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

Zhao, Huaiyan; Feng, Xionghan; Lee, Sungsik; Reinhart, Benjamin; Elzinga, Evert J.

doi:10.1016/j.chemgeo.2022.121281

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

Journal Article · Thu Dec 22 23:00:00 EST 2022 · Chemical Geology

DOI:https://doi.org/10.1016/j.chemgeo.2022.121281· OSTI ID:2406041

Zhao, Huaiyan ^[1]; Feng, Xionghan ^[2]; Lee, Sungsik ^[3]; Reinhart, Benjamin ^[3]; Elzinga, Evert J. ^[4]

Rutgers University, Newark, NJ (United States); Huazhong Agricultural University, Wuhan (China); Anhui Agricultural University, Hefei (China)
Huazhong Agricultural University, Wuhan (China)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Rutgers University, Newark, NJ (United States)

The sorption of aqueous Mn(II) (1 mM) and Co(II) (50 and 200 μM) 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 experiments 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 μM) 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 μM), 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 solution. 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. Finally, the results of this work demonstrate that aqueous Mn(II) may significantly affect the reactivity of phyllomanganate sorbents towards dissolved Co(II), and therefore impact the speciation and solubility of this trace metal in anoxic and suboxic geochemical environments.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2406041

Journal Information:: Chemical Geology, Journal Name: Chemical Geology Vol. 618; ISSN 0009-2541

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Sorption and oxidation of Co(II) at the surface of birnessite: Impacts of aqueous Mn(II)

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