Environ. sci. Technol. 1994, 28, 877-881 Arsenic Species in Groundwaters of the Blackfoot Disease Area, Taiwan Shun-Long Chen, Shlaan I?.Dzeng, and Mo-Hslung Yang' Institute of Nuclear Science, National Tsing Hua University, Hsinchu, Taiwan, Republic of China Kong-Hwa Chlu, Guan-Mlng Shleh, and Chlen M. Wai' Department of Chemistry, University of Idaho, Moscow, Idaho 83843 The groundwaters collected from three wells in the Blackfootdisease (BFD) area in southwest Taiwan contain, on the average, 671 i 149 r g of total dissolved arsenic/L. The arsenic contents in the well waters of Hsinchu, a city in the northwest of the island where no BFD has ever been reported, are less than 0.7 pg/L. The predominant arsenic species in the well waters of the BFD area is As3+with an average As3+/As5+ ratio of 2.6. The methyl arsenicals, monomethylarsinic acid and dimethylarsonic acid, are below detection limits (C1 pg/L), and the insoluble suspended arsenic accounts for about 3% of the total arsenic in the water. Ultrafiltration experiments indicate that the dissolved arsenic species can be roughly divided into two main groups, one with molecular mass <lo00 and the other with molecular mass >300 000 Da. The results obtained from the BFD area are compared with similar arsenic studies conducted in the United States. The importance of arsenic speciation in environmental water studies and the possible cause of BFD are discussed. Introduction Blackfoot disease (BFD) is a peripheral vascular disease found in a limited area on the southwest coast of Taiwan. The BFD area consists mainly of four villages located about 20 km north of Tainan. The symptoms of BFD start with spotted discoloration on the skin of the extremities, especially the feet. The spots change from white to brown and eventually to black, hence the name BFD. The affected skin gradually thickens, cracks, and ulcerates. Amputation of the affected extremities is often the final resort to save the BFD victims. The disease, first observed in the southwest coast area of Taiwan in the 1930s and was reported to correlate with the peaking in the 1950~1, consumption of groundwater by local inhabitants (1). Outbreak of the disease increased rapidly around 1950 when the number of deep artesian wells drilled by local villagers for drinking reached a maximum. A map of the BFD area, its geological descriptions, and early investigations of arsenic in the artesian wells of this area were reported by Tseng et al. (1). The number of patients suffering from this disease has been decreasing since 1956 after purified tap water was made available to the local dwellers. In 1975, a total of 1141 BFD patients were identified in this area (2). The cause of BFD is still unknown, but it is generally attributed to the high concentrations of arsenic found in the deep well waters (1). According to the US.Code of Federal Regulations (CFR) published in 1992,the maximum contaminant level (MCL) of arsenic in community water systems is 0.05 mg/L (3). This is also the permissible level of arsenic in bottled water according to the CFR (4). The CFR standard is actually based on the interim MCL of arsenic in drinking water 0013-938X/94/09280877$04.50/0 0 1994 American Chemlcal Soclety recommended by the US. Environmental Protection Agency (U.S. EPA). The U.S.EPA is in the process of revising the MCL of arsenic in drinking water, and the new MCL is expected to be lower than the interim MCL value (5). The chemical form of arsenic in drinking water is not specified by the CFR, although it is well-established that the toxicity of arsenic depends on its chemical form. Arsenic is known to exist in natural waters in different oxidation states depending on the redox environment.The trivalent inorganic species arsenite is more toxic to the biological systems than the pentavalent species arsenate (6). Organoarsenicals such as monomethylarsinic acid (MMA) and dimethylarsonic acid (DMA) also exist in the natural environments, but their toxicities are lower than the inorganic arsenic species (5). Information on the distribution of arsenic species is therefore important to assess its toxicity in drinking water. The distribution of arsenic species and other trace