Diffusion mechanism of sodium ions in compacted montmorillonite under different NaCl concentration

Compacted bentonite, the major mineral being montmorillonite, is a candidate buffer material for geological disposal of high-level radioactive waste. The diffusion behavior of radionuclides in the compacted montmorillonite is an important issue to be clarified for the safety assessment of geological disposal. In this study, one-dimensional, non-steady diffusion experiments using 22Na at different diffusion temperatures and the measurement of the basal spacings by XRD were conducted for Na-montmorillonite saturated with NaCl solutions of different concentrations. Some basal spacings of the montmorillonite were found to decrease from 1.88 to 1.56 nm as the NaCl concentration increased from 0 to 0.1 M. The apparent self-diffusion coefficients at 298 K obtained in this study slightly increased as the NaCl concentration increased from 0 to 0.5 M, while the activation energies, calculated from the temperature dependences of the diffusion coefficients, were found to be 14, 22, and 17 kJ mol−1 at NaCl concentrations of 0, 0.1, and 0.5 M, respectively. These NaCl concentration dependences of the diffusion coefficients and their activation energies can be explained by assuming three independent diffusion processes (diffusion in pore water, on external surface of montmorillonite, and in interlayer of montmorillonite).