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Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemita. Weapons Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assemblecl Chemical Weapons Boa rcl on Army Science and Technology Commission on Engineering and Technical Systems National Research Council NATIONAL ACADEMY PRESS Washington, D.C. 1999

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NATIONAL ACADEMY PRESS 2101 Constitution Avenue, N.W. Washington, DC 20418 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. The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distin- guished scholars engaged in scientific and engineering research, dedicated to the furtherance of sci- ence 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. Bruce Alberts is president of the National Acad- emy 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 spon- sors engineering programs aimed at meeting national needs, encourages education and research, and recognizes the superior achievements of engineers. Dr. William A. Wulf 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. Bruce M. Alberts and Dr. William A. Wulf are chairman and vice chairman, respectively, of the National Research Council. This is a report of work supported by Contract DAAG55-97-C-0044 between the U.S. Army and the National Academy of Sciences. Any opinions, findings, conclusions, or recommendations ex- pressed in this publication are those of the authorts) and do not necessarily reflect the view of the organizations or agencies that provided support for the project. International Standard Book Number 0-309-06639-5 Limited copies are available from: Board on Army Science and Technology National Research Council 2101 Constitution Avenue, N.W. Washington, D.C. 20418 Additional copies are available for sale from: National Academy Press Box 285 2101 Constitution Ave., N.W. Washington, D.C. 20055 800-624-6242 or 202-334-3313 (in the Washington Metropolitan Area) http://www.nap.edu Copyright 1999 by the National Academy of Sciences. All rights reserved. Printed in the United States of America

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COM M ITTEE ON REVI EW AN D EVALUATION OF ALTERNATIVE TECH NOLOG I ES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS ROBERT A. BEAUDET, chair, University of Southern California, Los Angeles RICHARD J. AYEN, Waste Management, Inc.(retired), Geneva, Illinois JOAN B. BERKOWITZ, Parkas Berkowitz & Company, Washington, D.C. NOSA O. EGIEB OR, Tuskegee University, Tuskegee, Alabama WILLARD C. GEKLER, PLG, Inc., Newport Beach, California HANK C. JENKINS-SMITH, University of New Mexico, Albuquerque JOHN L. MARGRAVE, Rice University, Houston, Texas WALTER G. MAY, University of Illinois (retired), Urbana KIRK E. NEWMAN, Naval Surface Warfare Center, Indian Head Division, Yorktown, Virginia JIMMIE C. OXLEY, University of Rhode Island, Kingston WILLIAM R. RHYNE, H&R Technical Associates, Inc., Oak Ridge, Tennessee STANLEY I. SANDIER, University of Delaware, Newark WILLIAM R. SEEKER, Energy and Environmental Research Corporation, Irvine, California LEO WEITZMAN, LVW Associates, Inc., West Lafayette, Indiana Board on Army Science and Technology Liaison LAWRENCE J. DELANEY, Delaney Group, Potomac, Maryland Staff ROBERT T. BAILEY, Study Director HARRISON T. PANNELLA, Research Associate JENIFER M. AUSTIN, Senior Project Assistant . . .

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BOARD ON ARMY SCIENCE AND TECHNOLOGY WILLIAM H. FORSTER, chair, Northrop Grumman Corporation, Baltimore, Maryland THOMAS L. MCNAUGHER, vice chair, RAND Corporation, Washington, D.C. GARY L. BORMAN, University of Wisconsin, Madison RICHARD A. CONWAY, Union Carbide Corporation, Charleston, West Virginia GILBERT S. DECKER, Consultant, Los Gatos, California LAWRENCE J. DELANEY, Delaney Group, Potomac, Maryland ROBERT J. HEASTON, Guidance and Control Information Analysis Center (retired), Naperville, Illinois ELVIN R. HEIBERG, Heiberg Associates, Inc., Mason Neck, Virginia GERALD J. IAFRATE, University of Notre Dame, Notre Dame, Indiana KATHRYN V. LOGAN, Georgia Institute of Technology, Atlanta JOHN H. MOXLEY, Korn/Ferry International, Los Angeles, California STEWART D. PERSONICK, Bell Communications Research, Inc., Morristown, New Jersey MILLARD F. ROSE, Auburn University, Auburn, Alabama GEORGE T. SINGLEY III, Hicks and Associates, Inc., McLean, Virginia CLARENCE G. THORNTON, Army Research Laboratories (retired), Colts Neck, New Jersey JOHN D. VENABLES, Venables and Associates, Towson, Maryland JOSEPH J. VERVIER, ENSCO, Inc., Melbourne, Florida ALLEN C. WARD, Ward Synthesis, Inc., Ann Arbor, Michigan Staff BRUCE A. BRAWN, Director MICHAEL A. CLARKE, Associate Director MARGO L. FRANCESCO, Staff Associate ALVERA WILSON, Financial Associate DEANNA SPARGER, Senior Project Assistant V