and minor elements in well waters of the BFD area have not been reported in the literature. This information is of fundamental importance for understanding the cause of BFD and the potential hazards of arsenic in the aquatic environment. Recently, we have conducted a systematic study of arsenic species and other minor and trace elements in the well waters of a representative village (Putai) in the BFD area in southwest Taiwan for a period of 1 year. The metal contents in the well waters of the BFD area are compared with those obtained from another city in Taiwan where no BFD case has ever been reported. Correlations between the arsenic species and other elements in the well waters and the occurrence of BFD in Taiwan are discussed. Experimental Section Reagents. Stock solutions (1000 mg/L) of arsenite, arsenate, DMA, and MMA were prepared from sodium arsenite (E. Merck), disodium hydrogen arsenate (E. Merck), sodium dimethylarsinate trihydrate (E. Merck), and disodium methylarsonate (Chem Service), respectively, and stored at 4 "C until use. Working standards for each arsenic species (usually in the range 0.1-0.8 mg/ L) were prepared fresh daily in 0.2% (v/v) sulfuric acid solution. Stock solutions of other elements were prepared from the E. Merck Titrisol standard solutions (1.000 f 0.002 g) by diluting to 1 L with deionized water. The counterion of eluent in the pairing ion chromatography (PIC) was 5 X 10-3 M tetrabutylammonium phosphate (PIC-A, Waters) in 5% methanol solution. All acids and bases used in this work were of superpure grade (E.Merck). The NIST standard reference material SRM 1643b (trace elements in water) and the ICP multi-element standard solution from E. Merck (QC 11355) were used as the references for quality control of analytical data. Sampling and Pretreatment Procedure. Groundwater samples were collected from three deep wells in the BFD endemic district, Putai, Taiwan. These wells were Envlron. Sci. Technol., Vol. 28, No. 5, 1994 877 previously used by local dwellers as sources of drinking water before tap water was made available to this area. Groundwater samples were also collected from three wells in another city Hsinchu, which is about 200 km north of Putai and is the hometown of National Tsing Hua University. No BFD case has ever been reported in the Hsinchu area. Water samples were collected from the wells of these two locations every two months for 1 year (from July 1991 to May 1992). High-density polyethylene bottles were used as containers for groundwater collection. The bottles were precleaned with 10% nitric acid and then rinsed with deionized water. The well water was allowed to run through the pumping pipe for at least 10 min prior to sample collection. One liter of the collected water was filtered through a 0.45-pm Millipore membrane immediately after collection. The water was acidified by adding 2 mL of sulfuric acid and was stored at 4 "C for arsenic speciation studies. The preservation of arsenic species in water by sulfuric acid was reported in the literature (7). Another 5 L of the water was also filtered through a 0.45pm Millipore membrane, adjusted to pH <2 by nitric acid, and stored at 4 "C for ICP-AES, ICP-MS,HPIC, or GFAAS analysis. The insoluble fraction collected on the membrane was washed with deionized water and dried in a desiccator for neutron activation analysis (NAA). Analytical Methods. A Perkin-Elmer Model 5100PC atomic absorption spectrometer equipped with an HGA300 graphite furnace atomizer was used to determine total As, Se, Cd, Pb, and Cu. A mercury/hydride generation system (MHS-10) was also used for total As, Se, and Hg determination in conjunction with the AAS according to the procedures recommended by EPA (8). The detection limit for total As using the hydride generation method is 0.7 pg/L. A simultaneous ICP-AES (Therm0 Jarrell Ash Model ICAP 9000) was used for the determination of Ba, Ca, Cr, Fe, K, Mg, Mn, Na, P, Sr, and Zn. A one-MW TRIGA nuclear reactor with a steady neutron flux of 6 X 1012 n cm-2 s was used for the irradiation of filter membranes to determine insoluble arsenic. A highresolution ORTEC Ge(Li) detector and an EG&G ORTEC ADCAM (Model 950) multichannel analyzer