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Toxicity of Military Smokes and Obscurants

Volume 1

SUBCOMMITTEE ON MILITARY SMOKES AND OBSCURANTS

COMMITTEE ON TOXICOLOGY

BOARD ON ENVIRONMENTAL STUDIES AND TOXICOLOGY

COMMISSION ON LIFE SCIENCES

NATIONAL RESEARCH COUNCIL

NATIONAL ACADEMY PRESS
WASHINGTON, D.C.,
1997



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Toxicity of Military Smokes and Obscurants Volume 1 SUBCOMMITTEE ON MILITARY SMOKES AND OBSCURANTS COMMITTEE ON TOXICOLOGY BOARD ON ENVIRONMENTAL STUDIES AND TOXICOLOGY COMMISSION ON LIFE SCIENCES NATIONAL RESEARCH COUNCIL NATIONAL ACADEMY PRESS WASHINGTON, D.C., 1997

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NATIONAL ACADEMY PRESS 2101 Constitution Avenue, NW Washington, DC 20418 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 report has been reviewed by a group other than the authors according to procedures approved by a Report Review Committee consisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. 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 Alberts and Dr. William A. Wulf are chairman and vice chairman, respectively, of the National Research Council. The project was supported by the U.S. Department of Defense under contract DAMD 17-89-C-9086. Additional copies of this report are available from the Board on Environmental Studies and Toxicology, 2101 Constitution Avenue, NW, Washington, DC 20418. Copyright 1997 by the National Academy of Sciences. All rights reserved. Printed in the United States of America.

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Subcommittee on the Assessment of Military Smokes and Obscurants MICHELE A. MEDINSKY (Chair), Chemical Industry Institute of Toxicology, Research Triangle Park, N.C. DEBORAH A. CORY-SLECHTA, University of Rochester School of Medicine, Rochester, N.Y. CHARLES E. FEIGLEY, University of South Carolina School of Public Health, Columbia, S.C. DONALD E. GARDNER, Inhalation Toxicology Associates, Raleigh, N.C. SIDNEY GREEN, Corning Hazelton, Inc., Vienna, Va. ROGENE F. HENDERSON, Lovelace Biomedical and Environmental Research Institute, Albuquerque, N.Mex. CAROLE A. KIMMEL, U.S. Environmental Protection Agency, Washington, D.C. Staff KULBIR S. BAKSHI, Program Director for the Committee on Toxicology MARGARET M. MCVEY, Project Director RUTH E. CROSSGROVE, Editor CATHERINE M. KUBIK, Senior Program Assistant LINDA V. LEONARD, Senior Project Assistant LUCY V. FUSCO, Program Assistant Sponsor: U.S. Department of Defense

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Committee on Toxicology ROGENE F. HENDERSON (Chair), Lovelace Biomedical and Environmental Research Institute, Albuquerque, N.Mex. DONALD E. GARDNER (Vice-Chair), Inhalation Toxicology Associates, Raleigh, N.C. GERMAINE M. BUCK, State University of New York at Buffalo, N.Y. DEBORAH A. CORY-SLECHTA, University of Rochester, N.Y. KEVIN E. DRISCOLL, Procter & Gamble Company, Cincinnati, Ohio ELAINE M. FAUSTMAN, University of Washington, Seattle, Wash. CHARLES E. FEIGLEY, University of South Carolina, Columbia, S.C. DAVID W. GAYLOR, U.S. Food and Drug Administration, Jefferson, Ark. IAN A. GREAVES, University of Minnesota, Minneapolis, Minn. SIDNEY GREEN, Corning Hazleton, Inc., Vienna, Va. WILLIAM E. HALPERIN, National Institute for Occupational Safety and Health, Atlanta, Ga. LOREN D. KOLLER, Oregon State University, Corvallis, Oreg. GEORGE B. KOELLE, University of Pennsylvania, Philadelphia, Pa. DANIEL KREWSKI, Health Canada, Ottawa, Ontario THOMAS E. MCKONE, University of California, Berkeley, Calif. MICHELE A. MEDINSKY, Chemical Industry Institute of Toxicology, Research Triangle Park, N.C. JOHN L. O'DONOGHUE, Eastman Kodak Company, Rochester, N.Y. ROBERT SNYDER, Environmental and Occupational Health Sciences Institute, Piscataway, N.J. BERNARD M. WAGNER, Wagner Associates, Inc., Millburn, N.J. BAILUS WALKER JR., Howard University, Washington, D.C. ANNETTA P. WATSON, Oak Ridge National Laboratory, Oak Ridge, Tenn. HANSPETER R. WITSCHI, University of California, Davis, Calif. GAROLD S. YOST, University of Utah, Salt Lake City, Utah

