Water Research Pergamon Press 1972. Vol. 6, pp. 1259-1274.

Printed in Great Britain

A REVIEW OF THE ARSENIC CYCLE IN NATURAL WATERS*

JOHN F. FERGUSON a n d JEROME GAV1S Department of Geography and Environmental Engineering, The Johns Hopkins University, Baltimore, Maryland 21218, U.S.A.
(Received 16 November 1971)

Ahstract--A review of the occurrence and cycling of arsenic in fresh waters is presented. The fate of arsenic in natural waters has received little attention in past years, in spite of the fact that arsenic is toxic and probably carcinogenic through exposure by drinking water. The chemistry of arsenic in aqueous systems is reviewed. Thermodynamic information is summarized in an Eh-pH diagram for a system including sulfur. Mechanisms for removal of arsenic from the solution phase to the sediments are discussed. The possible microbiallymediated reactions of arsenic, including oxidation of arsenite, methylation of arsenic species, and reduction of arsenate, are discussed with reference to the locale of the reaction in the water column or in the sediments and to the toxicological significance of the reaction products and the rates of reaction. A cycle of reactions for arsenic in a stratified lake is proposed and evidence is summarized relating to the occurrence and importance of particular reactions. The potential pollutional hazard of arsenic is from ingestion of drinking water with high concentrations of arsenic, rather than consuming arsenic containing aquatic organisms. Although arsenic is greatly concentrated in aquatic organisms, it is evidently not progressively concentrated along a food chain. In addition, arsenic when consumed as an organically-bound species in flesh evidently has low toxicity. The global cycle of arsenic is discussed. While volcanic activity is the original source of much of the arsenic in sedimentary rocks, in recent times weathering of arsenic has been approximately in balance with deposition of arsenic in sediments. Human activities, including the use of arsenic, the burning of fossil fuels, increased erosion of land and the mining and processing of sulfide minerals, have increased the amount of arsenic entering the oceans by at least a factor of 3. This increase will have no effect on the concentration in the oceans for many hundreds of years. However, these cultural contributions are the source of high localized concentrations in many fresh waters. Careful surveillance and increased knowledge of the fate or arsenic in the aquatic environment are needed to insure that there will be no public health hazard. THE DISCOVERY that mercury is readily cycled from the sediments to solution a n d c o n c e n t r a t e d by organisms t h r o u g h the food chain has led to speculation that similar cycles m a y occur with other trace elements. M u c h of this speculation has centered o n arsenic. Arsenic, like mercury, has been widely used a n d misused for its toxic properties, a n d large a c c u m u l a t i o n s due to h u m a n activities n o w exists in soils a n d sediments. This p a p e r is i n t e n d e d as a c o m p a n i o n to the previous p a p e r (GAvIS a n d FERGUSON, 1972) that discussed the cycle of mercury in n a t u r a l water systems. The same considerations apply. The same a p p r o a c h will be used. But the central question, whether arsenic p o l l u t i o n is a n i m p o r t a n t threat to aquatic organisms or h u m a n health, must be examined in a slightly different way. A l t h o u g h there have been instances of arsenical p o i s o n i n g to h u m a n s t h r o u g h water ingestion, there are no c u r r e n t examples of toxic a c c u m u l a t i o n s in food organisms. Arsenic has a long history of use for its toxic a n d medicinal properties. Arsenical c o m p o u n d s were used in medicine 2000-3000 yr ago in the Orient. Therapeutic applications have c o n t i n u e d t h r o u g h the ages. Arsenic also gained the r e p u t a t i o n of a * Presented at the XV General Assembly of the IUGG, Moscow, U.S.S.R., August, 1971.
WATER 6[ 1 1 - - n 1259

