DISPOSAL OF ACTIVATED CARBON FROM CHEMICAL AGENT DISPOSAL FACILITIES

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DISPOSAL OF ACTIVATED CARBON FROM CHEMICAL AGENT DISPOSAL FACILITIES Committee to Examine the Disposal of Activated Carbon from the Heating, Ventilation, and Air Conditioning Systems at Chemical Agent Disposal Facilities Board on Army Science and Technology Division on Engineering and Physical Sciences

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THE NATIONAL ACADEMIES PRESS 500 Fifth Street, N.W. Washington, DC 20001 NOTICE: The project that is the subject of this report was approved by the Governing Board of the National Research Council, whose members are drawn from the councils of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of the committee responsible for the report were chosen for their special competences and with regard for appropriate balance. This study was supported by Contract No. W911NF-08-C-0048 between the National Academy of Sciences and the U.S. Army. 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-13: 978-0-309-13818-5 International Standard Book Number-10: 0-309-13818-3 Cover: The photograph on the cover shows part of a bank of activated carbon filter trays used for the ��AC The systems at chemical agent disposal facilities. A detailed view of the structure and airflow through a filter tray can be seen in Figure 2-4. Courtesy of the U.S. Army Anniston Chemical Agent Disposal Facility, Anniston, Alabama. Limited copies of this report are available from Additional copies are available from Board on Army Science and Technology The National Academies Press National Research Council 500 Fifth Street, N.W. 500 Fifth Street, N.W., Room 940 Lockbox 285 Washington, DC 20001 Washington, DC 20055 (202) 334-3118 (800) 624-6242 or (202) 334-3313 (in the Washington metropolitan area) Internet, http://www.nap.edu Copyright 2009 by the National Academy of Sciences. All rights reserved. Printed in the United States of America

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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. Ralph J. Cicerone 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 Sci - ences, 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 govern - ment. 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. Charles M. �est 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. �arvey �. Fineberg is president of the Institute of Medicine. The National Research Council was organized by the National Academy of Sciences in 1916 to associate the broad community of science and technology with the Academy’s purposes of furthering knowledge and advising the federal government. Functioning in accordance with general policies determined by the Academy, the Council has become the principal operating agency of both the National Academy of Sciences and the National Academy of Engineering in providing services to the government, the public, and the scientific and engineering communities. The Council is administered jointly by both Academies and the Institute of Medicine. Dr. Ralph J. Cicerone and Dr. Charles M. �est are chair and vice chair, respectively, of the National Research Council. www.national-academies.org

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COMMITTEE TO EXAMINE THE DISPOSAL OF ACTIVATED CARBON FROM THE HEATING, VENTILATION, AND AIR CONDITIONING SYSTEMS AT CHEMICAL AGENT DISPOSAL FACILITIES ROBERT A. BEAUDET, Chair, University of Southern California, Los Angeles TERESA J. BANDOSZ, City College of New York JOAN B. BERKOWITZ, Farkas Berkowitz and Company, Washington, D.C. �EREK L. CLACK, Illinois Institute of Technology, Chicago WILLARD C. GEKLER, ABS Consulting Inc., Los Alamitos, California LOREN D. KOLLER, Loren Koller and Associates, Corvallis, Oregon M. DOUGLAS Le�AN, �anderbilt University, Nashville, Tennessee JO�N A. PENDERGRASS, Environmental Law Institute, Washington, D.C. KRISTA S. WALTON, Kansas State University, Manhattan WALTER J. WEBER, JR., University of Michigan, Ann Arbor YU-C�U YANG, Independent Consultant, Bel Air, Maryland Staff MARGARET N. NO�ACK, Study Director �ARRISON T. PANNELLA, Senior Program Officer NIA D. JO�NSON, Senior Research Associate JAMES C. MYSKA, Senior Research Associate ALICE �. WILLIAMS, Senior Program Assistant v

