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. Bruce 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. William A. Wulf is interim 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 interim vice chairman, respectively, of the National Research Council.
This is a report of work supported by Contract DAAH04-95-C-0049 between the U.S. Army and the National Academy of Sciences.
Library of Congress Catalog Card Number 96-61747
International Standard Book Number 0-309-05525-3
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Copyright 1996 by the National Academy of Sciences. All rights reserved.
Printed in the United States of America.
PANEL ON REVIEW AND EVALUATION OF ALTERNATIVE CHEMICAL DISPOSAL TECHNOLOGIES
RICHARD S. MAGEE, Chair,
New Jersey Institute of Technology, Newark
JOAN B. BERKOWITZ,
Farkas Berkowitz & Company, Washington D.C.
GENE H. DYER, Consultant,
San Rafael, California
FREDERICK T. HARPER,
Sandia National Laboratories, Albuquerque, New Mexico
JOSEPH A. HEINTZ, Consultant,
Schererville, Indiana
DAVID A. HOECKE,
Enercon Systems Inc., Elyria, Ohio
DAVID S. KOSSON,
Rutgers, the State University of New Jersey, Piscataway
WALTER G. MAY,
University of Illinois, Urbana
ALVIN H. MUSHKATEL,
Arizona State University, Tempe
LAURANCE ODEN,
U.S. Bureau of Mines (retired), Albany, Oregon
GEORGE W. PARSHALL,
Dupont Company (retired), Wilmington, Delaware
L. DAVID PYE,
Alfred University, Alfred, New York
ROGER W. STAEHLE, Consultant,
North Oaks, Minnesota
WILLIAM TUMAS,
Los Alamos National Laboratory, Los Alamos, New Mexico
Board on Army Science and Technology Liaison
ROBERT A. BEAUDET,
University of Southern California, Los Angeles
Staff
BRUCE A. BRAUN, Director,
Division of Military Science and Technology
MICHAEL A. CLARKE, Study Director
ROBERT J. KATT, Technical Writer/Consultant
MARGO L. FRANCESCO, Administrative Associate
DEBORAH B. RANDALL, Senior Secretary/Project Assistant
BOARD ON ARMY SCIENCE AND TECHNOLOGY
GLENN K. OTIS, Chair,
U.S. Army (retired), Newport News, Virginia
CHRISTOPHER C. GREEN, Vice Chair,
General Motors Corporation, Warren, Michigan
ROBERT A. BEAUDET,
University of Southern California, Los Angeles
GARY L. BORMAN,
University of Wisconsin, Madison
ALBERTO COLL,
U.S. Naval War College, Newport, Rhode Island
LAWRENCE J. DELANEY,
BDM Europe, Munich, Germany
WILLIAM H. FORSTER,
Northrop Grumman Corporation, Baltimore, Maryland
ROBERT J. HEASTON,
Guidance and Control Information Analysis Center, Chicago
THOMAS L. MCNAUGHER, RAND,
Washington, D.C.
NORMAN F. PARKER,
Varian Associates (retired), Cardiff by the Sea, California
STEWART D. PERSONICK,
Bell Communications Research, Inc., Morristown, New Jersey
KATHLEEN J. ROBERTSON,
Booz · Allen and Hamilton, McLean, Virginia
JAY P. SANFORD,
University of Southwestern Health Sciences Center, Dallas, Texas
HARVEY W. SCHADLER,
General Electric (retired), Schenectady, New York
JOYCE L. SHIELDS,
Hay Management Consultants, Arlington, Virginia
CLARENCE G. THORNTON,
Army Research Laboratories (retired), Colts Neck, New Jersey
JOHN D. VENABLES,
Martin Marietta Laboratories (retired), Towson, Maryland
ALLEN C. WARD,
University of Michigan, Ann Arbor
Staff
BRUCE A. BRAUN, Director
MICHAEL A. CLARKE, Senior Program Officer
ROBERT J. LOVE, Senior Program Officer
ERIC T. SHIMOMURA, Senior Program Officer
DONALD L. SIEBENALER, Senior Program Officer
MARGO L. FRANCESCO, Administrative Associate
ALVERA GIRCYS, Financial Associate
JACQUELINE CAMPBELL-JOHNSON, Senior Project Assistant
CECELIA L. RAY, Senior Project Assistant
SHIREL R. SMITH, Senior Project Assistant
DEBORAH B. RANDALL, Senior Secretary/Project Assistant
Preface
In 1985, Public Law 99-145 mandated an "expedited" effort to dispose of M55 rockets containing unitary chemical warfare agents because of the potential for self-ignition of these particularly hazardous munitions during storage. This program soon expanded into the Army Chemical Stockpile Disposal Program (CSDP), whose mission was to eliminate the entire stockpile of unitary chemical weapons. The CSDP developed the current baseline incineration system. In 1992, after setting several intermediate goals and dates, Congress enacted Public Law 102-484, which directed the Army to dispose of the entire stockpile of unitary chemical warfare agents and munitions by December 31, 2004. Since 1987, the Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program (the Stockpile Committee) of the National Research Council (NRC) has overseen the Army's disposal program and has endorsed the baseline incineration process as an adequate technology for destroying the stockpile.
