Competing Sorption of Se(IV) and Se(VI) on Schwertmannite

Schwertmannite (SHM) is a naturally occurring mineral that has been shown to effectively scavenge oxyanions from contaminated water. In this study, Fourier-transform infrared spectroscopy and X-ray absorption spectroscopy techniques in combination with wet-chemical techniques were used to study the competitive sorption of Se(IV) and Se(VI) at pH3. The experiments were conducted with three types of schwertmannite obtained from oxidative synthesis, biogenic synthesis and high-pressure compaction at different initial Se concentrations and mixing ratios for 48 h and 56 days, respectively. A threshold value for the uptake mechanisms was identified, which reflects the amount of easily exchangeable sulphate (similar to 0.5 mmol/g). At adsorbate concentrations below this threshold, an inner-sphere corner-sharing bidentate binuclear complex forms upon exchange with sulphate. At higher concentrations, both oxyanions become bound to SHM through co-occurrence of mainly inner-sphere and partly outer-sphere corner-sharing bidentate binuclear complexes with Fe(III) containing surface sites. Single species experiments clearly indicate a higher affinity of SHM for Se(IV). However, in mixed species experiments, competitive sorption occurs with equal or even preferential uptake of Se(VI) at concentrations much lower than the threshold value, presumably due to geometrical similarity between selenate and sulphate, and increasing preference for Se(IV) at high Se concentrations.