Stable Isotope Forensics

Name: Stable Isotope Forensics | Methods and Forensic Applications of Stable Isotope Analysis
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Methods and Forensic Applications of Stable Isotope Analysis

Wolfram Meier-Augenstein(Autor*in)

Wiley-Blackwell (Verlag)

2. Auflage

Erschienen am 6. Oktober 2017

512 Seiten

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Beschreibung

The number-one guide, internationally, to all aspects of forensic isotope analysis, thoroughly updated and revised and featuring many new case studies
This edition of the internationally acclaimed guide to forensic stable isotope analysis uses real-world examples to bridge discussions of the basic science, instrumentation and analytical techniques underlying forensic isotope profiling and its various technical applications. Case studies describe an array of applications, many of which were developed by the author himself. They include cases in which isotope profiling was used in murder, and drugs-related crime investigations, as well as for pharmaceutical and food authenticity control studies.
Updated with coverage of exciting advances occurring in the field since the publication of the 1st edition, this 2nd edition explores innovative new techniques and applications in forensic isotope profiling, as well as key findings from original research. More than a simple update, though, this edition has been significantly revised in order to address serious problems that can arise from non-comparable and unfit-for-purpose stable isotope data. To that end, Part II has been virtually rewritten with greater emphasis now being placed on important quality control issues in stable isotope analysis in general and forensic stable isotope analysis in particular.
* Written in a highly accessible style that will appeal to practitioners, researchers and students alike
* Illustrates the many strengths and potential pitfalls of forensic stable isotope analysis
* Uses recent case examples to bridge underlying principles with technical applications
* Presents hands-on applications that let experienced researchers and forensic practitioners match problems with success stories
* Includes new chapters devoted to aspects of quality control and quality assurance, including scale normalisation, the identical treatment principle, hydrogen exchange and accreditation
Stable Isotope Forensics, 2nd Edition is an important professional resource for forensic scientists, law enforcement officials, public prosecutors, defence attorneys, forensic anthropologists and others for whom isotope profiling has become an indispensable tool of the trade. It is also an excellent introduction to the field for senior undergraduate and graduate forensic science students.
"All students of forensic criminology, and all law enforcement officers responsible for the investigation of serious crime , will want to study this book. Wolfram highlights the value, and future potential, of Stable Isotope Forensics as an emerging powerful tool in the investigation of crime."
--Roy McComb, Deputy Director, Specialist Investigations, National Crime Agency (NCA), UK
"A single author text in these days is rare and the value of this book lies in the dedication and experience of the author which is evident in the clarity of prose, the honest illustration of evidence and the realistic practical application of the subject - it makes this a text of genuine scientific value."
-- Prof Dame Sue Black, PhD, DBE, OBE, FRSE, Leverhulme Research Centre for Forensic Science, University of Dundee, U

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Inhalt

Series Foreword xi

Foreword: Dame Sue Black xiii

Foreword: Mark Harrison xv

Foreword to the 1st Edition xvii

Book Endorsements xix

Preface to the 2nd Edition xxi

List of Abbreviations xxv

About the Companion Website xxvii

Introduction: Stable Isotope 'Profiling' or Chemical 'DNA':

A New Dawn for Forensic Chemistry? xxix

I How it Works 1

I.1 What are Stable Isotopes? 2

I.2 Natural Abundance Variation of Stable Isotopes 4

I.3 Chemically Identical and Yet Not the Same 12

I.4 Isotope Effects, Mass Discrimination and Isotopic Fractionation 15

I.4.1 Physical Chemistry Background 15

I.4.2 Fractionation Factor a and Enrichment Factor e 17

I.4.3 Isotopic Fractionation in Rayleigh Processes 19

I.4.3.1 Isotopic Fractionation Summary 20

I.5 Stable Isotopic Distribution and Isotopic Fractionation of Light Elements in Nature 22

