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EFFECTS OF DEGRADED AGENT AND MUNITIONS ANOMALIES ON CHEMICAL STOCKPILE DISPOSAL OPERATIONS Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program Boa rcl on Army Science and Technology Division on Engineering and Physical Sciences NATIONAL RESEARCH COUNCIL OF DIE NATIONAL ACADEMIES THE NATIONAL ACADEMIES PRESS Washington, D C www.nap.edu

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THE NATIONAL ACADEMIES PRESS 500 Fifth Street, N.W. Washington, DC 20001 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 competences and with regard for appropriate balance. This is a report of work supported by Contract DAAD19-03-C-0005 between the U.S. Army and the National Academy of Sciences. Any opinions, findings, conclusions, or recommendations expressed in this publication are those of the authoress and do not necessarily reflect the views of the organizations or agencies that provided support for the project. International Standard Book Number 0-309-08918-2 (Book) International Standard Book Number 0-309-50842-8 (PDF) Limited copies are available from: Board on Army Science and Technology National Research Council 500 Fifth Street, N.W. Washington, DC 20001 (202) 334-3118 Additional copies are available from: The National Academies Press 500 Fifth Street, N.W. Lockbox 285 Washington, DC 20055 (800) 624-6242 or (202) 334-3313 (in the Washington metropolitan area) www.nap.edu Copyright 2004 by the National Academy of Sciences. All rights reserved. Printed in the United States of America

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THE NATIONAL ACADEMIES Advisers to the Nation on Science, Engineering, and 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. Bruce M. Alberts 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. Wm. 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. Harvey V. Fineberg 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. Wm. A. Wulf are chair and vice chair, respectively, of the National Research Council. www.national-academies.org

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COMMITTEE ON REVIEW AND EVALUATION OF THE ARMY CHEMICAL STOCKPILE DISPOSAL PROGRAM PETER B. LEDERMAN, Chair, New Jersey Institute of Technology (Ret.), Newark CHARLES I. McGINNIS, Vice-Chair, United States Army (Ret.), Charlottesville, Virginia DAVID H. ARCHER, Carnegie Mellon University, Pittsburgh, Pennsylvania JOHN J. COSTOLNICK, Exxon Chemical Company (Ret.), Houston, Texas ELISABETH M. DRAKE, Massachusetts Institute of Technology (Ret.), Cambridge DEBORAH L. GRUBBE, E.I. du Pont de Nemours & Company, Wilmington, Delaware DAVID A. HOECKE, Enercon Systems, Inc., Elyria, Ohio DAVID H. JOHNSON, ABS Consulting, Irvine, California JOHN L. MARGRAVE, Rice University, Houston, Texas JAMES F. MATHIS, Exxon Corporation (Ret.), Houston, Texas FREDERICK G. POHLAND, University of Pittsburgh, Pennsylvania ROBERT B. PUYEAR, Consultant, Chesterfield, Missouri CHARLES F. REINHARDT, E.I. du Pont de Nemours & Company (Ret.), Chadds Ford, Pennsylvania W. LEIGH SHORT, URS Greiner Woodward-Clyde (Ret.), Mount Pleasant, South Carolina JEFFREY I. STEINFELD, Massachusetts Institute of Technology, Cambridge RAE ZIMMERMAN, New York University Board on Army Science and Technology Liaison RICHARD A. CONWAY, Union Carbide Corporation (Ret.), Charleston, West Virginia NRC Staff DONALD L. SIEBENALER, Study Director HARRISON T. PANNELLA, Program Officer CARTER W. FORD, Senior Project Assistant JAMES C. MYSKA, Research Associate ~v