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Staff of the Committee on Toxicology KULBIR S. BAKSHI, Program Director MARGARET E. MCVEY, Program Officer RUTH E. CROSSGROVE, Editor CATHERINE M. KUBIK, Senior Program Assistant LUCY V. FUSCO, Program Assistant LINDA V. LEONARD, Senior Project Assistant

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Board on Environmental Studies and Toxicology PAUL G. RISSER (Chair), Oregon State University, Corvallis, Oreg. MAY R. BERENBAUM, University of Illinois, Urbana, III. EULA BINGHAM, University of Cincinnati, Cincinnati, Ohio PAUL BUSCH, Malcolm Pirnie, Inc., White Plains, N.Y. EDWIN H. CLARK II, Clean Sites, Inc., Alexandria, Va. ELLIS COWLING, North Carolina State University, Raleigh, N.C. GEORGE P. DASTON, The Procter & Gamble Co., Cincinnati, Ohio PETER L. DEFUR, Virginia Commonwealth University, Richmond, Va. David L. Eaton, University of Washington, Seattle, Wash. DIANA FRECKMAN, Colorado State University, Ft. Collins, Colo. ROBERT A. FROSCH, Harvard University, Cambridge, Mass. DANIEL KREWSKI, Health & Welfare Canada, Ottawa, Ontario RAYMOND C. LOEHR, The University of Texas, Austin, Tex. WARREN MUIR, Hampshire Research Institute, Alexandria, Va. GORDON ORIANS, University of Washington, Seattle, Wash. GEOFFREY PLACE, Hilton Head, S.C. BURTON H. SINGER, Princeton University, Princeton, N.J. MARGARET STRAND, Bayh, Connaughton and Malone, Washington, D.C. BAILUS WALKER, JR., Howard University, Washington, D.C. GERALD N. WOGAN, Massachusetts Institute of Technology, Cambridge, Mass. TERRY F. YOSIE, E. Bruce Harrison Co., Washington, D.C. Staff JAMES J. REISA, Director DAVID J. POLICANSKY, Associate Director and Program Director for Natural Resources and Applied Ecology CAROL A. MACZKA, Program Director for Toxicology and Risk Assessment LEE R. PAULSON, Program Director for Information Systems and Statistics RAYMOND A. WASSEL, Program Director for Environmental Sciences and Engineering

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Commission on Life Sciences THOMAS D. POLLARD (Chair), The Salk Institute, La Jolla, Calif. FREDERICK R. ANDERSON, Cadwalader, Wickersham & Taft, Washington, D.C. JOHN C. BAILAR III, University of Chicago, Chicago, III. PAUL BERG, Stanford University School of Medicine, Stanford, Calif. JOHN E. BURRIS, Marine Biological Laboratory, Woods Hole, Mass. SHARON L. DUNWOODY, University of Wisconsin, Madison, Wisc. URSULA W. GOODENOUGH, Washington University, St. Louis, Mo. HENRY W. HEIKKINEN, University of Northern Colorado, Greeley, Colo. HANS J. KENDE, Michigan State University, East Lansing, Mich. SUSAN E. LEEMAN, Boston University School of Medicine, Boston, Mass. THOMAS E. LOVEJOY, Smithsonian Institution, Washington, D.C. DONALD R. MATTISON, University of Pittsburgh, Pittsburgh, Pa. JOSEPH E. MURRAY, Wellesley Hills, Mass. EDWARD E. PENHOET, Chiron Corporation, Emeryville, Calif. EMIL A. PFITZER, Research Institute for Fragrance Materials, Hackensack, N.J. MALCOLM C. PIKE, University of Southern California, Los Angeles, Calif. HENRY C. PITOT III, University of Wisconsin, Madison, Wisc. JONATHAN M. SAMET, The Johns Hopkins University, Baltimore, Md. CHARLES F. STEVENS, The Salk Institute, La Jolla, Calif. JOHN L. VANDEBERG, Southwest Foundation for Biomedical Research, San Antonio, Tex. PAUL GILMAN, Executive Director

