vvEPA United States Environmental Protection Agency Office of Water Regulations and Standards Criteria and Standards Division Washington DC 20460 Ambient Water Quality Criteria for 2-chlorophenol EPA440/SaHB4 October 1980 C-l ------- AMBIENT WATER QUALITY CRITERIA FOR 2-CHLOROPHENOl 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 ------- 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. 11 ------- FOREWORD Section 304 (a)(l) 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)(l) 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)(l) 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 111 ------- ACKNOWLEDGEMENTS Aquatic Life Toxicology: William A. Brungs, ERL-Narragansett U.S. Environmental Protection Agency David J. Hansen, ERL-Gulf Breeze U.S. Environmental Protection Agency Mammalian Toxicology and Human Health Effects: Gary Osweiler (author) University of Missouri John F. Risher (doc. mgr.) ECAO-Cin U.S. Environmental Protection Agency Jerry F. Stara (doc. mgr.) ECAO-Cin U.S. Environmental Protection Agency Rolf Hartung University of Michigan Terri Laird, ECAO-Cin U.S. Environmental Protection Agency Steven D. Lutkenhoff, ECAO-Cin U.S. Environmental Protection Agency Gordon Chesters University of Wisconsin Patrick Durkin Syracuse Research Corporation Terence M. Grady, ECAO-Cin U.S. Environmental Protection Agency Van Kozak University of Wisconsin Robert Lingg, HERL U.S. Environmental Protection Agency David Ritter, OPP 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, R. Rubinstein. IV ------- TABLE OF CONTENTS Criteria Summary Introduction A_j Aquatic Life Toxicology B_]_ Introduction g_l Effects g~i Acute Toxicity g_j_ Chronic Toxicity g_2 Plant Effects B_2 Residues g_2 Miscellaneous g_2 Summary g_3 Criteria g_4 References g_^ Mammalian Toxicology and Human Health Effects C-l Introduction £_]_ Exposure Q_2 Ingestion from Water Q_2 Ingestion from Food Q_3 Inhalation Q_]_2 Dermal Q_^5 Pharmacokinetics CI15 Absorption Q_^ Distribution r lfi ,. , , . . L-ID Metabolism ^_-^7 Excretion r 10 Effects ^"Jg Acute, Subacute, and Chronic Toxicity C-18 Synergism and/or Antagonism Q_22 Teratogenicity and Mutagenicity C-22 Carcinogenicity £_22 Criterion Formulation C-29 Existing Guidelines and Standards C-29 Current Levels of Exposure C_2g Special Groups at Risk c_30 Basis and Derivation of Criterion r 30 References ------- CRITERIA DOCUMENT 2-CHLOROPHENOL CRITERIA Aquatic Life The available data for 2-chlorophenol indicate that acute toxicity to freshwater aquatic life occurs at concentrations as low as 4,380 yg/1 and would occur at lower concentrations among species that are more sensitive than those tested. No definitive data are available concerning the chronic toxicity of 2-chlorophenol to sensitive freshwater aquatic life but flavor impairment occurs in one species of fish at concentrations as low as 2,000 wg/1. No saltwater organisms have been tested with 2-chlorophenol and no statement can be made concerning acute or chronic toxicity. Human Health Sufficient data is not available for 2-chlorophenol to derive a level which would protect against the potential toxicity of this compound. Using available organoleptic data, for controlling undesirable taste and odor qualities of ambient water, the estimated level is 0.1 ug/1. It should be recognized that organoleptic data as a basis for establishing a water quality criterion have limitations and have no demonstrated relation- ship to potential adverse human health effects. VI ------- INTRODUCTION 2-Chlorophenol is a commercially produced chemical used entirely as an intermediate in the production of other chemicals. It represents a basic chemical feedstock in the manufacture of higher chlorophenols for such uses as fungicides, slimicides, bactericides, antiseptics, disinfectants, and wood and glue preservatives. 2-Chlorophenol is also used to form intermedi- ates in the production of phenolic resins, and has been utilized in a pro- cess for extracting sulfur and nitrogen compounds from coal. 2-Chlorophenol (ortho- or o-chlorophenol) is a substituted phenol hav- ing the empirical formula CgHcOCl. It has a molecular weight of 128.56, a density of 1.2573 at 25°C, and a vapor pressure of 1 mm Hg at 12.1°C (Sax, 1975; Stecher, 1968). 2-Chlorophenol melts at 8.7°C and exhibits a boiling point range of 175 to 176°C (Rodd, 1954; Judson and Kilpatrick, 1949). The spatial configuration and resonance effect of 2-chlorophenol may suppress the activity of the halogen atom by hydrogen bonding, which partly accounts for the lower toxicity than the 3- and 4-chlorophenol isomers (Huang and Gloyna, 1968). In aqueous solution, 2-chlorophenol is slightly soluble (1,000 mg/1) at 25°C and neutral pH (Henshaw, 1971; U.S. EPA, 1973). The log of the octa- nol/water partition coefficient for 2-chlorophenol is 2.16 (U.S. EPA, 1978). 2-Chlorophenol is weakly acidic, possesses a pKa of 8.48 in water at 25°C, and dissociates in alkaline solutions (Judson and Kilpatrick, 1949; Pearce and Simpkins, 1968). Its monovalent salts, in particular, are soluble in aqueous solutions, and the degree of solubility is pH-dependent. Information concerning the presence and fate of 2-chlorophenol is in- complete or nonexistent. However, the generation of waste sources from the A-l ------- commercial production of 2-chlorophenol, its chemically derived products, and the inadvertent synthesis of 2-chlorophenol due to chlorination of phenol in effluents and drinking water sources, may clearly indicate its importance in potential point source and non-point source water contamina- tion. The chlorination of phenol from dilute aqueous solutions (Aly, 1968; Barnhart and Campbell, 1972) and from sewage effluents (Jolley, 1973; Jolley, et al. 1975) has been demonstrated. Microbial degradation of 2-chlorophenol under laboratory conditions has been reported. Studies on the metabolism of the herbicide, 2,4-dichloro- phenoxyacetic acid (2,4-D), have demonstrated the dechlorination and aro- matic ring degradation of 2-chlorophenol by an Arthrobacter species (Loos, et al. 1966). Nachtigall and Butler (1974) reported the complete oxidation of 2-chlorophenol by Pseudomonas sp. isolated from activated sludge. A-2 ------- REFERENCES Aly, O.M. 1968. Separation of phenols in waters by thin-layer chromato- graphy. Water Res. 2: 587. Barnhart, E.L. and G.R. Campbell. 1972. The effect of chlorination on selected organic chemicals. U.S. Government Printing Office, Washington, D.C. Henshaw, T.B. 1971. Adsorption/filtration plant cuts phenols from efflu- ent. Chem. Eng. 78: 47. Huang, J. and E.F. Gloyna. 1968. Effect of organic compounds on photosyn- thetic oxygenations. I. Chlorophyll destruction and suppression of photo- synthetic oxygen production. Water Res. 2: 317. Jolley, R.L. 1973. Chlorination effects on organic constituents in efflu- ents from domestic sanitary sewage treatment plants. Ph.D. dissertation. University of Tennessee. Jolley, R.L., et al. 1975. Chlorination of cooling water: A source of environmentally significant chlorine-containing organic compounds. Proc. 4th Natl. Symp. Radioecology. Corvallis, Oregon. Judson, O.M. and M. Kilpatrick. 1949. The effects of substituents on the dissociation constants of substituted phenols. I. Experimental measurements in aqueous solutions. Jour. Am. Chem. Soc. 74: 3110. A-3 ------- Loos, M.A., et al. 1966. Formation of 2,4-dichlorophenol and 2,4-dichloro- phenoxyacetate by Arthrobacter sp. Can. Jour. Microbiol. 13: 691. Nachtigall, M.H. and R.G. Butler. 1974. Metabolism of phenols and chloro- phenols by activated sludge microorganisms. Abstr. Annu. Meet. Am. Soc. Microbiol. 74: 184. Pearce, P.J. and R.J.J. Simpkins. 1968. Acid strengths of some substituted picric acids. Can. Jour. Chem. 46: 241. Rodd, E.H. 1954. Chemistry of Carbon Compounds. III-A. Aromatics. Else- vier Publishing Co., Amsterdam. Sax, N.I. 1975. Dangerous Properties of Industrial Materials. 4th ed. Van Nostrand Reinhold Co., New York. Stecher, P.G. (ed.) 1968. The Merck Index. 