Uptake of actinides by calcium silicate hydrate (C-S-H) phases

The sorption of actinides (Th, U – Am) was studied in dependence of the solid-to-liquid (S/L) ratio (0.5–20.0 g/L) and the calcium-to-silicon (C:S) ratio. The C:S ratio was varied between 1.80 and 0.70 to simulate the changing composition of the C-S-H phases during cement degradation from high to low C:S ratios. The decrease of the calcium content in the C-S-H phases by time is accompanied by a decrease in pH in the corresponding suspensions from 12.6 to 10.2. X-ray photoelectron spectroscopy (XPS) of the C-S-H phases showed an increasing depletion of Ca on the surface with increasing C:S ratio in comparison to the composition of the solid phase as a whole.
The sorption experiments were performed with the redox stable species Am(III), Th(IV) and U(VI), as well as the redox sensitive Np(V) and Pu(III). The average distribution coefficients Rd for all investigated actinides are around 105 L/kg. The oxidation state of Pu retained by the C-S-H phases was investigated with high-energy resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy. Samples with C:S ratios of 0.75 and 1.65 showed that the initially added Pu(III) was oxidized to Pu(IV) in the course of the experiment.