ANALYSIS OF ENGINEERING DESIGN STUDIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS AT BLUE GRASS ARMY DEPOT
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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 DAAD19-00-C-0009 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 author(s) and do not necessarily reflect the view of the organizations or agencies that provided support for the project.
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COMMITTEE ON REVIEW AND EVALUATION OF ALTERNATIVE TECHNOLOGIES FOR DEMILITARIZATION OF ASSEMBLED CHEMICAL WEAPONS: PHASE II
ROBERT A. BEAUDET, Chair,
University of Southern California, Los Angeles
RICHARD J. AYEN,
Waste Management, Inc. (retired), Wakefield, Rhode Island
JOAN B. BERKOWITZ,
Farkas Berkowitz and Company, Washington, D.C.
RUTH M. DOHERTY,
Naval Surface Warfare Center, Indian Head, Maryland
WILLARD C. GEKLER,
ABS Consulting/PLG
(retired),
Irvine, California
SHELDON E. ISAKOFF,
E.I. du Pont de Nemours and Company
(retired),
Chadds Ford, Pennsylvania
HANK C. JENKINS-SMITH,
Texas A&M University, College Station
DAVID S. KOSSON,
Vanderbilt University, Nashville, Tennessee
FREDERICK J. KRAMBECK, Consultant,
Alexandria, Virginia
JOHN A. MERSON,
Sandia National Laboratories, Albuquerque, New Mexico
WILLIAM R. RHYNE, Consultant,
Oak Ridge, Tennessee
STANLEY I. SANDLER,
University of Delaware, Newark
WILLIAM R. SEEKER,
General Electric Energy and Environmental Research Corporation, Irvine, California
LEO WEITZMAN,
LVW Associates, Inc., West Lafayette, Indiana
Board on Army Science and Technology Liaison
JOSEPH J. VERVIER,
ENSCO, Inc., Melbourne, Florida
Staff
PATRICIA P. PAULETTE, Study Director
HARRISON T. PANNELLA, Program Officer
GWEN ROBY, Senior Project Assistant (through July 2002)
JAMES C. MYSKA, Research Associate
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
ROBERT L. CATTOI,
Rockwell International (retired), Dallas, Texas
RICHARD A. CONWAY,
Union Carbide Corporation
(retired),
Charleston, West Virginia
GILBERT F. DECKER,
Walt Disney Imagineering
(retired),
Glendale, California
ROBERT R. EVERETT,
MITRE Corporation
(retired),
New Seabury, Massachusetts
PATRICK F. FLYNN,
Cummins Engine Company, Inc.
(retired),
Columbus, Indiana
HENRY J. HATCH, Army Chief of Engineers (retired),
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
(retired),
Alexandria, Virginia
CLARENCE W. KITCHENS,
IIT Research Institute, Alexandria, Virginia
SHIRLEY A. LIEBMAN,
CECON Group
(retired),
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
(retired),
Ellicott City, Maryland
JOHN H. MOXLEY,
Korn/Ferry International, Los Angeles, California
STEWART D. PERSONICK,
Drexel University, Philadelphia, Pennsylvania
MILLARD F. ROSE,
Radiance Technologies, Huntsville, Alabama
JOSEPH J. VERVIER,
ENSCO, Inc., Melbourne, Florida
Staff
BRUCE A. BRAUN, Director
MICHAEL A. CLARKE, Associate Director
WILLIAM E. CAMPBELL, Administrative Coordinator
CHRIS JONES, Financial Associate
GWEN ROBY, Administrative Assistant (through July 2002)
DEANNA P. SPARGER, Senior Project Assistant
DANIEL E.J. TALMAGE, JR., Research Associate
Preface
The United States has been destroying its chemical munitions for well over a decade. Initially, the U.S. Army, with recommendations from the National Research Council (NRC), decided to use incineration as its destruction method at all sites. However, citizens in some states with stockpile storage sites have opposed incineration on the grounds that it is impossible to determine the exact nature of the effluents escaping from the stacks. Although the Army has continued to pursue incineration at four of the eight storage sites in the continental United States, in response to growing public opposition to incineration in Maryland and Indiana and a 1996 report by the NRC, Review and Evaluation of Alternative Chemical Disposal Technologies, the Army is developing alternative processes to neutralize chemical agents by hydrolysis. These processes will be used to destroy the VX nerve agent at Newport, Indiana, and the mustard agent at Aberdeen, Maryland, both of which are stored in bulk one-ton containers.
