U(VI) sorption and reduction kinetics on the magnetite (111) surface. 2012

David M Singer, and Shawn M Chatman, and Eugene S Ilton, and Kevin M Rosso, and Jillian F Banfield, and Glenn A Waychunas
Department Earth & Planetary Sciences, University of California, Berkeley, CA, USA. dmsinger@lbl.gov

Sorption of contaminants onto mineral surfaces is an important process that can restrict their transport in the environment. In the current study, uranium (U) uptake on magnetite (111) was measured as a function of time and solution composition (pH, [CO(3)](T), [Ca]) under continuous batch-flow conditions. We observed, in real-time and in situ, adsorption and reduction of U(VI) and subsequent growth of UO(2) nanoprecipitates using atomic force microscopy (AFM) and newly developed batch-flow U L(III)-edge grazing-incidence X-ray absorption spectroscopy near-edge structure (GI-XANES) spectroscopy. U(VI) reduction occurred with and without CO(3) present, and coincided with nucleation and growth of UO(2) particles. When Ca and CO(3) were both present no U(VI) reduction occurred and the U surface loading was lower. In situ batch-flow AFM data indicated that UO(2) particles achieved a maximum height of 4-5 nm after about 8 h of exposure, however, aggregates continued to grow laterally after 8 h reaching up to about 300 nm in diameter. The combination of techniques indicated that U uptake is divided into three-stages; (1) initial adsorption of U(VI), (2) reduction of U(VI) to UO(2) nanoprecipitates at surface-specific sites after 2-3 h of exposure, and (3) completion of U(VI) reduction after ~6-8 h. U(VI) reduction also corresponded to detectable increases in Fe released to solution and surface topography changes. Redox reactions are proposed that explicitly couple the reduction of U(VI) to enhanced release of Fe(II) from magnetite. Although counterintuitive, the proposed reaction stoichiometry was shown to be largely consistent with the experimental results. In addition to providing molecular-scale details about U sorption on magnetite, this work also presents novel advances for collecting surface sensitive molecular-scale information in real-time under batch-flow conditions.

UI MeSH Term Description Entries
D007501 Iron A metallic element with atomic symbol Fe, atomic number 26, and atomic weight 55.85. It is an essential constituent of HEMOGLOBINS; CYTOCHROMES; and IRON-BINDING PROTEINS. It plays a role in cellular redox reactions and in the transport of OXYGEN. Iron-56,Iron 56
D007700 Kinetics The rate dynamics in chemical or physical systems.
D010084 Oxidation-Reduction A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471). Redox,Oxidation Reduction
D010316 Particle Size Relating to the size of solids. Particle Sizes,Size, Particle,Sizes, Particle
D004777 Environment The external elements and conditions which surround, influence, and affect the life and development of an organism or population. Environmental Impact,Environmental Impacts,Impact, Environmental,Impacts, Environmental,Environments
D000327 Adsorption The adhesion of gases, liquids, or dissolved solids onto a surface. It includes adsorptive phenomena of bacteria and viruses onto surfaces as well. ABSORPTION into the substance may follow but not necessarily. Adsorptions
D013499 Surface Properties Characteristics or attributes of the outer boundaries of objects, including molecules. Properties, Surface,Property, Surface,Surface Property
D014501 Uranium A radioactive element of the actinide series of metals. It has an atomic symbol U, atomic number 92, and atomic weight 238.03. U-235 is used as the fissionable fuel in nuclear weapons and as fuel in nuclear power reactors.
D017356 Synchrotrons Devices for accelerating protons or electrons in closed orbits where the accelerating voltage and magnetic field strength varies (the accelerating voltage is held constant for electrons) in order to keep the orbit radius constant. Synchrotron
D052203 Ferrosoferric Oxide Iron (II,III) oxide (Fe3O4). It is a black ore of IRON that forms opaque crystals and exerts strong magnetism. Ferumoxytol,Feraheme,Ferriferrous Oxide,Magnetite,Oxide, Ferriferrous,Oxide, Ferrosoferric

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