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Preface The United States has been in the process of destroy . 1ng its chemical munitions for more than a decade. In keeping with recommendations from the National Research Council (NRC), the U.S. Anny selected incineration as the destruction method at all storage sites. However, some citizens near those sites are opposed to incineration because they believe that the exact nature of the effluents escap- ing from the stacks is unknown. Because of public opposition and a report by the NRC on alternatives to incineration for destroying bulk agent, the Anny has selected chemical hydrolysis for destroying the VX and mustard stored in one-ton containers at Newport, Indiana, and Aberdeen, Maryland. In 1996, persuaded by public opposition to incineration in Richmond, Kentucky, and Pueblo, Colorado, the Congress enacted Public Law 104-201, which instructed the Department of Defense (DOD) to "conduct an assessment of the chemical demilitarization program for destruction of assembled chemical munitions and of the alternative demilitarization technologies and processes (other than incineration) that could be used for the destruction of the lethal chemical agents that are associated with these munitions." DOD established a program manager for Assembled Chemical Weapons Assessment (ACWA) to respond to the Congress. Public Law 104-208 required that the new program manager ''identify and demonstrate not less than two alternatives to the baseline incineration process for the demilitarization of assembled chemical munitions." The mandate from Congress included a provision that DOD "coordinate" with the NRC through- out the program. In response to this mandate, the NRC established the Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons to oversee the ACWA program. I was requested by the NRC to chair this committee. Being aware of the urgent need to destroy these weapons as soon as possible, I enthusiastically accepted. I have frequently been asked if I believe that assembled chemical weapons should be destroyed by incin- eration, but the capabilities of incinerators are not at issue in the ACWA program. Many citizens of the states where the weapons are stored are strongly opposed to that method, and chemical meth . . .. .. . .. . .. . . . .. .. . .. .. . . . . . oafs, potentially more acceptable to the stakeholders, could potentially be used Instead. Unlike earlier Army chemical demilitarization programs, ACWA has involved citizen stake- holders in every aspect of the program, including the procurement process. The ACWA program manager hired a nonprofit organization, the Keystone Center, to institute a unique public involve- ment process the Dialogue on ACWA. In July 1997, DOD requested proposals from industry for complete technical packages for destroying assembled chemical munitions and, with assistance from the Dialogue, selected seven proposals submitted by industrial teams, called technology pro- viders, for initial consideration. After two additional evaluation steps, three of the seven (those proposed by Burns and Roe, General Atomics, and Parsons-Alliedsignal) were chosen by DOD to proceed to demonstration. At the writing of this report, the demonstrations were under way. v

