Theoretical analysis of anion exclusion and diffusive transport through platy-clay soils

Diffusive transport through geosynthetic clay liners and engineered compacted clay landfill liners is the primary mechanism for mass transport from well-engineered modern landfills. For this reason, accurate estimates of diffusion coefficients for clay soils are essential for the design of engineered liner systems. A long-standing theoretical problem is the role of anion exclusion on the estimation of diffusion coefficients for ionic solutes migrating through charged porous media. This paper describes the steady-state solution of a fully coupled set of transport equations modeling ion movement through a permanently charged platy-clay soil. The microscale analysis takes into account the actual diffusion coefficient for each ion species, ion-pairing (as required by electroneutrality of the solution), as well as anion exclusion and cation inclusion, arising from the permanent charge on clay particles. To render the problem tractable, the theoretical analysis focuses on an extremely small two-dimensional unit cell in an ideal, saturated, two-phase porous medium. The analysis presented here is limited to a particular geometrical example, but this example is sufficiently general for characteristic behaviours of systems of this kind to be identified. Most importantly, new insight is gained into the mechanism of ion migration through a charged platy-clay soil. The numerical results obtained from this study show that the identification of macroscopic transport quantities such as effective diffusion coefficients and membrane potentials from diffusion cell tests using standard diffusion theory only hold for a specific system. While ion exclusion behaviours are often referred to in the literature, as far as the authors are aware there has been no previous detailed microscale analysis of their role in steady-state diffusion through a charged platy-clay soil