Impacts of Aqueous Mn(II) on the Sorption of Zn(II) by Hexagonal Birnessite

We used a combination of batch studies and spectroscopic analyses to assess the impacts of aqueous Mn(II) on the solubility and speciation of Zn(II) in anoxic suspensions of hexagonal birnessite at pH 6.5 and 7.5. Introduction of aqueous Mn(II) into pre-equilibrated Zn(II)-birnessite suspensions leads to desorption of Zn(II) at pH 6.5, but enhances Zn(II) sorption at pH 7.5. XAS results show that Zn(II) adsorbs as tetrahedral and octahedral triple-corner-sharing complexes at layer vacancy sites when reacted with birnessite in the absence of Mn(II). Addition of aqueous Mn(II) causes no discernible change in Zn(II) surface speciation at pH 6.5, but triggers conversion of adsorbed Zn(II) into spinel Zn(II)1-xMn(II)xMn(III)2O4 precipitates at pH 7.5. This conversion is driven by electron transfer from adsorbed Mn(II) to structural Mn(IV) generating Mn(III) surface species that coprecipitate with Zn(II) and Mn(II). Our results demonstrate substantial production of these reactive Mn(III) surface species within 30 min of contact of the birnessite substrate with aqueous Mn(II). Their importance as a control on the sorption and redox reactivity of Mn-oxides toward Zn(II) and other trace metal(loid)s in environments undergoing biogeochemical manganese redox cycling requires further study.