Field to Laboratory 140IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  141. 141. © 2016 Chemistry Matters Inc. Packing Samples • Keep “like with like” (fire debris samples not mixed in with product samples) – decrease chance of cross contamination • Sort samples for laboratory – Easiest preventable error can happen at check-in – Sample Log-In very important connection between laboratory and field work • Tape cooler shut and sign the seam 141 f04-03-9780444594242 IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  142. 142. © 2016 Chemistry Matters Inc. Transport to Laboratory • Samples in sample jars – in your custody • Every attempt to prevent degradation and preserve sample prior to laboratory receipt and analysis must be taken • Samples should be kept cool (general between 0oC and 4oC) • Samples should be hand delivered to the laboratory if possible – The less links in the chain, the better 142IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  143. 143. © 2017 Chemistry Matters Inc. Laboratory Analysis 143IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  144. 144. © 2016 Chemistry Matters Inc. Laboratory Analysis • Laboratory is capable of conducting analysis • Laboratory certification does not guarantee high quality data • Laboratory is competent with legal chain of custody – Proper legal sample handling procedures – Minimal links in the chain for legal samples 144IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  145. 145. © 2016 Chemistry Matters Inc. Future of Forensic Analysis of ILRs 145IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  146. 146. © 2016 Chemistry Matters Inc. How complex can we handle? 146 Unresolved Complex Matter Nelson et al. Environmental Forensics, 7:33–44, 2006 IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  147. 147. © 2016 Chemistry Matters Inc. How does 2D-GC-MS Work? 147 Modulator 1st Column 2nd Column Inlet Detector 1st Column 2ndColumn 0.25 mm I.D. 0.10 mm I.D. IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  148. 148. © 2016 Chemistry Matters Inc. Fourth Dimension? 148 148 40 60 80 100 120 140 160 180 200 220 240 260 500 1000 93 77 39 12167 10750 136 Peak True - sample "L1019714-37 straight:1", peak 435, at 2486 , 1.350 sec , sec 40 60 80 100 120 140 160 180 200 220 240 260 500 1000 93 77 41 12110553 67 136 Library Hit - similarity 836, "à-Pinene" 4D 1D 2D 3D IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  149. 149. © 2016 Chemistry Matters Inc. 2D-GC-TOFMS of Crude Oil 149 Nelson et al. Environmental Forensics, 7:33–44, 2006 IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  150. 150. © 2016 Chemistry Matters Inc. Diesel Fuel by 2D-GC-TOFMS 150IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  151. 151. © 2017 Chemistry Matters Inc. Are All Gasolines the Same? 151IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  152. 152. © 2016 Chemistry Matters Inc. Comparison of Gasolines Gas Station 1 Gas Station 2 Hundreds of compounds in gasoline 152IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  153. 153. © 2016 Chemistry Matters Inc. Diesel 2 Diesel 1 © 2015 Chemistry Matters Inc. 153IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  154. 154. © 2016 Chemistry Matters Inc. Applied to Arson Samples Standard Analysis– Example 1 154IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  155. 155. © 2016 Chemistry Matters Inc. Applied to Arson Samples 2DGC-TOFMS Analysis 155 Stereoisomers of Camphene Verbenene Multiple unresolved compounds p-cymene ɑ-Pinene IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  156. 156. © 2016 Chemistry Matters Inc. Applied to Arson Samples Standard Analysis – Example 2 156IAAI 2017 – Demystifying COC & Forensic Arson Analysis Cannot identify distinctive castle group pattern with routine analysis.
  157. 157. © 2016 Chemistry Matters Inc. Applied to Arson Samples 2DGC-TOFMS Analysis 157IAAI 2017 – Demystifying COC & Forensic Arson Analysis Camphene Verbenene ɑ-Pinene
  158. 158. © 2016 Chemistry Matters Inc. 2DGC-TOFMS of Gasoline 158 12 compounds used by standard analysis identified above IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  159. 159. © 2016 Chemistry Matters Inc. 2DGC-TOFMS of Gasoline 159 Total of 153 individual compounds used for gasoline markers IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  160. 160. © 2016 Chemistry Matters Inc. Fingerprinting Gasoline on Woodchips 160 PCA HCA IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  161. 161. © 2016 Chemistry Matters Inc. Data Interpretation Outcomes o Level 1. Determine the presence or absence of an ILR in a sample of fire debris. o Level 2. Distinguish the type of Ignitable Liquid. Classification can be an important aid for fire scene investigators. o Level 3. Commonality - Statistical tests can determine if a group of samples present the same origin of ignitable liquid. o Level 4. If potential source fuels are presented for analysis, advanced chemical analysis and data interpretation can determine a potential IL source. 161IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  162. 162. © 2016 Chemistry Matters Inc. Conclusions • Using 2DGC-TOFMS, individual gas station sources may be identified on evidence samples • Can reduce interferences providing more confident identification of ILRs • Lower detection limits 162IAAI 2017 – Demystifying COC & Forensic Arson Analysis
  163. 163. © 2016 Chemistry Matters Inc. Thank You Contact Info: Chemistry Matters Inc. Court Sandau Cell: 403.669.8566 URL: chemistry-matters.com Twitter: @Chem_Matters LinkedIn: ca.linkedin.com/in/courtsandau Slideshare: www.slideshare.net/csandau IAAI 2017 – Demystifying COC & Forensic Arson Analysis

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