Tài liệu tiếng anh về hợp chất PCP - PENTACHLOROPHENOL pps

INTERNATIONAL PROGRAMME ON CHEMICAL SAFETY ENVIRONMENTAL HEALTH CRITERIA 71 PENTACHLOROPHENOL This report contains the collective views of an international group of experts and does not necessarily represent the decisions or the stated policy of the United Nations Environment Programme, the International Labour Organisation, or the World Health Organization. Published under the joint sponsorship of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization World Health Orgnization Geneva, 1987 The International Programme on Chemical Safety (IPCS) is a joint venture of the United Nations Environment Programme, the International Labour Organisation, and the World Health Organization. The main objective of the IPCS is to carry out and disseminate evaluations of the effects of chemicals on human health and the quality of the environment. Supporting activities include the development of epidemiological, experimental laboratory, and risk-assessment methods that could produce internationally comparable results, and the development of manpower in the field of toxicology. Other activities carried out by the IPCS include the development of know-how for coping with chemical accidents, coordination of laboratory testing and epidemiological studies, and promotion of research on the mechanisms of the biological action of chemicals. ISBN 92 4 154271 3 The World Health Organization welcomes requests for permission to reproduce or translate its publications, in part or in full. Applications and enquiries should be addressed to the Office of ublications, World Health Organization, Geneva, Switzerland, which will be glad to provide the latest information on any changes made to the text, plans for new editions, and reprints and translations already available. (c) World Health Organization 1987 Publications of the World Health Organization enjoy copyright protection in accordance with the provisions of Protocol 2 of the Universal Copyright Convention. All rights reserved. The designations employed and the presentation of the material in this publication do not imply the expression of any opinion whatsoever on the part of the Secretariat of the World Health Organization concerning the legal status of any country, territory, city or area or of its authorities, or concerning the delimitation of its frontiers or boundaries. The mention of specific companies or of certain manufacturers' products does not imply that they are endorsed or recommended by the World Health Organization in preference to others of a similar nature that are not mentioned. Errors and omissions excepted, the names of proprietary products are distinguished by initial capital letters. CONTENTS ENVIRONMENTAL HEALTH CRITERIA FOR PENTACHLOROPHENOL 1. SUMMARY 1.1. Identity, physical and chemical properties, analytical methods 1.2. Sources of human and environmental exposure 1.3. Environmental transport, distribution, and transformation 1.4. Environmental levels and human exposure 1.5. Effects on organisms in the environment 1.6. Kinetics and metabolism 1.7. Effects on experimental animals and in vitro test systems 1.8. Effects on man 2. IDENTITY, PHYSICAL AND CHEMICAL PROPERTIES, ANALYTICAL METHODS 2.1. Identity 2.1.1. Pentachlorophenol (PCP) 2.1.2. Sodium pentachlorphenate (Na-PCP) 2.1.3. Pentachlorophenyl laurate 2.2. Impurities in pentachlorophenol 2.2.1. Formation of PCDDs and PCDFs during thermal decomposition 2.3. Physical, chemical, and organoleptic properties 2.4. Conversion factors 2.5. Analytical methods 2.5.1. Sampling methods 2.5.2. Analytical methods 3. SOURCES OF HUMAN AND ENVIRONMENTAL EXPOSURE 3.1. Natural occurrence 3.2. Man-made sources 3.2.1. Industrial production 3.2.1.1 Manufacturing processes 3.2.1.2 Emissions during production 3.2.1.3 Disposal of production wastes 3.2.1.4 Production levels 3.3. Uses 3.3.1. Commercial use 3.3.2. Agricultural use 3.3.3. Domestic use 3.3.4. Use for control