Bacteria are known for their abilities to influence the geochemical processes and affect the mobility of contaminants in the subsurface. Arthrobacter strain G975 was studied to improve our understanding of their effect on uranium’s fate and transport. The research experimentally identified and compared several parameters, including cell growth rate, cell viability, and the bacteria partition coefficient, Kd, under various uranium and bicarbonate concentrations mimicking Hanford Site subsurface environmental conditions, as well as the microbes ability to interact with uranyl phosphate minerals. The results show that the G975 strain can uptake up to 90% of the U(VI) concentrations tested, following linear isotherm models whose uptake capacity was measured up to 150.2 ± 71.4 mg/g and decreased with increasing bicarbonate concentrations. AFM and SEM/EDS analysis confirmed surface membrane uranium precipitates. The research presented here is part of a large effort to advance the understanding of the biogeochemistry processes and plausible remediation strategies concerning uranium contamination.

Some reactions leading to several anhydrous Uranium fluorosulfates through the use of fluorosulfonic acid or peroxydisulfuryl di-fluoride have been studied. It was found that HS0F can oxidize uranium 3metal to the +4 state or the +2 state depending on the reaction conditions. The synthesis of the tan solid; U(S03F)4 and the pale green solid thought to be U(S03F)2 were prepared in this manner. It was found that S206F2 can also oxidize uranium to yield the green solid U(S03F)3. S206F2 was also found to be a convenient reagent for placing a fluorosulfonate group on uranium tetrahalides to form addition or displacement products; the yellow solid UF4(S03F)2 and the tan solid U(S03F)4 were prepared in this manner. Other reactions involving the fluorosulfate, U(S03F)4 as a reactant are also discussed. Analytical data and infrared spectra are reported for the compounds and x-ray powder data and magnetic susceptibility data are presented for U(S03F)2 and U(S03F)4. The reaction of the fluorinated anhydride µ -oxo-bis (phosphoryl difluoride), P203F4 with some group VI B metal oxide salts has found to form the corresponding difluorophosphates. Five new compounds were prepared; KCr02(P02F2)3·P203F4, Cs2Cr02(P02F2)4, Na2MO02 (P02F2)4, Na2W02(P02F2)4. Physical constants, analytical data and infrared spectra are presented supporting the proposed structures for these compounds. A method for the preparation of K2Cr02(CF3S03)4 from K2Cr04 and (CF3S02)20 is also presented. Analytical data, infrared spectra and the x-ray powder spectra for this compound are given.

No description available.

<p> New uranium(VI) complexes of a-hydroxyquinoline ligands of formulae U02(R-Q)2 R-QH have been prepared. In these compounds, the additional liquid is likely bonded as a zwitterion. Appropriate substitution in the 2- and 7-positions lead to interesting steric effects. Some uranium(VI) complexes reported in the literature have been re-examined and found to be incorrectly formulated. </p> <p> The scandium(III) complex of a-hydroxyquinoline obtained from aqueous solution was. found to be Sc(C9H6N0) 3 •H20 and not Sc(CgH&N0) 3 •C 9H7NO as previously reported. In the absence of water, Sc (CgH&NO) 3 •C 9H7NO 'Was obtained. New scandium(III) complexes of formulae Sc(R-Q) 3 •R-QH and Sc(R-Q) 3 •H20 have been prepared. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.

No description available.

No description available.

