Incorporating solid solutions in reactive transport equations using a kinetic discrete-composition approach

A new approach is proposed for incorporating solid solution reactions into mass conservation equations describing reaction paths in both closed and open systems. The method is applicable to problems involving advective, dispersive, and diffusive transport in a porous medium. By representing the continuously variable solid solution composition with a discrete set of stoichiometric solids that span composition space, combined with a kinetic formulation of their rates of reaction, a self-determining spatial and temporal evolution of the solid solution concentration and composition is obtained. It is demonstrated that equilibrium of an aqueous solution with a stoichiometric solid derived from a solid solution corresponds to equilibrium of the solid solution itself if and only if equilibrium of the stoichiometric solid is stable. One advantage of this approach is that it is unnecessary to introduce any additional compositional variables to represent the solid solution. Discretization may be over the entire range of composition space, or over some subset depending on the system. A major consequence of the kinetic discrete-composition solid solution representation is that modeling solid solutions is similar to modeling pure mineral phases with the exception of a weighting factor applied to reaction rates of stoichiometric solids corresponding to a common solid solution. With this approach, precipitation leads to a discrete zonation of the solid solution that approximates the continuous variation in composition expected for the actual solid solution. The approach is demonstrated for a hypothetical ideal and non-ideal binary solid solution AxB1−xC for a reaction path formulation and reactive transport involving advection and diffusion.