Open questions on bonding involving lanthanide atoms

In-depth understanding of the bonding characteristics of the lanthanide ions in contemporary lanthanide-based materials is mandatory for tailoring their properties for novel applications. Here, the authors elaborate on open questions regarding the bonding situation in mainly molecular lanthanide (4f) compounds, where, as compared to their actinide (5f) analogs in which covalency of the bonds is a common feature, this is still under discussion for the 4f compounds

5d-5f Electric-multipole Transitions in Uranium Dioxide Probed by Non-resonant Inelastic X-ray Scattering

Non-resonant inelastic x ray scattering (NIXS) experiments have been performed to probe the 5d-5f electronic transitions at the uranium O(4,5) absorption edges in uranium dioxide. For small values of the scattering vector q, the spectra are dominated by dipole-allowed transitions encapsulated within the giant resonance, whereas for higher values of q the multipolar transitions of rank 3 and 5 give rise to strong and well-defined multiplet structure in the pre-edge region. The origin of the observed non-dipole multiplet structures is explained on the basis of many-electron atomic spectral calculations. The results obtained demonstrate the high potential of NIXS as a bulk-sensitive technique for the characterization of the electronic properties of actinide materials.Comment: Submitted to Physical Review Letters on 31 December 200

Synthesis and characterization of thorium, uranium and cerium oxide nanoparticles

We describe the synthesis of cerium, thorium and uranium oxide nanoparticles embedded in a mesoporous matrix as template in a kind of nanocasting technique. The solid matrix is used as a template to obtain and stabilize the actinide oxide nanoparticles. We apply high resolution transmission electron microscopy (HR-TEM) to show evidence of metal oxide incorporation into the matrix pores and analyze their structure. Measured interplanar distances and calculated lattice parameters for synthesized nanosized CeO2−x and ThO2 samples differ from their bulk crystalline counterparts. We obtain with our synthesis CeO2−x particles containing both Ce4+ and larger sized Ce3+. The lattice parameter for these ceria nanoparticles is found to be larger than the bulk value due to the presence of Ce3+ with its larger ionic radius. The presence of Ce3+ was established by means of high resolution X-ray emission spectroscopy (HRXES), applied to the investigation of nanoparticles for the first time. The ThO2 nanoparticles exhibit a decrease in interplanar distances, as one might generally expected for these nanoclusters. However, the lattice distance decrease for our particles is remarkable, up to 5%, indicating that contact with the surrounding silica matrix may exert a bond distance shortening effect such as through significant external pressure on the particle surface

Uptake of actinides by calcium silicate hydrate (C-S-H) phases

The sorption of actinides (Th, U – Am) was studied in dependence of the solid-to-liquid (S/L) ratio (0.5–20.0 g/L) and the calcium-to-silicon (C:S) ratio. The C:S ratio was varied between 1.80 and 0.70 to simulate the changing composition of the C-S-H phases during cement degradation from high to low C:S ratios. The decrease of the calcium content in the C-S-H phases by time is accompanied by a decrease in pH in the corresponding suspensions from 12.6 to 10.2. X-ray photoelectron spectroscopy (XPS) of the C-S-H phases showed an increasing depletion of Ca on the surface with increasing C:S ratio in comparison to the composition of the solid phase as a whole. The sorption experiments were performed with the redox stable species Am(III), Th(IV) and U(VI), as well as the redox sensitive Np(V) and Pu(III). The average distribution coefficients Rd for all investigated actinides are around 105 L/kg. The oxidation state of Pu retained by the C-S-H phases was investigated with high-energy resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy. Samples with C:S ratios of 0.75 and 1.65 showed that the initially added Pu(III) was oxidized to Pu(IV) in the course of the experiment

Probing Covalency in the UO3 Polymorphs by U M4 edge HR- XANES

Local atomic and electronic structure investigations of uranium trioxide (UO3) crystalline phases performed by the U M4 edge HR-XANES technique is presented. The experimental U M4 edge HR-XANES spectra of α-UO3, β-UO3 and γ-UO3 polymorphic phases are compared with spectra of uranate (CaU2O7) and uranyl (UO3•1-2(H2O)) compounds. We describe a finger print approach valuable for characterization of variations of U-O axial bond lengths. Theoretical calculations of spectra using full-multiple-scattering theory (FEFF9.6 code) are performed. We have tested and selected input parameters, which provide best agreement between experimental and calculated spectra

U redox state and speciation of U in contact with magnetite nanoparticles : High resolution XANES, EXAFS, XPS and TEM study

