Trivalent manganese on vacancies triggers rapid transformation of layered to tunneled manganese oxides (TMOs): Implications for occurrence of TMOs in low-temperature environment

Yang, Peng; Lee, Seungyeol; Post, Jeffrey E.; Xu, Huifang; Wang, Qian; Xu, Wenqian; Zhu, Mengqiang

doi:10.1016/j.gca.2018.08.014

Trivalent manganese on vacancies triggers rapid transformation of layered to tunneled manganese oxides (TMOs): Implications for occurrence of TMOs in low-temperature environment

Journal Article · Tue Aug 14 00:00:00 EDT 2018 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2018.08.014· OSTI ID:1487031

Yang, Peng ^[1]; Lee, Seungyeol ^[2]; Post, Jeffrey E. ^[3]; Xu, Huifang ^[2]; Wang, Qian ^[1]; Xu, Wenqian ^[4]; Zhu, Mengqiang ^[1]

Univ. of Wyoming, Laramie, WY (United States)
Univ. of Wisconsin-Madison, Madison, WI (United States)
Smithsonian Institution, Washington, D.C. (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Tunneled Mn oxides (TMOs) are common minerals in natural environment, particularly in ferromanganese nodules of oceanic and lake sediments. Their structures host a considerable amount of transition and rare earth metals, thus mediating metal cycling and bearing potential economic interest for exploiting these metals. TMOs form through topotactic transformation of layered Mn oxides (LMOs), such as vernadite, in natural environment. Trivalent Mn (Mn(III)) in the LMO structure is a critical player in the transformation, and the transformation is believed to be extremely slow at room temperature. However, the specific role of Mn(III) and its impacts on the transformation kinetics remains unknown. In the present study, we show that the formation of Mn(III) on vacancies of an LMO is the initial transformation step leading to TMOs, and that the transformation can be rapid at room temperature and circumneutral pH. Specifically, after pre–adsorbed with Mn(II) on vacancies at pH 4, δ–MnO₂, a hexagonal birnessite analogous to vernadite, starts to transform to a 4 × 4 TMO at 1 h upon incubation at pH 7 and 21 °C under anoxic conditions. The rapid transformation is triggered by the comproportionation reaction between the vacancy-adsorbed Mn(II) and Mn(IV) in δ-MnO₂ that produces Mn(III) on the vacancies. Such intermediate Mn(III)-rich product acts as a precursor for subsequent rapid structural rearrangement to form tunnels. An incubation at lower or higher pH retards the transformation due to an insufficient amount of Mn(III) (pH 6) or the formation of triclinic birnessite (pH 8) as an intermediate product. The presence of O₂ favors the formation of triclinic birnessite at pH 8 and thus retards the transformation whereas O₂ enhances production of Mn(III)–rich hexagonal birnessite at pH 6 and 7 and promotes the transformation. We propose a novel transformation mechanism of LMOs to TMOs, highlighting the role of vacancy–adsorbed Mn(III) in the transformation. Furthermore, this work changes our understanding of TMO formation kinetics and suggests TMOs can readily form in low-temperature redox-fluctuating environment, such as lake and oceanic sediments where Mn(II) often coexists with LMOs.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Wyoming, Laramie, WY (United States)

Sponsoring Organization:: National Aeronautic and Space Administration (NASA); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Experimental Program to Stimulate Competitive Research (EPSCoR)

Grant/Contract Number:: AC02-06CH11357; SC0016272

OSTI ID:: 1487031

Alternate ID(s):: OSTI ID: 1854157

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Journal Issue: C Vol. 240; ISSN 0016-7037

Publisher:: The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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