Forensic Chemistry Handbook
, by Kobilinsky, Lawrence
- ISBN: 9780471739548 | 0471739545
- Cover: Hardcover
- Copyright: 11/29/2011
This book focuses on topics in each of the major chemistry-related areas of forensic science. With chapter authors that span the forensic chemistry fields, the book exposes readers to the state-of-the-art on such subjects as: serology (including blood, semen, and saliva), DNA/molecular biology, explosives and gun shots, toxicology, pharmacology, instrumental analysis, and arson investigation. It covers the modern applications of forensic science and allows forensic scientists to understand the mechanisms of reactions used in their laboratories.
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.
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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