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At least 721 records · Page 40

Evaluation and Specifications for In-Line Uranium Separations Using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) Detection for Trace Elemental Analysis

Automated introduction platforms integrated with inductively coupled plasma optical emission spectroscopy (ICP-OES) systems are continuously being improved. Expanding on the introduction systems, a newly developed automated ion chromatography system was explored for performing rapid in-line separations coupled to ICP-OES for the detection of trace elements in uranium. Trace elements are separated from a uranium material and the analytes are directed into the ICP-OES for subsequent detection. Detection parameters such as exposure time frequency, wavelength selection, and settling times were explored to gain insight on optimal detection schemes for in-line trace elemental analysis. The methodology was applied in the analysis of a uranium oxide (U3O8) certified reference material, CRM-124. It was found here that the sensitivity and uncertainty of the technique are greatly affected by how the ICP-OES is employed to collect data. Overall it was determined that faster exposure replicates can provide greater peak resolution with higher fidelity measurements but are limited with respect to the total analysis time (i.e., limited in detection timely separations). In conclusion zeta scores, which combine accuracy and uncertainty of certified values and experimental values, were used to validate the ICP-OES modes of operation.

47 OTHER INSTRUMENTATION↗

Neutronics Studies of Uranium-bearing Fully Ceramic Micro-encapsulated Fuel for PWRs

Our study evaluated the neutronics and some of the fuel cycle characteristics of using uranium-based fully ceramic microencapsulated (FCM) fuel in a pressurized water reactor (PWR). Specific PWR lattice designs with FCM fuel have been developed that are expected to achieve higher specific burnup levels in the fuel while also increasing the tolerance to reactor accidents. The SCALE software system was the primary analysis tool used to model the lattice designs. A parametric study was performed by varying tristructural isotropic particle design features (e.g., kernel diameter, coating layer thicknesses, and packing fraction) to understand the impact on reactivity and resulting operating cycle length. Moreover, to match the lifetime of an 18-month PWR cycle, the FCM particle fuel design required roughly 10% additional fissile material at beginning of life compared with that of a standard uranium dioxide (UO 2 ) rod. Uranium mononitride proved to be a favorable fuel for the fuel kernel due to its higher heavy metal loading density compared with UO 2 . The FCM fuel designs evaluated maintain acceptable neutronics design features for fuel lifetime, lattice peaking factors, and nonproliferation figure of merit.

10 SYNTHETIC FUELS↗

Expanded Validation of Uranium Systems with the KENO Monte Carlo Codes and SCALE 6.2.4

The development of accident-tolerant fuel and advanced reactors fueled with high-assay low-enriched uranium has created an increased focus on systems with uranium enrichments between 5 and 20 wt % 235 U. SCALE criticality safety validation reports generated at Oak Ridge National Laboratory contain very few benchmark experiments in this range. The work presented herein is an initial investigation of expanded validation of the entire range of enrichments for uranium-fueled systems, including consideration of over 300 newly developed KENO models. The vast majority of the new models are between 4.4 wt % and 37.5 wt % enrichment and include a variety of thermal, intermediate, and mixed neutron spectra. This work finds no strong evidence of an enrichment-dependent bias, but there are indications of a spectrum-dependent bias. There are, however, only a limited number of independent experiments included at this time to distinguish intermediate enrichment effects from intermediate spectrum effects. Further work in this area is ongoing for intermediate enrichment systems. In the long run, the addition of these models to the Verified, Archived Library and Inputs and Data is planned, as funding and staff availability allow.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Comparative analysis of uranium bioassociation with halophilic bacteria and archaea

Rock salt represents a potential host rock formation for the final disposal of radioactive waste. The interactions between indigenous microorganisms and radionuclides, e.g. uranium, need to be investigated to better predict the influence of microorganisms on the safety assessment of the repository. Hence, the association process of uranium with two microorganisms isolated from rock salt was comparatively studied. Brachybacterium sp. G1, which was isolated from the German salt dome Gorleben, and Halobacterium noricense DSM15987T , were selected as examples of a moderately halophilic bacterium and an extremely halophilic archaeon, respectively. The microorganisms exhibited completely different association behaviors with uranium. While a pure biosorption process took place with Brachybacterium sp. G1 cells, a multistage association process occurred with the archaeon. In addition to batch experiments, in situ attenuated total reflection Fourier-transform infrared spectroscopy was applied to characterize the U(VI) interaction process. Biosorption was identified as the dominating process for Brachybacterium sp. G1 with this method. Carboxylic functionalities are the dominant interacting groups for the bacterium, whereas phosphoryl groups are also involved in U(VI) association by the archaeon H. noricense.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A first principles study of energetics and electronic structural responses of uranium-based coordination polymers to Np incorporation

