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At least 667 records · Page 37

Development of a Self-Consistent Model of Plutonium Sorption: Quantification of Sorption Enthalpy and Ligand-Promoted Dissolution

This university lead SBR project is a collaboration lead by Dr. Brian Powell (Clemson University) with co-principal investigators Dan Kaplan (Savannah River National Laboratory), Yuji Arai (presently at the University of Illinois), Udo Becker (U of Michigan) and Rod Ewing (presently at Stanford University). Hypothesis: The underlying hypothesis of this work is that strong interactions of plutonium with mineral surfaces are due to formation of inner sphere complexes with a limited number of high-energy surface sites, which results in sorption hysteresis where Pu(IV) is the predominant sorbed oxidation state. The energetic favorability of the Pu(IV) surface complex is strongly influenced by positive sorption entropies, which are mechanistically driven by displacement of solvating water molecules from the actinide and mineral surface during sorption. Objectives: The overarching objective of this work is to examine Pu(IV) and Pu(V) sorption to pure metal (oxyhydr)oxide minerals and sediments using variable temperature batch sorption, X-ray absorption spectroscopy, electron microscopy, and quantum-mechanical and empirical-potential calculations. The data will be compiled into a self-consistent surface complexation model. The novelty of this effort lies largely in the manner the information from these measurements and calculations will be combined into a model that will be used to evaluate the thermodynamics of plutonium sorption reactions as well as predict sorption of plutonium to sediments from DOE sites using a component additivity approach.

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Optimized Dissolution Flowsheet for Uranium Metal

The U.S. Department of Energy’s National Nuclear Security Administration (NNSA) has entered into cooperative agreements with commercial businesses to establish a reliable domestic source of 99 Mo that will be produced without the use of highly enriched uranium (HEU).

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Dissolution of Light Curium Oxide with a Catalyzed Electrolytic Process

The ability to produce transcurium elements and isotopes, such as 249 Bk and 252 Cf, requires the appropriate feed material and a high thermal neutron flux. Currently, at Oak Ridge National Laboratory (ORNL), the High Flux Isotope Reactor (HFIR) provides one of the world’s highest steady state thermal neutron fluxes. The feed material consists of recycled curium from the decades of production of 249 Bk, 252 Cf, 253 Es, and 255/257 Fm at the Radiochemical Engineering Development Center (REDC). Over time, the feed material has been depleted and needs to be replenished. The current feed material is called “heavy recycled curium” and consists of over 50 wt% of 246/248 Cm isotopes. In order to replenish this stock material, additional curium is needed. The only curium material that is currently available consists predominantly (greater than 80 wt%) of 244 Cm. This material also contains 240 Pu from the radioactive decay of the 244 Cm. Because of the amount of 244 Cm is greater than 50% of the total Cm, this material is termed “light curium.” Today, 249 Bk and 252 Cf are produced in only two places in the world: the United States and Russia. In the United States, the US Department of Energy and its predecessors have made these isotopes and others available to research agencies and commercial users since the late 1960s as part of the Department of Energy heavy-element production program located at ORNL. Currently these materials are provided through the DOE Office of Science Nuclear Physics-Isotope Development and Production for Research and Applications and the Basic Energy Science-Heavy Element Chemistry. Feedstock for the production of 252 Cf and other transcurium element by-product isotopes was originally prepared by means of irradiation of multi-kilograms of 239 Pu in the large production reactors at the Savannah River Site. Products of the Savannah River Site irradiation were predominantly 242 Pu, 243 Am, and 244 Cm. These materials were shipped to ORNL for production of multi-milligram amounts per year of 252 Cf and other transcurium element isotopes by means of irradiation in the HFIR, followed by separation and purification processing in the Radiochemical Engineering Development Center (REDC). The transcurium element isotopes produced were distributed to other US and collaborating foreign laboratories for research studies to determine the nuclear and chemical properties of these rare materials. The Cm feed material plays a key role in the efficient production of 252 Cf. The early targets irradiated in HFIR contained only the 242 Pu, 243 Am, and 244 Cm produced at Savannah River Site, and the rate of production of 252 Cf was less than 1 mg per 8 g of target material as shown in Figure 1. Also, shown in Figure 1 is the significant difference in 252 Cf production between the light and heavy curium; it differs by approximately 2 orders of magnitude.

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Characterization of Tank 9h Salt Dissolution Batch 2C In Support of Tank Closure Cesium Removal (TCCR) 1A Batch 2 Preparations

Savannah River Mission Completion (SRMC) is currently preparing the second batch of material to be processed through the Tank Closure Cesium Removal (TCCR) 1A system. The feed for TCCR 1A consists of dissolved saltcake from Tank 9H. The third batch of salt to make up processing Batch 2 (Batch 2C) has recently been dissolved in Tank 9H and transferred to Tank 10H where it was composited with the first part of the batch (Batches 2A and 2B) in preparation for processing through the TCCR 1A unit. Savannah River National Laboratory (SRNL) received samples from the recent batch (2C) of dissolved salt for characterization.

