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Pentavalent Uranium Enriched Mineral Surface under Electrochemically Controlled Reducing Environments

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    Pentavalent Uranium Enriched Mineral Surface under Electrochemically Controlled Reducing Environments
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    ACS Earth and Space Chemistry

    Cite this: ACS Earth Space Chem. 2022, 6, 5, 1204–1212
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    https://doi.org/10.1021/acsearthspacechem.1c00413
    Published March 18, 2022
    Copyright © 2022 American Chemical Society
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    Abstract

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    Redox reactions of uranium (U) in aqueous environments have important impacts on the mobility and isotopic fractionation of U in the geosphere. Pentavalent U as the cationic uranyl ion, UO2+, is rarely observed in naturally occurring samples because of its limited lifetime, but it may be an important intermediate state controlling the redox kinetics between hexavalent and tetravalent U. Increasing evidence has indicated that U(V) can be stabilized under laboratory conditions. Here, we showed that U(V) is the dominant species on the magnetite (Fe3O4) surface under reducing conditions controlled by electrochemical methods. Cyclic voltammetry reveals coupled redox peaks corresponding to the U(VI)O22+/U(V)O2+ one-electron redox reaction. Magnetite electrodes polarized at a series of potentials to reduce U(VI)O22+ were characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and Auger electron mapping. The results showed that up to twice the amount of U(V) to U(VI) was present on the magnetite surface. U(V) adopted a typical uranyl-type structure, and the U coverage on the magnetite surface increased with decreasing potentials. The formation of mixed-valence U(V)/U(VI) species on the surface of magnetite may hinder the U(V) disproportionation reaction, thereby eliminating the presence of tetravalent U. These results show that U(V) can exist over short time scales as the dominant U species on mineral surfaces under selected reducing conditions by the controlled polarization of a mineral electrode.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsearthspacechem.1c00413.

    • Cyclic voltammograms, calculated net charges, values of OCP, XPS spectra and fitting parameters, EXAFS data, and best fit values of the EXAFS data (PDF)

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    Cited By

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    This article is cited by 9 publications.

    1. Zezhen Pan, Luca Loreggian, Yvonne Roebbert, Barbora Bartova, Myrtille O. J. Y. Hunault, Stefan Weyer, Rizlan Bernier-Latmani. Pentavalent U Reactivity Impacts U Isotopic Fractionation during Reduction by Magnetite. Environmental Science & Technology 2024, 58 (15) , 6595-6604. https://doi.org/10.1021/acs.est.3c10324
    2. Takumi Yomogida, Daisuke Akiyama, Kazuki Ouchi, Yuta Kumagai, Kotaro Higashi, Yoshihiro Kitatsuji, Akira Kirishima, Naomi Kawamura, Yoshio Takahashi. Application of High-Energy-Resolution X-ray Absorption Spectroscopy at the U L3-Edge to Assess the U(V) Electronic Structure in FeUO4. Inorganic Chemistry 2022, 61 (50) , 20206-20210. https://doi.org/10.1021/acs.inorgchem.2c03208
    3. Noah Edward Jemison, Fernando H. Garzon, Stephen E. Cabaniss, Peter C. Lichtner, Angelica Benavidez, Elijah Jessop, José M. Cerrato. Effect of Organic Compounds and Copper on Chromium(VI) Reduction: Electrochemical Investigation of Electron Transfer Rates. ACS ES&T Water 2022, 2 (12) , 2471-2480. https://doi.org/10.1021/acsestwater.2c00309
    4. Nadine Kabengi, (Guest Editor)Udo Becker, (Guest Editor)Gordon E. Brown, Jr. (Guest Editor). Virtual Special Issue of ACS Earth and Space Chemistry in Honor of Prof. Michael F. Hochella, Jr.. ACS Earth and Space Chemistry 2022, 6 (9) , 2115-2117. https://doi.org/10.1021/acsearthspacechem.2c00250
    5. Eugene S. Ilton, Richard N. Collins, Cristiana L. Ciobanu, Nigel J. Cook, Max Verdugo-Ihl, Ashley D. Slattery, David J. Paterson, Sebastian T. Mergelsberg, Eric J. Bylaska, Kathy Ehrig. Pentavalent Uranium Incorporated in the Structure of Proterozoic Hematite. Environmental Science & Technology 2022, 56 (16) , 11857-11864. https://doi.org/10.1021/acs.est.2c02113
    6. Yi Yu, Yucheng Hao, Bin Xiao, Eike Langer, Sergei A. Novikov, Harry Ramanantoanina, Ivan Pidchenko, Dieter Schild, Thomas E. Albrecht‐Schoenzart, Rüdiger‐A. Eichel, Tonya Vitova, Evgeny V. Alekseev. U(V) Stabilization via Aliovalent Incorporation of Ln(III) into Oxo‐salt Framework. Chemistry – A European Journal 2024, 30 (40) https://doi.org/10.1002/chem.202401033
    7. Ashutosh Srivastava, Sk. Musharaf Ali, Rama Mohan Rao Dumpala, Sumit Kumar, Pranaw Kumar, Neetika Rawat, P. K. Mohapatra. Unusual redox stability of pentavalent uranium with hetero-bifunctional phosphonocarboxylate: insight into aqueous speciation. Dalton Transactions 2024, 53 (17) , 7321-7339. https://doi.org/10.1039/D4DT00173G
    8. Fábio L. Melquiades, Rodrigo O. Bastos, Leandro Rampim, Israel Isaías Sandrino, Duvan Gil Rodriguez, Paulo S. Parreira. Thorium and uranium rapid quantification in soil with portable X‐ray fluorescence. Soil Science Society of America Journal 2024, 88 (2) , 557-564. https://doi.org/10.1002/saj2.20639
    9. Connor Hopkins, Harriet M. Simmonds, Jonathan D. Cryer, David J. Moulding, Debbie L. Jones, Simon Randall, Louise S. Natrajan. Molecular and environmental facets of pentavalent uranium chemistry. 2024, 231-266. https://doi.org/10.1016/bs.hpcre.2024.08.002
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    ACS Earth and Space Chemistry

    Cite this: ACS Earth Space Chem. 2022, 6, 5, 1204–1212
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsearthspacechem.1c00413
    Published March 18, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

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