United States Office of Water EPA 440 5-80-051 Environmental Protection Regulations and Standards October 1980 Agency Criteria and Standards Division Washington DC 20460 EPA Ambient Water Quality Criteria for Halomethanes AMBIENT WATER QUALITY CRITERIA FOR HALOMETHANES Prepared By U.S. ENVIRONMENTAL PROTECTION AGENCY Office of Water Regulations and Standards Criteria and Standards Division Washington, D.C. Office of Research and Development Environmental Criteria and Assessment Office Cincinnati, Ohio Carcinogen Assessment Group Washington, D.C. Environmental Research Laboratories Corvalis, Oregon Duluth, Minnesota Gulf Breeze, Florida Narragansett, Rhode Island i DISCLAIMER This report has been reviewed by the Environmental Criteria and Assessment Office, U.S. Environmental Protection Agency, and approved for publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. AVAILABILITY NOTICE This document is available to the public through the National Technical Information Service, (NTIS), Springfield, Virginia 22161. ii FOREWORD Section 304 (a)(1) of the Clean Water Act of 1977 (P.L. 95-217), requires the Administrator of the Environmental Protection Agency to publish criteria for water quality accurately reflecting the latest scientific knowledge on the kind and extent of all identifiable effects on health and welfare which may be expected from the presence of pollutants in any body of water, including ground water. Proposed water quality criteria for the 65 toxic pollutants listed under section 307 (a)(1) of the Clean Water Act were developed and a notice of their availability was published for public comment on March 15, 1979 (44 FR 15926), July 25, 1979 (44 FR 43660), and October 1, 1979 (44 FR 56628). This document is a revision of those proposed criteria based upon a consideration of comments received from other Federal Agencies, State agencies, special interest groups, and individual scientists. The criteria contained in this document replace any previously published EPA criteria for the 65 pollutants. This criterion document is also published in satisifaction of paragraph 11 of the Settlement Agreement in Natural Resources Defense Council, et. al. vs. Train, 8 ERC 2120 (D.D.C. 1976), modified, 12 ERC 1833 (D.D.C. 1979). The term "water quality criteria" is used in two sections of the Clean Water Act, section 304 (a)(1) and section 303 (c)(2). The term has a different program impact in each section. In section 304, the term represents a non-regulatory, scientific assessment of ecological ef- fects. The criteria presented in this publication are such scientific assessments. Such water quality criteria associated with specific stream uses when adopted as State water quality standards under section 303 become enforceable maximum acceptable levels of a pollutant in ambient waters. The water quality criteria adopted in the State water quality standards could have the same numerical limits as the criteria developed under section 304. However, in many situations States may want to adjust water quality criteria developed under section 304 to reflect local environmental conditions and human exposure patterns before incorporation into water quality standards. It is not until their adoption as part of the State water quality standards that the criteria become regulatory. Guidelines to assist the States in the modification of criteria presented in this document, in the development of water quality standards, and in other water-related programs of this Agency, are being developed by EPA. STEVEN SCHATZOW Deputy Assistant Administrator Office of Water Regulations and Standards iii ACKNOWLEDGEMENTS Aquatic Life Toxicology: William A. Brungs, ERL-Narragansett John H. Gentile, ERL-Narragansett U.S. Environmental Protection Agency U.S. Environmental Protection Agency Mammalian Toxicology and Human Health Effects: Joseph Santodonato Julian Andelman Syracuse Research Corporation University of Pittsburgh Michael Dourson (doc. mgr.) ECAO-Cin Jacqueline V. Carr U.S. Environmental Protection Agency U.S. Environmental Protection Agency Jerry F. Stara (doc. mgr.) ECAO-Cin Patrick Durkin U.S. Environmental Protection Agency Syracuse Research Corporation Terri Laird, ECAO-Cin Si Duk Lee, ECAO-Cin U.S. Environmental Protection Agency U.S. Environmental Protection Agency Steven D. Lutkenhoff, ECAO-Cin Yin-Tak Woo U.S. Environmental Protection Agency Sorrell Schwartz Roy E. Albert* Georgetown University Carcinogen Assessment Group U.S. Environmental Protection Agency Technical Support Services Staff: D.J. Reisman, M.A. Garlough, B.L. Zwayer, P.A. Daunt, K.S. Edwards, T.A. Scandura, A.T. Pressley, C.A. Cooper, M.M. Denessen. Clerical Staff: C.A. Haynes, S.J. Faehr, L.A. Wade, D. Jones, B.J. Bordicks, B.J. Quesnell, T. Highland, B. Gardiner. *CAG