Diffusion of U(VI) in Opalinus Clay: Influence of temperature and humic acid

Abstract

The diffusion of U(VI) (c0=1×10−6mol/L) in compacted Opalinus Clay from the Mont Terri underground laboratory, Switzerland, was studied in the absence and presence of humic acid (10mg/L) at two different temperatures (25°C, 60°C) under anaerobic conditions. As background electrolyte synthetic Opalinus Clay pore water (pH 7.6, I=0.36mol/L) was used. The diffusion-accessible porosity, ε, was determined for each Opalinus Clay bore core sample by through-diffusion experiments with tritiated water (HTO) before the U(VI) diffusion experiments were carried out. The values for the effective diffusion and distribution coefficients De and Kd obtained for U(VI) and humic acid at 25°C as well as at 60°C showed that humic acid has no significant influence on the U(VI) diffusion. The diffusion profiles of humic acid in Opalinus Clay at 25 and 60°C indicate the contributions of two different humic acid particle size fractions (<1kDa and 10–100kDa). The small-sized humic acid fraction diffused through the whole Opalinus Clay samples at both temperatures within the 3 month duration of the U(VI) diffusion experiments. At 60°C, diffusion profiles of two different U(VI) species were observed. In a separate experiment the U(VI) speciation in the source reservoir solution at 60°C was analyzed by laser-induced fluorescence spectroscopy, photon correlation spectroscopy and scanning electron microscopy with an energy dispersive X-ray detector. The two diffusion profiles could be attributed to an unknown colloidal and a known aquatic U(VI) species (Ca2UO2(CO3)3(aq)). The diffusion results showed that the interaction of U(VI) and of the large-sized humic acid colloid fraction with the clay is stronger at 60°C. An increase of Kd from 0.025±0.003m3/kg at 25°C to 0.25±0.05m3/kg for U(VI)colloidal at 60°C was determined. In addition, the value for De of U(VI) increased with increasing temperature. Using the De values at 25 and 60°C, a preliminary activation energy for the diffusion of U(VI) through Opalinus Clay of 10kJ/mol was calculated. The observed increased Kd and De values for U(VI)aqueous at 60°C compensated each other to almost equal values of the apparent diffusion coefficient Da at 25 and 60°C. Hence, an elevated temperature of 60°C does not impact the migration of U(VI) through OPA significantly.