Growing public concerns about and opposition to incineration, coupled with the rising cost of the CSDP, have raised interest in alternatives. The Stockpile Committee, which has been following the state of alternative technologies, reviewed a NRC study of alternative technologies by a separate NRC committee and in 1994 recommended that the Army continue research on neutralization.
In the summer of 1995, the assistant secretary of the Army for research, development and acquisition informally explored the issue of examining alternative chemical disposal technologies with the Stockpile Committee. Following numerous discussions between the Army and the NRC, a decision was made to conduct a new NRC study to reexamine the status of a limited number of maturing alternative chemical disposal technologies (including the two neutralization-based processes on which the Army was currently conducting research) for possible implementation at the two bulk-storage sites at Aberdeen Proving Ground, Maryland, and the Newport Chemical Activity, Indiana.
The NRC established the Panel on Review and Evaluation of Alternative Disposal Technologies (the AltTech Panel) to conduct the new study. The panel includes six members of the Stockpile Committee, who have accumulated experience in dealing with the complex issues involved in monitoring the destruction of the unitary chemical agent stockpile, and eight new members who possess specific expertise for thoroughly evaluating the alternative technologies.
The panel received detailed briefings from the Army and the three companies that had proposed alternative technologies for the Army's consideration (hereafter, the technology proponent companies, or TPCs). Before the briefings on individual technologies, the panel compiled a questionnaire to elicit information needed to evaluate the technologies on a range of factors. The questionnaire was sent to the TPCs and to the Army team for neutralization-based technologies. The responses to the questionnaires and subsequent follow-up conversations were supplemented with site visits by teams of panel members to inspect each TPC's technology.
In addition to gathering technical information on the alternative technologies, the AltTech Panel met with members of the public from the communities near the Aberdeen and Newport sites. These meetings included public forums, which were open to all, and meetings with the Citizens Advisory Commissions for Maryland and Indiana. (These commissions are formal groups established as a channel of communication with communities near stockpile sites.) The panel also met with regulators from the state agencies responsible for review and approval of permits required by agent destruction facilities and for implementing other relevant regulations and state laws.
Parallel with the AltTech Panel activities and under Army supervision, the TPCs conducted small-scale tests of their technologies on actual chemical agent. The Army also contracted with MitreTek Systems, Inc., to perform a preliminary accident hazard assessment for
each technology. The test results and the contractor's report were provided to the panel for consideration.
The activities described above formed the basis for the findings and recommendations in this report.
To the members of the Stockpile Committee who agreed to perform double duty by serving on the AltTech Panel, I owe a great deal of gratitude. To the new members, I want to express my appreciation for the fresh insights they provided. Without their help, the evaluations would have suffered. I thank all these volunteers for the time and energy they contributed at the expense of other responsibilities. The travel and inconvenience of conducting a fast-track study were considerable; each member spent a great deal of time analyzing information, arriving at consensus evaluations and judgments, and capturing the results in writing. On behalf of the National Research Council, I thank each of them.
The AltTech panel recognizes and appreciates the substantial support provided by the Army staff and the program office for chemical demilitarization. The panel also recognizes the efforts of the TPCs. You were all cordial, responsive, forthcoming, and generous with your time. Thank you.
The panel greatly appreciates the support of panel activities and the timely production of the report by NRC staff members Michael Clarke, Margo Francesco, and Deborah Randall as well as the services of the reports officer of the Commission on Engineering and Technical Systems, Carol Arenberg, the consulting technical writer, Robert Katt, the electronic composition by Mary Beth Mason and Sally Naas and the graphics by consultant James Butler.
