Arsenic sorption to nanoparticulate mackinawite (FeS): An examination of phosphate competition

Nanoparticulate mackinawite (FeS) can be an important host-phase for arsenic (As) in sulfidic, subsurface environments. Although not previously investigated, phosphate (PO₄³⁻) may compete with As for available sorption sites on FeS, thereby enhancing As mobility in FeS-bearing soils, sediments and groundwater systems. In this study, we examine the effect of PO₄³⁻ on sorption of arsenate (As(V)) and arsenite (As(III)) to nanoparticulate FeS at pH 6, 7 and 9. Results show that PO₄³⁻ (at 0.01–1.0 mM P) did not significantly affect sorption of either As(V) or As(III) to nanoparticulate FeS at initial aqueous As concentrations ranging from 0.01 to 1.0 mM. At pH 9 and 7, sorption of both As(III) and As(V) to nanoparticulate FeS was similar, with distribution coefficient (K_d) values spanning 0.76–15 L g⁻¹ (which corresponds to removal of 87–98% of initial aqueous As(III) and As(V) concentrations). Conversely, at pH 6, the sorption of As(III) was characterized by substantially higher K_d values (6.3–93.4 L g⁻¹) than those for As(V) (K_d = 0.21–0.96 L g⁻¹). Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy indicated that up to 52% of the added As(V) was reduced to As(III) in As(V) sorption experiments, as well as the formation of minor amounts of an As₂S₃-like species. In As(III) sorption experiments, XANES spectroscopy also demonstrated the formation of an As₂S₃-like species and the partial oxidation of As(III) to As(V) (despite the strictly O₂-free experimental conditions). Overall, the XANES data indicate that As sorption to nanoparticulate FeS involves several redox transformations and various sorbed species, which display a complex dependency on pH and As loading but that are not influenced by the co-occurrence of PO₄³⁻. This study shows that nanoparticulate FeS can help to immobilize As(III) and As(V) in sulfidic subsurface environments where As co-exists with PO₄³⁻. - Highlights: • A competitive effect of PO₄³⁻ was examined on sorption of As(V) and As(III) to nanoparticulate FeS. • PO₄³⁻ did not affect sorption of either As(V) or As(III) to nanoparticulate FeS at pH 6, 7 and 9. • XANES spectroscopy indicated the involvement of several As redox transformations and formation of sorbed species. • Nanoparticulate FeS immobilized 99% As in sulfidic reduced environments, in the presence of PO₄³⁻. - Our findings reveal that the nanoparticulate FeS can remove As(III) and As(V) in reduced sulfidic environments in the presence of PO₄³⁻.