I.5.1 Hydrogen 22

I.5.2 Oxygen 26

I.5.3 Carbon 27

I.5.4 Nitrogen 30

I.5.5 Sulfur 32

I.5.6 Isoscapes 35

I.6 Stable Isotope Forensics in Everyday Life 40

I.6.1 "Food Forensics" 42

I.6.1.1 Authenticity and Provenance of Single-Seed Vegetable Oils 42

I.6.1.2 Authenticity and Provenance of Beverages 45

I.6.1.3 Caveats 49

I.6.2 Authenticity and Provenance of other Premium Products 53

I.6.3 Counterfeit Pharmaceuticals 54

I.6.4 Environmental Forensics 59

I.6.5 Wildlife Forensics 61

I.6.6 Anti-Doping Control 62

I.7 Summary of Part I 65

References Part I 67

II Instrumentation, Analytical Techniques and Data Quality 81

II.1 Mass Spectrometry versus Isotope Ratio Mass Spectrometry 82

II.1.1 Stability, Isotopic Linearity and Isotopic Calibration 85

II.2 Instrumentation for Stable Isotope Analysis 90

II.2.1 Dual-Inlet IRMS Systems 92

II.2.2 Continuous-Flow IRMS Systems 93

II.2.3 Bulk Material Stable Isotope Analysis 94

II.2.3.1 13C, 15N and 34S 94

II.2.3.2 2H and 18O 96

II.2.4 Compound-Specific Stable Isotope Analysis of Volatile Organic Compounds 98

II.2.4.1 Compound-Specific 13C or 15N Analysis by GC/C-IRMS 98

II.2.4.2 Compound-Specific 2H or 18O Analysis by GC/HTC-IRMS 100

II.2.4.3 Position-Specific Isotope Analysis 101

II.2.5 Compound-Specific 13C/15N Analysis of Polar, Non-Volatile Organic Compounds by LC-IRMS 101

II.2.6 Compound-Specific Isotope Analysis and Forensic Compound Identification 103

II.3 Quality Control and Quality Assurance in Continuous-Flow Isotope Ratio Mass Spectrometry 106

II.3.1 Compliance with IUPAC Guidelines is a Prerequisite not a Luxury 106

II.3.2 The Identical Treatment Principle 111

II.3.3 The Importance of Scale Normalization 112

II.3.3.1 Scale Normalization of Measured d2H Values to VSMOW 114

II.3.3.2 Scale Normalization of Measured d13C Values to VPDB 120

II.3.3.3 Scale Normalization of Measured d18O Values to VSMOW 122

II.3.3.4 Scale Normalization of Measured d15N Values to Air 126

II.3.3.5 Scale Normalization of Measured d34S Values to VCDT 127

II.4 Points of Note for Stable Isotope Analysis 128

II.4.1 Preparing for Analysis 128

II.4.2 Generic Considerations for BSIA 131

II.4.2.1 Scale Normalization of BSIA 132

II.4.2.2 Keeping Your Powder Dry 134

II.4.2.3 Isobaric Interference 135

II.4.2.4 Ionization Quench Effect 137

II.4.3 Particular Considerations for BSIA 140

II.4.3.1 Bulk 15N Analysis of Nitrates 140

II.4.3.2 Bulk 2H Analysis of Nitrogen-Rich Compounds 141

II.4.3.3 Total d2H versus True d2H Values 141

II.4.3.4 Organic Compounds with Exchangeable Hydrogen and Implications for 2H Abundance Analysis 144

II.4.3.4.1 Chemical and Biochemical Considerations - Example: Hair 152

II.4.3.5 2H Analysis of Human Hair 158

II.4.3.5.1 Two-Point Equilibration with Water at Ambient Temperature 161

II.4.3.5.2 Two-Point End-Member Comparative Equilibration 166

II.4.3.5.3 On-Line Two-Point End-Member Comparative Steam Equilibration 170

II.4.4 Points of Note for CSIA 172

II.4.4.1 Scale Normalization of GC-IRMS Analyses 172

II.4.4.2 Isotope Effects in GC-IRMS during Sample Injection 175

II.4.4.3 The Chromatographic Isotope Effect in GC-IRMS 176

II.4.4.4 Derivatization of Polar Compounds for GC-IRMS 178

II.4.4.5 Compound-Specific 2H Analysis of N- or Cl-Rich Compounds 181

II.5 Statistical Analysis of Stable Isotope Data within a Forensic Context 183

II.5.1 Chemometric Analysis 183

II.5.2 Bayesian Analysis 185

II.6 Quality Control and Quality Assurance in Forensic Stable Isotope Analysis 194

II.6.1 Accreditation to ISO 17025 195

II.6.1.1 Who Assesses the Assessors? 197

II.6.2 The Forensic Isotope Ratio Mass Spectrometry Network 205

II.7 Summary of Part II 207

II.A How to Set Up a Laboratory for Continuous-Flow Isotope Ratio Mass Spectrometry 209