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v! PREFACE When the committee began meeting and organizing this study, DOD had not selected the three technology packages for demonstration, and the program manager's stated policy was to demon- strate as many technologies as he could afford. In addition, the NRC's stringent peer-review pro- cess prior to publishing its reports usually requires about four months to complete from the time that the draft report is submitted for review. Thus, to publish this report in time for DOD' s final report to Congress (September 30, 1999), the committee had to proceed without the test results from the demonstrations. Therefore, the committee has investigated and evaluated all technologies that passed DOD's initial screening. Our rationale was that any of these technologies could easily be resubmitted when requests for proposals for the Kentucky and Colorado sites are issued. This report provides the results of this NRC study based on the technical information that was available before March 15, 1999. I wish to express my gratitude to the members of this committee. They served unselfishly, but they also provided their expertise in chemical processing, permitting and re~ulationLs- energetic . . .. - . ~. . .. . . . . _ _ a ~ 7 - -- - - a - -- - materials, and public acceptance. Bach member attended plenary meetings, visited the technology providers at various sites, visited the sites where the demonstrations were being held, and reviewed the extensive literature provided by the technology providers in the form of proposals, data-gap responses, and demonstration plans. We all served as volunteers. The committee also recognizes and appreciates the assistance of the DOD ACWA team, which provided the committee with valuable information, and the members of the Dialogue on ACWA, particularly the Citizens' Advisory Technical Team, who attended all of our meetings and shared their opinions with us. We also appreciated the openness and the cordiality of the technology providers. Thanks are also due to the reviewers who provided valuable and constructive comments on the draft of the report. These individuals, who were not known to the committee at the time of the review, also served as volunteers. A study such as this requires extensive logistical, administrative, and technical support. We are all indebted to the NRC staff for their assistance. I would like to particularly acknowledge the program director for this study, Dr. Robert Bailey, with whom I developed a close working rela- tionship. Robert and I worked as a team during this study. We spoke on the phone daily and e- mailed each other incessantly. Robert provided the technical, writing, and editorial skills that en- abled us to complete this report. He also provided the organizational skills that I lacked. Harrison Panella, NRC research associate, also provided the committee and me with invaluable help. He took extensive minutes at all of our meetings, provided suggestions on how to best organize this report, and assisted in its development. In addition, Jenifer Austin, NRC senior project assistant, provided the logistical support that allowed us to concentrate on our task. Special thanks are also due to Carol Arenberg for her technical editing of the report, and Margo Francesco for her manage ment of the publication process. I would also like to acknowledge Sidney Cullipher, a graduate student in the Department of Political Science and the University of New Mexico, who assisted the committee in the develop- ment of the public acceptance portions of this report. Finally, I would like to thank one additional person who was never directly involved with this study, but whose assistance was essential to me. I am indebted to Professor David A. Dows, my colleague in the Chemistry Department at the University of Southern California, who willingly took over my teaching duties while I traveled on behalf of this study. ROBERT A. BEAUDET, Chair Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons

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Acknowledgment of Reviewers This report has been reviewed by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures approved by the National Research Council's Report Review Committee. The purpose of this independent review is to provide candid and critical com- ments that will assist the authors and the National Research Council in making the published report as sound as possible and to ensure that the report meets institutional standards for objectivity, evidence, and responsiveness to the study charge. The content of the review comments and draft manuscript remain confidential to protect the integrity of the deliberative process. We wish to thank the following individuals for their participation in the review of this report: David Archer, Westinghouse Electric Company (retired), Pittsburgh, Pennsylvania Gene Dyer, Bechtel Corporation (retired), San Rafael, California Richard Magee, New Jersey Institute of Technology, Newark, New Jersey Raymond McGuire, Lawrence Livermore National Laboratory, Livermore, California Alvin Mushkatel, Arizona State University, Tempe, Arizona Vernon Myers, U.S. Environmental Protection Agency, Washington, D.C. Robert Olson, Consultant, Clinton, Tennessee George Parshall, E.I. DuPont de Nemours & Company, Wilmington, Delaware Janice Phillips, Lehigh University, Bethlehem, Pennsylvania Cesar Pruneda, Lawrence Livermore National Laboratory, Livermore, California Martin Sherwin, ChemVen Group, Inc., Boca Raton, Florida While the individuals listed above have provided many constructive comments and suggestions, responsibility for the final content of this report rests solely with the authoring committee and the National Research Council. . . vat

