Building the bridge between U(VI) and Ca-bentonite : Influence of concentration, ionic strength, pH, clay composition and competing ions

Abstract

In the context of a high-level nuclear waste disposal, the retention of U(VI) on non-pre-treated Ca-bentonite as potential technical barrier is studied. The objective of this study is to reveal the retention behaviour of U(VI) under extreme geochemical conditions, such as hyperalkaline pH range as well as high salinity at the same time, and taking into account other relevant parameters. This should lead to a better understanding of necessary safety precautions for avoiding a release of U(VI) in the environment. Batch experiments were conducted to determine the influence of the initial U(VI) concentration, salinity, pH value, clay composition and the presence of other elements (Ca(II), I−, Cs(I), Eu(III)). After the sorption experiments, the remaining U(VI) concentration in solution was determined via mass spectrometry with inductively coupled plasma. U(VI) can be immobilised from 10% to 100% under all investigated conditions. Precipitation plays a role in the U(VI) retention but only at higher concentrations (≥10−5 mol L−1). The retention is reversible especially with decreasing pH (<10.5) as the aquo complex Ca2UO2(CO3)3(aq) is formed. Ca(II) strongly enhances the U(VI) adsorption onto Ca-bentonite in the hyperalkaline pH range, probably due to the formation of Ca(II)-bridges. The best retention could be observed on natural bentonite compared to pure montmorillonite and altered bentonite. From a waste cocktail containing important elements of the repository inventory (Cs(I), Eu(III), U(VI) and iodide), only Eu(III) as homologous element to trivalent actinoids competes with U(VI) for binding sites, especially at low metal concentrations, but also facilitates the precipitation at higher concentrations.