1260

JOHNF. FERGUSON and JEROME GAVIS

dangerous poison in the Middle Ages, and until the nineteenth century was the preferred poison of most homocidal practitioners. In the nineteenth century, the therapeutic use of arsenicals against trypanosomal or spirochaetal organisms became classical examples of chemotherapy. These demonstrated the widely differing toxicity and effectiveness of arsenic in different oxidation states and combined with different organic ligands. In addition, arsenic tonics have been used widely for spurious medical purposes; now arsenic has few legitimate therapeutic uses (WEBB, 1966). Exposure to arsenic has been correlated with carcinogenesis (NEUBAUER, 1947). According to HEUPER (1960) arsenic is the classical and unique example of carcinogenesis in man associated with the consumption of drinking water containing a known carcinogen. However, induction of cancer in laboratory animals has proved unsuccessful and the possible role of arsenic in carcinogenesis is still controversial (VALLEEet al., 1960). Arsenic and its compounds have been widely used in pigments, as insecticides and herbicides, as an alloy in metals, and were developed as chemical warfare agents. Synthetic organic compounds have substantially supplanted arsenicals for these uses since World War II, however. The primary stimuli for arsenical research have come from (a) the long history of arsenic as a homicidal poison, (b) the industrial use of arsenicals and the resultant exposures to them, (c) the clinical application of the arsenicals in protozoal and neoplastic diseases and (d) the use of arsenicals in chemical warfare (WEBB, 1966). Although the possibility of arsenic contamination of water has not been a great stimulus to research, considerable study of the toxicology, the occurrence, and the chemistry of arsenic in water has been performed by public health workers and by geochemists. Arsenic in water supplies has occasionally caused poisoning, usually of a chronic rather than acute nature. Chronic arsenic poisoning has been reported to be caused by ingestion of drinking water containing 0.21 mg 1-1 (FAIRHALL,1941), 0.31 mg 1-1 (BADo, 1939) and 0.4-10.0 mg 1-i (WYLLIE, 1937). In a typical case, in Reichenstein, Silesia, arsenic poisoning, including the production of cancers, occurred (NEU~AUER, 1947). There the drinking water had been polluted with wastes from the smelting of arsenic bearing ores. Others have reported that ingestion of drinking water with concentrations of arsenic of 0.05 -0.25 mg 1-1 is without ill effect (MCKEEand WOLF, 1963). The toxicity of arsenic increases greatly when arsenic is reduced from a -k 5 to a + 3 oxidation state. Based on the descriptions in the literature, we may conclude that As is present in the reduced form as arsenite in most instances of chronic arsenosis at low exposure levels. Standards for maximum allowable arsenic concentrations have been established by many agencies. The WORLDHEALTHORGA~ZATION(1958) established a permissible limit of 0.2 mg 1-1; in 1963 the limit was revized to 0.05 mg 1-1. The UNITEr) STATES PUBLIC HEALTH SERVICE (1962) has a recommended maximum concentration of 0.01 mg 1-1 and a maximum permissible limit of 0.05 mg 1-1 for arsenic in a public drinking water supply. In a survey of 37 drinking water supplies in the United States in 1943, arsenic was not found in excess of the U. S.P. H.S. (1962) standards. The maximum concentration found

A Review of the Arsenic Cycle in Natural Waters

1261

was 0.008 mg 1-1, and arsenic was undetected ( < 0.002 mg 1-1) in 30 samples. In 1969 a survey of 969 water supplies found arsenic exceeding 0.01 mg I-1 in 0.5 per cent of the samples and exceeding 0.05 mg 1-1 in 0.2 per cent of the supplies surveyed (McCABE et al., 1970). The occurrence of high arsenic concentrations in water supplies is very low, indicating no current threat to public health in the U.S. However, in analyses of fresh surface waters in the U.S. arsenic was found in about 7 per cent of the 1500 samples from 150 rivers (KoPP and KRONER, 1970), and in 21 per cent of 727 samples from rivers and lakes (DuRuM et al., 1971). In nearly every case that arsenic was detected, the concentration exceeded the recommended limiting concentration of 0.01 mg 1-1. The mean of arsenic values in the first survey that were in violation of the U.S.P.H.S. permissible limit was 0.1 mg 1-1, a factor of 10 above the permissible limit and 2 above the maximum limit. The U.S.P.H.S. standards (which are used as guidelines for the States and are not mandatory national standards) were exceeded far more frequently for arsenic than for any other element potentially hazardous to human health. There are many other observations of high concentrations in lakes and impoundments in the U.S. (CHAMBERLAINand SHAPIRO, 1969; ULLMAN et al., 1961). It is probable that arsenic concentrations in natural waters often approach or exceed values thought to be safe for drinking water. There are several questions that arize from these observations of arsenic levels in surface waters: l. What portion of the current levels of arsenic result from natural sources, and how much is derived from human activities ? 2. What is the relationship of total arsenic concentration to toxicity ? What are the relative amounts of highly toxic reduced forms and less toxic oxidized forms in given water systems ? 3. What are the mechanisms and relative rates by which arsenic is removed from solution and incorporated into the sediments ? 4. Is arsenic recycled back into solution from the sediments ? How, at what rate ? This paper is addressed to answering these questions when possible and to pointing to areas where present knowledge is inadequate. It describes the aquatic chemistry of arsenic, including inorganic and organic species, the effects of organisms on their distribution, and the natural and cultural sources of arsenic. It proposes and discusses a local cycle of arsenic in natural waters and presents an estimate of the global cycle. INORGANIC CHEMISTRY IN NATURAL WATER SYSTEMS Arsenic in aquatic systems has an unusually complex and interesting chemistry with oxidation-reduction, ligand exchange, precipitation, and adsorption reactions all taking place. Arsenic is stable in four oxidation states ( + 5 , + 3 , 0, --3) under Eh conditions occurring in aquatic systems. As metal occurs only rarely, and --3 As at extremely low Eh values. In addition, the covalent compound, AsS (realgar), is stable at low p H and moderately low Eh conditions. Based on available thermodynamic data (TABLE 1), E h - p H diagram for arsenic (total As concentration 10 -5 tool 1-1) in a system including oxygen, H 2 0 and sulfur (total S concentration 10-3 mol I-1) showing the predominant soluble species and the solids with solubilities low enough to occur in this system is illustrated in FIG. 1. Regions of solubility less than I 0-5. a mol 1-1 are indicated by the crosshatched area with the solid species enclosed by parentheses.

