Toxicity of Military Smokes and Obscurants

Volume 3

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.



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Toxicity of Military Smokes and Obscurants: Volume 3 Toxicity of Military Smokes and Obscurants Volume 3 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.

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Toxicity of Military Smokes and Obscurants: Volume 3 NATIONAL ACADEMY PRESS 2101 Constitution Ave., N.W. Washington, D.C. 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 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 project was supported by Contract Nos. DAMD17-89-C-9086 and DAMD 17-99-C-9049 between the National Academy of Sciences and the U.S. Department of Defense. 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 this project. International Standard Book Number 0-309-06599-2 Additional copies of this report are available from: National Academy Press 2101 Constitution Ave., NW Box 285 Washington, DC 20055 800-624-6242 202-334-3313 (in the Washington metropolitan area) http://www.nap.edu Copyright 1999 by the National Academy of Sciences. All rights reserved.

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Toxicity of Military Smokes and Obscurants: Volume 3 SUBCOMMITTEE ON MILITARY SMOKESAND OBSCURANTS MICHELE A. MEDINSKY (Chair), Chemical Industry Institute of Toxicology, Research Triangle Park, North Carolina KEVIN E. DRISCOLL, The Procter and Gamble Company, Cincinnati, Ohio CHARLES E. FEIGLEY, University of South Carolina School of Public Health, Columbia, South Carolina DONALD E. GARDNER, Inhalation Toxicology Associates, Raleigh, North Carolina SIDNEY GREEN, Howard University, Washington, D.C. ROGENE F. HENDERSON, Lovelace Respiratory Research Institute, Albuquerque, New Mexico CAROLE A. KIMMEL, U.S. Environmental Protection Agency, Washington, D.C. HANSPETER R. WITSCHI, University of California, Davis, California GAROLD S. YOST, University of Utah, Salt Lake City, Utah Staff KULBIR S. BAKSHI, Program Director for the Committee on Toxicology ABIGAIL STACK, Project Director RUTH E. CROSSGROVE, Editor MIRSADA KARALIC-LONCAREVIC, Information Specialist LINDA V. LEONARD, Senior Project Assistant LUCY V. FUSCO, Project Assistant CHRISTINE PHILLIPS, Project Assistant Sponsor U.S. DEPARTMENT OF DEFENSE

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Toxicity of Military Smokes and Obscurants: Volume 3 COMMITTEE ON TOXICOLOGY BAILUS WALKER, JR. (Chair), Howard University Medical Center, Washington, D.C. MELVIN E. ANDERSEN, Colorado State University, Denver, Colorado GERMAINE M. BUCK, State University of New York at Buffalo GARY P. CARLSON, Purdue University, West Lafayette, Indiana JACK H. DEAN, Sanofi Pharmaceuticals, Inc., Malveme, Pennsylvania ROBERT E. FORSTER II, University of Pennsylvania, Philadelphia, Pennsylvania PAUL M.D. FOSTER, Chemical Industry Institute of Toxicology, Research Triangle Park, North Carolina DAVID W. GAYLOR, U.S. Food and Drug Administration, Jefferson, Arkansas JUDITH A. GRAHAM, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina SIDNEY GREEN, Howard University, Washington, D.C. WILLIAM E. HALPERIN, National Institute for Occupational Safety and Health, Cincinnati, Ohio CHARLES H. HOBBS, Lovelace Respiratory Research Institute and Lovelace Biomedical and Environmental Research Institute, Albuquerque, New Mexico FLORENCE K. KINOSHITA, Hercules Incorporated, Wilmington, Delaware MICHAEL J. KOSNETT, University of Colorado Health Sciences Center, Denver, Colorado MORTON LIPPMANN, New York University School of Medicine, Tuxedo, New York THOMAS E. MCKONE, University of California, Berkeley, California ERNEST E. MCCONNELL, Toxpath, Inc., Raleigh, North Carolina DAVID H. MOORE, Battelle Memorial Institute, Bel Air, Maryland GÜNTER OBERDÖRSTER, University of Rochester, Rochester, New York JOHN L. O'DONOGHUE, Eastman Kodak Company, Rochester, New York GEORGE M. RUSCH, Allied Signal, Inc., Morristown, New Jersey MARY E. VORE, University of Kentucky, Lexington, Kentucky ANNETTA P. WATSON, Oak Ridge National Laboratory, Oak Ridge, Tennessee Staff KULBIR S. BAKSHI, Program Director SUSAN N.J. PANG, Program Officer ABIGAIL STACK, Program Officer RUTH E. CROSSGROVE, Publications Manager KATHRINE J. IVERSON, Manager, Toxicology Information Center LUCY V. FUSCO, Project Assistant LEAH PROBST, Project Assistant EVELYN SIMEON, Project Assistant

