title: Chemical reduction of actinides probed by resonant inelastic X-ray scattering.
abstract: The study addresses the possibilities of immobilizing the mobile species of actinides in the geosphere using metallic iron. Sorption on corroding iron is well-known, but there have been uncertainties with regard to the possibilities of reducing the actinyl species to sparingly soluble oxides and, thereby, permanently immobilizing them. Resonant inelastic X-ray scattering (RIXS) measurements at the actinide 5d edges on Fe foils exposed to uranium(VI) and neptunium(V) solutions in groundwater unambigiously indicate reduction of actinides to, respectively, uranium(IV) and neptunium(IV) on iron surfaces. The reduction manifests itself in an appearance of distinct specific signatures of uranium(IV) and neptunium(IV) in the RIXS profile of 5f-5f excitations. Such signatures and RIXS intensity/cross-section behavior with varying energy of incident photons can be reproduced by model atomic-multiplet calculations of the RIXS spectra. By normalizing the RIXS signal of corresponding 5f-5f excitations to core-to-core 6p-to-5d characteristic fluorescence transitions of actinides, their reduction rates on Fe samples with different exposure to actinide solutions can be estimated. Observed reduction implies similar processes in the nuclear waste canister thus suggesting reduced probability of nuclear waste release with ground waters from the canister.
authors.affiliation: Department of Physics and Astronomy, Uppsala University , Box 516, SE-751 20 Uppsala, Sweden.
authors.forename: Sergei M
authors.initials: SM
authors.lastname: Butorin
authors.forename: David K
authors.initials: DK
authors.lastname: Shuh
authors.forename: Kristina O
authors.initials: KO
authors.lastname: Kvashnina
authors.forename: Jinghua
authors.initials: J
authors.lastname: Guo
authors.forename: Lars
authors.initials: L
authors.lastname: Werme
authors.forename: Joseph
authors.initials: J
authors.lastname: Nordgren