title: Nano-FeS inhibits UO2 reoxidation under varied oxic conditions.
abstract: Bioreductive in situ treatment of U-contaminated groundwater can convert soluble U(VI) species to immobile reduced U(IV) solid phases such as UO2(s) to contain U movement. Once active bioremediation is halted, UO2 may be subsequently reoxidized if oxidants such as oxygen enter the reducing zone. However, iron sulfide minerals that form during bioreduction may serve as electron sources or oxygen scavengers and inhibit UO2 reoxidation upon oxygen intrusion. In this study, flow-through reactor experiments examined the abiotic kinetics of UO2 oxidative dissolution in the presence of oxygen and nanoparticulate FeS as a function of pH, dissolved oxygen (DO) concentration, and FeS content. The UO2 dissolution rates in the presence of FeS were over 1 order of magnitude lower than those in the absence of FeS under otherwise comparable oxic conditions. FeS effectively scavenged DO and preferentially reacted with oxygen, contributing to a largely unreacted UO2 solid phase during an "inhibition period" as determined by X-ray absorption spectroscopy (XAS). The removal of DO by FeS was significant but incomplete during the inhibition period, resulting in surface-oxidation-limited dissolution and greater UO2 dissolution rate with increasing influent DO concentration and decreasing FeS content. Although the rate was independent of solution pH in the range of 6.1-8.1, the length of the inhibition period was shortened by substantial FeS dissolution at slightly acidic pH. The reducing capacity of FeS was greatest at basic pH where surface-mediated FeS oxidation dominated.
authors: Department of Civil and Environmental Engineering, University of Michigan , Ann Arbor, Michigan 48109, United States.
authors: Yuqiang
authors: Y
authors: Bi
authors: Kim F
authors: KF
authors: Hayes
mesh_terms: D001673:Biodegradation, Environmental; D005296:Ferrous Compounds / Q000737:chemistry*; D060587:Groundwater / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007501:Iron / Q000737:chemistry; D007700:Kinetics; D008962:Models, Theoretical; D049329:Nanostructures / Q000737:chemistry; D010084:Oxidation-Reduction; D012996:Solutions; D017974:Uranium Compounds / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000737:chemistry; D056928:X-Ray Absorption Spectroscopy
chemical_list: D005296:Ferrous Compounds; D012996:Solutions; D017974:Uranium Compounds; D014874:Water Pollutants, Chemical; D007501:Iron; C012597:uranium dioxide; C022597:ferrous sulfide