Water samples from Xikuangshan (China), the world largest antimony (Sb) mine with a Sb mining and smelting history of more than 200 years, were analyzed. These water samples ranged from stream water in the vicinity of the mining and smelting area that received seepage from ore residues to the underground mine-pit drainage. The concentrations of total Sb, Sb (III) and Sb (V) of the samples were determined by HPLC-ICP-MS. In addition, water pH and concentrations of major cations and anions were analyzed. All 18 samples demonstrated total Sb concentrations with ppm levels from 0.33 ppm to 11.4 ppm, which is two to three orders of magnitude higher compared to the typical concentration of dissolved Sb in unpolluted rivers (less than 1 ppb). This is probably the first time that such high Sb contents have been documented with complete environmental information. Distribution of total Sb and Sb species was investigated, taking into account the respective local environment (in the mining area or close to the smelter, etc.). Sb (V) was the predominant valence in all 18 samples. Only trace levels of Sb (III) were detected in 4 of the 18 samples. Geochemical speciation modeling showed the dominant species was Sb(OH)(6)(-). It is also probably the first time that such high Sb contents have been documented in the natural environment with Sb speciation distribution information. Several potential oxidation pathways are also discussed that might have facilitated the oxidation of Sb (III) in the natural environment. Signs of intoxication were observed among local mine workers with extensive exposure to different forms of Sb for a long period of time.

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Monomethylarsonous acid (MMAIII) was detected in groundwater from a former herbicide production plant in the USA. The site has total arsenic concentrations up to thousands of mg/L, representing one of the most severe cases of arsenic contamination ever reported. Structure-specific detection of MMAIII, along with arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMAV), and dimethylarsinic acid (DMAV), was achieved using liquid chromatography separation with electrospray ionization tandem mass spectrometry detection (HPLC-ESI-MS/MS). To enable the electrospray of MMAIII and AsIII, dimercaptosuccinic acid (DMSA) was used to derivatize these trivalent arsenicals online, so that their complexes with DMSA could be detected using negative ionization ESI-MS/MS. The presence of MMAIII was verified using high resolution mass spectrometry to measure accurate mass, tandem mass spectrometry to monitor fragmentation, and three different separation techniques to resolve arsenic species. The measured accurate mass of the suspected MMAIII compound in a groundwater sample was 122.9607+/-0.0003 amu, which was in good agreement with the theoretical value and that of the MMAIII standard. Simultaneous monitoring of AsO+ at m/z 91 and SO+ at m/z 48 using HPLC-ICPMS operating in dynamic reaction cell mode ruled out possible confounding from any sulfur-containing arsenic compound. The concentrations of MMAIII found in the groundwater samples from a contaminated site were as high as 3.9-274 mg/L, the highest ever observed in the environment.