Mono-, di-, tri-, and tetrathioarsenate, as well as methylated arsenic oxy- and thioanions, were determined besides arsenite and arsenate in geothermal waters of Yellowstone National Park using anion-exchange chroma tography inductively coupled plasma mass spectrometry. Retention time match with synthetic standards, measured S:As ratios, and molecular electrospray mass spectra support the identification. Acidification was unsuitable for arsenic species preservation in sulfidic waters, with HCl addition causing loss of total dissolved arsenic, presumably by precipitation of arsenic-sulfides. Flash-freezing is preferred for the preservation of arsenic species for several weeks. After thawing, samples must be analyzed...