of vectors 3.3.5. Formulations 4. ENVIRONMENTAL TRANSPORT, DISTRIBUTION, AND TRANSFORMATION 4.1. Transport and distribution between media 4.1.1. Volatilization 4.1.2. Adsorption 4.1.3. Leaching 4.2. Biotransformation 4.2.1. Abiotic degradation 4.2.2. Microbial degradation 4.2.2.1 Aquatic degradation 4.2.2.2 Degradation in soil 4.3. Degradation by plants 4.4. Ultimate fate following use 4.4.1. General aspects 4.4.2. Disposal of waste water 4.4.3. Incineration of wastes 5. ENVIRONMENTAL LEVELS ANS HUMAN EXPOSURE 5.1. Environmental levels 5.1.1. Air 5.1.2. Water and sediments 5.1.3. Soil 5.1.4. Aquatic and terrestrial organisms 5.1.4.1 Aquatic organisms 5.1.4.2 Terrestrial organisms 5.1.5. Drinking-water and food 5.1.6. Consumer products 5.1.7. Treated wood 5.2. Occupational exposure 5.3. General population exposure 5.4. Human monitoring data 6. KINETICS AND METABOLISM 6.1. Absorption 6.1.1. Animal studies 6.1.2. Human studies 6.2. Distribution 6.2.1. Animal studies 6.2.2. Human studies 6.3. Metabolic transformation 6.3.1. Animal studies 6.3.2. Human studies 6.4. Elimination and excretion 6.4.1. Animal studies 6.4.2. Human studies 6.5. Retention and turnover 6.5.1. Animal studies 6.5.2. Human studies 6.6. Reaction with body components 7. EFFECTS ON ORGANISMS IN THE ENVIRONMENT 7.1. Microorganisms 7.2. Aquatic organisms 7.2.1. Plants 7.2.2. Invertebrates 7.2.3. Vertebrates 7.3. Terrestrial organisms 7.3.1. Plants 7.3.2. Animals 7.4. Population and ecosystem effects 7.5. Biotransformation, bioaccumulation, and biomagnification 7.5.1. Aquatic organisms 7.5.2. Terrestrial organisms 8. EFFECTS ON EXPERIMENTAL ANIMALS AND IN VITRO TEST SYSTEMS 8.1. Acute toxicity 8.2. Short-term toxicity 8.2.1. Pure or purified PCP 8.2.2. Technical grade PCP 8.2.3. Comparative studies 8.3. Long-term toxicity 8.4. Effects on reproduction and fetal development 8.5. Mutagenicity 8.6. Carcinogenicity 8.7. Other studies 8.8. Contaminants affecting toxicity 8.8.1. Octachlorodibenzodioxin (OCDD) 8.8.2. Heptachlorodibenzodioxin (H7CDD) 8.8.3. Hexachlorodibenzodioxin (H6CDD) 8.8.4. Polychlorinated dibenzofurans (PCDFs) 8.8.5. Polychlorodiphenyl ethers (PCDPEs) 8.8.6. Other microcontaminants 8.9. Mechanism of toxicity 9. EFFECTS ON MAN 9.1. Acute toxicity - poisoning incidents 9.2. Effects of short- and long-term exposures 9.2.1. Occupational exposure 9.2.1.1 Skin and mucous membranes 9.2.1.2 Liver and kidney 9.2.1.3 Blood and haemopoetic system 9.2.1.4 Nervous system 9.2.1.5 Immunological system 9.2.1.6 Reproduction 9.2.1.7 Cytogenetic effects 9.2.1.8 Carcinogenicity 9.2.1.9 Other systems 9.2.2. General population exposure 10. EVALUATION OF HUMAN HEALTH RISKS AND EFFECTS ON THE ENVIRONMENT 10.1. Evaluation of human health risks 10.1.1. Occupational exposure 10.1.1.1 Exposure levels and routes 10.1.1.2 Toxic effects 10.1.1.3 Risk evaluation 10.1.2. Non-occupational exposure 10.1.2.1 Exposure levels and routes 10.1.2.2 Risk evaluation 10.1.3. General population exposure 10.1.3.1 Exposure levels and routes 10.1.3.2 Risk evaluation 10.2. Evaluation of effects on the environment 10.3. Conclusions 11. RECOMMENDATIONS 11.1. Environmental contamination and human exposure 11.2. Future research 11.2.1. Human exposure and effects 11.2.2. Effects on experimental animals and in vitro test systems 11.2.3. Effects on the ecosystem 12. PREVIOUS EVALUATIONS BY INTERNATIONAL BODIES REFERENCES WHO TASK GROUP ON PENTACHLOROPHENOL Members … NOTE TO READERS OF THE CRITERIA DOCUMENTS Every effort has been made to present information in the criteria documents as accurately as possible without unduly delaying their publication. In the interest of all users of the environmental health criteria documents, readers are kindly requested to communicate any errors that may have occurred to the Manager of the International Programme on Chemical Safety, World Health Organization, Geneva, Switzerland, in order that they may be included in corrigenda, which will appear in