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BOARD ON ARMY SCIENCE AND TECHNOLOGY JOHN E. MILLER, Chair, Oracle Corporation, Reston, Virginia GEORGE T. SINGLEY III, Vice-Chair, Hicks and Associates, Inc., McLean, Virginia NORVAL L. BROOME, MITRE Corporation (Ret.), Suffolk, Virginia ROBERT L. CATTOI, Rockwell International (Ret.), Dallas, Texas RICHARD A. CONWAY, Union Carbide Corporation (Ret.), Charleston, West Virginia GILBERT F. DECKER, Walt Disney Imagineering (Ret.), Glendale, California ALAN H. EPSTEIN, Massachusetts Institute of Technology, Cambridge ROBERT R. EVERETT, MITRE Corporation (Ret.), New Seabury, Massachusetts PATRICK F. FLYNN, Cummins Engine Company, Inc. (Ret.), Columbus, Indiana HENRY J. HATCH, Army Chief of Engineers (Ret.), Oakton, Virginia EDWARD J. HAUG, University of Iowa, Iowa City GERALD J. IAFRATE, North Carolina State University, Raleigh MIRIAM E. JOHN, California Laboratory, Sandia National Laboratories, Livermore DONALD R. KEITH, Cypress International (Ret.), Alexandria, Virginia CLARENCE W. KITCHENS, Hicks and Associates, Inc., McLean, Virginia ROGER A. KRONE, Boeing Integrated Defense Systems, Philadelphia, Pennsylvania SHIRLEY A. LIEBMAN, CECON Group (Ret.), Holtwood, Pennsylvania KATHRYN V. LOGAN, Georgia Institute of Technology (professor emerita), Roswell STEPHEN C. LUBARD, S-L Technology, Woodland Hills, California JOHN W. LYONS, U.S. Army Research Laboratory (Ret.), Ellicott City, Maryland JOHN H. MOXLEY, Korn/Ferry International, Los Angeles, California MILLARD F. ROSE, Radiance Technologies, Huntsville, Alabama WALTER D. SINCOSKIE, Telcordia Technologies, Inc., Morristown, New Jersey JOSEPH J. VERVIER, ENSCO, Inc., Melbourne, Florida NRC Staff BRUCE A. BRAWN, Director WILLIAM E. CAMPBELL, Administrative Officer CHRIS JONES, Financial Associate DEANNA P. SPARGER, Administrative Associate DANIEL E.J. TALMAGE, JR., Research Associate

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In memory of Dr. John L. Margrave, National Academy of Sciences 193 1 -2004 and Dr. Frederick G. PohIanc3, National Academy of Engineering 1924-2003

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Preface The purpose of this report is to examine the effects of leakers and other anomalies in stored munitions on the operation of chemical agent disposal facilities. To do this, the Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program evalu- ated the munitions' history, reviewed and evaluated leaker detection and reduction activities, reviewed un- usual occurrences resulting from the delivery of atypi- cal (i.e., anomalous) munitions and containers to dis- posal facilities, reviewed and evaluated the implications of atypical agents and munitions for risks to workers, and assessed the impacts of these atypical munitions on the Army's Chemical Stockpile Disposal Program (CSDP). The United States has maintained the current stock- pile of chemical warfare agents and munitions since World War II. In 1985, Public Law 99-145 mandated the expeditious destruction of M55 rockets containing chemical agents because of the chance that theY might self-ignite. The program was soon expanded Into the CSDP, which was given the mission of disposing of the entire 31,496 tons of nerve and mustard agents in the chemical stockpile. The stockpile of munitions has already been destroyed at one site, Johnston Island (part of Johnston Atoll), in the Pacific Ocean southwest of Hawaii. The remainder of the stockpile is dispersed among eight storage sites in the continental United States. The United States is a signatory to the Chemical Weapons Convention treaty, which requires that the entire stockpile be destroyed by April 29, 2007, with the possibility of a 5-year extension. Recently, the Army indicated that this extension would be necessary to complete disposal operations. vim Congress mandated that the Army seek outside, un- biased advice on how best to dispose of the stockpile. In 1987, at the request of the Under Secretary of the Army, the National Research Council (NRC) estab- lished the Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program (the Stockpile Committee) to provide scientific and techni- cai aclv~ce and counsel on the CSDP. The committee has since produced 30 full-length and letter reports covering the evolution of the CSDP from the design and construction of the first incineration-based chemi- cal agent disposal facility on Johnston Island in 1990 to the present. The Johnston Island facility is now be- ing closed. A second incineration-based facility has been operating for more than 7 years at Tooele, Utah, adjacent to the largest stockpile site. The third incin- eration facility, at Anniston, Alabama, has just begun operations. Similar incineration facilities are being constructed at Pine Bluff, Arkansas, and Umatilla, Or- egon. Although details differ at the five sites, the basic technology is the baseline incineration system. At the four other sites Aberdeen, Maryland; Newport, Indi- ana; Pueblo, Colorado; and Blue Grass, Kentucky- technologies other than incineration are being imple- mented. STATEMENT OF TASK This report has been prepared by the National Re- search Council (NRC) in response to a request from the Program Manager for Chemical Demilitarization (PMCD) suggesting that a better understanding of the condition of the stockpile in storage might enable im-

