Ground water to surface water: Chemistry of thermal outflows in Yellowstone National Park

Abstract

Geothermal waters in the earth’s subsurface boil with steam separation and may mix with dilute ground waters (that may or may not contain sulfuric acid from sulfur oxidation), resulting in a wide range of compositions when they discharge and emerge at the surface. As they discharge onto the ground surface they undergo evaporative cooling, degassing, oxidation, and mineral precipitation. Within this aquatic environment of rapidly changing physical and chemical parameters, numerous microbial communities develop—some of which affect oxidation and mineral precipitation. Microbes are responsible for rapid oxidation of iron and arsenic in thermal outflows, and for catalyzing the production of sulfuric acid from the oxidation of elemental sulfur. The attractive visual display of colors observed in Yellowstone’s geothermal waters reflects this interplay of physical, chemical, and biological phenomena. Oxidation of dissolved sulfide to thiosulfate occurs abiotically, and thiosulfate can be found in many of Yellowstone’s thermal waters—at any pH, temperature, and composition. Polythionates, on the other hand, are rarely found in Yellowstone waters but are associated with sulfur hydrolysis in Cinder Pool. Oxidation rates of iron and arsenic in overflows have been estimated at 1-3 mM/h and 0.04-0.1 mM/h, respectively—orders of magnitude faster than the abiotic rate. The abiotic production of thiosulfate from oxidation of dissolved sulfi de at Angel Terrace and Ojo Caliente is about 3-30 µM/min, faster by 2-3 orders of magnitude than the laboratory rate at 25°C. The partitioning of dissolved sulfide between that volatilized to the air and that oxidized to thiosulfate has been estimated at Angel Terrace and at Ojo Caliente. For the pH range of 6-8 and the temperature range of 50-93°C, 67-86% of the dissolved sulfide is lost to the atmosphere and 10-33% is oxidized to thiosulfate. Only a very small percentage, if any, forms elemental sulfur under these conditions.