The role of diffusion induced electro-osmosis in the coupling between hydraulic and ionic fluxes through semipermeable clay soils

Most of the experimental research conducted to date has provided evidence on the semipermeable membrane behaviour of smectite-rich clay soils, the extent of which is typically quantified through the reflection coefficient, when the permeant (electrolyte) solution contains a single monovalent or divalent salt. Under such conditions, the osmotic flow of solution is controlled to a great extent by the different accessibility of ions and water molecules to the soil porosity, which is referred to as the chemico-osmotic effect. However, theoretical simulations of coupled solute and solvent transport suggest that, when two or more cations that diffuse in water at different rates are present simultaneously in the permeant solution, the electro-osmotic effect, which stems from the condition of null electric current density through the porous medium, can be enhanced compared to the case of a single salt to such an extent that it becomes comparable to or even greater than the chemico-osmotic effect. An original closed-form analytical solution to the problem of calculating the diffusion potential, which in turn controls the magnitude of the electro-osmotic effect, is here illustrated, and the relative importance of the aforementioned contributions to multi-electrolyte systems is examined through the interpretation of laboratory test results from the literature pertaining to a bentonite amended clay soil in equilibrium with aqueous mixtures of potassium chloride (KCl) and hydrochloric acid (HCl). The proposed mechanistic model is shown to be able to quantitatively capture the impact of both chemico-osmosis and electro-osmosis on the measured reflection coefficient of smectite clays, thereby breaking new ground in the experimental and theoretical research on the osmotic properties of engineered clay barriers in contact with mixed aqueous electrolyte solutions.