NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of the committee responsible for the report were chosen for their special competencies and with regard for appropriate balance.
The National Academy of Sciences is a private, nonprofit, self-perpetuating society of 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 vice chairman, respectively, of the National Research Council.
This is a report of work supported by Contract DAAG55-98-C-0021 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.
International Standard Book Number 0-309-06043-5
Limited copies are available from:
Board on Army Science and Technology
National Research Council
2101 Constitution Avenue, N.W.
Washington, DC 20418
(202) 334-3118
Copies are available for sale from: National Academy Press
2101 Constitution Avenue, N.W. Washington, DC 20418 800-624-6242 or 202-334-3313
Copyright 1998 by the National Academy of Sciences. All rights reserved.
Printed in the United States of America.
COMMITTEE ON REVIEW AND EVALUATION OF THE ARMY CHEMICAL STOCKPILE DISPOSAL PROGRAM
RICHARD S. MAGEE, chair,
New Jersey Institute of Technology, Newark
ELISABETH M. DRAKE, vice chair,
Massachusetts Institute of Technology, Cambridge
DENNIS C. BLEY,
Buttonwood Consulting, Inc., Oakton, Virginia
J. ROBERT GIBSON,
DuPont Agricultural Products, Wilmington, Delaware
MICHAEL R. GREENBERG,
Rutgers, The State University of New Jersey, New Brunswick
KATHRYN E. KELLY,
Delta Toxicology, Crystal Bay, Nevada
CHARLES E. KOLB,
Aerodyne Research, Inc., Billerica, Massachusetts
DAVID S. KOSSON,
Rutgers, The State University of New Jersey, New Brunswick
JAMES F. MATHIS,
Exxon Corporation (retired), Summit, New Jersey
WALTER G. MAY,
University of Illinois, Urbana
ALVIN H. MUSHKATEL,
Arizona State University, Tempe
GEORGE W. PARSHALL,
DuPont Company (retired), Wilmington, Delaware
H. GREGOR RIGO,
Rigo & Rigo Associates, Inc., Berea, Ohio
ARNOLD F. STANCELL,
Georgia Institute of Technology, Atlanta
WILLIAM TUMAS,
Los Alamos National Laboratory, Los Alamos, New Mexico
Board on Army Science and Technology Liaison
RICHARD A. CONWAY,
R.A. Conway Associates, Charleston, West Virginia
Staff
BRUCE A. BRAUN, Director,
Division of Military Science and Technology
DONALD L. SIEBENALER, Study Director
HARRISON T. PANNELLA, Consultant
SHIREL R. SMITH, Senior Project Assistant
BOARD ON ARMY SCIENCE AND TECHNOLOGY
CHRISTOPHER C. GREEN, chair,
General Motors Corporation, Warren, Michigan
WILLIAM H. FORSTER, vice chair,
Northrop Grumman Corporation, Baltimore, Maryland
GARY L. BORMAN,
University of Wisconsin, Madison
RICHARD A. CONWAY,
Union Carbide Corporation, Charleston, West Virginia
GILBERT F. DECKER, Consultant,
Los Gatos, California
LAWRENCE J. DELANEY,
Delaney Group, Potomac, Maryland
MARYE ANNE FOX,
University of Texas, Austin
ROBERT J. HEASTON,
Guidance and Control Information Analysis Center (retired), Naperville, Illinois
ELVIN R. HEIBERG, III,
Heiberg Associates, Inc., Mason Neck, Virginia
GERALD J. IAFRATE,
University of Notre Dame, Indiana
KATHRYN V. LOGAN,
Georgia Institute of Technology, Atlanta
THOMAS L. MCNAUGHER,
RAND Corporation, Washington, D.C.
JOHN H. MOXLEY, III,
Korn/Ferry International, Los Angeles, California
STEWART D. PERSONICK,
Bell Communications Research, Inc., Morristown, New Jersey
MILLARD F. ROSE,
Auburn University, Auburn, Alabama
CLARENCE G. THORNTON,
Army Research Laboratories (retired), Colts Neck, New Jersey
JOHN D. VENABLES,
Venables and Associates, Towson, Maryland
JOSEPH J. VERVIER,
ENSCO, Inc., Melbourne, Florida
ALLEN C. WARD,
Ward Synthesis, Inc., Ann Arbor, Michigan
Staff
BRUCE A. BRAUN, Director
MARGO L. FRANCESCO, Staff Associate
ALVERA GIRCYS, Financial Associate
DEANNA SPARGER, Project Assistant
Preface
The United States has maintained a stockpile of highly toxic chemical agents and munitions for more than half a century. In 1985, Public Law 99-145 mandated an “expedited” effort to dispose of M55 rockets containing unitary chemical warfare agents because of their potential for self-ignition. 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 for that purpose. Since 1987, the National Research Council (NRC), through its Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program (Stockpile Committee), has overseen the Army's disposal program and has endorsed the baseline incineration system as an adequate technology for destroying the stockpile. 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.