8th ed. Merck and Co., Rah- way, New Jersey. U.S. EPA. 1973. Preliminary environmental assessment of chlorinated naph- thalenes, silicones, fluorocarbons, benzene polycarboxylates, and chloro- phenols. Syracuse Univ. Res. Corp., Syracuse, New York. U.S. Environ. Prot. Agency. U.S. EPA. 1978. In-depth studies on health and environmental impacts of selected water pollutants. EPA Contract No. 68-010-4646. U.S. Environ. Prot. Agency, Cincinnati, Ohio. A-4 ------- Aquatic Life Toxicology* INTRODUCTION Most of the toxicity data available for 2-chlorophenol have been ac- quired under static testing conditions without chemical measurements. Al- though this compound is quite soluble in water, one would expect some loss of the chemical through absorption by the animals and by the testing envir- onment, which could result in a low estimate of toxicity. Only one chronic test has been conducted, and since no threshold level was attained, the data have limited value. Although 2-chlorophenol does not appear to be extremely toxic to freshwater aquatic life, it has been shown to impair the flavor of the edible portions of fish at very low concentrations. No data are available on the effects of 2-chlorophenol on saltwater aquatic life. EFFECTS Acute Toxicity Ten acute tests have been conducted on four fish and one invertebrate species (Table 1). Of these, only one was a flow-through test with measured concentrations. The LCgg values ranged from 2,580 yg/1 for Daphnia magna (U.S. EPA, 1978) to 20,170 yg/1 for the guppy (Pickering and Henderson, 1966). The species mean acute values (in ug/1) were 4,380 for Daphnia magna, 8,210 for bluegill, 12,370 for goldfish, 12,400 for the fathead minnow, and 20,170 for the guppy. *The reader is referred to the Guidelines for Deriving Water Quality Criter- ia for the Protection of Aquatic Life and Its Uses in order to better under- stand the following discussion and recommendation. The following tables contain the appropriate data that were found in the literature, and at the bottom of each table are calculations for deriving various measures of tox- icity as described in the Guidelines. B-l ------- The 96-hour LC_n values for chlorinated phenols and bluegills are directly related to,the degree of chlorination. These values decrease from 6,590 ug/1 for 2-chlorophenol and 3,830 ug/1 for 4-chlorophenol to 60 and 77 ug/1 for pentachlorophenol. No acute tests have been conducted with 2-chlorophenol and any saltwater species. Chronic Toxicity One chronic test was conducted with the fathead minnow (U.S. EPA, 1978), but no adverse effects were observed at the highest test concentration of 3,900 ug/1 (Table 2). There are no data available on chronic effects on freshwater invertebrate species or on any saltwater species. Species mean acute and chronic values are summarized in Table 3. Plant Effects Only one test was conducted with plants (Huang and Gloyna, 1967), and the effect level (500,000 ug/1) for a freshwater algal species indicates that plants may not be sensitive to 2-chlorophenol (Table 4). Residues A bioconcentration factor was found only for the bluegill (U.S. EPA, 1978). The test was conducted using ^C-2-chlorophenol for 28 days at an exposure concentration of 9.2 ug/1, and the factor dermined was 214 (Table 5). The depuration rate was rapid with a half-life of less than one day. Miscellaneous As stated in the introduction, 2-chlorophenol was found to impair the flavor of fishes at lower concentrations than those at which it had a toxic effect (Henderson, et al. 1960; Shumway and Palensky, 1973) (Table 6). In the former study, bluegills were exposed for periods of one to four weeks to S-2 ------- 2,000 ug/1 of 2-chlorophenol and various concentrations of a number of or- ganic nitriles. A taste panel of twelve members recorded their reaction to the cooked and coded fish samples. The only chemical that caused a definite panel reaction was 2-chlorophenol, which reaction ranged from mild to quite severe nausea. No attempt was made to establish a level of exposure which would not cause flavor impairment. The other experiment (Shumway and Palen- sky, 1973), was designed to provide this information. In this study, rain- bow trout were exposed for 48 hours to a range of concentrations of 2-chlo- rophenol, and a panel of fifteen judges scored the flavor of the flesh on an increasing impairment scale of 0 to 6. The results were then plotted against exposure concentrations and graphically interpreted to arrive at an estimate of the highest concentration which would not impair the flavor of the flesh. For 2-chlorophenol, this concentration was estimated to be 60 ug/1 in the exposure water. The additional toxicity data (Table 6) do not appear to differ dramat- ically from the data already discussed. Summary The LCgQ values for four freshwater fish and one invertebrate species and 2-chlorophenol range from 2,580 to 20,170 ug/1. The chronic data are of little value since no threshold level was reached. Flesh-tainting data in- dicate that the edible portions of fishes may become tainted at water con- centrations as low as 2,000 ug/1. No data are available for any saltwater species and 2-chlorophenol. B-3 ------- CRITERIA The available data for 2-chlorophenol indicate that acute toxicity to freshwater aauatic life occurs at concentrations as low as 4,380 yg/1 and would occur at lower concentrations among species that are more sensitive than those tested. No definitive data are available concerning the chronic toxicity of 2-chlorophenol to sensitive freshwater aauatic life but flavor impairment occurs in one species of fish at concentrations as low as 2,000 ug/1. No saltwater organisms have been tested with 2-chlorophenol and no statement can be made concerning acute or chronic toxicity. B-4 ------- Table 1. Acute values for 2-chlorophenol CO I CTI LC50/EC50 Species Method* (|ig/l) Species Mean Acute Value (ug/l) Reference FRESHWATER SPECIES Cladoceran, S, U 7,430 Daphnla magna Cladoceran, S, U 2,580 Daphnla magna Goldfish, S, U 12,370 Carasslus auratus Fathead minnow S, U 11,630 Plmephales promelas Fathead minnow S, U 14,480 Plmephales promelas Fathead minnow, FT, M 12,400 Plmephales promelas Guppy S, U 20,170 Poec ilia r et 1 cu 1 ata Bluegill, S, U 6,590 Lepomis macrochirus Bluegill, S, U 10,000 Lepomis macrochirus Bluegill (juvenile), S, U 8,400 Lepomis macrochirus Kopperman, et at. 1974 4,380 U.S. EPA, 1978 12,370 Pickering & Henderson, 1966 Pickering i Henderson, 1966 Pickering & Henderson, 1966 12,400 Phipps, et at. Manuscript 20,170 Pickering & Henderson, 1966. U.S. EPA, 1978 Pickering i Henderson, 1966 8,210 Henderson, et al. 1960 * S = static, FT = flow-through, U = unmeasured, M = measured No Final Acute Value is calculable since the minimum data requirements are not met. ------- 00 I CTl Table 2. Chronic values for 2-chlorophenoI (U.S. EPA, 1978) Species Mean Limits Chronic Value Species Method* pig/I) (ug/l) FRESHWATER SPECIES Fathead minnow, E-L >3,900 Plmephales promelas * E-L = embryo-IarvaI No acute-chronic ratio is calculable. ------- Table 3. Species mean acute and chronic values for 2-chlorophenol I -J Number 5 4 3 2 1 Spec 1 es Guppy, Poecllla reticulata Fathead minnow, Plmephales promelas Goldfish, Carassius auratus Bluegll 1 (juvenl le) Lepomls macrochirus Cladoceran, Daphnla inagna Species Mean Species Mean Acute Value* Chronic Value (ug/l) (ug/l) FRESHWATER SPECIES 20,170 12,400 12,370 8,210 4,380 Acute-Chronic Ratio" - * Rank from high concentration to low concentration by species mean acute value. **See the Guidelines for derivation of this ratio. ------- Table 4. Plant values for 2-chlorophenol (Huang & Gloyna, 1967) Result Effect (ug/l) FRESHWATER SPECIES I oo Alga, Reduction 500,000 Chlorella pyrenoldosa in chlorophyll In 72 hrs ------- Table 5. Residues for 2-chlorophenoI (U.S. EPA, 1978) BioconcentratIon Duration Tissue Factor (days) FRESHWATER SPECIES Bluegill, Whole body 214 28 Lepomls macrochlrus 03 I >£> ------- Table 6. Other data for 2-chlorophenol 03 I Species Rainbow trout, Salmo gairdnerl Goldfish, Carassfus auratus Goldfish, Carasslus auratus Fathead minnow, Plmephales prone las Bluegl 1 1, Lepomls macrochlrus Bluegl 1 1 ( juvenl le), Lepomls macrochlrus Duration 48 hrs 8 hrs 24 hrs 192 hrs 1 wk 48 hrs Effect FRESHWATER SPECIES ETC* 42? mortality LC50 LC50 F 1 a vor I mpa 1 rment LC50 Result (ug/l) 60 31,100 16,000 6,340 2,000 8,100 Reference Shumway & Palensky, 1973 Gersdorff & Smith, 1940 Kobayashl, et al. 1979 Phlpps, et al. Manuscript Henderson, et al. 1960 Lammerlng & Bur bank, 1960 *ETC = the highest estimated concentration of material that will not impair the flavor of flesh of exposed fish. ------- REFERENCES Gersdorff, W.A. and L.'E. Smith. 1940. Effect of introduction of the halo- gens into the phenol molecule on toxicity to goldfish. I. Monochlorophe- nols. Am. Jour. Pharmacol. 112: 197. Henderson, C., et al. 1960. The effect of some organic cyanides (nitriles) on fish. Proc. 15th Ind. Waste Conf., Purdue Univ., Eng. Bull. Ed. 45: 120. Huang, J. and E. Gloyna. 