The eastern margin of the Proterozoic Athabasca Basin in northern Saskatchewan is host to several of the highest-grade unconformity-related (U/C-related) uranium deposits in the world. Many researchers agree that uranium deposition occurred due to oxidized basinal brines transporting uranium mixing with reducing fluids or interacting with reduced rock causing uranium to precipitate, although the source of the uranium is still an unresolved and highly debated subject. Boron isotopic signatures, preserved in refractory minerals such as tourmaline, can aid in determining the source of fluids and P-T conditions during crystallization whereas lithium isotopic fractionation is indicative of weathering, hydrothermal alteration, and/or igneous and metamorphic processes. For this study a suite of fresh to strongly altered basement samples were selected from multiple sites below the eastern Athabasca Basin to measure the bulk delta7Li, delta11B and Pb-Pb isotopic signatures. Kinetic modelling of the Li and B isotopic systems suggest that both systems are slightly conservative of their original fluid reservoir, and by calculating the Damkohler numbers (ND) it is predicted that delta11B will be more indicative of the fluid source whereas lithium isotopes will equilibrate over shorter distance. However, both isotopic systems will fractionate with large concentration changes. Significant variations were observed for both delta7Li and delta11B, delta7Li values ranged from 0 to 14 ‰, the range in delta7Li was interpreted to be representative of both partial melting of metasediments to form granitic pegmatites and hydrothermal fluids. In comparison the range for delta11B was much larger from -16 to +17‰, within the dataset there appeared to be regional isotopic differences but unfortunately this dataset was too small to determine regional isotopic patterns. For each region the delta11B for the pegmatites was often heavier than the metasedimentary samples suggesting a metasedimentary source for the granitic pegmatites. Elevated U concentrations and decreasing 207Pb/206Pb ratios in both altered and unaltered samples suggest radiogenic Pb and U are present both in the basement and in fluids transporting U through the basement. Partial digestion 207Pb/206Pb ratios range from the common 207Pb/206Pb ratios of 0.7 to radiogenic 207Pb/206Pb ratios of 0.1. The radiogenic 207Pb/206Pb are indicative of either resetting of residual material during fluid migration or radiogenic fluids sources interacting with the rocks of this study.

Two Paleoproterozoic basins, the western Thelon Basin, and the Otish Basin, Canada, were investigated using basin analysis to evaluate critical factors for the formation of unconformity-related uranium deposits. The results serve to guide ongoing exploration at two under-studied uranium prospects in each basin, and help predict whether or not these basins have the potential to host high-grade uranium deposits in other locations. Sequence stratigraphy, in combination with mineral paragenesis indicates that unmetamorphosed basinal sandstones overlying the Boomerang Lake prospect, western Thelon Basin, were compacted and occluded by kaolinite and muscovite during diagenesis, and became diagenetic aquicludes that were unable to effectively conduct uranium-bearing basinal brines. Based on the high δ18O values of basinal and basement-influenced fluids, and the preservation of pre-Thelon-Basin 40Ar/39Ar dates of poorly-crystalline phyllosilicates in the basement rocks, hydrothermal alteration and uranium mineralization must have occurred at low water/rock ratios. This produced uneconomic amounts of U-bearing phosphate that was misidentified as uraninite in a previous report. A significant uranium deposit is unprobable based on the lack of unsupported radiogenic Pb near the prospect. However, intersections of thick, stratigraphically-higher diagenetic aquifers, which are marked by abundant dickite, and structurally-reactivated basement rocks on a different exploration trend remain the most prospective locations for a uranium deposit in the area. At the Camie River prospect, Otish Basin, diagenesis of basinal sediments in thick diagenetic aquifers was associated with fluids that were isotopically similar to seawater-derived basinal brines. The 1721 ±20 Ma Pb/Pb date obtained for Camie River uraninite coincides with intrusions of the Otish Gabbro, which triggered basinal fluid flow in diagenetic aquifers and uranium mineralization throughout the basin. The effects of late hydrothermal, metamorphic, and meteoric fluid events are restricted to fractures and faults. These zones also preferentially host radiogenic Pb and pathfinder elements that dispersed from the prospect, which can be utilized to vector towards additional deposits. The unconformity-type deposit model can be extended to basins as old as 2.0 Ga, as the Otish Basin demonstrates that atmospheric oxygen contents were high enough at this time to allow the evolution of U-leaching oxidizing basinal brines. / Thesis (Ph.D, Geological Sciences & Geological Engineering) -- Queen's University, 2011-01-29 15:45:53.651

Les gisements d’U de type discordance sont associés à des circulations de saumures chlorurées acides et caractérisés par des tonnages et concentrations exceptionnels ce qui amènent à s’interroger sur les processus de transport et de dépôt de l’U contribuant à leur genèse. Cette thèse est donc dédiée à des études expérimentales de la spéciation de l’U6+ et sa précipitation en UO2 par réduction en U4+ en condition hydrothermale. Concernant le transport de l’U, l’étude de la spéciation de l’U6+ dans ces fluides chlorurés (T ≤ 350°C) est réalisée par spectroscopie Raman et XAS. Les résultats montrant la coexistence de plusieurs complexes d’uranyle chlorurés UO2Cln2-n (n=0-5) dont certaines constantes de complexation sont proposées. Ainsi, la complexation de l’uranyle par les chlorures explique la forte capacité de transport en U6+ par les saumures chlorurées acides, condition nécessaire à la formation de gisements de fort tonnage. Pour le dépôt de l’U, les cinétiques de réduction de l’U6+ en U4+ par H2, CH4, Fe2+ et C-graphite sont mesurées et paramétrées en fonction de la température, de la chlorinité, du pH et de la concentration en réducteur. H2, CH4 et le C-graphite sont être très efficaces, contrairement au Fe2+. Le caractère mobile des gaz réducteurs explique en partie les minéralisations massives et focalisées observées dans ces gisements. Enfin des coefficients de partage UO2/fluide d’éléments en traces, dont certaines ETR, sont mesurés, ouvrant de nouvelles perspectives quant à (i) la compréhension de la signature des ETR caractéristiques de chaque type de gisement d’U, et (ii) la composition des fluides à l’origine des minéralisations uranifères / Circulations of acidic chloride brines are associated with unconformity-related uranium (URU) deposits. The spectacular high grade combined with the large tonnage of these deposits is at the origin of the key questions concerning the geological processes responsible for U transport and precipitation. The aim of this work is to performed experimental studies of U6+ speciation and its reduction to U4+ subsequently precipitation to UO2 under hydrothermal condition. About U transport, the study of U6+ speciation in acidic brines at high temperature is performed by Raman spectroscopy and XAS, showing the coexistence of several uranyl chloride complexes UO2Cln2-n (n=0-5). From this study, complexation constants are proposed. The strong capability of chloride to complex uranyl is at the origin of the transport of U6+ at high concentration in acidic chloride brines. Concerning U precipitation, the reactivity of four potential reductants under conditions relevant for URU deposits genesis is investigated: H2, CH4, Fe2+ and the C-graphite. The kinetics of reduction reaction is measured as a function of temperature, salinity, pH and concentration of reductant. H2, CH4, and the C-graphite are very efficient while Fe2+ is not able to reduce U6+ in same conditions. These mobile and efficient gaseous reductant could be at the origin of the extremely focus and massive character of ore in URU deposits. Finally, first partition coefficients UO2/fluid of trace elements are obtained. This last part opens-up new perspectives on (i) REE signatures interpretation for a given type of U deposit (ii) and reconstruction of mineralizing fluids composition