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provements in operational efficiency and reduce risk to the public and plant employees. The statement of task is as follows: The NRC study will accomplish the following: Evaluate the history of munitions and containers delivered to op- erating and closing chemical disposal facilities. Review storage leaker detection and leak reduction activities cur- rently in place at chemical agent storage facilities. Review unusual occurrences resulting from the delivery of atypi- cal agents, munitions, or containers to disposal facilities for destruc- tion. Review resulting corrective actions and effects on disposal op- erations. Review worker risk implications of atypical agent arid munitions delivered to disposal facilities. Assess programmatic impacts, including stakeholder perceptions. Among the issues addressed are the state of the stockpile munitions and containers as delivered to dis- posal facilities and the effects that any atypical muni- tions and containers have had, are having, or might have on processing, handling, and monitoring during disposal operations. Atypical conditions include corro- sion, leakage, agent deterioration, agent solidification, explosives deterioration, environmental exposure, and overpack operations. The report also addresses consid- erations pertaining to public and worker risks. COMMITTEE MEMBERSHIP AND ACTIVITIES The Stockpile Committee consists of members with expertise in the following areas: analytical chemistry; biochemical engineering; chemistry; chemical engineering; chemical industry manage- ment; chemical technology and manufacturing; civil and environmental engineering; combustion technol- ogy; engineering design and management; environ- mental planning and management; environmental res- toration; facility closure; hazardous waste manage- ment; health risk assessment; incineration; industrial hygiene; materials science; mechanical engineering, monitoring and instrumentation; occupational medi- cine; risk assessment, management, and communica- tion; safety; toxicology; urban planning; and waste treatment and minimization. The committee met with selected personnel from PMCD and the Soldier Biological and Chemical Com- mand (SBCCOM) throughout the development of this report. Members were provided with numerous docu- ments containing data on stockpile surveillance activi- ties and on the occurrence of leakers and other anoma- lies. Site visits were conducted. The report developed by the committee was peer reviewed by several experts in accordance with NRC procedures prior to publication. The Stockpile Committee would like to recognize the assistance given by Army staff and contractors in providing information and answering questions from the committee. It is likewise grateful for the assistance of NRC staff members Donald L. Siebenaler, Harrison T. Pannella, Carter W. Ford, James C. Myska, William E. Campbell, Richard E. Rowberg, and Elizabeth Fikre in producing this report. The committee is also grateful for the assistance provided by Stephen P. Bailey of DuPont Engineering Technology. Peter B. Lederman, Chair Charles I. McGinnis, Vice-Chair Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program . . . vail

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Acknowledgment of Reviewers This report has been reviewed in draft form by indi- viduals chosen for their diverse perspectives and tech- nical expertise, in accordance with procedures ap- proved 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 institution in making its published report as sound as possible and to ensure that the report meets institutional standards for objectivity, evidence, and re- sponsiveness to the study charge. The review com- ments and draft manuscript remain confidential to pro- tect the integrity of the deliberative process. We wish to thank the following individuals for their review of this report: Dennis C. They, Buttonwood Consulting Inc., Jere H. Brophy, Independent Consultant, B. John Garrick, Independent Consultant, Six Robert L. Mason, Southwest Research Institute, George W. Parshall, Independent Consultant, James P. Pastorick, GEOPHEX UXO, Ltd., and Peter S. Spencer, Oregon Health and Science University. Although the reviewers listed above have provided many constructive comments and suggestions, they were not asked to endorse the conclusions or recom- mendations, nor did they see the final draft of the re- port before its release. The review of this report was overseen by John C. Bailar III, University of Chicago. Appointed by the NRC, he was responsible for making certain that an independent examination of this report was carried out in accordance with institutional proce- dures and that all review comments were carefully con- sidered. Responsibility for the final content of this re- port rests entirely with the authoring committee and the institution.