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BOARD ON ARMY SCIENCE AND TECHNOLOGY MALCOLM R. O’NEILL, Chair, Lockheed Martin Corporation (retired), �ienna, �irginia ALAN �. EPSTEIN, Vice-Chair, Pratt & Whitney, East �artford, Connecticut DUANE ADAMS, Carnegie Mellon University (retired), Arlington, �irginia ILESANMI ADESIDA, University of Illinois at Urbana-Champaign RAJ AGGARWAL, Rockwell Collins, Cedar Rapids, Iowa SET� BONDER, The Bonder Group, Ann Arbor, Michigan JAMES CARAFANO, The �eritage Foundation, Washington, D.C. W. PETER C�ERRY, Science Applications International Corporation, Ann Arbor, Michigan DARRELL W. COLLIER, U.S. Army Space and Missile Defense Command (retired), Leander, Texas JAY C. DA�IS, Lawrence Livermore National Laboratory (retired), Livermore, California PATRICIA K. FALCONE, Sandia National Laboratories, Livermore, California RONALD P. FUC�S, The Boeing Company, Seattle, Washington PETER F. GREEN, University of Michigan, Ann Arbor CARL GUERRERI, Electronic Warfare Associates, Inc., �erndon, �irginia JO�N J. �AMMOND, Lockheed Martin Corporation (retired), Fairfax, �irginia M. FREDERICK �AWT�ORNE, University of Missouri, Columbia MARY JANE IRWIN, Pennsylvania State University, University Park ELLIOT D. KIEFF, Channing Laboratory, �arvard University, Boston, Massachusetts LARRY LE�OWICZ, Quantum Research International, Arlington, �irginia ROBIN MURP�Y, Texas A&M University, College Station RIC�ARD R. PAUL, Consultant, Bellevue, Washington EDWARD K. REEDY, Georgia Tech Research Institute (retired), Atlanta DENNIS J. REIMER, DFI International (retired), Arlington, �irginia JONAT�AN M. SMIT�, University of Pennsylvania, Philadelphia MARK J.T. SMIT�, Purdue University, West Lafayette, Indiana MIC�AEL A. STROSCIO, University of Illinois, Chicago JUDIT� L. SWAIN, University of California at San Diego, La Jolla WILLIAM R. SWARTOUT, Institute for Creative Technologies, Marina del Rey, California EDWIN L. T�OMAS, Massachusetts Institute of Technology, Cambridge ELLEN D. WILLIAMS, University of Maryland, College Park JOSEP� YAKO�AC, J�M LLC, �ampton, �irginia Staff BRUCE A. BRAUN, Director C�RIS JONES, Financial Associate DEANNA P. SPARGER, Program Administrative Coordinator vi

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Preface For more than two decades, the United States has seemed simple at first, it turned out to be complex. For been in the process of destroying its chemical agent and one thing, the carbon is used in different kinds of filter munitions stockpile. At this time, except for the nerve units throughout the facility. Which of them are actu- agent stored at a site where Congress has forbidden ally contaminated with agent? Most of the carbon is incineration and a few containers of legacy nerve agent not contaminated and could be disposed of as ordinary GA (also known as tabun) at another site where they hazardous waste. Another complication is that some of will soon be destroyed, the nation’s entire stockpile of the mustard munitions contain high levels of mercury, nerve agents has been destroyed. The operating chemi- a challenge for disposal. To address the mercury con- cal agent disposal sites are in the process of destroying tamination requires changing the carbon in some filter the remaining mustard agent munitions. The Army is units to sulfur-impregnated carbon, which will adsorb now turning its attention to preparing for the closure the mercury. Fortunately, the mercury-contaminated of these facilities and the disposal of all the secondary carbon is not expected to be exposed to agent unless wastes that have been stored on-site. One of the second- there is a severe operational upset. ary wastes is an estimated total of more than 1,300 tons Still another issue, already noted, is that the agents of activated carbon that has been used as an adsorptive on the carbon degrade by reacting with the water medium to protect site personnel and adjacent com- adsorbed on the carbon and forming the usual hydro- munities from potential exposure to the agents. Some lysis products. But how much agent remains on the of this carbon (about 20 percent) has been exposed filters? Is this level below the waste control limits to chemical agents, although over time the adsorbed established by regulatory authorities? �ow can one agents have reacted with the water also adsorbed on the measure the amounts of residual agent on the carbon carbon and formed hydrolysis products. In most cases, given the very low parts-per-billion (ppb) level? �ow only trace amounts of agent remain on this carbon. can one minimize or altogether prevent the re-forma- The remaining carbon (about 80 percent) has not been tion of nerve agent GB (also known as sarin) during exposed to agent but continues to be available for this analysis? These are some of the issues that concerned purpose as one of the safety measures designed into the committee during this study, and they all have the facilities. implications for how and where the activated carbon The U.S. Army’s Chemical Materials Agency (CMA) used in the course of destroying chemical agents can asked the National Research Council to convene a com- be disposed of. Fortunately, I believe the committee mittee to study the disposal of all the carbon used at has “gotten its arms around this gorilla.” As its chair, I chemical agent disposal facilities. While this project thank the members, who have worked as volunteers, for vii

