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Alternative Technologies for the Destruction of Chemical Agents and Munitions Alternative Technologies for the Destruction of Chemical Agents and Munitions COMMITTEE ON ALTERNATIVE CHEMICAL DEMILITARIZATION TECHNOLOGIES BOARD ON ARMY SCIENCE AND TECHNOLOGY COMMISSION ON ENGINEERING AND TECHNICAL SYSTEMS NATIONAL RESEARCH COUNCIL National Academy Press Washington, D.C. 1993
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Alternative Technologies for the Destruction of Chemical Agents and Munitions NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of the committee responsible for the report were chosen for their special competencies and with regard for appropriate balance. This report has been reviewed by a group other than the authors according to procedures approved by a Report Review Committee consisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The National Academy of Sciences, is a private, nonprofit, self-perpetuating society of distinguished scholars engaged in scientific and engineering research, dedicated to the furtherance of science and technology and to their use for the general welfare. Upon the authority of the charter granted to it by the Congress in 1863, the Academy has a mandate that requires it to advise the federal government on scientific and technical matters. Dr. Frank Press is president of the National Academy of Sciences. The National Academy of Engineering was established in 1964, under the charter of the National Academy of Sciences, as a parallel organization of outstanding engineers. It is autonomous in its administration and in the selection of its members, sharing with the National Academy of Sciences the responsibility for advising the federal government. The National Academy of Engineering also sponsors engineering programs aimed at meeting national needs, encourages education and research, and recognizes the superior achievements of engineers. Dr. Robert M. White is president of the National Academy of Engineering. The Institute of Medicine was established in 1970 by the National Academy of Sciences to secure the services of eminent members of appropriate professions in the examination of policy matters pertaining to the health of the public. The Institute acts under the responsibility given to the National Academy of Sciences by its congressional charter to be an adviser to the federal government and, upon its own initiative, to identify issues of medical care, research, and education. Dr. Kenneth I. Shine is president of the Institute of Medicine. The National Research Council was organized by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academy’s purposes of furthering knowledge and advising the federal government. Functioning in accordance with general policies determined by the Academy, the Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in providing services to the government, the public, and the scientific and engineering communities. The council is administered jointly by both Academies and the Institute of Medicine. Dr. Frank Press and Dr. Robert White are chairman and vice chairman, respectively, of the National Research Council. This is a report of work supported by Contract DAAL03-90-C-0035 (CLIN 001) between the U.S. Department of the Army and the National Academy of Sciences. Library of Congress Catalog Card Number 93-84706 International Standard Book Number 0-309-04946-6 Copies available from: National Academy Press 2101 Constitution Avenue, N.W. Box 284 Washington, D.C. 20418 1-800-24-6242 (202) 334-3313 (in the Washington Metropolitan area) B-170 Copyright 1993 by the National Academy of Sciences. All rights reserved. Printed in the United States of America
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Alternative Technologies for the Destruction of Chemical Agents and Munitions COMMITTEE ON ALTERNATIVE CHEMICAL DEMILITARIZATION TECHNOLOGIES JOHN P. LONGWELL (Chairman), Massachusetts Institute of Technology, Cambridge GEORGE APOSTOLAKIS, University of California, Los Angeles JOSEPH F. BUNNETT, University of California, Santa Cruz PETER S. DALEY, Waste Management International, London, England GENE H. DYER, Consultant, San Raphael, California DAVID S. KOSSON, Rutgers, The State University of New Jersey, Piscataway WALTER G. MAY, University of Illinois, Urbana MATTHEW MESELSON, Harvard University, Cambridge, Massachusetts HENRY SHAW, New Jersey Institute of Technology, Newark THOMAS O. TIERNAN, Wright State University, Dayton, Ohio BARRY M. TROST, Stanford University, Stanford, California JAMES R. WILD, Texas A&M University, College Station Staff DONALD L. SIEBENALER, Study Director JAMES J. ZUCCHETTO, Co-Study Director MARGO L. FRANESCO, Senior Program Assistant ALLISON P. KNIGHT, Administrative Secretary ANN COVALT, Consulting Editor
