600/1-76-020 1976RESEARCH REPORTING SERIES. Research reports of the Office of Research and Development, U.S. Environ- ‘mental Protection Agency, have been grouped into five series. These five broad categories were established to facilitate further development and application of environmental technology. Elimination of traditional grouping was con- sciously planned to foster technology transfer and a maximum interface in related fields. The five series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4, Environmental Monitoring 5. Socioeconomic Environmental Studies This report has been assigned to the ENVIRONMENTAL HEALTH EFFECTS RESEARCH series. This series describes projects and studies relating to the tolerances of man for unhealthful substances or conditions. This work is gener- ally assessed from a medical viewpoint, including physiological or psycho- logical studies. in addition to toxicology and other medical specialities, study areas include biomedical instrumentation and health research techniques uti- lizing animals—but always with intended application to human health measures. This document is available to the public through the National Technical Informa- tion Service, Springfield, Virginia 22161EPA-600/1-76-020 April 1976 CHLORINE AND HYDROGEN CHLORIDE By Subcommittee on Chlorine and Hydrogen Chloride National Academy of Sciences National Research Council Committee on Medical and Biologic Effects of Environmental Pollutants Washington, D.C. Contract No. 68-02-1226 Project Officer F, Gordon Hueter Criteria and Special Studies Office Health Effects Research Laboratory Research Triangle Park, N.C. 27711 U.S. ENVIRONMENTAL PROTECTION AGENCY OFFICE OF RESEARCH AND DEVELOPMENT HEALTH EFFECTS RESEARCH LABORATORY RESEARCH TRIANGLE PARK, N.C. 27711DISCLAIMER This report has been reviewed by the Health Effects Research Laboratory, U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. 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 Acadeny 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 work on which this publication is based was performed pursuant to Contract No, 68-02-1226 with the Environmental Protection Agency. iiSUBCOMMITTEE ON CHLORINE AND HYDROGEN CHLORIDE RALPH G. SMITH, University of Michigan School of Public Health, Ann Arbor, Chairman, MARIO C. BATTIGELLI, University of North Carolina School of Medicine, Chapel Hill. RALPH R. COOK, Dow Chemical Company, Midland, Michigan. WARREN S. FERGUSON, Allied Chemical Corporation, Morristown, New Jersey. NORMAN LACASSE, Spring Mills, Pennsylvania. WILBUR D. SHULTS, Oak Ridge National Laboratory, Oak Ridge, Tennessee. Consultants JOSEPH COLUCCI, General Motors Research Laboratories, Warren, Michigan. ROBERT DUCE, Graduate School of Oceanography, University of Rhode Island, Kingston. GEORGE M, HIDY, Environmental Research and Technology, Inc., Westlake Village, California. ALEX KATONA, Hooker Chemical Company, Niagara Falls, New York. CHARLES G. KRAMER, Dow Chemical Company, Midland, Michigan. RICHARD W. MC BURNEY, Diamond Shamrock Corporation, Painesville, Ohio. BERNARD P, MC NAMARA, Edgewood Arsenal, Maryland. ELIZABETH E. FORCE, Division of Medical Sciences, National Research Council, Washington, D.C., Staff Officer. JAMES A, FRAZIER, Division of Medical Sciences, National Research Council, Washington, D.C., Staff Officer. idCOMMITTEE ON MEDICAL AND BIOLOGIC EFFECTS OF ENVIRONMENTAL POLLUTANTS HERSCHEL E. GRIFFIN, Graduate School of Public Health, University of Pittsburgh, Pennsylvania, Chairman. DAVID M. ANDERSON, Environmental Quality Control Division, Bethlehem Steel Corporation, Pennsylvania. RICHARD U, BYERRUM, College of Natural Science, Michigan State University, East Lansing. RONALD F. COBURN, Department of Physiology, University of Pennsylvania School of Medicine, Philadelphia. TIMOTHY CROCKER, Department of Community and Environmental Medicine, University of California College of Medicine, Irvine. SHELDON K, FRIEDLANDER, W. M. Keck Laboratories, California Institute of Technology, Pasadena. SAMUEL A. GUNN, Department of Pathology, University of Miami School of Medicine, Florida. ROBERT I. HENKIN, National Heart and Lung Institute, National Institutes of Health, Bethesda, Maryland. IAN T. T. HIGGINS, School of Public Health, University of Michigan, Ann Arbor. JOE W. HIGHTOWER, Department of Chemical Engineering, Rice University, Houston, Texas. ORVILLE A, LEVANDER, Nutrition Institute, Agricultural Research Center, Beltsville, Maryland. DWIGHT F. METZLER, Kansas State Department of Health and Environment, Topeka. I. HERBERT SCHEINBERG, Department of Medicine, Albert Einstein College of Medicine, Bronx, New York. RALPH G. SMITH, Department of Environmental and Industrial Health, School of Public Health, University of Michigan, Ann Arbor. ivcuaPTER 1 INTRODUCTION Each year, many millions of tone of chlorine are produced to seet the demands of the chentcal Andustry and to satisfy che denand for chlorine in the purification of donestie water supplies. As a consequence of the manufacture and use of this element, sone chlorine gas escapes to the atmosphere. In addition, the action of sunlight on chloride-contsining aerosols has been shown to produce swall asounts of chlorine. Oceastonally, exposure of populations to high concentrations of chlorine has occurred, usually as a result of accidents involving the transportation of chlorine by rail, truck, or