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Toxicity of Military Smokes and Obscurants: Volume 3 BOARDON ENVIRONMENTAL STUDIESAND TOXICOLOGY GORDON ORIANS (Chair), University of Washington, Seattle, Washington DONALD MATTISON (Vice Chair), March of Dimes, White Plains, New York DAVID ALLEN, University of Texas, Austin, Texas INGRID C. BURKE, Colorado State University, Fort Collins, Colorado WILLIAM L. CHAMEIDES, Georgia Institute of Technology, Atlanta, Georgia JOHN DOULL, The University of Kansas Medical Center, Kansas City, Kansas CHRISTOPHER B. FIELD, Carnegie Institute of Washington, Stanford, California JOHN GERHART, University of California, Berkeley, California J. PAUL GILMAN, Celera Genomics, Rockville, Maryland BRUCE D. HAMMOCK, University of California, Davis, California MARK HARWELL, University of Miami, Miami, Florida ROGENE HENDERSON, Lovelace Respiratory Research Institute, Albuquerque, New Mexico CAROL HENRY, Chemical Manufacturers Association, Arlington, Virginia BARBARA HULKA, University of North Carolina, Chapel Hill, North Carolina JAMES F. KITCHELL, University of Wisconsin, Madison, Wisconsin DANIEL KREWSKI, University of Ottawa, Ottawa, Ontario JAMES A. MACMAHON, Utah State University, Logan, Utah MARIO J. MOLINA, Massachusetts Institute of Technology, Cambridge, Massachusetts CHARLES O'MELIA, Johns Hopkins University, Baltimore, Maryland WILLEM F. PASSCHIER, Health Council of the Netherlands KIRK SMITH, University of California, Berkeley, California MARGARET STRAND, Oppenheimer Wolff Donnelly & Bayh, LLP, Washington, D.C. TERRY F. YOSIE, Chemical Manufacturers Association, Arlington, Virginia Senior Staff JAMES J. REISA, Director DAVID J. POUCANSKY, Associate Director and Senior Program Director for Applied Ecology CAROL A. MACZKA, Senior Program Director for Toxicology and Risk Assessment RAYMOND A. WASSEL, Senior Program Director for Environmental Sciences and Engineering KULBIR BAKSHI, Program Director for the Committee on Toxicology LEE R. PAULSON, Program Director for Resource Management

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Toxicity of Military Smokes and Obscurants: Volume 3 COMMISSIONON LIFE SCIENCES MICHAEL T. CLEGG (Chair), University of California, Riverside, California PAUL BERG (Vice Chair), Stanford University, Stanford, California FREDERICK R. ANDERSON, Cadwalader, Wickersham & Taft, Washington, D.C. JOHN C. BAILAR III, University of Chicago, Chicago, Illinois JOANNA BURGER, Rutgers University, Piscataway, New Jersey SHARON L. DUNWOODY, University of Wisconsin, Madison, Wisconsin DAVID EISENBERG, University of California, Los Angeles, California JOHN EMMERSON, Portland, Oregon NEAL FIRST, University of Wisconsin, Madison, Wisconsin DAVID J. GALAS, Keck Graduate Institute of Applied Science, Claremont, California DAVID V. GOEDDEL, Tularik, Inc., South San Francisco, California ARTURO GOMEZ-POMPA, University of California, Riverside, California COREY S. GOODMAN, University of California, Berkeley, California HENRY HEIKKINEN, University of Northern Colorado, Greeley, Colorado BARBARA S. HULKA, University of North Carolina, Chapel Hill, North Carolina HANS J. KENDE, Michigan State University, East Lansing, Michigan CYNTHIA KENYON, University of California, San Francisco, California MARGARET G. KIDWELL, University of Arizona, Tucson, Arizona BRUCE R. LEVIN, Emory University, Atlanta, Georgia OLGA F. LINARES, Smithsonian Tropical Research Institute, Miami, Florida DAVID LIVINGSTON, Dana-Farber Cancer Institute, Boston, Massachusetts DONALD R. MATTISON, March of Dimes, White Plains, New York ELLIOT M. MEYEROWITZ, California Institute of Technology, Pasadena, California ROBERT T. PAINE, University of Washington, Seattle, Washington RONALD R. SEDEROFF, North Carolina State University, Raleigh, North Carolina ROBERT R. SOKAL, State University of New York, Stony Brook, New York CHARLES F. STEVENS, The Salk Institute, La Jolla, California SHIRLEY M. TILGHMAN, Princeton University, Princeton, New Jersey JOHN L. VANDEBERG, Southwest Foundation for Biomedical Research, San Antonio, Texas RAYMOND L. WHITE, University of Utah, Salt Lake City, Utah Staff WARREN R. MUIR, Executive Director JACQUELINE K. PRINCE, Financial Officer BARBARA B. SMITH, Administrative Associate KIT W. LEE, Administrative Assistant

