Redox Reactions In Water Research Articles

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

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.

Development of reaction models for ground-water systems

Methods are described for developing geochemical reaction models from the observed chemical compositions of ground water along a hydrologic flow path. The roles of thermodynamic speciation programs, mass balance calculations, and reaction-path simulations in developing and testing reaction models are contrasted. Electron transfer is included in the mass balance equations to properly account for redox reactions in ground water. The mass balance calculations determine net mass transfer models which must be checked against the thermodynamic calculations of speciation and reaction-path programs. Although reaction-path simulations of ground-water chemistry are thermodynamically valid, they must be checked against the net mass transfer defined by the mass balance calculations. An example is given testing multiple reaction hypotheses along a flow path in the Floridan aquifer where several reaction models are eliminated. Use of carbon and sulfur isotopic data with mass balance calculations indicates a net reaction of incongruent dissolution of dolomite (dolomite dissolution with calcite precipitation) driven irreversibly by gypsum dissolution, accompanied by minor sulfate reduction, ferric hydroxide dissolution, and pyrite precipitation in central Florida. Along the flow path, the aquifer appears to be open to CO 2 initially, and open to organic carbon at more distant points down gradient.