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Acknowledgment of Reviewers This report has been reviewed by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures approved by the National Research Council's Report Review Committee. The purpose of this independent review is to provide candid and critical comments that will assist the authors and the National Research Council in making the published report as sound as possible and to ensure that the report meets institutional standards for objectivity, evidence, and responsiveness to the study charge. The content of the review comments and draft manuscript remain confidential to protect the integrity of the deliberative process. We wish to thank the following individuals for their participation in the review of this report: David Archer, Westinghouse Electric Company (retired), Pittsburgh, Pennsylvania Richard Magee, New Jersey Institute of Technology, Newark, New Jersey Raymond McGuire, Lawrence Livermore National Laboratory, Livermore, California Alvin Mushkatel, Arizona State University, Tempe, Arizona Vemon Myers, U.S. Environmental Protection Agency, Washington, D.C. Robert Olson, Consultant, Clinton, Tennessee George Parshall, EN DuPont de Nemours & Company, Wilmington, Delaware Janice Phillips, Lehigh University, Bethlehem, Pennsylvania Cesar Pruneda, Lawrence Livermore National Laboratory, Livermore, California Martin Sherwin, ChemVen Group, Inc., Boca Raton, Florida While the individuals listed above have provided many constructive comments and suggestions, responsibility for the final content of this report rests solely with the authoring committee and the National Research Council. . . . vzzz

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Contents EXECUTIVE SUMMARY 1 INTRODUCTION The Call for Disposal, 9 The Call for Alternatives to Incineration, 9 Description of the Stockpile, 10 Agents, 10 Containers and Munitions, 10 Geographical Distribution, 11 Historical Role of the NRC in Chemical Demilitarization, 11 Evolution of the ACWA Program, 14 ACWA Program Organization, 14 Phases of the ACWA Program, 15 The Role of the National Research Council, 18 Statement of Task, 18 Scope and Approach of the Study, 20 Sources of Information, 21 Organization of This Report, 22 2 EVALUATION FACTORS Process Efficacy, 24 Effectiveness, 24 Sampling and Analysis, 27 Process Maturity, 27 Process Robustness, 28 Process Monitoring and Control, 28 Process Applicability, 29 Process Safety, 29 Worker Health and Safety, 29 Public Safety, 30 Transportation Accidents, 30 Human Health and the Environment, 31 Characterization of Effluents and Their Impact on Human Health and the Environment, 31 Mix 9 23

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XCONTENTS Completeness of Effluent Characterization, 32 Effluent-Management Strategy, 32 Resource Requirements, 32 Environmental Compliance and Permitting, 32 Public Acceptance, 33 Closing Remarks, 34 3 AEA SILVER II TECHNOLOGY PACKAGE Introduction and Overview, 36 Description of the Technology Package, 38 SILVER II Process Chemistry, 38 SILVER II Process Arrangement, 39 Disassembly of Munitions and the Removal of Agent/Energetic, 40 Treatment of Chemical Agent, 42 Treatment of Energetics, 43 Treatment of Metal Parts, 43 Treatment of Dunnage, 44 Process Instrumentation, Monitoring, and Control, 44 Feed Streams, 44 Effluent Streams, 44 Startup and Shutdown, 48 Evaluation of the Technology Package, 48 Process Efficacy, 48 Process Safety, 52 Human Health and the Environment, 54 Steps Required for Implementation, 56 Findings, 57 4 ARCTECH ACTODEMIL TECHNOLOGY PACKAGE Introduction and Overview, 58 Background on Humic Acid, 58 Description of the Technology Package, 59 Disassembly of Munitions and the Removal of Agent/Energetics, 59 Treatment of Chemical Agent, 60 Treatment of Energetics, 62 Treatment of Metal Parts, 63 Treatment of Dunnage (and Protective Suits), 64 Process Instrumentation, Monitoring, and Control, 64 Feed Streams, 64 Waste Streams, 64 Start-up and Shutdown, 65 Evaluation of the Technology Package, 65 Process Efficacy, 65 Process Safety, 68 Human Health and the Environment, 69 36 58