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viii PREFACE their contributions to this report. They included travel- asked to endorse the committee’s conclusions or rec- ing and attending meetings at various sites, followed by ommendations, nor did they review the final draft of a series of virtual meetings to write the report. this report before its release, although board members The committee is grateful to Timothy Garrett, who with appropriate expertise may be nominated to serve was the committee’s point of contact at CMA for the as formal members of study committees or as report study. It was he who organized the presentations and reviewers. The BAST was established in 1982 by the hosted the meeting in Anniston, Alabama. Also, we National Academy of Sciences at the request of the thank all the Army participants, who gave up their Army. It brings broad military, industrial, and academic time, traveled to meetings, and openly discussed their experience and scientific, engineering, and manage- problems with us. Finally, we thank the staff of the ment expertise to bear on Army technical challenges Board on Army Science and Technology (BAST) for and other issues of importance to senior Army lead- its support and logistical help. In particular we thank ers. BAST also discusses potential studies of interest; Margaret Novack, the program director for this project; develops and frames study tasks; ensures proper project �arrison Pannella, who reviewed the report for us in planning; suggests potential committee members and detail and provided sound advice; and Nia Johnson, reviewers for reports produced by fully independent, who provided project research support. ad hoc study committees; and convenes meetings to The BAST members, listed on page vi, were not examine strategic issues. Robert A. Beaudet, Chair Committee to Examine the Disposal of Activated Carbon from the �eating, �entilation, and Air Conditioning Systems at Chemical Agent Disposal Facilities

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Acknowledgment of Reviewers This report has been reviewed in draft form by George W. Parshall, NAS, DuPont (retired), individuals chosen for their diverse perspectives and Danny Reible, NAE, University of Texas, technical expertise, in accordance with procedures William R. Rhyne, Consultant, approved by the National Research Council’s (NRC’s) William J. Walsh, Pepper �amilton, LLP, and Report Review Committee. The purpose of this inde- Calvin Willhite, State of California Environmental pendent review is to provide candid and critical com- Protection Agency. ments that will assist the institution in making its published report as sound as possible and to ensure that Although the reviewers listed above have provided the report meets institutional standards for objectiv- many constructive comments and suggestions, they ity, evidence, and responsiveness to the study charge. were not asked to endorse the conclusions or recom- The review comments and draft manuscript remain mendations, nor did they see the final draft of the confidential to protect the integrity of the deliberative report before its release. The review of this report was process. We wish to thank the following individuals for overseen by John R. �owell, NAE. Appointed by the their review of this report: National Research Council, he was responsible for making certain that an independent examination of this Madan M. Bhasin, NAE, Dow Chemical Company report was carried out in accordance with institutional (retired), procedures and that all review comments were care- Richard A. Conway, NAE, Union Carbide Corpo- fully considered. Responsibility for the final content of ration (retired), this report rests entirely with the authoring committee Gary S. Groenewold, Idaho National Laboratory, and the institution. ix

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Contents SUMMARY 1 1 INTRODUCTION 8 Activated Carbon and Chemical Demilitarization, 8 Chemical Stockpile Disposal Program, 9 Overview, 9 Brief Description of the Chemical Agent Destruction Process, 10 Use of Carbon Filtration Systems at Chemical Agent Disposal Facilities, 11 Statement of Task, 11 Study Scope, 13 Organization of This Report, 13 2 USES AND MANAGEMENT OF ACTI�ATED CARBON AT C�EMICAL 15 AGENT DISPOSAL FACILITIES Used Carbon Sources, 15 Management of Used Carbon, 20 References, 24 3 REGULATIONS GO�ERNING CARBON DISPOSAL 25 Regulatory Framework and Considerations, 25 Overview of State-Specific Regulatory Requirements, 27 Alabama, 27 Arkansas, 28 Oregon, 28 Utah, 29 Commonalities and Differences Specific to Activated Carbon Practices and Permit Requirements, 29 Requirements Relating to Transportation, 31 General, 31 Existing Requirements for Transporting Carbon Off-site, 31 References, 32 xi

