Kinetics of evaporite mineral-brine interactions: mathematical modeling and experimental determination of the effect of gamma radiation and threshold crystallization inhibition on Permian Basin brine composition

The San Andres and Salado bedded salt formations in the evaporitic Permian Basin contain fluid phases in equilibrium with the host rock. Anthropogenic perturbations such as emplacing heat-generating high level radioactive wastes (HLW) in a mined repository mobilize this brine. Kinetic factors are of extreme importance in the precipitation and dissolution of evaporites and may govern the diagenesis of phosphate, sulfate, and chloride phases in the type of environment occurring at both the time of the original deposition of the sediment and in the very nearfield of a HLW repository. Using the computer code XLRATE, newly-formulated geometric models incorporating critical aspects of mineralogical defects and dislocations describe a wide variety of kinetic data for the dissolution of apatite and irradiated Permian Basin rock salt. The lattice damage in rock salt caused by gamma radiation increases the halite dissolution rate. The escape of chlorine gas and the radiolysis of trace impurities moves the NaCl concentration of saturated brines made from irradiated salt to lower values with Cl- decreasing to a greater extent than Na+. A new model incorporating nucleation time best describes crystallization kinetics in the calcium sulfate system. The solubilities and saturation indices of irradiated Permian Basin rock salt and calcium sulfates in brines of different ionic strengths were numerically modeled. Seventy-five naturally-occurring and commercial crystallization inhibitors including carboxylic acids, amino acids, carbohydrates, humic and tannic substances, and organic polyelectrolytes were tested for their effect on gypsum/anhydrite and rock salt precipitation and dissolution. Of these, 70% proved relative or very effective