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Arsenic in Drinking Water (1999) / Chapter Skim
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3 Chemistry and Analysis of Arsenic Species in Water and Biological Materials
Pages 27-82

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From page 27...
... Summary Of Arsenic Compounds In Water And Food Table 3-1 lists the most important arsenic compounds and species known to be present in water and food consumed by humans. The identified compounds that are not listed are (1)
From page 28...
... 2 [CH 3 AsO] n Dimethylarsinic acid DMA (CH 3 )
From page 29...
... Unidentified species ("hidden species" not detected by using hydride generation; see section Hidden Arsenic Species) , however, can reach up to 22% of total arsenic in river water (Sturgeon et al.
From page 30...
... . High concentrations of inorganic arsenic (38-61% of total arsenic)
From page 31...
... , in aiding the elimination of arsenic species from humans, is believed to result from the displacement of bound arsenic from a protein because of the formation of a more stable complex (Equation 3-2)
From page 32...
... . The end products can be trimethylarsine oxide or trimethylarsine for fungi, the tetramethylarsonium ion for clams, and probably DMA for humans (Cullen and Reimer 1989; Cullen et al.
From page 33...
... Page 33 SAM is probably the source of the adenosyl group that is found in the arsenosugars (Francesconi and Edmonds 1997)
From page 34...
... ; negligible removal of As(III) from drinking water is achieved by coagulation with alum (Hering et al.
From page 35...
... . Analysis Of Arsenic Compounds The discovery by Scheele in 1775 that arsenic compounds could react under reducing conditions to produce a volatile gas, arsine (AsH 3 )
From page 36...
... to spectrophotometry (e.g., graphite-furnace atomic absorption (GFAA) or inductively coupled plasmaatomic emission spectrometry (ICP-AES)
From page 37...
... . When a mixture of arsines is obtained following hydride generation, the arsines must be separated before quantification can be achieved.
From page 38...
... Compounds that are not detected by hydride generation are sometimes referred to as "hidden arsenic" species. That term originated in the era when hydride generation was the only method readily available for arsenic speciation.
From page 39...
... 30 High Yes Yes Yes Yes voltammetry                 Spectroscopic                 Flame atomic absorption   1 mg/L 20 Low No No No No Graphite furnace AAS   1 µg/L 80 High Yes Yes No No DCP or ICP-AES   10 m g/L 80 Very high Yes Yes No No ICP-MS   0.05 µg/L 200 Very high Yes Yes Yes No a Silver diethyldithiocarbamate. Abbreviations: AAS, atomic absorption spectroscopy; DC, direct current; ICP-MS, inductively coupled plasma-mass spectrometry; DCP, direct current plasma; AES, atomic emission spectroscopy.
From page 40...
... . Mass Spectrometry for Arsenic Speciation The most recent development in speciation methodology has been to combine the separation capability of HPLC with the molecular-recognition capability of mass spectrometry.
From page 41...
... Unless special circumstances, such as pollution by arsenical herbicides or high biological activity, exist, Irgolic argued that determination of arsenic species in water supplies is unnecessary; knowledge of the inorganic arsenic content is sufficient for regulatory purposes. The subcommittee evaluated that conclusion, as described below.
From page 42...
... ; 93(10) 219-110 0.3 Dimethylarsinic acid 138 139 139(100)
From page 43...
... Insoluble suspended arsenic accounted for about 3 % of the total arsenic in the water from the three wells, and ultrafiltration revealed that about 11% of the soluble arsenic, mainly As(III) , was associated with molecules of molecular mass greater than 300,000 daltons.
From page 44...
... The nonhydride and active species constituted 22 % of the total arsenic, and the authors suggested that the compound or compounds are similar to AsB. However, the workup of the sample, which involved the use of a strong cation-exchange column, could have changed the species originally present.
From page 45...
... attempted to determine the practical quantification level (PQL) for total arsenic in drinking water.
From page 46...
... . Food collected in Canadian cities in the years 1985-1988 was analyzed for total arsenic, and the food groups containing the highest mean arsenic concentrations were fish (1,662 ng/g)
From page 47...
... The question has been raised whether organic arsenic can be broken down to inorganic arsenic species during the HC1 distillation (Mushak and Crocetti 1995) , thus increasing the proportion of inorganic species in the sample.
From page 48...
... 1994. information, and regression analysis of the data indicates that the proportion of inorganic arsenic falls from about 1% at very low total-arsenic concentrations to about 0.5% at total-arsenic concentrations of 20 mg/kg.
From page 49...
... 62 45.4 4.25 2.90 7.15 70+ (M) 74 69.4 6.63 3.10 9.70 a Based on the assumption that 10 % and 100% of the total arsenic is inorganic arsenic in seafood and all other foods, respectively.
From page 50...
... (1998) to estimate daily dietary intakes of inorganic arsenic ranging from 8.3 to 14 µ g per day in the United States and from 4.8 to 12.7 µ g per day in Canada, on the basis that inorganic arsenic constitutes 20-40% of the total dietary intake.
From page 51...
... in 1975 was found to contain detectable amounts of arsenic mainly in the 0.1-0.7 mg/kg (total arsenic) range.
From page 52...
... Although total-arsenic concentrations are known to be lower in freshwater fish than in marine animals, little is known about arsenic speciation in freshwater fish (Cullen and Reimer 1989)
From page 53...
