Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions: Closed system experiments

Emmi Myllykylä, Kaija Ollila

    Research output: Book/ReportReport

    Abstract

    The aim of these experiments is to investigate the potential reduction of U(VI) carbonate and hydroxide complexes by aqueous Fe(II). This reduction phenomenon could be important under the disposal conditions of spent fuel. If groundwater enters the copper/iron canister, alpha radiolysis of the water may locally induce oxidizing conditions on the surface of UO2 fuel, leading to the dissolution of UO2 as more soluble U(VI) species. A potential reducing agent in the intruding water is Fe(II)(aq) from anaerobic corrosion of the copper/iron canister. The reduction of U(VI) to U(IV) would substantially decrease the solubility of U as well as co-precipitate other actinides and radionuclides. The interaction experiments were conducted in 0.01 M NaCl and 0.002 M NaHCO3 solutions using an initial uranium concentration of either 8.4 • 10-8 or 4.2 • 10-7 mol/L with an initial Fe(II) concentration of 1.8 • 10-6  in the NaCl solutions and 1.3 • 10-6 mol/L in the NaHCO3 solutions. Only after an equilibration period for U(VI) complexation was Fe(II) added to the solutions. The reaction times varied from 1 week to 5 months. For extra protection against O2, even inside a glove-box (N2 atmosphere), the plastic reaction vessels were closed in metallic containers. The concentrations of U, FeTOT and Fe(II) were analysed as a function of time for unfiltered, micro- and ultrafiltered samples. In addition, the precipitate on the ultrafilters was analysed with ESEM-EDS. The evolution of pH and Eh values was measured. The oxidation state of U in solution was preliminarily analysed for chosen periods. The results of the tests in 0.01 M NaCl showed an initial rapid decrease in U concentration after the addition of Fe(II) to the solution. The U found on test vessel walls at the end of the reaction periods, as well as the ESEM-EDS analyses of the filtered precipitates from the test solutions, showed that precipitation of U had occurred. The oxidation state analyses showed the presence of U(IV) in the solutions after 3 and 6 weeks’ reaction time. These results suggest that the reduction of U(VI) by Fe(II) occurred in NaCl solution. The observed change in U concentration in 0.002 M NaHCO3 solution was small and very slow. Uranium(IV) was also found in solution in this test, showing that some reduction occurred in spite of the stabilising effect of carbonates on U(VI) solutions.
    Original languageEnglish
    Place of PublicationOlkiluoto, Eurajoki
    PublisherPosiva
    Number of pages35
    Publication statusPublished - 2011
    MoE publication typeD4 Published development or research report or study

    Publication series

    SeriesPosiva Working Report
    Number2011-06

    Fingerprint

    anoxic conditions
    aqueous solution
    experiment
    uranium
    vessel
    copper
    carbonate
    oxidation
    iron
    actinide
    complexation
    hydroxide
    radionuclide
    corrosion
    solubility
    plastic
    dissolution
    water
    groundwater
    test

    Keywords

    • Uranium
    • reduction
    • iron
    • Fe2+(aq)
    • anoxic conditions
    • spent fuel

    Cite this

    Myllykylä, E., & Ollila, K. (2011). Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions: Closed system experiments. Olkiluoto, Eurajoki: Posiva. Posiva Working Report, No. 2011-06
    Myllykylä, Emmi ; Ollila, Kaija. / Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions : Closed system experiments. Olkiluoto, Eurajoki : Posiva, 2011. 35 p. (Posiva Working Report; No. 2011-06).
    @book{7fca23b0f0384db1803eb4766efc5070,
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    author = "Emmi Myllykyl{\"a} and Kaija Ollila",
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    language = "English",
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    Myllykylä, E & Ollila, K 2011, Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions: Closed system experiments. Posiva Working Report, no. 2011-06, Posiva, Olkiluoto, Eurajoki.

    Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions : Closed system experiments. / Myllykylä, Emmi; Ollila, Kaija.

    Olkiluoto, Eurajoki : Posiva, 2011. 35 p. (Posiva Working Report; No. 2011-06).

