Title: Critical behavior in magnetic phase diagrams of uranium compounds Author: Bc. Petr Opletal Department: Department of Condensed Matter Physics Supervisor: RNDr. Jan Prokleška, Ph.D., Department of Condensed Matter Physics Abstract: This work is focused on study of phase diagrams and related critical effects in the pseudoternary UCo1-xRuxAl compound. Three single crystals of nominal composition UCo0.99Ru0.01Al, UCo0.995Ru0.005Al and UCo0.9975Ru0.0025Al have been prepared by Czochralski method in triarc furnace. Quality of single crystals was checked by EDX analysis, Laue method and XRPD. For UCo0.99Ru0.01Al Curie temperature was determined as TC = 16 K. UCo0.995Ru0.005Al shows transition from paramagnetic to ferromagnetic phase at TC= 4.5 K and at higher temperatures we observe a metamagnetic transition of first order with a critical field HC = 0.04 T. UCo0.9975Ru0.0025Al is paramagnetic to low temperatures with metamagnetic transition of first order and critical field HC = 0.55 T. Experiments in hydrostatic pressure on UCo0.995Ru0.005Al and UCo0.9975Ru0.0025Al showed decay of ferromagnetism and increase of critical field. This behavior is similar to evolution of magnetism in UCoAl and URhAl in applied hydrostatic pressure. Keywords: UCoAl, URuAl, ferromagnetism, metamagnetism

Uranium contaminations of the subsurface in the vicinity of nuclear materials processing sites pose a health risk as the uranyl ion in its oxidized state, U(VI), is highly mobile in aquifers. Current remediation strategies such as pump and treat or excavation are invasive and expensive to implement on a large scale. In situ bioremediation represents an alternative strategy that uses the ability of local microbial communities to immobilize contaminants and is actively studied for uranium remediation. The immobilization of U(VI) in groundwater is achieved either by bioreduction to solid uraninite (U(IV)), adsorption to the soil matrix, or non-reductive precipitation of uranium phosphate minerals through the activity of bacterial phosphatases. Bioreduction has been widely studied for remediation of the saturated zone, as anaerobic conditions typically prevail in these environments. This process is only efficient at circumneutral pH, however, and the end product uraninite is unstable under aerobic conditions or in the presence of manganese oxides, nitrite, or even freshly formed iron oxides. Although non-reductive biomineralization of uranium catalyzed by bacterial phosphatase activity successfully removes uranium from the vadose zone, further studies are needed to assess the ability of microbial communities to hydrolyze organophosphate compounds in the saturated zone where oxygen is often depleted and uranium bioreduction may be significant. To investigate this process under anaerobic conditions, low pH soil samples from a uranium contaminated site at the Oak Ridge Field Research Center were incubated anaerobically in flow through reactors in the presence of exogenic organophosphate compounds to stimulate the natural microbial communities in the original soil matrix. Aqueous uranium was injected continuously in the reactors to determine the fraction of uranium removed during these incubations. The reactors amended with organophosphate produced inorganic phosphate in the effluent, suggesting that bacterial phosphatase activity can be stimulated even in anaerobic environments at low pH. Removal of U(VI) in a control amended with organophosphate over a short time period was similar compared to reactors amended with organophosphate for long times suggesting that adsorption may also play a role in U(VI) immobilization. A sequential extraction technique was optimized to differentiate the fraction of uranium loosely adsorbed and the fraction of uranium precipitated as phosphate minerals and batch adsorption experiments were performed to obtain thermodynamic parameters that could be used to predict the fraction of U(VI) adsorbed onto the soil matrix. Results indicated that 100% uranium adsorption was favorable from pH 5 to 10 (without the presence of phosphate), and that most of the solid phase uranium was extracted in the step defined for the strongly adsorbed/uranium phosphate mineral in both long and short-term amended reactors. Overall, these results demonstrate that the biomineralization of uranium phosphate minerals is a viable bioremediation strategy in both the vadose and saturated zones of aquifers at both low and high pH, provided an organophosphate source is available.

Thesis (Ph. D.)--Auburn University, 2005. / Abstract. Vita. Includes bibliographical references.

