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

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.