Multicomponent reactive transport modeling in variably saturated porous media using a generalized formulation for kinetically controlled reactions

{[}1] A generalized formulation for kinetically controlled reactions has been developed and incorporated into a multicomponent reactive transport model to facilitate the investigation of a large variety of problems involving inorganic and organic chemicals in variably saturated media. The general kinetic formulation includes intra-aqueous and dissolution-precipitation reactions in addition to geochemical equilibrium expressions for hydrolysis, aqueous complexation, oxidation-reduction, ion exchange, surface complexation, and gas dissolution-exsolution reactions. The generalized approach allows consideration of fractional order terms with respect to any dissolved species in terms of species activities or in terms of total concentrations, which facilitates the incorporation of a variety of experimentally derived rate expressions. Monod and inhibition terms can be used to describe microbially mediated reactions or to limit the reaction progress of inorganic reactions. Dissolution-precipitation reactions can be described as surface-controlled or transport-controlled reactions. The formulation also facilitates the consideration of any number of parallel reaction pathways, and reactions can be treated as irreversible or reversible processes. Two groundwater contamination scenarios, both set in variably saturated media but with significantly different geochemical reaction networks, are investigated and demonstrate the advantage of the generalized approach. The first problem focuses on a hypothetical case study of the natural attenuation of organic contaminants undergoing dissolution, volatilization, and biodegradation in an unconfined aquifer overlaid by unsaturated sediments. The second problem addresses the generation of acid mine drainage in the unsaturated zone of a tailings impoundment at the Nickel Rim Mine Site near Sudbury, Ontario, and subsequent reactive transport in the saturated portion of the tailings.