In 1996, persuaded by the public opposition in Lexington, Kentucky, and Pueblo, Colorado, 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.” The Army established a Program Manager for Assembled Chemical Weapons Assessment (PMACWA) to respond to Congress. In Public Law 104-208, PMACWA was required to “identify and demonstrate not less than two alternatives to the baseline incineration process for the demilitarization of assembled chemical munitions.” Following an elaborate selection process and the demonstration of six technologies, PMACWA selected three as candidates for destroying the weapons at Blue Grass Army Depot. The three technologies—AEA SILVER II™, Eco Logic, and General Atomics Total Solution—have since progressed to the engineering design phase of DoD’s Assembled Chemical Weapons Assessment (ACWA) program. This report evaluates the engineering design studies for these three candidates.
Congress mandated that the Army coordinate with the NRC during the ACWA program. In response, the NRC established the Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons (ACW I Committee) in 1997 to oversee this program. The issue before the committee was not whether incineration is an adequate technology but, given that some citizens are strongly opposed to incineration, whether other disposal methods acceptable to the stakeholders could be used. A second committee, the Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: Phase II (ACW II Committee), was established in the spring of
2000 for the engineering design phase of the ACWA program.
This report provides an independent technical evaluation of the engineering-design packages of the three candidate processes being considered for use at the Blue Grass Army Depot. A separate chapter is devoted to each technology package that addresses all aspects of demilitarization, from disassembly of the weapons to disposal of the waste streams. Specific recommendations related to the technology are found in these chapters but are not repeated in the Executive Summary. The committee’s evaluation is expected to contribute to DoD’s record of decision (ROD) for the selection of a technology for the Lexington Blue Grass site. The ROD was scheduled to be released in September 2002. Therefore, to be of value in the selection process, this report had to be published by August 2002. Unfortunately, not all of the tests associated with the three packages were completed at the time that data gathering for this report was terminated to meet the mid-July deadline.
This report documents the ACW II Committee’s completion of its final task. Since 1997, the ACW I and ACW II Committees have produced four full reports and one letter report (NRC, 1999, 2000a, 2001a, 2001b, 2001c). Usually, NRC study committees are constituted to produce only a single report during their tenure. The aim of the ACW I and ACW II Committees has been to provide constructive advice to PMACWA. Questions that committee members asked at meetings attended by the ACWA team and its support contractors have supplemented the advice contained in the reports.
The environment in which the ACW II Committee works has changed since the events of September 11, 2001. Destruction of the stockpile has become more urgent, and this has made the general findings in this report more pertinent than ever. The committee confirms its belief that technologies using hydrolysis to destroy both agent and energetics are now mature, safe, straightforward, and effective. Moreover, the products from the hydrolysis no longer exhibit the acute toxicity of the agents and could be treated at commercial toxic or hazardous waste facilities if the states permit it. A precedent was established at Aberdeen Proving Ground: The mustard in bulk containers is being destroyed by hydrolysis, using mostly the facilities that already exist on site and sending the products to a commercial treatment facility.
I wish to express my gratitude to the members of the ACW II Committee, all of whom served as volunteers and most of whom served with me on the ACW I Committee. They have all given unselfishly of their time and knowledge. These technology packages are complex and voluminous, and it required extensive work to properly evaluate them. The committee members’ areas of expertise include chemical processing, biological remediation, environmental regulations and permitting, energetic materials, public involvement, and public acceptance. Each member attended plenary meetings, visited the headquarters of technology providers and test sites, observed design-review sessions, and studied the extensive literature, including engineering charts and diagrams, given by the technology providers. Fortunately for me, the members are all brighter and more experienced in chemical processing than am I, a physical chemist.