were used fortheanalysisof7~As(559keV,t~p=l.lday) afterneutron activation. The details of NAA of arsenic are given in the literature (9). Two methods were used to determine arsenic species in water samples. One method of arsenic speciation was done using the pairing ion high-performance liquid chromatography (PIC-HPLC, Waters Model 501) coupled to a hydride generation AAS. The technique of PIC-HPLC separation of arsenic species is given in the literature (10, 11). Usually, 100 pL of water sample was loaded into the sample loop and then injected on a separation column. The polystyrene divinylbenzene reversed-phase columns Dionex NG-1 and NS-1 were used as the guard column and the separation column, respectively. The arsenic species were eluted from the separation column with a solution consisting of 5 X 10-3 M tetrabutylammonium phosphate in 5% methanol solution adjusted to pH 7.3 at a flow rate of 1 mL/min. Under these conditions, the elution times for As3+,DMA, MMA, and As5+are 2.1,3.2, 4.0, and 6.3 min, respectively. The effluent was mixed with 1 M HC1 and 4 % w/v sodium borohydride on-line, and the arsine generated was determined by AAS at 193.7 nm. The detection limits for As3+,As5+,MMA, and DMA 678 Envlron. Scl Technol.,Vol. 28, No. 5, le94 Allowing well water to flow through the pumpinq,tube for 10 min , , 5 L water sample 1 L water sample I I 0.45pm millipore filtration at the sampling site 0.45 &m millipore I filtration Adding 2 mL H p , I I fraction retained by the f iltsr I NAA for insoluble tb by PIC-HGAAS I I 1 L adjusted to pH<Z with "0, and stored at 4'C 1 4L (unacidified) for ultranitration I 0.1 L (unacidified) for anion determination by HPIC speciation by solvent extraction Multielemental Filtrate analysis by adjusted to ICP/rnS, pHc2 with HN03 ICP/MS, or GFAAS, 1 total As As determination determination by ICP/MS by HGAAS or NAA Flgure I. Procedures of sampling, pretreatment, and analysis of the groundwaters collected from the BFD area. using this method are 0.7, 1.5, 1.0, and 1.0 pg/L, respectively. Another method of arsenic speciation involved a solvent extraction procedure using ammonium pyrrolidinedithiocarbamate (APDC) as a ligand for complexation with As3+followed by NAA of the extracted complex. The pentavalent As5+was determined by reduction to As3+ with sodium thiosulfate and potassium iodide followed by the extraction of the trivalent species. The difference in arsenic concentration between the two aliquots with and without reduction was used to calculate the As5+concentration. The detailed procedure of arsenic speciation by APDC extraction is given in the literature (9). The ultrafiltration technique was used to further characterizethe distribution of dissolved arsenic in water. The well waters were first filtered through a 0.45-pm Millipore membrane. The filtered water (unacidified) was separated into five aliquots for size distribution studies. An ultrafiltration apparatus (Model XX42PRK60, Millipore, Waters) with four different membranes (Millipore Pellicon minicassette, 1,5, 10, and 300 kDa) was used to differentiate the molecular sizes of the dissolved arsenic in water. One aliquot was used as the reference, and the other four aliquots were each filtered through a different membrane to determine the dissolved arsenic in each size fraction by ICP-MS (Perkin-Elmer,Sciex Elan 5000).The procedure of ultrafiltration technique for size differentiation is described in the literature (12). Anions in the water samples were determined by HPIC (Dionex Model 4500i) following the procedures recommended by the EPA (8). The overall procedures of arsenic speciation and chemicalanalysis of other trace elements in the well waters are illustrated in Figure 1. Results and Discussion The total dissolved arsenic and the distribution of As3+, As5+,MMA, DMA, and insoluble arsenic in the well waters of Putai are given in Table 1. The concentrations of the arsenic species given in Table 1are the averages of triplicate bimonthly samples obtained from each of the three wells in Putai during the 1-yearstudy period. The concentration ranges of the arsenic species are given in parentheses. The average concentrationsof the soluble arsenic found in