Bull. Org. mond. Santd 1970, 43, 479-508 Bull. Wld Hlth Org. Polynuclear Aromatic Hydrocarbons in the Water Environment* JULIAN B. ANDELMAN, PH.D.1 & MICHAEL J. SUESS, Sc.D.2 Many polynuclear aromatic hydrocarbons (PAH) are known to be carcinogenic to animals andprobably to man. This review is concerned with carcinogenic and non-carcino- genic PAH in the water environment, with emphasis on 3,4-benzpyrene (BP) because it is ubiquitous, is one ofthe mostpotent ofthe carcinogenic PAHandhas been widely studied. Although PAH are formed in combustion and other high-temperature processes, there is also evidence for their endogenous formation in plants, which may explain their ubiquity therein. Although the solubility of these compounds in pure water is very low, they may be solubilized by such materials as detergents, or they may otherwise occur in aqueous solution associated with or adsorbed on to a variety of colloidal materials or biota, and thereby be transported through the water environment. A notable characteristic of PAH is their sensitivity to light. PAH have been found in industrial and municipal waste effluents, and occur in soils, ground waters and surface waters, and their sediments and biota. With the exception of filtration or sorption by activated carbon, conventional water treatment processes do not efficiently remove them, and they have been found in domestic water supplies. Because of the ubiquity of PAH in the environment, it is impossible to prevent completely man's exposure to them; nevertheless their surveillance should be continued and their concen- trations in the environment should be reduced where practicable. INTRODUCTION Many polynuclear aromatic hydrocarbons (which will be referred to as PAH) are known to be car- cinogenic to animals and probably to man (Badger, 1962; Falk et al., 1964; Hueper & Conway, 1964). The potential hazard of PAH to man in water supplies has been noted by the WHO Expert Com- mittee on the Prevention of Cancer (1964) which states: Industrial effluents and atmospheric pollutants can find their way into water supplies. Water purification pro- * The major portion of this work is abstracted from the dissertation of Michael J. Suess, which was submitted to the Graduate School of Public Health, University of Pitts- burgh, USA, in partial fulfilment of the requirements for the degree of Doctor of Science in Environmental Health, December 1967. This study was supported in part by Grant No. I-1 from the Health Research and Services Foundation, Pittsburgh, Pa., USA. Paper first submitted 21 May 1968; revised paper submitted 3 January 1969. 1 Graduate School of Public Health, University of Pittsburgh, Pittsburgh, Pa., USA. 2Environmental Health Service, World Health Organi- zation, Regional Office for Europe, Copenhagen, Denmark. cedures in general use are designed to deal with bacterio- logical hazards and specific chemical impurities. Each chemical impurity may necessitate special measures. It is important that attention should be given to this problem in terms of carcinogenic compounds. In surveying the literature concerning the incidence and significance of such PAH in natural and treated waters, it became apparent that the large majority of these studies were being performed in Europe. For example, Wedgwood & Cooper, in England, have studied PAH in industrial effluents and sewage (Wedgwood, 1952a, 1952b, 1953; Wedgwood & Cooper, 1953, 1954, 1955, 1956). Borneff and co- workers, in Germany, have investigated the incidence and origin of PAH in, and adjacent to, fresh water and water supplies, as well as the effectiveness of various treatment processes (Borneff, 1960, 1963a, 1963b, 1964a, 1964b, 1965, 1967, 1969; Borneff & Knerr, 1959a, 1959b, 1960; Borneff & Fischer, 1961a, 1961b, 1961c, 1962a, 1962b, 1962c, 1962d, 1963; Borneff & Kunte, 1963, 1964, 1965, 1967, 1969; Borneff, Engelhardt et al., 1968; Kunte, 2576 -479- J. B. ANDELMAN & M. J. SUESS 1967, 1969; Muller, 1968; Muller & Reichert, 1969; Munch, 1966; Reichert, 1968a, 1968b, 1968c). Mallet and co-workers, in France, have performed similar studies, mainly in marine waters (Mallet, 1960, 1961, 1962, 1964, 1965a, 1965b, 1966, 1967; Mallet & Heros, 1960, 1961, 1962; Mallet & Lami, 1964; Mallet & Le Theule, 1961; Mallet & Priou, 1967; Mallet & Sardou, 1964, 1965; Mallet & Schneider, 1964; Mallet & Tissier, 1965; Mallet et al., 1960, 1963a, 1963b, 1967; Binet & Mallet, 1963; Bourcart et al., 1961; Bourcart & Mallet, 1965; Depuis, 1960; Greffard & Meury, 1967; Lalou, 1963, 1965; Lalou et al., 1962; Perdriau, 1964a, 1964b), while several investigators from the USSR have investigated PAH in industrial wastes (Gortalum & Dikun, 1958; Cherkinsky et al., 1959; Grigorev, 1960; Makhi- nenko & Dikun, 1962; Yanysheva et al., 1962; Dikun & Makhinenko, 1963; Fedorenko, 1964; Veldre et al., 1965a, 1965b; Ershova, 1968; Ershova & Mints, 1968; Samoilovich & Redkin, 1968). Ilnitsky & Varshavskaya (1964) reviewed some of the literature up to 1962 concerning water as a possible vehicle for the transmission of carcinogens through the environment. Their review principally discussed 3,4-benzpyrene (which will be referred to as BP), which they note is increasingly polluting natural waters. A discussion on possible pollution control measures followed in a later review (Ilnitsky, 1966). It is both timely and useful to bring the above and other recent studies to the attention of a wider group of readers, at the same time interrelating and reviewing their various aspects, especially as the recommendation has now been made that treated surface water that is used for drinking-water supplies should be examined for PAH (World Health Orga- nization, 1970). For this purpose, a routine ana- lysis method has been suggested for the determina- tion of 6 PAH, of which 3 are carcinogenic (Borneff & Kunte, 1969). Carcinogenic substances may enter natural waters, and thereby public water supplies, with the discharge of urban and domestic sewage, the release of indus- trial wastes, and through rain- and storm-water which contain atmospheric and surface carcinogenic contaminants. Carcinogens of natural or industrial origin adsorbed on to vegetation or incorporated into soil may leach into the ground water as well (Hueper, 1960). The rapidly increasing urbanization and indus- trialization of our society is accompanied by an increased demand on water resources-rivers, lakes and underground reservoirs. Thus, the danger of exposure to carcinogenic PAH from the consump- tion of contaminated drinking-water will grow in the future. The present review is concerned primarily with PAH in the water environment, with emphasis on BP because it is ubiquitous, is one of the most potent of the carcinogenic PAH and is widely studied. Whenever BP concentrations alone are mentioned it is because no other PAH were reported. The review will also discuss other carcinogenic and non-carcino- genic PAH. Pertinent physico-chemical properties of these materials, such as solubility and stability, will be reviewed as will analytical techniques. The sources and origins of these chemicals in the aquatic environment will be considered, as well as the mode of transport to natural waters and their incidence in surface, ground, marine and drinking water. The effect of water- and waste-treatment processes in removing PAH will be reviewed. Finally, the significance of water-borne carcinogenic PAH for humans will be discussed. Contamination of air by PAH has been widely studied and reviewed elsewhere (for example, Sawicki & Cassel, 1962) and will be discussed only as a source of contamination of water. PHYSICO-CHEMICAL PROPERTIES AND ANALYSIS OF PAH Table 1 lists the various PAH compounds referred to in this review, along with their abbreviations, empirical formulae and relative carcinogenic potency. As indicated there, BP is one of the most potent car- cinogens. The chemical structures of two PAH are given in the accompanying diagram. One of the most important characteristics of PAH relative to their incidence in water is solubility. As would be expected from their high molecular weight and lack of polar substituent groups, their solubility in pure water is extremely low. For example, after equilibrating water for two years with crystals of DBA, none of this material could be detected in TYPICAL POLYNUCLEAR AROMATIC HYDROCARBONS I/<3 1 ,2,5,6-dibenzanthracene 480 r _"11. 