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CONTENTS Xt Steps Required for Implementation, 70 Findings, 70 5 BURNS AND ROE TECHNOLOGY PACKAGE Introduction and Overview, 71 Background on Plasma, 71 Description of the Technology Package, 71 Disassembly of Munitions and the Removal of Agent/Energetics, 71 Description of Plasma Waste Converter, 72 Treatment of Chemical Agent, 74 Treatment of Energetics, 74 Treatment of Metal Parts, 74 Treatment of Dunnage, 75 Process Instrumentation, Monitoring, and Control, 75 Feed Streams, 75 Waste Streams, 75 Start-up and Shutdown, 77 Evaluation of the Technology Package, 77 Process Efficacy, 77 Process Safety, 82 Human Health and the Environment, 83 Steps Required for Implementation, 86 Findings, 86 6 GENERAL ATOMICS TECHNOLOGY PACKAGE Introduction and Overview, 88 Description of the Technology Package, 88 Disassembly of Munitions and the Removal of Agent/Energetics, 88 Treatment of Chemical Agent, 91 Treatment of Energetics, 92 Treatment of Hydrolysate with Supercritical Water Oxidation, 93 Treatment of Metal Parts, 93 Treatment of Dunnage, 93 Process Instrumentation, Monitoring, and Control, 93 Feed Streams, 93 Waste Streams, 94 Start-up and Shutdown, 94 Evaluation of the Technology Package, 94 Process Efficacy, 94 Process Safety, 98 Human Health and the Environment, 100 Steps Required for Implementation, 100 Findings, 101 71 88

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xlv CONTENTS APPENDICES A DESCRIPTION OF ASSEMBLED CHEMICAL WEAPONS B MEETINGS AND SITE VISITS C BASELINE DISASSEMBLY PROCESS D AGENT NEUTRALIZATION BY HYDROLYSIS E NEUTRALIZATION OF ENERGETIC MATERIALS BY HYDROLYSIS F SUPERCRITICAL WATER OXIDATION G FLUID-JET CUTTING OR ORDNANCE AND HIGH-PRESSURE CLEAN-OUT OF ENERGETIC MATERIALS H INSIGHTS FROM STATE REGULATORS I BIOGRAPHICAL SKETCHES OF THE COMMITTEE MEMBERS 189 192 197 203 213 230 235 240 241

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Figures and Tables FIGURES 1-1 1-2 3-1 3-2 3-3 4-1 5-1 5-2 6-1 6-2 6-3 6-4 7-1 7-2 8-1 Structural formulas for GB, VX, and HD, 11 Types of agent, quantities of agent, types of munitions, and percentage of total agent stockpile at each storage site, 12 Schedule for the assessment and evaluation phase of DOD's ACWA Program, 16 Overview of the AEA technology package, 36 SILVER II block flow diagram, 37 SILVER II process flow diagram, 41 Schematic drawing of ARCTECH's ACTODEMIL process, 60 Schematic diagram of the Burns and Roe technology package, 72 Schematic diagram of a typical plasma waste converter (PWC) for treating agent, 73 Schematic drawing of General Atomic's proposed technology package, 89 Block flow diagram for the treatment of projectiles/mortars, 90 Block flow diagram for the treatment of rockets, 91 Block flow diagram for the treatment of land mines, 92 Process flow for the LMIDS, 103 Transpiring-wall SCWO platelet liner, 106 Process flow diagram for the treatment of assembled chemical weapons by WHEAT, 120 Block flow diagram of the technology package proposed by Teledyne Commodore, 135 xv

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xv! FIGURES AND TABLES 9-3 9-5 9-6 The sequence of cuts for ammoniajet cutting and wash-out of M55 rockets, 136 The sequence of cuts for ammoniajet cutting and wash-out of projectiles and mortars, 137 9-4 Schematic diagram of the process proposed for disassembly of M23 land mines, 138 Formulas for the more complex reaction products from SET/hydrolysis of GB, 139 Formulas for the more complex reaction products from SET/hydrolysis of VX, 141 11-1 Schedule for the Aberdeen Chemical Agent Disposal Facility as of January 6, 1999, 181 11-2 Schedule for the Newport Chemical Agent Disposal Facility as of January 6, 1999, 181 A-1 A-2 A-5 A-6 105-mm M360 projectile, 190 155-mm M121 projectile, 190 8-inch M426 projectile, 191 A-4 4.2-inch M2 mortar, 191 115-mm M55 rocket, 191 M23 land mine, 191 C-1 C-2 C-3 D-1 E-4 Baseline disassembly of M55 rockets, 199 Baseline disassembly of projectiles/mortars, 199 Baseline disassembly of land mines, 200 Primary reactions involved in VX hydrolysis, 206 Reversible formations of the sulfonium ion aggregates in the hydrolysis of mustard, 210 Conversion of nitrogen (N) during pressurized alkaline decomposition of propellant P2, 224 Conversion of carbon (C) during pressurized alkaline decomposition of propellant P2, 224 Conversion of nitrogen (N) during pressurized alkaline decomposition of propellant P5 under different alkaline conditions, 225 Conversion of carbon (C) during pressurized alkaline decomposition of propellant P5 under different alkaline conditions, 225 F-1 Typical flow sheet for supercritical water oxidation, 231 G-1 Waterjet velocity at which explosives will initiate 50 percent of the time as a function of the fluidjet diameter, 236

