Dissolution and phase transformation processes of hausmannite in acidic aqueous systems under anoxic conditions

Luo, Yao; Tan, Wenfeng; Suib, Steven L.; Qiu, Guohong; Liu, Fan

doi:10.1016/j.chemgeo.2018.04.016

Dissolution and phase transformation processes of hausmannite in acidic aqueous systems under anoxic conditions

Journal Article · Sun Apr 15 00:00:00 EDT 2018 · Chemical Geology

DOI:https://doi.org/10.1016/j.chemgeo.2018.04.016· OSTI ID:1597865

Luo, Yao ^[1]; Tan, Wenfeng ^[2]; Suib, Steven L. ^[3]; ^[2]; Liu, Fan ^[2]

Huazhong Agricultural Univ., Hubei Province (China); Univ of Connecticut
Huazhong Agricultural Univ., Hubei Province (China)
Univ. of Connecticut, Storrs, CT (United States)

Hausmannite is the most widely distributed spinel-structured manganese oxide in soils and sediments. The transformation of this metastable manganese oxide to Mn(IV) oxides with higher adsorption capacity has attracted much research interest, while the transformation mechanisms and influencing factors still remain largely unknown, especially under acidic condition. In this work, the transformation processes of hausmannite at different pH values and the influence of cations were studied. Results indicated that hausmannite was transformed into manganite at pH 5.0–9.0. The dissolution of hausmannite was initiated and promoted by protons (≤ 7.0), and the decrease of pH accelerated its conversion to Mn(IV) oxides. The tunnel-structured Mn(IV) oxide was generated via two steps during the dissolution process of hausmannite at pH ≤ 3.0. Hausmannite was disproportionated to δ-MnO₂ at first, which was then transformed to nsutite in the presence of Na⁺ and H⁺ through the transfer of electrons from adsorbed Mn(II) to structural Mn(IV). The disproportionation of hausmannite to δ-MnO₂ was not affected by other cations, while the presence of K⁺ promoted the further transformation of δ-MnO₂ to cryptomelane. The structural rearrangement process of δ-MnO₂ was the rate-determining step for the formation of final products. Finally, this work expands the understanding of the formation, transformation and geochemical processes of manganese oxides in supergene environments.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Connecticut, Storrs, CT (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Natural Science Foundation of China; National Key Research and Development Program of China; Fok Ying-Tong Education Foundation

Grant/Contract Number:: FG02-86ER13622

OSTI ID:: 1597865

Alternate ID(s):: OSTI ID: 1538096

Journal Information:: Chemical Geology, Journal Name: Chemical Geology Journal Issue: C Vol. 487; ISSN 0009-2541

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Dissolution and phase transformation processes of hausmannite in acidic aqueous systems under anoxic conditions

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