3,4-benzpyrene POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT TABLE 1 LIST OF PAH COMPOUNDS Symbol Compound Carcinogenica Empirical ompoun ~~~~potencyj formula AC anthracene ? C14Hio AF alkylfluoranthene ? AN acenaphthylene C12Hs AP alkylpyrene ? AT anthanthrene _ C22H12 BA 1,2-benzanthracene + CiaH,2 3,4-BF 3,4-benzfluoranthene + + C2oH12 10,11-BF 10,11-benzfluoranthene + + C2oH12 11 ,12-BF 11 ,12-benzfluoranthene - C2oH12 BP 3,4-benzpyrene + + + C2oH12 1,2-BP 1,2-benzpyrene + C2oH12 BPR 1,12-benzperylene C22H,2 CH chrysene + C.sH.2 CR coronene _ C24H,2 DBA 1 ,2,5,6-dibenzanthracene + + + C22H,4 DMBA 9,10-dimethyl-1 ,2-benzanthracene (active) C2oHis FL fluorenthene _ C6lHlo FR fluorene C13Hio IP indeno (1,2,3-cd) pyrene + C22H,2 MCA 3-methylcholanthrene (active) C2iHis PA phenanthrene ? C14H1o PR perylene _ C2oH,2 PY pyrene _ Ci.H,o TP triphenylene _C-2 a Potency notation: +++, active; ++, moderate; +, weak; -,inactive; ?, unknown. (Com- pounds labelled " active" are so listed by several authors). The notation is taken from Hoffman & Wynder (1962). b Reference from Grgf & Nowak (1966). distilled water by an analytical technique sensitive to 0.01 ,ug/litre (Bomeff & Knerr, 1960). The increase in solubility of PAH by the addition of water-soluble organic compounds is a phenomenon that is important in the passage of these compounds into and through environmental waters. Of special interest is the phenomenon of solubiliza- tion (Klevens, 1950; McBain & Hutchinson, 1955), which is defined by the latter as " a process in which otherwise insoluble matter is brought into solution by colloidal matter, specifically by micelles." The solubilization of PAH by micelles is of par- ticular interest because the latter are formed in water by synthetic detergents. However, it should be noted that solubilization does not occur until a sufficient amount of the solubilizing agent has been added and the region of the critical micelle concen- tration (CMC) reached. Once the vicinity of the CMC is reached, the increase in concentration of solubilizing agent results in increased solubility of PAH, although the relationship is often not a linear one. In general, the CMC for synthetic detergents 481 J. B. ANDELMAN & M. J. SUESS is high, one study measuring a value of 40 mg/litre of a linear alkylbenzene sulfonate in drinking-water (Bohm-G6ssl & Kruger, 1965). Thus, for most natural and treated waters the detergent concentra- tions are lower than the minimum amount required to solubilize. One must also consider the phenomenon of hydro- tropy, that is, the increase in PAH solubility in water as a result of the introduction of other organic chemicals not associated with colloid formation; for example the increased BP water solubility by lactic acid (Ekwall & Sjoblom, 1952), purines, such as caffeine (Weil-Malherbe, 1946), acetone (Graf & Nothhafft, 1963; Suess, 1967), and ethyl alcohol (Brock et al., 1938; Suess, 1967). There is sufficient evidence to indicate the possibility of the increased solubility of PAH as a result of the presence of a wide variety of organic compounds that may be found in these waters. Finally, it should be noted that highly polluted water containing emulsions of organic solvents would be capable of containing relatively large quantities of PAH. The sorption of PAH on to surfaces is an impor- tant characteristic in relation to their presence in environmental waters. The ability of BP to con- centrate on activated carbon, calcareous material, silica, glass and plastics by sorption has been noted (Brock et al., 1938; Borneff & Knerr, 1959a; Mallet & Schneider, 1964; Knorr & Giitzschmann, 1966; Suess, 1967). Hence, the presence of minerals and other suspended and settled particulates in environ- mental waters should be considered in relation to their ability to contain and carry PAH. The stability of PAH, especially as affected by light and oxygen, is an important characteristic in relation to their presence in water or any other environment. Recently, a study was made of the degradation of BP and 12 other PAH dissolved in cyclohexane and dichloromethane (Kuratsune & Hirohata, 1962). Sunlight, fluorescent lamps, and an ultraviolet source consisting mostly of the 365 m,t and 366 m,u mercury lines, were the sources of illumination, the solutions being irradiated for up to 377 hours. The most light-sensitive compounds were naphthacene and DMBA, with BP and AC following. The other PAH generally did not decom- pose. Degradation was similarly affected by daylight- type fluorescent lamps and sunlight when using reasonably comparable light intensities and exposure times. Using an ultraviolet source, the decomposi- tion of BP was compared in oxygen- and nitrogen- saturated solutions. The nitrogen-saturated solution reduced somewhat the BP degradation compared with the solution that had been exposed to air prior to sealing and irradiation. However, BP in the oxygen- saturated solution decomposed at a much higher rate. Several other investigations were performed, studying similar effects of various light sources, organic solvents in pure form or as mixed aqueous solutions, and the presence of oxygen on the degra- dation of BP and other PAH (Kriegel & Herforth, 1957; Woenckhaus et al., 1962; Reske & Stauff, 1963, 1964; Tanimura, 1964; Reske, 1966; Masuda & Kuratsune, 1966; Harrison & Raabe, 1967; Suess, 1967; Jiiger & Kassowitzova, 1968). A study was made of the degradation ofBP sorbed on to surfaces of calcium carbonate in aqueous sus- pensions exposed to fluorescent light (Suess, 1967; Andelman & Suess, in press). Such a system is likely to simulate BP behaviour in natural water environments, particularly because of the demon- strated ability of BP to sorb on to mineral surfaces. The effects of light intensity, oxygen concentration, temperature, pH and ionic strength on the photo- decomposition rate were determined, and the mecha- nism of this process was discussed. The results indicated that while higher light intensity, oxygen concentration and temperature accelerated BP degra- dation, pH and ionic strength in the ranges studied had no effect. Of immediate implications for environmental waters was one study in which a comparison was made of the light sensitivity of BP in crystalline form, vegetable oil and aqueous detergent solutions, using ultraviolet irradiation and daylight (Borneff & Knerr, 1959b). The degradation was greatest in the aqueous detergent solution, next in the oil solution, and least in the crystalline form. With daylight illumination ofabout 8000 lux (1.2 mW/cm2) approxi- mately 20 hours were required to degrade 90% of the BP in the aqueous solution, and 60-90 hours in oil. The shorter ultraviolet wave lengths were particularly effective. Because these PAH have varying degrees of sensitivity, their relative concen- trations in the environment need not reflect those in the contaminating sources. The presence of oxygen and other oxidizing agents will significantly increase rate of degradation of the PAH. In aqueous and mixed aqueous solutions they will degrade faster than in pure organic solvents or in crystalline form. The analytical, concentration and separation tech- niques for examining PAH in environmental samples have been comprehensively reviewed (Sawicki, 1964). Sawicki emphasized that in environmental samples 482 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT these compounds are generally present in very small quantities, along with many other kinds of organic materials. Thus, prior to using instrumental methods for their analysis, it is necessary to separate the PAH from other classes of compounds and from each other. In addition they must often be concen- trated prior to the instrumental analysis. Solid- liquid and liquid-liquid extraction techniques have been used in the initial stages of separation and concentration, often followed by column, paper and thin-layer chromatography. Gas chromatography has also been used as a separation-analysis tech- nique. The most frequently used instrumental methods for identification and quantitative analysis are based on the ultraviolet-visible absorption spec- tra, as well as the fluorescence spectra. A concise description of the simultaneous determination of 13 PAH is given by Grimmer & Hildebrandt (1965a). For a routine determination of PAH in drinking- water, however, a simplified procedure is referred to by the World Health Organization (1970), sug- gesting the evaluation of only 6 PAH-namely, 3,4-BF; 11,12-BF; BP; FL; BPR and IP (Borneff & Kunte, 1969) (Table 1). It is not the intention of this review to examine in detail the techniques used in the analysis of environmental samples. Yet, an extensive series of studies should be mentioned, as they are particularly useful in describing the methodology for the exami- nation of a wide variety of water and water-related samples. There are discussions of adsorption spectra and chromatographic techniques (Borneff & Knerr, 1959a; Kunte, 1967), extraction of BP from water and sand (Borneff& Knerr, 1959b), and fluorescence analysis (Borneff, 1960; Kunte, 1967). In Borneff's paper the greater sensitivity of fluorescence com- pared with ultraviolet-absorption analysis (10-fold) was noted. This is also discussed elsewhere (Sawicki, 1964), although this sensitivity ratio was there stated to be in the range of 10-1000. Extraction of PAH from activated carbon, as well as losses encountered in the subsequent steps of distillation, column and paper chromatography were discussed (Borneff & Fisher, 1961a). Descriptions were given for tech- niques used in the analysis of filter mud (Borneff & Fischer, 1961b), zooplankton and phytoplankton (Borneff & Fischer, 1961c), soil (Borneff & Fischer, 1962d), the centrifugate from surface water (Borneff & Fischer, 1963), and liquid-liquid extraction of river, lake and tap water (Borneff & Kunte, 1964). Although bioassay with conventional laboratory animals has long been used in testing the carcino- genicity of specific compounds or extracts containing unknown materials, the use of bacteria for assaying carcinogenic PAH may have advantages in terms of speed and sensitivity (Won & Thomas, 1962). A photodynamic bioassay using Paramecium cau- datum has been developed as a presumptive index of carcinogenicity from PAH and used to ana- lyse carbon-filter extracts of finished drinking-water (Epstein & Taylor, 1966). The correlation of this assay with detailed instrumental-chemical analyses of PAH could obviate the need for the latter and be particularly useful in the analysis of large numbers of water samples for