each Table 1, Average Concentrations and Ranges of Arsenic Species in Well Waters of Putai, Taiwan ( d L P 1 total soluble As 734 i 92 (662-897) As3+ 365 f 42 (318-434) As5+ 346 f 43 (303-420) insoluble As 7.6 f 1.8 (5.0-9.7) well no. 2 3 av. of all samples 748 & 45 (687-810) 593 & 41 (542-634) 115 f 60 (33-174) 28.2 f 18.9 (15.0-53.2) 583 f 132 (470-754) 451 f 122 (358-683) 128 f 36 (89-190) 29.8 f 13.2 (16.7-44.0) 671 f 149 (470-897) 462 f 129 (318-683) 177 f 109 (33-420) 21.9 12.4 (5.0-53.2) * MMA and DMA are below detection limits (<1 pg/L). of the three wells over the 12-month period are 583 f 133, 734 f 92, and 748 f 45 pg/L. The total amounts of dissolved arsenic were determined by the hydride generation-atomic absorption spectrometry (HGAAS)and by NAA of the filtered water samples directly. The total dissolved arsenic in the water collected from each individual well shows some variation. The variation of the average value is about 25% from 583 pg/L for the low arsenic well to 748 pg/L for the high arsenic well. Averaging over the three wells, the total dissolved arsenic concentration is 671 f 149 pg/L, with a range of 470-897 pg/L for all the well waters (a total of 54 samples) collected from the Putai area. The average value of the dissolved arsenic in all the well waters analyzed by this study is about 13 times greater than the CFR’s MCL for arsenic in drinking water. The main arsenic species found in the well waters of the BFD area are As3+ and As5+,with a total average ratio of As3+/As5+about 2.6. The individual wells show a variation of As3+/As5+ratio from about 1.1to 5.2. The high concentration of As3+ species present in these waters reflects the reduced environment of the aquifer, which may be caused by the low oxygen fugacity or the presence of other reducing agents, or both, in the groundwater system. According to the information provided by the local dwellers, the depth of the wells chosen for this study is estimated to be around 150 m. This estimate was based on the number of bamboo tubes and their average length used in drilling the wells some 40 years ago. The methyl arsenicals (MMA and DMA) are below detection (<1pg/L) in the well waters, and the insoluble suspended arsenic is about 3% relative to the total soluble arsenic. The sum of As3+and As5+accounts for about 95 % of the total dissolved arsenic according to the datagiven in Table 1. Some other soluble forms of arsenic, not detectable by our speciation techniques, are probably also present in the well waters. In comparison with the arsenic contents in the well waters of Hsinchu where no BFD has ever been reported, the BFD waters are about 3 orders of magnitude higher. The average total arsenic in the well waters of Hsinchu is less than 0.7 pg/L (n = 54). The insoluble suspended arsenic and the soluble MMA and DMA in the well waters of Hsinchu were not detectable (<1 pg/L). The chemical forms of the inorganic arsenic species present in natural waters depend on the pH and the redox potential of the aquatic system. The pH values of the well waters collected from the Putai area are in the range of 8.1 f 0.4. The chemical forms of As3+ and As5+ at pH values around 8 should be H3AsO3 and HAs0d2-,respectively, according to the known thermodynamic data (13). The organoarsenicals found in the environment are primarily derived from biomethylation, i.e., the synthesis Table 2. Size Distribution of Soluble Arsenic Species in Well Waters of Putai, Taiwan molecular mass range (kDa) concn (pg/L) range (Wg/L) % soluble As >300 300-10 86 f 14 (76-102) 10.8 5f4 (1-10) 0.6 10-5 5-1 <1 * 15 f 11 43 f 18 645 147 (4-27) (13-69) (485-775) 5.4 81.2 1.9 of organoarsenic compounds requires the involvement of a living organism and, presumably the intervention of arsenic within the metabolic pathways of the cell (14). Besides MMA and DMA, other biologically produced organoarsenicals with more complex organic moieties are also known, these also possess methyl groups. According to Cullen and Reimer, MMA and DMA are the only organoarsenicalsthat have been found as dissolved species in natural waters (14). The low MMA and DMA concentrations found in the well waters of the Putai area suggest that other