Arson: The Science of Fire and Chemical Fingerprints Left Behind - MRU 2017
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Wildfire frequency, severity and damages are increasing as climate change causes earlier snow melts and overall drier conditions. Forest fire can be caused by natural through lightning strikes, but the majority of wildfires are caused by humans. Of the 1200 wildfires reported in Alberta each year, over half are human caused. It is the job of a fire investigator to gather evidence at wildfires to determine the origin and causes of the wildfire. Roles of the investigator may include fire scene examination through to delivering court room evidence. Fire investigations require the highest quality in sampling, legal chain of custody & sample handling, and testing & interpretation of ignitable liquid residues (ILRs). This role can be ideally filled by a chemist/scientist who has an in depth understanding of how all facets of a field program and how the analysis of samples can impact the interpretation and results. Ultimately, prosecution will depend on reliable ILR results and relaying these results to the fire investigators. Dr. Sandau, and his team at Chemistry Matters, are one of Canada’s leading resources for wildfire arson investigation and have led investigations for some of the largest wildfires in North America. This presentation will explore the chemistry behind wildfire investigations. The chemistry starts from the field work and sampling with the use of canine detection units. It is then carried forward to the instrumentation used for laboratory analysis which is used for the interpretation and ending in testifying in a courtroom setting. This presentation will examine the evolution of our detection systems that allow us to measure molecules at the lowest levels and use their patterns to chemically fingerprint the ignitable liquid residues and other products used which provides valuable cutting edge evidence for potential convictions.
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Arson: The Science of Fire and Chemical Fingerprints Left Behind - MRU 2017
- 1. © 2017 Chemistry Matters Inc. Arson: The Science of Fire and Chemical Fingerprints Left Behind April 5, 2017 2017 Mount Royal Science & Technology Day Court Sandau, PhD
- 2. © 2017 Chemistry Matters Inc. 2Footer Here - Edit with the "Header and Footer" option at top Copyright Statement 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.
- 3. © 2017 Chemistry Matters Inc. Introduction 3 -Worked 5 years at Environment Canada laboratory during PhD - PCBs, metabolites, persistent pesticides, Dioxins and POPs - Polar bears, Bald Eagles, Alligators and humans -Worked 4 years at Centers for Disease Control and Prevention (CDC), Atlanta, Georgia - PAH metabolites and chemical warfare agents - Method development for rapid analysis of 1000s of samples -Returned to Calgary in 2004 – Environmental Consultant and Expert Witness - Testifying on sampling, analysis and interpretation - Specializing in environmental forensics - Since 2011, working on arson Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 7. © 2017 Chemistry Matters Inc. What do I actually do? • Provide scientific support to arson investigations • Provide legal sampling services – Collect samples in defensible manner and with legal chain of custody • Analyze samples for ignitable liquid residues (ILRs) • Interpret data • Testify in court room as expert witness 7Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 8. © 2017 Chemistry Matters Inc. Alberta Wildfires • Over 1200 wildfires are reported yearly in Alberta – 47% caused by lightning strikes – Over 50% are human caused – Unknown how many are arson 8Arson: The Science of Fire and Chemical Fingerprints Left Behind http://www.cbc.ca/news/canada/british-columbia/b-c-wild-fire-budget-spring-fires-fort-mcmurray-1.3605619
- 10. © 2017 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 10Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 11. © 2017 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. 11 Generalized sensitivity comparisons: K-9 – Part per trillion Human – Parts per billion Lab – Parts per million/billion Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 12. © 2017 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 12 www.pbs.org/wgbh/nova/nature/dogs-sense-of-smell.html Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 15. © 2017 Chemistry Matters Inc. Laboratory Analysis 15 Heat volatilizes target compounds into headspace Carbon strip adsorbs compounds Heated Can Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 16. © 2017 Chemistry Matters Inc. Look for Distinctive Patterns 16 Three Musketeers C2-benzenes Castle Group C3-benzenes Gang of Four C4-benzenes Twin Towers C1-naphthalenes Five Fingers C2-naphthalenes Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 21. © 2017 Chemistry Matters Inc. Vegetation 21Arson: The Science of Fire and Chemical Fingerprints Left Behind Pinene Limonene 4-isopropyl toluene secbutyl benzene Lots of natural chemicals, but can still see pattern of gasoline
- 23. © 2017 Chemistry Matters Inc. How complicated can it be? 23 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
- 25. © 2017 Chemistry Matters Inc. 25 Burn Tests • Develop a test to see how much gasoline remains after burn • Determine optimum gasoline amount to get in linear range of instrumentation (70 grams of wood chips) • Burn to varying degrees to determine when gasoline is not detectable (0.5 min, 1 min, 2 min, 4 min) Arson: The Science of Fire and Chemical Fingerprints Left Behind 30 sec 60 sec 120 sec 240 sec
- 26. © 2017 Chemistry Matters Inc. Comfortable with Volumes? 26 What is 100 µL of fluid (0.003 ounces)? A B C D 250 µL 100 µL 50 µL 25 µL Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 28. © 2017 Chemistry Matters Inc. Burn Test Results 28 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. Arson: The Science of Fire and Chemical Fingerprints Left Behind Less than 0.1% of 5 µL present after 6 min! That’s 0.005 µL!
