Mechanism analysis of selenium (VI) immobilization using alkaline-earth metal oxides and ferrous salt

The immobilization of selenate (SeO₄^2-) using metal oxides (CaO and MgO) and ferrous salt as the immobilization reagents were examined by the leaching test and solid-phase analysis via XRD, XAFS, TGA, and XPS. The results indicated that nearly all of SeO₄^2- was reduced to SeO₃^2- in the CaO-based reaction within 7 days. Then, the generated SeO₃^2- was mainly sorbed onto the iron-based minerals (Fe₂O₃ and FeOOH) through the formation of both bidentate mononuclear edge-sharing (¹E) and monodentate mononuclear corner-sharing (¹V) inner-sphere surface complexes, suggested by PHREEQC simulation and EXAFS analysis. Differently, less amount of SeO₄^2- (approximately 45.50%) was reduced to SeO₃^2- for the MgO-based reaction. However, if the curing time increases to a longer time (more than 7 days), the further reduction could occur because there are still Fe(II) species in the matrix. As for the associations of Se in the solid residue, most of the selenium (SeO₃^2- and SeO₄^2-) was preferentially distributed onto the Mg(OH)₂ through outer-sphere adsorption. Definitely, this research can provide a deep understanding of the immobilization of selenium using alkaline-earth metal oxide related materials and ferrous substances.