more complicated organoarsenicals are probably not present in significant amounts in the well water. It is possible that some of the dissolved arsenic species may be associated with high molecular weight organic materials such as humic substances in the well water. Humic substances have been detected in the well water of the BFD area (15). The molecular weight distribution of soluble arsenic species in the well waters of the BFD area determined by the ultrafiltration technique is given in Table 2. The predominant molecular mass of the dissolved arsenic in the well waters is less than lOOODa (about 81% ), suggesting that the major forms of the arsenic species in the well water are probably individual ions or molecular species. A significant fraction of the dissolved arsenic in the well waters is probably associated with the humic substances based on the data given in Table 2. The molecular mass of humic substances is roughly in the range of 104-106 Da. The fraction with molecular mass >300 000 Da accounts for about 11% of the total dissolved arsenic. The average concentration of arsenic in this fraction is about 86 f 14 pg/L, significantly greater than the CFR’s MCL of arsenic in drinking water. According to the ultrafiltration data, the distribution of dissolved arsenic in the well waters can be roughly divided into two main groups, one with molecular mass <lo00 Da and the other with molecular mass >300 000 Da. When a >300 000 Da fraction sample was injected into the PIC-HPLC, two peaks were observed corresponding to the elution times of As3+and As5+. The ratio of As3+/As5+concentrations is 9:l. The rest of the arsenic in the high molecular weight fraction could not be eluted from the column. The majority of the arsenic in the elutable fraction appears to be As3+. The chemical nature of these high molecular weight arsenic containing species is unknown. Isolation and characterization of the dissolved arsenic species in the well water may provide very useful information for understanding the toxicity of arsenic and the cause of BFD. The concentrations of 19other trace and minor elements in the well waters of the BFD and the Hsinchu area are given in Table 3. The available CFR’s MCL in drinking water for some of the listed elements are also given in the table (3,4).Except manganese, none of the elements listed in Table 3 exceeds the CFR’s MCL. The average concentration of Mn is only slightly above the CFR’s MCL for bottled water. The ratios of the trace element Environ. Scl. Technol., Vol. 28, No. 5, 1994 878 Table 3. Average Concentrations and Ranges of Minor and Trace Elements in Well Waters of Putai and Hsinchu, Taiwan element Cd co Cr cu Fe Hg Mn Ni P Pb Sb Se Zn Na K Mg Ca Sr Ba Putai (pglL) 0.09 f 0.02 (0.07-0.11) 37.2 f 27.2 (6.7-111.0) 10.3 f 3.6 (7.5-14.3) 1.82 f 1.13 (0.92-3.88) 176.2 f 98.4 (33.9-386.0) 0.41 & 0.34 (0.06-1.04) 54.7 f 16.5 (28.7-90.7) <9 85.8 f 63.6 (15.0-225.7) 4.99 f 5.35 (0.71-14.10) 0.8 f 0.3 <0.08 18.3 f 10.9 (11.0-56.5) (26.3 f 8.67) X lo4 (16.6-48.7) X lo4 (8.04 f 2.52) X lo3 (4.99-14.2) X lo3 (9.91 i 5.54) x 103 (3.70-22.1) X lo3 (25.2 f 8.25) X lo3 (13.4-43.9) X lo3 216 f 62 (129-336) 146 f 116 (36-399) Hsinchu (pg/L) ratio of Putail Hsinchu 0.10 f 0.04 (0.06-0.14) 25.0 f 19.5 (5.7-60.2) C1.4 0.9 2.45 f 1.22 (0.75-5.33) 78.3 f 65.7 (1.6-190.0) 0.34 f 0.20 (0.08-0.68) 135 f 42 (99-183) e9 24.9 f 17.5 (7.2-63.0) 1.16 f 0.50 (0.68-1.86) <0.2 C0.08 15.9 f 9.6 (4.5-37.6) (3.07 f 1.86) X 104 (0.98-5.76) X 104 (7.90 f 8.25) X lo3 (1.69-22.8) X 103 (22.5 f 16.9) x 103 (8.85-54.7) X lo3 (55.2 f 8.76) X lo3 (38.6-74.7) X lo3 323 dz 88 (230-530) 47 f 30 (16-111) 0.7 1.5 7.4 2.3 1.2 0.4 3.4 4.3 4.0 1.2 8.6 1.0 0.4 0.5 0.7 3.1 a 40 CFR 8 141.11, for community water systems, revised in July 1992. 