1967. Effects of toxic organics of photosynthetic reoxygenation. Environ. Health Engin. Res. Lab. PB 216-729. Kobayashi, «., et al. 1979. Relation between toxicity and accumulation of various chlorophenols in goldfish. Bull. Japan Soc. Sci. Fish. 45: 173. Kopperman, H.L., et al. 1974. Aaueous chloronation and ozonation studies. I. Structure-toxicity correlations of phenolic compounds to Daphnia magna. Chem. Biol. Inter. 9: 245. Lammering, M.W. and N.C. Burbank. 1960. The toxicity of phenol, o-chloro- phenol and o-nitrophenol to bluegill sunfish. Engin. Bull., Purdue Univ. Engin. Ext. Serv. 106: 541. Phipps, G.L., et al. The acute toxicity of phenol and substituted phenols to the fathead minnow. (Manuscript) B-ll ------- Pickering, Q.H. and C. Henderson. 1966. Acute toxicity of some important petrochemicals to fish. Jour. Water Pollut. Control Fed. 38: 1419. Shumway, D.L. and J.R. Palensky. 1973. Impairment of the flavor of fish by water pollutants. U.S. Environ. Prot. Agency, EPA-R3-73-010, U.S. Govern- ment Printing Office, Washington, D.C. U.S. EPA. 1978. In-depth studies on health and environmental impacts of selected water pollutants. U.S. Environ. Prot. Agency, Contract No. 68-01- 4646. B-12 ------- Mammalian Toxicology and Human Health Effects INTRODUCTION The potential for exposure of man to any synthetic chemical exists through any of several modes. These modes include: 1) exposure of indus- trial workers during synthesis, formulation, packaging, or transport; 2) ex- posure of users of the product at either a commercial or retail level; 3) contact with residues or metabolites of the product as a result of using commodities or environments containing the material; and 4) contact with the chemical as a metabolite of some other product. To understand the route of entry of a chemical, one must first examine the sources and properties of the material. 2-Chlorophenol is a commercial- ly produced chemical used as an intermediate in the production of other chemicals, and represents a basic chemical feedstock for the manufacture of higher chlorophenols. Direct chlorination of phenol leads to the formation of both 2- and 4-chlorophenols. These isomers can be separated by fractional distillation, since the difference in their boiling points is greater than 40°C. Most of the commercially used 2-chlorophenol in the U.S. is recovered as a byproduct of the manufacture of 4-chlorophenol by direct chlorination of phenol. The chlorination of phenol in aqueous solutions to form 2-chlorophenol and higher phenols has been demonstrated under conditions similar to those used for the disinfection of wastewater effluents and may represent a source of contamination (Aly, 1968; Barnhart and Campbell, 1972). Since chlorine and phenol do not normally occur in stoichiometric amounts, the concentra- tions of 2-chlorophenol actually produced in FLO are likely to be lower than those found in experimental studies (Barnhart and Campbell, 1972). C-l ------- Higher levels of chlorination become increasingly less favored. 2-Chloro- phenol has been synthesized from phenol and chlorine at concentrations as low as 10 and 20 mg/1, respectively, within one hour (Barnhart and Campbell, 1972). Other studies have demonstrated the formation of 2-chlorophenol (1.7 ug/1) and numerous other chlorinated compounds during the chlorination of sewage effluents and power plant cooling waters (Jolley, 1973; Jolley, et al. 1975). EXPOSURE Ingestion from Water 2-Chlorophenol may exist in the aquatic environment in the dissolved form, associated with suspended matter and bottom sediments, and absorbed in biological tissues. Metal salts of this compound have greater water solu- bility, and if introduced or formed j£ situ would exist primarily in the dissolved form. Chlorophenols, being weak acids tend to ionize, depending upon the pH of the system. They are almost completely nonionized in aqueous solutions with a pH lower than 5, and become increasingly dissociated as the pH rises (Cserjesi, 1972). No information could be found on the amounts of 2-chlorophenol present in finished water intended for human consumption. In one study, industrial waste discharge was the principal point source of water pollution. During the manufacture of chlorophenols and 2,4-D, there is chemical waste generated as the result of incomplete reaction of the starting reactants, by-product formation, and incomplete recovery of desired products. Thus, the wastes contain a mixture of chlorophenols and other compounds. Waste arising from the manufacture of phenoxyalkanoic her- bicides showed amounts of 2-chlorophenol ranging from a trace to 6 percent (Sidwell, 1971) (Tables 1 and 2) of the total phenols and chlorophenols. C-2 ------- TABLE 1 Chlorophenols in Industrial Plant Waste* 0 1 oo Date Temp. °C PH Chlorophenols (mg/1) Phenoxy Acids (mg/1) Total Solids (mg/1) 25 January 12 7.5 68 167 6,960 3 March 18 7.6 118 183 40,100 21 April 21 7.4 125 241 76,320 28 May 28.5 7.4 112 235 104,860 27 August 24 7.0 74 199 11,000 *Source: Sidwell, 1971 ------- TABLE 2 Relative Chlorophenol Content of Industrial Waste* Date Phenol Type 2-chloro phenol 2,6-DCP 2,5-DCP 2,4-DCP 2,4,6-TCP 4-chloro 2,4,5-trichloro 25 January 2.9 3.4 9.9 trace 73.6 2.8 2.5 4.7 3 March 21 April 28 May Percent of Total Phenols Present 6.1 6.2 41.7 6.2 17.9 9.9 12.1 trace trace 1.7 38.8 1.7 20.0 19.5 18.3 trace trace 24.8 30.5 trace 11.4 13.3 20.0 trace 27 August trace trace 3.0 1.8 89.0 3.4 2.8 trace *Source: Si dwell, 1971 ------- Other possible point sources are chemical spills and the washing of containers or drums in which chlorophenols or the herbicide 2,4-dichloro- phenoxyacetic acid (2,4-D) are stored. Contamination of water with 2-chlorophenol may occur by (1) chlorina- tion of phenol present in natural water and primary and secondary effluents of waste treatment plants (Burttschell, et al. 1959; Eisenhauer, 1964; Barn- hart and Campbell, 1972), (2) direct addition of the chemicals or as contam- inants or degradation products of 2,4-0 used for aquatic weed control, and (3) wet and dry atmospheric fallout. No direct data were found to show actual measured concentrations of 2-chlorophenol in water courses, impoundments, wells, or other human water supply sources. Based on the relatively limited sources of water contamination by 2-chlorophenol, as well as the demonstrated decomposition in many aquatic situations, water should be a minor route of ingestion of 2-chlorophenol. 2-Chlorophenol may be removed from water by several mechanisms. One study (Ettinger and Ruchhoft, 1950) indicates that the dissipation of 2-chlorophenol is largely microbiological. Persistence appears to be short, but limnological factors, such as oxygen deficiency, may delay degradation (Aly and Faust, 1964). Microorganisms found in activated sludge and waste lagoons have been demonstrated to degrade 2-chlorophenol rather readily (Sidwell, 1971; Nachtigall and Butler, 1974). Ettinger and Ruchhoft (1950) found that low concentrations (1 mg/1) of 2-chlorophenol added to a usual dilution of domestic sewage were not removed during periods of 20 to 30 days, presumably due to the absence of microorga- nisms capable of attacking the chemical. When a similar concentration was added to polluted river waters, the compound dissipated in 15 to 23 days. C-5 ------- Addition of a seed, consisting of water from a previous persistence experi- ment, increased significantly the removal of 2-chlorophenol. Apparently, the seed introduced some organisms already adapted to the chemical. This study also indicated that the removal of monochlorophenols requires the presence of an adapted microflora. Ingols, et al. (1966) obtained data indicating the dechlorination of 2-chlorophenol and other monochlorophenols within three days of exposure to an activated sludge system (Table 3). Primary treatment consists essentially of settling solids, after screening off large materials. Settling may not remove 2-chlorophenol from water, since it is adsorbed poorly on particulate or suspended matter. Secondary treatment involves the removal of organic matter from waste water by biological processes. Since 2-chlorophenol and 2,4-dichlorophenol (2,4-DCP) are known to be easily biodegradable, secondary treatment should provide excellent removal of these chemicals. Baird, et al. (1974), employing Warburg respiratory techniques, demon- strated that biodegradation of 2-chlorophenol at 1 mg/1 in activated sludge was complete within three hours. Increasing the concentration to 100 mg/1 considerably reduced the rate of respiration such that only 20 percent was degraded in six hours. This is probably