Many-body effects in the 4f x-ray photoelectron spectroscopy of the U5+ and U4+ free ions

This article discusses many-body effects in the 4f x-ray photoelectron spectroscopy of the U5+ and U4+ free ions

Nanoscale Oxygen Defect Gradients in the Actinide Oxides

Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the first use of aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy to resolve changes in the local oxygen defect environment in UO$_2$ surfaces. We observe large image contrast and spectral changes that reflect the presence of sizable gradients in interstitial oxygen content at the nanoscale, which we quantify through first principles calculations and image simulations. These findings reveal an unprecedented level of excess oxygen incorporated in a complex near-surface spatial distribution, offering new insight into defect formation pathways and kinetics during UO$_2$ oxidation.Comment: 26 pages, 12 figure

Nanoscale oxygen defect gradients in UO2+x surfaces.

Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the use of aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy to resolve changes in the local oxygen defect environment in [Formula: see text] surfaces. We observe large image contrast and spectral changes that reflect the presence of sizable gradients in interstitial oxygen content at the nanoscale, which we quantify through first-principles calculations and image simulations. These findings reveal an unprecedented level of excess oxygen incorporated in a complex near-surface spatial distribution, offering additional insight into defect formation pathways and kinetics during [Formula: see text] surface oxidation

Nanoscale oxygen defect gradients in UO_2+x surfaces

Oxygen defects govern the behavior of a range of materials spanning catalysis, quantum computing, and nuclear energy. Understanding and controlling these defects is particularly important for the safe use, storage, and disposal of actinide oxides in the nuclear fuel cycle, since their oxidation state influences fuel lifetimes, stability, and the contamination of groundwater. However, poorly understood nanoscale fluctuations in these systems can lead to significant deviations from bulk oxidation behavior. Here we describe the use of aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy to resolve changes in the local oxygen defect environment in&nbsp;</p

Geochemical Characterization of Chromate Contamination in the 100 Area Vadose Zone at the Hanford Site

The major objectives of the proposed study were to: 1.) determine the leaching characteristics of hexavalent chromium [Cr(VI)] from contaminated sediments collected from 100 Area spill sites; 2.) elucidate possible Cr(VI) mineral and/or chemical associations that may be responsible for Cr(VI) retention in the Hanford Site 100 Areas through the use of i.) macroscopic leaching studies and ii.) microscale characterization of contaminated sediments; and 3.) provide information to construct a conceptual model of Cr(VI) geochemistry in the Hanford 100 Area vadose zone. In addressing these objectives, additional benefits accrued were: (1) a fuller understanding of Cr(VI) entrained in the vadose zone that will that can be utilized in modeling potential Cr(VI) source terms, and (2) accelerating the Columbia River 100 Area corridor cleanup by providing valuable information to develop remedial action based on a fundamental understanding of Cr(VI) vadose zone geochemistry. A series of macroscopic column experiments were conducted with contaminated and uncontaminated sediments to study Cr(VI) desorption patterns in aged and freshly contaminated sediments, evaluate the transport characteristics of dichromate liquid retrieved from old pipelines of the 100 Area; and estimate the effect of strongly reducing liquid on the reduction and transport of Cr(VI). Column experiments used the < 2 mm fraction of the sediment samples and simulated Hanford groundwater solution. Periodic stop-flow events were applied to evaluate the change in elemental concentration during time periods of no flow and greater fluid residence time. The results were fit using a two-site, one dimensional reactive transport model. Sediments were characterized for the spatial and mineralogical associations of the contamination using an array of microscale techniques such as XRD, SEM, EDS, XPS, XMP, and XANES. The following are important conclusions and implications. Results from column experiments indicated that most of contaminant Cr travels fast through the sediments and appears as Cr(VI) in the effluents. The significance of this for groundwater concentrations would, however, depend on the mass flux of recharge to the water table. adsorption of Cr(VI) to sediments from spiked Cr(VI) solution is low; calculated retardation coefficients are close to one. Calcium polysulfide solutions readily reduced Cr(VI) to Cr(III) in column experiments. However a significant amount of the Cr(VI) was mobilized ahead of the polysulfide solution front. This has significant implications for in-situ reductive remediation techniques. The experiments suggest that it would be difficult to design a remedial measure using infiltration of liquid phase reductants without increasing transport of Cr(VI) toward the water table. The microscopic characterization results are consistent with the column studies. Cr(VI) is found as ubiquitous coatings on sediment grain surfaces. Small, higher concentration, chromium sites are associated with secondary clay mineral inclusions, with occasional barium chromate minerals, and reduced to Cr(III) in association with iron oxides that are most likely magnetite primary minerals. Within the restricted access domains of sediment matrix, ferrous iron could also diffuse from in situ, high-surface-area minerals to cause the reductive immobilization of chromate. This process may be favored at microscale geochemical zones where ferrous iron could be supplied. Once nucleated, micrometer-scale precipitates are favored as growing locales for further accumulation, causing the formation of discrete zones of Cr(III)

