Forensic Chemistry Handbook
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More About This Title Forensic Chemistry Handbook

English

A concise, robust introduction to the various topics covered by the discipline of forensic chemistry

The Forensic Chemistry Handbook focuses on topics in each of the major chemistry-related areas of forensic science. With chapter authors that span the forensic chemistry field, this book exposes readers to the state of the art on subjects such as serology (including blood, semen, and saliva), DNA/molecular biology, explosives and ballistics, toxicology, pharmacology, instrumental analysis, arson investigation, and various other types of chemical residue analysis. In addition, the Forensic Chemistry Handbook:

  • Covers forensic chemistry in a clear, concise, and authoritative way

  • Brings together in one volume the key topics in forensics where chemistry plays an important role, such as blood analysis, drug analysis, urine analysis, and DNA analysis

  • Explains how to use analytical instruments to analyze crime scene evidence

  • Contains numerous charts, illustrations, graphs, and tables to give quick access to pertinent information

Media focus on high-profile trials like those of Scott Peterson or Kobe Bryant have peaked a growing interest in the fascinating subject of forensic chemistry. For those readers who want to understand the mechanisms of reactions used in laboratories to piece together crime scenes—and to fully grasp the chemistry behind it—this book is a must-have.

English

Lawrence Kobilinsky is currently the Chairman of the Department of Sciences and Professor of Biology and Immunology at John Jay College of Criminal Justice. An internationally renowned forensic scientist, he is a Fellow of the American Academy of Forensic Sciences as well as the New York Microscopical Society. He has published extensively in the areas of identification and individualization using protein genetic markers and DNA analysis, and is the coauthor of Wiley's DNA: Forensic and Legal Applications.

