The Role of Reduced Surface Sulfur Species in the Removal of Se(VI) by Sulfidized Nano Zero-Valent Iron

Titelangaben

Peiffer, Stefan ; Mohanraj, John ; Hockmann, Kerstin ; Göttlicher, Jörg ; Thelakkat, Mukundan ; Marouane, Bouchra:
The Role of Reduced Surface Sulfur Species in the Removal of Se(VI) by Sulfidized Nano Zero-Valent Iron.
In: Minerals. Bd. 16 (2026) Heft 1 . - 68.
ISSN 2075-163X
DOI: https://doi.org/10.3390/min16010068

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Abstract

Sulfidized nano zero-valent iron (S-nZVI) particles are known to stimulate the reductive removal of various oxyanions due to enhanced electron selectivity and electron conductivity between the Fe(0) core and the target compound. Sulfidation creates a number of reactive sulfur species, the role of which has not yet been investigated in the context of S-nZVI. In this study, we investigated the contribution of reactive sulfur species to Se(VI) reduction by S-nZVI at different molar S/Fe ratios (0, 0.1 and 0.6) and Se(VI) concentrations (0, 5 and 50 mg L−1). In the presence of S-nZVI, the rate of reduction was accelerated by a factor of up to ten. X-ray Absorption Near-Edge Structure (XANES) spectroscopy and surface-sensitive X-ray photoelectron spectroscopy (XPS) identified Se(0) as the predominant reduction product (~90%). The reduction reaction was accompanied by a loss of FeS and the formation of surface-bound Fe(II) polysulfide (FeSx) and S(0) species. Likewise, wet chemical extraction techniques suggested a direct involvement of acid volatile sulfide (AVS) species (surface-bound FeS) in the reduction of Se(IV) to Se(0) and formation of S(0). Mass balance estimates reveal that between 9 and 15% of the conversion of Se(0) originates from oxidation of FeS to FeSx. From these findings, we propose that surface-bound Fe sulfide species are important but previously overlooked reactants contributing to the reduction of oxyanions associated with S-nZVI particles, as well as in natural environments undergoing sulfidation reactions.