Arsenic and Old Mustard: Chemical Problems in the Destruction of Old Arsenical and 'Mustard' Munitions NATO ASI Series Advanced Science Institute Series
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Arsenic and Old Mustard: Chemical Problems in the Destruction of Old Arsenical and 'Mustard' Munitions NATO ASI Series Advanced Science Institute Series A Series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences Plenum Publishing Corporation B Physics London and New York C Mathematical and Physical Sciences Kluwer Academic Publishers D Behavioural and Social Sciences Dordrecht, Boston and London E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Global Environment Change PARTNERSHIP SUB-SERIES 1. Disarmament Technologies Kluwer Academic Publishers 2. Environment Springer-Verlag / Kluwer Academic Publishers 3. High Technology Kluwer Academic Publishers 4. Science and Technology Policy Kluwer Academic Publishers 5. Computer Networking Kluwer Academic Publishers The Partnership Sub-Series incorporates activities undertaken in collaboration with NATO's Cooperation Partners, the countries of the CIS and Central and Eastern Europe, in Priority Areas of concern to those countries. NATO-PCO-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to about 50,000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible via a CD-ROM "NATO Science and Technology Disk" with user-friendly retrieval software in English, French, and German (©WTV GmbH and DATAWARE Technologies, Inc. 1989). The CD-ROM contains the AGARD Aerospace Data base. The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. 1. Disarmament Technologies - Vol. 19 Arsenic and Old Mustard: Chemical Problems in the Destruction of Old Arsenical and 'Mustard' Munitions edited by Joseph F. Bunnett University of California, Santa Cruz, California, U.S.A. and Marian Mikolajczyk Centre of Molecular and Macromolecular Studies, Polish Academy of SCiences, l6d~ Poland Springer-Science+Business Media, B.v. Proceedings of the NATO Advanced Research Workshop on Chemical Problems Associated with Old Arsenical and 'Mustard' Munitions l6dz. Poland 17-19 March 1996 A C.I.P. Catalogue record for this book is available from the Library of Congress. ISBN 978-90-481-5069-4 ISBN 978-94-015-9115-7 (eBook) DOI 10.1007/978-94-015-9115-7 Printed on acid-free paper All Rights Reserved © 1998 Springer Science+Business Media Oordrecht Originally published by Kluwer Academic Publishers in 1998 Softcover reprint of the hardcover 1st edition 1998 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. CONTENTS Preface .................................................... IX Acknowledgments. .. xi Structures of Prominent Arsenical and 'Mustard' Agents . .. xii IUPAC Names of Prominent Chemical Warfare Agents ................... xiii Organizing Committee Membership ................................ xiv Glossary of Agent Codes and Common Names . .. xv LECTURES The Problem of Old Chemical Weapons which Contain "Mustard Gas" or Organoarsenic Compounds: An Overview Ron G. Manley ............................................ 1 Destruction of Old Chemical Munitions Daniel Froment ........................................... 17 Recovered Old Arsenical and 'Mustard' Munitions in Germany: Technologies, Plans and Problems Hermann Martens . 33 Practical Actions of Russia on Preparations for Destruction of Stockpiled Lewisite and 'Mustard' S. V. Petrov, V.l. Kholstov, V.P. Zoubrilin, N. V. Zavialova ............. 79 Recovered Old Arsenical and 'Mustard' Munitions in Poland: Technologies, Plans and Problems Zhigniew Wertejuk, Mieczyslaw Koch, Wlodzimierz Marciniak . ........... 91 Composition and Remediation of Tarry 'Mustard' P.R. Norman. .. 105 Kinetic and Toxicological Parameters of 'Mustard' (HD) Hydrolysis and Biodegradation Steven P. Harvey, Timothy A. Blades, Linda L. Szajraniec, William T. Beaudry, Mark V. Haley, Thomas Rosso, Gerald P. Young, James P. Earley, Robert L. Irvine . .. 115 Arsenic in the Environment W.R. Cullen ............................................ 123 Biotransformation of Arsenic in Freshwater Organisms Shigeru Maeda . .. 135 vi POSTER ABSTRACTS Investigations in Organoarsenic Chemistry Ionel Haiduc, Luminitsa Silaghi-Dumitrescu ....................... 149 HPLC-ICP-MS Methods for the Detennination of Inorganic and Organic Arsenic Compound W. Goessler, D. Kuehnelt, K.J. Irgolic . .. 151 A Method for Mutual Disposal of Old Chemical Weapons Alexander L Chimishkyan ................................... 