due to microbial toxicity from 2-chlorophenol at this concentration. In a sludge not acclimated with high levels of 2-chlorophenol, certain amounts of the compound may be degraded initially, while oxidative intermediates that appear subsequently could be toxic to the microbial population. This indicates that 2-chlorophenol may persist longer, due to direct or indirect toxic effects, if waste containing high levels of the chemical is discharged into an unacclimated body of water. C-6 ------- TABLE 3 Degradation of Chlorophenols in Acclimated, Activated Sludgea>') o Compound 2-chlorophenol 3-chlorophenol 4-chlorophenol 2,4-DCP 2,5-DCP 2,4,6-TCP NaPCP Dichloroquinone 2,5-DCP benzoquinone Amount of of % 100 100 100 100 52 100 0 100 30 ring degradation compound days 3 2 3 5 4 3 4 1 1 Development % 100 100 100 100 16 75 0 50 0 of Chloride Ion days 4 3 3 5 4 3 4 3 1 aSource: Modified from Ingols, et al. 1966 bConcentration of 100 mg/1 ------- While a number of studies indicate rapid dissipation of 2-chlorophenol from waters by several mechanisms, human exposure cannot be fully evaluated unless studies are conducted measuring the 2-chlorophenol content in waters receiving wastes from point sources of chlorophenols or their precursors. Evidence of such studies was not found. Ingestion from Food Contamination of human foods with 2-chlorophenol could occur via soil, plants, animals, or aquatic sources. In all cases, any contamination is probably indirect and primarily a result of the use and subsequent metabo- lism of phenoxyalkanoic herbicides. In 1971, U.S. farmers applied almost 16,000,000 kg of 2,4-0, represent- ing 15 percent of all organic herbicide usage [U.S. Department of Agricul- ture (USDA), 1974]. Although 2-chlorophenol appears to be short-lived in soils, the data are inconclusive, and factors affecting its persistence need further study. However, microbial degradation is the apparent major route of dissipation for chlorophenols in soils. For 2,4-OCP, which is more likely to reach the soil system as a contaminant and degradation product of 2,4-D, its degrada- tion under field conditions could be faster than degradation of the herbi- cide itself. The role of microorganisms in the degradation of 2,4-D has been conclusively demonstrated (Loos, 1975), and under favorable conditions 2,4-D disappears from soils in about 30 days (Kearney, et al. 1969). Warm, moist, well-aerated soils with ample organic matter content promote the pro- liferation of microorganisms known to metabolize 2,4-D. One of the chemi- cals in the metabolic pathway may be 2-chlorophenol. Limited information indicates the biodegradability of 2-chlorophenol (Walker, 1954; Baird, et al. 1974). Several genera of bacteria isolated from soil are capable of C-8 ------- metabolizing 2-chlorophenol. Pseudomonas sp., Nocardia sp., Mycobacterium coeliacum, and Bacillus sp. were demonstrated to oxidize 2-chlorophenol to 3-chlorocatechol (Spokes and Walker, 1974). The fate of the catechol inter- mediate was elucidated in a study by Evans, et al. (1971) of the metabolism of 2,4-0 by Pseudomonas sp. Using 2,4-D as sole carbon source for Pseudo- monas strains isolated from soil, the herbicide was metabolized to 2,4-OCP, 2-chlorophenol, 3,5-dichlorocatechol, and a-chloromuconate, which was fur- ther metabolized to release Cl" and unidentified metabolites. The appear- ance in culture of 2-chlorophenol suggests the nonoxidative elimination of chlorine from 2,4-OCP or, possibly, 2,4-0 itself. The accumulation of m-chloromuconate is probably a further manifestation of this phenomenon, since it is likely formed by enzymatic cleavage of 3-chlorocatechol, derived from either 2-chlorophenol or 3,5-dichlorocatechol. It is probable that the sorption behavior of 2-chlorophenol is similar to 2,4-0. In natural soil systems, sorption may not be extensive, thereby favoring downward movement in soil with water. The persistence of 2-chlorophenol in soils was studied by Walker (1954) using the percolation technique. Solutions of 2-chlorophenol (1.0 g/4 1 tap water) were allowed to percolate through 100 g of a Rothamsted soil (light clay with a pH of 6.8), and the disappearance of the initial and subsequent doses was measured. Two-thirds of the initial dose disappeared in 10 days. Disappearance of subsequent doses occurred approximately twice as rapidly as that of the first dose, suggesting microbial participation. Further evi- dence of microbial decomposition was indicated by the more rapid disappear- ance of 2-chlorophenol in fresh than in sterilized soil within seven days of percolation. C-9 ------- Furthermore, the participation of soil microorganisms in the dissipa- tion of 2-chlorophenol and other chlorophenols was reported by Alexander and Aleem (1961) using suspensions of two silt loam soils. Metabolism of the chemicals was evidenced by more rapid disappearance of incremental additions of the compounds than initial enrichments. Also, inhibition of degradation occurred on addition of sodium azide, a toxic agent. 2-Chlorophenol disap- peared rapidly in suspensions of Dunkirk and Mardin silt loams; disappear- ance was faster for the latter soil. No information was found on the uptake, absorption, and translocation of 2-chlorophenol by plants. The movement of 2-chlorophenol can only be inferred from the few available studies of 2,4-DCP in plants and from the potential for 2-chlorophenol to occur as a metabolic intermediate in the degradation of 2,4-0. The metabolism of 2-chlorophenol in vascular plants is not well stud- ied. The only available report demonstrated that 2-chlorophenol may be in- activated by glycoside formation in plant tissue. It has been demonstrated that when certain nonnaturally occurring chemicals are absorbed by various plants, glycoside formation takes place with the foreign chemical serving as the aglycon. Miller (1941) demonstrated that the metabolic fate of 2-chlo- rophenol in tomato plants included glycoside formation. s-o->chlorophenyl - gentiobioside (a glycoside of 2-chlorophenol) was isolated from the roots of these tomato plants. No evidence for the formation of this glycoside in shoots was found. The fate of this metabolic product of 2-chlorophenol in plants is not known and warrants further investigation. Domestic animals, including poultry, could ingest feeds containing pes- ticides or drink water contaminated directly with 2-chlorophenol and 2,4-DCP. Although some studies indicate the appearance and distribution of C-10 ------- fn) 2,4-OCP in tissues of animals fed with 2,4-0 and Nemacide0' [0-(2,4-dichlo- rophenol)-0,0-diethylphosphorothioate] (Clark, et al. 1975; Sherman, et al. 1972), in none of the studies was there evidence cited to indicate residues of 2-chlorophenol. Furthermore, Bjerke, et al. (1972) reported no contami- nation of milk and cream from cows given a 2,4-0 (100 to 1,000 mg/kg) diet. A bioconcentration factor (BCF) relates the concentration of a chemical in aquatic animals to the concentration in the water in which they live. The steady-state BCF for a lipid-soluble compound in the tissues of various aquatic animals seems to be proportional to the percent lipid in the tissue. Thus, the per capita ingestion of a lipid-soluble chemical can be estimated from the per capita consumption of fish and shellfish, the weighted average percent lipids of consumed fish and shellfish, and a steady-state BCF for the chemical. Data from a recent survey on fish and shellfish consumption in the United States were analyzed by SRI International (U.S. EPA, 1980). These data were used to estimate that the per capita consumption of freshwater and estuarine fish and shellfish in the United States is 6.5 g/day (Stephan, 1980). In addition, these data were used with data on the fat content of the edible portion of the same species to estimate that the weighted average percent lipids for consumed freshwater and estuarine fish and shellfish is 3.0. A measured steady-state bioconcentration factor of 214 was obtained for 2-chlorophenol, using bluegills containing about 1 percent lipids (U.S. EPA, 1978). An adjustment factor of 3.0/4.8 = 0.625 can be used to adjust the measured BCF from the 3.0 percent lipids of the bluegill to the 2.3 percent lipids that is the weighted average for consumed fish and shellfish. Thus, C-ll ------- the weighted average bioconcentration factor for 2-chlorophenol and the edi- ble portion of all freshwater and estuarine aquatic organisms consumed by Americans is calculated to be 214 x 0.625 = 134. Inhalation The dispersal and distribution of 2-chlorophenol