Water and ion diffusion in partially-water saturated compacted kaolinite: Role played by vapor-phase diffusion in water mobility.

Diffusion is the main transport process of water and solutes in clay-rich porous media owing to their very low permeability, so they are widely used as barriers against contaminant spreading. However, the prediction of contaminant mobility can be very complicated when these media are partially water-saturated. We conducted diffusion experiments for water (HTO and HDO) and ions (Na and I) through partially water saturated compacted kaolinite, a weakly charged clay material, to quantify the distinct diffusive behavior of these species. The osmosis method was used to set kaolinite samples at 67, 86 and 100% saturation. The results showed that desaturation led to a sharp decrease in diffusive rates by factors of 6.5, 18 and 35 for HTO, I and Na, respectively, from 100 to 67% of the degree of saturation. Thus, to interpret water diffusivities, we proposed a model taking into account the diffusion of water in both gas and liquid phases, using diffusion data obtained for ions, considered as inert species. This model was capable of properly predicting water diffusive flux, especially at a low degree of saturation (67% saturation), for which the assumption made for the occurrence of air phase continuity throughout the sample appears to be more relevant than at 86% saturation.