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xii CONTENTS 4 INTERACTIONS OF C�EMICAL AGENTS WIT� ACTI�ATED CARBON 33 Fundamentals of Adsorption, 33 Adsorption of Chemical Agents on �eating, �entilation, and Air Conditioning Carbon, 35 Reactions of Chemical Agents on Activated Carbon, 37 GB Reactions, 37 �X Reactions, 39 Mustard Agent Reactions, 40 Summary of Studies of Agent Reactions on Carbon, 41 Methods for Determining Chemical Agent Loading on Activated Carbon, 42 References, 44 5 COMMERCIAL AND INDUSTRIAL PRACTICES FOR ACTI�ATED CARBON 45 MANAGEMENT Commercial and Industrial Use of Activated Carbon, 45 Overview, 45 Mercury Removal as an Emerging Market for Activated Carbon, 45 Treatment and Disposal of Activated Carbon from Commercial and Industrial Applications, 46 References, 48 6 USE AND DISPOSAL OF SULFUR-IMPREGNATED CARBON FOR MERCURY 49 ADSORPTION Known Characteristics of Mustard Agent Stockpiles, 49 Fate of Mercury Within Thermal Destruction Processes at Chemical Agent Disposal Facilities, 50 References, 51 7 DISPOSAL OF CARBON FROM C�EMICAL AGENT DISPOSAL FACILITIES 52 Past Experience with Disposal of Used Activated Carbon, 52 Incineration of Used Carbon at JACADS, 52 Disposal of Used Carbon at ABCDF, 53 Disposal of Used Carbon at NECDF, 54 On-site Disposal of Exposed Carbon at Operating Disposal Facilities, 54 Current CMA Carbon Management Strategy, 55 Alternative Methods for Disposal of Carbon, 57 Use of Decontamination Solution for Off-site Disposal of Exposed Carbon, 57 Reactivation of Unexposed Carbon, 58 General Findings and Recommendations, 58 References, 60 APPENDIXES A Calgon Carbon Corporation General Carbon Acceptance Criteria for Reactivation 63 B Committee Meetings, Site �isits, and �irtual Meetings 66 C Biographical Sketches of Committee Members 68

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Tables and Figures TABLES S-1 Summary of Sources and Estimated Inventories (in Pounds) of Carbon Exposed to Agent at CMA Incineration Sites During Operations and Closure, 2 S-2 Summary of Sources and Estimated Inventories (in Pounds) of Unexposed Carbon Used at CMA Incineration Sites During Operations and Closure, 3 S-3 Current Status of Permit Requirements for Shipping Carbon Off-site from Chemical Agent Disposal Facilities, 3 2-1 Uses of Activated Carbon Filters at Chemical Agent Disposal Facilities, 21 2-2 Estimated Carbon Waste Inventories (in Pounds) for CMA Chemical Agent Disposal Facilities as of September 29, 2008, 22 2-3 Summary of Sources and Estimated Inventories (in Pounds) of Carbon Exposed to Agent at CMA Incineration Sites During Operations and Closure, 22 2-4 Summary of Sources and Estimated Inventories (in Pounds) of Unexposed Carbon Used at CMA Incineration Sites During Operations and Closure, 22 2-5 Pertinent Physical Properties of the Chemical Agents and Mercury, 23 3-1 Current Status of Permit Requirements for Shipping Carbon Off-site from Chemical Agent Disposal Facilities, 31 4-1 Agent Loadings on Cocoanut Activated Carbon, 35 4-2 Analytical Results of ��AC and PFS Carbon Samples Collected from ANCDF in January 2007, 36 4-3 Chemical Formulas for Mustard Agent and Its �ydrolysis Products, 41 4-4 Analysis of GB and �X on Carbon and Method Detection Limits (MDLs), 43 7-1 Agent Mass Limits per Drum for Off-site Shipment of Secondary Waste, 57 FIGURES 1-1 Schematic of the baseline incineration system, 10 1-2 Sources of used carbon in a typical chemical agent disposal facility, 12 xiii