in air has apparently not been studied. One potential source of environmental pollution by 2-chlorophenol, however, is the manufacture of 2,4-D herbicides. Secondly, since 2-chlorophenol is volatile (1 mm Hg at 12°C), any 2-chlorophenol gen- erated as a decomposition product of applied 2,4-0 could be subject to gen- eral environmental dispersal. A third possibility for inhalation exposure could be the burning of containers, trash, or plant material contaminated with 2-chlorophenol. No data addressing the monitoring of air or workplace environments for 2-chlorophenol have been found. Therefore, the potential sources for human exposure through inhalation remain speculative. Because of the volatility of 2-chlorophenol and the processes employed in its manufacture, the most probable source of inhalation exposure to 2-chlorophenol would occur in manufacturing plants producing 2-chlorophenol or possibly 2,4-0. The separation of 2-chlorophenol from 2,4-dichlorophenol involves fractional distillation which, if not done with regard to worker safety, could result in exposure by inhalation. The potential for airborne exposure to 2-chlorophenol in the general environment as a result of point source pollution has not been reported. Although inhalation exposure to 2-chlorophenol associated with related products in general use (e.g., 2,4-D herbicide) does not seem likely, no data to verify atmospheric 2-chlorophenol presence or absence under such conditions have been found. Potential for such exposure seems quite low for several reasons. First, the principal general environmental source of C-12 ------- 2-chlorophenol would be 2,4-D or its decomposition products. Since there is little evidence of 2-chlorophenol occurring as a permanent soil or plant metabolite of 2,4-D, the amount available to be volatilized would be either limited or absent. Secondly, any 2-chlorophenol which might be formed in soil or water is rapidly degraded by microorganisms (see Ingestion section), while 2-chlorophenol in plants is inactivated as a glycoside (Miller, 1941). A third potential route of exposure, the burning of chlorophenol-con- taining products, has not been studied. Incineration of phenoxy herbicides should be accompanied by investigations of potential formation and/or dis- persal of 2-chlorophenol, as well as other chlorophenols. Direct studies of potential or actual exposure to 2-chlorophenol have not been found. However, after considering the nature of the production, uses, and persistence of 2-chlorophenol, inhalation exposure of the general population does not seem a significant threat, except for specific occupa- tional settings in cases of large accidental spills. A recent case involv- ing potential exposure of the general population to 2-chlorophenol is in- cluded here for reference purposes. On January 11, 1979, a chemical spill occurred at Sturgeon, Missouri, as a result of a train derailment. Ortho-chlorophenol and phenol were major components of the spilled material. As a result, U.S. Environmental Protec- tion Agency personnel were asked to supervise the clean-up of the spill. C-13 ------- Values of ortho-chlorophenol determined by the U.S. EPA (Fairless, 1979) at several dates after the spill are as follows: Date of Collection 2-Chlorophenol Concentration 1979 in Air (ppm) January 11 0.013 January 11 0.004 January 11 0.190 January 29 <0.0005 January 29 <0.0005 January 29 <0.0005 March 6 <0.0003 March 6 <0.0003 March 6 <0.0003 March 6 0.0029 Analyses for 2-chlorophenol were made from the urine of several individuals working or residing in Sturgeon, Missouri, within several months after the spill. Results of those analyses conducted for the American Public Health Association (1979) are as follows: 1. Four adult males assisting in clean-up operations at the spill site had a mean 2-chlorophenol urine concentration of 1.98 ppm (range 1.4 - 2.6) on March 7, 1979. By April 11, 1979, when these same four individuals were again sampled, all had no detectable amount of 2-chlorophenol in their urine, (detection limit 0.25 ppm). 2. Nine persons residing in Sturgeon, Missouri within 40 to 200 feet of the spill site all had no detectable amount of 2-chlorophenol in their urine when sampled on April 11, 1979. These nine persons had no history of direct contact with 2-chlorophenol at the spill site and did not assist in clean-up operations. The only obvious source of exposure to 2-chlorophenol would have been via inhala- tion of chlorophenol from the atmosphere in Sturgeon. It should be noted that even though extremely low levels of 2-chlorophenol were measured by the U.S. EPA, a noticeable odor of chlorophenols could be detected for several months after the spill. Thus, organoleptic detection of chlorophenols is possible, even when measurable levels in air or urine cannot be found. C-14 ------- Dermal 2-Chlorophenol dermal absorption data have not been found. Since the compound is lipid soluble and likely to be poorly ionized at an environment- al pH (Farquharson, et al. 1958), it could be readily absorbed through in- tact skin. Dermal absorption and resultant body burdon merit study. As indicated for inhalation exposure, the only potentially significant dermal exposure to 2-chlorophenol would occur in the manufacture of handling of 2-chlorophenol or products which contain it. Ordinary and accepted meth- ods of skin protection would be expected to prevent dermanl exposure to 2-chlorophenol. Dermal exposure to 2-chlorophenol from other sources (soil water, plant metabolites of 2,4-D) is considered to be insignificant for the same reasons as stated in the section on inhalation. PHARMACOKINETICS Absorption Direct data on the absorption of 2-chlorophenol by man or experimental animals have not been found. Chlorophenol compounds are generally consid- ered readily absorbed, as would be expected from their high lipid solubility and low degree of ionization at physiological pH (Doedens, 1963; Farquhar- son, et al. 1958). Although skin irritation and dermal absorption are re- ported as characteristic of monochlorophenols, direct quantitative data con- cerning the irritant potential of 2-chlorophenol have not been found. Tox- icity studies to be discussed later indicate that 2-chlorophenol can be ab- sorbed and can result in toxicosis; however, quantitative data for 2-chloro- phenol absorption by various routes have not been found. 2-Chlorophenol may occur in mammals as a metabolite of other compounds. Exposure of rabbits to chlorobenzene has resulted in the formation of 2-chlorophenol (Lindsay-Smith, et al. 1972). C-15 ------- In addition, Selander, et al. (1975) reported the conversion of chloro- benzene to a mixture of monochlorophenols in perfused rat liver. Apparent- ly, three different enzyme systems catalyze the conversion of chlorobenzene to 2-, 3-, and 4-chlorophenols. Investigation of 2,4-D metabolism in mammals (Clark, et al. 1975) has not indicated 2-chlorophenol to be a metabolite of such exposure, while 2,4-OCP is considered the major metabolite. Distribution Direct information about the distribution and transportation of 2-chlo- rophenol is not available. However, at least two reports (Spencer and Wil- liams, 1950; von Oettingen, 1949) on the rabbit and dog, respectively, indi- cate urinary excretion of 2-chlorophenol. Furthermore, since metabolites of 2-chlorophenols are identified as glucuronide and sulfate conjugates, it is possible that the liver might contain proportionally large amounts of 2-chlorophenol. Two reports concerning lesions induced by 2-chlorophenol (Patty, 1963; Bubnov, et al. 1969) indicate changes in liver and kidney, thus visually confirming the renal and hepatic distribution. No information concerning hepatic excretion or any indication of an enterohepatic cycle was found. While compounds of high lipophilia (which would include 2-chloro- phenol) are often considered to accumulate in adipose tissue, no information to this effect was found for 2-chlorophenol. In fact, related compounds (2,4-dichlorophenol and pentachlorophenol) are considered to have relatively short half-lives (Clark, et al. 1975; Osweiler, et al. 1977). Whether this is true for 2-chlorophenol remains to be established. Since animals dosed with 2-chlorophenol display convulsive activity within several minutes of exposure (Farquharson, et al. 1958; Angel and Rogers, 1972), it can be as- sumed that the compound traverses the blood brain barrier and is distributed C-16 ------- in part in the central nervous system. The concentrations of 2-chlorophenol in brain and other