1262

JOHN F . FERGUSON a n d JEROME GAVlS TABLE 1. FREE ENERGIES OF FOR.MATION FOR ARSENIC SPECIES AT 2 5 C , AND ONE

ATMOSPHERE (AGf , kcal m o l e - 1) Species H3AsO, H 2AsO*HAsO42 AsO4 a H3AsO3 H2AsOaH A s O a 2HAsS2 ASS2AsS As2S3 As AsHa AsHa As2Oa As2Os State aq. aq. aq. aq. aq. aq. aq. aq. aq. s S s aq. g s s AGf -- 184.0 -- 181.0 -- 171.5 -- 155.8 -- 154.4 -- 141.8 -- 125.3 -- 11.61 -- 6.56 -- 16.81 -- 40.25 0 23.8 16.5 -- 140.8 --186.9 Reference SERGEYEVA a n d KHODAKOVSKIY (1969) SERGEYEVA a n d KHODAKOVSKIY (1969) SERGEYEVA a n d KHODAKOVSKn" (1969) SERGEYEVA a n d KHODAKOVSKIV (1969) SERGEYEVA a n d KHODAKOVSKIY (1969) SERGEYEVA a n d KHODAKOVSKW (1969) SERGEYEVA a n d KI-IODAKOVSKIY(1969) SILLEN a n d MARTELL (1964) SILLEN a n d MAR.TELL (1964) ROBIn a n d WALDBAUM (1968) ROBIE a n d WALDBAUM (1968) R o m e a n d WALDBAUM (1968) SERGEYEVA a n d KHODAKOVSKtY (1969) SER.GEWVA a n d KHODAKOVSKn' (1969) SERGEYEVA a n d KHODAKOVSKIY (1969) SER.GEYEVA a n d KHODAKOVSKIY (1969)

....

0.75 0.5 H3AsO3 H2AsO4-

0.25

HAsO~0 - HAsS z

AsO2ILl

-0.25 -0.5

AsH3(a'~ PAsH3 : I

-0.75

4 pH

I0

12

14

FIG. 1. T h e E h - p H d i a g r a m for A s at 25C a n d one a t m o s p h e r e with total arsenic 10- 5 mol 1a n d total sulfur 10 -3 tool 1-1. Solid species are enclosed in parentheses in cross-hatched area, which indicates solubility less t h a n 10 -5.3 tool 1-t.

A Reviewof the ArsenicCyclein Natural Waters

1263

If iron were included, ferric arsenate (pK~v 20.24) would have a small region of stability at pH below 2.3 and Eh above +0.74 V. Arsenic has no other significant interactions with ions that change the predominance areas of the soluble species depicted on the diagram. At the high Eh values encountered in oxygenated waters, arsenic acid species (H3AsO4, HzAsO4-, HAsO42- and AsO,~3-) are stable. At Eh value characteristic of mildly reducing conditions, arsenious acid species (Ha AsO3, H2AsO3 - and HAsO32 -) become stable. Neither of the arsenic oxides, As2Os and As2Oa, are insoluble enough to appear on the diagram. Under conditions where --2 S is stable, realgar, AsS, and orpiment, As2S3, have low solubilities and occur as stable solids at pH values below about 5.5 and Eh values about 0 V. HAsS2(aq) is the predominant species at low pH in the presence of sulfide: it has maximum solubility of 10-6.5 mol 1-1 (0.025 mg 1-1 As). ASS2- predominates at pH greater than 3.7, and above pH 5.5 its solubility is 10 -5 mol 1-1. At still lower Eh values As metal is thermodynamically stable. Although As metal solubility in water has not been reported, it is undoubtedly low. At very low Eh values, ASH3, arsine, may be formed. Arsine is only slightly soluble; the calculated line for a concentration of 10-5.3 mol 1-1 in solution corresponds to a partial pressure of about 1 atm. A decrease in the activity of arsenic in the calculations decreases predominance of the solid species, but otherwise does not affect the diagram. A decrease in the sulfide activity changes the lower boundary between the arsenic sulfides and As metal. Arsenic sulfides are sufficiently stable so that the upper boundary with arsenious acid species is determined entirely by the reduction of S(s) and SO42- to --2 S. The stabilities of organic arsenicals have not been included. Except at extremely low Eh values, these compounds are unstable with respect to oxidation of the organic part of the molecule. The thermodynamic information describes only the system at equilibrium and indicates the direction a non-equilibrium system will move. Except for a few oxidation-reduction reactions that are used in analytical chemistry, very little information about the rates of arsenic reactions in solution exists, and specific rate constants are unknown. The rate of oxidation of arsenite to arsenate with 02, for example, is reported to be very slow at neutral pH values; but the reaction proceeds measurably in several days in strongly alkaline or acid solutions (KOLTHOFF, 1921). Copper salts and carbon are reported to catalyze the reaction (REINDERS and VLES, 1925). No quantitative information is available about the rate of the reaction in aerobic surface waters.

