Influence of geochemical parameters on the sorption and desorption behaviour of europium and gadolinium onto kaolinite

Abstract

In this study we investigated the sorption and desorption behaviour of europium and gadolinium (homologues of the actinides americium and curium) onto the clay mineral kaolinite KGa-1b. In the model system metal/kaolinite, sorption isotherms and pH-edges were determined in different batch experiments. Calcium and magnesium as competing cations were used to simulate the influence of water hardness on the sorption and desorption processes. After centrifugation, the free metal ions in the supernatant solution were analysed by ICP-MS. With increasing lanthanide concentration, especially the relative desorption of these metals from kaolinite rises significantly before the cation exchange capacity (CEC) of 0.94 meq per 100 g is reached. This indicates that low lanthanide concentrations will result in a relatively lower metal migration due to sorption reactions at higher active sites in comparison with higher lanthanide concentrations. The K_d-values and sorption isotherms of Eu(III) and Gd(III) were determined at pH 5.0 (±0.02) and analysed with Freundlich and Langmuir sorption models. The experimental data can best be fitted by Langmuir sorption isotherm. The pH-value has only a minor influence on the sorption onto kaolinite. Only at low pH-values (<pH 4), relevant changes in migration behaviour have to be expected. One important influence factor on lanthanide sorption found in our study is naturally occurring competing cations such as alkaline earth metals. With Ca and Mg concentrations close to those found in nature, lanthanide sorption decreases dramatically. Desorption experiments show that after four consecutive equilibration steps, nearly all the lanthanide has been mobilised from kaolinite to the aquifer.