Geochemical Modeling of pH Neutralization of High Alkaline-Saline Waste Fluids in Unsaturated Sediments

Leakage of high alkaline-saline fluids, such as those stored in Hanford, a site of the U.S. Department of Energy (DOE) in Washington State, has raised attention of scientific community. These fluids have unique thermodynamic and physical properties. Chemical components in the fluids are incompletely dissociated, especially those containing divalent or polyvalent ions. A number of laboratory experiments through injecting synthetic high alkaline-saline fluids (up to 10M of sodium nitrate, pH >12) into the sediments sampled from the DOE Hanford site were conducted to study the reactive transport processes of the fluids in subsurface environments. The experimental results observed show that the composition of the high alkaline sodium nitrate fluids can be drastically changed due to fluid-rock interactions, and eventually lead to pH neutralization of the fluid in the plume front. The dominant fluid-rock interactions are cation exchanges (Na⁺-K⁺-Ca⁺²-Mg⁺²-H⁺), precipitation of calcium and magnesium minerals, and dissolution of silica. In order to precisely model the reactive transport of these processes, a coupling of the Pitzer's ion-interaction geochemical model and a flow and transport model would be highly needed. The extended existing reactive geochemical transport code, BIO-CORE^2Dc, incorporating a comprehensive Pitzer ion-interaction model, is capable of predicting the experimental observations. In addition, the developed model was tested against two reported cases. In both cases, the measured mean ionic activity coefficients were well reproduced by our model, while the Debye-Hückel model, usually used to calculate aqueous species activities in dilute solutions, was unable to predict the experimental data. Finally, modeling study based on our laboratory column experiment was performed. Our simulation is able to capture the observed pH trends, changes in exchangeable cations such as Ca⁺², Mg⁺², and formation of secondary precipitation phases in the plume front.