Forensic Science -

Forensic Science (eBook)

Maciej J Bogusz (Herausgeber)

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2011 | 2. Auflage
1046 Seiten
Elsevier Science (Verlag)
978-0-08-055425-9 (ISBN)
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The book presents the applications of separation methods, manly chromatography, in forensic practice.
The first part, devoted to forensic toxicology, contains reviews on forensic relevant groups of compounds, like: Opiate agonists, cocaine, amphetamines, hallucinogens, cannabinoids, sedatives and hypnotics, antidepressive and antipsychotic drugs, analgesics, antidiabetics, muscle relaxants, and mushroom toxins.
In these parts, the preliminary immunochemical tests were also included, together with separation methods.
Screening procedures used in forensic toxicology were presented in separate chapters on forensic screening with GC, GC-MS, HPLC, LC-MS, CE, and LC-ICP-MS.
In the part on actual and emerging problems of forensic toxicology, following chapters were included: Analytical markers of alcohol abuse, toxicological aspects of herbal remedies, drugs and driving, analysis in alternative matrices, doping analysis, pharmacogenomics in forensic toxicology, and quality assurance.
The second part presents application of separation methods in forensic chemistry, and comprises chapters on: Explosives, chemical warfare agents, arson analysis, and writing media.
Third part on forensic identification contains chapter on forensic genetics.
All chapters are written up-to-date and present specific information up to 2006. The authors of each chapter are known not only from their scientific activity, but are also reputed experts, proven in everyday forensic casework.

- Wide spectrum of topics presented
- Up-to-date presentation of topics
- Data are presented in comparative mode
- Special stress put on screening procedures
Forensic Science, Second Edition presents the applications of separation methods, manly chromatography, in forensic practice. The first part, devoted to forensic toxicology, contains reviews on forensic relevant groups of compounds, like: Opiate agonists, cocaine, amphetamines, hallucinogens, cannabinoids, sedatives and hypnotics, antidepressive and antipsychotic drugs, analgesics, antidiabetics, muscle relaxants, and mushroom toxins.In these parts, the preliminary immunochemical tests were also included, together with separation methods. Screening procedures used in forensic toxicology were presented in separate chapters on forensic screening with GC, GC-MS, HPLC, LC-MS, CE, and LC-ICP-MS. In the part on actual and emerging problems of forensic toxicology, following chapters were included: Analytical markers of alcohol abuse, toxicological aspects of herbal remedies, drugs and driving, analysis in alternative matrices, doping analysis, pharmacogenomics in forensic toxicology, and quality assurance. The second part presents application of separation methods in forensic chemistry, and comprises chapters on: Explosives, chemical warfare agents, arson analysis, and writing media. Third part on forensic identification contains chapter on forensic genetics.All chapters are written up-to-date and present specific information up to 2006. The authors of each chapter are known not only from their scientific activity, but are also reputed experts, proven in everyday forensic casework. Wide spectrum of topics presented Up-to-date presentation of topics Data are presented in comparative mode Special stress put on screening procedures