... Arsenic Concentration (mg/kg, Wet Wt.) Arsenobetaine Content (% of Total Arsenic)
From page 54...
... . In addition, several unidentified arsenicals were present, amounting to 60% of the total arsenic.
From page 55...
... The arsenic-containing moieties in such compounds should be available to mild extractants unless there is some physical barrier, such as a cell wall, to the extractant. On the same basis, inorganic arsenic species should be extractable unless there is a barrier.
From page 56...
... . Total Arsenic in Urine Some foods, especially those of marine origin, have high concentrations of arsenic, and consumption results in a surge in the concentration of arsenic in the urine.
From page 57...
... . Total arsenic was determined by HG-AA following dry ashing (MgNO 3 and MgO at 600°C)
From page 58...
... Total arsenic was determined following dry ashing, and OF arsenic was determined by difference. There was good agreement between the two methods, which were used in different laboratories, although detection limits were not reported.
From page 59...
... Abbreviations: DMA, dimethylarsinic acid; MMA, monomethylarsonic acid; OF, other forms of arsenic determined by difference in this case; As(T) , arsenic total (sum of species and is not determined)
From page 60...
... The urinary arsenic concentrations are much higher in native Andean women exposed to high concentrations of arsenic in drinking water (Vahter et al. 1995, Table 3-14)
From page 61...
... Mean 1.8 1.4 16.1 20.6   Confidence           intervals 1.3-2.5 1.1-1.7 11.5-22.6 15.1-28.0 Abbreviations: AsT, arsenic total; MMA, monomethylarsonic acid; DMA, dimethylarsinic acid. The maximal total-arsenic concentration of 956 µg/g of creatinine was measured (hydride generation)
From page 62...
... Hydride generation was used by five of the seven participating laboratories. It should be noted that this limit is just above the practical quantification level of 4 µg/L for inorganic arsenic in drinking water, reflecting the increased difficulty of the analyses (see previous section Practical Quantification Level for Arsenic in Drinking Water)
From page 63...
... Arsenic Species in Blood Blood is a more difficult matrix than urine for chemical analysis, so until very recently, only total-arsenic concentrations in whole blood were reported. The sample was first decomposed by using wet or dry ashing, prior to analysis by conventional methods.
From page 64...
... .) The detection limits in blood were 1.0, 1.3, 1.5, and 1.4 µg/L for MMA, DMA, AsB, and AsC, respectively.
From page 65...
... Inorganic arsenic accounted for 73% of the total, and DMA accounted for 27%. DMA was also found in the hair of hamsters (Yamauchi and Yamamura 1984)
From page 66...
... The available data indicate that, as in marine organisms, concentrations of inorganic arsenic in freshwater fish are probably low. Mushrooms (total arsenic at more than 1 ppm)
From page 67...
... , MMA, DMA, and inorganic arsenic are essentially the only species present, and the mean total-arsenic concentrations can be as much 561.3 µg/g of creatinine in an exposed population and 20.6 µg/g in controls. In other populations, high concentrations of additional species are found, for example, in Taiwan, where the mean total-arsenic concentration in the urine of one exposed group, 55.6 µg/g includes unidentified arsenic species at 36.1 µg/g.
From page 68...
... Quality-control data and certified standards for arsenic speciation are also needed to help legitimize interlaboratory and intralaboratory studies. More comprehensive studies should be undertaken to determine the arsenic content in food, especially after food processing.
From page 69...
... 1981. Urinary excretion of inorganic arsenic and its metabolites after repeated ingestion of sodium metaarsenite by volunteers.
From page 70...
... 1996. Arsenic speciation by liquid chromatography coupled with ionspray tandem mass spectrometry.
From page 71...
... 1994. Determination of the growth promoter, 4-hydroxy-3-nitrophenylarsonic acid  in  chicken  tissue  by  coupled  high-performance  liquid chromatography-inductively coupled plasma mass spectrometry.
From page 72...
... 1982. Fingerprinting inorganic arsenic and organoarsenic compounds in in situ oil shale retort and process waters using a liquid chromatograph coupled with an atomic absorption spectrometer as a detector.
From page 73...
... 1994. Determination of total arsenic and arsenic compounds in drinking water.
From page 74...
... 1994. Determination of arsenic species by inductively coupled plasma mass spectrometry with ion chromatography.
From page 75...
... 1993a. Arsenic speciation in seafood samples with emphasis on minor constituents: An investigation using high-performance liquid chromatography with detection by inductively coupled plasma mass spectrometry.
From page 76...
... 1990. Fluorescent humic substances and blackfoot disease in Taiwan.
From page 77...
... 1987. Organic vs Inorganic Arsenic in Selected Food Samples.
From page 78...
... 1997b. Determination often organoarsenic compounds using microbore high-performance liquid chromatography coupled with electrospray mass spectrometry-mass spectrometry.
From page 79...
... 1992. Arsenic speciation by ion chromatography with inductively coupled plasma mass spectrometric detection.
From page 80...
... 1993. Potential of liquid chromatographyinductively coupled plasma mass spectrometry for trace metal speciation.
From page 81...
... 1996a. Arsenic speciation in serum of uraemic patients based on liquid chromatography with hydride generation atomic absorption spectrometry and on-line UV photooxidation digestion.
From page 82...
... Page 82 Zingaro, R.A., and J.K. Thomson.


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