Arsenic analysis
Inorganic arsenic in water is commonly analyzed by means of colorimetric methods utilizing colored complexes formed with diethyldithiocarbamide or molybdate. (AMERICAN PUBLIC HEALTHASSOCIATION,1971; SORRENTINOand PAUL, 1970; SUGAWARAand KANAMORI,1964). Arsenic may also be detected at low concentrations by means of neutron activation, polarographic techniques, atomic absorption spectroscopy and emission spectroscopy. The differentiation of oxidation states of inorganic arsenic is accompfished by means of colorimetric (SuGAWARA and KANAMORI, 1964) and polarographic (WHITNACK and BROPHY, 1969) methods. CHALLENrERet al. (1933) detected methylated arsines

1264

JOHNF. FEROUSONand JEROME GAVtS

by precipitating salts in Biginelli's solution and subsequent chemical characterization of the salts. However, techniques used for analysis of methylmercury compounds, including gas-liquid and thin layer chromatography and mass spectroscopy, should be more sensitive and readily applicable to arsenic compounds. COVALENT CARBON AND SULFUR COMPOUNDS OF ARSENIC Arsenic forms kinetically stable bonds to sulfur and carbon in organic compounds. Like mercury, arsenic (+3) reacts with sulfhydryl groups of cysteine in proteins, and enzyme inactivation by this mechanism is the primary mode of arsenic toxicity (WEBB,1966). The compounds which are formed are thermodynamically unstable but persistent. Arsenate does not react with sulfhydryl groups. It can be reduced to +3 As in organisms, however. Arsenic +3 and + 5 both form compounds with carbon-arsenic bonds. Many thousands of these compounds have been synthesized and tested for effectiveness against various pests, including human parasites, weeds, insects; they have even been used against humans. Phenylarsenic acid, C6HsAsO(OH)2 and other substituted phenyl- and diphenyl-diarseno-compounds have been used in chemotherapy of trypanosomal infections. Cacodylic acid, (CHa)EAsOOH and methane arsonic acid, CH3AsO(OH)2, have had application, along with inorganic arsenicals, as pesticides. Methanearsonates have been reported to be broken down in the soil with the residual arsenic largely retained in the soil but in an inorganic form (JOHNSON and HITTBOLD, 1969). Compounds such as lewisite, CHaCH=CHAsC12, have been developed as chemical warfare agents. Some of these compounds persist in water; others are rapidly oxidized, hydrolyzed or otherwise degraded. An important group of compounds is the methylarsines. Trimethylarsine, (CH3)3As, is formed by microorganisms from inorganic arsenic compounds (BIRD et al., 1948). Under some circumstances it is highly toxic. It has been identified as an important reservoir of arsenic in certain organisms (CHAPMAN, 1926), and has caused human poisoning through exposure in air (CnALLENGER, 1945). Although (CHa)aAs is considered insoluble in water, it is in fact soluble enough to be of environmental interest. It is undoubtedly more soluble in hydrocarbons than water, which may account for its toxicity and for its accumulation in certain organisms. Neither its stability with respect to oxidation by oxygen in air or in water nor its adsorptive behaviour appear to have been studied. Organic arsenicals synthesized by organisms or formed by reaction with constituents of organisms can affect the distribution and form of arsenic in the water masses and the sediments. There is a need for information about the occurrence, concentration, and stability of such compounds. REACTIONS THAT REMOVE ARSENIC FROM SOLUTION The reactions resulting in removal of arsenic from the solution phase include adsorption onto clays or coprecipitation into metal ion precipitation. Arsenate, the stable form in aerobic water, may be removed by several mechanisms. LA PEINTRE (1954) showed that arsenate species coprecipitate with or adsorb onto hydrous iron oxides. SHNVUKOV(1963) observed that iron ores are always enriched with arsenic, owing to the high adsorptive capacity of the hydrous iron oxides, while arsenic is nearly absent from manganese ores. The fact that iron oxide has a positive

A Reviewof the ArsenicCyclein Natural Waters

1265

surface charge in most geologic environments and preferentially adsorbs anions while manganese oxide is negatively charged and adsorbs cations, has been cited as an explanation of such distributions of arsenic (GOLDSCmalDT, 1937). In addition, ferric arsenate is very insoluble while manganous arsenate and presumably manganic arsenate are much more soluble. Arsenate species are adsorbed by aluminum hydroxide and by clays; however, bauxite and silicates are usually only moderately enriched in arsenic (ONISm and SANDELL, 1955). Arsenate is chemically similar to phosphate and may isomorphously substitute and be enriched in phosphate minerals (KRAtJSKOPF, 1955). However, in Florida phosphate pebbles, arsenic content is proportional to the iron content and inversely proportional to phosphate, indicating that the chemical affinity of arsenic for iron is predominant (Srowz, 1969). Arsenite, +3 As, species may also be present in surface waters if the Eh is less than about 0.1 V or if oxidation to arsenic + 5 is incomplete. Arsenious acid species will adsorb or coprecipitate with iron oxide (GuPTA and GHOSH, 1953) in a manner similar to arsenic acid. The adsorption of arsenite onto clays, carbonates, or other hydroxides has not been investigated. As +3 has strong affinity for sulfur; it readily adsorbs or coprecipitates with metal sulfides. GOLDSCH~IDT and PETERS (1934) report up to 3000 mg kg-1 arsenic in sedimentary pyrite, FeS:. BIOLOGICAL EFFECTS ON THE DISTRIBUTION OF ARSENIC Organisms affect the distribution of arsenic by accumulating, transporting and transforming it. Some of the transformations, such as oxidation of arsenite to arsenate, are probably catalyzed by the presence of organisms, but occur in their absence; others, such as methylation, are not thermodynamically favorable in water and can occur only in the presence of organisms. Toxicity to aquatic organisms is not an important factor in the distribution of arsenic, since environmental concentrations are usually much below acutely toxic levels. However, the ability to minimize toxic effects could increase the ability of a species to compete against others and may be of some importance in ecological selection.

