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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.
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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