subsequent volumes. * * * A detailed data profile and a legal file can be obtained from the International Register of Potentially Toxic Chemicals, Palais des Nations, 1211 Geneva 10, Switzerland (Telephone no. 988400 - 985850). ENVIRONMENTAL HEALTH CRITERIA FOR PENTACHLOROPHENOL A WHO Task Group on Environmental Health Criteria for Pentachlorophenol met at the Fraunhofer Institute for Toxicology and Aerosol Research, Hanover, Federal Republic of Germany from 20 to 24 October, 1986. Dr W. Stöber opened the meeting and welcomed the members on behalf of the host Institute, and Dr U. Schlottmann spoke on behalf of the Federal Government, who sponsored the meeting. Dr K.W. Jager addressed the meeting on behalf of the three co-operating organizations of the IPCS (UNEP/ILO/WHO). The Task Group reviewed and revised the draft criteria document and made an evaluation of the risks for human health and the environment from exposure to pentachlorophenol. The drafts of this document were prepared by DR G. ROSNER of the Fraunhofer Institute for Toxicology and Aerosol Research, Hanover, Federal Republic of Germany, and DR A. GILMAN of the Health Protection Branch, Ottawa, Canada. The efforts of all who helped in the preparation and finalization of the document are gratefully acknowledged. * * * Partial financial support for the publication of this criteria document was kindly provided by the United States Department of Health and Human Services, through a contract from the National Institute of Environmental Health Sciences, Research Triangle Park, North Carolina, USA - a WHO Collaborating Centre for Environmental Health Effects. The United Kingdom Department of Health and Social Security generously supported the costs of printing. 1. SUMMARY 1.1. Identity, Physical and Chemical Properties, Analytical Methods Pure pentachlorophenol (PCP) consists of light tan to white, needlelike crystals and is relatively volatile. It is soluble in most organic solvents, but practically insoluble in water at the slightly acidic pH generated by its dissociation (pKa 4.7). However, its salts, such as sodium pentachlorophenate (Na-PCP), are readily soluble in water. At the approximately neutral pH of most natural waters, PCP is more than 99% ionized. Apart from other chlorophenols, unpurified technical PCP contains several microcontaminants, particularly polychlorinated dibenzo- p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), of which H6CDD is the most relevant congener toxicologically. 2,3,7,8-T4CDD has only once been confirmed in commercial PCP samples (0.25 - 1.1 µg/kg). Depending on the thermolytic conditions, thermal decomposition of PCP or Na-PCP may yield significant amounts of PCDDs and PCDFs. The use and the uncontrolled incineration of technical grade PCP is one of the most important sources of PCDDs and PCDFs in the environment. Most of the analytical methods used today involve acidification of the sample to convert PCP to its non-ionized form, extraction into an organic solvent, possible cleaning by back-extraction into a basic solution, and determination by gas chromatography with electron-capture detector (GC-EC) or other chromatographic methods as ester or ether derivatives (e.g., acetyl-PCP). Depending on sampling procedures and matrices, detection limits as low as 0.05 µg/m3 in air or 0.01 µg/litre in water can be achieved. 1.2. Sources of Human and Environmental Exposure PCP is mainly produced by the stepwise chlorination of phenols in the presence of catalysts. Until 1984, Na-PCP was partly synthesized by means of the alkaline hydrolysis of hexachlorobenzene, but it is now produced by dissolving PCP flakes in sodium hydroxide solution. World production of PCP is estimated to be of the order of 30 000 tonnes per year. Because of their broad pesticidal efficiency spectrum and low cost, PCP and its salts have been used as algicides, bactericides, fungicides, herbicides, insecticides, and molluscicides with a variety of