Participating Members: Elizabeth L. Anderson, Larry Anderson, Dolph Arnicar, Steven Bayard, David L. Bayliss, Chao W. Chen, John R. Fowle III, Bernard Haberman, Charalingayya Hiremath, Chang S. Lao, Robert McGaughy, Jeffrey Rosen- blatt, Dharm V. Singh, and Todd W. Thorslund. iv TABLE OF CONTENTS Page Criteria Summary Introduction A-1 Aquatic Life Toxicology B-1 Introduction B-1 Effects Acute Toxicity B-1 Chronic Toxicity B-2 Plant Effects B-3 Residues B-3 Summary B-3 Criteria B-4 References B-9 Mammalian Toxicology and Human Health Effects C-1 Introduction C-1 Exposure Ingestion from Water C-3 Ingestion from Food C-9 Inhalation C-13 Dermal C-20 Pharmacokinetics C-21 Absorption, Distribution, Metabolism and Excretion C-21 Effects C-28 Acute, Subacute, and Chronic Toxicity C-28 Synergism and/or Antagonism C-56 Teratogenicity C-56 Mutagenicity C-57 Carcinogenicity C-59 Criterion Formulation C-66 Existing Guidelines and Standards C-66 Special Groups at Risk C-70 Basis and Derivation of Criteria C-71 References C-79 Appendix C-110 v CRITERIA DOCUMENT HALOMETHANES CRITERIA Aquatic Life The available data for halomethanes indicate that acute tox- icity to freshwater aquatic life occurs at concentrations as low as 11,000 µg/l and would occur at lower concentrations among species that are more sensitive than those tested. No data are available concerning the chronic toxicity of halomethanes to sensitive fresh- water aquatic life. The available data for halomethanes indicate that acute and chronic toxicity to saltwater aquatic life occur at concentrations as low as 12,000 and 6,400 µg/l, respectively, and would occur at lower concentrations among species that are more sensitive than those tested. A decrease in algal cell numbers occurs at concen- trations as low as 11,500 µg/l. Human Health For the maximum protection of human health from the potential carcinogenic effects due to exposure of chloromethane, bromo- methane, dichloromethane, bromodichloromethane, tribromomethane, dichlorodifluoromethane, trichlorofluoromethane, or combinations of these chemicals through ingestion of contaminated water and contam- inated aquatic organisms, the ambient water concentration should be zero based on the non-threshold assumption for this chemical. How- ever, zero level may not be attainable at the present time. There- fore, the levels which may result in incremental increase of cancer vi risk over the lifetime are estimated at 10e5, 10 -6 and 10 -7 . The corresponding recommended criteria are 1.9 ,ug/l, 0.19 yg/l, and 0.019 pg/l, respectively. If the above estimates are made for con- sumption of aquatic organisms only, excluding consumption of water, the levels are 157 pg/l, 15.7 rg/l, and 1.57 pug/l, respectively. vii INTRODUCTION The halomethanes are a subcategory of halogenated hydro- carbons. This document reviews the following halomethanes: chloromethane, bromomethane, methylene chloride, bromoform, bromo- dichlorometharte, trichlorofluoromethane, and dichlorodifluoro- methane. Methyl chloride is also known as chloromethane (Windholz, 1976). It is a colorless, flammable, almost odorless gas at room temperature and pressure. It is used as a refrigerant, a methylat- ing agent, a dewaxing agent, and catalytic solvent in synthetic rubber production (MacDonald, 1964). Methyl bromide has been re- ferred to as bromomethane, monobromomethane, and Embafume® (Windholz, 1976). It has been widely used as a fumigant, fire extinguisher, refrigerant, and insecticide (Kantarjian and Shaheen, 1963). Today the major use of methyl bromide is as a fumigating agent, and this use has caused sporadic outbreaks of serious human poisoning. Methylene chloride has been referred to as dichloromethane, methylene dichloride, and methylene bichloride (Windholz, 1976). It is a common industrial solvent found in insecticides, metal cleaners, paints, and paint and varnish removers (Balmer, et al. 1976). In 1976, 244,129 metric tons (538,304,000 lbs) were pro- duced in the United States with an additional 19,128 metric tons (42,177,000 lbs) imported (U.S. EPA, 1977a). Trichlorofluoromethane is also known as trichloromonofluoro- methane, fluorotrichloromethane, Frigen 11®, Freon 11®,and A-1 Arcton 9®. Dichlorodifluoromethane has been referred to as di- fluorodichloromethane, Freon 12®, Frigen 12®, Arcton 6R, Genetron 12®, Halon®, and Isotron 2®. Freon compounds are or- ganic compounds which contain fluorine. They have many desirable characteristics which include a high degree of chemical stability and relatively low toxicity, and they are nonflammable. Freon com- pounds have found many applications ranging from use as propellants to refrigerants and solvents (Van Auken, et al. 1975). Bromoform is