Thesis -- Columbia University. / Cover title. Includes bibliographical references.

Uranium exists in carbonate solution in its hexavalent state as the complex ion U0₂(C0₃)₃---- . In most ores uranium occurs as pitchblende (U₃0₈). It has been found possible to dissolve uranium in carbonate-bicarbonate solutions from these ores by leaching them in the presence of oxygen. The overall reaction is as follows: U₃O₈ + ½0₂+ 3C0₃ˉ˭ + 6HCO₃- → 3U0₂(C0₃)₃---- + 3H₂0 The objective of the present research was to examine the kinetics of this reaction with a view to determining the mechanism of the reaction and to establish the variables upon which the rate depends. Two series of experiments were conducted on two types of materials: (a) Pitchblende specimens of measured surface area were suspended in a solution containing sodium carbonate and sodium bicarbonate. Above the solution a desired pressure of oxygen was maintained. (b) A pulp of low grade pitchblende ore in carbonate, solutions was agitated in an autoclave, in the presence of oxygen maintained at the desired pressures. The rate of solution of uranium was measured by sampling and analyzing the solutions at regular time intervals. The effect of oxygen pressure, temperature, and reagent concentration on the rate was studied in each series. The kinetic results were examined by the methods of the absolute reaction rate theory. The following conclusions were drawn from the leaching tests: (1) The absolute reaction rates are about the same for all the materials studied. (2) The reaction rate varies as the square root of the absolute oxygen pressure. (3) The activation energy is about 12,000 - 3000 calories per gram mole. (4) Minimum amounts of carbonate and bicarbonate are necessary to dissolve the oxidized uranium. Further increases beyond this minimum amount result in only minor increases in the rate of the reaction. A mechanism for the leaching rate is proposed in which the oxidation is the rate controlling step. / Applied Science, Faculty of / Mining Engineering, Keevil Institute of / Graduate

This paper deals with a new method of separating uranium from pitchblende. The main feature of this separation is the use of an ion exchange resin, Amberlite IRC-50. The purity of the uranium has been checked, chemically and spectrographically. By this method, uranium of high purity can be obtained even in the presence of large quantities of impurities. / Science, Faculty of / Chemistry, Department of / Graduate

Les plus anciens gisements d’uranium connus sur Terre sont les gisements de type paléo-placer hôtes de conglomérats à cailloux de quartz d’âge compris entre 3,09 et 2,2 Ga. Ces gisements représentent les reliques de l’ancienne croûte continentale archéenne maintenant érodée. L’origine de leurs concentrations primaires, correspondant à des accumulations de grains détritiques d’uraninite, est toujours sujette à controverse et la nature et les processus de formation des roches sources archéennes demeurent incertains.Ce travail présente l’analyse minéralogique et géochimique détaillée des minéralisations de différents paléo-placers (Witwatersrand en Afrique du Sud, Elliot Lake au Canada et séries Jatuliennes en Russie) ainsi que de granitoïdes archéens et paléoprotérozoïques enrichis en uranium (séries granitiques calco-alcalines à potassiques du craton de Kénéma Man en Guinée, granites tardi-orogéniques du craton de Pilbara en Australie Occidentale, pegmatite peralumineuse de Tanco du Bouclier Canadien et pegmatites à uraninite du Bouclier Baltique en Finlande et Russie). L’étude comparative de ces roches uranifères échantillonnées tout autour du globe prouve à la fois i) l’existence précoce (>3,1 Ga) de granitoïdes différenciés produits par la fusion partielle d’une croûte pré-enrichie tels que des granites peralumineux ou de type S, ii) nécessairement la présence d’un mécanisme permettant de produire ce type de granites comme les zones de subduction ou de collision générées par le mouvement des plaques tectoniques, iii) l’origine magmatique des uraninites thorifères des paléo-placers, iv) la présence d’une atmosphère réductrice avant 2,2 Ga permettant la préservation des uraninites durant leur transport, v) et finalement l’augmentation de l’oxygène libre dans l’atmosphère paléo-protérozoïque à partir de 2,2 Ga provoquant la disparition des paléo-placers uranifères en faveur de l’altération et de l’oxydation des concentrations préexistantes, de la remobilisation de l’uranium et de la formation de dépôts secondaires / The oldest known uranium deposits on the Earth are the paleoplacer-type deposits hosted in quartz-pebble conglomerates from 3.09 to 2.2 Ga in age. These deposits are representative of the ancient Archean continental crust now eroded. The origin of the primary ores corresponding to accumulation of detrital uraninite is still controversy and the nature and forming processes of the Archean source rocks remain uncertain.This work provides the detail mineralogical and geochemical analysis of mineralization from different paleoplacer-type deposits (Witwatersrand in South Africa, Elliot Lake in Canada and the Jatulian series in Russia) and from Archean and Paleoproterozoic U-enriched granitoids (calco-alkaline to potassic granite series from the Kenema Man Craton in Guinea, late-orogenic granites from the Pilbara Craton in West Australia, the Tanco pegmatite from the Canadian Shield and uraninite bearing pegmatites from the Baltic Shield in Finland and Russia). The comparative study of these worldwide uraniferous rocks prove either i) the existence of highly differentiated granitoids produced by the partial melting of a pre-enriched crust as peraluminous and S-type granites in early time (>3.1 Ga), ii) obviously the presence of an effective mechanism to produce such granites as tectonic plate systems with subduction or collisional zones, iii) the magmatic origin of the thorian uraninites in paleoplacers, iv) the efficiency of a reductive atmosphere prior to 2.2 Ga permitting the preservation of uraninite during transportation, v) and finally the rise of the oxygen-free level in the paleoproterozoic atmosphere providing the disappearance of uraniferous paleoplacers in favour of weathering, oxidation of pre-existing concentrations, remobilization of uranium and formation of secondary deposits

