Improved interpretation of in-diffusion measurements with confined swelling clays

Diffusion is considered the principal transport mechanism of radio-nuclides and other low-molecular-weight pollutants in compacted clays used as barriers at various disposal and storage sites, for example, at projected deep repositories for radioactive waste. Porous filters are routinely used to confine swelling clays in diffusion studies of radio-tracers. The presence of the filter gives rise to considerable mass-transfer limitations at the clay boundary that result in erroneous diffusion parameters. We have solved the problem of in-diffusion with due account for this phenomenon by means of Fourier transforms. By using literature data on the in-diffusion of traces of radioactive cesium in an argillaceous rock (Opalinus clay) and a compacted bentonite (FEBEX bentonite), we have demonstrated that taking into account the mass-transfer limitations considerably improves the quality of the theoretical fit of the time evolution of radio-tracer concentration in the reservoir. Besides that, we have shown that ignoring the mass-transfer limitations leads to a noticeable underestimation of both the effective diffusion coefficient and the specific sorption capacity of the clay.