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Toxicity of Military Smokes and Obscurants: Volume 3 OTHER REPORTSOF THE BOARDON ENVIRONMENTAL STUDIESAND TOXICOLOGY Research Priorities for Airborne Particulate Matter: II. Evaluating Research Progress and Updating the Portfolio (1999) Ozone-Forming Potential of Reformulated Gasoline (1999) Risk-Based Waste Classification in California (1999) Arsenic in Drinking Water (1999) Research Priorities for Airborne Particulate Matter I. Immediate Priorities and a Long-Range Research Portfolio (1998) Brucellosis in the Greater Yellowstone Area (1998) The National Research Council's Committee on Toxicology: The First 50 Years (1997) Toxicologic Assessment of the Army's Zinc Cadmium Sulfide Dispersion Tests (1997) Carcinogens and Anticarcinogens in the Human Diet (1996) Upstream: Salmon and Society in the Pacific Northwest (1996) Science and the Endangered Species Act (1995) Wetlands: Characteristics and Boundaries (1995) Biologic Markers (5 reports, 1989-1995) Review of EPA's Environmental Monitoring and Assessment Program (3 reports, 1994-1995) Science and Judgment in Risk Assessment (1994) Ranking Hazardous Waste 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) 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) Copies of these reports may be ordered from the National Academy Press (800) 624-6242 or (202) 334-3313 www.nap.edu

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Toxicity of Military Smokes and Obscurants: Volume 3 OTHER REPORTS OF THE COMMITTEE ON TOXICOLOGY Review of the U.S. Army's Health Risk Assessments for Oral Exposure to Six Chemical-Warfare Agents (1999) Assessment of Exposure-Response Functions for Rocket-Emissions Toxicants (1998) Review of A Screening Level Risk Assessment for the Naval Air Facility at Atsugi, Japan (Letter Report) (1998) Toxicity of Military Smokes and Obscurants, Volume 1 (1997), Volume 2 (1999) Review of Acute Human-Toxicity Estimates for Selected Chemical-Warfare Agents (1997) The National Research Council's Committee on Toxicology: The First 50 Years (1997) Toxicologic Assessment of the Army's Zinc Cadmium Sulfide Dispersion Tests (1997) Toxicologic Assessment of the Army's Zinc Cadmium Sulfide Dispersion Tests: Answers to Commonly Asked Questions (1997) 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 1 (1994), Volume 2 (1996), 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)

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Toxicity of Military Smokes and Obscurants: Volume 3 Preface THE U.S. ARMY uses smokes and obscurants to shield armed forces from view, signal friendly forces, and mark positions. Military personnel are exposed to smokes and obscurants during training exercises. The Army would like to ensure that exposures to these substances during training do not adversely affect the health of Army personnel or the public living and working near military-training facilities. To assist with this effort, the Army requested the National Research Council (NRC) to review independently the available toxicity data on certain smokes and obscurants and to recommend exposure guidance levels for each. In response, the NRC's Committee on Toxicology (COT) convened the Subcommittee on Military Smokes and Obscurants, which prepared this report. This report (Volume 3 in the series) assesses toxicity data for seven colored smoke formulations. In Volume 1 of the series, fog oil, diesel fuel, red phosphorus, and hexachloroethane smokes were reviewed, and in Volume 2, white phosphorus, brass, titanium dioxide, and graphite smokes were reviewed. Several individuals assisted the subcommittee by providing information on the uses and toxicity of the colored smokes addressed in this report. We gratefully acknowledge Colonel Francis L. O'Donnell, Major James Martin, Colonel David Wilder, and the Office of the Surgeon General of the U.S. Army for their interest and support of this project. We also