Abstract Recently developed coordination polymers (CPs) and metal organic frameworks (MOFs) may find applications in areas such as catalysis, hydrogen storage, and heavy metal immobilization. Research on the potential application of actinide-based CPs (An-CP/MOFs) is not as advanced as transition metal-based MOFs. In order to modify their structures necessary for optimizing thermodynamic and electronic properties, here, we described how a specific topology of a particular actinide-based CP or MOF responds to the incorporation of other actinides considering their diverse coordination chemistry associated with the multiple valence states and charge-balancing mechanisms. In this study, we apply a recently developed DFT-based method to determine the relative stability of transuranium incorporated CPs in comparison to their uranium counterpart considering both solid and aqueous state sources and sinks to understand the mechanism and energetics of charge-balanced Np 5+ incorporation into three uranium-based CPs. The calculated Np 5+ +H + incorporation energies for these CPs range from 0.33 to 0.52 eV, depending on the organic linker, when using the solid oxide Np source Np 2 O 5 and U sink UO 3 . Incorporation energies of these CPs using aqueous sources and sinks increase to 2.85–3.14 eV. The thermodynamic and structural analysis in this study aides in determining, why certain MOF topologies and ligands are selective for some actinides and not for others. This means that once this method is extended across a variety of CPs with their respective linker molecules and different actinides, it can be used to identify certain CPs with certain organic ligands being specific for certain actinides. This information can be used to construct CPs for actinide separation. This is the first determination of the electronic structure (band structure, density of states) of these uranium- and transuranium-based CPs which may eventually lead to design CPs with certain optical or catalytic properties. While the reduction of the DFT-determined-bandgap goes from 3.1 eV to 2.4 eV when going from CP1 to CP3, showing the influence of the linker, Np 6+ incorporation reduces the bandgap for CP1 and CP3, while increasing it for CP2. The coupled substitution of U 6+ →Np 5+ +H + reduces the bandgap significantly, but only for CP3.

Chemistry↗

Uranium Anodic Dissolution under Slightly Alkaline Conditions Progress Report Full-Scale Demonstration with DU Foil

Argonne National Laboratory (Argonne) is developing an alternative method for digesting irradiated low enriched uranium (LEU) foil targets to produce 99 Mo in neutral/alkaline media. This method consists of the electrolytic dissolution of irradiated uranium foil in sodium bicarbonate solution, followed by precipitation of base-insoluble fission and activation products, and uranyl-carbonate species with CaO. The addition of CaO is vital for the effective anion exchange separation of 99 MoO 4 2- from the fission products, since most of the interfering anions (e.g., CO 3 2- ) are removed from the solution, while molybdate remains in solution. An anion exchange is used to retain and to purify the 99 Mo from the filtrate. The electrochemical dissolver has been designed and fabricated in 304 stainless-steel (SS), and tested for the dissolution of a full-size depleted uranium (DU) target, wrapped in Al foil. Future work will include testing with low-burn-up DU foil at Argonne and later with high-burn-up LEU foils at Oak Ridge National Laboratory.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Uranium Immobilization through Fe(II) bio-oxidation: A Column study