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Low level nuclear waste arising from UK nuclear sites, research establishments, hospitals and industry is currently disposed of at the Drigg Disposal Facility in Cumbria. Waste is packed into steel canisters before being compacted and grouted into larger steel storage containers. The aqueous chemistry of wastes, especially radionuclides, in the presence of grout material is of major interest. The gout used at the Drigg site is a mixture of Ordinary Portland Cement and Pulverised Fly Ash additive, from which ingressing water will leach high levels of calcium, sodium and potassium and produce waters of a high pH. Aerobic environments are expected to dominate over the early period of the vault life, after which the combined effect of canister corrosion and microbial activity will lead to anaerobic conditions. After a much longer period (100,000 years) anaerobic conditions may cease and yield once again an aerobic environment where migration of radionuclides may be sorption-controlled rather than on hydroxide precipitation at high pH. Work has been performed under both aerobic and anaerobic conditions to study uranium solubility in the presence of complexing ligands that may be present in the waters of the nearfield of a low-level waste disposal vault. Eleven ligands have been investigated: carbonate, phosphate, chloride, sulphate, acetate, citrate, EDTA, NTA and organic matter- humic acid, fulvic acid and iso-sacchannic acid. Anaerobic conditions were achieved by two different procedures; the first used ferrous ions in hydroxide solution and the second used dithionite in hydroxide solution. Both methods produce reducing electrode potentials and high pH. Computer software has been used to model experimental results, thereby predicting uranium solubilities and speciation, and to propose new formation constants to fit the experimental results more closely. Studies have also been perforined to measure uranium sorption by grout material at high pH in the presence of the above ligands. This work makes a significant contribution to the understanding of uranium solubility and speciation in waters. at high pH and under conditions relevant to low level nuclear waste disposal.

Conversion, the process by which natural uranium ore (yellowcake) is purified and converted through a series of chemical processes into uranium hexafluoride gas (UF6), has historically been excluded from the nuclear safeguards requirements of the 235U-based nuclear fuel cycle. With each step in the conversion process from yellowcake to feedstock for UF6, intermediary uranium oxide and uranium fluoride compounds become progressively attractive products for diversion toward activities noncompliant with international treaties. The diversion of this product material could potentially provide feedstock for a clandestine or undeclared enrichment for weapons development for state or non-state entities. With the realization of this potential, the International Atomic Energy Agency (IAEA) has only recently reinterpreted its policies to emphasize safeguarding this feedstock in response to such diversion pathways. This project employs a combination of simulation models and experimental measurements to develop and validate concepts of nondestructive assay monitoring systems in a natural uranium conversion plant (NUCP). In particular, uranyl nitrate (UN) solution exiting solvent extraction was identified as a key measurement point (KMP), where gamma-ray spectroscopy was selected as the process-monitoring tool. The Uranyl Nitrate Calibration Loop Equipment (UNCLE) facility at Oak Ridge National Laboratory was employed to simulate the full-scale operating conditions of a purified uranium-bearing aqueous stream exiting the solvent extraction process in an NUCP. This work investigates gamma-ray signatures UN circulating in the UNCLE facility and evaluates various gamma-ray detector (HPGe, LaBr3 and NaI) sensitivities to UN.

Title: Structure and magnetic properties of f-electron compounds and their hydrides Author: Silvie Mašková Department: Deparment of Condensed Matter Physics Supervisor: Doc. RNDr. Ladislav Havela, CSc., Deparment of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University, Prague, The Czech Republic Abstract: Magnetic properties were studied in several types of actinide- and lanthanide-based ternary compounds. We have shown indirect that anisotropy of compressibility and thermal expansion can be related to the direction of magnetic moments at U-compounds with "soft" directions (where the closest U-U links are) perpendicular to the moments direction. Comparison of U and RE compounds of the 2-2-1 type indicates that contrary to U compounds, RE compounds can absorb much more hydrogen. The involvement of the f-states in metallic bond, which takes place at actinides and not in lanthanides, makes the U-based compounds apparently more stable against hydrogenation. Basic electronic properties were established for ζ -Pu19Os, which is a close analogy to β-Pu, and for its low-temperature variety η -Pu19Os. The results confirm that the volume is not the main parameter driving Pu properties, as β-Pu with intermediate volume is the most strongly correlated Pu phase. Keywords: uranium compounds,...

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