barge. For o brief tine, during orld War I, chlorine was intentionally used in warfare, although by most standards it wi not @ very effective weapon. Hydrogen chloride 1s also an important besic chemical, and its close relationship to chlorine luakes it desirable to consider the tvo substances together in discussing environsental effects. ‘The purpose of this report 1 to discuss the medical, biologic, and environsental effects of chlorine pollution in the lower atnosphere, The next three chapters discuse the natural and anthropogenic sources of pollution by chlorine and hydrogen chloride, che varied industrial and other usages of chlorine and hydrogen chloride and the quantities consumed, the atnospheric cheaistry of their transformation and transport processes, and their spatial distribution. Later chapters deal with the effects of chlorine and hydrogen chloride on man, aninals, vegetation, ‘and materials. Chapters 9 and 10 present the summary and conclusions and offer recomendations for consideration in future studies. Methods of aonitoring and analyzing aqueous, gaseous, and biologic eemples for chlorine and hydrogen chloride are discussed in the Appendix. Unless stated otherwise, “chlorine” refers to the elenent and “hydrogen chloride" to the molecule HCL, "Gaseous chlorine" refers to the element when Lt 10 present as the diatonic molecule. Tt should be understood that gai ous chlorine and hydrogen chloride in the atmosphere are complexed with condensation nuclet of unspecified chemical composition. A balance was sought in apportioning the representation of expertise and interests of industry and acadeae in studying the two chemicals tn question. Each participant in the study wea asked to prepare ‘a section of the report based on a review and evaluation of the published information obtained from national and international sources that were avatlable up to July 1, 1974. The summary, conclusions, ‘and recommendations for each section vere prepared by its author and these were consolidated to form Caapters’9 and 10, The drafts of individual chapters vere reviewed and appropriately revised by neabers of the Subcommittee on Chlorine and Hydrogen Chloride. The complete manuscript vas also approved by the Comittee on Medical and Biologic Effects of Environmental Pollutants.CHAPTER 2 SOURCES OF CHLORINE AND HYDROGEN CHLORIDE CHLORINE AND HYDROGEN CHLORIDE IN THE ENVIRONMENT Industrial production of chlorine in the United States has grown and continues to grow at a high rate, In 1972, 9,859, 800 tons of chlorine were produced, compared with 5, 142, 876 tons in 1962 (an increase of about 6.7% per year), and production wasprojected to increase at the rate of approximately 7% per year through 1974. 7798 one major commercial sources of chlorine are the electrolysis of water solutions of the alkali chlorides (96. 6% of total installed U.S, production capacity in 1972) and the electrolysis of fused sodium chloride-calcium chloride salt mixture, in which chlorine is obtained as a by- product of sodium production (slightly under 3. 4% of total installed U.S. capacity in 1972). Or pecause the largest users of chlorine are the chemical industry (approximately 70% of total consumption) and the pulp and paper industry (approximately 18% of total consumption, Te number of sources of possible chlorine emission tends to be restricted, compared, for example, to the number of sources of possible emission of the oxides of sulfur and nitro- gen. Chlorine emission control is generally effective and has been in wide- spread use in industry for many years. The 7. 7% average annual growth in the industrial production of hydro- chloric acid (100% basis*) in the United States over the period 1962-1972 has slightly outstripped the 6.7% average annual growth in the production of chlorine, In 1972, 2,198,140 tons of hydrochloric acid (100% basis) (22. 3% of the chlorine tonnage) were produced, compared with 1,052, 116 tons in 1962 37100% basis" means on the basis of equivalent anhydrous hydrogen chloride. 2+98 (20. 5% of the chlorine tonnage), Production of hydrochloric acid (100% basis) is projected to increase over the next few years at an average annual rate of approximately 5-7%. oe In the United States, hydrogen chloride is produced by three major processes: anys byproduct of the chlorination of organic compounds; by reaction of chloride salt with sulfuric acid (the Mannheim process) or with sulfur dioxide, steam (water), and air (oxygen)-- the Hargreaves process--at high temperature to produce salt cake (sodium sulfate) and hydrogen chloride; and by reaction of chlorine with hydrogen gas. Only one large plant using the Hargreaves process is still in operation in the United States, In common with chlorine production, industrial hydrogen chloride production is confined largely to a few chemical organizations that use one or more of the three major processes and that use an estimated 55-60% of the total production. Theoretically, the essentially anhydrous gaseous hydrogen chloride produced via the three routes (with chlorine, chlorinated organic compounds, other organic materials, and other chemicals in the gas stream) represents a significant atmospheric emission control problem. In practice, however, such potential emission is most commonly, effectively, and inexpensively controlled by scrubbing the main exit-gas stream and any tail-gas stream with water to produce hydrochloric acid for use, sale, or disposal; and other emission control systems have been developed to meet special industrial requirements. The burning of huge amounts of chloride- or chlorine-containing fossil fuels--coal and fuel oil--is a very large source of emission of hydrogen chloride gas to the atmosphere. The magnitude of the problem is discussed further in the section on Combustion of Fuels.