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Committee on Review of Biotreatment, Water Recovery, and Brine Reduction Systems for the Pueblo Chemical Agent Destruction Pilot Plant Board on Army Science and Technology Division on Engineering and Physical Sciences

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THE NATIONAL ACADEMIES PRESS • 500 Fifth Street, NW • 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-12-01-0126 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:  978-0-309-26393-1 International Standard Book Number-10:  0-309-26393-X Limited copies of this report are available from Board on Army Science and Technology, National Research Council, 500 Fifth Street, NW, Room 940, Washington, DC 20001; (202) 334-3118. Additional copies of this report are available from the National Academies Press, 500 Fifth Street, NW, Keck 360, Washington, DC 20001; (800) 624-6242 or (202) 334-3313; http://www.nap.edu. Cover: Photographs courtesy of Pueblo Chemical Agent Destruction Pilot Plant staff. Copyright 2013 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 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. Charles M. Vest 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. Harvey V. 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. Vest are chair and vice chair, respectively, of the National Research Council. www.national-academies.org

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COMMITTEE ON REVIEW OF BIOTREATMENT, WATER RECOVERY, AND BRINE REDUCTION SYSTEMS FOR THE PUEBLO CHEMICAL AGENT DESTRUCTION PILOT PLANT ROBERT A. BEAUDET, University of Southern California, Pasadena, Chair PEDRO J.J. ALVAREZ, Rice University, Houston, Texas EDWARD J. BOUWER, Johns Hopkins University, Baltimore, Maryland DAVID L. FREEDMAN, Clemson University, Clemson, South Carolina KIMBERLY L. JONES, Howard University, Washington, D.C. RONALD M. LATANISION, NAE,1 Exponent, Inc., Natick, Massachusetts MICHAEL J. LOCKETT, NAE, University at Buffalo, State University of New York PAIGE J. NOVAK, University of Minnesota, Minneapolis GENE F. PARKIN, University of Iowa, Iowa City RONALD F. PROBSTEIN, NAS2/NAE, Massachusetts Institute of Technology, Cambridge ROBERT B. PUYEAR, Independent Consultant, Chesterfield, Missouri VERNON L. SNOEYINK, NAE, University of Illinois, Urbana Staff HARRISON T. PANNELLA, Study Director NIA D. JOHNSON, Senior Research Associate ANN F. LARROW, Research Assistant (from April 1 to August 10, 2012) JOSEPH L. PALMER, Senior Program/Project Assistant 1NAE, National Academy of Engineering. 2NAS, National Academy of Sciences. v

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BOARD ON ARMY SCIENCE AND TECHNOLOGY ALAN H. EPSTEIN, Pratt & Whitney, East Hartford, Connecticut, Chair DAVID M. MADDOX, Independent Consultant, Arlington, Virginia, Vice Chair DUANE ADAMS, Independent Consultant, Carnegie Mellon University (retired), Arlington, Virginia ILESANMI ADESIDA, University of Illinois at Urbana-Champaign EDWARD C. BRADY, Strategic Perspectives, Inc., Fort Lauderdale, Florida MARY E. BOYCE, Massachusetts Institute of Technology, Cambridge W. PETER CHERRY, Independent Consultant, Ann Arbor, Michigan EARL H. DOWELL, Duke University, Durham, North Carolina JULIA D. ERDLEY, Pennsylvania State University, State College LESTER A. FOSTER, Electronic Warfare Associates, Herndon, Virginia JAMES A. FREEBERSYSER, BBN Technology, St. Louis Park, Minnesota RONALD P. FUCHS, Independent Consultant, Seattle, Washington W. HARVEY GRAY, Independent Consultant, Oak Ridge, Tennessee JOHN J. HAMMOND, Lockheed Martin Corporation (retired), Fairfax, Virginia RANDALL W. HILL, JR., University of Southern California Institute for Creative Technologies, Playa Vista JOHN W. HUTCHINSON, Harvard University, Cambridge, Massachusetts ROBIN L. KEESEE, Independent Consultant, Fairfax, Virginia ELLIOT D. KIEFF, Channing Laboratory, Harvard University, Boston, Massachusetts WILLIAM L. MELVIN, Georgia Tech Research Institute, Smyrna ROBIN MURPHY, Texas A&M University, College Station SCOTT PARAZYNSKI, University of Texas Medical Branch, Galveston RICHARD R. PAUL, Independent Consultant, Bellevue, Washington JEAN D. REED, Independent Consultant, Arlington, Virginia LEON E. SALOMON, Independent Consultant, Gulfport, Florida JONATHAN M. SMITH, University of Pennsylvania, Philadelphia MARK J.T. SMITH, Purdue University, West Lafayette, Indiana MICHAEL A. STROSCIO, University of Illinois, Chicago DAVID A. TIRRELL, California Institute of Technology, Pasadena JOSEPH YAKOVAC, President, JVM LLC, Hampton, Virginia Staff BRUCE A. BRAUN, Director CHRIS JONES, Financial Manager DEANNA P. SPARGER, Program Administrative Coordinator vi