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FIGURES AND TABLES G-2 Comparison of the AWJ and ASJ (DIAJET) abrasivejet cutting techniques, 237 TABLES ES-1 Descriptions of the Seven Technology Packages that Passed DOD's Initial Evaluation, 3 1-1 1-2 1-3 1-4 1-5 1-6 1-7 2-1 3-1 3-2 3-4 3-6 3-7 3-8 3-9 3-10 3-11 Physical Properties of Chemical Warfare Agents, 11 Chemical Munitions Stored in the Continental United States, 13 Seven Technology Providers Selected in the ACWA GolNo-Go Evaluation Step, 16 Descriptions of the Seven Technology Packages that Passed DOD's Initial Evaluation, 17 Technology Demonstrations Performed by Burns and Roe, 19 Technology Demonstrations Performed by General Atomics, 19 Technology Demonstrations Performed by Parsons-AlliedSignal, 20 Throughput Rates Prescribed in the ACWA REP, 34 Summary of the AEA/CH2M HILL Approach, 38 Standard Electrode Potentials of Reactions Related to the SILVER II Process, 39 Anode Reactions of Ag(II) with Chemical Agent and Energetic Materials, 39 Energy Required for the Destruction of Chemical Agents and Energetics, 40 3-5 The Process Effluents and Treatment/Disposal Strategies Proposed by AEA for the Silver (II) Process, 45 Process Inputs for SILVER II per 155-mm Projectile, 46 Process Outputs for SILVER II per 155-mm Projectile, 46 Process Inputs for SILVER II per M55 Rocket, 47 Process Outputs for SILVER II per M55 Rocket, 47 Estimate of Spent Silver for Mustard-Filled 155-mm Projectiles, 48 Estimate of Spent Silver Sent for Recycling for VX-Filled M55 Rockets, 48 4-1 4-2 4-3 4-4 4-5 5-1 5-2 . . xv Summary of the ARCTECH ACTODEMIL Approach, 59 Summary of Experiments Conducted by ARCTECH with Agents at 90C, 61 Results of Analysis for Residual Agent during ACTODEMIL Neutralization Process at 90C, 62 Materials Required for Processing 100 g of VX Using the ACTODEMIL Process, 64 Feed and Product Masses and Concentrations for Hydrolysis of 100 g of VX in the Presence of Humic Acid, 66 Summary of the Burns and Roe Approach, 73 System Inputs for the Burns & Roe Mass Balance, 76

