Neptunium(V) and uranium(VI) reactions at the magnetite (111) surface

Pieter Bots, Arjen van Veelen, J. Frederick W. Mosselmans, Christopher Muryn, Roy A. Wogelius, Katherine Morris

    Research output: Contribution to journalArticlepeer-review

    Abstract

    Neptunium and uranium are important radionuclides in many aspects of the nuclear fuel cycle and are often present in radioactive wastes which require long term management. Understanding the environmental behaviour and mobility of these actinides is essential in underpinning remediation strategies and safety assessments for wastes containing these radionuclides. By combining state-of-the-art X-ray techniques (synchrotron-based Grazing Incidence XAS, and XPS) with wet chemistry techniques (ICP-MS, liquid scintillation counting and UV-Vis spectroscopy), we determined that contrary to uranium(VI), neptunium(V) interaction with magnetite is not significantly affected by the presence of bicarbonate. Uranium interactions with a magnetite surface resulted in XAS and XPS signals dominated by surface complexes of U(VI), while neptunium on the surface of magnetite was dominated by Np(IV) species. UV-Vis spectroscopy on the aqueous Np(V) species before and after interaction with magnetite showed different speciation due to the presence of carbonate. Interestingly, in the presence of bicarbonate after equilibration with magnetite, an unknown aqueous NpO 2 + species was detected using UV-Vis spectroscopy, which we postulate is a ternary complex of Np(V) with carbonate and (likely) an iron species. Regardless, the Np speciation in the aqueous phase (Np(V)) and on the magnetite (111) surfaces (Np(IV)) indicate that with and without bicarbonate the interaction of Np(V) with magnetite proceeds via a surface mediated reduction mechanism. Overall, the results presented highlight the differences between uranium and neptunium interaction with magnetite, and reaffirm the potential importance of bicarbonate present in the aqueous phase.

    Original languageEnglish
    Article number81
    JournalGeosciences (Switzerland)
    Volume9
    Issue number2
    Early online date8 Feb 2019
    DOIs
    Publication statusPublished - 2019

    Keywords

    • Geodisposal
    • Magnetite
    • Neptunium
    • Reduction
    • Surface
    • Synchrotron
    • Uranium
    • XAS
    • XPS

    Research Beacons, Institutes and Platforms

    • Dalton Nuclear Institute

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