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Preface The Army is preparing to destroy all the chemical agent in biotreatment were added to the Committee on Review of munitions stored at the Pueblo Chemical Depot in Colorado. Biotreatment, Water Recovery, and Brine Reduction Systems Construction of the facility that will perform this task, the for the Pueblo Chemical Agent Destruction Pilot Plant; the Pueblo Chemical Agent Destruction Pilot Plant (PCAPP), delivery date was extended, and the committee held two was completed in late 2012, and the facility is currently additional meetings. undergoing systemization (pre-operational testing) until Unfortunately, the committee was partially hampered agent destruction operations begin in the first half of 2015. by not having access to information that included some The depot stores a stockpile of projectiles and mortars, all bench tests for the brine reduction system considered to be of which contain the blister agent called mustard that will proprietary by Veolia Water Solutions & Technologies and, be destroyed by hydrolysis, followed by biotreatment of the therefore, had to depend on receiving direct answers to its hydrolysate. Because the facility requires large quantities of question in many cases. This report presents the committee’s water, which is a limited commodity in Colorado, as much findings and recommendations with the above caveat. of the water as possible will be purified and recycled back I and the committee thank particularly PCAPP chief sci- through the facility. entist George Lecakes and his team, consisting of Rebecca The site contractor team, Bechtel Pueblo, which is headed Spiva, Yakup Nurdogan, Ron Entz, Bill Steedman, Kate by Bechtel National, Inc., and includes Parsons Government Furman, and Paul Usinowicz, which took the time to answer Services, Inc.; URS Corporation; and Battelle Memorial our extensive sets of questions. The committee also had a Institute, has selected Veolia Water Solutions & Technolo- fruitful teleconference with Mark Patterson from Veolia gies as the designer and provider of the water recovery and Water Solutions & Technologies. brine reduction systems. This technology provider has had In addition, we thank the NRC staff, including Harrison T. extensive experience in designing and constructing water Pannella, the study director; Nia D. Johnson, senior research purification systems. However, because the nature of the associate; Ann F. Larrow, research assistant; and Joseph L. effluent to be treated at PCAPP is unique in its chemical Palmer, senior project assistant, for their support and assis- composition and is unlike any effluent treated at any other tance in producing this report. The final product could not facility, the PCAPP team and technology provider expect have been produced without their support. that adjustments will have to be made to operations of the system during systemization and the chemical agent start-up phase of the plant. Thus, they asked the National Research Council (NRC) to establish a committee to review the water recovery and brine reduction systems and to identify risks, possible problems, and modifications that may be required. After three meetings had taken place and the committee was well engrossed in the study, the Army requested that the study project be extended to include the biotreatment system Robert A. Beaudet, Chair that treats the hydrolysate produced by the neutralization of Committee on Review of Biotreatment, the mustard. The biotreatment process produces the bulk Water Recovery, and Brine Reduction Systems for the of the water to be treated in the water recovery and brine Pueblo Chemical Agent Destruction Pilot Plant reduction systems. Thus, four new members with expertise vii

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Acknowledgment of Reviewers This report has been reviewed in draft form by individuals Willie F. Harper, Air Force Institute of Technology, chosen for their diverse perspectives and technical expertise, David S. Kosson, Vanderbilt University, in accordance with procedures approved by the National Bruce E. Rittmann, NAE, Arizona State University, and Research Council’s (NRC’s) Report Review Committee. The W. Leigh Short, Consultant (retired), Williamstown, purpose of this independent review is to provide candid and Massachusetts. 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, Although the reviewers listed above have provided many and responsiveness to the study charge. The review com- constructive comments and suggestions, they were not asked ments and draft manuscript remain confidential to protect to endorse the conclusions or recommendations nor did they the integrity of the deliberative process. We wish to thank the see the final draft of the report before its release. The review following individuals for their review of this report: of this report was overseen by George Tchobanoglous, NAE, University of California, Davis. Appointed by the NRC, Richard J. Ayen, Independent Consultant, Jamestown, he was responsible for making certain that an independent Rhode Island, examination of this report was carried out in accordance with Ronald G. Ballinger, Massachusetts Institute of institutional procedures and that all review comments were Technology, carefully considered. Responsibility for the final content of Rick Bonds, Black & Veatch, this report rests entirely with the authoring committee and Clyde L. Briant, NAE, Brown University, the institution. viii