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Other Recent Reports of the Board on Environmental Studies and Toxicology Carcinogens and Anticarcinogens in the Human Diet: A Comparison of Naturally Occurring Synthetic and Natural Substances (1996) Upstream: Salmon and Society in the Pacific Northwest (1996) Science and the Endangered Species Act (1995) Wetlands: Characteristics and Boundaries (1995) Biologic Markers (Urinary Toxicology (1995), Immunotoxicology (1992), Environmental Neurotoxicology (1992), Pulmonary Toxicology (1989), Reproductive Toxicology (1989)) Review of EPA's Environmental Monitoring and Assessment Program (three reports, 1994-1995) Science and Judgment in Risk Assessment (1994) Ranking Hazardous Sites for Remedial Action (1994) Pesticides in the Diets of Infants and Children (1993) Issues in Risk Assessment (1993) Setting Priorities for Land Conservation (1993) Protecting Visibility in National Parks and Wilderness Areas (1993) Dolphins and the Tuna Industry (1992) Environmental Neurotoxicology (1992) Hazardous Materials on the Public Lands (1992) Science and the National Parks (1992) Animals as Sentinels of Environmental Health Hazards (1991) Assessment of the U.S. Outer Continental Shelf Environmental Studies Program, Volumes I-IV (1991-1993) Human Exposure Assessment for Airborne Pollutants (1991) Monitoring Human Tissues for Toxic Substances (1991) Rethinking the Ozone Problem in Urban and Regional Air Pollution (1991) Decline of the Sea Turtles (1990) Tracking Toxic Substances at Industrial Facilities (1990) Copies of these reports may be ordered from the National Academy Press (800) 624-6242 or (202) 334-3313

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Other Recent Reports of the Committee on Toxicology Toxicity of Alternatives to Chlorofluorocarbons: HFC-134a and HCFC-123 (1996) Permissible Exposure Levels for Selected Military Fuel Vapors (1996) Spacecraft Maximum Allowable Concentrations for Selected Airborne Contaminants, Volume I (1994), Volume 2 (1996), and Volume 3 (1996) Nitrate and Nitrite in Drinking Water (1995) Guidelines for Chemical Warfare Agents in Military Field Drinking Water (1995) Review of the U.S. Naval Medical Research Institute's Toxicology Program (1994) Health Effects of Permethrin-Impregnated Army Battle-Dress Uniforms (1994) Health Effects of Ingested Fluoride (1993) Guidelines for Developing Community Emergency Exposure Levels for Hazardous Substances (1993) Guidelines for Developing Spacecraft Maximum Allowable Concentrations for Space Station Contaminants (1992) Review of the U.S. Army Environmental Hygiene Agency Toxicology Division (1991) Permissible Exposure Levels and Emergency Exposure Guidance Levels for Selected Airborne Contaminants (1991)

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Preface U.S. ARMY personnel are exposed to various smokes and other obscurants during combat training. This report is intended to assist the Army in its efforts to ensure that exposures to these substances do not adversely effect the health of military personnel or the public living and working near military-training facilities. In this report, the National Research Council's Subcommittee on Military Smokes and Obscurants reviews the available toxicity data on four obscuring smokes—fog oil, diesel fuel, red phosphorus, and hexachloroethane—and develops exposure guidance levels for each. The subcommittee was greatly assisted by several individuals who provided information on the uses and toxicity of the smokes considered in this report. We gratefully acknowledge Colonel Francis L. O'Donnell, Major James Martin, Lieutenant Colonel Forrest Oliverson, and the Office of the Surgeon General of the U.S. Army for their interest and support of this project. We also thank other persons who provided information for the subcommittee, including Winnifred Palmer, Sandra Thomson, Stephen Kistner, and Michael Burnham (all from the U.S. Army), Ian Greaves (University of Minnesota), David Gaylor (U.S. Food and Drug Administration), and Catherine Aranyi (IIT Research Institute). We are grateful for the assistance of the NRC staff in the

