Sorption and oxidation of Co(II) at the surface of birnessite: Impacts of aqueous Mn(II)

The sorption of aqueous Mn(II) (1 mM) and Co(II) (50 and 200 mu M) onto hexagonal birnessite (0.1 g L-1) was studied under anoxic conditions at pH 6.5 and 7.5 in binary and ternary experiments using batch kinetic ex-periments and XRD, ATR-FTIR, and Co K-edge EXAFS analyses. In the binary systems, sorption of Co(II) was accompanied by partial oxidation to Co(III) yielding a mixture of corner-sharing Co(II) and edge-sharing Co(III) complexes at both pH values, while Mn(II)-birnessite interaction resulted in coordination of Mn(II/III) at layer vacancy sites at pH 6.5, and led to reductive transformation of birnessite into feitknechtite at pH 7.5. In the ternary systems, strong mutual interferences between Co(II) and Mn(II) co-sorbates reduced the rate and extent of sorption relative to the binary experiments. The introduction of Mn(II)aq into the high-Co systems (200 mu M) halted the slow sorption of Co(II) that was attributed to the incorporation of Co(III) into layer vacancies, while Co (II)aq prevented Mn(II)-driven transformation of birnessite into feitknechtite at pH 7.5. In the low-Co system (50 mu M), reductive transformation of birnessite by Mn(II)aq at pH 7.5 produced Co(II)-substituted feitknechtite, a conversion that was accompanied by reduction of sorbed Co(III) to Co(II) which was partially released to so-lution. The strong effects of co-sorption are attributed to the similarity in sorption mechanisms of Co(II) and Mn (II), which both sorb as a mixture of di-and trivalent species. The results of this work demonstrate that aqueous Mn(II) may significantly affect the reactivity of phyllomanganate sorbents towards dissolved Co(II), and there-fore impact the speciation and solubility of this trace metal in anoxic and suboxic geochemical environments.

Automated summary

This study investigated the sorption of aqueous Mn(II) and Co(II) onto hexagonal birnessite under anoxic conditions. The results showed that the co-sorption of Mn(II) and Co(II) led to reduced sorption rates and extent. The presence of Mn(II) affected the transformation of birnessite and the speciation of Co(II). These findings indicate the significant impact of aqueous Mn(II) on the reactivity and solubility of Co(II) in geochemical environments.