21 CFR § 103.35 for bottled water, revised in April 1992. concentrations in the well waters of Putai over those of Hsinchu are also given. Of the 19 elements listed, Cd, Cu, Mg, Mn, Ca, and Sr are actually lower in the well waters of the BFD area relative to the Hsinchu area. The concentrations of Co, Cr, Fe, Hg, P, Pb, Sb, Zn, Na, K, and Ba are all higher in the BFD well waters relative to the Hsinchu waters. The chemical properties of Sb are similar to As (16). For this reason, we also measured the distribution of Sb species in the water. The average total Sb concentration in the well waters of the BFD area is about 0.8 pg/L, within the range of its concentrations reported for natural waters (16). The predominant Sb species in the water is Sb5+, with a ratio of Sb3+/Sb5+ around 0.3. The average concentrations of the following anions in the well waters were obtained from HPIC analysis: C1- (322 f 3 mg/L), B r (0.97 f 0.01 mg/L), NO3 (0.22 f 0.01 mg/L), HP042- (5.1 f 0.1 mg/L), and Sod2(8.1 f 0.1 mg/L). Fluoride and nitrite ions were not detectable (<0.1mg/L) under our HPIC conditions. Based on the data obtained from this study, there is no compelling reason to suspect that any one of the elements listed in Table 3 is related to the cause of BFD. However, the synergistic effects of arsenic and other trace and minor elements in the well waters with respect to biological toxicity are unknown. It is possible that high arsenic contents combined with other trace or minor elements may enhance their toxicities for biological systems. 880 Environ. Sci. Technoi., Vol. 28, No. 5. 1994 In 1981, the Safe Drinking Water Committee, after reviewing the epidemiologicalstudies in the United States, found no positive relationship between high levels of arsenic in drinking water and adverse health effects (17). The US. epidemiological studies were conducted in Alaska, Oregon, and Utah. According to the literature, arsenic exposure is associated primarily with skin cancer. Associations with other cancersand cardiovasculardysfunctions have also been found (17). This relationship is consistent with the observations made in the BFD area in Taiwan. The standardized mortality ratio was found to be significantly higher in the BFD area relative to other areas in Taiwan for cancers of the skin, bladder, kidney, lung, liver, and colon for both sexes (18). In addition to the high cancer rates, there is BFD which is found only in this area of Taiwan according to the official record. There is also a strong correlation between skin cancer, BFD, and the content of arsenic in the drinking water of the BFD area according to Tseng ( I , 18). The difference between the U.S. epidemiologic studies and the BFD case in Taiwan may be caused by several factors. For example, the arsenic concentrations in the drinking waters of the U.S. epidemiological studies are significantly lower than those found in the BFD area. The Fairbanks, AK, study examined over 200 residents exposed to drinking water containing a mean arsenic level of 224 pg/L with the longest exposure in the study population about 10 years. The average arsenic concentrations in drinking water of the other two studies are lower than the Alaska study. Perhaps, more importantly, the prevailing arsenic species in the waters of the U.S. studies is the pentavalent state As5+ (19), which is known to be less toxic than the trivalent state As3+found predominantly in the waters of the BFD area. In addition, the durations of exposure to arsenic for the study population in the U.S. epidemiological studies are short compared with the BFD area in Taiwan, where BFD records have been kept over half of a century. The mobility of population in the BFD area is generally small. Most of the local inhabitants have been living in the same area for generations and some began using artesian wells with high arsenic levels in the early 1920s of this century. Perhaps these factors are responsible for this arsenicassociated chronic disease in Taiwan. The difference in other environmental factors between the U S . study areas and the BFD area in Taiwan should also be considered. Most of the people in the BFD area were engaged in farming, fishing, and salt production, and their socioeconomic status was considered poor. Lack of nutrition during and after the war might have exacerbated the effects of arsenic exposure in the BFD area. There are other data existing in the literature concerning high arsenic in drinking water. For example, in the community of Fallon, NV, arsenic in the level of 100 pg/L was found in an aquifer reported to be used by local people since 1941. No adverse health effect