Comparative dissolution kinetics of biogenic and chemogenic uraninite under oxidizing conditions in the presence of carbonate

The long-term stability of biogenic uraninite with respect to oxidative dissolution is pivotal to the success of in situ bioreduction strategies for the subsurface remediation of uranium legacies. Batch and flow-through dissolution experiments were conducted along with spectroscopic analyses to compare biogenic uraninite nanoparticles obtained from Shewanella oneidensis MR-1 and chemogenic UO2.00 with respect to their equilibrium solubility, dissolution mechanisms, and dissolution kinetics in water of varied oxygen and carbonate concentrations. Both materials exhibited a similar intrinsic solubility of similar to 10(-8) M under reducing conditions. The two materials had comparable dissolution rates under anoxic as well as oxidizing conditions, consistent with structural bulk homology of biogenic and stoichiometric uraninite. Carbonate reversibly promoted uraninite dissolution under both moderately oxidizing and reducing conditions, and the biogenic material yielded higher surface area-normalized dissolution rates than the chemogenic. This difference is in accordance with the higher proportion of U(V) detected on the biogenic uraninite surface by means of X-ray photoelectron spectroscopy. Reasonable sources of a stable U(V)-bearing intermediate phase are discussed. The observed increase of the dissolution rates can be explained by carbonate complexation of U(V) facilitating the detachment of U(V) from the uraninite surface. The fraction of surface-associated U(VI) increased with dissolved oxygen concentration. Simultaneously, X-ray absorption spectra showed conversion of the bulk from UO2.0 to UO2+x. In equilibrium with air, combined spectroscopic results support the formation of a near-surface layer of approximate composition UO2.25 (U4O9) coated by an outer layer of U(VI). This result is in accordance with flow-through dissolution experiments that indicate control of the dissolution rate of surface-oxidized uraninite by the solubility of metaschoepite under the tested conditions. Although U(V) has been observed in electrochemical studies on the dissolution of spent nuclear fuel, this is the first investigation that demonstrates the formation of a stable U(V) intermediate phase on the surface of submicron-sized uraninite particles suspended in aqueous solutions. (C) 2009 Elsevier Ltd. All rights reserved

Advancing radioactive material research method: the development of a novel in situ particle-attached microfluidic electrochemical cell

Introduction: This study aims to develop a microgram-scale microfluidic electrochemical cell (E-cell) for investigating the redox behavior of uranium oxide (UO2). The traditional bulk electrochemical methods may require shielded facilities to investigate the hazardous materials, e.g., spent nuclear fuel, due to high radiation levels. Microfluidic E-cells offer advantages such as reduced radiation exposure, control over fluid flow rates, and high-throughput capabilities.Methods: The design of the E-cell considers electrode morphology, adhesion to a thin membrane, electrode configuration, and vacuum compatibility. Three techniques, including FIB-SEM lift-out, Au coating, and polyvinylidene fluoride (PVDF) binder, are explored for fabricating and attaching microgram quantities of UO2 as working electrodes. The PVDF binder method proves to be the most effective, enabling the creation of a vacuum-compatible microfluidic E-cell.Results and discussion: The PVDF binder method demonstrates successful electrochemical responses and allows for real-time monitoring of UO2 electrode behavior at the microscale. It offers chemical imaging capabilities using in situ SEM/EDS analysis. The technique provides consistent redox outcomes similar to bulk electrochemical analysis.Conclusion: The development of a microgram-scale microfluidic electrochemical cell using the PVDF binder technique enables the investigation of UO2 redox behavior. It offers a low-risk approach with reduced radiation exposure and high-throughput capabilities. The technique provides real-time monitoring and chemical imaging capabilities, making it valuable for studying spent nuclear fuel systems and material characterization