Biological accumulation
Organisms are known to accumulate arsenic. In sea water containing arsenic ranging between 0.05 and 5/zg 1-1, marine plants are reported to have arsenic concentrations ranging between 1 and 12 mg kg-i (dry wt.), while marine animals have concentrations usually between 0.1 and 50 mg kg-1 (WEDEPOHL, 1969; Cox, 1925). Arsenic is sometimes present in shrimp and lobsters, probably as trimethylarsine, at concentrations as high as 200 mg kg-1 (CHAPMAN, 1926). Concentrations in fresh water plants and animals are much lower than in marine species (WEDEPOHL, 1969). In fresh water treated with sodium arsenite, GILOERr~Vs (1966) found concentrations in fish of the order of 1 mg kg -1, a factor of about 2 greater than the water concentration. With 0.01 mg 1-1 As in untreated water, the concentration in fish was between 0.1 and 0.2 mg kg-1. There is insufficient data to ascertain whether there is an increase in concentration with size or age of the organism. Concentrations in organisms are considerably higher than in the water in which they live, but unlike mercury, there is little, if any, concentration upward through the food chain.

1266

JOHNF. FERSUGONand JEROMEGAVIS

Toxicity
Arsenic is used primarily for its toxic properties. Sodium arsenite is applied to lakes at dosages up to 10 nag 1-1 to control rooted aquatic plants. Calcium and lead arsenates and organic arsenicals are used as herbicides and insecticides in a wide variety of agricultural applications. However, in this paper toxicity of environmental concentrations of arsenic to aquatic organisms and to humans is the primary concern. The toxicity of lower oxidation state arsenicals is much greater than the toxicity of more oxidized arsenicals. To humans, arsenate is about 60 times less toxic than arsenite, owing to the fact that arsenite reacts the sulfhydryl groups, while arsenate does not (WEBB, 1966). Arsenate exhibits varied metabolic interactions, but its toxicity is low and may only be manifested when reduced to the arsenite state. Inhaled arsine and trimethylarsine are even more toxic than arsenite (VALLEE et al., 1960). Paradoxically, arsenic (probably trimethylarsine) in shrimp flesh consumed by rats is excreted more rapidly and is much less toxic than arsenic trioxide (CouLsoN et al., 1935). This implies that trimethylarsine in food is less toxic than in air. In light of the recent experience with methyl- and dimethyl-mercury, further studies to confirm this are needed. The toxicity of arsenicals to aquatic organisms is similar. Arsenic + 5 is much less toxic than arsenic + 3 . MCKEE and WOLF (1963) cite studies showing that arsenite is toxic to aquatic organisms at concentrations between 1.0 and 45 mg 1-1 measured as As. In contrast, arsenate arsenic was lethal to minnows only at concentrations above 230 mg 1-1 The toxicity of methylarsines and most organic arsenicals to aquatic organisms or to animals through ingestion of water has not been evaluated.

Microbial transformations of arsenic species

The effects that living organisms have on arsenic compounds, in contract to the effects of arsenic compounds on organisms, are also of interest. As none of the transformations to be discussed have been identified in a typical fresh water environment, the discussion is based on studies in other environments. Certain fungi, yeasts and bacteria are known to methylate arsenic to gaseous derivatives of arsine. The reaction was first studied in 1892 by GosIo, who investigated poisoning resulting from fumes emitted into rooms whose walls were covered with wall paper containing arsenic pigments. CHALLENCER and coworkers (1933) in the 1930's identified the fumes as trimethylarsine emitted by fungi acting on arsenic pigments in the presence of moisture. In addition, at least one species of bacteria can carry out such reactions (ZuSSMANet al., 1961). Furthermore, the characteristic odors of methyl arsines have been observed in oysters and in humans exposed to sufficient quantities of arsenic (Cr~LLENGER, 1945). Recently, it has been reported (MCBRIDE and WOLFE, 1971) that methanogenic bacteria can methylate arsenic in solution to methyl and dimethyl arsine. The formation of toxic methylated derivatives is the current problem associated with mercury. The reactions leading to methyl and dimethyl mercury are known to occur under aerobic and possibly under anaerobic conditions (JENSEN and JERNELOV, 1969) and to be mediated by extracts from methanogenic bacteria (Wood et al., 1968). Since both methyl and dimethyl mercury are soluble at the concentrations occur-