Front cover 1
Forensic Science 4
Copyright 5
Preface to the second edition 6
Preface to the first edition 8
List of contributors 10
Contents 16
Part 1: Compounds of Importance in Forensic Toxicology 40
Chapter 1. Opioids: Methods of Forensic Analysis 42
1.1. Introduction 42
1.2. Preliminary Methods for Opiate Detection 42
1.3. Isolation of Opiates from Biosamples 47
1.4. Papaver Somniferum as a Source of Opiates 49
1.5. Heroin and Associated Illicit Opiate Formulations 53
1.6. Other Opiate Agonists 74
1.7. Concluding Summary 98
1.8. Abbreviations 99
1.9. References 101
Chapter 2. Current Methods for the Separation and Analysis of Cocaine Analytes 112
2.1. Introduction 113
2.2. Current Methods for the Determination of Cocaine 122
2.3. Conclusions and Perspectives 156
2.4. Abbreviations 157
2.5. References 159
Chapter 3. Amphetamines 166
3.1. Introduction 166
3.2. Extraction 168
3.3. Derivatization 174
3.4. Gas Chromatography 182
3.5. Liquid Chromatography 188
3.6. Alternative Techniques 191
3.7. Interpretation of Analytical Results 198
3.8. Conclusion 202
3.9. Abbreviations 203
3.10. References 204
Chapter 4. Hallucinogens 214
4.1. Introduction 214
4.2. Lysergic Acid Diethylamide (LSD) 216
4.3. Mescaline 226
4.4. Psilocybin 227
4.5. Phencyclidine (PCP) 230
4.6. Conclusion 237
4.7. Abbreviations 237
4.8. References 238
Chapter 5. Cannabinoids Analysis: Analytical Methods for Different Biological Specimens 242
5.1. Introduction 242
5.2. Analysis of Cannabinoids in Urine 243
5.3. Analysis of Cannabinoids in Blood 260
5.4. Analysis of Cannabinoids in Hair 266
5.5. Analysis of Cannabinoids in Meconium 268
5.6. Other Biological Specimens 269
5.7. Autopsy Materials 271
5.8. Analysis of Cannabinoids in Crude Cannabis Preparations 272
5.9. Concluding Remarks 274
5.10. References 274
Chapter 6. Sedatives and Hypnotics 282
6.1. Introduction 282
6.2. Barbiturates 283
6.3. Benzodiazepines 291
6.4. Zopiclone, Zolpidem, Zaleplon and Eszopiclone 300
6.5. Diphenhydramine 306
6.6. Other Sedatives and Hypnotics 309
6.7. Concluding Summary and Perspectives 312
6.8. References 313
Chapter 7. Antidepressants and Antipsychotics 326
7.1. Introduction 326
7.2. Analytical Techniques 336
7.3. Conclusion 352
7.4. Abbreviations 352
7.5. References 353
Chapter 8. Non-Opioid Analgesics 358
8.1. Introduction 358
8.2. Paracetamol 359
8.3. Acetylsalicylic Acid 368
8.4. Non-steroidal Anti-Inflammatory Drugs 375
8.5. Pyrazole Derivatives 383
8.6. Concluding Summary and Perspectives 386
8.7. References 387
Chapter 9. Other Therapeutic Drugs of Forensic Relevance 396
9.1. Introduction 396
9.2. Cardiac Glycosides 396
9.3. Antiarrhythmics 400
9.4. Oral Antidiabetics 412
9.5. Muscle Relaxants 417
9.6. Concluding Summary 421
9.7. References 421
Chapter 10. Mushroom Toxins 430
10.1. Introduction 430
10.2. Amatoxins 430
10.3. Orellanine 435
10.4. Gyromitrin 435
10.5. Psilocybin and Psilocin 436
10.6. References 437
Part 2: Screening Procedures Used in Forensic Toxicology 440
Chapter 11. Forensic Screening by Gas Chromatography 442
11.1. Introduction 442
11.2. Sample Preparation 443
11.3. Separation 443
11.4. Identification 449
11.5. Detection and Quantification 452
11.6. Established GC Screening for Basic Drugs 456
11.7. Conclusions 461
11.8. References 462
Chapter 12. Forensic Screening with GC-MS 464
12.1. Introduction 464
12.2. Screening Strategies 464
12.3. Samples and their Work-up 465
12.4. Screening in Blood Serum
12.5. Screening in Urine 467
12.6. Reference Mass Spectral Libraries as Basis for Full-Scan GC-MS Screening Procedures 478
12.7. Concluding Summary and Perspectives 480
12.8. Ackowledgements 480
12.9. References 481
Chapter 13. High Performance Liquid Chromatography in Forensic Toxicological Analysis 486
13.1. Introduction 486
13.2. Progress in HPLC Techniques 486
13.3. Applications of HPLC in Forensic Analysis 504
13.4. Concluding Remarks 523
13.5. References 524
Chapter 14. Forensic Screening with Liquid Chromatography-Mass Spectrometry 530
14.1. Introduction 530
14.2. Sample Preparation for Comprehensive LC-MS Screening 531
14.3. Liquid Chromatography Prior to Mass Spectrometry 532
14.4. Ionisation Techniques 535
14.5. Comprehensive Screening Procedures 537
14.6. Identification using LC-MS and LC-MS/MS Spectral Libraries 542
14.7. Discussion and Conclusions 547
14.8. Abbreviations 548
14.9. References 549
Chapter 15. Forensic Toxicological Screening with Capillary Electrophoresis and Related Techniques 552
15.1. Introduction 552
15.2. Technical Features and Instrumentation 553
15.3. Capillary Electrophoresis in Toxicological Screening 564
15.4. Conclusions 569
15.5. Abbreviations 570
15.6. References 571
Chapter 16. HPLC-ICP-MS Screening for Forensic Applications 574
16.1. Introduction 574
16.2. Instrumentation 576
16.3. Applications 579
16.4. Concluding remarks 598
