Trivalent lanthanide sorption onto illite in the presence of carbonate: A study combining thermodynamic sorption modeling, time-resolved laser fluorescence spectroscopy, and parallel factor analysis

Abstract

Formation of aqueous actinide complexes with dissolved inorganic carbon (DIC) in groundwater decreases the sorption of actinides onto clay minerals in a geological disposal environment. Hence, the effect of DIC on actinide sorption must be evaluated quantitatively. In this study, batch sorption experiments using Eu(III) and Sm(III) as the chemical analogs of trivalent actinides were performed to assess their sorption behavior onto illite in the presence of DIC. In the studied pH region between 8.4 and 11, the sorption was significantly lower in the presence of DIC, with the largest effect being observed at pH 9–10. The effect increased with increasing DIC from 10 to 50 mM. A thermodynamic sorption model (TSM) was used to evaluate the results of batch sorption experiments. The experimental results can only be predicted when ternary-surface complexes with carbonate ions are considered. Moreover, information on the chemical forms of sorbed Eu on illite was obtained via time-resolved laser fluorescence spectroscopy (TRLFS) measurements. Parallel factor analysis of TRLFS data indicated the presence of two chemical species of Eu. These chemical species exhibited pH dependence, which is consistent with that of the surface species predicted using the TSM. In the presence of DIC, the dominant chemical species showed a long fluorescence lifetime and was inferred to coordinate with carbonate ions, supporting the validity of the TSM.