applications in the industrial, agricultural, and domestic fields. However, in recent years, most developed countries have restricted the use of PCP, especially for agricultural and domestic applications. PCP is mainly used as a wood preservative, particularly on a commercial scale. The domestic use of PCP is of minor importance in the overall PCP market, but has been of particular concern because of possible health hazards associated with the indoor application of wood preservatives containing PCP. 1.3. Environmental Transport, Distribution, and Transformation The relatively high volatility of PCP and the water solubility of its ionized form have led to widespread contamination of the environment with this compound. Depending on the solvent, temperature, pH, and type of wood, up to 80% of PCP may evaporate from treated wood within 12 months. The adsorption and leaching behaviour of PCP varies from soil to soil. Adsorption of PCP decreases with rising pH and so PCP is most mobile in mineral soils, and least mobile in acidic clay and sandy soils. Solid or water-dissolved PCP can be photolysed by sunlight within a few days, yielding aromatic (lower chlorinated phenols, etc.) and nonaromatic fragments, as well as hydrogen chloride (HCl) and carbon dioxide (CO2). Traces of PCDDs, mainly OCDD are formed photochemically on irradiation of Na-PCP in aqueous solution. PCP degrading microorganisms have been isolated from waters and soils. High organic matter and moisture content, median temperatures, and high pH enhance microbial breakdown in soil (half-life = 7 - 14 days). Low oxygen conditions are generally unfavourable for the biodegradation of PCP, allowing it to persist in soil (half-life = 10 - 70 days under flooded conditions), water (half-life = 80 - 192 days in anaerobic water), and sediments (10% decomposition within 5 weeks to almost no degradation). Several studies have proved that PCP can be degraded by activated sludge. However, in full-scale treatment plants the treatment efficiency is often reduced. Numerous metabolites have been identified resulting from the methylation, acetylation, dechlorination, or hydroxylation of PCP. Of the possible metabolites, at least tetrachlorocatechol seems to be relatively persistent. However, there is a lack of data concerning the fate of the intermediate products of both the abiotic and biotic degradation of PCP. 1.4. Environmental Levels and Human Exposure The ubiquitous occurrence of PCP is indicated by its detection, even in ambient air of mountain rural areas (0.25 - 0.93 ng/m3). In urban areas, PCP levels of 5.7 - 7.8 ng/m3 have been detected. While elevated PCP concentrations can be found in groundwater (3 - 23 µg/litre) and surface water (0.07 - 31.9 µg/litre) within wood-treatment areas, the PCP level of surface waters is usually in the range of 0.1 - 1.0 µg/litre, with maximum values of up to 11 µg/litre. PCP concentrations in the mg/litre range can be encountered near industrial discharges. Sediments of water bodies generally contain much higher levels of PCP than the overlying waters. Soil samples from PCP or pesticide plants contain around 100 µg PCP/kg (dry weight); heavily contaminated soil (up to 45.6 mg PCP/kg) can be found in the vicinity of wood-treatment areas. Residues of PCP in the aquatic invertebrate and vertebrate fauna are in the low µg/kg range (wet weight). Very high levels (up to 6400 µg/kg) are found in fish from waters that are contaminated with wood preservatives, while sediment-dwelling organisms, such as clams, show PCP levels of up to 133 000 µg/kg. Fish kills result in PCP residues in fish of between 10 and 30 mg/kg. After agricultural PCP application, birds can be highly contaminated (47 mg/kg wet weight in liver). Exposure of farm animals to PCP-treated wood shavings used as litter causes a musty taint of the flesh as a result of contamination with pentachloroanisole, a metabolite of PCP biodecomposition. PCP levels ranging from not