II.A.1 Pre-Installation Requirements 210

II.A.2 Laboratory Location 210

II.A.3 Temperature Control 211

II.A.4 Power Supply 212

II.A.5 Gas Supply 213

II.A.6 Forensic Laboratory Considerations 216

II.A.7 Finishing Touches 217

II.B Sources of International Reference Materials and Tertiary Standards 219

II.C Selected Sample Preparation Protocols 220

II.C.1 Derivatization of Amino Acids for Compound Specific Isotope Analysis by GC-IRMS 220

II.C.2 Acid Digest of Carbonate from Bio-apatite for 13C and 18O Analysis 223

II.C.3 Preparing Silver Phosphate from Bio-apatite for 18O Analysis 225

II.C.4 Two-Point Water Equilibration Protocol for Determination of Non-ex d2H Values of Human Hair 227

II.D Internet Sources of Guidance and Policy Documents 231

References Part II 233

III Stable Isotope Forensics: Case Studies and Current Research 247

III.1 Forensic Context 248

III.1.1 Legal Context 249

III.2 Distinguishing Drugs 255

III.2.1 Natural and Semisynthetic Drugs 255

III.2.1.1 Marijuana 255

III.2.1.2 Morphine and Heroin 257

III.2.1.3 Cocaine 259

III.2.2 Synthetic Drugs 263

III.2.2.1 Amphetamines 263

III.2.2.2 Methamphetamine: Synthesis and Isotopic Signature 264

III.2.2.2.1 Two Different Synthetic Routes - Clandestine Conditions 268

III.2.2.3 MDMA: Synthesis and Isotopic Signature 270

III.2.2.3.1 Three Different Synthetic Routes - Controlled Conditions 273

III.2.2.3.2 One Synthetic Route - Variable Conditions 279

III.2.3 "Legal Highs" and "Designer Drugs" 284

III.2.3.1 Mephedrone 284

III.2.3.2 Piperazines 287

III.2.4 Excipients 291

III.2.5 Conclusions 293

III.3 Elucidating Explosives 296

III.3.1 Stable Isotope Analysis of Explosives and Precursors 297

III.3.1.1 Ammonium Nitrate (AN) 298

III.3.1.2 Hexamine, RDX, C4 and Semtex 300

III.3.1.3 Isotopic Product/Precursor Relationship 305

III.3.1.3.1 RDX and HMX 305

III.3.1.3.2 HMTD and TATP 309

III.3.1.4 Hydrogen Peroxide 315

III.3.2 Potential Pitfalls 321

III.3.3 Conclusions 323

III.4 Matching Matchsticks 324

III.4.1 13C-Bulk Isotope Analysis 325

III.4.2 18O-Bulk Isotope Analysis 326

III.4.3 2H-Bulk Isotope Analysis 328

III.4.4 Matching Matches from Fire Scenes 330

III.4.5 Conclusions 331

III.5 Provenancing People 333

III.5.1 Stable Isotope Abundance Variation in Human Tissue 336

III.5.1.1 Hair and Nails 338

III.5.1.1.1 Characteristics of Hair 340

III.5.1.1.2 Characteristics of Nails 342

III.5.1.1.3 Diagenetic Changes of Keratin 342

III.5.1.1.4 2H Isotopic Record in Hair and Nail 343

III.5.1.1.5 18O Isotopic Record in Hair and Nail 345

III.5.1.1.6 13C Isotopic Record in Hair and Nail 346

III.5.1.1.7 15N Isotopic Record in Hair and Nail 347

III.5.1.2 Bone and Teeth 350

III.5.1.2.1 Chemical Composition of Bone and Teeth 351

III.5.1.2.2 Static versus Remodelling Tissue Compartments 352

III.5.1.2.3 Diagenetic Changes of Bone and Teeth Mineral 354

III.5.1.2.4 Diagenetic Changes of Type I Collagen 356

III.5.1.2.5 18O Isotopic Record in Carbonate and Phosphate from Bio-apatite 357

III.5.1.2.6 13C Isotopic Record in Carbonate from Bio-apatite 363

III.5.1.2.7 Isotopic Record in Type I Collagen 364

III.5.1.3 Trophic Level Shift Effect on Stable Isotope Abundance Values in Human Tissue 365