In response to growing public concerns about, and opposition to, incineration, the Army has been investigating alternatives. In 1993-1994, the Stockpile Committee reviewed an earlier NRC study of alternative technologies and recommended that the Army continue research on four alternative technology combinations for agent destruction, all based on neutralization (chemical hydrolysis). The committee was concerned, however, that neutralization alone might not be sufficient to meet destruction and disposal requirements and recommended that the Army consider four different post-neutralization treatment options: biodegradation; incineration; wet air oxidation followed by biological oxidation; and supercritical water oxidation. The Army decided that it could pursue only two options within its funding and time constraints: neutralization; and neutralization followed by biological treatment.
In 1995, at the request of the assistant secretary of the Army for research, development and acquisition, the NRC established the Panel on Review and Evaluation of Alternative Disposal Technologies (AltTech Panel) 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 then conducting research) for possible implementation at the two bulk-storage sites at Aberdeen Proving Ground, Maryland, and the Newport Chemical Activity, Indiana.
The AltTech Panel's NRC report recommended that the Army pilot-test VX neutralization with sodium hydroxide solution at Newport. The report also recommended that, if on-site disposal of the VX hydrolysate (from the neutralization process) was preferable to shipping it off site for treatment, existing commercial processes other than biodegradation should be considered because research on existing biodegradation processes has shown that they do not achieve adequate destruction.
In 1997, after reviewing several secondary treatment options, the Army selected supercritical water oxidation (SCWO) as the most promising technology for treating the VX hydrolysate. SCWO technology has developed from bench-scale testing to a few pilot-scale demonstrations, as well as one current and several pending full-scale operations to treat hazardous wastes. The Army recognized that further development and testing would be necessary before a full-scale SCWO treatment system could be designed, installed, and operated and requested that the NRC evaluate whether SCWO would be an effective and appropriate method for treating VX hydrolysate for ultimate disposition. The NRC was not asked to conduct an in-depth analysis of the entire VX bulk agent destruction and disposal process for the Newport Chemical Agent Disposal Facility. When the facility design is being finalized (March 1999–April 2000), the NRC may be asked to assess all aspects of the facility design, including monitoring, containment, process control, and redundancy, as well as the quantitative risk assessment (QRA).
This report has been reviewed by individuals chosen for their diverse perspectives and technical expertise, in accordance with procedures approved by the NRC's
Report Review Committee. The purpose of this independent review is to provide candid and critical comments that will assist the authors and the NRC in making the published report as sound as possible and to ensure that the report meets institutional standards for objectivity, evidence, and responsiveness to the study charge. The content of the review comments and draft manuscript remain confidential to protect the integrity of the deliberative process. We wish to thank the following individuals for their participation in the review of this report:
Thomas Barton Brill, University of Delaware
Steven Joseph Buelow, Los Alamos National Laboratory
Emily A. Carter, University of California, Los Angeles
Robert E. Connick, University of California, Berkeley
Ruth M. Davis, Pymatuning Group, Inc.
Gene H. Dyer, Bechtel (retired)
Henry J. Hatch, Fluor Daniel Hanford, Inc. (U.S. Army, retired)
Keith Paul Johnston, University of Texas
Michael Klein, University of Delaware
John P. Longwell, Massachusetts Institute of Technology
Alexander MacLachlan, E.I. duPont de Nemours & Company (retired)
Barry M. Trost, Stanford University
While the individuals listed above have provided many constructive comments and suggestions, responsibility for the final content of this report rests solely with the authoring committee and the NRC.
The committee greatly appreciates the support and assistance of National Research Council staff members Donald L. Siebenaler, Shirel R. Smith, Margo L. Francesco, and Carol R. Arenberg, as well as NRC consultant Harrison T. Pannella, in the production of this report.