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Alternative Technologies for the Destruction of Chemical Agents and Munitions BOARD ON ARMY SCIENCE AND TECHNOLOGY PHILIP A. ODEEN (Chairman), BDM International, Inc., McLean, Virginia LAWRENCE J. DELANEY (Vice Chairman), Montgomery and Associates, Washington, D.C. ROBERT A. BEAUDET, University of Southern California, Los Angeles WILLIAM K. BREHM, Systems Research Applications Corporation, Arlington, Virginia WILLIAM H. EVERS, JR., W. J. Schafer Associates, Inc., Arlington, Virginia JAMES L. FLANAGAN, Center for Computer Aids in Industrial Productivity, Piscataway, New Jersey CHRISTOPHER C. GREEN, General Motors Research Laboratories, Warren, Michigan THOMAS MCNAUGHER, The Brookings Institution, Washington, D.C. GENERAL GLENN K. OTIS (Retired, U.S. Army), Coleman Research Corporation, Fairfax, Virginia NORMAN F. PARKER, Varian Associates (Retired), Cardiff by the Sea, California HARVEY W. SCHADLER, General Electric Company, Schenectady, New York F. STAN SETTLES, Office of Science and Technology, Washington, D.C. JOYCE L. SHIELDS, Hay Systems, Inc., Arlington, Virginia DANIEL C. TSUI, Princeton University, Princeton Staff BRUCE A. BRAUN, Director, Board on Army Science and Technology DONALD L. SIEBENALER, Senior Program Officer JAMES J. ZUCCHETTO, Senior Program Officer HELEN D. JOHNSON, Staff Associate ANN M. STARK, Program Officer MARGO L. FRANCESCO, Senior Program Assistant ALLISON P. KNIGHT, Administrative Secretary KELLY NORSINGLE, Administrative Secretary (until 4/16/93)
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Alternative Technologies for the Destruction of Chemical Agents and Munitions Preface The unitary chemical warfare agents and munitions that are the focus of this study have not been manufactured in the United States since 1968. Some agent and munitions have been destroyed, but approximately 25,000 tons of agent remain in thousands of tons of munitions and bulk containers in the U.S. stockpile. In 1978 the U.S. Army began to test various large-scale disposal methods at the Tooele Army Depot, Utah, where over 42 percent of the stockpile is located. These methods included several techniques to handle and disassemble munitions to gain access to the agent therein. Techniques tested for agent destruction included chemical treatment and incineration. At the request of the Army, the National Research Council (NRC) studied the overall disposal program and endorsed the Army's choice of incineration of agents and thermal treatment of energetics, metal parts, and containers in a 1984 report. A pioneer plant constructed at Johnston Island in the Pacific Ocean in the late 1980s recently completed Operational Verification Testing of a baseline technology involving incineration. At Tooele, construction of a larger, continental facility is nearing completion. Construction of similar but smaller facilities is proposed by the Army for seven additional storage sites in the continental United States. As a result of growing interest in alternatives to the baseline technology, in 1992 Congress instructed the Army to recommend disposal technologies for all sites by December 31, 1993. These recommendations are to be based on two NRC studies. The first by the Committee on Alternative Chemical Demilitarization Technologies is reported here. The second, by the Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program, will use the information and analyses provided here to formulate recommendations for the Army to use in developing its own recommendations to Congress. Thus, this report is the first step in a three-part national advisory process.
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Alternative Technologies for the Destruction of Chemical Agents and Munitions On January 13-15, 1993, an important step was taken when 132 countries signed the International Convention on Prohibition of the Development, Production, Stockpiling, and Use of Chemical Weapons and on their Destruction, known as the Chemical Weapons Convention. This convention specifies that stockpiled chemical warfare agents be destroyed in an "essentially irreversible manner" and that the weapons to apply them be rendered unusable. These demilitarization goals are to be met by December 31, 2004, with some possibility of schedule extension. The disposal technology to be used is not specified; however, within the United States the waste streams created by the chemical demilitarization