Stable Isotope Forensics: An Introduction to the Forensic Application of Stable Isotope Analysis / Edition 1

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Overview

When are two chemically identical compounds not the same? Is it possible to determine the geographic point of origin of seized cocaine? Can one unravel recent geographic movement of a terrorist suspect? Do matchsticks match and are all white paints just that? These are just some of the questions forensic scientists are increasingly confronted with to support intelligence led policing and to help achieve secure convictions. Stable Isotope Forensics shows how stable isotope signatures may be able to answer these questions and will be essential reading for students of forensic science and analytical chemistry as well as forensic scientists, police officers, defence and prosecution practitioners and the judiciary.

The first book solely dedicated to this new and exciting field of forensic science.

Introduces real-life examples to show how stable isotope analysis has already been successfully used to detect food fraud, counterfeit pharmaceuticals and doping in sports.

Includes examples of statistical analysis of multivariate isotope data and advice on potential pitfalls and how to avoid them.

Presents numerous case studies including the "Scissor Sisters" murder enquiry; an example of how stable isotope signatures of different human tissue can help identify a mutilated murder victim.

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Editorial Reviews

From the Publisher
"The book is timely and important, it is pleasantly written, generally with a positive ‘open' mind to what stable isotope analysis can and cannot contribute to forensic and scientific investigations. It is well produced and reasonably priced. The figures, tables, and photographs in the book are generally informative and this aiding the overall (educational) value of the book." (MassMatters, November 2010)

"In this comprehensive book, with its copious literature references, we are offered, for the first time, a carefully written account of an exciting new field of endeavour: its history, development, technology, modus operandi, potential and future." (Chemistry & Industry, August 23, 2010)

“This is the first book exclusively dealing with forensic isotope analysis and pulls together all existing research in this emerging field.” In the book, topics are introduced using examples and real-life case studies such as food quality control where isotope analysis has already had a major impact, in terms of consumer protection. These examples illustrate the underlying principles of isotope profiles or signatures.” (Bio-Dundee, 1 November 2010)

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Product Details

Table of Contents

Series Foreword: Developments in Forensic Science Niamh Nic Daéid ix

Foreword Sean Doyle xi

List of Figures xiii

List of Tables xix

Introduction: Stable Isotope 'Fingerprinting' or Chemical 'DNA': A New Dawn for Forensic Chemistry? xxi

I How It Works 1

I.1 What are Stable Isotopes? 3

I.2 Natural Abundance Variation of Stable Isotopes 5

I.3 Chemically Identical and Yet Not the Same 8

I.4 Isotope Effects, Mass Discrimination and Isotopic Fractionation 10

I.4.1 Physical Chemistry Background 10

I.4.2 Fractionation Factor α and Enrichment Factor ε 11

I.4.3 Isotopic Fractionation in Rayleigh Processes 13

I.4.4 Isotopic Fractionation Summary 14

I.5 Stable Isotopic Distribution and Isotopic Fractionation of Light Elements in Nature 16

I.5.1 Hydrogen 16

I.5.2 Oxygen 19

I.5.2.1 180 in Bone Bio-apatite and Source Water 20

I.5.2.2 Bone Remodelling 23

I.5.2.3 Bone Diagenesis 24

I.5.2.3.1 Diagenetic Changes of Bio-apatite 24

I.5.3 Carbon 25

I.5.4 Nitrogen 27

I.5.4.1 Food Chain and Trophic Level Shift 29

I.5.4.2 Diagenetic Changes of Structural Proteins 32

I.5.5 Sulfur 33

I.6 Stable Isotope Forensics in Everyday Life 36

I.6.1 'Food Forensics' 37

I.6.1.1 Authenticity and Provenance of Single-Seed Vegetable Oils 38

I.6.1.2 Authenticity and Provenance of Beverage? 39

I.6.1.3 Authenticity and Provenance of other Premium Foods 41

I.6.2 Counterfeit Pharmaceuticals 42

I.6.3 Environmental Forensics 43

I.6.4 Wildlife Forensics 46

I.6.5 Anti-Doping Control 47

I.7 Summary of Part I 49

I.8 Set problems 50

References 51

II Instrumentation and Analytical Techniques 65

II.1 Mass Spectrometry versus Isotope Ratio Mass Spectrometry 67

II.2 Instrumentation and δ Notation 72

II.2.1 Dual-Inlet Isotope Ratio Mass Spectrometry 74

II.2.2 Continuous Flow Isotope Ratio Mass Spectrometry 74

II.2.3 Bulk Material Stable Isotope Analysis 77

II.2.4 Compound Specific Stable Isotope Analysis 78

II.2.4.1 CSIA and Compound Identification 79

II.2.4.2 Position-Specific Isotope Analysis 81

II.2.4.3 CSIA of Polar, Non-Volatile Organic Compounds 83

II.3 Isotopic Calibration and Quality Control in Continuous Flow Isotope Ratio Mass Spectrometry 85