organs or tissues during toxicosis remain to be deter- mined. Metabolism The metabolism of 2-chlorophenol in man is not known. n experimental animals, von Oettingen (1949) cites work by Karpow (1893) showing that dogs excreted 87 percent of administered 2-chlorophenol as conjugates with sul- fate and glucuronic acid. The rabbit also apparently conjugates 2-chloro- phenol derived from chlorobenzene exposure (Lindsay-Smith, et al. 1972) by formation of sulfate and glucuronide conjugates. However, 2-chlorophenol was reported as only a minor metabolite of chlorobenzene in the rabbit (Lindsay-Smith, et al. 1972). Furthermore, only a small portion of the chlorophenols formed were monochlorophenols, and less than 6 percent of the free and metabolized chlorophenols was the 2-chlorophenol isomer. Selander, et al. (1975) demonstrated that chlorobenzene is converted to o-, m-, and p-chlorophenols in perfused rat livers, as well as by noncellu- lar systems including microsomes, post mitochondrial supernatant, and recon- stituted soluble hemoprotein-monooxygenase systems. Pretreatment with the inducing agents 3-methylcholanthrene and phenobarbital increased the forma- tion of chlorophenols, while carbon monoxide and SKF 525A^ (e-diethyl- aminoethyl diphenylpropylacetate) inhibited formation of o-, m-, and p-chlo- rophenols. The approximate j_n vivo ratios for formation of o-, m-, and p-chlorophenol were 1:2:4, respectively. Thus, formation of 2-chlorophenol via metabolism of chlorobenzene does not appear to be a significant or major route of exposure. While it is possible that 2-chlorophenol could form in man or animals as a result of exposure to phenoxyacetic acid herbicides, there are no data to support this conjecture. In fact, Clark, et al. C-17 ------- (1975), in studies of the metabolism of phenoxy herbicides, reported the major metabolite to be 2,4-OCP and did not mention detection of 2-chloro- phenol. Based on experimental work in two species (dogs and rabbits), it ap- pears that mammalian metabolism of 2-chlorophenol follows the expected route for phenol metabolism (i.e., formation of conjugates of glucuronides and sulfates, with detection of these metabolites primarily in the urine). Excretion Studies of the excretion route or rate for 2-chlorophenol in man were not found. As mentioned before, von Oettingen (1949) reviewed the data of Karpow (1893), in which dogs given 2-chlorophenol excreted 87 percent of the compound in urine as sulfate and glucuronide conjugates. However, data were not developed from which the rate of excretion or half-life could be calcu- lated. Lindsay-Smith, et al. (1972) identified phenolic metabolites in rab- bit urine after administration of chlorobenzene. Of the free and conjugated forms of chlorophenols in rabbit urine, less than 6 percent was present as 2-chlorophenol. No data have been found concerning measurement of tissue residues of 2-chlorophenol, either from direct administration or by formation as a metabolite of other compounds, nor have sufficient data accumulated to allow calculation of a half-life for 2-chlorophenol. EFFECTS Acute, Subacute, and Chronic Toxicity The acute toxicity of 2-chlorophenol has been studied in a variety of organisms. The compound is considered to be an uncoupler of oxidative phos- phorylation (Mitsuda, et al. 1963) and a convulsant poison (Farquharson, et al. 1958; Angel and Rogers, 1972). No reports of the subacute or chronic C-18 ------- toxicity of 2-chlorophenol have been found. This represents a serious data gap in the toxicologic evaluation of 2-chlorophenol. Mammalian toxicity of 2-chlorophenol has not been well studied. There are no reports of human or domestic animal toxicoses from accidental or intentional exposure to 2-chlorophenol. Furthermore, there is no evidence linking 2-chlorophenol exposure in industrial workers to the chloracne, an effect often associated with higher chlorophenols (Huff and Wassom, 1974), nor is there evidence to suggest that the toxic dioxins are contaminants of, or are formed from, 2-chlorophenol. Doedens (1963) briefly characterized the toxicity of 2-chlorophenol as being "likely" to be corrosive and irritating to the eyes and skin. How- ever, specific data on the effects of 2-chlorophenol were not presented. The data from relatively few acute toxicological studies in laboratory ani- mals are the only ones from which an evaluation of 2-chlorophenol can be made (Table 4). It may be seen by inspection of Table 4 that the subcutane- ous minimum lethal dose (MLD) of 2-chlorophenol in the rabbit (950 mg/kg) is approximately 8 times that of the intravenous MLD, implying that the subcu- taneous route retards bioavailability of 2-chlorophenol. At a physiological pH of 7.4, however, 2-chlorophenol is approximately only 5 percent ionized (Farquharson, et al. 1958); such a low degree of ionization would not ac- count for this lessening of toxicity by the subcutaneous route. The LD5Q data in Table 4 indicate that 2-chlorophenol is more toxic by the oral than the subcutaneous route. At relatively acidic pH (e.g., stomach), the pKa of 2-chlorophenol (8.65) would allow for a highly union- ized state, which is conducive to ready absorption from the stomach or the less acidic upper intestine. This effect could explain the greater oral toxicity of 2-chlorophenol. C-19 ------- TABLE 4 Lethal Doses of 2-Chlorophenol for Experimental Animals Animal Rat Rat Albino rat Rabbit i INJ 0 Rabbit Mouse Guinea pig Blue fox Unknown mammal Route of Administration Oral Subcutaneous Intraperitoneal Subcutaneous Intravenous Oral Subcutaneous Oral Oral LD50 (mg/kg) 670 950 2303 950 1203 670 8003 440 440 Source Deichmann, 1943 Deichmann, 1943 Farquharson, et al . 1958 Christensen and Luginbyhl, 1975 Kuroda, 1926, cited in von Oettingen, 1949 Bubnov, et al . 1969 Christensen and Luginbyhl, 1975 Bubnov, et al . 1969 Christensen and Luginbyhl, 1975 aMLD (minimum lethal dose) values ------- Among the various species tested by the same route, there is a surpris- ing similarity among acute toxicities. This would imply that initial ab- sorption, metabolism, detoxification, and affected organs are quite similar among various species. It would be expected then that chronic toxicity would vary according to ability of a species to metabolize, inactivate, and excrete 2-chlorophenol on a long term basis. Unfortunately, studies of long term or chronic effects have not been reported. Signs of 2-chlorophenol intoxication in rats are similar, whether the compound is administered subcutaneously, intraperitoneally, or orally. The toxicological picture includes restlessness and increased rate of respira- tion within a few miniutes following administration. Somewhat later, motor weakness develops, and tremors and convulsions induced by noise or touch occur. Eventually, dyspnea and the appearance of coma result and continue until death (Farquharson, et al. 1958). Following fatal poisoning, lesions in the rat include marked kidney injury, red blood cell casts in the tub- ules, fatty infiltration of the liver, and hemorrhages in the intestine (Patty, 1963). Bubnov, et al. (1969) report a similar pathological picture in the blue fox and the mouse. At lethal concentrations, 2-chlorophenol caused fatty degeneration of the liver, renal granular dystrophy, and necro- sis of the stomach and intestinal mucosa. These signs are very similar to acute phenol toxicosis (Patty, 1963). The convulsive action of 2-chlorophenol in mice was studied by Angel and Rogers (1972). Following intraperitoneal administration of 2-chloro- phenol, a rapid onset of convulsions was noted. A simple exponential decay of the convulsive effect was noted, which the authors speculated could have been a result of removal from the central nervous system (CNS) by a simple chemical reaction. However, no information directly addressing this point is available. C-21 ------- Farquharson, et al, (1958) state that as phenol is progressively chlo- rinated, the molar toxicity shows a tendency to increase when pK value falls below 7. Furthermore, convulsions are. the most characteristic effect of chlorophenols with pK values of 8.65 or higher. Thus, it may be that con- vulsions are in some way associated with undissociated molecules. No stud- ies were found which attempted to evaluate the passage of chlorophenols with different pK values across the blood-brain barrier. Synergism and/or Antagonism Reports of studies directly assessing the synergism or antagonism of 2-chlorophenol by other compounds were not found. Since 2-chlorophenol is a weak