Anion Diffusion in Compacted Clays by Pore‐Scale Simulation and Experiments

Accurate understanding of diffusion of anionic radionuclides in different clays is significant to predict long‐term performance of high‐level radioactive waste (HLW) repositories. The importance of electrical double layer (EDL) on anionic tracer diffusion in different clays has been studied by both through‐diffusion experiments and pore‐scale simulations in this work. The through‐diffusion experiments measured the effective diffusion coefficient and the accessible porosity of Re (VII) in compacted montmorillonite, Na‐bentonite, and illite/smectite mixed layer (I/S) at different salinities. The results showed that the accessible porosity and the effective diffusion coefficient of Re (VII) in montmorillonite and Na‐bentonite were similar but lower than those in I/S under the same conditions. For mechanism analysis and predictions, a pore‐scale modeling was implemented to simulate the diffusion of anions in compacted clays. In the simulations, the characteristics (porosity, density, and total surface area) of microstructures of montmorillonite and I/S were used to regenerate three‐dimensional pore structures numerically by a Quartet Structure Generation Set method. The Re (VII) diffusion was then simulated by directly solving coupled Poisson‐Nernst‐Planck equations via the lattice Boltzmann method. The diminished effect of EDL was therefore calculated and compared with Donnan and multiporosity models. As EDLs overlap in compacted clays, the Donnan model overestimates the influence of EDL on Re (VII) diffusion, while the multiporosity model underestimates it. The pore‐scale modeling, which captures the structure of overlapping EDLs automatically, can simulate the diffusion of anionic radionuclides in compacted clays without any fitting parameters. Key Points A method to link through‐diffusion experiments and a pore‐scale modeling Prediction of Re (VII) diffusion in montmorillonite, Na‐bentonite, and illite/smectite mixed layer Effect of the electrical double layer on Re (VII) diffusion in illite/smectite mixed layer decreases compared with that in montmorillonite