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Infrared and Raman Spectroscopy in Forensic Science RED BOX RULES ARE FOR PROOF STAGE ONLY. DELETE BEFORE FINAL PRINTING. Editors Editors John M. Chalmers Howell G. M. Edwards Michael D. Hargreaves Infrared and Raman Chalmers Spectroscopy Edwards Hargreaves Infrared and Raman in Forensic Science Science in Forensic Infrared and Raman Spectroscopy Editors Spectroscopy John M. Chalmers, VS Consulting, Stokesley, UK Howell G.M. Edwards, University of Bradford, West Yorkshire, UK Michael D. Hargreaves, Thermo Scientific, USA in Forensic Science For many years the practices of infrared and Raman spectroscopy were confined largely to dedicated academic, industrial or national research laboratories. Major technical advances over the last 10-20 years have resulted in smaller, easier to use instrumentation that is much more user-friendly. Demands and needs from users for increased portability of scientific instrumentation have produced spectrometers and interferometers of small dimensions and of sufficient quality such that handheld Raman and Fourier transform infrared (FT-IR) instruments have been realized over the last few years, opening up much wider application of Raman and infrared spectroscopy to forensic science applications, particularly for adoption into field usage. This unique reference book provides An introduction to the principles of forensic science and how Raman and infrared spectroscopy can be applied Relevant application examples, highlighting how infrared, Raman and THz spectroscopy can be applied to these fields Coverage of key areas of instrumentation, sampling, crime scenes, drugs of abuse and homeland security with case study chapters Extensively referenced chapters making further reading and investigation simpler for the reader This book is intended to introduce both a novice or an established spectroscopic practitioner of analytical chemistry to the technical elements of Raman and infrared spectroscopy as applied to forensic science, outlining several proven and potential applications within this field. Enjoyed this book? Why not tell others about it and write a review on your favourite online bookseller. Cover design by Dan Jubb Infrared and Raman Spectroscopy in Forensic Science Infrared and Raman Spectroscopy in Forensic Science Edited by JOHN M. CHALMERS HOWELL G.M. EDWARDS MICHAEL D. HARGREAVES This edition first published 2012 Ó 2012 by 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 www.wiley.com. 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 1988. 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. 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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 Infrared and Raman spectroscopy in forensic science / [edited by] John M. Chalmers, Howell G. M. Edwards, Michael D. Hargreaves. – 1 p. cm. Includes bibliographical references and index. ISBN 978-0-470-74906-7 (hardback) 1. Forensic sciences. 2. Infrared spectroscopy. 3. Raman spectroscopy. 4. Criminal investigation. I. Chalmers, John M. II. Edwards, Howell G. M., 1943- III. Hargreaves, Michael D. HV8073.I4424 2012 363.25’6–dc23 2011037212 A catalogue record for this book is available from the British Library. Print ISBN: 978-0470-749067 Set in 10/12pt Times New Roman by Thomson Digital, Noida, India John Chalmers would like to, yet again, apologise to his wife Shelley for her enduring the role of being a book editor’s partner, despite having promised previously not to take such a task on again; maybe this will be the last! Howell Edwards dedicates this book to his wife Gillian and daughter Katharine who have supported him throughout and to his research supervisor, Dr Leonard Woodward at the University of Oxford, who first stimulated what proved to be his lifelong interest in Raman spectroscopy. Mike Hargreaves would like to thank his partner Jen, family and his fellow editors for their patience and understanding and for sometimes failing to juggle everything. John M. Chalmers Howell G.M. Edwards Michael D. Hargreaves July 2011 Contents About the Editors xxi List of Contributors xxiii Preface xxvii SECTION I: INTRODUCTION 1 1 Introduction and Scope 3 John M. Chalmers, Howell G.M. Edwards and Michael D. Hargreaves 1.1 Historical Prologue 3 1.2 The Application of Infrared Spectroscopy and Raman Spectroscopy in Forensic Science 5 References 7 2 Vibrational Spectroscopy Techniques: Basics and Instrumentation 9 John M. Chalmers, Howell G.M. Edwards and Michael D. Hargreaves 2.1 Introduction 9 2.2 Vibrational Spectroscopy Techniques 9 2.2.1 The basics and some comparisons 9 2.2.1.1 Wavelength/Wavenumber Ranges and Selection Rules 10 2.2.1.2 Sampling Considerations 12 2.2.1.3 Sensitivity, Surfaces and Signal Enhancement Techniques 13 2.2.1.4 IR and Raman Bands 13 2.2.2 Quantitative and classification analyses 16 2.2.2.1 Multivariate Data Analyses 17 2.2.2.2 Data Pre-Processing 20 2.2.3 Reference databases and search libraries/algorithms 20 2.3 Vibrational Spectroscopy: Instrumentation 22 2.3.1 Spectrometers 22 2.3.1.1 Sources 22 2.3.1.2 Detectors 24 2.3.1.3 Spectrometers and Interferometers 24 2.3.2 Vibrational spectroscopy–microscopy systems 28 2.3.2.1 Mapping and Imaging 30 viii Contents 2.3.3 Fibre optics and fibre-optic probes 34 2.3.4 Remote, portable, handheld, field-use, and stand-off vibrational spectroscopy instrumentation 35 2.4 Closing Remarks 40 References 40 3 Vibrational Spectroscopy Sampling Techniques 45 John M. Chalmers, Howell G.M. Edwards and Michael D. Hargreaves 3.1 Introduction 45 3.2 Vibrational Spectroscopy: Sampling Techniques 47 3.2.1 Raman spectroscopy 47 3.2.1.1 Raman Spectroscopy: Sampling Techniques and Considerations 47 3.2.1.2 Resonance Raman Spectroscopy 50 3.2.1.3 Surface Enhanced Raman Spectroscopy and Surface Enhanced Resonance Raman Spectroscopy 51 3.2.1.4 Spatially Offset Raman Spectroscopy 51 3.2.1.5 Transmission Raman Spectroscopy 55 3.2.1.6 Raman Microscopy/Microspectroscopy and Imaging 55 3.2.1.7 Remote and Fibre-Optic Probe Raman Spectroscopy 56 3.2.2 Mid-infrared spectroscopy 58 3.2.2.1 Mid-Infrared Transmission Spectroscopy: Sampling Techniques 58 3.2.2.2 Mid-Infrared Reflection Spectroscopy Sampling Techniques 62 3.2.2.3 Mid-Infrared Photoacoustic Spectroscopy 70 3.2.2.4 Mid-Infrared Microscopy/Microspectroscopy and Imaging 71 3.2.3 Near-infrared spectroscopy: sampling techniques 76 3.2.3.1 Near-Infrared Transmission Spectroscopy 77 3.2.3.2 Near-Infrared Diffuse Reflection Spectroscopy 77 3.2.3.3 Near-Infrared Transflection Spectroscopy 78 3.2.3.4 Near-Infrared Spectroscopy: Interactance and Fibre-Optic Probe Measurements 78 3.2.3.5 Near-Infrared Microscopy and Imaging 79 3.2.4 Terahertz/far-infrared spectroscopy:
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