The microstructure of clays controls their transport properties. This is concluded from comparing microstructural parameter data with the hydraulic conductivity and the ion diffusive transport capacity. Illitic clays contain a number of interacting open voids with a high flow capacity while natural smectite-rich clays are more homogeneous with smaller voids and a lower hydraulic conductivity than illitic clays with the same density. Artificially prepared smectitic clays, like those proposed for embedding canisters with highly radioactive waste, have a higher conductivity than natural clays with the same smectite content because the microstructural homogeneity of the artificial clays is less good.

The anion diffusive transport capacity of smectite-rich clays with high density is much lower than that of clays with low density in contrast to the cation diffusive capacity. This is explained by using quantitative microstructural data.