system must be environmentally acceptable. Any gas stream from combustion-based processes is of particular concern to the public. Consequently, technologies to ensure environmental and public acceptability of this waste stream are also considered in this report. This study was initiated with the first meeting of the committee in March 1992, followed by a workshop in June 1992. The workshop included presentations on proposed alternative technologies, with time for commentary by interested observers. Subsequent discussions and written submissions were additional important sources of information. The committee ended its data collection efforts in February 1993. More recent data may be available, especially for those technologies that have substantial development programs. The workshop was followed by three additional meetings, in September, October, and November 1992. Specific recommendations are not made in this report, but it is hoped that the information and discussion presented will provide a basis for more specific recommendations to be developed by the NRC and the Army. The rapid pace of this study, the large number of contributions made to it, and the complexity of the subject offered substantial organizational and editorial challenges. The NRC staff, especially Margo Francesco, Allison Knight, Donald Siebenaler, and James Zucchetto, deserve special thanks and recognition for their essential roles in this study. John P. Longwell, Chairman Committee on Alternative Chemical Demilitarization Technologies
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Alternative Technologies for the Destruction of Chemical Agents and Munitions Contents EXECUTIVE SUMMARY 1 1 INTRODUCTION 22 The U.S. Chemical Stockpile Disposal Program 22 Risk and Community Concerns 27 Alternative Demilitarization Systems 29 Transportation of Untreated Weapons and Agents 31 Primary Goals and Strategies for Demilitarization 31 Scope and Organization of the Study 34 2 THE U.S. CHEMICAL WEAPONS STOCKPILE 37 Description of the Agents 37 Description of the Munitions 42 Geographical Distribution of the Stockpile 49 Summary 53 3 U.S. AND FOREIGN EXPERIENCE WITH CHEMICAL WEAPONS DESTRUCTION 54 U.S. Chemical Demilitarization Experience 54 Chemical Warfare Agent Destruction in Other Countries 62 Summary 74 4 REQUIREMENTS AND CONSIDERATIONS FOR CHEMICAL DEMILITARIZATION TECHNOLOGIES 75 Chemical Composition of Agents and Their Breakdown Products 76 Waste Streams in Chemical Weapons Destruction 77 Processing Rates 78
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Alternative Technologies for the Destruction of Chemical Agents and Munitions Performance Standards 81 Worker Standards 81 Air Quality Standards 81 Liquid Wastes 81 Solid Wastes 82 General Considerations in Assessing Untested Alternative Technologies 83 Decontamination Standards 84 Chlorinated Dioxins 85 Monitoring 86 Effluent Retention Time Requirements 88 Time Required for Technology Development and Demonstration 89 Technology Development and Demonstration Costs 91 Assessment Criteria for Alternative Technologies 92 5 THERMAL TREATMENT AND PREPROCESSING THE POSTPROCESSING OPERATIONS 94 Preprocessing Operations 95 Cryoprocessing 95 Mechanical Disassembly of Explosives Propellants and Solidified Agent 96 Thermal Treatment 97 Postprocessing Operations 98 Solid Wastes 98 Control of Nitrogen Oxides 101 Water Recycle 101 Reduction of Waste Gas Volume 102 Waste Gas Storage Requirement 103 Storage and Retention Technologies 105 Activated-Carbon (Charcoal) Adsorption Systems 106 6 LOW-TEMPERATURE, LIQUID-PHASE PROCESSES 109 Chemical Detoxification Processes 110 GB (Satin) 112 VX 116 H (Mustard) 118 Reduction Methods Conceivably Applicable to GB, VX, and H 121 Detoxication with Ionizing Radiation 122 Low-Temperature and Low-Pressure Oxidation Processes 123 Chemical Oxidation 123
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Alternative Technologies for the Destruction of Chemical Agents and Munitions Electrochemical Oxidation 124 Oxidizing Agents Plus UV Light 125 Biological Processes 126 Introduction and Overview 126 Direct Destruction of GB and VX 128 Biodegradation of the Reaction Products from the Chemical Processing of GB and VX 131 Chemical Hydrolysis and Bioremediation of Mustard 132 Bioremediation of Explosives and Energetics 132 Engineering Prospects 132 Summary of the Potential Application of Biological Processes 136 7 PROCESSES AT MEDIUM AND HIGH TEMPERATURES 137 Moderate-Temperature, High-Pressure Processes 138 Wet Air Oxidation 138 Supercritical Water Oxidation 146 High-Temperature, Low-Pressure Pyrolysis 152 Molten Metal Pyrolysis 152 Plasma Arc Processes 