uncoupler of oxidative phosphorylation (Mitsuda, et al. 1963), it may be expected that concomitant exposure to other uncouplers (e.g. pentachloro- phenol, dinitrophenol) would enhance that effect. In addition, exposure to chlorinated hydrocarbon insecticides, with their characteristic convulsant activity, might also produce a magnified response. Any agent causing liver damage sufficient to decrease the conjugation of 2-chlorophenol with glucuronide or sulfate could conceivably alter the excretion and/or toxicity of the parent compound. However, there are no specific studies to reflect such an effect, it is only speculative that the general tendency of conjugation to render a compound less toxic and more amenable to excretion would also operate in the case of 2-chlorophenol. Teratogenicity and Mutagenicity Pertinent data could not be located in the available literature con- cerning the teratogenicity and mutagenicity of 2-chlorophenol. Carcinogenicity The report of Boutwell and Bosch (1959) is the only one found dealing with the tumorigenicity of 2-chlorophenol, Repeated application of phenol C-22 ------- and some substituted phenols has been reported to promote skin tumors in mice after a single initiating dose of dimethylbenzanthracene (DMBA). Pap- illomas have developed in mice treated with phenol alone (not exposed to DMBA). In the studies of Boutwell and Bosch (1959), two trials included evaluation of 2-chlorophenol. In one of these, 25 \i1 of a 20 percent solu- tion of 2-chlorophenol was applied twice weekly to female Sutter mice two to three months of age for 15 weeks. This application followed an initiating dose of 0.3 percent DMBA in benzene. Tumorigenic response was measured as fo11ows: (1) The percentage of surviving mice bearing one or more papillo- mas was ascertained. (2) The total number of papillomas on all surviving mice was counted and divided by the number of^urvivors to give the average number of papillomas per mouse. (3) The number of mice bearing malignant tumors was determined. Results of the promoter trial with 2-chlorophenol are presented in Table 5. Related promoter experiments with phenol, as well as the benzene control, are included for comparative purposes. Based on the data, the authors concluded that the promoting activity of 2-chlorophenol is similar to that of phenol. In a second experiment, Boutwell and Bosch (1959) administered in a similar manner 20 percent 2-chlorophenol in dioxane, but for 12 weeks and without an initiator. Results of this trial are also included in Table 5. In both trials, 2-chlorophenol was associated with a high incidence of pap- illomas. When DMBA was used as an initiator, 10 percent of the survivors developed carcinoma at the skin site of application; however when 2-chloro- phenol alone was used, no carcinogenic response was observed. Since the study was designed primarily to detect promoting activity, the effect of 2-chlorophenol as a primary carcinogen is not well defined. C-23 ------- TABLE 5 Appearance of Skin Tumors in Mice Treated Cutaneously with Phenols following a Cutaneous Dose of 0.3X Dimethylbenzanthracene (DMBA) in Acetone a Treatments'* Benzene control 10% phenol in benzene. No DMBA. ^itX phenol in acetone. 20% phenol in benzene. 20% 2-chlorophenol in benzene. 20% ?-chlorophenol in dioxane. No DMBA. Time Animals Examine (weeks) 12 20 12 24 15 12 No. of mice (survivors/total ) 12/12 24/30 21/24 10/33 31/35 28/30 Survivors with Papillomas 0 33 56 100 61 46 Average Papillomas per Survivor 0 0.62 _ 3.20 1.48 0.64 Survivors with Epithelial Carcinomas * 0 1 t 5 20 10 0 aSource: Modified from Boutwell and Bosch, 1959 ^All received DMBA except where stated ------- The study uses dermal applications of a phenolic compound at 20 percent con- centration in organic solvents. The concentration is high enough that hair follicles and sebaceous glands are destroyed, and the papillomatous response observed may have developed in response to chemical and/or physical damage from application of an irritant compound. Even with this harsh treatment, no malignant neoplasia were observed, except when DMBA had been used as an initiator. The only neoplasia observed were at the site of the direct ap- plication. This study does not evaluate systemic carcinogenesis, and the route of administration is not appropriate to the prescribed models for car- cinogenic risk assessment. The route of administration (dermal) has no established relationship to oral exposure. Odor and taste thresholds for 2-chlorophenol in water have been report- ed by a number of investigators. Hoak (1957) reported the odor threshold of phenol and 19 phenolic compounds. In this study conducted at the Mellon In- stitute in Pittsburgh, Pennsylvania, a panel of two or four persons sniffed samples of pure phenolic compounds in odor-free water, which had been heated to 30 or 60°C. A flask of plain odor-free water was provided for compari- son. The various samples were placed in random order before the test per- sons, and the flask with the lowest perceptible odor was noted by each indi- vidual sniffer. The lowest concentration detected was considered to be the threshold of the chemicals tested; chlorinated phenols were the compounds most easily detected. The odor thresholds reported for 2-chlorophenol were 0.33 ug/1 at 30°C and 2.5 wg/l at 60°C (Hoak, 1957). Hoak speculated that odor should be expected to become more noticeable as temperature increases; however, in evaluating a series of chlorophenols and cresols, it was found that some compounds had higher odor thresholds at 30°C, while others were higher at 60°C. C-25 ------- Burttschell, et al (1959) made dilutions of 2-chlorophenol in carbon- filtered tap water and used a panel of from four to six persons to evaluate odor and taste. Tests were carried out at room temperature, which the in- vestigator estimated to be 25°C. If a panel member's response was doubtful, the sample was considered negative. The geometric mean (2 u9/l for odor and yg/1 for taste) of the panel responses was used as the organoleptic thresholds. Since the data presented did not indicate a range of responses, it is very possible that the odor threshold for some people in the Burtt- schell group was near the 0.33 ug/1 value of Hoak. Campbell, et al. (1958) studied the taste thresholds of six odor-pro- ducing chemicals. Solutions of the chemicals were prepared using redis- tilled water. Panels of 21 or 22 experienced judges participated in differ- ent organoleptic tests of the triangle type. Concentrations of chemicals chosen for the triangle tests were such that the odd sample would be identi- fied by more than 35, but less than 100 percent of the judges. Samples were served in 25 ml portions, and the judges were asked only to identify odd sample. When 50 percent of the judges correctly separated the samples in a given triangle test, the concentration of 2-chlorophenol used in that test was considered to be the threshold level. Although a number of judges were able to detect the presence of 2-chlorophenol at a concentration of 2 yg/1, a threshold level of 6 yg/1 was reported based on the experimental methodol- ogy used. It is interesting to note that, in this same study, a concentra- tion of 1 ug 2-chlorophenol/I was determined to be the threshold for impair- ment of coffee brew, while eight of the tasters noted some impairment at 0.5 wg/l. Dietz and Traud (1978) used a panel composed of 9 to 12 persons of both sexes and various age groups to test the organoleptic detection thresholds C-26 ------- for 126 phenolic compounds. To test for odor thresholds, 200 ml samples of the different test concentrations were placed in stoppered odor-free glass bottles, shaken for approximately five minutes, and sniffed at room tempera- ture (20 to 22°C). For each test, water without the phenolic additive was used as a background sample. The odor tests took place in several individ- ual rooms in which phenols and other substances with intense odors had not been used previously. Geometric mean values were used to determine thresh- old levels. To determine taste threshold concentrations of selected phenol- ic compounds, a panel of four test individuals tasted water samples contain- ing various amounts of phenolic additives. As a point of comparison, water without phenolic additives was tasted first. Samples with increasing phe- nolic concentrations were then tested. Between samples, the mouth was rinsed with the comparison water and the test person ate several bites of dry white bread to "neutralize" the taste. Geometric mean