Determination of methylated arsenic-sulfur compounds in groundwater

Arsenic speciation was determined by anion-exchange chromatography-inductively coupled plasma-mass spectrometry (AEC-ICP-MS) in groundwater samples collected from an aquifer impacted by methylated As pesticides. Besides the four expected arsenic species AsO3(3-), As4(3-), (CH3)AsO3(2-) and (CH3)2AsO2-, up to nine other arsenic species were encountered, which constituted a major fraction of the total arsenic concentration in most samples. We then synthesized the thio-derivatives of (CH3)AsO3(2-) and (CH3)2AsO2-, and characterized the formed products by electrospray-tandem mass spectrometry (ES-MS-MS). The presence of (CH3)AsO2S2-, (CH3)AsOS2(2-), (CH3)2AsOS- and (CH3)2AsS2-, was confirmed in the groundwater by retention time matching plus ES-MS-MS in collected AEC fraction, and the presence of the trivalent methylated arsenic species (CH3)AsO2(2-) was suggested based on retention time matching only. These arsenic species have not been observed in ambient waters before, and are likely to occur in many environments containing methylated arsenic species and reduced sulfur compounds. They can persist in some of these particular samples for periods of up to six months without preservation, but tend to convert into the corresponding pentavalent oxy-species. Acidification with HCI shifted speciation equilibria rapidly, and is thus unsuitable for stabilizing samples containing these novel arsenic species; cryofreezing or no sample preservation avoided this artifact.