* Increasing effort is being directed toward the development of adequate and economical scrubber systems for *Page 21the control of emission of sulfur dioxide, nitrogen oxides, and hydrogen chloride from coal- and oil-fired industrial heating plants and electric generatill] plants, such systems are not now in general use in the United States. The incineration of chloride- or chlorine-containing refuse, paper, and plastics (particularly polyvinylchloride) is another important source of emission of hydrogen chloride gas to the atmosphere. The magnitude of this source is also unknown and is being looked into. * There is evidence that hydrogen chloride gas is emitted to the atmosphere in the exhaust resulting from the combustion of hydrocarbon fuels in transportation. If it is emitted, data to determine its extent are not avail- able. Hydrogen chloride from such a source would probably be in the form of hydrochloric acid aerosol because of the water present in exhaust. The only transportation fuel considered even potentially significant as a source of hydrogen chloride gas emission is motor gasoline that contains the ethylene dichloride scavenger used with lead antiknock compounds. The potential for hydrogen chloride gas emission from transportation sources will decrease significantly, as the EPA imposes regulations to decrease the lead content of gasoline. The National Aeronautics and Space Administration (NASA) Office of Space Science (OSS) Launch Vehicle and Propulsion Programs, in a final en- vironmental statement published in July 1973, indicated that, with respect to global or even national significance, the contribution of NASA launch vehicles for automated missions to environmental pollution appears to be much smaller than that of other sources. ee ‘The environmental effects of hydrogen chloride gas emitted from rocket engines in tests, launches, on-pad accidents, and in- flight abort situations have been considered.Concentrations of hydrogen chloride gas in the ambient atmosphere have not been reported. Under normal atmospheric conditions, hydrogen chloride is an aqueous acid aerosol; usually low relative humidity may allow it to exist as anhydrous hydrogen chloride. ne There has been one report of hydrochloric acid aerosol concentrations in the atmospheric air near a Russian magnesium plant. ee Studies of hydrochloric acid aerosol concentrations in atmospheric air have undoubtedly been hindered because of the unavailability of an analytic method with high specificity for hydrogen chloride itself. Most analytic methods for hydrogen chloride are based on its acidity or on total-chloride determination, and these conventional methods are subject to interferences from other contaminants commonly found in atmospheric air (see the Appendix). Determinationsof background concentrations of chlorine in the ambient atmosphere have not been reported. The air in a 6-square-mile area around a 1961 chlorine tank-car derailment in Louisiana was sampled for chlorine 253 emission, NATURAL SOURCES OF CHLORINE AND HYDROGEN CHLORIDE Minute quantities of hydrogen chloride gas are present in volcanic gases, ore but it is readily converted to hydrochloric acid aerosol by the moisture in the air. All human body fluids contain chlorine: blood at 0. 45% (expressed as 46la sodium chloride) and gastric juices at 0. 4-0. 5% (as hydrochloric acid). “5.The formation of hydrochloric acid in the gastric juices is closely associated with the parietal cells of the gastric glands; one accepted theory is that the hydrochloric acid forms in the absence of carbonates as a result of the inter- change of ions between sodium chloride and carbonic acid. * Nothing in the literature suggests that emission of chlorine or hydrogen chloride gas to the atmosphere results from biochemical reactions; it is extremely unlikely that chlorine or hydrogen chloride gas can be emitted to the atmosphere as a result of biochemical reactions. 266 Chlorine at low concentrations may be formed by atmospheric reactions. For example, chloride compounds and nitrogen dioxide may react to form nitrosyl chloride, which can decompose photochemically to yield free chlorine and nitric oxide. Free chlorine may also be formed in the atmosphere by the reaction of chloride ion and ozone.* It is pointed out in Chapter 4 that there is considerable circumstantial evidence (measurements of the chloride: sodium ratio in the atmosphere in West Coast cities) that sea salt particles (sodium chloride) in the presence of moisture undergo attack by acid-forming gases, such as nitrogen dioxide, to release hydrogen chloride gas. In urban areas, where concentrations of nitrogen dioxide may be relatively high, the chloride:sodium ratio is much lower than would be expected if it were reduced by addition of only soil dust to the sea salt aerosol. See Chapter 4 regarding this an other possible atmospheric reactions leading to the formation of hydrdgen chloride gas. +See also page 103