English

Preface xv

Contributors xxi

1. Forensic Environmental Chemistry 1
Anthony Carpi and Andrew J. Schweighardt

1.1 Introduction 2

1.2 Chemical Fingerprinting 4

1.2.1 Hydrocarbon Mixtures 4

1.2.2 Polycyclic Aromatic Hydrocarbons 6

1.2.3 Biomarkers 11

1.2.4 Additives 11

1.2.5 Isotopes 12

1.2.6 Tracers 13

1.2.7 Methods of Detection 16

1.2.8 Weathering 18

1.3 Spatial Association of Environmental Incidents 18

References 20

2. Principles and Issues in Forensic Analysis of Explosives 23
Jimmie C. Oxley, Maurice Marshall, and Sarah L. Lancaster

2.1 Introduction 24

2.2 Sample Collection 25

2.3 Packaging 29

2.4 Sorting 30

2.5 Documentation 31

2.6 Environmental Control and Monitoring 31

2.7 Storage 33

2.8 Analysis 33

2.9 Records 36

2.10 Quality Assurance 36

2.11 Safety and Other Issues 37

Conclusion 37

References 38

3. Analysis of Fire Debris 41
John J. Lentini

3.1 Introduction 42

3.2 Evolution of Separation Techniques 43

3.3 Evolution of Analytical Techniques 47

3.4 Evolution of Standard Methods 49

3.5 Isolating the Residue 51

3.5.1 Initial Sample Evaluation 51

3.5.2 ILR Isolation Method Selection 51

3.5.3 Solvent Selection 54

3.5.4 Internal Standards 54

3.5.5 Advantages and Disadvantages of Isolation Methods 56

3.6 Analyzing the Isolated ILR 56

3.6.1 Criteria for Identification 63

3.6.2 Improving Sensitivity 90

3.6.3 Estimating the Degree of Evaporation 95

3.6.4 Identity of Source 98

3.7 Reporting Procedures 101

3.8 Record Keeping 102

3.9 Quality Assurance 105

Conclusion 105

References 106

4. Forensic Examination of Soils 109
Raymond C. Murray

4.1 Introduction 110

4.2 Murder and the Pond 111

4.3 Oil Slicks and Sands 113

4.4 Medical Link 114

4.5 Examination Methods 114

4.5.1 Color 115

4.5.2 Particle-Size Distribution 117

4.5.3 Stereo Binocular Microscope 120

4.5.4 Petrographic Microscope 122

4.5.5 Refractive Index 124

4.5.6 Cathodoluminescence 124

4.5.7 Scanning Electron Microscope 125

4.5.8 X-Ray Diffraction 126

4.6 Chemical Methods 127

4.6.1 FTIR and Raman Spectroscopy 128

4.7 Looking Ahead 129

References 130

5. Analysis of Paint Evidence 131
Scott G. Ryland and Edward M. Suzuki

5.1 Introduction 132

5.2 Paint Chemistry and Color Science 134

5.2.1 Binders 134

5.2.2 Pigments 136

5.3 Types of Paint 139

5.3.1 Automotive Finish Systems 139

5.3.2 Architectural Coatings (Structural Paints or House Paints) 140

5.3.3 Other Coatings 141

5.4 Paint Evidence Interpretation Considerations 141

5.5 Analytical Methods 142

5.5.1 Microscopic Examinations 143

5.5.2 Physical Nature of the Transfer 147

5.5.3 Microscopy 149

5.5.4 Microspectrophotometry 152

5.5.5 Infrared Spectroscopy 158

5.5.6 Raman Spectroscopy 175

5.5.7 Pyrolysis Gas Chromatography and Pyrolysis Gas Chromatography–Mass Spectrometry 178

5.5.8 Elemental Analysis Methods 188

5.5.9 Other Methods 205

5.6 Examples 208

5.6.1 Example 1 208

5.6.2 Example 2 210

5.6.3 Example 3 213

References 217

6. Analysis Techniques Used for the Forensic Examination of Writing and Printing Inks 225
Gerald M. LaPorte and Joseph C. Stephens

