Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons

A Supplemental Review for Demonstration II

Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: Phase II

Board on Army Science and Technology

Division on Engineering and Physical Sciences

National Research Council

NATIONAL ACADEMY PRESS
Washington, D.C.



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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons A Supplemental Review for Demonstration II Committee on Review and Evaluation of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: Phase II Board on Army Science and Technology Division on Engineering and Physical Sciences National Research Council NATIONAL ACADEMY PRESS Washington, D.C.

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II NATIONAL ACADEMY PRESS 2101 CONSTITUTION AVE, N.W. WASHINGTON, DC 20055 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 views of the organizations or agencies that provided support for the project. International Standard Book Number 0-309-07634-X 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 Additional copies are available from: National Academy Press 2101 Constitution Avenue, N.W. Lockbox 285 Washington, DC 20055 (800) 624–6242 or (202) 334–3313 (in the Washington metropolitan area) http://www.nap.edu Copyright 2001 by the National Academy of Sciences. All rights reserved. Printed in the United States of America

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II THE NATIONAL ACADEMIES National Academy of Sciences National Academy of Engineering Institute of Medicine National Research Council 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. 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. Wm.A.Wulf are chairman and vice chairman, respectively, of the National Research Council.

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II 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), Jamestown, 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, EQE International/PLG, Irvine, California SHELDON E.ISAKOFF, E.I. du Pont de Nemours and Company (retired), Chadds Ford, Pennsylvania HANK C.JENKINS-SMITH, University of New Mexico, Albuquerque DAVID S.KOSSON, Vanderbilt University, Nashville, Tennessee FREDERICK J.KRAMBECK, Mobil Technology Company, Paulsboro, New Jersey JOHN A.MERSON, Sandia National Laboratories, Albuquerque, New Mexico WILLIAM R.RHYNE, H&R Technical Associates, Inc., 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., Indiatlantic, Florida Staff PATRICIA P.PAULETTE, Study Director HARRISON T.PANNELLA, Program Officer JAMES C.MYSKA, Research Associate WILLIAM E.CAMPBELL, Administrative Coordinator GWEN ROBY, Senior Project Assistant

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II BOARD ON ARMY SCIENCE AND TECHNOLOGY WILLIAM H.FORSTER, Chair, Northrop Grumman Corporation, Baltimore, Maryland JOHN E.MILLER, Vice Chair, Oracle Corporation, Reston, 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 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, Sandia National Laboratories, Livermore, California DONALD R.KEITH, Cypress International (retired), Alexandria, Virginia CLARENCE W.KITCHENS, IIT Research Institute, Alexandria, Virginia KATHRYN V.LOGAN, Georgia Institute of Technology (professor emerita), Roswell JOHN W.LYONS, 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 GEORGE T.SINGLEY III, Hicks and Associates, Inc., McLean, Virginia CLARENCE G.THORNTON, Army Research Laboratory (retired), Colts Neck, New Jersey JOHN D.VENABLES, Venables and Associates, Towson, Maryland JOSEPH J.VERVIER, ENSCO, Inc., Indiatlantic, Florida Staff BRUCE A.BRAUN, Director MICHAEL A.CLARKE, Associate Director WILLIAM E.CAMPBELL, Administrative Coordinator CHRIS JONES, Financial Associate GWEN ROBY, Administrative Assistant DEANNA P.SPARGER, Senior Project Assistant DANIEL E.TALMAGE, JR., Research Associate

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II Preface The United States has been in the process of destroying its chemical munitions for well over a decade. Initially, the U.S. Army, guided by 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 oppose incineration on the grounds that the exact nature of the effluents escaping from the stacks cannot be determined. The Army has continued to pursue incineration at four of the eight storage sites in the continental United States where that process seemed appropriate. Nevertheless, influenced by growing public opposition to incineration and the 1996 NRC report Review and Evaluation of Alternative Chemical Disposal Technologies, the Army has also been developing technologies based on chemical hydrolysis for the remaining sites. These processes will be used to destroy the VX nerve agent stored at Newport, Indiana, and the mustard agent stored at Aberdeen, Maryland, both of which are stored only in bulk one-ton containers and not in assembled munitions. In 1996, persuaded by public opposition in Lexington, Kentucky, and Pueblo, Colorado, Congress enacted Public Law 104–201, which instructed the U.S. 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.” In response, the Army established the program manager for the Assembled Chemical Weapons Assessment (PMACWA). In Public Law 104–208, the PMACWA was required to “identify and demonstrate not less than two alternatives to the baseline incineration process for the demilitarization of assembled chemical weapons.” During the first phase of the Assembled Chemical Weapons Assessment (ACWA) program, seven technologies were evaluated. Three of them proceeded to demonstration testing (Demo I) and one was dropped completely. In August 1999, the PMACWA selected two of the Demo I technologies as candidates for the destruction of the assembled munitions weapons at Pueblo Chemical Depot. The two packages, General Atomics Total Solution (GATS) and Parsons/Honeywell (formerly Parsons-Allied Signal) water hydrolysis of explosives and agent technology (WHEAT), were advanced to the engineering design study phase of the ACWA program. The PMACWA has involved the citizen stakeholders in every aspect of the program, including the procurement process. The Keystone Center, a nonprofit organization, was hired to facilitate public involvement through a process known as the Dialogue, which has become a model for public involvement in matters of public concern.1 The 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 question before the committee was not whether incineration was an adequate technology for destroying assembled chemical weapons but whether other chemical processes acceptable to the stakeholders could be 1   The U.S. Department of Energy and the National Aeronautics and Space Administration have both adopted this approach. For example, at the NASA Jet Propulsion Laboratory, the Dialogue process will be used in developing a Mars sample-return mission, which is scheduled for 2012.

