Arsenic and antimony in geothermal waters of Yellowstone National Park, Wyoming, USA
A total of 268 thermal spring samples were analyzed for total soluble As using reduced molybdenum-blue; 27 of these samples were also analyzed for total Sb using flame atomic absorption spectrometry. At Yellowstone the Cl As "> ClAs atomic ratio is nearly constant among neutral-alkaline springs with Cl > 100 mg L −1 , and within restricted geographic areas, indicating no differential effects of adiabatic vs . conductive cooling on arsenic. The Cl As "> ClAs ratio increases with silica and decreases with decreasing Cl ΣCO 3 "> ClΣCO3 ; the latter relationship is best exemplified for springs along the extensively sampled SE-NW trend within the Lone Star-Upper-Midway Basin region. The relationship between Cl As "> ClAs and Cl ΣCO 3 "> ClΣCO3 at Yellowstone suggests a possible rock leaching rather than magmatic origin for much of the Park's total As flux. Condensed vapor springs are low in both As and Cl. Very high Cl As "> ClAs ratios ( > 1000) are associated exclusively with highly diluted (Cl < 100 mg L −1 ) mixed springs in the Norris and Shoshone Basins and in the Upper White Creek and Firehole Lake areas of Lower Basin. The high ratios are associated with acidity and/or oxygen and iron; they indicate precipitation of As following massive dilution of the Asbearing high-Cl parent water. Yellowstone Sb ranged from 0.009 at Mammoth to 0.166 mg L −1 at Joseph's Coat Spring. Within basins, the Cl Sb "> ClSb ratio increases as the Cl ΣCO 3 "> ClΣCO3 ratio decreases, in marked contrast to As. Mixed springs also have elevated Cl Sb "> ClSb ratios. White (1967) and Weissberg (1969) previously reported stibnite (Sb 2 S 3 ), but not orpiment (As 2 S 3 ), precipitating in the near surface zone of alkaline geothermal systems.