carcinogenic PAH. ORIGIN, SOURCE AND VEHICLES OF TRANSMISSION OF PAH In this discussion the term "origin " will refer to the formation of PAH, while "source " will signify the object or material in which they are concen- trated and from which they may be disseminated into the environment. The vehicles of transmission are industrial and domestic effluents, atmospheric fall-out, precipitation and run-off water. The ubi- quity of PAH, in spite of their instability, particu- larly with exposure to light and oxidizing agents, and their very low solubility in water, prompt one to consider their possible origins. Origin and sources ofPAH in the environment Until recently the evidence available seemed to indicate that the carcinogenic hydrocarbons in the environment are formed only at high temperatures (Badger, 1962; Badger et al. 1966). Badger (1962) notes that coal tar, which is produced by heating coal in the absence of air, consists of relatively large quantities of BP and other PAH when pro- duced at high temperatures (e.g., 700°C), as com- pared with 300'C-450'C when the products are mostly paraffins, cycloparaffins, olefins, and phenols. The carcinogenic effect ofpetroleum asphalt, cooking oil and coal tar has been studied (Hueper & Payne, 1960; Hueper & Conway, 1964; and others). The materials associated with such high temperature pyrolysis that have been shown to contain PAH, and which may act as a source of them for the water environment, include coal tar and coal-tar pitch, shale oil (Cahnmann, 1955), and carbon black, which is used in many manufacturing processes, par- ticularly being incorporated into automobile tyres (Badger, 1962). Thus, the wear of the latter on roads can be a source of PAH. Bitumen or asphalt used 483 J. B. ANDELMAN & M. J. SUESS in constructing roads contain PAH, as does dust that may be collected from their surfaces and car- ried by run-off water (Borneff & Kunte, 1965). BP has been isolated from cracked mineral oils but carcinogenic PAH have generally not been isolated from uncracked oils (Cook et al., 1958; Badger, 1962). However, there is some evidence for the occurrence of some PAH in crude oil (Meinschein, 1959), and the presence of BP in concentrations of about 1 mg/litre has been demonstrated (Graf & Winter, 1968). Shipping and harbour oils have been connected with contamination of water by PAH (Shimkin et al., 1951; Cahnmann & Kuratsune, 1956; Mallet, Tendron & Plessis, 1960; Mallet & Le Theule, 1961; Borneff, 1964a), as have effluents from a variety of industries using pyrolytic processes. The question of endogenous formation of PAH in plants and micro-organisms (Mallet & Heros, 1962; Borneff, 1963b, 1964a; Graf, 1964, 1965; Graf & Diehl, 1966), arises because of their ubiquity in the environment, particularly in a wide variety of materials which were not likely to have been associated with pyrolytic processes. Several PAH were found in forest soils remote from human habitation and in other soils (Kern, 1947; Mallet & Heros, 1962; Binet & Mallet, 1963; Graf, 1965; Mallet, 1965a, 1966; Zdrazil & Picha, 1966). In gen- eral, the upper layer of the earth contains carcino- genic PAH in the range of 100lg/kg-1000 pg/kg; although these soils are a source of PAH for surface waters, their contribution is small (Borneff, 1964a). The presence of BP cannot be attributed only to fall-out from polluted air; rather, it seems to be indigenous to the soil and might be the product of living organisms (Blumer, 1961). The synthesis of PAH by micro-organisms to account for their pres- ence in filtration wash-water sludge has been sug- gested (Knorr, 1965), and was later verified by a laboratory study of various bacteria which accumu- lated BP through synthesis in amounts of 2 pg/kg- 6 ,g/kg of dried material (Knorr & Schenk, 1968). Laboratory culture studies of the fresh water alga Chlorella vulgaris have shown that it synthesizes several PAH (Borneff, 1964a; Borneff, Selenka et al., 1968a; Borneff, Selenka et al., 1968b). The extracted algae contained carcinogenic PAH in the range of 10 ,ug/kg-50 ,ug/kg (Borneff, 1964b). The presence of PAH has been demonstrated in a wide variety of plants from diverse sources (Guddal, 1959; Borneff, 1963b; Grimmer, 1966). Of special interest is some recent research on the synthesis of PAH and their physiological functions in plants (Graf, 1964, 1965; Graf & Diehl, 1966; Griif & Nowak, 1966). Wheat and rye were grown hydro- ponically in solutions made from reagent-grade chemicals which were free of PAH and in the presence and absence of light. Whereas the seeds contained only traces of BP the seedlings contained 10 ug-20 ,g BP per kg of dried material after 8-10 days of growth. It was concluded that the BP was synthesized by the plants, both in the presence and absence of light. In another series of experiments it was shown that BP added to the soil or nutrient media accelerated the growth ofkohlrabi, cauliflower, wheat, rye, and tobacco. In the case of rye, the grain output was 3 times greater when the BP was added. It was found that BP was not stored in these experiments, but was utilized. Similar experiments with DBA, a strong carcinogen, and BA, a weaker one, suggested a direct relationship between carcinogenic potency in animals and the ability of PAH to promote growth. The investigator concluded that it is likely that there is a world-wide synthesis of PAH in plants, and that they have always been present in man's environment. Although additional research on the synthesis of PAH by plants is required to justify the conclusions that the process is a universal one, the great amount of evidence of the ubiquity of PAH supports the likelihood of such syntheses. Vehicles of transmission ofPAH Various industrial entreprises are a potential source of PAH, and contaminate the water environment when releasing their large amounts of waste-water effluents into lakes, rivers and coastal waters (Bourcart et al., 1961; Mallet & Le Theule, 1961; Borneff, 1964a; Borneff & Kunte, 1965; Bourcart & Mallet, 1965). Industrial effluents, loaded with PAH, may be produced by refineries, industries utiliz- ing solid and liquid fuel materials for manufacturing chemical by-products, the plastics and dyestuffs industries, high-temperature furnaces, the lime indus- try and others (Mallet & Le Theule, 1961). Although industrial waste-water has been generally recognized as a potential vehicle of transmission of PAH, only few quantitative investigations have been conducted. The majority of the reports were published by British and Soviet authors (Table 2). The British authors studied the PAH content in industrial efflu- ents before entering the city sewers, while the Soviet authors put the emphasis on the study of BP con- centration in the effluents of various processing stages of the solid fuel by-product industry (Gortalum 484 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT TABLE 2 PAH CONCENTRATION IN INDUSTRIAL EFFLUENTS Industry Source of waste-water BP concentration Reference Shale-oil 320 Makhinenko & Dikun, 1962 Dikun & Makhinenko, 1963 After treatment for dephenolization 5Graf,1s s 2 Veldre et al., 1965a,1965b Coke by-products Not indicated present . Yanysheva et al., 1962 After biochemical treatment 12-16 Fedorenko, 1964 After oil separation (5 samples) 6.5, 130, 250, 290 and Cherkinsky et al., 1959 " big " quantity Spent gas liquor very small quantity a Wedgwood, 1952b Coke or oil-gas works Before discharge to sewer not indicated b Wedgwood & Cooper, 1955 Before discharge to sewer (2 plants) 1 000 and 340 c Wedgwood & Cooper, 1956 Oil-gas works After oil separation (3 samples) 3, 6, and 30 Cherkinsky et al., 1959 Oil refinery After oil separation (3 samples) none detected Cherkinsky et al., 1959 Tar paper Not indicated present Grigorev, 1960 Acetylene Not indicated 0.015-0.100 d Filippov & Ruchena, 1965 Ammonium sulfate After cooling and settling about 0e Wedgwood & Cooper, 1955 a Also present were: AT, BA, CH, FL, PR, and PY. b Present or suspected were: AC, AN, BPR, FR, and PA. c Also present were: AC, BPR, FL, and PY. d The figures were taken from Chemical Abstracts, but appear to be too low. read 15-100 pg/litre. e Also present: AP, AT, BA, 1,2-BP, CH, FL, PR, PY, and TP. & Dikun, 1958; Dikun & Makhinenko, 1963) as well as in the finally treated waste-water (Veldre et al., 1965b). The results indicated that BP concen- tration increased with increased cracking tempera- ture, but it was not detected at all in waste-water from operations under 500'C (Cherkinsky et al., 1959; Veldre et al., 1965a). Municipal wastes (Table 3) often contain large quantities of industrial effluents (Wedgwood & Cooper, 1955, 1956). During the rainy season the sewer system may also be affected by run-off water passing over roads. In addition, human urine was found to contain BP (Mallet & Heros, 1960), while the human metabolite 8-hydroxy-3,4-BP was iden- tified in both the urine and faeces (Iversen, 1947). It is assumed that the correct values should It was noted that PAH were actually present in sewage sludge whether or not industrial wastes enter the system (Wedgwood, 1952b; Wedgwood & Cooper, 1956). The presence and fate ofPAH in the polluted atmo- sphere have been widely studied, and discussed in detail in the literature. It has been shown that some of the PAH in air find their way to the ground adsorbed on to aerosols and bacteria (Mallet & Heros, 1961), either by direct settling or through precipitation. Run-off water can then collect the PAH from