6.1 Introduction 226

6.2 Ink 226

6.2.1 Ink Composition 227

6.3 Ink Analysis 230

6.3.1 Physical Examinations 233

6.3.2 Optical Examinations 236

6.3.3 Chemical Examinations 238

6.3.4 Ink Dating 240

6.4 Office Machine Systems 242

6.4.1 Inkjet Ink 242

6.4.2 Inkjet Ink Analysis 243

6.4.3 Toner Printing 245

6.4.4 Toner Analysis 246

Conclusion 247

References 248

7. The Role of Vibrational Spectroscopy in Forensic Chemistry 251
Ali Koçak

7.1 Introduction to Vibrational Spectroscopy 252

7.2 Infrared Spectroscopy 253

7.3 Infrared Sampling Techniques 255

7.3.1 Transmission Spectroscopy 255

7.3.2 External Reflection Spectroscopy 255

7.3.3 Attenuated Total Reflectance 256

7.3.4 Diffuse Reflectance Spectroscopy 258

7.3.5 Infrared Microspectroscopy 259

7.4 Raman Spectroscopy 260

7.5 Raman Spectroscopic Techniques 262

7.5.1 Surface-Enhanced Raman Spectroscopy 262

7.5.2 Resonance Raman Scattering 263

7.5.3 Coherent anti-Stokes Raman Spectroscopy 263

7.5.4 Confocal Raman Spectroscopy 263

7.6 Applications of Vibrational Spectroscopy in Forensic Analysis 264

References 265

8. Forensic Serology 269
Richard Li

8.1 Introduction 270

8.2 Identification of Blood 271

8.2.1 Oxidation–Reduction Reactions 272

8.2.2 Microcrystal Assays 275

8.2.3 Other Assays for Blood Identification 275

8.3 Species Identification 278

8.3.1 Immunochromatographic Assays 278

8.3.2 Ouchterlony Assay 280

8.3.3 Crossed-Over Immunoelectrophoresis 281

8.4 Identification of Semen 282

8.4.1 Visual Examination 282

8.4.2 Acid Phosphatase Assays 283

8.4.3 Microscopic Examination of Spermatozoa 284

8.4.4 Immunochromatographic Assays 285

8.4.5 RNA-Based Assays 286

8.5 Identification of Saliva 286

8.5.1 Visual and Microscopic Examination 287

8.5.2 Identification of Amylase 287

8.5.3 RNA-Based Assays 289

References 289

9. Forensic DNA Analysis 291
Henrietta Margolis Nunno

9.1 Introduction 292

9.1.1 Background on DNA Typing 292

9.1.2 DNA Structure 294

9.1.3 Nuclear and Mitochondrial DNA Organization 295

9.2 Methodology 296

9.2.1 Sample Collection and DNA Extraction 296

9.2.2 DNA Quantification 297

9.2.3 Polymerase Chain Reaction 298

9.2.4 Short Tandem Repeats 298

9.2.5 PCR of STRs 300

9.2.6 Separation and Sizing of STR Alleles 301

9.2.7 Combined DNA Index System (CODIS) Database 305

9.2.8 Frequency and Probability 306

9.3 Problems Encountered in STR Analysis 307

9.3.1 Low-Copy-Number DNA 307

9.3.2 Degraded DNA and Reduced-Size (mini) STR Primer Sets 308

9.3.3 PCR Inhibition 310

9.3.4 Interpretation of Mixtures of DNA 310

9.3.5 Null Alleles and Allele Dropout 311

9.3.6 Factors Causing Extra Peaks in Results Observed 312

9.3.7 Stutter Product Peaks 312

9.3.8 Nontemplate Addition (Incomplete Adenylation) 313

9.3.9 Technological Artifacts 313

9.3.10 Single-Nucleotide Polymorphism Analysis of Autosomal DNA SNPs 313

9.3.11 Methods Used for SNP Analysis 314

9.3.12 Mitochondrial DNA Analysis 315

9.4 Methodology for mtDNA Analysis 316

9.4.1 Preparation of Samples 316

9.4.2 MtDNA Sequencing Methods 316

9.4.3 Reference Sequences 317

9.4.4 Screening Assays for mtDNA 318

9.4.5 Interpretation of mtDNA Sequencing Results 319

9.4.6 Statistics: The Meaning of a Match for mtDNA 320

9.4.7 Heteroplasmy 320

9.4.8 The Future of DNA Analysis 321

References 322

10. Current and Future Uses of DNA Microarrays in Forensic Science 327
Nathan H. Lents

10.1 Introduction 328

10.2 What is a DNA Microarray? 328

10.2.1 cDNA Microarray 329

10.2.2 Other Types of DNA Arrays 330

10.2.3 The Birth of “-omics” 331

10.3 DNA Microarrays in Toxicogenomics 332

10.3.1 Sharing Information 333

10.3.2 Forensic Application 333

10.4 Detection of Microorganisms Using Microarrays 334

10.4.1 Historical Perspective 334

10.4.2 DNA Fingerprinting 335

10.4.3 DNA Fingerprinting by Microarrays 336

10.4.4 DNA Sequence-Based Detection 337

10.4.5 Where DNA Microarrays Come In 337

10.4.6 Looking Forward: Genetic Virulence Signatures 338

10.5 Probing Human Genomes by DNA Microarrays 340

10.5.1 STR Analysis 340

10.5.2 SNP Analysis 343

10.5.3 Exploring an Unknown Genome? 344

Conclusion 345

References 345

11. Date-Rape Drugs with Emphasis on GHB 355
Stanley M. Parsons

11.1 Introduction 357

11.2 Molecular Mechanisms of Action 357

11.2.1 Receptors and Transporters 357

11.2.2 Real GHB Receptors 359

11.3 Societal Context of Date-Rape Agents 361

11.3.1 Acute Effects of Date-Rape Agents on Cognition and Behavior 361

11.3.2 Medicinal Uses of Date-Rape Drugs 361

11.3.3 Self-Abuse 362

11.3.4 Date Rape, Death, and Regulation 363

11.4 Metabolism Fundamentals 363

11.4.1 Complexity in Unraveling Metabolism of GHB-Related Compounds 363

11.4.2 Isozymes in GHB-Related Metabolism 364

11.4.3 Subcellular Compartmentalization of Enzymes, Transporters, and Substrates 364