The uranium price decline has negatively impacted on the uranium mining industry. This decline in price requires that uranium metallurgical processes be made to operate more efficiently. Some key parameters that influence the dissolution and kinetics of leaching uraninite (one of the main minerals from which uranium can be extracted) are pH, oxidationreduction potential and iron concentration. A good understanding of the effect these parameters have on the leach kinetics would lead to an efficient operation of metallurgical processes. The objective of this work was therefore to investigate the effects of these key drivers on leach kinetics of Rӧssing Uranium ore. Added to this, was an attempt to come up with a mathematical model which can successfully replicate the leach kinetics. A series of laboratory leach experiments were performed on Rӧssing ore where the pH, oxidationreduction potential and total iron were varied, one at a time, to establish the effects they have on the leach kinetics and on the uranium extraction. Analysis of the data collected from this study showed that the leach kinetics are more dependent on the oxidation-reduction potential, followed by the iron concentration and least affected by the pH. It was further shown that oxidation-reduction potential is a function of total iron. An integral method was used to analyse the kinetic data. A literature study reveals that uraninite dissolution follows first order kinetics, but of interest in these results was that the uranium dissolution was found to closely follow the second order. Further research is recommended to look at ascertaining these results. Two models were developed, one using regression and the other by curve fitting method. Both models could fit the experimental data well enough. / Dissertation (MSc)--University of Pretoria, 2016. / Materials Science and Metallurgical Engineering / MSc / Unrestricted