RICHARD S. MAGEE, CHAIR
PANEL ON REVIEW AND EVALUATION OF ALTERNATIVE CHEMICAL DISPOSAL TECHNOLOGIES
Tables and Figures
Tables
1-1 |
Physical Properties of Chemical Warfare Agents |
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1-2 |
Chemical Munitions Stored in the Continental United States |
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1-3 |
Composition of VX from Ton Containers Stored at Newport |
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1-4 |
Composition of HD from Ton Containers Stored at Aberdeen |
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4-1 |
Calculated Solubility of VX and Cofeed Elements in Iron at 1600°C and Time to Saturate the Iron Bath at Processing Conditions |
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4-2 |
Status of CEP Units from Bench Scale to Commercial- Scale |
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4-3 |
CEP Heat and Material Balances for VX Gas Handling |
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4-4 |
Expected Composition of CEP Gas Streams prior to and after Combustion in a Gas Turbine Generator |
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4-5 |
Nominal Composition of CPU-2 Metal Phase |
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4-6 |
Flow Rates in the Gas Handling Train for HD Processing |
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4-7 |
Summary of Utility Requirements for a CEP Facility |
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4-8 |
Specific Processing Rates of Bench Tests Relative to Full-Scale Design Rates |
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4-9 |
CEP Unit Operations by Process Area |
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4-10 |
Critical Activities in the Program Schedule |
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5-1 |
Feed Stream Compositions and Quantities |
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5-2 |
Mass Balance for HD Destruction |
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5-3 |
Mass Balance for VX Destruction |
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5-4 |
Elements of a Supervisory Control and Data System for Silver II |
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5-5 |
Hazard and Operability Challenges |
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6-1 |
Composition of Reformer Gas |
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6-2 |
Daily Energy Requirements to Process HD at 9 Metric Tons Per Day |
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7-1 |
Aquatic Toxicity of Bioreactor Feed and Effluent from Laboratory and Bench-Scale SBR Testing |
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7-2 |
Summary of Unit Operations and Inputs Required for Each Process Configuration |
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7-3 |
Summary of Waste Streams and Quantities for Each Process Configuration |
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7-4 |
Summary of Energy Requirements for Each Process Configuration |
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8-1 |
Toxicity of VX and VX Hydrolysates as Measured by 24-Hour Intravenous LD50 in Mice |
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9-1 |
Summary of Community Issues Raised in Public Meetings with the AltTech Panel |
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10-1 |
Process Engineering Data for Alternative Technologies |
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10-2 |
Summary of Comparison Criteria for VX at Newport and HD at Aberdeen |
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E-1 |
Elemental Breakdown of Mass Balances for VX Destruction |
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E-2 |
Elemental Breakdown of Mass Balances for HD Destruction |
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F-1 |
Material Flows to and from GPCR Reactor |
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F-2 |
Material Balance for HD in the ECO LOGIC Process |
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G-1 |
Process Inputs for HD Neutralization, Configuration 1 |
G-2 |
Process Outputs for HD Neutralization, Configuration 1 |
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G-3 |
Process Inputs for HD Neutralization, Configuration 2 |
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G-4 |
Process Outputs for HD Neutralization, Configuration 2 |
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G-5 |
Process Inputs for HD Neutralization, Configuration 3 |
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G-6 |
Process Outputs for HD Neutralization, Configuration 3 |
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G-7 |
Process Inputs for HD Neutralization, Configuration 4 |
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G-8 |
Process Outputs for HD Neutralization, Configuration 4 |
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H-1 |
Process Inputs for VX Neutralization |
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H-2 |
Process Outputs for VX Neutralization |
Figures
1-1 |
Types of agent and munitions and percentage of total agent stockpile at each storage site |
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4-1 |
Primary agent and residue process flows for a chemical demilitarization CEP facility |
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4-2 |
High level block diagram for the destruction of HD by CEP |
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4-3 |
High level block diagram for the destruction of VX by CEP |
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4-4 |
Block flow diagram for CEP facility |
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4-5 |
CEP process flow diagram for VX feed injection system into CPU-2, with premelting chamber for ton containers |
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4-6 |
CEP process flow diagram for VX CPU-2 offgas treatment |
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4-7 |
CEP process flow diagram for VX CPU-1 gas handling train |
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4-8 |
CEP process flow diagram for VX relief system |
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4-9a |
CPU block diagram and material balances for HD treatment |
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4-9b |
CPU block diagram and material balances for HD treatment |