detection level values for both tests provided threshold levels of 0.1 ug/1 for taste and 10 ug/1 for odor for 2-chlorophenol. None of the four organoleptic studies described above, however, indi- cated whether the determined threshold levels made the water undesirable or unfit for consumption. Studies on the impairment of fish flavor by 2-chlorophenol have also been reported. Henderson, et al. (1960) found that a concentration of 2,000 ug/1 caused impaired flavor of bluegill sunfish after a 28-day static, re- newal exposure. Only one concentration was tested, so no dose-related threshold was determined. Shumway and Palensky (1973) found 60 ug/1 to be an estimated threshold concentration during a 48-hour flow-through exposure of rainbow trout. Schulze (1961) determined that 15 ug/1 affected the fla- vor of carp after a 3-day flow-through exposure. Boetius (1954) studied the C-27 ------- flavor impairment of eels and oysters (species unspecified) in static sys- tems, and found flavor impairment in brackish water at a concentration of 0.125 ug/l after 11 days for eels and four days for oysters. Methodology for determining flavor impairment was particularly lacking in the Boetius paper. Because of the subjectivity of flavor impairment, test methodology (especially in the selection of, and evaluation by, the test panel) is par- ticularly important in the critical evaluation of a flavor impairment study. C-28 ------- CRITERION FORMULATION Existing Guidelines and Standards As can be determined from the available literature, no standards or guidelines exist for 2-chlorophenol. Current Levels of Exposure Overall, exposure of the general population to 2-chlorophenol would most likely occur in the form of consumption of phenol-containing chlorinat- ed drinking water. This would limit exposure primarily to water supplies contaminated by a point source of 2-chlorophenol. Such sources should be relatively easy to identify and monitor, since analytical techniques for detection of 2-chlorophenol are available. Apparently, such monitoring is not being done. Since 2-chlorophenol is not a universally reported metabolite of 2,4-D, exposure of the general population through use of 2,4-0 is only speculative. If small amounts of 2-chlorophenol are formed and gain access to ground water or the soil, they are not expected to persist, in view of 2-chlorophe- nol 's ready susceptibility to microbial attack. Inhalation or dermal exposure have not been identified as significant routes of exposure for the general population. Since 2-chlorophenol is not used directly for any broad environmental application, it is logical to ex- pect little exposure for the general population. However, due to lack of atmospheric monitoring data, any estimates of potential exposure are purely speculative. There have been no reported investigations of the persistence, movement, and fate of 2-chlorophenol in the atmosphere (U.S. EPA, 1979). For industrial workers manufacturing or handling 2-chlorophenol, inha- lation exposure should be considered a possible hazard, since the compound is volatile. Dermal exposure could also occur, since both phenol and cer- C-29 ------- tain chlorophenols are known to be dermally absorbed. However, specific absorption studies for 2-chlorophenol were not found (Doedens, 1963). Ac- cording to a recent review by the U.S. Environmental Protection Agency, "No data on the routes or rates of entry of 2-chlorophenol in humans were found" (U.S. EPA, 1979). Due to the lack of monitoring data or human body burden values, the extent of human exposure cannot be determined. Special Groups at Risk The only special group expected to be at risk of high exposure to 2-chlorophenol is industrial workers involved in the manufacture or handling of 2-chlorophenol. No data were found to relate exposure or body burden to conditions of contact with 2-chlorophenol. Basis and Derivation of Criterion Insufficient data exist to indicate that 2-chlorophenol is a carcino- genic agent. The only study performed (Boutwell and Bosch, 1959) was de- signed to detect the promoting activity of 2-chlorophenol with dimethylbenz- anthracene-initiated tumors. (Under certain environmental conditions, 2-chlorophenol may produce a small amount of dibenzo-p-dioxins.) The recent National Cancer Institute (NCI, 1978) bioassay report of possible carcinoge- nicity of dibenzo-p-dioxin has concluded that it was not carcinogenic for Osborne-Mendel rats or B6C3F1 mice. Due to the absence of sufficient tox- icological data on which to base a criterion, the ambient water quality cri- terion for 2-chlorophenol is based on organoleptic data. As substantive and reliable human and other mammalian toxicity data become available, a crite- rion level based upon health effects may be postulated. The data from Hoak (1957), Burttschell, et al. (1959), and Oietz and Traud (1978) all indicated that low microgram concentrations of 2-chlorophe- C-30 ------- no! in water are capable of producing a discernible odor. Burttschell, et al. (1959), Campbell, et al. (1958), and Oietz and fraud (1978) further ob- served a distinct flavor alteration of water at low microgram or sub-micro- gram levels of this chemical. The Burttschell, et al. (1959) and Dietz and Traud (1978) odor studies did not indicate a range of responses; however, because of the variability inherent in such procedures, it is certainly pos- sible that the odor threshold for some evaluators (at least in the Burtt- schell, et al. group) would extend downward toward the 0.33 ug/1 value of Hoak. Similarly, Burttschell, et al. (1959) did not indicate a range of concentrations in their taste test, and Campbell, et al. (1958) did not test concentrations of 2-chlorophenol below 2 u9/l; so it is also possible that some of the tasters in these tests could have at least been capable of de- tecting, if not actually detecting in the case of the Burttschell, et al. group, concentrations of 2-chlorophenol down near the 0.1 ug/1 taste thresh- old determined by Dietz and Traud (1978). Thus, the data from these four studies are considered to be reasonably mutually supportive (i.e., Hoak's 0.33 pg/1 for odor; Burttschell, et al. group's geometric mean values of 2 ug/1 for odor and 4 ug/1 for taste; Campbell, et al.'s derived 6 ug/1 threshold for taste; and Dietz and Traud's geometric mean values of 10 ug/1 for odor and 0.1 ug/1 for taste). The taste threshold determined by Oietz and Traud (1978) for the detec- tion of 2-chlorophenol in water is used as the basis for the ambient water quality criterion. The Dietz and Traud study was chosen for a number of reasons. These authors present a recent study involving well-defined proce- dures and a number of documented controls. This study utilized "fresh" water from the base outlet of the Verse Dam (Germany) for all experiments. The water was described as clear and neutral with respect to both odor and C-31 ------- taste. These conditions are considered to more closely approximate the con- ditions of ambient water found in lakes, rivers, and streams than would those of the Hoak (1957), Burttschell, et al. (1959), or Campbell, et al. (1958) studies, which utilized carbon-filtered laboratory distilled or re- distilled water. The 20 to 22°C temperature of the water in the Dietz and Traud odor and taste tests might also more closely approximate the tempera- ture at which water is normally consumed than do the 30*C or 25°C tempera- tures used in the studies of Hoak (1957) and Burttschell, et al. (1959), respectively [Campbell, et al. (1958) did not indicate the temperature of the water used in their study]. However, it is recognized that the tempera- ture of water consumed by humans is quite obviously variable, and no study will represent the temperature of water consumed by all Americans. Therefore, based on the prevention of undesirable organoleptic charac- teristics, the criterion level for 2-chlorophenol in water is 0.1 ug/1. It should be emphasized that this criterion is based on aesthetics rather than health effects. C-32 ------- REFERENCES Alexander, M. and M.I.H. Aleem. 1961. Effect of chemical structure on microbial decomposition of aromatic herbicides. Jour. Agric. Food Chem. 9: 44. Aly, O.M. 1968. Separation of phenols in waters by thin layer chromato- graphy. Water Res. 2: 587. Aly, O.M. and S.D. Faust. 1964. Studies on the fate of 2,4-D and ester derivatives in natural surface waters. Jour. Agric. Food Chem. 12: 541. American Public Health Association. 1979. Report received from Lois L. 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