The committee recognizes and appreciates the extensive support of the Army ACWA team and the committee interactions with stakeholders and the Dialogue group, particularly the four members of the Dialogue known as the Citizens Advisory Technical Team (CATT). Members of the CATT attended all open meetings of the committee and shared information and their views with us. I believe our relationship with the sponsor, PMACWA, and his team and support contractors has been effective and constructive and that the committee has been given the best available information to conduct this evaluation of the three technologies.
The committee also appreciates the openness and cordiality of the representatives of the technology providers. They and the Army provided it with early drafts of test reports and other documentation to facilitate the writing of this report while work was still in progress.
A study like this always requires extensive logistic support, and the committee is indebted to the NRC staff for their assistance. I would like to acknowledge particularly the close working relationship I had with the NRC study director for this study, Patricia P. Paulette. Working as a team in leading this study, she and I spoke on the phone daily and e-mailed each other incessantly. Invaluable contributions were also made by Harrison T. Pannella, who took extensive notes at all of our meetings, edited draft text for the report, and provided suggestions for organizing the report. In addition, Gwen Roby provided the logistic support that freed us to concentrate on our task. Assistance was also pro-
vided by James C. Myska. The report was edited by Liz Fikre of the Division on Engineering and Physical Sciences. I am also indebted to colleagues in the Chemistry Department at the University of Southern California, who willingly substituted for me in 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: Phase II
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 institution in making its 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 review comments and draft manuscript remain confidential to protect the integrity of the deliberative process. We wish to thank the following individuals for their review of this report:
Ronald Ballinger, Massachusetts Institute of Technology,
Steven Konkel, Eastern Kentucky University,
Richard S. Magee, Carmagen Consulting,
Walter May (NAE), Consultant, Urbana, Illinois,
Digby McDonald, Pennsylvania State University,
Ray McGuire, Consultant, Livermore, California,
George Parshall (NAS), Chemical Science (retired),
and
Bruce E. Watkins, Lawrence Livermore National Laboratory.
Although the reviewers listed above have provided many constructive comments and suggestions, they were not asked to endorse the conclusions or recommendations, nor did they see the final draft of the report before its release. The review of this report was overseen by Hyla S. Napadensky (NAE), Napadersky Energetics, Inc. (retired). Appointed by the National Research Council, she was responsible for making certain that an independent examination of this report was carried out in accordance with institutional procedures and that all review comments were carefully considered. Responsibility for the final content of this report rests entirely with the authoring committee and the institution.
Figures and Tables
FIGURES
ES-1 |
AEA SILVER II™ demilitarization process, |
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ES-2 |
Schematic flow diagram of the Eco Logic technology package, |
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ES-3 |
GATS Blue Grass block flow diagram, |
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3-1 |
AEA SILVER II™ demilitarization process, |
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3-2 |
SILVER II™ process system for agent or energetic destruction, |
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3-3 |
AEA 12-kW SILVER II™ test setup for EDS II, |
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4-1 |
Schematic flow diagram of the Eco Logic technology package, |
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4-2 |
Schematic diagram of Foster Wheeler transpiring-wall SCWO reactor, |
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4-3 |
CO and HC spiking profiles during transpiring-wall SCWO operation, |
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5-1 |
GATS Blue Grass block flow diagram, |
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5-2 |
GATS SCWO liner materials and configuration, |
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A-1 |
A 155-mm projectile, M110, H/HD; M121A1, VX, |
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A-2 |
An 8-inch howitzer projectile, M426, GB, |
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A-3 |