11.4.4 Dynamics and Equilibria for Enzymes and Transporters 365

11.4.5 Thermodynamics-Based Analysis of Metabolic Flux 366

11.4.6 Metabolism of Endogenous GHB Versus Ingested GHB and Prodrugs 367

11.4.7 Directionality of in Vivo and in Vitro Enzymatic Activity 367

11.4.8 Transporters and Enzymes Mediating GHB-Related Metabolism 367

11.5 Biosynthesis of Endogenous GHB 368

11.5.1 First Step for GHB Biosynthesis in the Known Pathway 368

11.5.2 Second Step for GHB Biosynthesis in the known Pathway 368

11.5.3 Third Step for GHB Biosynthesis in the known Pathway 371

11.5.4 Which Step in GHB Biosynthesis is Rate Limiting? 373

11.5.5 Are There Other Biosynthetic Pathways to Endogenous GHB? 374

11.6 Absorption and Distribution of Ingested GHB 376

11.6.1 Gastrointestinal Tract 376

11.6.2 Blood 377

11.7 Initial Catabolism of GHB 377

11.7.1 Transport into Mitochondria 377

11.7.2 Iron-Dependent Alcohol Dehydrogenase ADHFe1 377

11.7.3 Poorly Characterized Catabolism of GHB 379

11.8 Chemistry of GHB and Related Metabolites not Requiring Enzymes 380

11.9 Experimental Equilibrium Constants for Redox Reactions of GHB 380

11.10 Estimated Equilibrium Constants for Redox Reactions of GHB in Vivo 381

11.11 Different Perspectives on Turnover of Endogenous GHB are Consistent 384

11.12 Disposition of Succinic Semialdehyde 385

11.13 Conversion of Prodrugs to GHB and Related Metabolites 386

11.13.1 ?-Butyrolactone 386

11.13.2 1,4-Butanediol 387

11.14 Subcellular Compartmentalization of GHB-Related Compounds 388

11.15 Comparative Catabolism of Ethanol, 1,4-Butanediol, Fatty Acids, and GHB 389

11.16 Catabolism of MDMA, Flunitrazepam, and Ketamine 390

11.17 Detection of Date-Rape Drugs 390

11.17.1 Compounds Diagnostic for Dosing by Synthetic Date-Rape Drugs 390

11.17.2 Compounds Diagnostic for Dosing by GHB 390

11.17.3 Gold-Standard Testing 391

11.17.4 Many Applications for Reliable Field Tests 392

11.17.5 Hospital Emergency Department Example 392

11.17.6 Preparation of a Sample for Delayed Analysis 393

11.17.7 Time Window Available to Detect Dosing 393

11.17.8 Extending the Time Window 394

11.18 Special Circumstances of GHB 395

11.18.1 Industrial Connection 395

11.18.2 Enzymes Acting on GHB in Bacteria, Yeast, and Plants 395

11.18.3 Possible Accidental Intoxication by GHB in the Future 395

11.19 Considerations During Development of Field Tests 396

11.19.1 Shortcomings of Antibody-Based Screens for Simple Analytes 396

11.19.2 Advantages of Enzyme-Based Screens for Simple Natural Analytes 397

11.20 Development of an Enzymatic Test for GHB 399

11.20.1 Sensitivity Required for the Hospital Emergency Department 399

11.20.2 Choice of Enzyme 399

11.20.3 Reliable Field Test for GHB 400

Conclusion 402

Notes 404

References 406

12. Forensic and Clinical Issues in Alcohol Analysis 435
Richard Stripp

12.1 Introduction 436

12.2 Blood Alcohol Concentration 437

12.3 Alcohol Impairment and Driving Skills 441

12.4 Field Sobriety Tests 443

12.5 Blood Alcohol Measurements 444

12.5.1 Enzymatic Methods 444

12.5.2 Headspace Gas Chromatography 445

12.5.3 Breath Alcohol Testing 446

12.5.4 Breath Alcohol Instrumentation 447

12.5.5 Extrapolation from BrAC to BAC 449

12.5.6 Urine and Saliva 450

12.5.7 Ethyl Glucuronide 450

12.5.8 Postmortem Determination of Alcohol 451

12.5.9 Quality Assurance of Alcohol Testing 452

References 453

13. Fundamental Issues of Postmortem Toxicology 457
Donald B. Hoffman, Beth E. Zedeck, and Morris S. Zedeck

13.1 Introduction 458

13.2 Tissue and Fluid Specimens 460

13.2.1 Blood 460

13.2.2 Urine 461

13.2.3 Vitreous Humor and Cerebrospinal Fluid 461

13.2.4 Gastric Contents 462

13.2.5 Meconium 463

13.2.6 Brain 464

13.2.7 Liver and Bile 464

13.2.8 Lung, Spleen, Kidney, and Skin 465

13.2.9 Muscle 465

13.2.10 Bone, Teeth, Nails, and Hair 465

13.2.11 Other Materials for Analysis 466

13.3 Specimen Collection and Storage 466

13.4 Extraction Procedures 467

13.5 Analytical Techniques 467

13.6 Interpretation 470

13.6.1 Postmortem Redistribution 470

13.6.2 Pharmacogenomics 471

13.6.3 Drug Interactions 472

13.6.4 Drug Stability and Decomposed Tissue 473

13.6.5 Effects of Embalming Fluid 474

Conclusion 475

References 476

14. Entomotoxicology: Drugs, Toxins, and Insects 483
Jason H. Byrd and Michelle R. Peace

14.1 Introduction 484

14.2 The Fly and Forensic Science 484

14.2.1 History of Forensic Entomology, Toxicology, and the Rise of Entomotoxicology 485

14.2.2 Drugs and the Fly Life Cycle 488

14.2.3 Why Use Insects as a Toxicological Specimen? 490

14.2.4 Drug Extraction Methods 492

14.2.5 Qualitative Versus Quantitative 493

14.2.6 Changes in Insect Development: Toxins and Drugs 494

14.2.7 The Future of Entomotoxicology 494

References 495

Index 501

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