III.5.2 Case Examples 370

III.5.2.1 The Skull from the Sea 371

III.5.2.2 A Human Life Recorded in Hair 375

III.5.2.3 Found in Newfoundland 379

III.5.2.4 The Case of "The Scissor Sisters" 384

III.5.2.5 Too Short a Life 390

III.5.2.6 Saltair Sally 393

III.5.2.7 A Tale of Two Cultures 394

III.5.3 Conclusions and Caveats 397

III.6 Stable Isotope Forensics of Other Physical Evidence 401

III.6.1 Microbial Isotope Forensics 402

III.6.2 Toxins and Poisons 404

III.6.3 Paper, Plastic (Bags) and Parcel Tape 404

III.6.3.1 Paper 404

III.6.3.2 Plastic and Plastic Bags 407

III.6.3.3 Parcel Tape 408

III.6.4 Conclusions 412

III.7 Evaluative Interpretation of Forensic Stable Isotope Data 413

III.7.1 Not Scale Referenced d-Values 415

III.7.2 Unresolved Contradictory Data 418

III.7.2.1 Example: "Geographic Provenance of a Murder Victim" 418

III.7.2.2 Example: "Manslaughter due to Negligence" 420

III.7.3 Foregone Conclusions 422

III.7.4 Logical Fallacies 424

III.7.5 Untested Assumptions 426

III.7.6 Conclusion 428

III.8 Summary of Part III 430

III.A An Abridged List of Forensic Stable Isotope Laboratories Worldwide 432

References Part III 434

Introduction

Stable Isotope 'Profiling' or Chemical 'DNA': A New Dawn for Forensic Chemistry?

Starting with the conclusion first, I would say neither of the above two terms is appropriate, although I am convinced information locked into the stable isotopic composition of physical evidence may well represent a new dawn for forensic chemistry.

The title for this general introduction was chosen deliberately as an analogy for the term "DNA fingerprinting," coined by Professor Sir Alec J. Jeffreys, to draw the reader's attention to the remarkable analogy between the organic, life-defining material DNA and the more basic, and on their own lifeless, chemical elements in their various isotopic forms when examined in the context of forensic sciences in general and human provenancing in particular. It is also my intention to alert readers from the start to the dangers of expecting miracles of stable isotope forensics. DNA evidence is at its most powerful when it can be matched against a comparative sample or a database entry, and the same is true to a degree for the information locked into the isotopic composition of a given material. Similarly, the random match probability of 1 in 1 billion for a DNA match based on 10 loci and the theoretical match probability of an accidental false positive match of a multi-isotope signature are also seemingly matched, with a multivariate or multifactor probabilistic equation being the common denominator for both. If we consider a material such as hair keratin and we make the simplifying assumption this material may exist naturally in as many different isotopic states per element as there are whole numbers in the natural abundance range for each stable isotope on the d-scale (Fry, 2006), we can calculate a hypothetical figure for the accidental match probability of such a multi-element isotope analysis that is comparable to that of a DNA fingerprint.

For example, the widest possible natural abundance range for carbon-13 is 110 % (Fry, 2006) so for the purpose of this example we could say keratin can assume 110 different integer carbon-13 values. Analysing hair keratin for its isotopic composition with regard to the light elements hydrogen (H), carbon (C), nitrogen (N), oxygen (O) and sulfur (S) could thus theoretically yield a combined specificity ranging from 1 in 638 million to 1 in 103.95 billion. In fact, one can calculate that the analysis of hair keratin for its isotopic composition with regards to H, C, N and S would theoretically yield a combined specificity of 1 in 1 billion, thus suggesting a "stable isotope profile" or "stable isotope signature" based on these four letters of the chemical alphabet having the same accidental match probability as a DNA fingerprint that ultimately is based on the four letters of the DNA alphabet, A (adenine), C (cytosine), G (guanine) and T (thymine) (see Box). However, it has to be stressed that it has as yet not been fully explored if this hypothetical level of random match probability, and hence level of discrimination, is actually achievable given that the natural abundance ranges in which compounds or materials can occur are usually much narrower than the widest possible theoretical range. We will learn more about this in the course this book. Forensic scientists and statisticians such as Jurian Hoogewerff (University of Canberra) and James Curran (University of Auckland) suggest more conservative estimates, putting the potentially realised random match probability of stable isotope signatures at levels between 1 in 10,000 and 1 in 1 million depending on the nature and history of the material under investigation. However, even at these levels stable isotope profiling is still a potentially powerful forensic tool.