Les principales cibles d'exploration pour les gisements d’uranium de type discordance du bassin d’Athabasca (Canada) sont les structures graphiteuses du socle. Toutes ces structures ne sont pourtant pas fertiles et elles présentent des histoires plus ou moins complexes de circulations fluides successives. Cette thèse propose de déconvoluer les caractéristiques propres à chaque évènement de circulations fluides par une étude multidisciplinaire focalisée sur l’exemple de l’environnement proche du gisement de Cigar Lake. Au cours de l’exhumation tardi-orogénique du socle, la formation de failles ductile-cassantes associées à une circulation intense de fluides à C-O-H-N a permis des enrichissements en graphite et une première évolution pétrophysique des zones endommagées. Ces structures du socle particulièrement fragilisées par la déformation cassante fini-Hudsonienne ont pu être réactivées après dépôt du bassin et devenir des lieux favorables à la convection de saumures sédimentaires. La circulation de saumures sodiques dans le socle a favorisé des interactions fluides-roches à l’origine de la solubilisation de l’uranium, d’altérations K-Mg et d’évolution de composition du fluide vers un pôle plus calcique de plus forte salinité. Enfin une méthodologie d’analyse intégrée des compositions élémentaires majeures, traces et isotopiques U-Pb-O sur oxydes d’uranium est proposée, permettant de déconvoluer les effets des évènements fluides ultérieurs sur la minéralisation primaire. Cinq évènements ont ainsi contribué aux caractéristiques actuelles du gisement de Cigar Lake : Un évènement primaire de circulation de saumures à 1290-1380 Ma, à l’origine de l’ensemble du stock d’uranium ; un événement de circulations fluides à ca. 900 Ma à l’échelle régionale qui n’est pas associé à une reprécipitation d’uranium mais a brechifié et perturbé la chimie des oxydes primaires ; deux évènements tardifs de circulations fluides à ca. 340 et 220 Ma qui ont significativement remobilisé le stock primaire d’uranium. Enfin un dernier épisode récent de circulation d’eaux météoriques est à nouveau à l’origine d’un changement de chimie des oxydes antérieurs et d’une remise à zéro des systèmes isotopiques / The main exploration targets for unconformity-related U deposits of the Athabasca Basin are the graphite-rich structures in the basement. But these are not necessarily fertile. They show distinct features expressing specific events of fluid circulations. This study aims, through a multidisciplinary approach, at unravelling the complex history of fluid flow events recorded in the vicinity of the Cigar Lake deposit. During the basement uplift, at the end of the Trans-Hudson Orogeny, the formation of ductile-brittle shear zones associated to the circulation of C-O-H-N fluids led to hydrothermal graphite enrichments and a petrophysical evolution of damages zones. These graphite-rich shear zones that were specifically weakened by the ante-Athabasca brittle reactivation have been reactivated once more after basin deposition allowing the formation of a developed damage zone especially favorable for sedimentary brine convection. Circulations of NaCl-rich brines in the basement led to brine-rock interactions, and subsequent uptake of uranium and other metals from the basement rocks. The latter have subsequently undergone strong K-Mg alteration whereas the NaCl dominated brines evolved toward a CaCl2-dominated composition with higher salinities. Finally, this thesis sets out an integrated methodology allowing to decipher the complex superimposed geochemical signatures of distinct fluid flow events on the primary uranium oxides. Five fluid flow events contributed to the present day state of the Cigar Lake deposit: a primary event of brine circulation occurred at 1290-1380 Ma and is at the origin of the main U stock; a second basin-scale event of fluid flow occurred at ca. 900 Ma, it brecciated and strongly disturbed the deposit; two later events of fluid flow strongly remobilized the deposit at ca. 340 and 220 Ma and greatly contributed to the actual state of the deposit. Finally a last, rather recent event of fluid flow was at the origin of strong chemical changes in the uranium oxides compositions and strong isotopic resetting

As a consequence of rising uranium prices an interest in Sweden’s U deposits has emerged. This raises the important question of the possible environmental impacts of U mining operations. One of the most significant and serious issues is the contamination of groundwater by U following mining activities. The processes of uranium release and subsequent transport in groundwater is closely tied to its aqueous chemistry i.e. aqueous speciation, adsorption to mineral surfaces and dissolved organic carbon (DOM). The chemical parameters exerting the most control over these processes are pH and redox potential. The redox potential plays a decisive role because it controls the solubility of uraninite, a common uranium mineral and ore in Sweden’s bedrock deposits. Thus, by gaining insight into how changing redox conditions affect uraninite solubility, assessments can be made in order to estimate the extent of uranium transport by groundwater. Therefore the effects of the redox po-tential on U mobility will be examined in this work by means of computer modeling in the geochemical software VISUAL MINTEQ 3.0. The composition of the water used for modeling resembled that of a typical bedrock groundwater of Northern Sweden in the areas above the highest coastline. The simulations were carried out under different redox potentials at different pH levels in the presence of ferrihydrite and DOM to include the effects of U adsorption. The results show that the redox potential at which the uraninite mineral dissolves varies depending on the pH of the groundwater. From pH 4.0 to 7.5 the redox potential at which uraninite oxidizes decreases from 240-250 mV to 50-60 mV. This means higher redox conditions are needed for the dissolution of uraninite at low pH. Additionally, it is further concluded that the adsorption of U to ferrihydrite and DOC is important at pH 5-8 and pH < 7 respectively, which therefore play an important role in controlling the mobility of U in the modeled groundwater.