Investigation of nitride fuels and their properties has, for decades, been propelled on the basis of their desirable high metal densities and high thermal conductivities, both of which oer intrinsic advantages to performance, economy, and safety in fast and light water reactor systems. In this time several key obstacles have been identied as impeding the implementation of these fuels for commercial applications; namely chemical interactions with air and steam, the noted diculty in sintering of the material, and the high costs associated with the enrichment of 15N. The combination of these limitations, historically, led to the well founded conclusion that the most appropriate use of nitride fuels was in the fast reactor fuel cycle, where the cost burdens associated with them is substantially less. Indeed, it is within this context that the vast majority of work on nitrides has been and continues to be done. Nevertheless, following the 2011 Fukushima-Daiichi nuclear accident, a concerted governmental-industrial eort was embarked upon to explore the alternatives of so-called \accident tolerant" and \high performance" fuels. These fuels would, at the same time, improve the response of the fuel-clad system to severe accidents and improve the economy of operation for light water reactor systems. Among the various candidates proposed are uranium nitride, uranium silicide, and a third \uranium nitride-silicide" composite featuring a mixture of the former. In this thesis a method has been established for the synthesis, fabrication, and characterization of high purity uranium nitride, and uranium nitride-silicide composites, prepared by the spark plasma sintering (SPS) technique. A specic result has been to isolate the impact of the processing parameters on the microstructure of representative fuel pellets, essentially permitting any conceivable microstructure of interest to be fabricated. This has enabled the development of a highly reproducible technique for the production of pellets with microstructures tailored towards any desired porosity between 88-99.9%TD, any grain size between 6-24 μm, and, in the case of  the uranium nitride-silicide composite, a silicide-coated UN matrix. This has permitted the evaluation of these microstructural characteristics on the performance of these materials, specically with respect to their role as accident tolerant fuels. This has generated results which have tightly coupled nitride performance with pellet microstructure, with important implications for the use of nitrides in water-cooled reactors. / Under artionden har forskning om nitridbranseln och dess egenskaper bedrivits pa grundval av nitridbransletsatravarda egenskaper avseende dess hoga metall tathet och hog varmeledningsformaga. Dessa egenskaper besitter vasentliga fordelar avseende prestanda, ekonomi och sakerhet for metallkylda som lattvatten reaktorer. Genom forskning har aven centrala begr ansningar identierats for implementering av nitridbranslen for kommersiellt bruk. Begransningar avser den kemiska interaktionen med luft och vattenanga, en uppmarksammad svarighet att sintring av materialet samt hoga kostnader forknippade med den nodvandiga anrikningen av 15-N. Kombinationen av dessa begransningar resulterade, tidigare, i en valgrundad slutsats att nitridbranslet mest andamalsenliga anvandningsomrade var i karnbranslecykeln for snabba reaktorer. Detta da kostnaderna forenade med implementeringen av branslet ar avsevart lagre. Inom detta sammanhang har majoriteten av forskning avseende nitrider bedrivits och fortskrider an idag. Dock, efter karnkraftsolyckan i Fukushima-Daiichi 2011, inleddes en samlad industriell och statlig anstrangning for att undersoka alternativ till sa kallade \olyckstoleranta" och \hogpresterande" branslen. Dessa branslen skulle samtidigt forbattra reaktionstiden for bransleinkapsling systemet mot allvarliga olyckor samt forbattra driftsekonomin av lattvattenreaktorer. Foreslagna kandidater ar urannitrid, uransilicid och en tredje \uran nitrid-silicid", komposit bestaende av en blandning av de foregaende. Genom denna avhandling har en metod faststallts for syntes, tillverkning och karaktarisering av uran nitrid av hog renhet samt uran nitrid-silicid kompositer, forberedda med tekniken SPS (Spark Plasma Sintering). Ett specikt resultat har varit att isolera eekten av processparametrar pa mikrostrukturen pa representativa branslekutsar. Detta mojliggor, i princip, framstallningen av alla tankbara mikrostrukturer utav intresse for tillverkning. Vidare har detta mojliggjort utvecklingen av en hogeligen reproducerbar  teknik for framstallningen av branslekutsar med mikrostrukturer skraddarsydda for onskad porositet mellan 88 och 99.9 % TD, och kornstorlek mellan 6 och 24 μm. Dartill har en metod for att belagga en matris av uran nitrid-silicid framarbetats. Detta har mojliggjort utvarderingen av dessa mikrostrukturella parametrars paverkan pa materialens prestanda, sarskilt avseende dess roll som olyckstoleranta branslen. Detta har genererat resultat som ar tatt sammanlankat nitridbranslets prestanda till kutsens mikrostruktur, med viktiga konsekvenser for den potentiella anvandningen av nitrider i lattvatten reaktorer. / <p>QC 20170210</p>

En Afrique du Sud, le supergroupe Pongola s’est déposé sur le craton du Kaapvaal à environ 3 milliards d’années. Le groupe Mozaan repose sur le groupe basal Nsuze et contient des pélites, des arénites quartziques, des grès et des conglomérats. Dans ce type de conglomérat, des gisements d’uranium et des minéralisations d’or ont été reconnus dans le monde, au Canada, au Brésil, en Australie et en Afrique du Sud. Des petites minéralisations ont été avérées dans le groupe Mozaan, très différentes de celles qui ont été exploitées dans le bassin voisin du Witwatersrand. Ce travail pétrographique, minéralogique et géochimique concerne les formations conglomératiques et gréseuses basales du Mozaan Group dans le Denny Dalton. Il est fondé sur l’étude de deux carottes dans lesquelles des minéralisations en uranium ont été reconnues. Une attention particulière a été portée sur le matériel détritique car, dans ces conglomérats, les gisements sont de type placer avec des remobilisations plus ou moins marquées. Les grains détritiques identifiés associés à la pyrite détritique, sont la monazite fréquente, les oxydes de titane, les minéraux d’uranium thorium (coffinite, thorite, thorianite), le zircon, l’apatite, la chromite ainsi que d’autres sulfures (chalcopyrite, arsénopyrite). La roche source est vraisemblablement de matériel acide avec un faible apport basique ainsi que métamorphique. La morphologie des minéraux suggère un transport court de la source vers le bassin de Pongola. Les analyses pétrographiques et chimiques mettent en évidence les différentes minéralisations qui caractérisent les processus diagénétiques et hydrothermaux qui ont affecté le groupe Mozaan. Des observations nouvelles ont été réalisées sur les minéraux d’uranium avec la mise en évidence de phospho-coffinite, de phosphates alumineux hydratés de terres rares et des altérations très développées qui affectent les grains de monazite. Ces assemblages minéralogiques révèlent une diagenèse avec la circulation de fluides acides comme l’atteste la présence de pyrite et des APS dans la porosité secondaire des roches. Aucun grain d’uraninite détritique ni d’uraninite authigène n’a été observé dans cette étude. L’hypothèse la plus vraisemblable est que l’uranium des zones minéralisées provient de l’altération des grains de monazite à 2.54 Ga par des fluides acides. La remobilisation se fait en milieu ouvert et l’uranium cristallise essentiellement en bordures des grains de pyrite sous forme de phospho-coffinite. / In South Africa, the Pongola Supergroup was deposited on the craton Kaapvaal about 3 Ga years. The Mozaan group based on the basal Nsuze group and contains mudstones, arenites, sandstones and conglomerates. In this type of conglomerate, uranium and gold mineralization deposits have been recognized in the world, Canada, Brazil, Australia and South Africa. Small mineralization have been proved to in the Mozaan group, very different from those that have been exploited in the the neighbor of the Witwatersrand Basin. The petrographic, mineralogical and geochemical work concerns basal conglomerate and sandstone formations of Mozaan Group in Denny Dalton. It is based on the study of two cores where uranium mineralizations have been recognized. Particular attention was focused on the detrital material, because in these conglomerates, the deposits are placer type with the remobilizations more or less marked. The detrital grains identified associated with the detrital pyrite are frequent monazite, titanium oxides, thorium uranium minerals (coffinite, thorite, and thorianite), zircon, apatite, chromite and other sulphides (chalcopyrite, arsenopyrite). The source rock is likely acidic material with low basic contribution and metamorphic.The mineral morphology suggests a short transport the source to the Pongola basin. Petrographic and chemical analyzes show that characterize the different diagenetic mineralization and hydrothermal processes that have affected the Mozaan group. New observations were made on uranium minerals with the detection of phospho-coffinite, aluminous hydrated rare earth phosphates and highly developed alterations affecting monazite grains. These mineral assemblages reveal a diagenesis with the flow of acidic fluids as evidenced by the presence of pyrite and APS in the secondary porosity of the rocks. Detrital and authigène uraninite grains were not observed in this study. The most likely hypothesis is that the uranium mineralized zones comes from the weathering of monazite grains to 2.54 Ga by acidic fluids. Remobilization is done in open and uranium mainly crystallizes edges of pyrite grains in the form of phospho-coffinite.

