Geochemical modeling of the Madison aquifer in parts of Montana, Wyoming, and South Dakota

Stable isotope data for dissolved carbonate, sulfate, and sulfide are combined with water composition data to construct geochemical reaciton models along eight flow paths in the Madison aquifer in parts of Wyoming, Montana, and South Dakota. All reaction models reproduce the observed chemical and carbon and sulfur isotopic composition of the final waters and are partially validated by predicting the observed carbon and sulfur isotopic compositions of colomite and anhydrite from the Madison Limestone. The geochemical reaction models indicate that the dominant groundwater reactionin the Madison aquifer is dedolomitization (calcite precipitation and dolomite dissolution driven by anhydrite dissolution). Sulfate reduction, [Ca2+ + Mg2+]/Na+ cation exchange, and halite dissolution are locally important, particularly in central Montana. The groundwater system is treated as closed to CO2 gas from external sources such as the soil zone or cross-formational leakage but open to CO2 from oxidation of organic matter coupled with sulfate reduction and other redox processes occurring within the aquifer. The computed mineral mass transfers and modeled sulfur isotopic composition of Madison anhydrites are mapped throughout the study area. Carbon 14 groundwater ages, adjusted for the modeled carbon mass transfer, range from modern to about 23,000 years B.P. and indicate flow velocities of 7-87 ft/yr (2.1-26.5 m/yr). Most horizontal hydraulic conductivities calculated from Darcy's Law using the average 14C flow velocities are within a factor of 5 of those based on digital simulation. The calculated mineral mass transfer and adjusted 14C groundwater ages permit determination of apparent rates of reaction in the aquifer