II.3.1 Two-Point or End-member Scale Correction 86

II.3.1.1 Scale Correction of Measured δ2H Values 87

II.3.1.2 Scale Correction of Measured δ13C Values 88

II.4 Statistical Analysis of Stable Isotope Data within a Forensic Context 91

II.4.1 Chemometric Analysis 91

II.4.2 Bayesian Analysis 94

II.5 Forensic Stable Isotope Analytical Procedures 100

II.5.1 FIRMS Network 101

II.6 Generic Considerations for Stable Isotope Analysis 102

II.6.1 Generic Considerations for Sample Preparation 102

II.6.2 Generic Considerations for BSIA 104

II.6.2.1 Isobaric Interference 104

II.6.3 Particular Considerations for 2H-BSIA 105

II.6.3.1 Keeping Your Powder Dry 106

II.6.3.2 Total δ2H versus True δ2H Values 106

II.6.3.2.1 2H Isotope Analysis of Human Hair 108

II.6.3.3 Ionization Quench Effect 113

II.6.4 Generic Considerations for CSIA 116

II.6.4.1 Isotopic Calibration during GC/C-IRMS 116

II.6.4.2 Isotope Effects in GC/C-IRMS during Sample Injection 117

II.6.4.3 Chromatographic Isotope Effect in GC/C-IRMS 118

II.7 Summary of Part II 121

II.8 Set Problems 122

II.A How to Set up a Laboratory Continuous Flow Isotope Ratio Mass Spectrometry 123

II.A.1 Pre-Instatlation Requirements 124

II.A.2 Laboratory Location 124

II.A.3 Temperature Control 125

II.A.4 Power Supply 125

II.A.5 Gas Supply 126

II.A.6 Forensic Laboratory Considerations 129

II.A.7 Finishing Toucnes 130

References 136

III Stable Isotope Forensics: Case Studies and Current Research 143

III.1 Forensic Context 145

III.2 Distinguishing Drugs 149

III.2.1 Natural and Semisynthetic Drugs 149

III.2.1 Marijuana 149

III.2.2 Morphine and Heroin 150

III.2.3 Cocaine 152

III.2.2 Synthetic Drugs 154

III.2.2.1 Amphetamines 154

III.2.2.2 MDMA: Synthesis and Isotopic Signature 157

III.2.2.2.1 Three Different Synthetic Routes - Controlled Conditions 157

III.2.2.2.2 One Synthetic Route - Variable Conditions 164

III.2.2.3 Methamphetamine: Synthesis and Isotopic Signature 164

III.2.3 Conclusions 167

III.3 Elucidating Explosives 169

III.3.1 Bulk Isotope Analysis of Explosives and Precursors 170

III.3.1.1 Ammonium Nitrate 171

III.3.1.2 Hexamine, RDX and Semtex 172

III.3.1.3 Hydrogen Peroxide and Peroxides 176

III.3.2 Isotopic Product/Precursor Relationship 179

III.3.3 Potential Pitfalls 182

III.3.4 Conclusions 183

III.4 Matching Matchsticks 184

III.4.1 13C-Bulk Isotope Analysis 185

III.4.2 18C-Bulk Isotope Analysis 186

III.4.3 2H-Bulk Isotope Analysis 187

III.4.4 Matching Matches from Fire Scenes 188

III.4.5 Conclusions 189

III.5 Provenancing People 190

III.5.1 Stable Isotope Abundance Variation in Human Tissue 191

III.5.2 The Skull from the Sea 194

III.5.3 A Human Life Recorded in Hair 197

III.5.4 Found in Newfoundland 201

III.5.5 The Case of The Scissor Sisters' 207

III.5.6 Conclusions 211

III.6 Stable Isotope Forensics of other Physical Evidence 214

III.6.1 Microbial Isotope Forensics 214

III.6.2 Paper, Plastic (Bags) and Parcel Tape 215

III.6.2.1 Paper 215

III.6.2.2 Plastic and Plastic Bags 216

III.6.2.3 Parcel Tape 218

III.6.3 Conclusions 221

III.7 Summary 222

III.A 'Play True?': Stable Isotopes in Anti-doping Control or Quis custodiet ipsos custodes 224

III.A.1 Testosterone Metabolism and 13C Isotopic Composition 226

III.A.2 Analytical Methodology: Gas Chromatography and Peak Identification 230

III.B Sample Preparation Procedures 236

III.B.1 Preparing Silver Phosphate from Bio-apatite for 180 Isotope Analysis 236

III.B.2 Acid Digest of Carbonate from Bio-apatite for 13C and 180 Isotope Analysis 238

III.B.3 Standard Protocol for Preparing Hair Samples for 2H Isotope Analysis 240

References 242

Government Agencies and Institutes with Dedicated Stable Isotope Laboratories 253

Acknowledgements 255

Recommended Reading 257

Author's Biography 261

Index 263

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