- 31. © 2017 Chemistry Matters Inc. How low can we go? 31 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 Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 32. © 2017 Chemistry Matters Inc. Extreme Sensitivity – 2,3,7,8-TCDD 32 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 Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 33. © 2017 Chemistry Matters Inc. 33Footer 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
- 34. © 2017 Chemistry Matters Inc. How Complex can we handle? 34 Unresolved Complex Matter Nelson et al. Environmental Forensics, 7:33–44, 2006 Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 35. © 2017 Chemistry Matters Inc. How does 2D-GC-MS Work? 35Arson: The Science of Fire and Chemical Fingerprints Left Behind Modulator 1st Column 2nd Column Inlet Detector 1st Column 2ndColumn 0.25 mm I.D. 0.10 mm I.D.
- 36. © 2017 Chemistry Matters Inc. Fourth Dimension? 36 36 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 Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 37. © 2017 Chemistry Matters Inc. 2D-GC-TOFMS of Crude Oil 37 Nelson et al. Environmental Forensics, 7:33–44, 2006 Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 42. © 2017 Chemistry Matters Inc. 2DGC-TOFMS of Gasoline 42 12 compounds used by standard analysis identified above Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 43. © 2017 Chemistry Matters Inc. 2DGC-TOFMS of Gasoline 43 Total of 153 individual compounds used for gasoline markers Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 45. © 2017 Chemistry Matters Inc. Can the gas station source of the gasoline be determined? • Sampled gasoline from gas stations within 100 km of fire • Only 9 gas stations • Analyzed for 153 marker compounds of gasoline • Conducted burn tests with different gasolines 45Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 46. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 46 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 47. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 47 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) Gas station samples extracted from woodchips Sampled from same gas station, 6 months apart. Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 48. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 48 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) Fresh gasoline on woodchips Burnt gasoline on soil (mild) Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 49. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 49 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) Fresh gasoline on woodchips Burnt gasoline on soil woodchips log (mild)+ Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 50. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 50 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) Fresh gasoline on woodchips Burnt gasoline on woodchips (extreme)x Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 51. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 51 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) PC1 describes process of fire-alteration Fresh gasolinesBurnt gasolines Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 52. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 52 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) Added site samples Site samples present as a cluster with heavily burnt reference samples. Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 53. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 53 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) Added site samples Site log samples present as partial burnt fingerprint. Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 54. © 2017 Chemistry Matters Inc. Determine Source of Gasoline? 54 -8 -6 -4 -2 0 2 4 6 8 10 -10 -8 -6 -4 -2 0 2 4 6 8 10 12 PC2(13.31%) PC1 (61.03%) Added site samples Establishes link between site samples and 2 gas stations. Removing 7 other gas stations. Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 55. © 2017 Chemistry Matters Inc. Conclusions • Using 2DGC-TOFMS, the source of the gasoline can be identified on evidence samples • We able to provide investigators gas station to follow up for receipt purchases and video surveillance 55Arson: The Science of Fire and Chemical Fingerprints Left Behind
- 56. © 2017 Chemistry Matters Inc. 56 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 Arson: The Science of Fire and Chemical Fingerprints Left Behind