Long-term storage of high-level radioactive waste is associated with potential radioecological hazards. One chemical element of high interest is uranium (U), which can mainly exists as a mobile U(VI) (oxidizing conditions) and sparingly soluble U(IV) (reducing conditions) species. It is expected that the main inorganic reducing agent for U(VI) in the environment are ferrous species in magnetite, formed on the steel canisters surface as an intermediate iron (Fe) corrosion product [1]. Results obtained from laboratory experiments for the interaction of U(VI) with magnetite nanoparticles point to partial reduction of U(VI) [2] or the formation of ~3 nm uranium dioxide (UO₂) particles on the surface layer [3]. The evidence for U(VI) reduction to intermediate U(V) state was found with no direct evidence of U(IV), which is in contradiction with thermodynamic calculations [4]. Continuous interaction and related phase dissolution/recrystallization processes can also lead to U redox changes and structural U incorporation into Fe oxides, resulting in U immobilization [5]. U redox state and speciation analyses are still very challenging due to simultaneous formation of several different species in such mineral systems. New advanced spectroscopic methods for characterization of such systems will provide more precise results from speciation studies. The main goal of our investigation is to assess the U M4 edge high energy resolution X-ray absorption near edge structure (HR-XANES) spectroscopy technique for detection of U(V) possibly co-existing with U(IV) and U(VI) under reducing conditions on/in Fe containing minerals. The U M4 edge HR-XANES has an advantage compared to the conventional U L3 edge XANES, as the measured spectra are less dominated by corehole lifetime broadening effects and therefore have narrower spectral features [6-8]. This technique facilitates the detection of minor contribution of one oxidation state in mixtures. We have investigated the U redox states and speciation in a set of samples where U coprecipitated with magnetite nanoparticles (~ 20 nm) with U concentrations varying in the 1000-10000 ppm range (1000, 3000, 6000 and 10000 ppm). In addition to U M4 edge HR-XANES, U L3 edge extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) techniques have been applied. The studied system models the interaction of U(VI) with magnetite in aqueous solution, important for the understanding of the retarding effect of Fe corrosion products on U in the context of deep geological spent nuclear fuel disposal. These spectroscopic results can be compared with thermodynamic calculations and geochemical models describing this interaction. After 10 days U interaction with magnetite U M4 edge HR-XANES results indicate the formation of U(IV), U(V) and U(VI) mixtures in varying ratios, depending on the initial U loading. Going from 10000 to 3000 ppm, the U(VI) content decreases continuously and is no longer found in the 1000 ppm sample. At the same time the U(IV) and U(V) fractions increase. U(V) is stabilized as the main U redox state in the 1000 ppm sample along with a smaller U(IV) contribution. After 20 days of contact time XPS data show the predominance of U(IV) and U(V) species in the 6000 ppm sample. However, mostly U(V) and some U(IV) is found for the 1000 ppm sample. For all samples aged for 240 days U L3 XANES and EXAFS strongly suggest the formation of a UO₂ phase, UO₂ is the dominating species in the 10000 ppm sample with U-O bond distance 2.33. Å as determined by EXAFS. UO₂ crystalline clusters with about 5 nm size formed on the surface of the magnetite nanoparticles are also found by TEM in the 10000 and 3000 ppm samples. The major and minor contributions of U(V) and U(IV), respectively, for the 1000 ppm sample after 240 days confirm the assumption that the U redox kinetics has completed within less than 10 days at this U concentration. EXAFS analyses reveal U(V)-Fe interaction in the second U coordination sphere, which substantially increases from the 10000 to 1000 ppm sample and is the dominating species in the 1000 ppm sample

Persistence of the Isotopic Signature of Pentavalent Uranium in Magnetite

Uranium isotopic signatures can be harnessed to monitor the reductive remediation of subsurface contamination or to reconstruct paleo-redox environments. However, the mechanistic underpinnings of the isotope fractionation associated with U reduction remain poorly understood. Here, we present a coprecipitation study, in which hexavalent U (U(VI)) was reduced during the synthesis of magnetite and pentavalent U (U(V)) was the dominant species. The measured δ$^{238}$U values for unreduced U(VI) (∼−1.0‰), incorporated U (96 ± 2% U(V), ∼−0.1‰), and extracted surface U (mostly U(IV), ∼0.3‰) suggested the preferential accumulation of the heavy isotope in reduced species. Upon exposure of the U-magnetite coprecipitate to air, U(V) was partially reoxidized to U(VI) with no significant change in the δ$^{238}$U value. In contrast, anoxic amendment of a heavy isotope-doped U(VI) solution resulted in an increase in the δ$^{238}$U of the incorporated U species over time, suggesting an exchange between incorporated and surface/aqueous U. Overall, the results support the presence of persistent U(V) with a light isotope signature and suggest that the mineral dynamics of iron oxides may allow overprinting of the isotopic signature of incorporated U species. This work furthers the understanding of the isotope fractionation of U associated with iron oxides in both modern and paleo-environments