Analogies between DNA and stable isotopes of light elements Biological DNA versus Chemical "DNA" Alphabet of Biological DNA comprises the letters Alphabet of Chemical "DNA" comprises the letters A 2H C 13C G 15N D 18O [U] [34S]

The random match probability of Biological DNA is approximately 1 : 1 billion (1 × 109) for a DNA profile based on 10 loci.

The random match probability of a five-element stable isotope profile can theoretically range from 1 : 693 million (6.93 × 108) to as high as 1 : 1.04 × 1011.

Note: This is for illustrative purposes only and does not denote any equivalence between DNA bases and chemical elements.

While one can make a good case that the isotopic abundances of 2H, 13C, 15N and 34S are independent variables and figures representing their abundance range can hence be combined in a probabilistic equation, the same is not entirely the case for 2H and 18O, which when originating from water may behave like dependent variables. More relevant to this issue is the question if and to what degree isotopic abundance varies for any given material or compound. While across all materials and compounds known to man 13C isotopic abundance may indeed stretch across a range of 110 d-units, its range in a particular material, such as coca leaves, may only extend to 7 d-units (Ehleringer et al., 2000).

Another reason why the analogy between DNA fingerprinting and stable isotope profiling should only be used in conjunction with qualifying statements is the fact that both a DNA fingerprint and a physical fingerprint are immutable, that is, they do not change over time. Drawing on an example from environmental forensics, calling a gas chromatography (GC) or gas chromatography-mass spectrometry (GC/MS) profile from a sample of crude oil spillage a fingerprint of that oil is a misnomer since ageing processes such as evaporation will lead to changes in the oil's composition with regard to the relative abundance of its individual constituents. Incidentally, due to isotopic fractionation during evaporation the isotopic composition of any residual oil compound will also have changed when compared to its isotopic composition at the point of origin. A more apt analogy would therefore be the use of the term stable isotope signature. Just as a person's signature can change over time or under the burden of stress, so the stable isotopic composition of the residual sample from a material susceptible to evaporative loss may have changed by the time it ends up in our laboratories. Furthermore, in the same way a forensic expert relies on more than one physicochemical characteristic as well as drawing on experience and contextual information to arrive at an interpretation regarding similarity or dissimilarity, the stable isotope scientist combines measured data with experience, expertise and contextual information to come to a conclusion as to what a given stable isotope signature does or does not reveal.

Despite these caveats it is easy to see why the prospect of having such powerful a tool at one's disposal for combating crime and terrorism has caused a lot of excitement in both the end-user and scientific communities. However, if the history of applying DNA fingerprinting in a forensic context has taught us anything then it is this: great potential is no substitute for good forensic science, and good forensic science cannot be rushed or packaged to meet externally driven agendas. At first there was no great interest in this new forensic technique, but after a few spectacular successes demand for what seemed to be the silver bullet to connect suspect perpetrators to victims or crime scenes increased faster than research still concerned with answering underlying fundamental questions could keep up with, and history has all but repeated itself recently on the subject of low template DNA. Good forensic science cannot be rushed but is the outcome of good forensic science teaching and research, which in turn become the foundation of good forensic practice. While the former requires proper funding the latter requires proper regulation, and both requirements must be addressed and met.

Not surprisingly, therefore, even at the time of writing the second edition of this book we still have a mountain to climb to turn stable isotope forensics into a properly validated forensic analytical tool or technique that is fit for purpose. Even though this technique has been successfully applied in a number of high-profile criminal cases where salient questions could be answered by comparative analysis, this should not blind us to the fact that a considerable amount of time, effort, money and careful consideration still has to be spent to develop and finely hone this technique into the sharp investigative tool it promises to be.

Similar to DNA, data have to be generated and databases have to be compiled for a statistically meaningful underpinning of this technique and the interpretation of its analytical results. Equally important, if not more so, all the steps from sample collection, sample storage and sample preparation to analytical measurement and the final data reduction have to be carefully examined either to avoid process artefacts or, if unavoidable, to quantify such artefacts and develop fit-for-purpose correction protocols to avoid stable isotope forensics suffering the same fate as low template DNA.

One way of ensuring appropriate and well-advised use of this technique in a forensic context is to advise and instruct current and future generations of forensic scientists in this technique as...

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