FORENSIC ANALYTICAL TECHNIQUES

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3 FORENSIC ANALYTICAL TECHNIQUES

4 Analytical Techniques in the Sciences (AnTS) Series Editor: David J. Ando, Consultant, Dartford, Kent, UK A series of open learning/distance learning books which covers all of the major analytical techniques and their application in the most important areas of physical, life and materials sciences. Titles available in the Series Analytical Instrumentation: Performance Characteristics and Quality Graham Currell, University of the West of England, Bristol, UK Fundamentals of Electroanalytical Chemistry Paul M.S. Monk, Manchester Metropolitan University, Manchester, UK Introduction to Environmental Analysis Roger N. Reeve, University of Sunderland, UK Polymer Analysis Barbara H. Stuart, University of Technology, Sydney, Australia Chemical Sensors and Biosensors Brian R. Eggins, University of Ulster at Jordanstown, Northern Ireland, UK Methods for Environmental Trace Analysis John R. Dean, Northumbria University, Newcastle, UK Liquid Chromatography Mass Spectrometry: An Introduction Robert Ardrey, University of Huddersfield, Huddersfield, UK Analysis of Controlled Substances Michael D. Cole, Anglia Polytechnic University, Cambridge, UK Infrared Spectroscopy: Experimentation and Applications Barbara H. Stuart, University of Technology, Sydney, Australia Practical Inductively Coupled Plasma Spectroscopy John R. Dean, Northumbria University, Newcastle, UK Bioavailability, Bioaccessibility and Mobility of Environmental Contaminants John R. Dean, Northumbria University, Newcastle, UK Quality Assurance in Analytical Chemistry Elizabeth Prichard and Vicki Barwick, Laboratory of the Government Chemist, Teddington, UK Extraction Techniques in Analytical Sciences John Dean, Northumbria University, Newcastle, UK Forensic Analysis Techniques Barbara H. Stuart, University of Technology, Sydney, Australia

5 FORENSIC ANALYTICAL TECHNIQUES Barbara Stuart University of Technology, Sydney, Australia A John Wiley & Sons, Ltd., Publication

6 This edition first published John Wiley & Sons, Ltd. Registered office John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom For details of our global editorial offices, for customer services and for information about how to apply for permission to reuse the copyright material in this book please see our website at The right of the author to be identified as the author of this work has been asserted in accordance with the Copyright, Designs and Patents Act All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permission of the publisher. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic books. Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book are trade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendor mentioned in this book. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold on the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional should be sought. The publisher and the author make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of fitness for a particular purpose. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for every situation. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of further information does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it may make. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was written and when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall be liable for any damages arising herefrom. Library of Congress Cataloging-in-Publication Data applied for. A catalogue record for this book is available from the British Library. HB ISBN: PB ISBN: Set in 10/12pt Times by Laserwords Private Limited, Chennai,India. Printed in [Country] by [Printer]

7 Contents Series Preface Preface About the Author Acronyms, Abbreviations and Symbols xiii xv xvii xix 1 The Chemistry of Forensic Evidence Introduction Evidence Types Polymers Fibres Paint Documents Glass Soil Explosives Firearms Arson Body Fluids Drugs and Toxicology Fingerprints Introduction to Data Analysis Summary 24 References 24 2 Preliminary Tests Introduction 27

8 vi Forensic Analytical Techniques 2.2 Chemical Tests Methods Drugs and Toxicology Body Fluids Gunshot Residue Explosives Paint Documents Density Methods Glass Soil Polymers Light Examination Methods Fingerprints Body fluids Documents Summary 39 References 39 3 Microscopic Techniques Introduction Optical Microscopy Methods Interpretation Fibres Paint Drugs Glass Soil Documents Firearms Transmission Electron Microscopy Method Interpretation Paint Scanning Electron Microscopy Methods Interpretation Gunshot Residue 56