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. . . xvit! FIGURES AND TABLES 5-3 5-4 5-5 5-6 5-7 5-8 6-1 6-2 6-3 6-4 6-5 7-1 7-2 8-1 8-2 8-3 9-1 9-2 9-3 9-4 9-5 9-6 9-7 9-8 9 9 Mass Outputs for the Burns & Roe System, 76 Predicted Composition of Product Gas from the PWCs (Prior to Scrubbing), 77 Predicted Composition of Product Gas from the Plasma Waste Converters after Scrubbing, 77 Theoretical Equilibrium Composition of Product Gas from Plasma Treatment of Agents, 78 Theoretical Equilibrium Composition of Product Gas from Plasma Treatment of Energetics, 78 Comparison of Experimental and Predicted Gas Compositions Subsequent to Plasma Treatment, 79 Summary of the General Atomics Approach, 88 Process Inflow Streams for the General Atomics Technology Package (80 VX-filled 155-mm projectiles per hour), 94 Potential Air Emission Points for the General Atomics Technology Package, 95 Process Outflow Streams for the General Atomics Technology Package (80 VX-filled 155-mm projectiles per hour), 95 Routine Start-up Procedures for the General Atomics Technology Package, 96 Summary of the LMIDS Approach, 103 Process Inflow Streams (lb/hr) from Outside the Process for Blue Grass VX Base Case Campaign (14 M55 rockets/hr and 14 M121A1 projectiles/hr), 108 Process Outflow Streams (lb/hr) to the environment for the Blue Grass VX Base Case Campaign (14 M55 rockets/hr and 14 M121A1 projectiles/hr), 109 Summary of the Parsons-AlliedSignal Technology Package, 119 Mass Balance for Processing HD 4.2-inch Mortars (lbAb HD), 125 Mass Balance for Processing GB 8-inch Projectiles (lb/ lb GB), 125 Summary of the Teledyne-Commodore SET Technology Package, 134 Measured Results for the SET/Hydrolysis Reaction of HD based on Laboratory Data and Scaled Up to 100 lb of Agent, 138 Measured Results for the SET/Hydrolysis Reaction of GB based on Laboratory Data and Scaled Up to 100 lb of Agent, 138 Predicted Solid and Aqueous Reaction Products of SETIHydrolysis of GB, 140 Measured Results for the SET/Hydrolysis Reactions of VX based on Laboratory Data and Scaled Up to 100 lb of Agent, 140 Predicted Solid and Aqueous Reaction Products of SETIHydrolysis of VX, 142 Identified SET Reaction Products of Treatment of TNT, 143 Identified SET Reaction Products of Treatment of RDX, 143 Identified SET Reaction Products of Treatment of Comp B. 144

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FIGURES AND TABLES 9-11 9-12 10-3 9-10 Identified SET Reaction Products of Treatment of M28 Propellant, 144 Process Inputs for the Teledyne-Commodore Technology Package for VX-filled M55 Rockets Processed at a rate of 20/hr, 146 Process Inputs for the Teledyne-Commodore Technology Package for HD-filled 155 mm Projectiles Processed at a rate of 100/hr, 146 Process Waste Streams Released to the Environment, 147 Process Outputs for the Teledyne-Commodore Technology Package for VX-filled M55 Rockets Processed at a rate of 20/hr, 148 Process Outputs for the Teledyne-Commodore Package for HD-Filled 155 mm Projectiles at a rate of 100/hr, 148 10-1 Schedule Slippages of Chemical Weapons Demilitarization, 164 10-2 DOD's Estimated Life-Cycle Costs for Chemical Weapons Demilitarization (in $ billions), 165 List of Participants in the Dialogue on Assembled Chemical Weapons Assessment as of July 10, 1998, 166 11-1 Summary of the Key Process-Engineering Data for the Seven Technology Packages, 174 A-1 D-3 D-4 D-5 D-6 Assembled Chemical Weapons in the U.S. Stockpile, 190 D-1 Examples of Large-Scale Neutralizations, 204 D-2 Effect of pH on Equilibrium of Remaining GB, 205 Results of the VX Ton Container Survey Program (Organics), 207 Results of the VX Ton Container Survey Program (Metals), 207 Analysis of Homogenized VX Hydrolysate after 240-Minute Reaction Time, 208 Residual VX and EA 2192 Concentrations from 12-Liter Reactor Tests, 208 D-7 Typical Composition of HD Agent, 209 D-8 Concentration of Metals in HD Agent, 209 D-9 Complex Organic Compounds in HD Heel by NMR (mole percent), 209 D-10 Content of HD Agent and Volatile Organic Compounds in Initial Ton Container Vapor, 210 Dell Organic Compounds in HD Hydrolysate (Mole Percent), 211 E-1 E-2 E-3 E-4 E-5 ax Hydrolysis Rates Obtained at Laboratory Scale, 216 Hydrolysis Using a Bench-Scale Rotary Hydrolyzer, 217 Observed First-Order Rate Constants for Hydrolysis in Excess NaOH Solution (8.048 x 10-2 M) at 25C, 218 Second-Order Rate Constants for Hydrolysis of RDX in NaOH Solutions from 0.02 to 0.25 M, 218 Formation of Nitrite Ion during Hydrolysis of RDX (7.07 x 10-5 M) at 45C (113F) with Excess NaOH Solution (6.82 x 10-2M), 219