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Contents EXECUTIVE SUMMARY 1 3 INTRODUCTION Overview of the Chemical Stockpile Disposal Program, 3 Purpose of the Report, 4 OCCURRENCES AND ORIGINS OF ANOMALIES Overview of Origins of Anomalies, 5 Description of Munitions and Containers, 6 Manufacturing Process Origins of Anomalies, 9 Agent Characteristics, 9 Munition Assembly, Quality Control, and Component Compatibility, 10 Deterioration Processes for Agents, 11 Surveillance of Agent Deterioration, 11 Mechanisms and Products of Agent Deterioration, 12 Deterioration Processes for Energetic Materials, 17 Observed Leak Factors and Occurrences by Munition Type, 17 Summary, 17 TRACKING AND ANALYSIS OF STOCKPILE LEAKERS The Army's Storage Monitoring and Inspection Program, 20 Stockpile Leaker Data, 26 Statistical Approach of the Stockpile Committee, 27 Summary, 34 4 OPERATIONAL AND RISK IMPLICATIONS Of ANOMALIES Introduction, 36 Risk Implications Covered in Quantitative Risk Assessments, 36 Leaking M55 Rockets, 37 Energetics Sensitivity, 37 Container Degradation, 38 Autoignition of M55 Rockets, 38 x~ 3 5 19 36

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Summary of Implications of Anomalies and Corrective Actions, 40 General, 40 Progressive (Chemical-Related) Anomalies, 40 Stable Anomalies Related to Manufacturing and Handling, 41 Worker Risk Incident to the Storage and Processing of Anomalous Munitions, 43 CSDP Programmatic Impacts, 44 General, 44 Schedule and Cost, 44 Stakeholder Perceptions and Reactions, 45 Summary, 46 FINDINGS AND RECOMMENDATIONS REFERENCES APPENDIXES Autoignition and the M55 Rocket Leakers by Munition Type Biographical Sketches of Committee Members . . x~ 47 50 55 58 64

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List of Tables, Figures, and Boxes TABLES 2-1 Composition of Munitions in the U.S. Chemical Stockpile, 9 2-2 Expected Products from Chemical Agent Decomposition Due to Age, 12 SMI Requirements for Toxic Chemical Items, 21 Total Number of Leakers for All Years, All Sites, and All Categories, 24 Munition Leakers by Type of Agent, 24 M55 GB Rocket Sampling Plan and M55 GB Rocket Storage Monitoring Inspection, 25 Period III Category 1 Leaks at Each Site by Year, 31 Period III Category 1 Leaks at Each Site by DODIC, 31 Period III Category 1 Leaks at Each Site by Agent Type, 32 Period III Category 1 Leaks by Agent Type and DODIC, 32 Period III Category 1 Leaks by Agent Type and DODIC for ANCA Site, 32 4-1 Median Site-Specific Annual Autoignition Probability for Overpacked Rockets, 39 4-2 Median Site-Specific Annual Autoignition Probability for Nonoverpacked Leaking Rockets, 39 4-3 Comparison of Site-Specific Autoignition Probabilities with the Probabilities for Other Accidental Ignition Events (probability in 1 year), 39 A-1 Calculated Best-Estimate Autoignition Probabilities for M55 Rocket Sites, 56 B-1 M55 Rocket Leaker Detection by GB Agent Type, 60 B-2 Acidity Levels for Various Types of GB-Filled M55 Rockets, 60 B-3 Distribution of GB Rocket Lots by Storage Location and GB Agent Type, 61 B-4 Condition of M55 Rocket Warheads Examined: Average Number of Pits in the Warhead Sample as a Function of Warhead Condition and Pit Depth, 61 B-5 Results of Visual Inspection for Sampled M55 Rocket Warheads, 62 . . . x~