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II used. The second NRC committee (ACW II committee) was established in the spring of 2000 to evaluate the two engineering design studies for the destruction facilities at Pueblo, Colorado, and Richmond, Kentucky, and to evaluate the demonstration testing of the three technology packages that had not been selected for those sites or for previous demonstration testing. Although the PMACWA had no intention of demonstrating these three technologies, Public Law 106–79 (2000) mandated that the PMACWA “conduct evaluations of [the] three additional alternative technologies under the ACWA program.” Furthermore, the PMACWA was directed to “proceed under the same guidelines as contained in Public Law 104–208 and continue to use the Dialogue process and Citizens’ Advisory Technical Team and their consultants.” Accordingly, the PMACWA initiated a program commonly referred to as Demo II to demonstrate the three technologies (AEA SILVER II™, the Foster Wheeler/Eco Logic/ Kvaerner integrated demilitarization process, and Teledyne-Commodore’s solvated electron process) that had not been selected during the first phase. The ACW II committee was asked to determine if and how the Demo II results affected its commentary, findings, and recommendations and the steps that were suggested for implementation in the ACW I report. This report presents the committee’s evaluation of the second set of demonstration tests. I wish to gratefully acknowledge the hard work of members of the ACW II committee, all of whom served as volunteers and provided the expertise necessary to carry out this enormous task. They gave relentlessly and unselfishly of their time and effort throughout the study. Their areas of expertise included chemical processing, biological remediation, environmental regulations and permitting, energetic materials, and public acceptance. Committee members attended plenary meetings, visited the technology providers’ headquarters and test sites, observed design-review sessions, and studied the extensive literature, including engineering charts and diagrams, provided by the technology providers. On behalf of the committee, I would like to also express appreciation for the extensive support of the Army ACWA team and its interactions with stakeholders and the Dialogue, particularly the group’s Citizens Advisory Technical Team, whose members attended all open meetings of the committee and shared information and views with it. The committee also appreciated the openness and cordiality of the representatives of the technology providers. They and the Army provided early drafts of their test reports and other documentation to facilitate the committee’s evaluation. A study such as this requires extensive logistic support; the committee is indebted to the NRC staff for their assistance. I would particularly like to acknowledge the close working relationship I had with the NRC study director, Patricia Paulette. We worked as a team in leading this study. We spoke on the phone daily and e-mailed each other incessantly. The efforts of William Campbell, who took extensive notes and provided real-time report corrections at all our meetings as well as suggestions on how to best organize the report, were invaluable to the committee and to me. Gwen Roby provided the logistic support that enabled us to concentrate on our task. I am also indebted to my colleagues in the Chemistry Department at the University of Southern California who willingly took over 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

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II Acknowledgments This report has been reviewed in draft form 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 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: Steven Konkel, Eastern Kentucky University Richard Magee, New Jersey Institute of Technology Walter May, Consultant Ray McGuire, Consultant Vernon Myers, Environmental Protection Agency Headquarters George Parshall, E.I. du Pont de Nemours (retired) Robert Olson, Consultant Donald Sadoway, Massachusetts Institute of Technology Martin B.Sherwin, Chemical Engineer (retired) William Tumas, Los Alamos 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 Royce Murray, University of North Carolina, appointed by the National Research Council. He 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.

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II Contents     EXECUTIVE SUMMARY   1 1   INTRODUCTION   6     Background,   6     Role of the National Research Council,   8     Statement of Task,   8     Scope and Approach of This Study,   9     Organization of This Report,   9 2   AEA SILVER II™ TECHNOLOGY PROCESS   10     Description of the Systems,   10     2 kW SILVER II™ System,   10     12 kW SILVER II™ System,   10     Testing,   12     Agent Tests,   12     Energetics Tests,   13     Test Results,   13     Destruction and Removal Efficiency,   13     Materials of Construction,   15     Characteristics of Gaseous, Liquid, and Solid Process Streams,   15     Electrochemical Efficiency,   16     AEA Design Changes Based on Test Results,   17     Reevaluation of Steps Required for Implementation,   17     Review of the ACW I Committee’s Findings,   19     Supplemental Findings,   22     Supplemental Recommendations,   22 3   FOSTER WHEELER/ECO LOGIC/KVAERNER INTEGRATED DEMILITARIZATION PROCESS   23     Transpiring-Wall Supercritical Water Oxidation Unit,   23     Other Observations,   25     Gas-Phase Chemical Reduction System,   26     Safety Concerns,   27