Richard S. Magee, chair
Elisabeth M. Drake, vice chair
Committee on Review and Evaluation of the Army Chemical Stockpile Disposal Program
List of Figures and Tables
Figures
|
ES-1 |
Overview of the disposal process for VX ton containers, |
|||
|
2-1 |
Block diagram of the overall neutralization and SCWO treatment process, |
|||
|
3-1 |
Schematic diagram of a transpiring wall reactor, |
|||
|
3-2 |
MPA DRE without sodium hydroxide and at 200 percent stoichiometric oxygen and 27.6 MPa as a function of temperature and residence time, |
|||
|
3-3 |
Simplified SCWO process flow diagram for pilot-scale testing with salt simulants and VX hydrolysate treatability studies (August 1996), |
|||
|
3-4 |
Normalized salt transport through the reactor during the pilot-scale treatability testing with salt simulants and with VX hydrolysate (August 1996), |
|||
|
3-5 |
Reactor wall temperature, pressure, and sampling history during the eight-hour hydrolysate test, |
|||
|
3-6 |
Internal reactor temperature for the uppermost region (feed end) of the reactor, |
|||
|
3-7 |
Liquid effluent pH and salt balance during the VX hydrolysate test campaign, |
|||
|
5-1 |
Overview of the disposal process for VX ton containers, |
|||
|
A-1 |
Process flow diagram for the SCWO process step (design basis), |
|||
|
A-2 |
Process flow diagram for the evaporation process step (design basis), |
|||
|
B-1 |
Process flow diagram for the integrated NECDF process, |
Tables
|
1-1 |
Composition of Hydrolysate from Neutralization of VX, |
|||
|
3-1 |
Summary and Comparison of the Newport Chemical Agent Disposal Facility (NECDF) with Pilot Testing and Full-Scale Operation of SCWO Treatment Processes to Date, |
|||
|
3-2 |
Summary and Comparison of Full-Scale SCWO Treatment Processes Planned or under Construction as of December 1997, |
|||
|
3-3 |
Liquid Effluent Concentrations of VX Hydrolysate Constituents and DREs Observed during Pilot-Scale Treatability Testing (August 13, 1996), |
|||
|
3-4 |
Composition of Off-Gas Produced during Pilot-Scale Treatability Testing (August 13, 1996), |
|||
|
3-5 |
Analyses of Feed and Liquid Effluent for Specific Hydrolysate Constituents, TOC, and COD, |
|||
|
3-6 |
Analytical Precision and Accuracy Testing Results for TOC, MPA, and VX Thiol, |
|
3-7 |
Calculated DREs Based on Liquid Effluent Samples, |
|||
|
3-8 |
Composition of Effluent Gas, |
|||
|
3-9 |
Summary of Evaporator Installations Similar to the Design Specifications for NECDF, |
|||
|
4-1 |
Comparison of Full-Scale Design with Pilot-Scale Design Tested with VX Hydrolysate (February 1997), |
|||
|
5-1 |
Composition of the Post-Treatment SCWO Aqueous Effluent and the Solid Salt Streams, |
|||
|
5-2 |
Technology Implementation Timeline at NECDF (as of February 5, 1998), |
|||
|
B-1 |
NECDF Inputs for Process Mass Balance, |
|||
|
B-2 |
NECDF Outputs for Process Mass Balance, |
|||
|
B-3 |
Water Formation Resulting from the Neutralization of VX and Oxidation of the Hydrolysate during the NECDF Process, |
Acronyms
COD
chemical oxygen demand
CSDP
Chemical Stockpile Disposal Program
CWC
Chemical Weapons Convention
DMMP
dimethyl methylphosphonate
DRE
destruction removal efficiency
EFFDRUM
effluent drum
EMPA
ethyl methylphosphonic acid
EPA
Environmental Protection Agency
HEPA
high-efficiency particulate air
µmhos/cm
micro siemens/centimeter (unit of conductance equal to the reciprocal of the ohm)
MPA
methylphosphonic acid
NECDF
Newport Chemical Agent Disposal Facility
NEPA
National Environmental Policy Act
NMR
nuclear magnetic resonance
NRC
National Research Council
PPE
personal protective equipment
QRA
quantitative risk assessment
RCRA
Resource Conservation and Recovery Act
SCWO
supercritical water oxidation
SIP
State Implementation Plan
TC
ton container
TCC
ton container cleanout
TDS
total dissolved solids
TOC
total organic carbon
TSDF
treatment, storage, and disposal facility
VOC
volatile organic compound
VX
a specific type of nerve agent