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xiv TABLES AND FIGURES 2-1 The nine activated carbon filter units for the MDB ��AC system, 16 2-2 Schematic representation of airflow through the six filter banks that make up each MDB ��AC filter unit, 17 2-3 A filter tray, 17 2-4 Airflow path through a filter tray, 18 2-5 PFS filter unit, 18 2-6 Schematic of the PAS/PFS flow configuration including the PFS filter unit, 19 2-7 Schematic representation of the combustion gas flow path through the PFS, 19 2-8 An M-40 protective mask with the filter C-2 canister attached, 20 2-9 A 95-gallon drum for storage of used carbon filter trays, 23 2-10 �estibule on the side of an MDB ��AC unit, 23 4-1 Mass transfer zone in a carbon adsorption bed, 34 4-2 Water adsorption isotherms on activated carbons made from different types of wood (W, W1, and W2) and coals (N, N1, and N2) at 25°C, 35 4-3 Phosphorus-31 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of 10 weight percent sarin (GB) on humidified (13 weight percent water) activated carbon over time: initial and after 6, 13, and 16 days, left to right, 38 4-4 MAS NMR spectra for 10 weight percent nerve agent �X absorbed on humidified (13 weight percent water) carbon, left to right: initial and at 24 days showing heterogeneous autocatalytic hydrolysis of �X over 24 days, left to right, 39 5-1 General schematic of the fate of spent activated carbon from commercial and industrial sources, 48 5-2 Calgon Carbon’s process for reactivation of spent carbon, 48

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Abbreviations and Acronyms ABCDF Aberdeen Chemical Agent Disposal ECBC U.S. Army Edgewood Chemical and Facility Biological Center ACAMS automatic continuous air monitoring EMPA ethyl methylphosphonic acid system EONCs enhanced on-site containers ACS agent collection system EPA U.S. Environmental Protection Agency ADEM Alabama Department of Environmental Management GA nerve agent ADEQ Arkansas Department of Environmental GAC granulated activated carbon Quality GB nerve agent (sarin) AEGL acute exposure guideline level GC gas chromatography ANCDF Anniston Chemical Agent Disposal GPL general population limit Facility � mustard agent BGCAPP Blue Grass Chemical Agent Destruction �Cl hydrochloric acid Pilot Plant �D distilled mustard agent BTRA boundary transportation risk assessment �F hydrofluoric acid �g mercury CERCLA Comprehensive Environmental �T distilled mustard mixed with bis(2- Response, Compensation, and chloroethylthioethyl) ether Liability Act ��AC heating, ventilation, and air C� mustard chlorohydrin conditioning C�-TG sulfonium ion CMA Chemical Materials Agency IMPA isopropyl methylphosphonic acid CMS carbon micronization system CWC Chemical Weapons Convention JACADS Johnston Atoll Chemical Agent Disposal System DAAMS depot area air monitoring system DFS deactivation furnace system LDR land disposal restrictions DOT Department of Transportation LIC liquid incinerator DPE demilitarization protective ensemble xv

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xvi ACRONYMS AND ABBREVIATIONS MAS magic angle spinning ppmw parts per million by weight MDB munitions demilitarization building MDL method detection limit RCRA Resource Conservation and Recovery MPF metal parts furnace Act MS mass spectrometry MWI municipal waste incinerator STEL short-term exposure limit STL short-term limit (no time component NaO� sodium hydroxide specified) NECDF Newport Chemical Agent Disposal SwRI Southwest Research Institute Facility NMR nuclear magnetic resonance TCLP toxic chemical leaching procedure NRC National Resource Council TG thiodiglycol TOCDF Tooele Chemical Agent Disposal ODEQ Oregon Department of Environmental Facility Quality TRA transportation risk assessment ONCs on-site containers TSDF treatment, storage, and disposal facility OTS off-gas treatment system UDEQ Utah Department of Environmental PAC powdered activated carbon Quality PAS pollution abatement system UMCDF Umatilla Chemical Agent Disposal PBCDF Pine Bluff Chemical Agent Disposal Facility Facility PCAPP Pueblo Chemical Agent Destruction �SL vapor screening level Pilot Plant �X nerve agent PCC permit compliance concentration �X-pyro diethyl dimethylpyrophosphonate PFS PAS filtration system ppb parts per billion WAP waste analysis plan ppm parts per million WCL waste control limit