Effect of mineral reactions on the hydraulic properties of unsaturated soils: Model development and application

The selective radius shift model was used to relate changes in mineral volume due to precipitation/dissolution reactions to changes in hydraulic properties affecting flow in porous media. The model accounts for (i) precipitation/dissolution taking place only in the water-filled part of the pore space and further that (ii) the amount of mineral precipitation/dissolution within a pore depends on the local pore volume. The pore bundle concept was used to connect pore-scale changes to macroscopic soil hydraulic properties. Precipitation/dissolution induces changes in the pore radii of water-filled pores and, consequently, in the effective porosity. In a time step of the numerical model, mineral reactions lead to a discontinuous pore-size distribution because only the water- filled pores are affected. The pore-size distribution is converted back to a soil moisture characteristic function to which a new water retention curve is fitted under physically plausible constraints. The model equations were derived for the commonly used van Genuchten/Mualem hydraulic properties. Together with a mixed‐form solution of Richards’ equation for aqueous phase flow, the model was implemented into the geochemical modelling framework PHREEQC, thereby making available PHREEQC’s comprehensive geochemical reactions. Example applications include kinetic halite dissolution and calcite precipitation as a consequence of cation exchange. These applications showed marked changes in the soil’s hydraulic properties due to mineral precipitation/dissolution and the dependency of these changes on water contents. The simulations also revealed the strong influence of the degree of saturation on the development of the saturated hydraulic conductivity through its quadratic dependency on the van Genuchten parameter alpha. Furthermore, it was shown that the unsaturated hydraulic conductivity at fixed reduced water content can even increase during precipitation due to changes in the pore-size distribution.