A Reviewof the ArsenicCyclein Natural Waters

1267

ring in natural water systems, a means of established of recycling toxic compounds from the sediments back into the solution. A similar cycle for arsenic is an obvious, although as yet untested, possibility. The biological function of methylation of metals, including arsenic, mercury and selenium, is not known. Since these metals are not always available to microorganisms, it seems highly unlikely that their methylation has any obligatory function. It is possible the methylation serves as a means of detoxification. Alternatively, methylation of metals could be purely adventitious. In an anaerobic environment, it may be energetically preferable for organisms to transmethylate metals rather than to synthesize methane. Only aerobic metabolism has been found to yield methyl arsines, and methylation may occur in the aerobic upper layer of the sediment. However, there is no a priori reason that aerobic conditions are required, and such reactions might take place in sediments under anaerobic conditions. The probable mobility of methylarsines from the sediments to solution and to the food chain make their possible occurrence in sediments worthy of study. GREEN (1918) and TURNER and LE~E (1954) showed that at least fifteen strains of bacteria could oxidize arsenite in cattle dip solutions to arsenate. Turner and Legge found specific enzymatic activity (arsenite dehydrogenase) in purified preparations and showed that cytochrome a enhanced arsenite oxidation, suggesting that the bacteria were obtaining energy from the oxidation. Because they grew the bacteria in the presence of organic carbon, they could not establish an energy yield from arsenite oxidation, however. The presence of arsenite oxidizing organisms could significantly affect the relative concentrations of arsenite and arsenate in natural water systems, since the reaction is slow in the absence of microorganisms at neutral pH. Another possible microbial reaction is the use of arsenate as an electron acceptor in heterotrophic metabolism in the absence of 02 and NO 3-. This reaction, which has not been investigated, in energetically favored compared to sulfate reduction which does occur in similar environments. Finally, although weathering reactions are only indirectly connected to the aquatic environment, microorganisms have been shown to increase the rate of arsenic release from minerals including orpiment (As2S3) enargite, (CuaAsS4) and arsenopyrite (FeAsS) (EHRLICH 1963, 1964). For these sulfides, autotrophic bacteria probably catalyze the oxidation of sulfide to sulfate and ferrous iron to ferric iron. Oxidation of arsenic to arsenate, which also occurs, could be purely chemical. The effect of bacteria on weathering of arsenides such as FeAs has evidently not been investigated. While none of the reactions have yet been investigated in natural water systems, conditions comparable to those occurring in other systems do occur in water. The potential importance of the arsenic cycle warrants investigation of these reactions in the aquatic environment.

LOCAL CYCLING OF ARSENIC A cycle for arsenic in a stratified lake is illustrated in FIG. 2. The reactions include transfers from solution to solid phases, conversions from one oxidation state to another and ligand exchanges. Some of the processes are chemical, some may occur only

1268

JOHN F. FERGU$ONand JEROMEGAVIS

'~._
\ \
~ .

HAsO?__
--~ ~-

oxidahon
, ~

HAsO2-^u

~ ,~ /~Epilimni0n

. . . . . . . reduction 2HAs02 ~
torecio. ~

i ~ v n o-~_/Thermocline pH 6-7/ H2As04/ Hypolimnion

J,

Iprecip.

- . 4
Sediments

\As2S3" T k, " ~ e . g . F ; A s O

4 /

F[o. 2. Local cycle of arsenic in a stratified lake.

through microbial mediation, and others may occur either chemically or with microbial mediation. Since such a cycle has not yet been investigated, some of the reactions are hypothesized to occur based on studies of arsenic in other environments. The cycle, however, is thermodynamically consistent, and the reactions are possible in lakes. In the aerobic epilimnetic water, reduced forms of arsenic tend to be oxidized to arsenate, which coprecipitates with ferric hydroxide. Turbulent dispersion and convection transport some of the arsenate across the thermocline to the oxygen-depleted hypolimnion, where reduction to HAsO2 and ASS2- take place, depending on the sulfur concentration and the Eh. Coprecipitation, adsorption and epitaxial crystal growth cause arsenic to be removed to the sediments, where reduction of ferric iron, arsenate and arsenite result in either solubilization or stabilization as an insoluble sulfide or arsenic metal. Microbial transmethylation or reduction to arsine solubilize the arsenic, and diffusion through the sediments or mixing by currents or burrowing organisms cause the arsenic to re-enter the water column. Fish and plankton enter the cycle by concentrating arsenic, especially trimethylarsine. On death, they settle to the bottom where the arsenic is removed to the sediments or recycled, depending on the physical and chemical conditions. Oxidation to arsenate probably rarely proceeds to completion. Measurements by SUGAWARA and KANAMORI (1964) in ocean water show the + 5 As/total As ratio to be close to 0.8. In lakes the residence times are much shorter, and unless microorganisms catalyze the reaction, it cannot advance very far. Since sodium arsenite is often introduced directly into lakes and impoundments to kill submerged aquatic weeds, knowledge of the rate of its oxidation is important for an assessment of the hazards of using the water as a drinking water supply. Measurements of arsenic concentrations in sodium arsenite treated lakes have shown that removal of arsenic from solution and accumulation in the sediments sometimes occurs (MACKENTHUM, 1950). Thus removal of H3AsO3 and H 2 A s O , - species may be rapid, and removal with ferric iron is the probable mechanism of removal. Others, however, have reported little removal of sodium arsenite from solution and substantial leaching of arsenic from arsenic-rich soils or sediments (FREAR, 1951; GILDERHUS, 1966). In a particular body of water it is possible to estimate which of the many possible reactions are likely; however, it is not possible to describe the rates or the extent of