has been reported from this city either. According to the tests, the arsenic in Fallon's water is all in the pentavalent state As5+ (20). These documented cases in the United States indicate that the presence of the pentavalent arsenic species in drinking water at the specified levels probably would not create a health hazard. The adverse health effects of the trivalent arsenic species and other arsenic species in drinking water cannot be evaluated in the U.S. studies. The World Health Organization estimated that a lifetime exposure to arsenic in drinking water at a concentration of 200 pg/L might give a 5% risk of getting skin cancer (21). The chemical form of the arsenic was not specified. According t o a recent report, the U.S.EPA is reviewing the carcinogenicity of arsenic and the anticipated MCLG (maximum contaminant level goal) for noncancer effects would probably be around 2 pg/L (5). We recommend that the chemical species of arsenic should be included in this and other future evaluations. Based on the extensive chemical and arsenic speciation data of the groundwaters obtained from the BFD area by this study, we tend to conclude that arsenic is still the primary suspect for the cause of BFD. Because of its unique occurrence in Taiwan, BFD may provide an important case study for understanding the environmental hazard of long-term exposure to arsenic and the cause of this painful chronic disease. Further study in identifying and characterizing the chemical forms of the dissolved arsenic in the well waters of the BFD area is highly desirable for the BFD research. Acknowledgments This work was supported by a grant from the National Science Council of Taiwan. Neutron irradiations performed at the Washington State University Nuclear Radiation Center were supported by a Reactor Sharing Program funded by the U.S. Department of Energy. Literature Cited (1) Tseng, W. P.; Chu, H. M.; How,S. W.; Fong, J. M.; Lin C. S.; Yeh S. J . Natl. Cancer Inst. 1968,40,453. (2)Chen, C. J.; Chuang, Y. C.; Lin, T. M.; Wu, H. Y. Cancer Res. 1985,45,5895. ( 3 ) Code ofFederal Regulations, 40 CFR $141.11,revised July 1992,U.S. Government Printing Office: Washington, DC, 1992. (4) Code ofFederal Regulations, 21 CFR 5103.35,revisedApril 1992,U.S. Government Printing Office: Washington, DC, 1992. (5) Pontius, F. W. J.Am. Water Works Assoc. 1992,84(3),36. (6) National Academy of Sciences. Arsenic-Medical and Bi- ological Effects ofEnvironmenta1 Pollutants;Government Printing Office: Washington, DC, 1977. (7) Cheam, V.; Agemian, H. Analyst 1980,105,737. (8) US.EPA. Methods for Chemical Analysis of Water and Wastes, Method 200.7, 206.5, 245.1, and 270.3. EPA Cincinnati, OH,1983. (9) Mok, M. W.; Wai, C. M. Anal. Chem 1987,59,233. (10) Hakala, E.; Pyy, L. J . Anal. Atom. Spectrosc. 1992,7,191. (11) Chana, B.S.;Smith, N. J. Anal. Chim. Acta 1987,197,177. (12) Tanizaki,Y.;Shimokawa,T.;Yamazaki,M. WaterRes. 1992, 26,55. (13) Cherry, J. A.; Shaikh, A. U.; Tallman, D. E.; Nicholson, R. V. J . Hydrol. 1979,43,373. (14) Cullen, W. R.; Reimer, K. J. Chem. Rev. 1989,89,713. (15) Lu, F. J.; Hsieh, H. P.; Yamauchi,H.; Yamamura, Y. Appl. Organmet. Chem. 1991,5,507. (16) Mok, W. M.; Wai, C. M. Environ. Sci. Technol. 1990,24, 102. (17) Safe Drinking Water Committee. Drinking Water and Health; National Academy Press: Washington, DC, 1983; VOl. 5. (18) Tseng, W. P. Environ. Health Perspect 1977,19,109. (19) U.S.Senate,Committee on Environmentand Public Works. A legislative history of the Safe Drinking Water Act Amendments 1983-1992,together witha section-by-section index;Prepared by the Environmentand Natural Resources Policy Division of the Congressional Research Service of the Library of Congress;U.S. Government Printing Office: Washington, DC, 1993;p 131-139. (20) Steward, J. C. Drinking Water Hazards; Envirographics: Hiram, OH, 1990;p 67. (21) World Health Organization.GuidelinesforDrinking Water; WHO: Geneva, 1984;p 66. Received for review July 14,1993.Revised manuscript received January 10, 1994. Accepted January 13,1994.' * Abstract published in Advance ACS Abstracts, February 15, 1994. Environ. Scl. technol., Vol. 28, No. 5, 1994 881
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