A 115-mm rocket, M55, GB, VX, |
TABLES
ES-1 |
Description of the Chemical Weapons in the Blue Grass Army Depot Stockpile, |
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1-1 |
The Original Seven Candidate Technologies Under Consideration for the ACWA Program, |
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1-2 |
Physical Properties of Chemical Warfare Agents, |
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1-3 |
Description of the Chemical Weapons in the Blue Grass Army Depot Stockpile, |
1-4 |
Composition of M28 Propellant, |
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2-1 |
Nominal Composition of Energetic Materials Used in Chemical Munitions, |
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2-2 |
Conditions Used in the Commissioning Runs at HAAP, |
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2-3 |
Test Matrix for the Army Hydrolysis Study at HAAP, |
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2-4 |
Residual Energetic Material in End-of-Run Hydrolysate Samples, |
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2-5 |
Picrate Formation in the Hydrolysis of Energetics, |
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3-1 |
Key Plant Performance Requirements for SILVER II™ Technology at Blue Grass Army Depot, |
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3-2 |
Summary of SILVER II™ Plant Electrochemical Cells, |
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3-3 |
EDS Tests and Studies Used for SILVER II™, |
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3-4 |
AEA 12-kW SILVER II™ Tests, |
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3-5 |
Typical Transfer Rates for Concentrations of 0.5 Moles/L of Feed, |
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3-6 |
Materials Selection for Key Sections of a SILVER II™ Full-Scale Plant, |
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4-1 |
Summary of the Eco Logic Technology, |
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5-1 |
Key Design Parameters for GATS ERH and PRH, |
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5-2 |
Key Design Parameters for Each GATS Cryofracture Train, |
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5-3 |
Key Design Parameters for the GATS Projectile Agent Hydrolysis System, |
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5-4 |
SCWO System Design Parameters, |
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5-5 |
Waste Materials to Be Processed per Munition, |
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5-6 |
Munition Processing Rates and Durations, |
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5-7 |
Major SCWO System Test Campaigns Conducted in Support of GATS Design Considered by the Committee, |
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5-8 |
Corrosion of Titanium Liners During GATS EDS Workup Tests with HD Hydrolysate, |
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5-9 |
Liner Lifetime and Replacement Calculations for Blue Grass Facility SCWO Reactors, |
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5-10 |
500-hr Test Effluent Quality, |
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5-11 |
Status of Recent Developments on Treatment of Various Waste Streams by SCWO, |
Acronyms, Abbreviations, and Chemical Symbols
ACAMS
automatic continuous air monitoring system
ACW I
Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons
ACW II
Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: Phase II
ACWA
Assembled Chemical Weapons Assessment
Ag2+
silver ion having a valence of 2
AgCl
silver chloride
a-HAX
solution containing potassium hydroxide and humic acid
AHSV
agent hydrolysate surge vessel
ANR
agent neutralization reactor
AQS
agent quantification system
ARDEC
Armament Research, Development and Engineering Center
BIF
boiler and industrial furnace
BPCS
basic process control system
BWM
burster washout machine
CAMDS
chemical agent munitions disposal system
CATOX
catalytic oxidation
CEES
chloroethyl ethyl sulfide
CEMS
continuous emission monitoring system
CO
carbon monoxide
CO2
carbon dioxide
COINS
continuous indexing neutralization system
Composition B
an energetic material that contains (nominally) 59.5 percent RDX, 39.5 percent TNT, and 1.0 percent wax
CSDP
Chemical Stockpile Disposal Program
CST
continuous steam treater
CWC
Chemical Weapons Convention
DAAMS
depot area air monitoring system
Demo I
Demonstration I (demonstration testing of the initial three technologies selected for the first phase of ACWA technology testing)
Demo II
Demonstration II (demonstration testing of the second set of three technologies selected for the first phase of ACWA technology testing)
DMMP
dimethyl methylphosphonate
DoD
U.S. Department of Defense
DPE
demilitarization protective ensemble
DRE