areas covered with atmospheric fall-out and road-dust (Wedgwood & Cooper, 1954; Borneff, 1964a; Borneff & Kunte, 1965), as well as from freshly tarred or oiled surfaces (Hueper & Ruchhoft, 485 J. B. ANDELMAN & M. J. SUESS TABLE 3 PAH CONCENTRATION IN DOMESTIC EFFLUENTS Concentration (Mg/litre) a Source B Carcinogenic Total ReferenceBP ~PAH PAH Domestic effluent from a small community after primary treatment 0.170 3.0 15.0 Borneff & Kunte, 1964 Waste effluents entering Rotach River: Borneff & Kunte, 1965 Sample I 0.015 0.2 0.5 Sample II 0.047 1.1 2.7 Sample III 0.079 1.0 6.6 Sample IV 0.100 0.5 5.1 Sample V 0.038 0.3 0.8 Waste effluent of Stockach 0.100 5.0 15.0 Borneff & Kunte, 1965 Waste effluent of Radolfzell 0.368 2.8 8.6 Borneff & Kunte, 1965 Waste effluents of Hegne: Borneff & Kunte, 1965 Sample I 0.001 0.1 0.8 Sample II 0.011 1.2 4.2 Sample III 1.840 37.9 87.5 Sample IV 0.450 31.6 68.0 Vegetable cold wash-water: Grimmer, 1966 Sample I 1.60 8.1 25.2 Sample II 1.02 5.8 22.6 Urine from Paris inhabitants(4 samples) I to 3 Mallet & Heros, 1960 Sewage of Leningrad present Poglazova et al., 1966 Sewage, final effluent 0.15-1.50 Wedgwood & Cooper, 1954, 1956(4 plants-8 samples) present PY, AN. AP and FL Sludge from secondary treatment AC, AN, AT, BA, Wedgwood, 1952b(humus) present FL, PR, and PY Wedgwood & Cooper, 1954,1955 Humus, dried 3 000 Wedgwood & Cooper, 1954 a Detailed tables with figures for the various carcinogenic and non-carcinogenic PAH are presented in Borneff & Kunte, 1964,1965; Grimmer, 1966. 1954). A part of the run-off water gets into the city sewers or the natural surface water, while another part of it may infiltrate through the soil into the ground-water. Only a few samples of precipitation and run-off water have been analysed for their PAH content. Nevertheless, PAH were recovered from rain, and freshly fallen snow (Cooper & Lindsey, 1953; Gilbert & Lindsey, 1955). PAH IN ENVIRONMENTAL WATERS Borneff & Kunte (1964) divided fresh waters into 4 categories with respect to their carcinogenic PAH concentration (Table 4), these being correlated in general with their degree of pollution. However, in this review environmental waters are divided into 4 different categories. The first two, marine and surface water, include flora, fauna and sediments, 486 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT TABLE 4 CONCENTRATION OF CARCINOGENIC PAH IN FRESH WATERS a Concentration Water type range(isg/litre) Ground-water 0.001-0.010 Treated river and lake water 0.010-0.025 Surface water 0.025-0.100 Surface water, strongly contaminated >0.100 a Taken from Borneff & Kunte, 1964. in addition to the water itself. The other two cate- gories are ground- and drinking-water. The majority of the investigations in the marine environment were performed by Mallet & co-workers (Suess, 1970). Systematic studies were made of the Atlantic, Channel and Mediterranean coasts of France (Mallet et al., 1960; Mallet, 1960, 1961; Bourcart et al., 1961; Mallet & Le Theule, 1961; Lalou et al., 1962; Mallet & Sardou, 1964; Mallet & Schneider, 1964; Mallet & Lami, 1964; Perdriau, 1964a; Mallet, 1965; Mallet & Sardou, 1965; Lalou, 1965; Greffard & Meury, 1967; Mallet, 1967) the Bay of Naples, Italy (Bourcart & Mallet, 1965), and the western coast of Greenland (Mallet, Perdriau & Perdriau, 1963a, 1963b; Perdriau, 1964b) (Ta- bles 5-8). The latter, a practically unpopulated coast with little shipping and water vegetation was, nevertheless, found to contain on the average the same order of BP contamination as the French coasts, thus indicating the ubiquity of BP in the oceans. In a number of locations along the French coast the fish and molluscs contained notable amounts of BP, while the alluvial deposits at the same location showed only traces, possibly indicat- ing that certain marine organisms are able to con- centrate and fix hydrocarbons. In the past it has been suggested that hydrocarbons may possibly be transported in the oceans by sea streams from industrialized and heavily polluted areas to remote and unpopulated regions (Bourcart et al., 1961; Mallet & Sardou, 1964). However, recent reports on endogenous synthesis of PAH in flora (see previous section) indicate that they may be formed in these areas. This can be supported by studies on the origin of petroleum which showed the presence of aromatic (and other) hydrocarbons in phytoplankton and which postulated that the amount of aliphatic and aromatic hydrocarbon compounds produced by phytoplankton per square kilometre of ocean may be as high as 3 tons (2.7 metric tonnes) per year (Smith, 1954). In addition, plankton may be able to fix them from exogenous sources (Mallet TABLE 5 CONCENTRATION OF BP IN MARINE PLANKTON BP concentration Source (gg/kg of dry Reference sam pie) Greenland a 5.5 Mallet, Perdriau & Perdriau, 1963a Italy b 6.1-21.2 Bourcart & Mallet, 1965 French Channel coast 400 Mallet & Sardou, 1964 French Mediterranean coast c not detected to 5 Mallet & Sardou, 1964, 1965 Estuary, French Channel coast 100 Mallet & Lami, 1964 Ditto e 350 Mallet & Lami, 1964 Diatoms serving as fllters in food Industry 5.5 Mallet & Schneider, 1964 a One sample from depth of 30 m. b Six samples collected on water surface and from a depth of 2 m. c Fifteen samples. d Plankton debris in foam immediately downstream of dam. 6 Plankton debris west of outlet, downstream from dam. 487 J. B. ANDELMAN & M. J. SUESS TABLE 6 CONCENTRATION OF BP IN MARINE ALGAE BP concentration Source (iAg/kg of dry Reference sample) Greenland, west coast a 60 Mallet, Perdriau & Perdriau, 1963a Greenland, west coast b 60 Mallet, Perdriau & Perdriau, 1963a Italy 2.2 Bourcart & Mallet, 1965 French Channel coast not detected Mallet, 1961 a Sample from depth of 40 m. b Samples from bottom of the sea and shore. CONCENTRATION TABLE 7 OF BP IN MARINE FAUNA Source Sample BP concentration(izg/kg of dry sample) Reference Cod fish 15 Mallet, Perdriau & Perdriau, 1963a Mollusc 60 Greenland, west coast a Holothurian not detected Mussel: shell 18 body 55 Italy, Bay of Naples b Mussel: shell 11 Bourcart & Mallet, 1965 body 130 and 540 Italy, Bay of Naples c Mollusc 2.4 Italy, Bay of Naples d Sardine 65 Various French coasts e Shrimp, oyster, mussel, not detected to traces to Mallet, 1961 mollusc, crab, etc. 1.5-90 French Atlantic coast Oyster: shell 3.5 Mg/dozen Mallet, Tendron & Plessis, 1960 body 0.4 tAg/dozen French Channel coast Oyster: lower shell 70 Mallet & Schneider, 1964 upper shell 112 France, Toulon harbour Mussel 16-22 f Greffard & Meury, 1967 Alabama Oyster: shell 24 Mallet & Schneider, 1964 Virginia Oyster 2-6 g Cahnmann & Kuratsune, 1957 California Goose barnacle present Koe & Zechmeister, 1952 California Thatched barnacle present Shimkin et al.. 1951; Koe & Zechmeister, 1952 a Sample from depth of 40 m. b Two samples. c Sample from depth of 35 m. d Sample from water surface. e Mallet (1961) presents a detailed list of 25 samples covering 13 species. f Total PAH was about 1100-3400 Mg/kg. g Total carcinogenic PAH was about 300 Mg/kg, and total PAH about 1200 Mg/kg. 488 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT TABLE 8 CONCENTRATION OF BP IN MARINE SEDIMENTS Sample ~Depth BP concentrationSource Sample | Depthm |B (jig/kg of dry Reference(in)sam ple) Greenland, west coast Italy, Bay of Naples (6 locations) French Mediterranean coast French Mediterranean coast Estuary, French Mediterranean French Mediterranean coast French Mediterranean coast French Channel coast French Channel and Atlantic coasts (11 locations) Sand Mud, sand, shell a Sand, shell Mud, sand Mud, sand, shell b Muddy sand Mud, sand c Sand Black mud Sand Sand Beige mud Sand Sand Sand Sand Mud Mud Mud, sand 0.20 15-45 13 2-65 55 120 0-0.03 0.03-0.08 0.08-0.13 0.13-0.18 0.23-0.28 0.33-0.38 0.48-0.53 1.00 2.00 14 16 48 58 82 1 4 5 102 5 1 000-3 000 7.5 10-530 260-960 1.4 100-560 1 800 3600 5 000 2 500 2 200 730 420 26 16 400 1 500 75 traces 400 34 20 15 25 not detected 50 20 15 000 not detected to 1 700 Mallet, Perdriau & Perdriau, 1963a Bourcart & Mallet, 1965 Lalou et al., 1962 Bourcart et al., 1961 Bourcart et al., 1961 Bourcart et al., 1961 Bourcart et al., 1961 Mallet, Tendron & Plessis, 1960 Mallet & Le Theule, 1961 a Five samples were collected 300 m from shore. Area is highly industrialized. b Four samples were collected in the vicinity of volcanic pollution. c Four samples. This Island Is affected by pollution. I 489 J. B. ANDELMAN & M. J. SUESS TABLE 9 CONCENTRATION OF PAH IN SURFACE WATERS Concentration (Ag/litre) aI Source Carcinogenic Total Reference BP PAH PAH 0.003 Borneff & Fischer, 1962b Bodensee 0.0004 c Borneff, 1964a 0.0013 0.030 0.065 Borneff & Kunte, 1964 Alprhine 0.005 C Borneff, 1964a River Rhine present Holluta & Talsky, 1955 River Rhine 0.050 to Borneff & Fischer, 1962a O.500d River Rhine at Mainz 0.080 c Borneff, 1964a River Rhine at Mainz (Mar. 1964) 0.049 0.240 0.73 Borneff & Kunte, 1964 (Mar. 1964) 0.114 0.730 1.50 River Main, at Seligenstadt 0.0024 0.155 0.48 Borneff & Kunte, 1964 River Danube, at Ulm Borneff & Kunte, 1964(Apr. 1964) 0.0006 0.055 0.28 (May 1964) 0.078 0.20 River Gersprenz, at Munster Borneff & Kunte, 1964 (Jan. 1964) 0.0096 0.055 0.16 (Apr. 1964) 0.038 0.12 River Aach, at Stockach c 0.50 Borneff, 1964a River Aach, at Stockach c Borneff & Kunte, 1965 Sample I 0.043 1.30 3.0 Sample II 0.016 0.90 2.5 Sample III 0.004 0.50 1.4 Sample IV 0.005 1.10 3.1 River Schussen (Bodensee) 0.50 c Borneff, 1964a River Schussen 0.01 0.20 1.0 Borneff & Kunte, 1965 River Argen (Bodensee) 0.07!' Borneff, 1964a River Seine Considerable Mallet, 1965,1966 amount River Plyussa: Dikun & Makhinenko, 1963 at discharge site of shale-oil effluent 12 3500 m downstream I at the water intake of Narvy 0.1 A river: 15 m below discharge of coke by-product, Fedorenko1964 effluent 8-12 500 m downstream 2-3 Peat (turf) water 0.05 Graf, 1965 a Detailed tables with figures for the various carcinogenic and non-carcinogenic PAH are presented In Borneff & Kunte, 1964,1965. b Extrapolated from rapid sand filtration lake mud analyses. c Extrapolated from centrifugate fractions. d Extrapolated from activated-carbon adsorption analyses. 