A Review of the Arsenic Cycle in Natural Waters

1269

the reactions. This means that we now have little capability to predict the fate of arsenic entering a lake or river. COMPARISON TO THE MERCURY CYCLE Arsenic is more mobile than mercury. Soluble species exist over a broader range of Eh and pH values. Like mercury, however, these soluble species may be removed from solution by coprecipitation or adsorption. Arsenic is not concentrated through food chains to the same extent as mercury. Concentration factors, which may be very high, are equivalent at all trophic levels. In addition, it is unlikely that consumption or arseno-organic compounds in fish or other organisms will constitute a hazard from arsenic poisoning. Rather the potential hazard is in the consumption of water containing high concentrations of 3 As or other arsenic species that can readily bind sulfhydryl groups. Unlike mercury, enough arsenic has been found in solution in natural water systems to constitute a hazard in drinking water supplies, although not enough information is available to estimate how much arsenic in surface water is in the toxic 3 As form. The marked difference in occurrence of excess levels of arsenic in samples from water supplies (0.5 per cent) and from rivers (7-21 per cent) in the U.S. indicates that water treatment processes may effectively remove arsenic. ANGINO et al. (1970) report that lime softening of Kansas River water removed 85 per cent of the total arsenic concentration. SKRIPACH et al. (1971) found that lime addition at p H 8 to a rare-earth industry waste removed arsenate if enough iron was present. Oxidation of arsenite to arsenate with H202 prior to lime treatment was used to reduce the total arsenic concentration to 0.05 mg l- 1. On the other hand, claims have been made that a defined water treatment plant, including coagulation, sedimentation and rapid sand filtration, will do little to remove arsenic from a water supply. (FEDERALWATER POLLUTION CONTROL ADMINISTRATION, 1968). The problems of arsenic pollution are likely to be more easily managed than those of mercury. Here we are concerned with possible contamination of drinking water supplies, and it is likely that arsenic can be removed from drinking water. In contrast, problems of mercury pollution are largely those of concentration in food organisms, and control of this problem involves management of the entire body of water and its sediments. GLOBAL CYCLING OF ARSENIC The principal pathways that arsenic follows from the continents to the oceans in the absence of human activities are weathering, including solubilization and transport of sediment and vulcanism. ONISH1 and SANDELL0955) in a review of the geochemistry of arsenic make a balance between the igneous rocks (arsenic content about 2 mg kg-1) and the sediments (arsenic in shales and deep sea sediments l0 mg kg-a, in sandstone and limestone 1.5 mg kg-1). They observe that if the quantity of sediments is about equal to the quantity of weathered rocks, then much of the arsenic in sediments must be derived from volcanic activity, not weathering. More recent estimates of crustal abundances of arsenic (VINOGRADOY,1960) change the numerical calculations but do not alter their conclusion. Although the contribution of vulcanism to the arsenic cycle over geological time is large, at present this contribution is small with weathering of continental rocks in

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JOHN F. FERGUSON and JEROME GAVIS

approximate balance with deposition in oceanic sediments. We can calculate a current balance using JuosoN's (1968) estimate that 9.3 109 metric tons of material are weathered and transported to the oceans each year (without the effects of human activity). If, after CONWAY (1942), the weathered material is approximately 20 per cent igneous rock, 65 per cent shale and 15 per cent limestone and sandstone, and if the arsenic content of these rock types are 1.8 mg kg -1 igneous (TAYLOR, 1964), 6.6 mg kg -1 shale (VINOGRODOW, 1960) and 1.5 mg kg -1 limestone and sandstone (ONISm and SANDELL, 1955), then the quantity of arsenic weathered is 45 103 tons y r - 1. If the relative abundance of shale to limestone to evaporite in recent sediments is about 7:2:1 (GAggLES and MACKENZIE, 1969), then there is no substantial imbalance between natural weathering and deposition of arsenic at present. Weathered arsenic may be in solution or part of the sediment load of rivers. Arsenic in rivers has most frequently been measured in the range of 0-10 leg 1-1 (TABLE 2).
TABLE 2. ARSENIC CONTENT OF NATURAL WATERS--SELECTED REPORTED OCCURRENCE* F r e s h waters Concentrations (t~g l-1)

Lakes in Greece Lakes in Japan Lakes in Wisconsin, U.S.A. Rivers and lakes, U.S.A. Rivers in Sweden Rivers in Japan Elbe River, Germany Columbia river, U.S.A. Oceans English Channel Pacific coastal water Northwest Pacific Indian Ocean South West Indian Ocean
* WEDEPOHL,

1.1-54.5 0.16-1.9 2-56 10-1100 0.2-0.4 0.25-7.7 (weighted av. 1.7) 20-25 av. 1.6 2-4 3-6 0.15-2.5 (av. 1.2) 1.3-2.2 (av. 1.6) 1.4-5.0 (av. 3)

CHAMBERLAINand SHAPIRO(1969) DURUM, HEM and HEIDEL(1971)

1969, unless noted otherwise.

