Xc. Le et al., EFFECT OF CYSTEINE ON THE SPECIATION OF ARSENIC BY USING HYDRIDE GENERATION ATOMIC-ABSORPTION SPECTROMETRY, Analytica chimica acta, 285(3), 1994, pp. 277-285
The use of hydride generation techniques for arsenic species is pH dep
endent. Identical responses can not be obtained from arsenite, arsenat
e, monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) when
the same acid concentration is used. Thus some methods commonly used f
or the direct determination of total arsenic under compromised conditi
ons are subject to error. This error is eliminated by the addition of
2% cysteine to samples prior to hydride generation. In the presence of
cysteine the optimum condition for the determination of these arsenic
species is in the same range, and a single arsenic species can be use
d for calibration. This finding is applied to the determination of ars
enic in human urine by using flow injection, hydride generation, and a
tomic absorption spectrometry methodology. The effect of cysteine and
thioglycerol is reported in detail, and it is proposed that arsenate,
MMAA and DMAA all in the As(V) state, are reduced to the As(III) state
as organo-sulfur-arsenic(III) compounds through the reaction between
the arsenic species and the thiol. These products, organosulfur deriva
tives of arsenic(III), easily react with tetrahydroborate(III) under s
imilar conditions to afford the arsines without interference from cyst
eine. Non-thiol-containing amino acids such as methionine, glycine and
histidine do not react with arsenic species in this way, and therefor
e they do not affect the pH dependence of the generation of arsenic hy
dride species.