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Testing of the Defense Waste Processing Facility Cold Chemical Dissolution Method in Sludge Batch 10 Qualification

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) tests the applicability of the digestion methods used by the DWPF Laboratory for elemental analysis of Sludge Receipt and Adjustment Tank (SRAT) Receipt samples and SRAT Product process control samples. DWPF SRAT samples are typically dissolved using a method referred to as the DWPF Cold Chemical or Cold Chem Method (CC), (see DWPF Procedure SW4-15.201- 2.1).

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Removal of Tc-99, Zr-95, and Nb-95, From Solutions Obtained After Dissolution of Irradiated Mo Targets

Decontamination of 99 Tc, Nb, and Zr impurities in dissolved irradiated Mo disks can be accomplished using Fe(II) precipitation. Here, we report bench-scale experiments and large-scale demonstrations on removal of 99 Tc (0.1 mM), 95 Nb, and 95 Zr from dissolved Mo disk simulant solutions. Tc removal is accomplished through the reduction and simultaneous immobilization of Tc(VII) by Fe(II), producing an insoluble, Tcincorporated Fe(II)-Fe(III) solid that is removed by filtration. Large-scale testing showed that Tc (97.6% ± 1.7%) is removed without affecting 99 Mo yields. Other important side reaction product impurities in irradiated Mo targets, namely various isotopes of Nb and Zr, are also removed (>99%) in this process. The effects of metal (Fe, Tc, Mo) concentrations, Fe(II)/Fe(III) ratio, pH, temperature, Fe addition method, and hydrogen peroxide addition were tested. The minimum amount of Fe(II) needed to remove up to 99% Tc is 10 mM and the optimal pH value for simultaneous removal of Tc, Nb, and Zr impurities is pH 13.

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Low Pressure Oxygen-Assisted Acidic Dissolution of U Metal Foils

Traditional methods of dissolving uranium in nitric acid involve the generation of nitrogen oxide gases (NO x ), which not only are hazardous but also contribute to increased pressure within the dissolver. When uranium metal foils are dissolved in nitric acid, a series of redox reactions occurs, leading to the formation of NO x , such as nitrogen dioxide (NO 2 ) and nitric oxide (NO).

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Reactive-transport modeling of fracture flow to quantify the changes in flow pathways from matrix thermal contraction and mineral precipitation and dissolution; influence of grid resolution

A series of reactive-transport models of Enhanced Geothermal Systems (EGS) were constructed using the reactive transport code PFLOTRAN to examine the effect of matrix thermal contraction and mineral dissolution/precipitation on fracture flow in the context of grid cell size and model complexity. It was found that for thermal drawdown at production well, the impact of fracture zone grid cell size is negligible.

Gatz-Miller, Hannah Sarah↗

FY24 Task 4: Studies of Phosphate and Fluoride Solubility for Dissolution of High Phosphate Tank Waste

Knowledge gaps have been identified in phosphate solubility in almost every single- and multi-component system, and particularly for aluminate in phosphate/hydroxide, where uncertainties in predicted values of aluminum solubility are greater than 50%. Solubility data of multicomponent, aqueous electrolytes containing sodium hydroxide, sodium fluoride, sodium phosphate, sodium nitrite, sodium nitrate, and dissolved gibbsite are also sparse. For example, for solutions of (i) sodium nitrate and sodium phosphate, data are only available at 30 and 50 °C, and for (ii) dissolved gibbsite in sodium hydroxide and sodium phosphate, only two data points are available at 20 and 40 °C. There is no data available on mixtures of sodium hydroxide, sodium phosphate, sodium fluoride, and dissolved gibbsite. These knowledge gaps were identified in a technical review of waste solubility data and the impact of dilution on solution stabilities and will be addressed in this work to predict aluminum hydroxide and sodium phosphate solubility in multicomponent electrolytes upon dilution, and upon variation of temperature. Results will provide the technical basis to develop accurate models for (i) gibbsite solubility and mass transfer of aluminum between solid and liquid forms following the sluicing of sludge and saltcake with water; and (ii) further blending of these suspensions with bismuth from bismuth phosphate waste, and zirconium and uranium left from the fuel decladding. This work will be essential to developing a disposition path for retrieval solutions from bismuth phosphate wastes. This effort would also support sludge washing to further reduce phosphate concentration if that process were to be added back to the flowsheet in the future.

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