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XFIGURES AND TABLES E-7 E-8 E-9 Analysis of RDX Hydrolysis Products with Different Hydroxide Concentrations (Mole ratio of product formed per RDX hydrolyzed), 219 Summary of Alkaline Decomposition Experiments for Comp B Performed by LANE, 219 Anionic Products from the Hydrolysis of Comp B. 220 Product Analysis for Sodium Carbonate Hydrolysis of HMX Powder, 220 E-10 Alkaline Decomposition of NC (12.2% N) at 30C (86F), 222 E-ll Alkaline Decomposition of NC (12.2% N) at 60C (140F), 222 E-12 German Propellant Formulations Used in Pressured Alkaline Decomposition Experiments, 223 E-13 Results for the Pressured Alkaline Decomposition of Propellants P1-P5, 223

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Abbreviations and Acronyms ACAMS automatic continuous air monitoring system ACFM actual cubic feet per minute ACTODEMIL process developed by ARCTECH ACWA Assembled Chemical Weapons Assessment AEA a technology provider a-MAX solution containing potassium hydroxide base and humic acid (defined by ARCTECH) AHR agent hydrolysis reactor AlTech Panel Panel on Review and Evaluation of Alternative Chemical Disposal Technologies BAA broad agency announcement BATNA best alternative to a negotiated agreement BIF boiler and industrial furnace CAA Clean Air Act CAC Citizens Advisory Committee CATT Citizens' Advisory Technical Team CLIN contract line item number CSDP Chemical Stockpile Disposal Program CSEPP Chemical Stockpile Emergency Preparedness Program CWA Clean Water Act CWC Chemical Weapons Convention CWWG Chemical Weapons Working Group DAAMS depot area air monitoring system DAD decide, announce, and defend DOD U.S. Department of Defense DPA diphenylamine DPE demilitarization protective ensemble (suits) DRE destruction and removal efficiency EMPA ethyl methylphosphonic acid xx

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xxt! ABBREVIATIONS AND ACRONYMS EPA ERH FEMA FTIR FY GAO GB GC GC/MS GPCR H HA HAZOP HD HEPA HMX HRA HT JACADS KOH LCIMS LMIDS MACT MDC MPF NEPA NMR NRC PAS PCB PETN PIC PRH PWC QRA RCRA Environmental Protection Agency energetics rotary hydrolyzer Federal Emergency Management Agency Fourier transform infrared fiscal year General Accounting Office a type of nerve agent gas chromatography gas chromatography/mass spectrometry gas-phase chemical reduction mustard agent humic acid hazards and operability study distilled mustard agent high efficiency particulate air cyclotetramethylene-tetranitramine health risk assessment a mix of agents H and T Johnston Atoll Chemical Agent Disposal System potassium hydroxide liquid chromatography/mass spectrometry Lockheed Martin Integrated Demilitarization System maximum achievable control technology material decontamination chamber metal parts furnace National Environmental Policy Act nuclear magnetic resonance National Research Council pollution abatement system polychlorinated biphenyl~s) pentaeryhritol tetranitrate product~s) of incomplete combustion projectile rotary hydrolyzer plasma waste converter quantitative risk assessment Resource Conservation and Recovery Act

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ABBREVIATIONS AND ACRONYMS RDX REP SCFM SCWO SET TCLP TNT TSCA UTS VX WHEAT . . . xx cyclotrimethylenetrinitramine request for proposal standard cubic feet per minute supercritical water oxidation solvated electron technology toxicity characteristic leachate procedure trinitrotoluene Toxic Substances Control Act universal treatment standards type of nerve agent water hydrolysis of explosives and agent technology

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