Table of Contents
Title Page
Copyright
About the Authors
Preface
Chapter 1: Historical Milieu
1.1 Organophosphorus Nerve Agents
1.2 Blister Agents
1.3 Sternutator Agents
1.4 Chemical Weapons Convention (CWC)
References
Chapter 2: Toxicity of Chemical Warfare Agents and their Degradation Products
2.1 Organophosphorus Nerve Agent Toxicity
2.2 Toxicity of Nerve Agent Degradation Products
2.3 Toxicity of Blister Agents
2.4 Toxicity of Sternutator Agents
References
Chapter 3: Analysis of Chemical Warfare Agents
3.1 Introduction
3.2 Minimally Invasive Detection Techniques
3.3 Separation and Detection Techniques
References
Chapter 4: Chemical Warfare Agent Degradation Products
4.1 Analysis of Nerve Agent Degradation Products
4.2 Analytical Techniques
4.3 Analysis of Sulfur Mustard Degradation Products
4.4 Analysis of Sternutator Degradation Products
References
Appendix
Index
This edition first published 2011
© 2011 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. If professional advice or other expert assistance is required, the services of a competent professional should be sought.
Library of Congress Cataloging-in-Publication Data
Kroening, Karolin K., 1974- author.
Analysis of Chemical Warfare Degradation Products / Karolin K. Kroening, Renee N. Easter, Douglas D. Richardson, Stuart A. Willison, Joseph A. Caruso.
p. cm
Includes bibliographical references and index.
ISBN 978-0-470-74587-8 (hardback)
1. Organophosphorus compounds–Deterioration. 2. Chemical agents (Munitions)–Deterioration. 3. Chemical agents (Munitions)–Analysis. 4. Decomposition (Chemistry) I. Title.
UG447.5.O74K76 2011
623.4′592–dc22
2010053414
A catalogue record for this book is available from the British Library.
Print ISBN: 9780470745878
e-PDF ISBN: 9781119993698
o-Book ISBN: 9781119993681
e-Pub ISBN: 9780470745878
Mobi ISBN: 9781119993698
About the Authors
Karolin K. Kroening, Ph.D.
University of Cincinnati, Cincinnati, OH, USA
Karolin received her Master's degree in 2006 from the University of Bologna, Italy, for research based on hydroxyapatite/chitosan composites for bone substitution. At the University of Cincinnati her research focused on the identification and cytotoxicity of chemical warfare agent degradation products and protein phosphorylation studies on cerebral spinal fluid, a study that may help in the development of drugs for patients diseased with a hemorrhagic stroke. She obtained her Ph.D. in December 2010 and is currently working for Procter and Gamble in Cincinnati, OH.
Renee N. Easter
University of Cincinnati, Cincinnati, OH, USA
Renee Easter earned a B.S. from Xavier University, Cincinnati, in 2007 and is currently pursuing a Ph.D. in Analytical Chemistry from the University of Cincinnati. Her research has focused on metallomics approaches to identifying proteins associated with cerebral vasospasm, as well as using internal tags, such as sulfur and phosphorus for identification and quantification of oligonucleotides for siRNA drug applications.
Douglas D. Richardson, Ph.D.
Merck Research Labs, Rahway, NJ, USA
Doug earned his B.S. in Forensic Chemistry with a minor in Biological Sciences from Ohio University in 2003. Following graduation Doug pursued his Ph.D. in the laboratory of Joseph A. Caruso at The University of Cincinnati. His research centered around advancements in elemental speciation, coupling a variety of separation techniques with element specific detection. This research was the first to utilize chromatographic techniques with inductively coupled plasma mass spectrometry for the analysis of nerve agent degradation products. In 2007, Doug defended his dissertation, earning his Ph.D. in Analytical Chemistry. Doug currently supports the development of novel pharmaceuticals within Merck Research Labs.
Stuart Willison, Ph.D.
National Homeland Security Research Center at the US Environmental Protection Agency, Cincinnati, OH, USA
Stuart Willison received his Ph.D. in Chemistry from the University of Cincinnati. He is currently working for the National Homeland Security Research Center at the US Environmental Protection Agency in Cincinnati, OH. His work involves environmental restoration following homeland security events, such as providing support in the detection, response to, and remediation of an area from a terrorist attack or an environmental disaster. Research areas include water protection and indoor/outdoor decontamination as well as method development of chemical warfare agent degradation products in various environmental matrices.
Joseph A. Caruso, Professor
University of Cincinnati, Cincinnati, OH, USA
Joe Caruso holds a Ph.D. from Michigan State University. After a one-year postdoctoral fellowship at The University of Texas – Austin, he joined the University of Cincinnati Chemistry faculty and since then he has authored or co-authored 380 scientific publications and presented more than 325 invited lectures at universities, scientific meetings, government and industry laboratories. His current research interests are in: metallomics studies involving transgenic plants and their phytoremediation mechanisms or enhancements; evaluating cell signaling changes through phospho- or metallo-proteomes as biomarkers in the CSF of certain stroke patients; investigating the metalloproteomes associated with viruses and their effect on viral capsid stability; and the effects on cell signaling changes when arsenic toxified cells are given selenium species as part of the nutrient mix.
Joe Caruso is a member of the American Chemical Society, Society for Applied Spectroscopy and a Fellow of the Royal Society of Chemistry (RSC). He is Chair of the RSC Metallomics Editorial Board. He has been honored many times including the 2000 Spectrochemical Analysis Award given by the Analytical Division of the American Chemical Society, the University of Cincinnati – Excellence in Doctoral Student Mentoring Award in 2006, and in 2007 he received the Rieveschl Award for Distinguished Scientific Research. His most recent award was to be elected Fellow of the Society of Applied Spectroscopy.
Preface
Lethal chemical warfare agents, including nerve agents and vesicants, still pose major threats to life around the world and our surrounding environment. Though their use has been forbidden by international conventions, nerve agents and vesicants are still produced and stockpiled by terrorist organizations. These agents degrade relatively easily. Therefore, it is understandably of great importance that these agents of interest and their degradation products are detected. Rapid and sensitive methods are required, in order to identify these warfare agents and their degradation products. This book describes the chemistry of nerve agents and vesicants, their decomposition and degradation products, in addition to their toxicity, and includes a list of appropriate detection and analysis techniques. Also included is a brief history of the research area, separation techniques, detection methods and detection limits together in a short, easy to read text, with an adequate number of tables and references for the reader who is looking for further detail.
The work to prepare this book was undertaken by the Caruso research group at the University of Cincinnati, including current and former graduate students, who, through their graduate studies, amassed a high degree of knowledge regarding warfare agents and the analysis of their degradation products through various analytical techniques. While we do not pretend to portray all analytical techniques and methods currently in use, for some may be proprietary or classified, our hope is that those who are generally interested in warfare agents will profit from this text. This includes those wishing to learn about analysis, also environmentalists, and more generally, those who have interest in small molecule phosphorus, sulfur and arsenic chemistry beyond warfare agents and their decomposition products, as in pesticides or herbicides. Overall, we have aspired to produce a product that will be of practical use as well as a motivating factor for continued research interest in this field.
Renee N. Easter
Karolin K. Kroening