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preparation of this report. In particular, the subcommittee wishes to acknowledge Kulbir S. Bakshi, program director for the Committee on Toxicology, and Margaret E. McVey, project director for the subcommittee. Other staff members who contributed to this effort are Paul Gilman, executive director of the Commission on Life Sciences; James J. Reisa, director of the Board on Environmental Studies and Toxicology; Carol A. Maczka, program director for toxicology and risk assessment; Ruth E. Crossgrove, editor; and Lucy Fusco and Linda V. Leonard, project assistants. Finally, we would like to thank all the members of the subcommittee for their expertise and dedicated effort throughout development of this report. Michele A. Medinsky, Ph.D. Chair, Subcommittee on Military Smokes and Obscurants Rogene F. Henderson, Ph.D. Chair, Committee on Toxicology

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Contents     LIST OF ABBREVIATIONS   xv     SUMMARY     1   INTRODUCTION   11     Smokes Reviewed in this Report   12     U.S. Army Policy Concerning Use of Obscurants   14     Subcommittee Task   16     Definitions of Exposure Guidance Levels   17     Approach to Developing Exposure Guidance Levels   19     Summary of Approach   22     References   24 2   DIESEL-FUEL SMOKE   26     Background Information   26     Toxicokinetics   28     Toxicity Summary   29     Existing Recommended Exposure Limits   51     Subcommittee Evaluation and Recommendations   51     Research Needs   56     References   56 3   FOG-OIL SMOKE   60

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    Background Information   60     Toxicokinetics   64     Toxicity Summary   64     Existing Recommended Exposure Limits   85     Subcommittee Evaluation and Recommendations   85     Research Needs   89     References   91 4   RED PHOSPHORUS SMOKE   98     Background Information   98     Toxicokinetics   101     Toxicity Summary: Elemental Red Phosphorus   101     Toxicity Summary: Red Phosphorus-Butyl Rubber   102     Existing Recommended Exposure Limits   118     Subcommittee Evaluation and Recommendations   119     Research Needs   123     References   124 5   HEXACHLOROETHANE SMOKE   127     Background Information   127     Toxicokinetics   137     Toxicity Summary   138     Existing Recommended Exposure Limits   151     Subcommittee Evaluation and Recommendations   151     Research Needs   156     References   156

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List of Abbreviations ACGIH American Conference of Governmental Industrial Hygienists COT Committee on Toxicology CT the product of concentration and time DOD U.S. Department of Defense EEGL emergency exposure guidance level EPA U.S. Environmental Protection Agency FDA U.S. Food and Drug Administration HCE hexachloroethane (the chemical) HC hexachloroethane (when combined with zinc oxide to produce a smoke) HEPA high-efficiency particulate air IARC International Agency for Research on Cancer LC50 lethal concentration for 50% of the test animals LCT50 lethal concentration multiplied by exposure time for 50% of the test animals LD50 lethal dose for 50% of the test animals LOAEL lowest-observed-adverse-effect level MOUT military operations in urban terrain NIOSH U.S. National Institute for Occupational Safety and Health NOAEL no-observed-adverse-effect level NRC National Research Council

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OSHA U.S. Occupational Safety and Health Administration PAH polycyclic aromatic hydrocarbons PEL permissible exposure limit PEGL permissible emergency guidance level PPEGL permissible public exposure guidance level RP-BR red phosphorus-butyl rubber SPEGL short-term public exposure guidance level STEL short-term exposure limit TLV Threshold Limit Value TWA time-weighted average VEESS vehicle-engine-exhaust-smoke system

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Toxicity of Military Smokes and Obscurants

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