destruction and removal efficiency
DSHS
dunnage shredding and handling system
DTS
dunnage treatment system
ECR
explosion containment room
EDP
engineering design package
EDS
engineering design study
EPA
Environmental Protection Agency
EPDM
ethylene propylene dimer
EPDR
energetics/propellant deactivation reactor
ERD
energetics rotary deactivator
ERH
energetics rotary hydrolyzer
ESS
emergency shutdown system
EST
engineering-scale test
GATS
General Atomics Total Solution (technology package)
GB
a nerve agent
GC/MS
gas chromatography/mass spectrometry
GPCR
gas-phase chemical reduction
H
undistilled mustard agent
H2
hydrogen
HAAP
Holston Army Ammunition Plant
HD
distilled mustard agent
HDC
heated discharge conveyor
HEPA
high-efficiency particulate air (filter)
HF
hydrofluoric acid
HMX
cyclotetramethylene-tetranitramine (an energetic material)
HNO3
nitric acid
HPLC
high-performance liquid chromatography
HRA
health risk assessment
HT
a mixture of H and T mustard agents
HVAC
heating, ventilating, and air-conditioning
ICB
immobilized-cell bioreactor
ICI
Imperial Chemical Industries
IITRI
Illinois Institute of Technology Research Institute
IMPA
isopropyl methylphosphonic acid
IRS
impurities removal system
JACADS
Johnston Atoll Chemical Agent Disposal System
KOH
potassium hydroxide
kPa
kilopascal (unit of pressure; 6.895 kPa equals 1 pound per square inch)
kPag
kilopascals gauge
kW
kilowatt
LANL
Los Alamos National Laboratory
LMIDS
Lockheed Martin Integrated Demilitarization System
M
molar concentration
M28
energetic material used for propulsion of certain assembled chemical weapons
MACT
maximum achievable control technology
MAV
modified ammunition van
MDB
munitions demilitarization building
MDM
munitions demilitarization machine
MEO
mediated electrochemical oxidation
MPA
methylphosphonic acid
MPa
megapascals
MPT
metal parts treater
MSB
munitions storage building
N2
nitrogen
N2O
nitrous oxide
NEPA
National Environmental Policy Act
NOx
nitrogen oxides
NRC
National Research Council
NSWC
Naval Surface Warfare Center
O2
oxygen
OB/OD
open burn/open detonation
PA
picric acid
PCP
pentachlorophenol
PCR
propellant collection reactor
PFA
perfluoroalkoxy
PGB
product gas burner
PHA
preliminary hazards analysis
PID
proportional integral differential controller
PLC
programmable logic control
PMACWA
Program Manager for Assembled Chemical Weapons Assessment
PMD
projectile mortar demilitarization (machine)
POTW
publicly owned treatment works
ppm
parts per million
PRH
projectile rotary hydrolyzer
PRR
propellant removal room
psi
pounds per square inch
psig
pounds per square inch gauge
PTFE
polytetrafluoroethylene (Teflon)
PVDF
polyvinylidene fluoride
PWS
projectile washout system
QRA
quantitative risk assessment
R3
resource, recovery, and recycling (process)
R&D
research and development
RAAP
Radford Army Ammunition Plant
RCRA
Resource Conservation and Recovery Act
RDM
rocket dismantling machine
RDX
cyclotrimethylenetrinitramine (an energetic material)
RFP
request for proposals
ROD
record of decision
RWM
rotary washout machine
scfm
standard cubic feet per minute
SCWO
supercritical water oxidation
SET™
solvated electron technology
SILVER II™
electrochemical oxidation using Ag2+ in nitric acid
SOx
sulfur oxides
SO2
sulfur dioxide
SVOC
semivolatile organic compound
TACOM
Tank-Automotive and Armaments Command
TBA
tributylamine
TCLP
toxicity characteristic leaching procedure
THC
total hydrocarbons
TNB
trinitrobenzene
TNBA
trinitrobenzoic acid
TNT
trinitrotoluene (an energetic material)
TOC
total organic carbon
TRBP
thermal reduction batch processor
TW-SCWO
transpiring-wall supercritical water oxidation
UPA
unpack area
VOC
volatile organic compound
VX
a nerve agent
WHEAT
water hydrolysis of explosives and agent technology
WMDM WHEAT
multipurpose demilitarization machine
WPMD
WHEAT projectile/mortar disassembly (machine)
3X
At the 3X decontamination level, solids are decontaminated to the point that agent concentration in the headspace above the encapsulated solid does not exceed the health-based, 8-hour, time-weighted average limit for worker exposure. The level for mustard agent is 3.0 mg/m3 in air. Materials classified as 3X may be handled by qualified plant workers using appropriate procedures but are not releasable to the environment or for general public reuse. In specific cases in which approval has been granted, a 3X material may be shipped to an approved hazardous waste treatment facility for disposal in a landfill or for further treatment.
5X
Treatment of solids to a 5X decontamination level is accomplished by holding a material at 1,000°F for 15 minutes. This treatment results in completely decontaminated material that can be released for general use or sold (e.g., as scrap metal) to the general public in accordance with applicable federal, state, and local regulations.