Arsenite sorption at the magnetite-water interface during aqueous precipitation of magnetite: EXAFS evidence for a new arsenite surface complex

The interaction of aqueous As(III) with magnetite during its precipitation from aqueous solution at neutral pH has been studied as a function of initial As/Fe ratio. Arsenite is sequestered via surface adsorption and surface precipitation reactions, which in turn influence the crystal growth of magnetite. Sorption samples were characterized using EXAFS spectroscopy at the As K-edge in combination with HRTEM observations, energy dispersive X-ray analysis at the nanoscale, electron energy loss spectroscopy at the Fe L₃-edge, and XRD-Rietveld analyses of reaction products. Our results show that As(III) forms predominantly tridentate hexanuclear As(III)O₃ complexes (³C), where the As(III)O₃ pyramids occupy vacant tetrahedral sites on {1 1 1} surfaces of magnetite particles. This is the first time such a tridentate surface complex has been observed for arsenic. This complex, with a dominant As-Fe distance of 3.53 ± 0.02 Å, occurs in all samples examined except the one with the highest As/Fe ratio (0.33). In addition, at the two highest As/Fe ratios (0.133 and 0.333) arsenite tends to form mononuclear edge-sharing As(III)O₃ species (²E) within a highly soluble amorphous As(III)-Fe(III,II)-containing precipitate. At the two lowest As/Fe ratios (0.007 and 0.033), our results indicate the presence of additional As(III) species with a dominant As-Fe distance of 3.30 ± 0.02 Å, for which a possible structural model is proposed. The tridentate ³C As(III)O₃ complexes on the {1 1 1} magnetite surface, together with this additional As(III) species, dramatically lower the solubility of arsenite in the anoxic model systems studied. They may thus play an important role in lowering arsenite solubility in putative magnetite-based water treatment processes, as well as in natural iron-rich anoxic media, especially during the reductive dissolution-precipitation of iron minerals in anoxic environments.