156 Gasification Processes 160 Synthetica Detoxifier 163 High-Temperature, Low-Pressure Oxidation 169 Catalytic Fluidized-Bed Oxidation 169 Molten Salt Oxidation 171 Catalytic Oxidation 174 Other Processes 176 Hydrogenation Processes 176 The Adams Process—Reaction with Sulfur 180 8 APPLICATION OF ALTERNATIVE TECHNOLOGIES TO THE DESTRUCTION OF THE U.S. CHEMICAL WEAPONS STOCKPILE 185 Destruction Technologies 185 Low-Temperature, Low-Pressure, Liquid-Phase, Detoxification 186 Low-Temperature, Low-Pressure, Liquid-Phase Oxidation 190 Moderate-Temperature, High-Pressure Oxidation 190 High-Temperature, Low-Pressure Pyrolysis 191 High-Temperature, Low-Pressure Oxidation 192 Waste Stream Handling Processes 193
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Alternative Technologies for the Destruction of Chemical Agents and Munitions Solid Waste 193 Gas Waste Streams 194 Liquid Wastes 196 Goals, Strategies, and Systems for Chemical Demilitarization 196 Program Goals 196 Strategies for Disposal 197 System Considerations 200 General Observations 205 APPENDICES 209 Appendix A, Statement of Task 209 Appendix B, Letter from James R. Ambrose, Dated October 21, 1987 210 Appendix C, Letter from Charles Baronian, Dated August 7, 1992 213 Appendix D, Biographical Sketches 237 Appendix E, Technology Developers That Supplied Information 244 Appendix F, Committee Meetings and Activities 250 Appendix G, Technology Status Worksheet 259 Appendix H, Excerpt From the U.S. Army's 5X Decontamination Review 262 Appendix I, Ionizing Radiation 271 Appendix J, Electrochemical Oxidation 274 Appendix K, Additional Data and Material Balances for Wet Air Oxidation, Supercritical Water Oxidation, and the Synthetica Detoxifier 279 REFERENCES 292 INDEX 311
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Alternative Technologies for the Destruction of Chemical Agents and Munitions Figures 1-1 Schematic of the baseline technology. 25 2-1 Principal Chemical warfare agents in the U.S. stockpile. 38 2-2 M55 rocket and M23 land mine. 43 2-3 105-ram, 155-ram, 8-inch, and 4.2-inch projectiles. 44 2-4 Bomb, spray tank, and ton container. 45 2-5 Physical envelopes of chemical munitions. 50 2-6 Types of agent and munitions and percentage of total agent stockpile (by weight of agent) at each storage site. 50 4-1 JACADS Demilitarization process. 79 7-1 WAO flow diagram. 140 7-2 SCWO flow sheet (MODAR type). 147 7-3 The Molten Metal Technology. 154 7-4 Process flow sheet of the Elkem Multipurpose Furnace and associated equipment. 155 7-5 The Westinghouse plasma system. 158 7-6 The Electro-Pyrolysis, Inc. (EPI) furnace design. 159 7-7 Lurgi gasifier. 162 7-8 Schematic flow sheet for the Synthetica Steam Detoxifier. 164 7-9 Molten salt oxidation system. 172 7-10 Block flow diagram of the UOP HyChlor conversion process. 177 7-11 A process flow sheet for the Adams process as presented by CHEMLOOP, L.P. 181 8-1 Unit processes in demilitarization Strategy 1: disassembly and agent detoxification, with storage or transportation of residue. 198 8-2 Unit processes for demilitarization Strategy 2: mineralization. 199 K-1 Apparent first-order arrhenius plot for oxidation of model compounds in supercritical water at 24.6 MPa. 286 K-2 Heat and Material Balances for the Synthetica System. 289
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Alternative Technologies for the Destruction of Chemical Agents and Munitions Tables 1-1 Schedule for the Construction and Operation of Chemical Stockpile Disposal Facilities 27 2-1 Physical Properties of Chemical Warfare Agents 39 2-2 Composition of Munitions in the U.S. Chemical Stockpile 47 2-3 Composition of Selected Chemical Munition Types, by Weight 48 2-4 Chemical Munitions Stored in the Continental United States 51 2-5 Approximate Amounts of Metals, Energetics and Agent Contained in the Chemical Weapons Stockpile (tons), by Site 52 3-1 U.S. Army Experience with Destruction of H (Mustard) by Incineration 55 3-2 U.S. Army Experience with Destruction of GB (Sarin) by Neutralization 56 3-3 U.S. Army Experience with Destruction of GB (Sarin) by Incineration, at CAMDS 57 3-4 U.S. Army Experience with Destruction of GB (Satin) by Incineration, at JACADS 58 3-5 U.S. Army Experience with Destruction of VX by Incineration, at CAMDS 59 3-6 U.S. Army Experience with Destruction of VX by Incineration, at JACADS 60 3-7 U.S. Army Experience with Destruction of HD by Incineration, at JACADS 61 3-8 Canadian Experience with Mustard Agent Destruction (1974 to 1976) 63 3-9 Canadian Experience with Mustard Destruction in 1990 to 1991 64 3-10 Canadian Experience with Nerve Agent Destruction 65 3-11 German Experience with Mustard Agent Destruction 66 3-12 Former Soviet Union Experience with Agent Destruction 67 3-13 Former Soviet Union Experience with VX Destruction 68 3-14 U.K Experience with Destruction of Mustard and World War I Gases 69