16.5. References 598
Part 3: Actual and Emerging Problems of Forensic Toxicology 604
Chapter 17. Analytical Markers of Acute and Chronic Alcohol Consumption 606
17.1. Introduction 606
17.2. Tests of Acute Alcohol Consumption 608
17.3. Tests of Chronic Alcohol Consumption 615
17.4. Future Aspects on Alcohol Testing and Alcohol Biomarkers 621
17.5. Conclusion 621
17.6. References 622
Chapter 18. Toxicological Aspects of Herbal Remedies 628
18.1. Introduction 628
18.2. Intrinsic Toxicity of Herbal Remedies 630
18.3. Toxic Metals in Herbal Remedies 638
18.4. Organic Contaminants of Herbal Remedies 640
18.5. Adulteration of Herbal Remedies with Pharmaceuticals 641
18.6. Conclusions 647
18.7. References 647
Chapter 19. Drugs and Driving 650
19.1. Introduction 650
19.2. Analytical Methods 654
19.3. Interpretation 675
19.4. Conclusion 682
19.5. Abbreviations 683
19.6. References 685
Chapter 20. Unconventional Samples and Alternative Matrices 692
20.1. Hair 693
20.2. Oral Fluid 707
20.3. Sweat 720
20.4. Meconium 722
20.5. Conclusion 727
20.6. Abbreviations 728
20.7. References 729
Chapter 21. Doping Substances in Human and Animal Sport 738
21.1. Introduction 738
21.2. Anabolic Androgenic Steroids 743
21.3. Stimulants 752
21.4. Diuretics 758
21.5. ß-Adrenergic Drugs (ß-Blockers and ß-Agonists) 761
21.6. Peptide Hormones 764
21.7. Antiinflammatory Drugs 767
21.8. Enhancement of Oxygen Transfer 770
21.9. Miscellanea 771
21.10. Legal Aspects 774
21.11. Abbreviations 776
21.12. Acknowledgements 777
21.13. References 778
Chapter 22. Pharmacogenomics for Forensic Toxicology in Enabling Personalized Medicine 784
22.1. Introduction – Inter-Relationship of Pharmacogenomics, Forensic Toxicology, and Personalized Medicine 784
22.2. Pharmacogenomics ‘‘Space’’ 785
22.3. Principles of Pharmacogenetics/Pharmacogenomics 789
22.4. Pharmacogenomics Tests and Methodologies 791
22.5. Clinical Applications 792
22.6. Forensic Applications 794
22.7. Conclusions 797
22.8. References 797
Chapter 23. Aspects of Quality Assurance in Forensic Toxicology 802
23.1. Introduction 802
23.2. A Quality Concept for Analytical Toxicological Laboratories 808
23.3. Quality of the outcome 844
23.4. Conclusions 852
23.5. References 853
Part 4: Forensic Chemistry 860
Chapter 24. Explosives 862
24.1. Introduction 862
24.2. Extraction and Clean-Up Procedures 862
24.3. Analysis of Explosives by Gas Chromatography (GC) 864
24.4. Analysis of Explosives by High-Performance Liquid Chromatography (HPLC) 865
24.5. Analysis of Explosives by GC/MS 867
24.6. Analysis of Explosives by LC/MS 870
24.7. Analysis of Explosives by Ion Mobility Spectrometry (IMS) 873
24.8. Concluding Summary 876
24.9. References 877
Chapter 25. Chemical Warfare Agents 878
25.1. Introduction 878
25.2. Chemical Warfare Agent Analysis – Overview 880
25.3. Sample Handling 882
25.4. Gas Chromatography-Mass Spectrometry 884
25.5. Liquid Chromatography-Mass Spectrometry 888
25.6. Other Instrumental Techniques 898
25.7. Field Analyses 902
25.8. Safety and Disposal 906
25.9. Conclusions 907
25.10. Annex 907
25.11. References 907
Chapter 26. Forensic Analysis of Fire Debris 912
26.1. Introduction 912
26.2. The Arson Problem 913
26.3. Ignitable Liquids 915
26.4. Analysis of Fire Debris 922
26.5. Quality Assurance 953
26.6. The Future of Fire Debris Analysis 956
26.7. References 958
Chapter 27. Writing Media and Documents 962
27.1. Introduction 962
27.2. Thin-Layer Chromatography 962
27.3. Gas Chromatography-Mass Spectrometry 966
27.4. High Performance Liquid Chromatography 971
27.5. Capillary Electrophoresis 972
27.6. Chromatographic Methods used for Dating ink on Documents 974
27.7. References 979
Part 5: Forensic Identification of Individuals and Biological Traces 982
Chapter 28. Forensic DNA Typing Technologies: A Review 984
28.1. Introduction 984
28.2. DNA Polymorphisms 985
28.3. DNA Typing Methods 986
28.4. STRs in Sexual Chromosomes and Mitochondrial DNA 989
28.5. SNP Typing 990
28.6. Standardization Efforts and the Value of the DNA Evidence 993
28.7. References 994
Chapter 29. Mitochondrial DNA: Future Challenges in Forensic Genetics 998
29.1. Introduction 998
29.2. Average and Site-Specific Mutation Rates 999
29.3. The Importance of Coding Region SNPs in Forensic Genetics 1000
29.4. High-Density DNA Arrays: Chips for mtDNA 1000
29.5. Using Phylogenetic Approaches to Correct Errors in mtDNA Datasets 1002
29.6. Troublesome mtDNA Databases 1002
29.7. Final Remarks: Validation of mtDNA in Forensic Genetics and Statistical Approach 1003
29.8. Acknowledgments 1004
29.9. References 1004
Chapter 30. The Human Y Chromosome Male-Specific Polymorphisms and Forensic Genetics 1008
30.1. Introduction 1008
30.2. Y Chromosome in Forensic Applications 1012
30.3. Y-Chromosome Markers in Forensics 1014
30.4. Acknowledgments 1031
30.5. References 1031
Subject Index 1040