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II     Reevaluation of Steps Required for Implementation,   27     Overarching Comment,   27     Pilot-Scale Evaluation for Hydrolysis of Energetics,   28     Pilot-Scale Evaluation for SCWO,   28     Pilot-Scale Evaluation for GPCR™,   28     Reevaluation of Findings from ACW I Report,   28     Supplemental Findings,   30     Supplemental Recommendations,   30 4   TELEDYNE-COMMODORE SOLVATED ELECTRON TECHNOLOGY PROCESS   31     Ammonia Fluid Jet Cutting and Washout,   31     Shredding of Metal Parts and Dunnage,   32     SET™ Treatment of Shredded Metal Parts and Dunnage,   32     Reevaluation of Steps Required for Implementation,   33     Reevaluation of Findings from ACW I Report,   33     Supplemental Finding,   34 5   UPDATE OF GENERAL FINDINGS AND RECOMMENDATIONS   35     Review of Earlier Findings and Recommendations,   35     Supplemental General Findings,   37     Supplemental General Recommendations,   37     REFERENCES   39     APPENDIXES         A Site Visits and Meetings   43     B Biographical Sketches of Committee Members   47

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II List of Figures and Tables FIGURES 2–1   AEA SILVER II™ total system solution,   11 2–2   Process flow diagram of the AEA 2 kW demilitarization process,   12 2–3   Process flow diagram of the AEA 12 kW demilitarization plant,   13 2–4   Revised process flow diagram of the AEA SILVER II™ demilitarization process,   18 3–1   Schematic diagram of the FW/EL/K demilitarization process,   24 4–1   Schematic diagram of the Teledyne-Commodore SET™ process,   32 TABLES ES–1   Summary Evaluation of the Maturity of Demo II Unit Operations and Processes,   3 1–1   Description of the Seven Technology Packages That Passed DoD’s Initial Evaluation,   7 2–1   Destruction Efficiency in the 2 kW Test Unit,   14 2–2   Anolyte Coupon Weights Before and After Testing,   15 5–1   Summary Evaluation of the Maturity of Demo II Unit Operations and Processes,   38

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II Acronyms, Chemical Symbols, and Abbreviations ACWA Assembled Chemical Weapons Assessment (program) 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 AEA AEA Technologies Corporation Ag2+ silver II ions AgCl silver chloride a-HAX solution containing potassium hydroxide and humic acid BIF boiler and industrial furnace CATOX catalytic oxidation CEES chloroethyl ethyl sulfide CEM continuous emission monitor CO carbon monoxide CO2 carbon dioxide Composition B an energetic material that contains (nominally) 59.5 percent RDX, 39.5 percent TNT, and 1.0 percent wax CWC Chemical Weapons Convention DAAMS depot area air monitoring system Demo I Demonstration I (demonstration testing 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 ECBC Edgewood Chemical and Biological Center EDP engineering design package EDS engineering design study EPA Environmental Protection Agency

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II FEK or FW/EL/K Foster Wheeler/Eco Logic/Kvaerner GATS General Atomics Total Solution GB a nerve agent GC/MS gas chromatography/mass spectrometry GPCR™ gas-phase chemical reduction H2 hydrogen HD distilled mustard agent HF hydrofluoric acid HNO3 nitric acid HPLC high-performance liquid chromatography HRA health risk assessment ICIImperial Chemical Industries IMPA isopropyl methylphosphonic acid IRS impurities removal system KOH potassium hydroxide LMIDS Lockheed Martin Integrated Demilitarization System MACT maximum achievable control technology MDM multipurpose demilitarization machine MPA methylphosphonic acid M28 energetic material used for propulsion of certain assembled chemical weapons N2 nitrogen NOx nitrogen oxides N2O nitrous oxide NRC National Research Council O2 oxygen PA picric acid PCP pentachlorophenol PGB product gas burner PMACWA program manager for the Assembled Chemical Weapons Assessment PMD projectile mortar demilitarization (machine) POTW publicly owned treatment works ppm parts per million PTFE polytetrafluoroethylene (Teflon) QRA quantitative risk assessment RCRA Resource Conservation and Recovery Act RDX cyclotrimethylenetrinitramine RFP request for proposals SCWO supercritical water oxidation

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Evaluation of Demonstration Test Results of Alternative Technologies for Demilitarization of Assembled Chemical Weapons: A Supplemental Review for Demonstration II SET™ solvated electron technology SILVER II™ electrochemical oxidation using silver II ions in nitric acid SOx sulfur oxides SO2 sulfur dioxide SVOC semivolatile organic compound TBA tributylamine TC Teledyne-Commodore TCLP toxicity characteristic leachate procedure 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 VOC volatile organic compound VX a nerve agent WHEAT water hydrolysis of explosives and agent technology 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, eight-hour, time-weighted average limit for worker exposure. The level for mustard agent is 3.0 mg per cubic meter 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 level 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. 5X treatment unit This unit is used to heat chemical solid waste materials to a level of decontamination where no residual contamination is detectable.