Current research on the bioremediation of heavy metals and radionuclides is focused on the ability of reducing organisms to use these metals as alternative electron acceptors in the absence of oxygen and thus precipitate them out of solution. However, many aspects of this proposed scheme need to be resolved, not the least of which is the time frame of the treatment process. Once treatment is complete and the electron donor addition is halted, the system will ultimately revert back to an oxic state and potentially result in the abiotic reoxidation and remobilization of the immobilized metals. In addition, the possibility exists that the presence of more electropositive electron acceptors such as nitrate or oxygen will also stimulate the biological oxidation and remobilization of these contaminants. The selective nitrate-dependent biooxidation of added Fe(II) may offer an effective means of “capping off” and completing the attenuation of these contaminants in a reducing environment making the contaminants less accessible to abiotic and biotic reactions and allowing the system to naturally revert to an oxic state. Our previous DOE-NABIR funded studies demonstrated that radionuclides such as uranium and cobalt are rapidly removed from solution during the biogenic formation of Fe(III)-oxides. In the case of uranium, X-ray spectroscopy analysis indicated that the uranium was in the hexavalent form (normally soluble) and was bound to the precipitated Fe(III)-oxides thus demonstrating the bioremediative potential of this process. We also demonstrated that nitrate-dependent Fe(II)-oxidizing bacteria are prevalent in the sediment and groundwater samples collected from sites 1 and 2 and the background site of the NABIR FRC in Oakridge, TN. However, all of these studies were performed in batch experiments in the laboratory with pure cultures and although a significant amount was learned about the microbiology of nitrate-dependent bio-oxidation of Fe(II), the effects of complex processes (such as advective flow) present in the natural environment are unknown. The objective of the current studies was to address some of these short-comings in an attempt to develop this bioremediative strategy into a robust, field applicable technology. This objective was approached by both pure culture studies investigating the mechanism of Fe(II) oxidation by nitrate reducing bacteria and examining the flow dynamics and microbial processes in advective flow columns amended with Fe(II) and nitrate over an extended period.

54 ENVIRONMENTAL SCIENCES↗

2012-13 Blue Room Low Enriched Uranium Sample Irradiation, Associated Gas Handling System, and Subsequent Separation Chemistry

An irradiation experiment was designed for the production of 100 mCi of medical isotope Mo-99 from a Low Enriched Uranium (LEU) solution. 300 mL of 150 gU/L LEU sulfate solution (pH1) was prepared and irradiated at the LANSCE Blue Room facility. The apparatus designed for the irradiation included a gas handling system, in which safe operation could be controlled by monitoring change in gas pressure. The gas handling system also contained a hydrogen oxygen recombiner, to recombine the gases generated through radiolysis of water, and an iodine trap, primarily for I-131. Pressure transients were observed during irradiation, which could be controlled by increasing the flow rate of the circulating pump. After irradiation the LEU solution was transferred to a hot cell facility for subsequent Mo-99 recovery using a titania column separation process, with samples also subsequently shipped to a radiochemical laboratory for further analysis. Gamma spectroscopy analysis revealed that ca. 70 mCi of Mo-99 was present at end of beam, in good agreement with the predicted value when actual beam history was included into the calculation. There was 80-85 % recovery of Mo-99 through a titania column separation, excluding losses through radioactive decay. The % Mo-99 recovery was lower than observed previously for the 1 mCi Mo-99 production (Target 4) experiments undertaken at LANL using the same separation apparatus, with on this occasion evidence of lower oxidation state molybdenum remaining irreversibly bound to the titania column. Subsequent postmortem analysis of the Blue room apparatus revealed that there had been no leaks in the gas handling system, the hydrogen and oxygen recombination appeared to work efficiently, and recovery of irradiated uranium trapped in the system allowed for >99% uranium mass balance.

07 ISOTOPE AND RADIATION SOURCES↗

Verification Of Column Design for Recovery of Mo from Low-Enriched Uranium Target Using Irradiated Target Tracer Solution

The Conversion Program of the Global Threat Reduction Initiative (GTRI) is developing technology necessary to enable the conversion of civilian facilities using high-enriched uranium (HEU) to low-enriched uranium (LEU) for fuels and targets. The conversion of conventional HEU dispersion targets to LEU for the production of 99Mo requires approximately five times the uranium to maintain the 99Mo yield per target. Under GTRI, Argonne is developing two front end options to the current processes to allow the use of LEU-foil targets. In both processes, the aim is to produce a product after the front end that will be compatible with current purification operations and that will, with the same number of targets irradiated, provide the same or higher yield of 99Mo at the end of processing. The goal of the front-end process is to deliver a product solution that is of the same or higher Mo purity than the current solution and is of equal or better compatibility with current purification processes.