490 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT & Sardou, 1964), and marine fauna may be con- taminated with BP, regardless of whether in pol- luted or unpolluted locations (Table 7). PAH are not considered normal metabolic products of marine fauna, but may be ingested in the course of filter- feeding (Shimkin et al., 1951; Koe & Zechmeister, 1952; Zechmeister & Koe, 1952; Mallet, Tendron & Plessis, 1960; Mallet, 1960). This may also explain the high BP concentration found in the calcareous shell of some organisms (Mallet & Schneider, 1964) (Table 7). The sources of PAH in the marine sediments include: surface effluents, ships, volcanic debris (Bourcart & Mallet, 1965), and activity of organisms, including bacteria. The latter may explain the very high BP concentration found at some points under the bottom of the Bay of Villefranche (Lalou et al., 1962) (Table 8). Carcinogenic PAH have been detected in many surface waters (Table 9). Mountain streams, such as the Alprhine, and relatively non-polluted lakes, such as the Bodensee (Lake Constance), have sig- nificantly lower concentrations of PAH compared with polluted rivers, such as the lower Rhine. Industrial and municipal effluents are an important source of PAH in surface water. Phytoplankton, TABLE 10 CONCENTRATION OF PAH IN SURFACE WATER ENVIRONMENT Concentration(tsgIkg of dry sample) a Source Sample Carcino | oalReference BP genic PAHPAH Laboratory Filamentous algae 10-50 Borneff, 1964a Bodensee Phytoplankton b 2 170 700 Borneff & Fischer, 1962c Bodensee Suspended solids c 50 1 250 1 500 Borneff & Fischer, 1962b Bodensee Suspended solids d 200 3 200 6000 Borneff & Fischer, 1963; Borneff, 1964a Bodensee Suspended solidse 3 000 Borneff, 1964a Alprhine, at Bregenz Suspended solids e: Aug. 1962 150 620 Borneff, 1964a; Borneff & Kunte, 1965 Sept. 1962 15 63 River Rhine Suspended solids e 300 2 600 8 000 Borneff & Fischer, 1963 River Rhine, at Mainz Suspended solids e 3 000 Borneff, 1964a River Main, at Seligenstadt 5 000 Borneff, 1964a River Aach, at Stockach Suspended solidse: Aug. 1962 600 6 700 17 000 Borneff, 1964a; Borneff & Kunte, 1965 Aug. 1962 2 000 6 400 50 000 June 1963 500 19 000 56 000 River Schussen (Bodensee) Suspended solids e 400 18000 55000 Borneff, 1964a; Borneff & Kunte, 1965 River Argen (Bodensee) Suspended solids e 100 3 700 9 600 Borneff, 1964a; Borneff & Kunte, 1965 Fresh-water pool, Italy Tubifex worms 50 Scaccini-Cicatelli, 1965, 1966 a Detailed tables with figures for the carcinogenic and non-carcinogenic PAH are presented in Borneff & Fischer, 1962b,1962c, 1963; Borneff & Kunte, 1965. b Up to 95% were diatoms, Asterionella formosa. c Coarse particles only, from rapid, sand-filter backwash water settled in a sedimentation basin. d Rapid, sand-filter mud centrifugate collected from backwash water after complete suspension (down to 1 4 e Centrifugate of water sample (down to 1 ). 10 491 J. B. ANDELMAN & M. J. SUESS one of the sources of PAH in the Bodensee, is, however, only a minor contributor when compared with industrial pollution and run-off water from roads (Borneff & Fischer, 1963; Borneff, 1964a; Borneff & Kunte, 1965). Suspended solids have been studied as vehicles of transmission of PAH in the water environment. The suspended solid fractions have been obtained either by centrifuging the water sample or by collecting rapid-sand-filtration mud (Table 10). Bottom sedi- ments demonstrated high concentrations of BP as well (Table 11). The values are comparable in range to those for marine sediments (Table 8). An investigation of PAH in ground-water was performed with the conclusion that, in general, uncontaminated ground-water has the lowest con- centration of carcinogenic PAH of all natural waters, ranging from 0.001 ,tg/litre-0.010 ,ug/litre (Borneff, 1964a; Borneff & Kunte, 1964) (Table 12). Potable water samples from the following sources were examined: untreated ground-water, mixed ground- and bank-filtered-water (Table 12), and treated river and lake water (Tables 13 and 14), all samples being taken at the tap. It was concluded that, in general, the carcinogenic PAH concentration in most drinking-water does not exceed 0.025 ,tg/litre (Borneff & Kunte, 1964). On the other hand, BP could not be detected in the chloroform and alcohol extracts of carbon filters from finished water at different locations in the United States, although there was some evidence of unidentified polynuclear hydrocarbons (Epstein & Taylor, 1966). However, TABLE 11 CONCENTRATION OF BP IN RIVER BOTTOM SEDIMENTS Source River Seine, about 40 km downstream from Paris: Core sample I Core sample 11 Core sample III Core sample IV Core sample V River Seine mud Bottom deposit of a river, below a coke by-product plant Depth(m) 5.9 7.1 9 10 0.8 3 10 2 5 9 BP concentration(Mg/kg of dry sample) 3 000 29 4 4 8500 6 500 50 10 000 390 100 15 000 8 200-17 000 Reference Mallet, 1965a, 1966 Depuis, 1960 Fedorenko, 1964 there is evidence that recovery from activated carbon may be incomplete. Because of this it may be preferable in analysing water for its PAH content to concentrate by liquid-liquid extraction, as is TABLE 12 PAH CONCENTRATION IN GROUND-WATER Concentration (Ag/litre)a Date of Source lCarcengenic Total colle ReferenceBP CAr TAl collectionPAHIPA Ground-water at Finthen Ground-water at Mainz Ground-water b: Sample I Sample II Mixed ground- and bank-filtered-water b 0.0001 0.0006 0.0003 0.002 0.005 0.001 0.004 0.009 0.045 0.034 0.140 May 1963 Aug. 1963 May 1963 Borneff, 1964a Borneff, 1964a Borneff & Kunte, 1964 Borneff & Kunte, 1964 a Detailed tables with figures for the various carcinogenic and non-carcinogenic PAH are presented in Borneff & Kunte, 1964. b Sampling locations not known. 492 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT TABLE 13 CONCENTRATION OF CARCINOGENIC PAH IN PURE WATER SAMPLES a Source Concentration(_g/litre) Tap water at Mainz mixed from different sources 0.007 Bodensee, centrifuged 0.010 Well water, south of Frankfurt 0.025 River Main, centrifuged 0.800 a Taken from Borneff, 1964a. currently recommended by the World Health Organization (1970). After studies of the carcinogenic characteristics of pipe coating materials it was suggested that the latter were possible sources of PAH in drinking- water (Druckrey et al., 1960; Zdraiil & Picha, 1962; Hettche, 1963; CAzaceanu & Trandafirescu, 1966). In laboratory studies PAH have been detected in water which was in contact with a protective varnish con- taining a coal-tar base (Rondia, 1966), as well as with bitumen used for painting the inside of pipes (Borneff & Kunte, 1965) (Table 15). The results of the latter experiment suggest the possibility of an increase in the initial PAH concentration in treated water while flowing through long bituminous water lines. However, after sufficient hardening and leach- ing, these materials probably become an insignificant source of PAH (Borneff & Kunte, 1964, 1965). EFFECT OF WATER AND WASTE-WATER TREATMENT ON PAH The effect of some water treatment processes on the removal of PAH has been studied. Table 14 shows the concentrations of BP, carcinogenic and total PAH found in untreated and treated river and lake water. As indicated there, the combination of rapid sand-filtration and chlorination or ozonation TABLE 14 EFFECT OF WATER TREATMENT ON PAH CONCENTRATION a Concentration (Mg/litre) Date Water source Treatment Carcinogenic Total of sampling BP CArcngei ToAl (1964) River Rhine b Sample I Untreated 0.114 0.73 1.49 Mar. 3 Sample II Untreated 0.049 0.24 0.73 Mar. 3 Bank-filtered and activated carbon filter 0.0005 0.015 0.13 May 11 Bodenseec Untreated 0.0013 0.030 0.065 May 20 Sample I cl Rapid sand 0.0115 0.054 0.234 Mar. 20 filtration and Sample II chlorination 0.0002 0.007 0.025 May 20 or ozonation Sample III 0.0005 0.010 0.039 Apr. 7 Sample IV 0.0014 0.017 0.062 May 21 Sample V 0.0024 0.025 0.072 May 21 Sample VI 0.0040 0.028 0.066 May 19 a Taken from Borneff & Kunte, 1964. b The 2 untreated samples were taken at Mainz on the same day with an interval of 6 hours. The treated sample was taken at an unknown location 2 months later. Therefore, the treatment effect cannot be directly evaluated. c The locations from which the various samples were collected are unknown, and the sam- pling dates varied. Therefore, the treatment effect cannot be directly evaluated. However, it is known that the untreated sample and the treated second sample were collected on the same day. d No satisfactory explanation can be given to the high values. 