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4-10a |
CPU block diagram and material balances for VX treatment |
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4-10b |
CPU block diagram and material balances for VX treatment |
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4-11 |
CEP program schedule and phasing concept |
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5-1 |
Schematic diagram of the basic cell module for mediated electrochemical oxidation |
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5-2 |
Exploded view of the FM21 electrochemical cell |
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5-3 |
Block flow diagram of the Silver II process total system |
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5-4 |
Process flow diagram for a single Silver II cell |
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5-5 |
Anolyte offgas condenser, NOx reformer, silver nitrate recovery circuit, and combined offgas treatment circuit |
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5-6 |
Silver management system |
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5-7 |
Silver chloride treatment system |
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5-8 |
Process flow diagram for services and utilities |
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5-9 |
Schematic flow diagram of the FM01 test rig |
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6-1 |
Schematic diagram of commercial-scale process |
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6-2 |
Main reactor in the gas-phase chemical reduction process |
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7-1 |
Process Configuration 1: Neutralization followed by on-site biodegradation, including water recycling and photochemical oxidation of VOCs |
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7-2 |
Process Configuration 2: Neutralization followed by on-site biodegradation. VOCs are treated by photochemical oxidation. Biodegradation process effluent is discharged to a FOTW |
7-3 |
Process Configuration 3: Neutralization followed by on-site biodegradation. VOCs are shipped to an off-site TSDF. Biodegradation process effluent is discharged to a FOTW |
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7-4 |
Process Configuration 4: Neutralization followed by off-site biodegradation of the hydrolysate at a TSDF. VOCs remain in the hydrolysate |
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7-5 |
Chemical reactions during the hydrolysis of HD |
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8-1 |
Block flow diagram of VX neutralization with sodium hydroxide and sodium hypochlorite |
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8-2 |
Reaction scheme for neutralization of VX with sodium hydroxide |
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G-1 |
HD neutralization, configuration 1. Neutralization followed by on-site biodegradation, including water recycling and photochemical oxidation of VOCs |
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G-2 |
HD neutralization, configuration 2. Neutralization followed by on-site biodegradation. VOCs are treated by photochemical oxidation. Biodegradation process effluent is discharged to a FOTW |
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G-3 |
HD neutralization, configuration 3. Neutralization followed by on-site biodegradation. VOCs are shipped to an off-site TSDF. Biodegradation process effluent is discharged to a FOTW |
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G-4 |
HD neutralization, configuration 4. Neutralization followed by off-site biodegradation of hydrolysate at a TSDF. VOCs remain in the hydrolysate |
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H-1 |
VX neutralization and treatment with oxidizing agent, followed by off-site treatment of oxidized hydrolysate |
Abbreviations and Acronyms
ACAMS
automatic continuous air monitoring system
APG
Aberdeen Proving Ground
ASME
American Society of Mechanical Engineers
ALTTECH
Panel on Review and Evaluation of Alternative Chemical Disposal Technologies
BDAT
best demonstrated available technology
CAC
Citizens Advisory Commission
CAIN
Citizen Against Incineration at Newport
CEPTM
catalytic extraction processing
CFR
Code of Federal Regulations
CPU
catalytic processing unit
CSDP
Army Chemical Stockpile Disposal Program
CSEPP
Chemical Stockpile Emergency Preparedness Program
CWC
Chemical Weapons Convention
CWWG
Chemical Weapons Working Group
DAAMS
depot area agent monitoring system
DC
direct current
DCS
distributed control system
DDT
dichlorodiphenyltrichloroethane
DRE
destruction removal efficiency
EMPA
ethylmethylphosphonic acid
EPA
Environmental Protection Agency
FMEA
failure modes and effects analysis
FOTW
federally owned treatment works
GB
sarin (a nerve agent, o-isopropylmethylphosphonofluoridate)
GC/MS
gas chromatography followed by mass spectrometry
HD
distilled mustard agent, bis(2-chloroethyl sulfide)
HLE
high level exposure (a statutory standard for exposure to an airborne hazardous substance)
HRT
hydraulic residence time
HVAC
heating, ventilation, and air conditioning
IDLH
immediately dangerous to life and health (a statutory standard for exposure to an airborne hazardous substance
JACADS
Johnston Atoll Chemical Agent Disposal System
LD50
lethal dose to 50 percent of a test population
MEA
monolethanolamine
MLSS
mixed liquors suspended solids
MPA
methylphosphonic acid
MPL
maximum permissible limit (a statutory standard for exposure to an airborne hazardous substance)
NPDES
national pollutant discharge elimination system
NRC
National Research Council
OPMAT&A
Office of the Product Manager for Alternative Technologies and Approaches
PCB
polychlorinated biphenyl
PMCD
program manager for chemical demilitarization
POTW
publicly owned treatment works
PPB
parts per billion
PPE
personal protective equipment
RCRA
Resource Conservation and Recovery Act
RPU
radioactive processing unit
SBR
sequencing batch reactor
SBV
sequential batch vaporizer
SCADA
supervisory control and data acquisition
SRT
solid residence time
TAGA
trace atmospheric Gas Analyzer
TPC
technology proponent company
TSDF
treatment, storage, and disposal facility
TWA
time-weighted average
TOCDF
Tooele Chemical Agent Disposal Facility
VOC
volatile organic compound
VX
a nerve agent (O-ethyl-S[2-diisopropyl amino)ethyl] methylphosphonothiolate