Reductive Transformation of Birnessite by Aqueous Mn(II)

Reaction of aqueous Mn(II) with hexagonal birnessite at pH 7.5 causes reductive transformation of birnessite into feitknechtite (beta-Mn(III)OOH) and manganite (gamma-Mn(III)OOH) through interfacial electron transfer from adsorbed Mn(II) to structural Mn(IV) atoms and arrangement of product Mn(III) into MnOOH, summarized by Mn (II) + Mn(IV)O(2) + 2 H(2)O -> 2 Mn(III)OOH + 2 H(+). Feitknechtite is the initial transformation product, and subsequently converted into the more stable manganite polymorph during ongoing reaction with Mn(II). Feitknechtite production is observed at Mn(II) concentrations 2 orders of magnitude below thermodynamic thresholds, reflecting uncertainty in thermodynamic data of Mn-oxide minerals and/or specific interactions between Mn(II) and birnessite surface sites facilitating electron exchange. Under oxic conditions, feitknechtite formation through surface-catalyzed oxidation of Mn(H) by O(2) leads to additional Mn(II) removal from solution relative to anoxic systems. These results indicate that Mn(II) may be an important moderator of the reductive arm of Mn-oxide redox cycling, and. suggest a controlling role of Mn (II) in regulating the solubility and speciation of phyllomanganate-reactive metal pollutants including Co, Ni, As, and Cr in geochemical environments.