Chapter 1 Opioids: methods of forensic analysis

Maciej J. Bogusz

Department of Pathology and Laboratory Medicine, King Faisal Specialist Hospital and Research Center, P.O. Box 3354, MBC 10, 11211, Riyadh, Saudi Arabia

Abstract

Publisher Summary


This chapter discusses the use of separation methods for the isolation, identification, and quantitative analysis of natural and synthetic opiates. The term “opiate” refers specifically to the products derived from the opium poppy. The chapter describes morphine derivatives and synthetic or semisynthetic opiates, showing agonistic action at opioid receptors OP1 (δ), OP2 (κ) or OP3 (μ). Preliminary testing for the opiates in field conditions is mainly performed by law-enforcement officers (police, prison, or customs officers). The testing devices are simple and robust and usually based on well-known color reactions. The main purpose of these tests is to select suspicious samples or materials for possible further examination with confirmatory methods. Preliminary methods used for biological fluids may be divided according to different criteria. From the technical point of view, these methods are divided into onsite and laboratory tests. These two groups of tests are discussed in the chapter in detail. Immunoassays are the most important techniques used for the preliminary testing of opiate agonists. The trend toward the use of immunoassays for alternative samples available in a noninvasive way—for example, saliva or sweat—is described in the chapter.

1.1 Introduction


In this chapter, the use of separation methods for the isolation, identification, and quantitative analysis of natural and synthetic opiates is reviewed. Strictly speaking, the term “opiate” refers specifically to the products derived from the opium poppy. The review focuses on morphine derivatives and synthetic or semisynthetic opiates, showing agonistic action at opioid receptors OP1 (δ), OP2 (κ) or OP3 (μ). The action of opiates on opioid receptors has been reviewed elsewhere [1,2]. The present overview focuses on forensic analytical applications, devoted mainly to biological samples. These applications are divided into several sub-chapters, convering:

– preliminary methods for opioid detection in non-biological and biological samples,
– isolation of opioids from different biological matrices,
– analysis of opium poppy constituents in plant material and in body fluids,
– separation and detection of heroin, its congeners and its specific metabolites in illicit drug preparations and in body fluids,
– analysis of morphine and other natural and synthetic opiates in body fluids and organs.

In each sub-chapter the relevant separation techniques: thin layer chromatography (TLC), gas chromatography (GC), high-performance liquid chromatography (HPLC), and capillary electrophoresis (CE), combined with various detection methods, are reviewed in turn.

1.2 Preliminary methods for opiate detection


Preliminary tests play a dual role in forensic toxicology. First of all their use fulfills the main condition of forensic analysis, i.e. the application of two independent methods for positive results whenever possible. The second purpose of these tests is to exclude samples that definetly do not contain any opiates. Since a negative result from a preliminary test is usually decisive, there is no room for false-negative results. Therefore, preliminary tests should show broad group specificity and possibly high sensitivity, whereas an absolute specificity is not required. An unequivocal identification and quantitation is usually carried out in the confirmatory step of analysis.

1.2.1 Methods used for street drugs


Preliminary testing in field conditions is mainly performed by law enforcement officers (police, prison, or customs officers). The testing devices are simple and robust, and usually based on well-known color reactions. The main task of these tests is to select suspicious samples or materials for possible further examination with confirmatory methods.