155 Destruction of Adamsite by Sodium M. Sokolowski, E. Bilger ................................... 157 Electrochemical and Biological Approach to the Destruction of Lewisite and 'Mustard' Alexander M. Boronin, Valentin G. Sakharovski, Ivan I. Starovoitov, Konstantin I. Kashparov, Valery N. Shvetsov, Ksenija M. Morozova, Igor A. Nechaev, Vladimir I. Tugoshov, Nikolai P. Kuzmin, Alexander I. Kochergin ..................................... 159 Reductive Decomposition of Deposits in Old 'Mustard' Munitions Joseph F. Bunnett......................................... 163 Use of 'Mustard' Aminolysis Products as Catalysts for Polyurethane Foam Production AL. Chimishkyan, S.1. Orlov, T.S. Serebryakova . .. 165 Breakdown of Sulfur 'Mustard' by Phase Transfer Catalyzed HCl Elimination: A Potential Destruction Method for 'Mustard' Stocks Ernst-Christian Koch ...................................... 169 GROUP DISCUSSION REPORTS Old 'Mustard' or Yperite Munitions: Methods for Destruction and Container Detoxification Yperite Discussion Group ................................... 175 Old Arsenical Munitions: Methods for Destruction and Site Cleanup Arsenicals Discussion Group ................................. 177 On the Handling of Recovered Munitions Recovered Munitions Discussion Group .......................... 185 vii APPENDICES A. Participants in this NATO ARW ............................. 189 B. Membership of IUPAC Committee on Chemical Weapons Destruction ... 193 C. On Wholesome Warfare ................................... 195 AUTHOR INDEX.. .. 196 SUBJECT INDEX................................. ....... 197 PREFACE Chemical warfare, involving substances often called "poison gases", was initiated by Gennan forces in 1915. It was soon taken up by the Allies and was actively practiced until the end of World War I in 1918.[1] The original chemical warfare (CW) agents were truly gases (i.e., chlorine, phosgene and hydrogen cyanide), but liquid Yperite or 'mustard' caused the majority of World War I "gas" casualties. Yperite is a vesicant; it raises huge blisters on exposed skin. Its worst effects were however on persons who inhaled mists or aerosols of Yperite; the damage to delicate lung tissue was often irreversible. Some arsenic compounds were also used as chemical warfare agents. Most of them (Clark I, Adamsite, etc.) induced sneezing or vomiting and were intended mainly to disorient enemy troops. Lewisite, an arsenical vesicant, was developed during World War I and produced in large quantity by the Soviet Union in the Cold War era, but has seen little battlefield use. Forces on both sides in World War II manufactured vast amounts of chemical munitions, but they were not used in the war. During the Cold War, the Soviet Union and the United States also armed themselves with prodigious amounts of chemical weapons, but again they were not used. Problems of destruction of those huge stockpiles of chemical munitions in Russia and the United States have justifiably received much attention, in both their technological and political aspects. But the problems in destroying "non-stockpile" munitions are even greater. Those "non-stockpile" munitions lie buried on old battlefields or military posts or sunken in estuaries or the sea. It is estimated that in Europe alone over ten million lost or abandoned World War I chemical munitions, many of them still charged with agent, are yet to be retrieved and destroyed. Many European nations in which that war was fought have departments to destroy the old munitions that are frequently found by citizens as they engage in activities such as construction, farming or fishing. There are major problems also in China, where Japanese forces abandoned chemical munitions in 1945. In the United States, the U.S. Anny has surveyed its substantial non-stockpile chemical munitions problem.[I] One aspect of it came to light in 1993, when abandoned chemical munitions and precursor chemicals were found buried in Spring Valley, Washington, D.C., a district of expensive homes. During World War I it was a chemical weapons development site. Chemical Problems A discovered old munition might be of either high explosive or chemical type. Weapons destroyers must detennine which it is, and if chemical what agent it contains. The internal structure of a munition can be revealed and often indications of its chemical content obtained by ultrasound and X-ray analysis.