493 J. B. ANDELMAN & M. J. SUESS TABLE 15 CONCENTRATION OF PAH IN BITUMEN AND CONTACT-WATER a Concentration(Mg/kg, and Mg/litre respectively) b Sample BP Carcinogenic TotalPAH PAH Bitumen 100 3 400 3 500 Water: Sample I C 0.0175 0.090 0.200 Sample II d 0.0035 0.043 0.110 a Taken from Borneff & Kunte, 1965. b Detailed tables with figures for the various carcinogenic and non-carcinogenic PAH are presented in Borneff & Kunte, 1965. c The sample was taken from distilled water after 10 days in contact with a coating of bitumen. d After Sample I was taken, the bitumenous coating was continuously washed for 4 weeks with water before a fresh distilled batch of water was put in for 10 days. were not particularly effective in reducing the con- centrations of these materials, while the activated carbon was primarily responsible for their reduction in the Rhine. River water, after seeping through the river-bank soil, still contains PAH, probably because the filtra- tion does not efficiently remove colloidal materials (Mallet, 1965, 1966). PAH have been recovered from activated carbon used to filter such river-bank- filtered water (Borneff & Fischer, 1962a; Borneff, 1964a). Similarly, the efficiency of rapid sand- filtration is not high; yet the examination of filter mud from backwash water of Bodensee rapid sand- filters indicates a high PAH concentration, thus showing some removal (Table 16). Although it is generally true that the better the sedimentation of the suspended solids, the better the water quality, it has to be kept in mind that no significant reduction of PAH in water should be expected because these compounds are mostly associated with particles too small to settle in a simple clarification process (Bomeff & Fischer, 1963; Borneff & Kunte, 1965). On the other hand, flocculation of raw river water was found more efficient in removal of PAH (Lawe- renz, 1967). A number of laboratory studies were conducted on the effectiveness of oxidizing agents, such as chlorine and ozone, on the reduction of BP and other carcino- genic PAH in water. The studies using chlorine (Graf& Nothhaft, 1963; Trakhtam & Manita, 1966) (Table 17), indicated relatively slow removal com- pared with the typical disinfection time of 1/2 hour by chlorine. Thus, while some reduction of BP is achieved, the efficiency of this treatment is question- able. Chlorination does not significantly increase the removal of PAH in lake-water treatment (Borneff, 1964a; Borneff & Kunte, 1964) (Table 14). On the other hand, experiments with gaseous chlordioxide in doses and contact periods commonly practised in water treatment indicated a very high percentage of BP removal, and yielded non-carcinogenic pro- ducts (Reichert, 1968a, 1968b, 1968c, Borneff, 1969). Similarly, the treatment of a BP aqueous solution with ozone-enriched air achieved a reduction of 99% within 30 minutes. However, interference in the process efficiency by organic trace contaminants has been observed (Bomeff, 1969). The removal of PAH TABLE 16 PAH RETAINED ON ACTIVATED-CARBON AND RAPID-SAND-FILTER MUD Source of PAH Concentration (Mg/kg of dry sample) a BP CarcinogenicPAH TotalPAH Reference Activated-carbon 1 150 8 700 Borneff & Fischer, 1962a The coarse settled particles from the backwash water of a rapid sand filter, collected from a sedimentation basin 50 1 250 15 000 Borneff & Fischer, 1962b The centrifuged particles (down to 1u) from the back- wash water of a rapid sand filter 200 3 200 6 200 Borneff & Fischer, 1963 a petailed tables with figures for the v.rious carvinogenic PAH ware presented in Borneff & Fischer, 1962a, 1962b, 1963. 494 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT TABLE 17 EFFECT OF CHLORINATION ON BP CONCENTRATION Initial Initial Time (h) needed to reduce BP chlorine BP concentration to: dose con- Reference (mg/litre) centration /2 Zero8/1(Mg/litre) value value value value Zero 0.3 5 3 - Graf & Nothhafft, 1963 0.5 5 2 20 - - - 0.5 2 2 - - - 13 0.3 1 - /2 - 2 - Trakhtman & Manita, 1966 0.5 1 - - 1/2 1 - from drinking-water using ozone was further dis- cussed by Reichert (1969). When comparing the degradation achieved for a number of examined carcinogenic PAH, BP was found to be the most resistant (Ilnitsky, 1968). The resistance of BP to degradation depended on its state, and was greater when it was adsorbed on soil particles than when in solution. Filtration through activated carbon is the most effective conventional process for the removal of PAH. Furthermore, the examination of fresh acti- vated carbon did not show the presence of PAH (Borneff & Fischer, 1961a), indicating that in this respect it is suitable for use in water treatment (Borneff, 1964a). Studies on the use of activated carbon for the treatment of river-bank-filtered water indicate that the carbon removed approximately 99% of the PAH (Borneff & Fischer, 1962a). It has been previously noted that BP and other PAH are sensitive to light of various wavelengths. It is thus likely that ultraviolet irradiation as a water treatment process will reduce the concentra- tions of these materials. As a significant part of the carcinogenic PAH may be present in raw water while adsorbed on particles or in suspension, mechanical treatment such as sedimentation and filtration as well as flocculation may have some effect on their removal. Adsorption on activated carbon has been found most effective. The best over-all results may be achieved from combined processes including both mechanical and chemical ones. By such methods removal of up to 99% has been achieved. However, no known method has yet been found to reduce the concentration of carcinogenic PAH below about 0.01 ,ug/litre, their common concentration in non-polluted ground-water (Reichert, 1968; Borneff, 1969). TABLE 18 REDUCTION OF PYRENE BY A SEWAGE TREATMENT a PY concentration(Mg/litre) % reduction sewage Infeedwaterto In final effluent 1.00 0.36 b 0.43 0.15-0.23 c 46-65 0.51 0.45 12 a Taken from Wedgwood & Cooper, 1956. b From an efficient trickling filtration sewage-treatment plant using recirculation. c From an overloaded trickling-filtration sewage-treatment plant. PAH in significant concentrations are found in effluents from municipal waste-water treatment plants, partially due to the slow rate of oxidation in biological processes (Wedgwood & Cooper, 1956), indicating the limited efficiency of the treatment processes. Table 18 presents data concerning the reduction of pyrene in sewage by trickling-filter treatment plants. The removal is not high. The activated-sludge process when studied in the labora- tory did not show any significant ability to oxidize carcinogenic PAH even after 144 hours (Lutin et al., 1965). The effect of dephenolization of shale-oil waste- water on the BP concentration was investigated (Gortalum & Dikun, 1958; Dikun & Makhinenko, 1963; Veldre et al., 1965a) (Table 19). It can be concluded that in many cases complete removal of BP is not achieved and additional treatment is necessary. However, filtration through a coke bed effects a high degree of removal. 495 J. B. ANDELMAN & M. J. SUESS TABLE 19 REDUCTION OF BP BY INDUSTRIAL EFFLUENT TREATMENT PROCESSES Dephenolization 10 900 Dephenolization 200 Dephenolization 5-20 Dephenolization 44 64 310 a 5 2 12-16 b 97 97.5 60-90 75 Dikun & Makhinenko, 1963 Gortalum & Dikun, 1958 Veldre et al., 1965a Fedorenko, 1964 Filtration through coke bed C 1 000 20 98 Wedgwood & Cooper, 1956 ________~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ a A butyl acetate process was used for dephenolization. b A biological process was used for dephenolization. c Similar removal efficiencies were achieved for AC and PY. HUMAN EXPOSURE TO PAH Before considering the possible effects of PAH on the health of man, it is useful to consider the quan- tities to which he is exposed. It has been postulated that as a result of the likely world-wide synthesis of PAH by plants, as well as their other origins, there exist environmental concentrations of BP of the order of magnitude of 10 ,ug/kg-20 ,ug/kg of dry organic substance (Graf& Diehl, 1966). BP, although a most potent carcinogen, represents only a relatively small portion of the total carcinogenic PAH found in environmental samples. The majority of investi- gators have dealt only with BP or another single compound, and only a few studies touched on a variety of carcinogenic PAH in the same environ- mental samples (Borneff & Fischer, 1962a, 1962b, 1962c, 1963; Borneff, 1964a; Borneff& Kunte, 1964, 1965, 1967). The latter studies led to the conclusion that there is no correlation between the concentration of BP and that of the total carcinogenic PAH in the environmental samples. However, BP does generally constitute between 1 % and 20% of the total carcino- genic PAH (Tables 3, 9, 10, 12, 14, 15 and 16). It has been previously noted that in one series of studies the general range of concentration of carcino- genic PAH in ground-water and treated surface water is between 0.001 pg/litre and 0.025 ,ug/litre (Table 4). This may be taken as a likely range of concentration in drinking-water supplies, although higher values have been reported (Table 13). There have been numerous reports on the pollu- tion of air by BP and other carcinogenic PAH (for example, Hoffmann & Wynder, 1962). Such sub- stances may occur in air, sorbed on to a variety of particulate materials, and be inhaled by man. Car- cinogenic PAH have also been identified in tobacco smoke (Bentley & Burgan, 1958; Wynder & Hoff- mann, 1959). It has also been found that carcino- genic PAH occur in fresh and air-cured tobacco leaves indicating that combustion is not required for their production (Cooper & Campbell, 1955; Campbell & Cooper, 1955; Campbell & Lindsey, 1956, 1957; Bentley & Burgan, 1958, 1960; Shanta & Krishnamurthi, 1963; Schmiihl, 1964). Man may also be exposed to