    Research output: Book/ReportReport

    TY - BOOK

    T1 - Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions

    T2 - Closed system experiments

    AU - Myllykylä, Emmi

    AU - Ollila, Kaija

    PY - 2011

    Y1 - 2011

    N2 - The aim of these experiments is to investigate the potential reduction of U(VI) carbonate and hydroxide complexes by aqueous Fe(II). This reduction phenomenon could be important under the disposal conditions of spent fuel. If groundwater enters the copper/iron canister, alpha radiolysis of the water may locally induce oxidizing conditions on the surface of UO2 fuel, leading to the dissolution of UO2 as more soluble U(VI) species. A potential reducing agent in the intruding water is Fe(II)(aq) from anaerobic corrosion of the copper/iron canister. The reduction of U(VI) to U(IV) would substantially decrease the solubility of U as well as co-precipitate other actinides and radionuclides. The interaction experiments were conducted in 0.01 M NaCl and 0.002 M NaHCO3 solutions using an initial uranium concentration of either 8.4 • 10-8 or 4.2 • 10-7 mol/L with an initial Fe(II) concentration of 1.8 • 10-6  in the NaCl solutions and 1.3 • 10-6 mol/L in the NaHCO3 solutions. Only after an equilibration period for U(VI) complexation was Fe(II) added to the solutions. The reaction times varied from 1 week to 5 months. For extra protection against O2, even inside a glove-box (N2 atmosphere), the plastic reaction vessels were closed in metallic containers. The concentrations of U, FeTOT and Fe(II) were analysed as a function of time for unfiltered, micro- and ultrafiltered samples. In addition, the precipitate on the ultrafilters was analysed with ESEM-EDS. The evolution of pH and Eh values was measured. The oxidation state of U in solution was preliminarily analysed for chosen periods. The results of the tests in 0.01 M NaCl showed an initial rapid decrease in U concentration after the addition of Fe(II) to the solution. The U found on test vessel walls at the end of the reaction periods, as well as the ESEM-EDS analyses of the filtered precipitates from the test solutions, showed that precipitation of U had occurred. The oxidation state analyses showed the presence of U(IV) in the solutions after 3 and 6 weeks’ reaction time. These results suggest that the reduction of U(VI) by Fe(II) occurred in NaCl solution. The observed change in U concentration in 0.002 M NaHCO3 solution was small and very slow. Uranium(IV) was also found in solution in this test, showing that some reduction occurred in spite of the stabilising effect of carbonates on U(VI) solutions.

    AB - The aim of these experiments is to investigate the potential reduction of U(VI) carbonate and hydroxide complexes by aqueous Fe(II). This reduction phenomenon could be important under the disposal conditions of spent fuel. If groundwater enters the copper/iron canister, alpha radiolysis of the water may locally induce oxidizing conditions on the surface of UO2 fuel, leading to the dissolution of UO2 as more soluble U(VI) species. A potential reducing agent in the intruding water is Fe(II)(aq) from anaerobic corrosion of the copper/iron canister. The reduction of U(VI) to U(IV) would substantially decrease the solubility of U as well as co-precipitate other actinides and radionuclides. The interaction experiments were conducted in 0.01 M NaCl and 0.002 M NaHCO3 solutions using an initial uranium concentration of either 8.4 • 10-8 or 4.2 • 10-7 mol/L with an initial Fe(II) concentration of 1.8 • 10-6  in the NaCl solutions and 1.3 • 10-6 mol/L in the NaHCO3 solutions. Only after an equilibration period for U(VI) complexation was Fe(II) added to the solutions. The reaction times varied from 1 week to 5 months. For extra protection against O2, even inside a glove-box (N2 atmosphere), the plastic reaction vessels were closed in metallic containers. The concentrations of U, FeTOT and Fe(II) were analysed as a function of time for unfiltered, micro- and ultrafiltered samples. In addition, the precipitate on the ultrafilters was analysed with ESEM-EDS. The evolution of pH and Eh values was measured. The oxidation state of U in solution was preliminarily analysed for chosen periods. The results of the tests in 0.01 M NaCl showed an initial rapid decrease in U concentration after the addition of Fe(II) to the solution. The U found on test vessel walls at the end of the reaction periods, as well as the ESEM-EDS analyses of the filtered precipitates from the test solutions, showed that precipitation of U had occurred. The oxidation state analyses showed the presence of U(IV) in the solutions after 3 and 6 weeks’ reaction time. These results suggest that the reduction of U(VI) by Fe(II) occurred in NaCl solution. The observed change in U concentration in 0.002 M NaHCO3 solution was small and very slow. Uranium(IV) was also found in solution in this test, showing that some reduction occurred in spite of the stabilising effect of carbonates on U(VI) solutions.

    KW - Uranium

    KW - reduction

    KW - iron

    KW - Fe2+(aq)

    KW - anoxic conditions

    KW - spent fuel

    M3 - Report

    T3 - Posiva Working Report

    BT - Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions

    PB - Posiva

    CY - Olkiluoto, Eurajoki

    ER -

    Myllykylä E, Ollila K. Interaction between U(VI) and Fe(II) in aqueous solution under anaerobic conditions: Closed system experiments. Olkiluoto, Eurajoki: Posiva, 2011. 35 p. (Posiva Working Report; No. 2011-06).