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Alternative Technologies for the Destruction of Chemical Agents and Munitions 3-15 U.K. Experience with GB Destruction 70 3-16 U.K. Experience with Mustard Destruction 71 3-17 U.N. Experience with Destruction of Mustard in Iraq 72 3-18 U.N. Experience with Destruction of Nerve Agents in Iraq 73 4-1 Permissible Agent Hazard Concentrations in Air and Lethal Doses 82 4-2 Time Estimates for Development and Demonstration of Alternative Technologies 91 5-1 Salt Formation from GB Oxidation Products 100 6-1 Oxidation Potential of Different Chemical Species 126 6-2 Enzymes Capable of Degrading Organophosphorus Neurotoxins 129 7-1 Recommended WAO Operating Temperatures and Saturation Pressures for Destruction of Chemical Warfare Agents and Propellants 142 7-2 Estimated Effluent Gas Composition for Two-Step Destruction of GB, Hydrolysis Followed by WAO (Using Air) 145 7-3 Some Characteristics of Gasifiers 161 8-1 Summary of Process Capabilities and Status 187 8-2 Low-and Moderate-Temperature Agent Detoxification Processes 201 8-3 Agent Mineralization Processes 202 8-4 Processes for Treatment of Energetics and Metal Parts and Containers 204 K-1 Chemicals Successfully Treated by Supercritical Water Oxidation and Typical Destruction Efficiencies 282
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Alternative Technologies for the Destruction of Chemical Agents and Munitions Acronyms and Abbreviations ACAMS Automatic Chemical Agent Monitoring System AChe Acetylcholine AChE Acetylcholinesterase ANAD Anniston Army Depot APG Aberdeen Proving Ground ARPA Advanced Research Projects Agency ASC Allowable Stack Concentration BOD Biological oxygen demand BRA Brine Reduction Area CAMDS Chemical Agent Munitions Disposal System CIS Commonwealth of Independent States, formerly the Soviet Union COD Chemical oxygen demand CRDEC Chemical Research, Development and Engineering Center CS Riot control agent CSDP Chemical Stockpile Disposal Program DAAMS Depot Area Air Monitoring System DMSO Dimethyl sulfoxide DOD U.S. Department of Defense DOE U.S. Department of Energy DPE Demilitarization Protective Ensemble DRE Destruction and Removal Efficiency DRMO Defense Reutilization and Marketing Office EIS Environmental Impact Statement EPA Environmental Protection Agency FRP Fiberglass Reinforced Plastic
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Alternative Technologies for the Destruction of Chemical Agents and Munitions GA Tabun GB Satin GPL General Population Levels H, HD, and HT Blister or mustard agents HLE High Level Exposure IARC International Agency for Research on Cancer IDLH Immediately Dangerous to Life and Health IUPAC International Union of Pure and Applied Chemistry JACADS Johnston Atoll Chemical Agent Disposal System L Lewisite LBAD Lexington Blue Grass Army Depot MBE Moving bed evaporator MDL Minimum Detection Limits MEO Mediated electrochemical oxidation MMT Molten Metal Technology MPF Metal Parts Furnace NAAP Newport Army Ammunition Plant NAS National Academy of Sciences NEPA National Environmental Policy Act NESHAP National Emission Standards for Hazardous Waste Pollutants NRC National Research Council OTA Office of Technology Assessment OVT Operational verification testing PBA Pine Bluff Arsenal PCB Polychlorinated biphenyl PCP Pentachlorophenol PEIS Programmatic Environmental Impact Statement PL Public Law PUDA Pueblo Army Depot R&D Research and development RCRA Resource Conservation and Recovery Act RDEC Research, Development and Engineering Center
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Alternative Technologies for the Destruction of Chemical Agents and Munitions SANA Scientists Against Nuclear Arms SCWO Supercritical water oxidation SNG Synthetic natural gas SRI Southwest Research Institute TCDD Tetrachlorodibenzodioxin TCDF Tetrachlorodibenzofuran TEAD Tooele Army Depot TNT Trinitrotoluene TSCA Toxic Substances Control Act TSDF Treatment, Storage, and Disposal Facilities TWA Time Weighted Average UMDA Umatilla Army Depot USATHAMA U.S. Army Toxic and Hazardous Materials Agency UV Ultraviolet VX Organophosphate nerve agent WAO Wet air oxidation
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Alternative Technologies for the Destruction of Chemical Agents and Munitions ALTERNATIVE TECHNOLOGIES FOR THE DESTRUCTION OF CHEMICAL AGENTS AND MUNITIONS
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