detectable to 8571 µg/kg have been found in the muscle tissue of wild birds. The general population is exposed to PCP through the ingestion of drinking-water (0.01 - 0.1 µg/litre) and food (up to 40 µg/kg in composite food samples). Apart from the daily dietary intake (0.1 - 6 µg/person per day) resulting from direct food contamination with PCP, continuous exposure to hexachlorobenzene and related compounds in food, which are biotransformed to PCP, may be another important source. In addition, because of its widespread use, the general population can be exposed to PCP in treated items such as textiles, leather, and paper products, and above all, through inhalation of indoor air contaminated with PCP. Generally, PCP concentrations of up to about 30 µg/m3 can be expected, for up to the first month, after indoor treatment of large surfaces; considerably higher levels (up to 160 µg/m3) cannot be excluded under unfavourable conditions. In the long term, values of between 1 and 10 µg/m3 are typical PCP concentrations after extensive treatments, though higher levels, up to 25 µg/m3, have been found in rooms treated one to several years earlier. For comparison, PCP indoor air levels in untreated houses are generally below 0.1 µg/m3. According to the usage pattern, the main sources of occupational exposure to PCP are the treatment of lumber in sawmills and treatment plants, and exposure to treated wood during carpentry and other wood- working activities. Most of the reported air concentrations at the work-place are below the TWA MAC value of 500 µg/m3 that has been established by several countries. Occupational exposure to PCP mainly occurs via inhalation and dermal exposure. Since the PCP concentrations in the sources (air, food) do not directly indicate the actual PCP intake by the different routes, extrapolation from urine residue data has been used to estimate human total body exposure. Mean or median urine-PCP levels range around 10 µg/litre for the general population without known exposure, around 40 µg/litre for non-occupationally exposed persons, and around 1000 µg/litre for occupationally exposed people. The ranges of urine levels observed in exposed and unexposed persons overlap considerably. This overlap probably occurs because occupational exposure does not necessarily involve high loading, while non-occupationally exposed people may, in some instances, be exposed to PCP at levels encountered at he work-place. 1.5. Effects on Organisms in the Environment As a result of its biocidal properties, PCP negatively affects non-target organisms in soil and water at relatively low concentrations. Algae appear to be the most sensitive aquatic organisms; as little as 1 g/litre can cause significant inhibition of the most sensitive algal species. Less sensitive species show EC50 values of around 1 mg/litre. Most aquatic invertebrates (annelids, molluscs, crustacea) and vertebrates (fish) are affected by PCP concentrations below 1 mg/litre in acute toxicity tests. Generally, reproductive and juvenile stages are the most sensitive, with LC50 values as low as 0.01 mg/litre for fish larvae. Low levels of dissolved oxygen, low pH, and high temperature increase the toxic effects of PCP. Concentrations causing sublethal effects on fish are in the low µg/litre range. As PCP contamination in many surface waters is in this range, [...]... PCDDs (mg/kg PCP) in the pyrolysate of technical PCP and Na-PCPa -PCP Na -PCP -2 ,3,7,8-T4CDD -b -c 1,2,3,7,8,9-H6CDD 53 2.1 1,2,3,6,7,8-H6CDD 66 0.95 Total H6CDD 455 10.5 H7CDD 5200 65 OCDD 15 000 200 -a From: Buser (1982) b Detection limit (1 mg/kg) c Detection limit (0.25 mg/kg) 2.3 Physical, Chemical, and Organoleptic Properties Pure pentachlorophenol. .. pentaphenate; phenol, pentachloro-, sodium derivative monohydrate; sodium PCP; sodium pentachlorophenate; sodium pentachlorophenolate; sodium pentachlorophenoxide Common trade names: Albapin; Cryptogil Na; Dow Dormant Fungicide; Dowicide G-St; Dowicide G; Napclor-G; Santobrite; Weed-beads; Xylophene Na; Witophen N CAS registry number: 13 1-5 2-2 (Na -PCP) ; 2773 5-6 4-4 (Na -PCP monohydrate) 2.1.3 Pentachlorophenyl... 