Kinetics of selenite interactions with Boom Clay: adsorption-reduction interplay

The speciation of selenium (Se) in clay-rich host rocks is important within the framework of geological disposal of radioactive waste since it affects its migration. Removal of selenite from solution can occur by reduction and adsorption. Adsorption could potentially inhibit or delay reduction. Here, the interplay of adsorption and reduction of selenite was investigated in batch experiments with Boom Clay (BC) and its separated size fractions. In all experiments, dissolved Se concentrations (Seaq) showed a fast initial decrease which was followed by a slower decline until removal was almost complete. X-ray absorption spectroscopy indicated that adsorption of selenite accounted for the fast removal of Seaq followed by slower selenite reduction. Eventually, almost all solid-bound SeIV became reduced to Se0 in all experiments. The progress of Seaq removal and SeIV reduction to Se0 could be described by a kinetic model involving reversible adsorption on clay minerals and reduction by pyrite. This implies that reduction of SeIV to Se0 is not significantly hindered or delayed by SeIV adsorption on clay minerals. Pyrite is likely the most relevant reductant for SeIV in BC although reduction by FeII structurally bound in clay minerals might provide an additional pathway for selenite reduction in clay rocks.