Narcopouch® (ODV Inc., Paris, ME, USA) is a battery of color tests for the detection of opiates, amphetamines, cocaine, barbiturates, cannabinoids, and lysergic acid diethylamide (LSD) in street samples. This test uses color reactions with several reagents, e.g. Marquis, Meyer’s, Mecke, Ehrlich’s, Fast Blue B, and Koppanyi. The whole procedure is performed in a plastic pouch by visual inspection. The Herosol® (Mistral Detection Ltd., Jerusalem, Israel) field kit consists of a spray reagent and special test paper. A suspected surface (e.g. skin) is wiped with the paper, which is then sprayed with Herosol. A violet color indicates the presence of heroin. A similar heroin test Detect Now™ is supplied by Test Medical Symptoms@Home, Inc., and is marketed via the internet as a simple test for parents who want to check their children for drug use. The NIK® (Public Safety Inc., Armor Holding, Jacksonville, FL, USA) narcotic field test consists of individual ampoule tests for the main groups of drugs of abuse, among them opiates/amphetamines, and heroin/opium. Drug Wipe and Drug Wipe II (Securetec AG, Germany) are immunochemical tests designed for the detection of drugs of abuse on different surfaces, e.g. luggage, passports, currency, and also on the skin or the tongue. Therefore, these tests may be used for the detection of drugs in sweat or saliva. The detection limit for opiates is 25 ng of morphine equivalent. With a portable reader a colorimetric quantitation may be performed.

1.2.2 Methods used for biological fluids


Preliminary methods used for biological fluids may be divided according to different criteria. From the technical point of view, it is obvious to divide these methods into on-site and laboratory tests. These two groups of tests are discussed below. However, preliminary tests may be used not only for forensic or preventive purposes, e.g. in employee screening, but also as a diagnostic procedure in suspected acute poisoning. In on-site tests applied in a clinical emergency ward, the confirmation analysis sometimes is not of primary importance. In the case of a suspected heroin overdose, the positive result of a preliminary opiate test is an indication for the administration of an opiate antagonist, e.g. naloxone, instead of waiting for the results of the confirmatory analysis. This practice is not limited to health professionals; the distribution of naloxone for administration in addicts’ home by their companions or family members is a novel approach, which is being tested in the USA, Germany, and the UK [3].

1.2.2.1 On-site tests


There is a multitude of socially critical situations that demand full sobriety and an unaffected psychomotorical condition. On-site tests are widely used among very different social groups, including automobile drivers, incarcerated criminals, the military, athletes, employees of the oil industry, and others. The particular value of the on-site test is in the testing of mobile groups located in remote areas. The most important is the ability to use non-invasive sampling. For this reason, testing of saliva or sweat instead of urine or blood has become particularly attractive. It should be added that on-site tests might also be very valuable in monitoring some therapeutic drugs. For these reasons, such tests carry an alternative name of “point-of-care tests”. Jenkins and Goldberger published a comprehensive review of on-site drug testing, comprising all aspects of this technique [4]. Table 1.1 shows some popular on-site testing devices used for opiate detection. All these tests use the immunoassay principle and are capable of detecting the whole panel of drugs of abuse, including amphetamines, benzodiazepine, cannabinoids, cocaine, and opiates.

Table 1.1 On-site tests used for opiate detection

Crouch et al.[5] performed a field evaluation of five on-site drug-testing devices: AccuSign, Rapid Drug Screen, TesT-Cup-5, TesTstik, and Triage. Four hundred urine samples were collected and tested at two sites. All positive results were confirmed using gas chromatography-mass spectrometry (GC-MS; for morphine and codeine) or liquid chromatography-mass spectrometry (LC-MS; for hydrocodone and hydromorphone). One false-negative result was observed. The false-positive rate was below 0.25% for all devices. Gronholm and Lillsunde [6] evaluated eight on-site devices for urine and oral fluid assay of opiates and other drugs. In the case of opiates, the accuracy ranged from 94 to 98% for both matrices. In a multicenter evaluation of the immunochromatographic on-site urine test Frontline® published by Wennig et al.[7], the sensitivity and specificity for opiates was above 99% for all centers involved. Buchan et al.[8] evaluated the accuracy and specificity of four on-site kits for urine testing. Opiates were correctly detected in 100% of cases by all the kits.

Barrett et al.[9] evaluated an ORALscreen System for the on-site analysis of drugs in oral fluids and found very good agreement with laboratory-based urine screening test results for...

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