Oxidative dissolution of UO2 in a simulated groundwater containing synthetic nanocrystalline mackinawite

• Published in: Geochimica et cosmochimica acta 2013-02, Vol.102, p.175-190
• Main Authors: Bi, Yuqiang, Hyun, Sung Pil, Kukkadapu, Ravi K., Hayes, Kim F.
• Format: Article
• Language: English
• Subjects: absorption; adsorption; buffers; dissolved oxygen; groundwater; hydroxides; iron; iron oxyhydroxides; lepidocrocite; nanocrystals; nitrites; oxidants; oxidation; oxygen; spectroscopy; sulfide minerals; sulfur; uranium; X-radiation; X-ray diffraction
• ISSN: 0016-7037; 1872-9533
• DOI: 10.1016/j.gca.2012.10.032

The long-term success of in situ reductive immobilization of uranium (U) depends on the stability of U(IV) precipitates (e.g., uraninite) in the presence of natural oxidants, such as oxygen, Fe(III) hydroxides, and nitrite. Field and laboratory studies have implicated iron sulfide minerals as redox buffers or oxidant scavengers that may slow oxidation of reduced U(IV) solid phases. Yet, the inhibition mechanism(s) and reaction rates of uraninite (UO2) oxidative dissolution by oxic species such as oxygen in FeS-bearing systems remain largely unresolved. To address this knowledge gap, abiotic batch experiments were conducted with synthetic UO2 in the presence and absence of synthetic mackinawite (FeS) under simulated groundwater conditions of pH=7, PO2=0.02atm, and PCO2=0.05atm. The kinetic profiles of dissolved uranium indicate that FeS inhibited UO2 dissolution for about 51h by effectively scavenging oxygen and keeping dissolved oxygen (DO) low. During this time period, oxidation of structural Fe(II) and S(-II) of FeS were found to control the DO levels, leading to the formation of iron oxyhydroxides and elemental sulfur, respectively, as verified by X-ray diffraction (XRD), Mössbauer, and X-ray absorption spectroscopy (XAS). After FeS was depleted due to oxidation, DO levels increased and UO2 oxidative dissolution occurred at an initial rate of rm=1.2±0.4×10−8molg−1s−1, higher than rm=5.4±0.3×10−9molg−1s−1 in the control experiment where FeS was absent. XAS analysis confirmed that soluble U(VI)-carbonato complexes were adsorbed by iron oxyhydroxides (i.e., nanogoethite and lepidocrocite) formed from FeS oxidation, which provided a sink for U(VI) retention. This work reveals that both the oxygen scavenging by FeS and the adsorption of U(VI) to FeS oxidation products may be important in U reductive immobilization systems subject to redox cycling events.