carcinogenic PAH from the use of unsmoked tobacco as snuff. Examples of levels of BP in such materials are 54 ug/kg in a mixture of pipe tobacco and 270 jug/kg in Zulu snuff. River and marine sediments, suspended solids, zoo- and phytoplankton and worms, have all been shown to contain various amounts of carcinogenic PAH (Tables 5, 6, 8, 10 and 11). Aqueous biota serve as a food and source of PAH for edible fish and shellfish (Table 7), from which the PAH may reach man. BP has been found in fish from the river Seine (Depuis, 1960) codfish (Mallet, Perdrian & Perdriau, 1963a), bluefish (Smith, 1954), and sar- dines (Bourcart & Mallet, 1965). PAH have also been detected in various oysters and edible molluscs (Cahnmann & Kuratsune, 1957; Mallet et al., 1960; Mallet, 1961; Mallet et al., 1963b; Mallet & Schneider, 1964; Perdriau, 1964b; Bourcart & Mallet, 1965). Carcinogenic PAH have been extracted from a large variety of fresh plants, and were detected in 496 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT considerable amounts in vegetables, salads, grains, fruits and edible mushrooms (Graf, 1964, 1965; Grimmer & Hildebrandt, 1965b, 1965c, 1966; Grim- mer, 1966; Graf & Diehl, 1966), as well as in vege- table oils (Jung & Morand, 1962, 1963; Ciusa et al., 1965; Ramel et al., 1965; Borneff & Faibian, 1966; Craft & Norman, 1966; Howard et al., 1966b; Le Clerc et al., 1966; Biemoth & Rost, 1967, 1968; Grimmer & Hildebrandt, 1967a, 1968; Fabian, 1968a); from these reports it appears that the BP content of active plant tissue is in the range of 10,ug/kg-20,ug/kg. In coconut oil its content may rise to about 50,tg/kg while in most other examined vegetable oils BP content was found to amount to only a few ,ug/kg. Numerous reports have been published on the existence and concentration of carcinogenic PAH in various fried, grilled, roasted and smoked fish and meat products as well as in coffee, with particular attention being given to BP (Bailey & Dungal, 1958; Gorelova & Dikun, 1958a, 1958b, 1961, 1965; Kuratsune & Hueper, 1958, 1960; Dansi & Zanini, 1959; Dungal, 1959, 1961a, 1961b; Gorelova et al., 1959, 1960, 1963a, 1963b; Nugmanov et al., 1961; Shabad, 1961; Lijinsky & Shubik, 1964, 1965a, 1965b; Dikun, 1965a, 1965b; Ramel et al., 1965; Grimmer, 1966; Grimmer & Hildebrandt, 1966, 1967a, 1967b; Howard et al., 1966a, 1966c; Le Clerc et al., 1966; Kuratsune et al., 1966; Masuda et al., 1966; Sigurjonsson, 1966a, 1966b; Lijinsky, 1967; Fabian, 1968b, 1969; Thorsteinsson & Thordarson, 1968; Kraybill, 1969; Thorsteinsson, 1969). Levels of BP in such processed foods are, for example, 37 ug/kg in smoked fish and 200,g/kg in coffee soot. A recent review (Haenni, 1968) discusses the scien- tific rationale and the analytical principles underlying control in the United States of America of the con- tamination of the food supply by potentially carcino- genic PAH arising from the use of food additives. The review supplements and brings up to date an earlier paper by Gunther & Buzzetti (1965) which is even broader in scope. HEALTH CONSIDERATIONS In order to consider the possible effect of PAH on man, it is pertinent to discuss their relative carcino- genicities. For the most part conclusions as to the potency of these carcinogens are based on laboratory animal experiments only, although one indirect and two direct applications of BP to the human skin have been reported (Klar, 1938; Cottini & Mazzone, 1939; Rhoads et al., 1954). The potency of these substances varies with the species. It is believed that some PAH are indeed carcinogenic to man, the most ubiquitous and potent one being possibly BP (Falk et al., 1964). On the other hand, the importance of weak carcinogens has been empha- sized, as these may be the significant agents in human carcinogenesis (Kennaway, 1955). A number of attempts have been made to compare the potency of the various carcinogenic PAH. Iball (1939) has introduced the " carcinogenic index ", defined by the percentage of tumours produced over the average latent period in days. Berenblum (1945) has suggested a series of 12 " carcinogenic grades ". For simplicity Badger's system involved 4 grades of carcinogenicity (Badger, 1948). More recently a " relative activity index " has been devel- oped using 3 grades only (Wynder & Hoffmann, 1959; Hoffmann & Wynder, 1962). Table 1 lists a variety of PAH graded by their method. In all the previously reported methods the grading has been based on the relative potency of the carcino- gens to the skin of mice, BP being among the most active. BP, although a potent carcinogen, constitutes only a relatively small portion of the total carcinogenic PAH found in environmental samples. Most investi- gators have determined the levels of a single, or at most a few, carcinogenic PAH in environmental samples. The work of Bomeff indicates that BP generally constitutes between 1% and 20% of the total carcinogenic PAH (Tables 3, 9, 10, 12, 14, 15 and 16). Although being carcinogenic to animal tissue, PAH do not produce carcinomas or cell changes in plants (Manil & Straszewska, 1950; Blochinger, 1961; and others). Further, it has previously been noted that PAH may promote the growth of plants and that this characteristic may be related to their carcino- genicity in animals (Graf, 1964, 1965). As some derivatives of BP and other carcinogenic PAH are formed during disinfection of water with oxidizing agents and ultraviolet 'radiation, and through various biochemical reactions, it is of inter- est to briefly examine the carcinogenicity of such derivatives. Except with the addition of methyl groups and homologous alkyl derivatives, most BP derivatives at most have weak carcinogenic acti- vity (Butenandt & Dannenberg, 1956). However, 10-chloro compounds do cause tumours. 5-Chloro- benzpyrene, formed during chlorination (Reichert, 1968a, 1968b), was first suspected to be carcinogenic 497 J. B. ANDELMAN & M. J. SUESS (Graf & Nothhafft, 1963) but proved in later ex- periments not to be so (Muller & Reichert, 1969). The quinones, on the other hand, some of which are also formed during chlorination (Reichert, 1968a, 1968b), do not produce tumours (Butenandt & Dannenberg, 1956), and may inhibit other carcino- gens (Buu-Hoi, 1959). There are very few studies concerning the statisti- cal correlation between cancer and drinking-water. Furthermore, no epidemiological evidence is avail- able as to the excessive liability to cancer of a popu- lation obtaining its drinking-water from bodies of polluted raw-water (Hueper & Conway, 1964). It was, nevertheless, noted that 4 London boroughs, supplied largely by well-water, had lower cancer mortalities than most of the other boroughs supplied with river water (Stocks, 1947). Another study con- cluded that the highest cancer death rates are for communities supplied by river water, followed by w-ell water, and heath water (Diehl & Tromp, 1954; Tromp, 1955). None of these studies attempted to correlate cancer morbidity with concentrations of PAH. Finally it should be noted that one epidemio- logical study of the incidence of gastric cancer con- cluded that social factors and the kinds of soils present reduced the correlations otherwise obtained with the type of domestic water supply (Wynne- Griffith & Davies, 1954; Davies & Wynne-Griffith, 1954). Although many experiments to determine the car- cinogenic activity of BP have been conducted on various laboratory test animals, it is not within the scope of this review to summarize, compare or evaluate the experimental results. Yet it should be noted that the possible distribution in the body of ingested BP has been demonstrated (Poel, 1963); when fed to mice the BP was absorbed from the alimentary tract and distributed to various body organs. Fore-stomach tumours have developed in some mice within a year when administered with as little as 0.0625 mg of BP per dose twice weekly in 0.1 ml Tween-60 by gastric intubation. However, differences in the carcinogenic susceptibility to BP among various species of test animals have been observed. For example, BP is highly potent for the skin of mice, but only weakly active for that of rabbits (Hueper & Conway, 1964). Therefore, it is not possible to deduce the effect of BP on humans from the results of experiments on animals. Experimental work with mice, studying the rela- tive tumour yield obtained with subcutaneous injec- tions of various amounts of BP (Payne & Hueper, 1960), has further confirmed " . . . the general impres- sion that repeated exposure to carcinogenic chemicals are more effective than an equivalent single exposure. ... Repeated doses of a carcinogen are, moreover, bound to overcome any modifying or inhibiting influences which any constitutional and genetically dependent factor of the host organism may exert on the development of the cancerous response " (Hueper & Conway, 1964). Therefore, the experiments de- scribed (Payne & Hueper, 1960; Poel, 1963; etc.) indicate the potential danger of continuous exposure to carcinogenic PAH introduced into the gastro- intestinal tract by water and food, even at low con- centrations. However, it can be assumed that a high percentage of the carcinogenic PAH or their meta- bolites will be eliminated quickly through the urine and faeces (Chang, 1943; Weigert & Mottram, 1946a, 1946b; Gerarde, 1960). It should be kept in mind that the usual relation- ship of effective doses of toxic compounds in propor- tion to body weight may not necessarily hold for carcinogens because a tumour