Diffusion of ionic species in bentonite.

We present a macroscopic model of ionic diffusion in bentonites including the effect of the hydraulic-electrical-chemical couplings expected in such charged porous medium. The anomalous concentrations of the ions in the pore water of the bentonite are modeled with a modified Donnan model in which we account for the partition of the counterions between the Stern and Gouy-Chapman layers. This is accomplished using an electric triple layer (TLM) model combined with an explicit complexation model at the mineral/water interface. The porosity entering into the determination of the formation factor of the medium is an effective porosity obtained by removing the fraction of hydration water covering the surface of the clay minerals. We investigate two different cases of diffusion. In the first case, we consider a salinity gradient between two reservoirs in contact with a cylindrical sample of bentonite. The model predicts an increase of the diffusivity of the salt with the salinity of the solution in contact with the bentonite in agreement with experimental data. In the second case, we analyze a self-diffusion experiment of an ionic tracer. The model predicts an increase of the diffusivity of anions with the effective porosity and with the ionic strength. This is also in good agreement with experimental data.