Column Design↗

Matrix Infrared Spectroscopic and Computational Investigations of Novel Small Uranium Containing Molecules - Final Technical Report

Direct reactions of f-element uranium, thorium and lanthanide metal atoms were investigated with small molecules. These metal atoms were generated by laser ablation and mixed with the reagent molecules then condensed with noble gases at 4K. The products were analyzed by absorption of infrared light to measure vibrational frequencies which were confirmed by quantum chemical calculations. We have learned more about the reactivity of uranium atoms with common molecules, which will aid in the develolpment of further applications of uranium.

Andrews, Lester↗

Uranium Concentration Measurement Technique Viability Analysis

This report incorporates experimental and modelling data in support of the uranium UV-vis concentration analysis technique as applied to uranium sulfate solutions, and a short literature survey on the ‘Industry Standard’ Davies-Gray titration method for uranium analysis. A preliminary screen of a suite of contaminants that could interfere with the UV-vis measurement has revealed ruthenium to be by far the most likely to negatively impact the analysis technique, and this element is worthy of a more detailed study. Other experimental work confirm technique reproducibility and solution uniformity over time, and the potential viability of adaption to online analysis, while the application of the Guide to Uncertainty Measurements (GUM) to the UV-vis technique has been explored for the first time. Preliminary modelling analysis using GUM Workbench indicate 0.5 % technique relative uncertainty at the equivalent of two standard deviations, with an associated uncertainty ‘budget’ which provides guidance as to where the technique can be further developed to lower uncertainties.

07 ISOTOPE AND RADIATION SOURCES↗

Uranium Biomineralization By Natural Microbial Phosphatase Activities in the Subsurface

This project investigated the geochemical and microbial processes associated with the biomineralization of radionuclides in subsurface soils. During this study, it was determined that microbial communities from the Oak Ridge Field Research subsurface are able to express phosphatase activities that hydrolyze exogenous organophosphate compounds and result in the non-reductive bioimmobilization of U(VI) phosphate minerals in both aerobic and anaerobic conditions. The changes of the microbial community structure associated with the biomineralization of U(VI) was determined to identify the main organisms involved in the biomineralization process, and the complete genome of two isolates was sequenced. In addition, it was determined that both phytate, the main source of natural organophosphate compounds in natural environments, and polyphosphate accumulated in cells could also be hydrolyzed by native microbial population to liberate enough orthophosphate and precipitate uranium phosphate minerals. Finally, the minerals produced during this process are stable in low pH conditions or environments where the production of dissolved inorganic carbon is moderate. These findings suggest that the biomineralization of U(VI) phosphate minerals is an attractive bioremediation strategy to uranium bioreduction in low pH uranium-contaminated environments. These efforts support the goals of the SBR long-term performance measure by providing key information on "biological processes influencing the form and mobility of DOE contaminants in the subsurface".

54 ENVIRONMENTAL SCIENCES↗

SIMS Analyses of Aerodynamic Fallout from a Uranium-Fueled Test

Five silicate fallout glass spherules produced in a uranium-fueled, near-surface nuclear test were characterized by secondary ion mass spectrometry, electron probe microanalysis, autoradiography, scanning electron microscopy, and energy-dispersive x ray spectroscopy. Several samples display distinctive compositional heterogeneity suggestive of incomplete mixing, and exhibit heterogeneity in U isotopes with 0.02 < 235 U/ 238 U < 11.8 among all five samples and 0.02 < 235 U/ 238 U < 7.81 within a single sample. In two samples, the 235 U/ 238 U ratio is correlated with major element composition, consistent with the agglomeration of chemically and isotopically distinct molten precursors. Two samples are quasi-homogeneous with respect to composition and uranium isotopic composition, suggesting extensive mixing possibly due longer residence time in the fireball. Correlated variations between 234 U, 235 U, 236 U and 238 U abundances point to mixing of end-members corresponding to uranium derived from the device and natural U ( 238 U/ 235 U = 0.00725) found in soil.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Study of Microbial Environmental Processes Related to the Natural Attenuation of Uranium at the Rifle Site using Systems-level Biology