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Toxicity of Military Smokes and Obscurants: Volume 3 thank Winnifred Palmer, Sandra Thomson, and Michael Burnham of the U.S. Army for providing information to the subcommittee. 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 for reviewing NRC and Institute of Medicine reports. The purpose of this independent review was to provide candid and critical comments to assist 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 review comments and draft manuscript remain confidential to protect the integrity of the deliberative process. We wish to thank the following individuals, who are neither officials nor employees of the NRC, for their participation in the review of this report: Michael Dorato, Lilly Research Laboratories; Andrea Hubbard, University of Connecticut; Robert Phalen, University of California, Irvine; Mary Vore, University of Kentucky; and George Rusch, Allied Signal Inc. (Review Coordinator). These individuals provided many constructive comments and suggestions. It must be emphasized, however, that responsibility for the final content of this report rests entirely with the authoring committee and the NRC. We are grateful for the assistance of the NRC staff in the preparation of this report. The subcommittee wishes to acknowledge Kulbir Bakshi, program director of the Committee on Toxicology, and Abigail Stack, project director for this report. Other staff members contributing to this report were Paul Gilman, former executive director of the Commission on Life Sciences; James Reisa, director of the Board on Environmental Studies and Toxicology; Carol Maczka, senior program director for toxicology and risk assessment; Ruth Crossgrove, editor; and Lucy Fusco, Linda Leonard, and Christine Phillips, project assistants. Finally, we would like to thank all the members of the subcommittee for their expertise and dedicated effort throughout the study. Michele A. Medinsky, Ph.D. Chair, Subcommittee On Military Smokes and Obscurants Bailus Walker, Ph.d., M.P.H. Chair, Committee On Toxicology

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Toxicity of Military Smokes and Obscurants: Volume 3 Contents     LIST OF ABBREVIATIONS   xiii     SUMMARY   1 1   INTRODUCTION   9     The Subcommittee's Task   9     Smokes Reviewed in this Report   10     U.S. Army Policy on Use of Colored Smokes   14     Definitions of Exposure Guidance Levels   16     Approach for Recommending Exposure Guidance Levels   17     Organization of the Report   18     References   19 2   OLD SMOKE FORMULATIONS   21     Yellow-Smoke Formulation   21     Green-Smoke Formulation   23     Red-Smoke Formulation   26     Violet-Smoke Formulation   29     Overall Evaluation of Toxicity   31     Previous Recommended Exposure Limits   32     Subcommittee Recommendations   32     References   33

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Toxicity of Military Smokes and Obscurants: Volume 3 3   NEW SMOKE FORMULATIONS   36     Yellow-Smoke Formulation   36     Green-Smoke Formulation   40     Red-Smoke Formulation   43     Overall Evaluation of Toxicity   46     Previous Recommended Exposure Limits   46     Subcommittee Recommendations   47     References   48 APPENDIX A:   BENZANTHRONE   50 APPENDIX B:   VAT YELLOW 4   55 APPENDIX C:   SOLVENT YELLOW 33   58 APPENDIX D:   SOLVENT GREEN 3   71 APPENDIX E:   SOLVENT RED 1   74 APPENDIX F:   DISPERSE RED 9   79 APPENDIX G:   DISPERSE RED 11   83 APPENDIX H:   1,4-DIAMINO-2,3-DIHYDROANTHRAQUINONE   88 APPENDIX I:   1,4-DIAMINOANTHRAQUINONE   90

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Toxicity of Military Smokes and Obscurants: Volume 3 LIST OF ABBREVATIONS AEHA U.S. Army Environment Hygiene Agency ACGIH American Conference of Governmental Industrial Hygienists BZA benzanthrone CO carbon monoxide COT Committee on Toxicology DAA 1,4-diaminoanthraquinone DBC vat yellow 4 (dibenzochrysenedione) DDA 1,4, diamino-2,3-dihydroanthraquinone DMA disperse red 11 (1,4-diamino-2-(2-quinolyl)-1,3-indandione) DOD U.S. Department of Defense EEGL emergency exposure guidance level EPA U.S. Environmental Protection Agency HGPRT hypoxanthine guanine phosphoribosyl transferase 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 MAA disperse red 9 (1-(methylamino)-9,-10-anthracenedione) MBN solvent red 1 (α-menthozbenzenazo-β-napthol) NOAEL no-observed-adverse-effect level NCI National Cancer Institute NRC National Research Council PTA solvent green 3 (1,4-di-p-toluidino-9,10-anthraquinone) QID solvent yellow 33 (2-(2-quinolyl)-1,3-indandione) REGL repeated exposure guidance level (referred to as permissible exposure guidance level in Volume 1) RPEGL repeated public exposure guidance level (referred to as permissible public exposure guidance level in Volume 1) SPEGL short-term public emergency guidance level

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