0.03 - 35 mg/kg (Firestone et al., 1972), 9 - 27 mg/kg (Johnson et al., 1973), and < 0.03 - 10 mg/kg (Buser & Bosshardt, 1976) According to Fielder et al (1982), the 1,2,3,6,7, 9-, 1,2,3,6,8, 9-, 1,2,3,6,7, 8-, and 1,2,3,7,8,9-isomers of H6CDD have been detected in technical PCP The 1,2,3,6,7,8and 1,2,3,7,8,9-H6CDDs predominated in commercial samples of technical PCP (Dowicide 7) and Na -PCP Octachloro-dibenzo-... forms of pentachlorophenol in terms of production and use Other derivatives such as the potassium salt, K -PCP, and the lauric acid ester, L -PCP are of minor importance Reflecting this minor role, few data on the physical and chemical properties of K -PCP and L -PCP are reported in the literature Hence, this section primarly concerns PCP and its sodium salt 2.1 Identity 2.1.1 Pentachlorophenol (PCP) Molecular... C6HCl5O Pentachlorophenol chlorophen; PCP; penchlorol; penta; pentachlorofenol; pentachlorofenolo; pentachlorphenol; 2,3,4,5, 6- pentachlorophenol Common trade names: Acutox; Chem-Penta; Chem-Tol; Cryptogil ol; Dowicide 7; Dowicide EC-7; Dow Pentachlorophenol DP-2 Antimicrobial; Durotox; EP 30; Fungifen; Fungol; Glazd Penta; Grundier Arbezol; Lauxtol; Lauxtol A; Liroprem; Moosuran; NCI-C 54933; NCI-C 55378;... toxic 2,3,7,8-tetrachlorodibenzo- p-dioxin (2,3,7,8-T4CDD) has only been confirmed once in commercial PCP samples In the course of a collaborative survey, one out of five laboratories detected 2,3,7,8T4CDD in technical PCP and Na -PCP samples at concentrations of 250 - 260 and 890 - 1100 ng/kg, respectively (Umweltbundesamt, 1985) Buser & Bosshardt (1976) found detectable amounts of T4CDD (0.05 - 0.23 mg/kg)... 55378; NCI-C 56655; Pentacon; Penta-Kil; Pentasol; Penwar; Peratox; Permacide; Permagard; Permasan; Permatox; Priltox; Permite; Santophen; Santophen 20; Sinituho; Term-i-Trol; Thompson's Wood Fix; Weedone; Witophen P CAS registry number: 8 7-8 6-5 2.1.2 Sodium pentachlorphenate (Na -PCP) Molecular formula: C6Cl5ONa C 6Cl5ONa x H2O (as monohydrate) Common synonyms: penta-ate; pentachlorophenate sodium; pentachlorophenol, ... isomers with 1,3,6, 8- and 1,3,7,9-T4CDD as the main and 2,3,7, 8- T4CDD as minor isomers The formation of PCDFs, including small amounts of 2,3,7,8-T4CDF, during either combustion or micropyrolysis (280 °C, 30 min) was only observed in technical PCP samples; purified Na -PCP was negative in this respect (Rappe et al., 1978b) Table 3 Physical, chemical, and organoleptic properties of PCP and Na -PCP ... ppm = 10.9 mg PCP/ m3 (25 °C, 101.3 kPa) 1 mg PCP/ m3 = 0.09 ppm Table 4 Amount of PCDDs in the original sample and in the smoke from combusted materials treated with purified Na -PCP or technical PCP -Birch leavesa Wood chipsb (mg PCDDs/kg Na -PCP (mg PCDDs/kg PCP (purified)) (technical)) Original Smokec Original Smokec,d sample sample -T4CDD < 0.02... the production of approximately 2000 tonnes of PCP or Na -PCP, respectively, per annum are given in Table 6 Table 6 Air emissions of phenolic and non-phenolic compounds during production (maximum values)a -Annual air emissions (kg/year) during production of: 2000 tonnes 2000 tonnes PCP/ year Na -PCP/ year -PCP 18 65 Other chlorophenols 9 5 Hexachlorobenzene . PCDDs (mg/kg PCP) in the pyrolysate of technical PCP and Na -PCP a PCP Na -PCP 2,3,7,8-T 4 CDD - b - c 1,2,3,7,8,9-H 6 CDD 53 2.1 1,2,3,6,7,8-H 6 CDD 66 0.95 Total H 6 CDD 455 10.5 H 7 CDD. (Dowicide 7) and Na -PCP. Octachloro-dibenzo- p-dioxin (OCDD) is present in relatively high amounts in unpurified technical PCP (Table 1). Recently, the identification of 2-bromo-3,4,5,6-tetrachlorophenol. Table 1. Impurities (mg/kg PCP) in different technical PCP products Component Specification, producer, PCP content (%) Tech- Tech- Tech- Techni- Techni- Techni- Technical f nical a nical b