Microbes exist in communities in the environment where they are fundamental drivers of global carbon, nutrient and metal cycles. In subsurface environments, they possess significant metabolic potential to affect these global cycles including the transformation of radionuclides. This study examined the influence of microbial communities in sediment zones undergoing biogeochemical cycling of carbon, nutrients and metals including natural attenuation of uranium. This study examined the relationship of both the microbiota (taxonomy) and their metabolic capacity (function) in driving carbon, nutrient and metal cycles including uranium reduction at the Department of Energy (DOE) Rifle Integrated Field Research Challenge (RIFRC). Objectives of this project were: 1) to apply systems-level biology through application of ‘metaomics’ approaches (collective analyses of whole microbial community DNA, RNA and protein) to the study of microbial environmental processes and their relationship to C, N and metals including the influence of microbial communities on uranium contaminant mobility in subsurface settings undergoing natural attenuation, 2) improve methodologies for data generation using metaomics (collectively metagenomics, metatranscriptomics and proteomics) technologies and analysis and interpretation of that data and 3) use the data generated from these studies towards microbial community-scale metabolic modeling. The strategy for examining these subsurface microbial communities was to generate sequence reads from microbial community DNA (metagenomics or whole genome shotgun sequencing (WGS)) and RNA (metatranscriptomcs or RNAseq) and protein information using proteomics. Results were analyzed independently and through computational modeling. Overall, the community model generated information on the microbial community structure that was observed using metaomic approaches at RIFRC sites and thus provides an important framework for continued community modeling development. The model as created is capable of predicting the response of the community structure in changing environments such as anoxic/oxic conditions or limitations by carbon or nutrients. The ability to more accurately model these responses is critical to understanding carbon and energy flows in an ecosystem is critical towards improving our ability to make predictions that can be used to design more efficient remediation and management strategies, and better understand the implications of environmental perturbations on these ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Non-Invasive Acoustic-Based Monitoring of Heavy Water and Uranium Process Solutions

This presentation includes slides on Project Goals; Heavy Water Production Monitoring: A New Challenge for the IAEA; Noninvasive Measurements in SFAI Cell; Large Scatter in Literature Values; Large Scatter in Literature Values; Highest Precision Sound Speed Data Available: New Standard in H/D; ~400 pts of data; Noninvasive Measurements in SFAI Cell; New funding from NA241 SGTech; Uranium Solution Monitoring: Inspired by IAEA Challenge in Kazakhstan; Non-Invasive Acoustic-Based Monitoring of Uranium in Solutions; Non-Invasive Acoustic-Based Monitoring of Uranium in Solutions; and finally a summary.

47 OTHER INSTRUMENTATION↗

Unreviewed Disposal Question Evaluation: Disposal of the Nevada National Security Site Uranium Powder at the Area 5 Radioactive Waste Management Site, Nevada National Security Site

This Unreviewed Disposal Question Evaluation (UDQE) assesses whether the Nevada National Security Site (NNSS) Uranium Powder (Normal, depleted uranium [DU], low-enriched uranium [LEU]) is suitable for shallow land burial (SLB) at the Area 5 Radioactive Waste Management Site (RWMS) on the Nevada National Security Site.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Deep Vadose Zone Treatability Test of Uranium Reactive Gas Sequestration for the Hanford Central Plateau: Final Report

The uranium reactive gas sequestration (URGS) test described herein was conducted as an element of the Deep Vadose Zone Treatability Test Plan for the Hanford Central Plateau. The URGS technology was tested as a potential remedy to decrease the mobility of uranium in the vadose zone as a mechanism to protect groundwater. Information about URGS obtained from this test is intended for use in subsequent feasibility studies for Hanford Central Plateau waste sites with uranium contamination in the deep vadose zone.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Special Analysis for the Disposal of the Portsmouth Uranium Fluoride Solids Waste Stream at the Area 5 Radioactive Waste Management Site, Nevada National Security Site, Nye County, Nevada

This special analysis (SA) evaluates whether the Portsmouth Gaseous Diffusion Plant (PORT) Uranium (U) Fluoride Solids waste stream is suitable for disposal by shallow land burial at the Area 5 Radioactive Waste Management Site on the Nevada National Security Site (NNSS). The PORT U Fluoride Solids waste stream consists of highly enriched uranium solids. The PORT U Fluoride Solids waste stream requires an SA to resolve whether it is acceptable to dispose of technetium-99 ( 99 Tc), uranium-234 ( 234 U), and thorium-230 ( 230 Th) with activity concentrations exceeding the NNSS Waste Acceptance Criteria Action Levels.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