Simultaneous Removal of Selenite and Selenate by Nanosized Zerovalent Iron in Anoxic Systems: The Overlooked Role of Selenite.

The application of nanosized zerovalent iron (nZVI) for reductive immobilization of selenite (Se(IV)) or selenate (Se(VI)) alone has been extensively investigated. However, as the predominant species, Se(IV) and Se(VI) usually coexist in the environment. Thus, it is essential to remove both species simultaneously in the solution by nZVI. Negligible Se(VI) removal (∼7%) by nZVI was observed in the absence of Se(IV). In contrast, the Se(VI) was completely removed in the presence of Se(IV), and the removal rate and electron selectivity of Se(VI) increased from 0.12 ± 0.01 to 0.29 ± 0.02 h-1 and from 1% to 4.5%, respectively, as the Se(IV) concentration increased from 0.05 to 0.20 mM. Se(IV) was rapidly removed by nZVI, and Se(VI) exerted minor influence on Se(IV) removal. Se(IV) promoted the generation of corrosion products that were mainly composed of magnetite (26%) and lepidocrocite (67%) based on the Fe K-edge XANES spectra and k3-weighted EXAFS analysis. Fe(II) released during the Se(IV) reduction was not the main reductant for Se(VI) but accelerated the transformation of F(0) to magnetite and lepidocrocite. The formation of lepidocrocite contributed to the enrichment of Se(VI) on the nZVI surface, and magnetite promoted electron transfer from Fe(0) to Se(VI). This study demonstrated that Se(IV) acted as an oxidant to activate nZVI, thus improving the reactivity of nZVI toward Se(VI), which displays a potential application of nZVI in the remediation of Se(IV)- and Se(VI)-containing water.