For an average value of 1/zg 1-1 in rivers free from arsenic pollution and a volume of r u n o f f o f 3.3 1016 1. y r - I (LIVINGSTONE, 1963), the soluble arsenic in rivers is 33 103 tons yr-~. Thus most of the weathered arsenic is transported to the oceans as part of the dissolved load of the rivers. The concentration of arsenic in the oceans has been estimated to be 2 txg 1-1, although measured values range from 0.15-6/zg 1-1 (TABLE 2). The volume of the oceans is about 1.4 1011 1, and the total arsenic content is about 2.8 109 metric tons. The residence time for arsenic in the oceans we calculate from the weathering flux is 6 104 yr, which is identical to the figure for mercury obtained in the previous paper. H U M A N ACTIVITY AND THE ARSENIC CYCLE The influence of human activity on the amounts of arsenic in surface waters is large, both for the global cycle of arsenic removed from the lithosphere and transported to the oceans, as well as for the many local cycles in particular bodies of water. The

A Review of the Arsenic Cycle in Natural Waters

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production and use of arsenic compounds results in the direct release of arsenic to the environment. Most arsenic is formulated into pesticides. However, small quantities ( < 5 per cent) are used to color glass and to make metal alloys. Estimates made from data in "Minerals Yearbook" (U.S. Geological Survey) of world arsenic production for ten year periods are shown in TABLE 3. Production at present is steady at about
TABLE 3.

W O R L D PRODUCTION OF ARSENIC - - 1 0 YR AVERAGES OF YEARLY PRODUCTION IN METRIC TONS ARSENIC Y R - 1

1911-1920 1921-1930 1931-1940 1941-1950 1951-1960 1961-1970 * Excluding U.S. production.

12,600 21,700 39,400 44,000 34,400 42,700*

50,000 metric tons yr -1 or arsenic with U.S. production about 1 5 ~ and U.S. consumption about 50 per cent of the total. Much of this arsenic, an amount greater than that contributed from natural weathering, is intentionally introduced into the environment and reaches rivers, lakes, and the ocean. Arsenic also is released unintentionally as a result of many human activities. Important among these are releases associated with smelting or roasting of any sulfide containing mineral and with combustion of fossil fuels, releases due to rapid leaching of exposed wastes from mining and ore processing activity, due to the manufacture of arsenicals, and due to the greatly accelerated erosion of the land. Of all the cultural sources of arsenic only increased land erosion always results in low concentrations ( < 0.01 mg 1-1) in the aquatic environment. All the other sources could result in local water pollution. High concentrations of arsenic in water, of course, also have frequently occurred due to weathering of natural arsenic containing formations. Many local instances of pollution have been reviewed and described (MCKEE and WOLF, 1963). We shall discuss primarily the effects of the major sources on the global cycle. The mass of material moved to the oceans is estimated to have increased from 9.3 109 to 24 l09 tons y r - 1 (JUDSON, 1968), due to rapid erosion caused by intensive land use. The quantity of arsenic has probably increased at least proportionately. Arsenic released during mineral processing and metal production is undoubtedly large. However, no method of estimating this contribution has been devised. Arsenic released during the combustion of fossil fuels is significant. The reported arsenic content of groups of coals range from 3 to 45 mg kg- a (WEDEPOIJL, 1969). Using an average value (5 mg kg-2) reported by BERTINEand GOLDBERC (1971), and assuming that half the arsenic is volatilized during combustion, we can calculate that 2.5 g arsenic would be released to the atmosphere for every ton of coal consumed. We estimated in the preceding paper (GAvIS and FERCUSON, 1972) that coal and lignite consumption between 1900 and 1971 was 117 109 tons. The quantity of arsenic released is then calculated to be 29 10 4 tons in 71 yr.

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Arsenic in crude petroleum has been measured to be much less than 1 mg k g - l (VEAL, 1966). The amount of arsenic from petroleum combustion is negligible. Arsenic from fuel combustion, smelting and roasting is released to the atmosphere. The residence time in the atmosphere for arsenic is not known. Cases of localized contamination in the vicinity of smelters and coal burning plants indicate that much of the arsenic is removed rapidly as dry fallout and in rainfall. In part it will enter the hydrosphere. The arsenic introduced with phosphates in detergents and with phosphate fertilizers is insignificant compared to other sources. The sum of the cultural contributions that can be estimated average 1 l0 103 tons yr-1 for this century, approximately 3 times the contribution due to weathering. The influence of this increase on the concentration of a well-mixed ocean would be negligible for many thousands of years. The influence of man on the global cycle of arsenic is much less profound than on the mercury cycle and those of other less abundant elements. There is no evidence that man is likely to change world-wide distribution of arsenic appreciably. However, arsenic is concentrated in many local environments due to human activity. The high toxicity of this element and possible cycling in a body of water require careful management of the use of arsenicals and surveillance of the environment for excess concentrations. We must conclude that present knowledge of the pathways of the arsenic cycle is inadequate to allow good management. Since water containing hazardous concentrations of arsenic is a potential public health problem, the chemical states and the toxicity of the various forms of arsenic in water must be firmly established. Knowledge of the nature and rates of the various arsenic reactions should then be established. With the ability to predict the concentration of various arsenic species, their movement through an aquatic system, and their toxicity, the problem of arsenic pollution could be controlled and rational management instituted to eliminate public health hazards.

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