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FIGURES Location and size (percentage of original stockpile) of eight continental U.S. storage sites, 6 (a) M55 rocket; (b) 105-mm projectile; (c) ton container, 8 Autocatalysis rate profile, product concentration versus time, 14 Distribution of leaking munitions in the U.S. chemical weapons stockpile from 1973 to June 30, 2002, 22 Distribution of leaking munitions in the Anniston stockpile from 1973 to June 30, 2002, 23 Number of leaks by munition type, all sites, 23 3-4 Seasonal distribution of 155-mm projectiles leaker occurrences at Umatilla by month and igloo temperature, 28 3-5 Pareto chart indicating Category 1 leaks by agent (across all sites and including all munition types), 29 3-6 Pareto chart of Category 1 leaks by DOD Identification Code for all sites, 30 3-7 Pareto chart of Category 1 leaks by site for all sites, 30 3-8 Regression analysis of aggregated-by-year-of-leak totals at ANCA versus year detected, 33 3-9 GB rocket leaks by agent subtype at ANCA from 1992 through July 2002, 33 3-10 GB rocket population by agent subtype at ANCA prior to start of disposal operations (2003), 34 B-1 Crater crack in MC-1 750-lb GB bomb, 59 BOXES 2-1 Excerpt from a Report on the Stability of the Stockpile of Chemical Weapons, 7 3-1 STS Database Fields Used by the Committee, 27 x~v

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List of Acronyms AMC Army Materiel Command FOIA Freedom ofInformation Act ANCA Anniston Chemical Activity FPEIS Final Programmatic ANOVA analysis of variance Environmental Impact Statement AQS agent quantification system GA tabun, a nerve agent (ethyl-N,N- BGCA Blue Grass Chemical Activity dimethylphosphoramidocyanidate) BRA brine reduction area GAO Government Accounting Office GB satin, a nerve agent CAMDS Chemical Agent Munition (methylphosphonofluoridate, Disposal System isopropyl ester) CDC Centers for Disease Control and Prevention H sulfur mustard, bis(2-chloroethyl) CRDEC Chemical Research, Development, sulfide and Engineering Center HD sulfur mustard, distilled H CSDP Chemical Stockpile Disposal HDC treated discharge conveyor Program HT sulfur mustard, 60 percent HD and 40 percent T. which is DA Department of the Army bis[2~2-chloroethylthio)ethyl] DAC Defense Ammunition Center ether DCD Deseret Chemical Depot DFS deactivation furnace system IMPA isopropylmethylphosphonic acid DICDI diisopropyl carbodiimide DIMP diisopropyl methylphosphonate JACADS Johnston Atoll Chemical Agent DOD Department of Defense Disposal System DODIC Department of Defense JI Johnston Island Identification Code DPE demilitarization protective LIC liquid incinerator ensemble MDM multipurpose demilitarization ECR explosion containment room machine EMPA ethyl methylphosphonic acid MPA methylphosphonic acid MPF metal parts furnace xv

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MPFA methylphosphonofluoridic acid RMA Rocky Mountain Arsenal MSN manufacturer stock number RO roundout agent RS restabilized agent NC nitrocellulose RSM rocket sheer machine NCRS nose closure removal system NDPA 2-nitrodiphenylamine SAIC Science Applications International NO nitroglycerine Corporation NRC National Research Council SBCCOM Soldier and Biological Chemical Command PAS Pollution Abatement System SET shipping end firing tube PBCA Pine Bluff Chemical Activity SMI Storage Monitoring and Inspection PCB polychlorinatedbiphenyl SRC single round container PCD Pueblo Chemical Depot STS Stockpile Tracking System PFS pollution abatement system filter SUPLECAM Surveillance Program for Lethal system Chemical Agents and Munitions PMCD Program Manager for Chemical Demilitarization TEA tributylamine PMD projectile/mortar disassembly TC ton container PRO preroundout agent TOCDF Tooele Chemical Agent Disposal PR-RS restabilized preroundout Facility PUCDF Pueblo Chemical Agent Disposal TWA time-weighted average Facility UMCD Umatilla Chemical Depot QASAS quality assurance specialist ammunition surveillance VX a nerve agent, O-ethyl S-~2- QRA quantitative risk assessment diisopropylaminoethyl) methyl- phosphonothiolate RCRA Resource Conservation and Recovery Act RD redistilled agent xv