L'uranium est un radionucléide qui possède une toxicité radiologique et chimique, causant des problèmes pour l’environnement et la santé humaine. Les micro-organismes du sol et l'uranium ont des relations complexes. L'objectif de cette étude est de décrire les interactions bactéries-uranium par l'utilisation de souches isolées d’environnements contaminés. Les quatre souches sont apparentées au genre Microbacterium et présentent un phénotype de tolérance à l'uranium contrasté. Différents mécanismes d'interaction avec l'uranium se produisent séquentiellement : une première étape de séquestration rapide de l'uranium due à de la biosorption passive, suivie d'une étape active d’efflux d'uranium et de phosphate, observée uniquement dans les souches tolérantes, et enfin, une accumulation intracellulaire de précipités de phosphate d'uranyle. Afin d'identifier les acteurs moléculaires impliqués dans les interactions cellule-uranium, une analyse comparative basée sur une approche protéogénomique a été réalisée. Les analyses statistiques sur les protéines identifiées ont révélé que l'exposition à l'uranium a un impact sur les métabolismes du phosphate et du fer. La protéine ayant le fold-change positif le plus élevé a fait l'objet d'études plus poussées. La protéine UipA est très affine pour l'uranium et le fer. Les analyses biophysiques ont révélé une coordination mono et bidentale pour l'uranium et le fer. En amont du gène uipA, deux gènes partageant l'homologie de séquence avec le système czcRS à deux composants ont été détectés. Les protéines UipRSA ne sont présentes que dans les souches tolérantes suggérant que ce cluster est impliqué dans la tolérance à l'uranium. / Uranium is a radionuclide used in nuclear energy. It has radiological and chemical toxicity, causing environmental and human health problems. Soil microorganisms and uranium have complex relationships. The goal of this study is to describe bacterium-uranium interactions through the use of bacteria isolated from contaminated environments. The four strains are related to the bacterial genus Microbacterium. They present a contrasted uranium tolerance phenotype from tolerant (ViU2a and Hg3) to sensitive (ViU22) and intermediate (A9). During exposure to uranium, different mechanisms of interaction with uranium occur sequentially: a first step of rapid sequestration of uranium due to passive biosorption, followed by an active step of uranium and phosphate efflux, observed only in tolerant strains, and finally, an active intracellular accumulation of uranyl phosphate precipitates. In order to identify the molecular actors involved in cell-uranium interactions, a comparative analysis based on a proteogenomic approach was performed. Between 1 100 and 2 000 proteins were identified. Statistical analyses revealed that uranium exposure impacts phosphate and iron metabolisms. The protein with the highest positive fold-change has been further studied. The UipA protein is a very affine and specific for uranium and iron, with Kd of the nanomolar order. Biophysic analyses revealed mono- and bidental coordination for uranium and iron. Upstream of the uipA gene, two genes sharing sequence homology with the two-component czcRS system were detected. The UipRSA cluster is only present in the tolerant strains. These data suggest that the uipRSA cluster is involved in uranium tolerance.