Ground Water Redox Reactions: An Analysis of Equilibrium State Applied to Eh Measurements and Geochemical Modeling

Abstract

Computer modeling of 611 high-quality analyses of normal ground waters from diverse geographic areas reveals that aqueous oxidation-reduction reactions are generally not at equilibrium. Multiple redox couples present in individual samples yield computed Nernstian Eh (redox potential) values spanning as much as 1000 millivolts. The computed Eh values do not agree with each other, nor do they agree with the single "master" value measured in the field with a platinum electrode. Because of internal disequilibrium, the use of any measured Eh value as input to equilibrium hydrogeochemical computer models will generally yield misleading results for normal ground waters.