can develop at the point of contact with the carcinogenic material. Therefore, the probability of cancer being produced in the human should not be directly related to animal size (Gerarde, 1960). Until recently, threshold limits for carcinogenic PAH have not been determined (Borneff & Fischer, 1962b), and many investigators believe that even the slightest exposure will cause irreversible effects (Ilnitsky & Varshavskaya, 1964). It is thus observed that carcinogens differ from some other toxic agents in that no safe level exists (Druckrey, 1954; Boyland, 1958). Therefore, it has been suggested that the threshold limit be set practically at zero (Gerarde, 1960). However, this recommendation is negated by the presence of carcinogenic PAH in so many plant tissues as to render the setting of such a limit impracticable. Man is exposed to carcinogenic PAH from many sources. A comparative study of their relative importance has, however, not yet been done. It has been suggested that the carcinogenic material ingested by man from drinking-water should not surpass a tenth of this material taken-up from normal urban air. This would limit the maximum permissible concentration (MPC) in water to 0.017 ,ug/litre, or with a daily consumption of 2.5 litres of drinking water, to about 15 ,ug yearly, and about 1 mg in a lifetime (Borneff & Fischer, 1962b; Kruse, 1965). The first recommendation has recently been made, concerning PAH in drinking-water supplies, propos- 498 POLYNUCLEAR AROMATIC HYDROCARBONS IN THE WATER ENVIRONMENT ing the normal concentration of 6 PAH, selected for easy determination, to be 0.1 ug/litre, and limiting the maximum recommended concentration (MRC) to 0.2 ,tg/litre (Bomeff & Kunte, 1969; World Health Organization, 1970). Of the 6 selected PAH only 3 are carcinogenic (3,4-BF, BP and IP) with an MRC of about 0.03 ,ug/litre, of which BP com- prises about one fourth. Calculations based on 4 drinking-water samples (Table 13) indicate an annual human consumption of carcinogenic PAH of about 6 ,ug, 9 ,tg, 22 ,ug, and 70 ,tg, respectively, for the population served. It may be estimated that bank-filtered water from the Rhine would result in a yearly total ingestion of 50 to 500 ,ug of carcinogenic PAH (Borneff & Fischer, 1962a). Similarly, a river water source con- taining 0.1 jtg/litre of BP would result in 90 ,ug per year (Dikun & Makhinenko, 1963). However, any current limits set on the amounts of these materials should be taken with reservation because they are not based on knowledge of their toxic effects. Although currently the consumption of PAH- containing water is probably not dangerous, the combination of sources cannot be excluded as a potential hazard. When one considers that animal experiments have shown that repeated exposure to carcinogens is more effective than an equivalent single dose, one should not neglect the possibility of cancer from the repeated life-long exposure to carcinogens in air, food and water. Kotin (1958) said that repeated observations on the cumulative effect of carcinogens strongly suggest that given enough time and a sufficient exposure in the pre- sence of other pathogenetic factors, the inevitability of cancer formation is one of the few certainties of life. Therefore, the presence of PAH carcinogens in water, food and air is undesirable. Moreover, because of the technically unavoidable contamina- tion from background, consideration should be given to avoiding increasing the level of carcinogenic PAH in food, such as from additives or processing, as well as limiting where practicable their concentrations in water and air. CONCLUSIONS The report of the WHO Expert Committee on the Prevention of Cancer (1964) touches on the environ- mental aspects and states: Effective measures are needed to prevent the introduc- tion of carcinogenic industrial wastes into the atmosphere and into public waters serving as sources of drinking- water supply. Such precautions are particularly neces- sary when these wastes are stable and cumulative. Although at present no clear evidence exists that such carcinogenic industrial contaminants of air and water have become an actual environmental cancer hazard to the general population, they should be viewed with serious concern, so as to forestall such complications in the future. The conclusions that can be drawn from reviewing the literature are as follows: (1) The health significance of traces of carcino- genic PAH in drinking-water is not yet known. (2) With the present trend to reduce the pollution of surface water, attention should be given to reduc- ing the amounts of carcinogenic PAH. (3) Good ground-water may contain on the aver- age 0.001 ,ug/litre-0.01 ,ug/litre of carcinogenicPAH, probably leached from the soil by infiltrating surface water, thus making such concentrations technically unavoidable. However, waters with higher concen- trations, such as in lakes and rivers, should be exam- ined for their carcinogenic content when considering their use as raw supplies. (4) Detergents and mineral oils in surface water may affect solubility of PAH. Generally, however, the present concentration of detergents is probably too low to have a significant effect. (5) River-bank filtration generally does not remove enough carcinogens, nor does sedimentation, rapid sand-filtration, or chlorination. On the other hand, activated-carbon filtration at a sufficiently low filtra- tion rate eliminates these carcinogenic substances to a great extent. Treatment with chlordioxide or ozone also appears to be promising. Because most current treatment processes do not free the water of carcinogenic PAH, these processes, as well as new methods, should be examined and developed with a view to improving their performance. (6) The difference in concentration of PAH car- cinogens naturally present in water (from soil, plants and plankton) on the one hand, and in contaminated effluents (of municipal and industrial origin, and road run-off) on the other, suggests that PAH are indicators of water contamination. (7) Because of the technically unavoidable natural background of carcinogenic PAH to which man is exposed from water, food and air, and due to the probably cumulative effect of those substances, the introduction of carcinogenic additives in food, such as dyes and preservatives, should be avoided, or at least limited as much as possible. 499 500 J. B. ANDELMAN & M. J. SUESS RESUME LES HYDROCARBURES AROMATIQUES POLYCYCLIQUES DANS LE MILIEU, ET EN PARTICULIER DANS L'EAU On sait que beaucoup d'hydrocarbures aromatiques polycycliques sont cancerogenes pour I'animal, et probablement aussi pour l'homme. L'etude actuelle passe en revue les divers aspects du probleme que pose la presence dans l'eau de ces composes, parmi lesquels le benzo-3,4 pyrene retient particulierement l'attention en raison de son ubiquite, de son pouvoir cancerogene eleve et des nombreuses recherches qui lui ont et consacrees. Les hydrocarbures aromatiques polycycliques sont generalement le produit de la combustion et de processus exigeant de tres hautes temperatures, mais leur omni- pr6sence dans le milieu amene a considerer comme vraisemblable leur synthese par les plantes et les micro- organismes. On les trouve dans des conditions excluant toute contamination resultant d'activites humaines, dans les forets vierges, les boues, les sediments et dans la flore et la faune de beaucoup d'eaux naturelles. Bien que spontanement tres peu solubles dans l'eau pure, ils peuvent etre solubilises par certaines substances comme les detergents et les huiles minerales. Ils peuvent etre vehicules a distance apres avoir ete adsorbes sur des elements de la faune et de la flore aquatiques. Une de leurs particularites est d'etre sensibles a la lumiere. De multiples activites entrainent la production d'hydro- carbures aromatiques polycycliques et les effluents indus- triels en deversent de grandes quantit6s dans le milieu. Les eaux d'egout en contiennent, de meme que l'urine humaine. L'examen d'eaux de diverses origines des- tinees ulterieurement aux usages domestiques montre que la concentration des hydrocarbures cancerogenes est minimale dans les eaux souterraines et qu'elle s'accroit dans les eaux traitees et surtout dans les eaux de sur- face. La plupart des techniques classiques de traitement des eaux (filtration rapide sur sable, chloration, traite- ment par l'ozone) n'ont qu'une efficacite limit6e en ce qui regarde l'elimination de ces composes. La filtration sur charbon active donne les meilleurs resultats. 11 est impossible de mettre l'homme completement a I'abri des effets des hydrocarbures aromatiques poly- cycliques qui sont partout presents dans le milieu. Ils representent donc une menace potentielle, bien que les concentrations decelees jusqu'a present ne paraissent pas dangereuses. REFERENCES 1 Andelman, J. B. & Suess, M. J. (1970) The photodecom- position ofBP sorbed on calcium carbonate. In: Organic compounds in aquatic environments (Proceedings of the Rudolfs Research Conference, New Brunswick, July 1969), New York, Marcel Dekker (in press) Badger, G. M. (1948) The carcinogenic hydrocarbons: chemical constitution and carcinogenic activity. Brit. J. Cancer, 2, 309-350 Badger, G. M. (1962) The chemical basis of carcinogenic activity, Springfield, Ill., Charles C. Thomas Badger, G. M., Kimber, R. W. L. & Spotswood, T. M. (1966) Mode of formation of BP in human environ- ment. Nature (Lond.), 187, 663-665 Bailey, E. 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