Diffusion of HTO, 36Cl and 22Na in the Mesozoic rocks of northern Switzerland: I. Effective diffusion coefficients and capacity factors across the heterogeneous sediment sequences

Argillaceous rocks are currently being examined worldwide as potential host rocks for repositories for radio-active waste and spent fuel due to their favourable characteristics such as the self-sealing ability or limited diffusive transport of fluids, solutes or gases. In this study, through-diffusion experiments focused on rock samples with different mineralogical compositions taken from deep boreholes in the Mesozoic rock sequence of northern Switzerland, to determine diffusion parameters of HTO, 36Cl- and 22Na+ perpendicular to the bedding plane. Both effective diffusion coefficients and accessible porosities were calculated from the data obtained. In the Opalinus Clay, the primary selected host rock of the repository, the effective diffusion coefficients (De) and accessible porosity values (epsilon) of the neutral species HTO within and across all study areas are relatively consistent (De = 8.8 +/- 1.9 x 10-12 m2 s- 1; epsilon = 0.12 +/- 0.02), indicating that the material can be considered homogeneous in terms of diffusion properties. Importantly, the chemical composition of the pore water has no effect on the values of the effective diffusion coefficients of HTO. On the other hand, the rocks above and below the Opalinus Clay, up to the next aquifer, consist of tight sedimentary units (carbonates, siliciclastics including argillaceous rocks) with a wider range of diffusion coefficients, indicating a higher level of heterogeneity. The diffusion coefficients of anions, such as 36Cl-, tend to be smaller due to anion exclusion effects, while those of cations, such as 22Na+, tend to be larger due to surface enhanced diffusion. The extent of these effects is largely determined by the composition of the pore water, and - in the case of cations - by the extent of sorption which depends also on the sorption capacity - indicated by the cation exchange capacity -of the solid. As a result, variations in the effective diffusion coefficient of 36Cl- and 22Na+ can be observed firstly between different rock types (i.e. composition, fabric), and secondly between the different study areas due to differences in the chemical composition of the pore waters in contact with the solid phase. Based on the analysis of around 130 samples, it has been observed that the diffusion coefficients of the Mesozoic units in northern Switzerland exhibit a significant correlation with the total clay content of the rocks. These findings pave the way for the establishment of a diffusion database for the relevant elements under consideration in the Swiss radioactive waste programme and the Safety Case.