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Contents SUMMARY 1 1 BACKGROUND 6 Brief Description of the PCAPP Process, 6 Statement of Task, 8 Scope, 8 Organization of This Report, 9 References, 9 2 THE PCAPP BIOTREATMENT SYSTEM 10 General Description of the Bioreactor System, 10 Committee’s Review of the System, 12 Complexity of the Influent Stream and Related Toxicity/Inhibition, 13 pH Impacts on Biodegradation, 16 Temperature Impacts on Biodegradation, 16 Solids Buildup Concerns, 17 Oxygen Demand and Flux Issues, 18 Start-up Issues, 20 Analysis and Composition of the Effluent and Off-Gas from the Bioreactors, 21 References, 21 3 THE WATER RECOVERY AND BRINE REDUCTION SYSTEMS 23 Acid Addition, Feed/Distillate Heat Exchange, and CO2 Stripping, 23 Evaporation with Steam Compression, 25 Crystallizer Description, 26 Belt Filtration, 27 Condensation of Vapor from the Deaerator, Evaporator, and Crystallizer, 27 Activated Carbon Adsorption, 28 Uses of Carbon, 28 Distillate Carbon Filters, 28 Issues Related to the Water Flow Stream, 28 Drinking Water Quality Requirement, 30 The Crystallizer, 30 The Evaporator, 31 The Deaerator, 31 Issues Related to the Gas Flow Stream, 31 Issues Related to the Solids Flow Stream, 31 ix

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x CONTENTS Issues Related to the Entire BRS, 31 References, 32 4 MATERIALS OF CONSTRUCTION REVIEW 33 Materials of Construction for the Biotreatment, Water Recovery, and Brine Reduction Systems, 33 Overview, 33 Corrosion Monitoring, 34 Corrosion-Monitoring Methods, 35 Use of Metallic Coupons, 36 Electrical Resistance Probes, 36 Polarization Resistance Measurement, 36 Electrochemical Noise, 36 Other Considerations Relevant to Corrosion Monitoring, 38 References, 38 APPENDIXES A Table of Materials of Construction 39 B Corrosion-Monitoring Guides and Testing Materials Suppliers 42 C Biographical Sketches of Committee Members 43 D Committee Meetings 47

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Tables and Figures TABLES 1-1 Summer and Winter Quantities and Percentages for the Units Using the Recycled Water at PCAPP, 7 2-1 Key Operating and Feed Characteristics for the Immobilized Cell Bioreactor Units, 13 2-2 HD Hydrolysate Characterization from 2003 Biotreatment Testing, 15 3-1 Design Basis for Combined System Feed to PCAPP Water Recovery and Brine Reduction Systems, 25 3-2 Mass Flow Rates for Combined Distillates to and from Brine Reduction System Distillate Activated Carbon Filters, 29 3-3 Contaminants of Potential Concern in the Brine Reduction System Effluent and Applicable Drinking Water Standards, 30 4-1 PCAPP Biotreatment Area Materials of Construction, 34 FIGURES S-1 Conceptual diagram for the 16 immobilized cell bioreactor (ICB) treatment units during planned normal operation, 3 S-2 Block diagram of the brine reduction system, 4 1-1 Overview block diagram of the PCAPP biotreatment, water recovery, and brine reduction systems, 7 2-1 Conceptual diagram for the 16 immobilized cell bioreactor (ICB) treatment units during planned normal operation, 11 2-2 Two of the four biotreatment modules at PCAPP, each of which has four immobilized cell bioreactor units, 11 2-3 Major components of one of four biotreatment modules at PCAPP, 12 3-1 Block diagram of the brine reduction system, 24 3-2 Brine reduction system installation at PCAPP, 24 3-3 Simplified diagram of the 596-tube brine concentrate (BC) evaporator and BC vapor washer, 26 3-4 Simplified diagram of the crystallizer, 27 3-5 Block diagram of the carbon filter system, 28 4-1  typical polarization resistance diagram, 37 A 4-2 Three-electrode polarization resistance probe (a) and schematics of installation of the probe in pipe fitting (b), in a welded line (c), and in a pipe tee (d), 37 xi

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Acronyms and Abbreviations ABCDF Aberdeen Chemical Agent Disposal Facility MOC materials of construction ACWA Assembled Chemical Weapons Alternatives MWS munition washout system BC brine concentrate NRC National Research Council BOD biochemical oxygen demand BRS brine reduction system OTS off-gas treatment system BTA biochemical treatment area PCAPP Pueblo Chemical Agent Destruction Pilot COD carbon oxygen demand Plant CSTR continuous-flow stirred tank reactor PCD Pueblo Chemical Depot PEO-ACWA Program Executive Office for Assembled DAP diammonium phosphate Chemical Weapons Alternatives DOC dissolved organic carbon DOD Department of Defense SBR sequencing batch reactor SRT solids retention time EDT explosive destruction technology SOUR specific oxygen uptake rate GAC granular activated carbon TDG thiodiglycol TOC total organic carbon HD distilled mustard agent TSS total suspended solids HT distilled mustard mixed with bis(2- chloroethylthioethyl) ether VOC volatile organic compound VSS volatile suspended solids ICB immobilized cell bioreactor WRS water recovery system MCL maximum contaminant level WRS-BRS water recovery system and brine reduction MLSS mixed liquor suspended solids system xii