Heterogeneous reactions at the mineral-water interface are of paramount importance in controlling the transport of contaminants. Herein, antimony (Sb) adsorption and subsequent precipitation on Fe2O3 facets were explored to understand its partitioning mechanisms by multiple complementary techniques. Our extended X-ray absorption fine structure spectroscopy and density functional theory results provided a consensus on the local coordination environment of Sb(III) and Sb(V) on Fe2O3 facets. We observed that Sb adsorption and the following precipitation are associated with both Sb concentrations and Fe2O3 facets, and a change in the Sb surface-binding mode from edge-sharing to corner-sharing is preferred in precipitation. Fe2O3 facets determine Sb binding structures, resulting in a facet-dependent transformation of adsorption to precipitation. The preferred corner-sharing complexes on the {001} facet facilitated the formation of Sb2O3 and NaSb(OH)6 precipitates at a lower Sb concentration compared with other two {110} and {214} facets. In addition, the facet-specific binding configuration renders a heterogeneous epitaxial growth of Sb2O3. Our study provides a molecular understanding of facet effects on Sb adsorption and precipitation on minerals. 

Mechanistic Study for Antimony Adsorption and Precipitation on Hematite Facets

Mechanistic and modeling insights into the immobilization of Cd and organic carbon during abiotic transformation of ferrihydrite induced by Fe(II)

Manganese (Mn) oxides, such as birnessite (δ-MnO2), are ubiquitous mineral phases in soils and sediments that can interact strongly with antimony (Sb). The reaction between birnessite and aqueous Mn(II) can induce the formation of secondary Mn oxides. Here, we studied to what extent different loadings of antimonate (herein termed Sb(V)) sorbed to birnessite determine the products formed during Mn(II)-induced transformation (at pH 7.5) and corresponding changes in Sb behavior. In the presence of 10 mM Mn(II)aq, low Sb(V)aq (10 μmol L-1) triggered the transformation of birnessite to a feitknechtite (β-Mn(III)OOH) intermediary phase within 1 day, which further transformed into manganite (γ-Mn(III)OOH) over 30 days. Medium and high concentrations of Sb(V)aq (200 and 600 μmol L-1, respectively) led to the formation of manganite, hausmannite (Mn(II)Mn(III)2O4), and groutite (αMn(III)OOH). The reaction of Mn(II) with birnessite enhanced Sb(V)aq removal compared to Mn(II)-free treatments. Antimony K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that heterovalent substitution of Sb(V) for Mn(III) occurred within the secondary Mn oxides, which formed via the Mn(II)-induced transformation of Sb(V)-sorbed birnessite. Overall, Sb(V) strongly influenced the products of the Mn(II)-induced transformation of birnessite, which in turn attenuated Sb mobility via incorporation of Sb(V) within the secondary Mn oxide phases.

Antimonate Controls Manganese(II)-Induced Transformation of Birnessite at a Circumneutral pH

Antimony isotope fractionation during adsorption on aluminum oxides.

Chemical oxidation of As(III) by iron (Fe) oxyhydroxides has been proposed to occur under anoxic conditions and may play an important role in stabilization and detoxification of As in subsurface environments. However, this reaction remains controversial due to lack of direct evidence and poorly understood mechanisms. In this study, we show that As(III) oxidation can be facilitated by Fe oxyhydroxides (i.e., goethite) under anoxic conditions coupled with the reduction of structural Fe(III). An excellent electron balance between As(V) production and Fe(III) reduction is obtained. The formation of an active metastable Fe(III) phase at the defective surface of goethite due to atom exchange is responsible for the oxidation of As(III). Furthermore, the presence of defects (i.e., Fe vacancies) in goethite can noticeably enhance the electron transfer (ET) and atom exchange between the surface-bound Fe(II) and the structural Fe(III) resulting in a two time increase in As(III) oxidation. Atom exchange-induced regeneration of active goethite sites is likely to facilitate As(III) coordination and ET with structural Fe(III) based on electrochemical analysis and theoretical calculations showing that this reaction pathway is thermodynamically and kinetically favorable. Our findings highlight the synergetic effects of defects in the Fe crystal structure and Fe(II)-induced catalytic processes on anoxic As(III) oxidation, shedding a new light on As risk management in soils and subsurface environments.

Iron Vacancy Accelerates Fe(II)-Induced Anoxic As(III) Oxidation Coupled to Iron Reduction.

The environmental mobility of antimony (Sb) is controlled by interactions with iron (Fe) oxides, such as ferrihydrite. Under near-neutral pH conditions, Fe(II) catalyzes the transformation of ferrihydrite to more stable phases, thereby potentially altering the partitioning and speciation of associated Sb. Although largely unexplored, Sb itself may also influence ferrihydrite transformation pathways. Here, we investigated the impact of Sb on the Fe(II)-induced transformation of ferrihydrite at pH 7 across a range of Sb(V) loadings (Sb:Fe(III) molar ratios of 0, 0.003, 0.016, and 0.08). At low and medium Sb loadings, Fe(II) induced rapid transformation of ferrihydrite to goethite, with some lepidocrocite forming as an intermediate phase. In contrast, the highest Sb:Fe(III) ratio inhibited lepidocrocite formation, decreased the extent of goethite formation, and instead resulted in substantial formation of feroxyhyte, a rarely reported FeOOH polymorph. At all Sb loadings, the transformation of ferrihydrite was paralleled by a decrease in aqueous and phosphate-extractable Sb concentrations. Extended X-ray absorption fine structure spectroscopy showed that this Sb immobilization was attributable to incorporation of Sb into Fe(III) octahedral sites of the neo-formed minerals. Our results suggest that Fe oxide transformation pathways in Sb-contaminated systems may strongly differ from the well-known pathways under Sb-free conditions.

Sara Schlagenhauff

Papers

Impact of Antimony(V) on Iron(II)-Catalyzed Ferrihydrite Transformation Pathways: A Novel Mineral Switch for Feroxyhyte Formation.