9 Contents vii Paint Fibres Documents Glass Atomic Force Microscopy Methods Interpretation Documents X-Ray Diffraction Methods Interpretation Explosives Paint Drugs Documents Soil Summary 66 References 66 4 Molecular Spectroscopy Introduction Infrared Spectroscopy Methods Interpretation Paint Fibres Polymers Documents Explosives Drugs Raman Spectroscopy Methods Interpretation Drugs Paint Fibres Documents Explosives Ultraviolet visible Spectroscopy Methods Interpretation 97

10 viii Forensic Analytical Techniques Fibres Paint Documents Drugs Toxicology Fluorescence Spectroscopy Methods Interpretation Body Fluids Toxicology Fibres Nuclear Magnetic Resonance Spectroscopy Methods Interpretation Drugs Explosives Summary 109 References Elemental Analysis Introduction Atomic Spectrometry Methods Interpretation Glass Gunshot Residue Toxicology Inductively Coupled Plasma Mass Spectrometry Methods Interpretation Glass Paint Gunshot Residue X-Ray Fluorescence Spectroscopy Methods Interpretation Glass Gunshot Residue Paint Particle-Induced X-Ray Emission Spectroscopy Methods Interpretation Glass 124

11 Contents ix 5.6 Neutron Activation Analysis Summary 125 References Mass Spectrometry Introduction Molecular Mass Spectrometry Methods Interpretation Drugs Explosives Isotope Ratio Mass Spectrometry Methods Interpretation Drugs Explosives Ion Mobility Spectrometry Methods Interpretation Explosives Drugs Summary 140 References Separation Techniques Introduction Paper Chromatography Methods Interpretation Documents Thin Layer Chromatography Methods Interpretation Drugs Documents Fibres Explosives Gas Chromatography Methods Interpretation Drugs Toxicology 152

12 x Forensic Analytical Techniques Arson Residues Explosives Liquid Chromatography Methods Interpretation Drugs and Toxicology Fibres Ion Chromatography Methods Interpretation Explosives Capillary Electrophoresis Methods Interpretation Drugs and Toxicology Explosives and Gunshot Residues Summary 163 References Thermal Analysis Introduction Pyrolysis Techniques Methods Interpretation Paint Fibres Polymers Documents Differential Scanning Calorimetry and Differential Thermal Analysis Methods Interpretation Polymers Fibres Thermogravimetric Analysis Methods Interpretation Polymers Explosives and Arson Residues Summary 178 References 178

13 Contents xi Responses to Self-Assessment Questions 181 Bibliography 195 Glossary of Terms 197 SI Units and Physical Constants 203 Periodic Table 207 Index 209

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15 Series Preface There has been a rapid expansion in the provision of further education in recent years, which has brought with it the need to provide more flexible methods of teaching in order to satisfy the requirements of an increasingly more diverse type of student. In this respect, the open learning approach has proved to be a valuable and effective teaching method, in particular for those students who for a variety of reasons cannot pursue full-time traditional courses. As a result, John Wiley & Sons, Ltd first published the Analytical Chemistry by Open Learning (ACOL) series of textbooks in the late 1980s. This series, which covers all of the major analytical techniques, rapidly established itself as a valuable teaching resource, providing a convenient and flexible means of studying for those people who, on account of their individual circumstances, were not able to take advantage of more conventional methods of education in this particular subject area. Following upon the success of the ACOL series, which by its very name is predominately concerned with analytical chemistry, the Analytical Techniques in the Sciences (AnTS) series of open learning texts has now been introduced with the aim of providing a broader coverage of the many areas of science in which analytical techniques and methods are now increasingly applied. With this in mind, the AnTS series of texts seeks to provide a range of books which will cover not only the actual techniques themselves, but also those scientific disciplines which have a necessary requirement for analytical characterization methods. Analytical instrumentation continues to increase in sophistication, and as a consequence, the range of materials that can now be almost routinely analysed has increased accordingly. Books in this series which are concerned with the techniques themselves will reflect such advances in analytical instrumentation, while at the same time providing full and detailed discussions of the fundamental concepts and theories of the particular analytical method being considered. Such books will cover a variety of techniques, including general instrumental analysis, spectroscopy, chromatography, electrophoresis, tandem techniques, electroanalytical methods, X-ray analysis and other significant topics. In addition, books in

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