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

The sandstone-hosted McArthur River Zone 4 U ore body and alteration system, located in the Athabasca Basin, are the focus of a detailed mineralogical and geochemical study aimed at reconstructing its evolution. The oxidation state of Fe in clay alteration from Zone 4 is measured using 57Fe Mössbauer spectroscopy and compared with other mineralized and barren sandstone-hosted alteration systems in the Athabasca Basin. The aim is to ascertain the role of Fe in forming U deposits and determine whether Fe oxidation state in alteration minerals can indicate proximity to mineralization. At Zone 4, early diagenetic kaolin is overprinted by zones of dravite, illite, chlorite, and late kaolinite forming around the P2 fault. Uranium mineralization occurred at ca. 1600 Ma and was triggered by mixing between oxidizing U-bearing basinal fluids and reducing basement-modified basinal fluids, the latter forming when basinal fluids interacted with basement lithologies. Early pre-ore silicification in the lower 200 metres of the Manitou Falls Formation above the ore body created favourable conditions for mineralization by focusing basinal fluids into the reduction site and enhancing ore preservation. However, it obstructed the post-ore migration of radiogenic Pb and U pathfinder elements from the deposit and limited the extent of hydrothermal sudoite alteration in the overlying strata. Sandstone-hosted alteration systems in the Athabasca Basin are commonly surrounded by an outer illite and an inner chlorite zone. Illites have high Fe3+/ƩFe ratios characteristic of formation from oxidizing basinal fluids, whereas, chlorites have lower and more varied Fe3+/ƩFe ratios, reflecting their origin from reducing, Fe2+-bearing basement-derived fluids having undergone variable mixing with oxidizing basinal fluids. Chlorites in mineralized systems where fluid-mixing occurred, such as at McArthur River Zone 4 and Maurice Bay, record higher Fe3+/ƩFe ratios than barren systems where fluid-mixing did not, such as at Wheeler River Zone K and Spring Point. The scarcity of U-bearing basinal fluids available for mixing with Fe2+-bearing basement fluids is a critical geochemical factor precluding mineralization in barren sandstone-hosted systems. The Fe3+/ƩFe ratio of chlorites has potential applications for discriminating barren and mineralized systems and as spatial vectors to ore when coupled with Pb isotope ratios. / Thesis (Master, Geological Sciences & Geological Engineering) -- Queen's University, 2012-11-01 14:08:33.51

A study of the Millennium and Eagle Point basement-hosted deposits was conducted to obtain a comprehensive understanding of the alteration in these two atypical uraniferous systems and to apply these findings in formulating effective exploration strategies. In addition, an investigation of the Wheeler River “apparently barren” sandstone-hosted alteration system was conducted to provide insights into the critical events needed in order to form sandstone-hosted unconformity-related deposits. At Millennium, the atypical alteration halo, wherein the inner chlorite halo is much smaller than other basement-hosted deposits, is the result of pervasive muscovite alteration of the basement rocks by Na-K-Fe basinal brines during the pre-ore stage at ca. 250°C. As alteration of the basement rocks progressed, the basinal brines acquired Ca, Fe and Mg while creating up to 20% voids in the basement rocks. Prior to the mineralizing event, the chemically modified basinal fluids formed a minor Fe-rich chamoisite halo that demarcates a redox front during the ca. 1590 Ma syn-ore stage, where uranium ore was precipitated. At Eagle Point, the atypical alteration halo, wherein dolomite and calcite alteration is more significant than other basement-hosted deposits, is the result of more intense pre-Athabasca Basin alteration. The Eagle Point deposit is also distinct by significant late remobilization of primary uraninite into secondary structures that occurred at ca. 535 Ma. At the Wheeler River “apparently barren” alteration system, the critical factor for the lack of uranium mineralization in the sandstone is the temporal relationship between the different fluids with the uranium-bearing oxidized basinal fluids present prior to the reduced chemically modified basinal fluids and reduced basement fluids. However, the possibility of a small basement-hosted uranium deposit at Wheeler River cannot be excluded because the sudoite-producing basement fluids may represent basinal brines that reacted with basement lithologies to become reducing and Mg-rich, and therefore may have precipitated uraninite during this process. The results of this study support the genetic model in which basinal fluids were likely the source of uranium deposits and that the basement fluids were unlikely significant sources of uranium in sandstone-hosted deposits. / Thesis (Ph.D, Geological Sciences & Geological Engineering) -- Queen's University, 2009-09-30 14:49:03.688

Shea Creek est un gisement d'uranium liée à la discordance entre un socle métamorphique et des roches sédimentaires d'origine fluviatile, d'âge Paléo-protérozoïque et situé dans la partie ouest du bassin d'Athabasca. Ce gisement majeur est le plus profond connu actuellement dans le bassin (entre 680 m et 1000 m de profondeur). Il rassemble en un même lieu tous les types de minéralisation associés à une discordance connus de par le monde. Cette étude s'appuie sur l'analyse de plus de 1200 échantillons du halo d'altération qui entoure le gisement et sur l'utilisation des données d'exploration minière. L'objectif est double. Il s'agit d'une part de déterminer des guides sédimentologiques, pétrographiques, minéralogiques et géochimiques pour la prospection des corps minéralisés en zone profonde et d'autre part d'utiliser ces critères pour construire une représentation tridimensionnelle simplifiée (minéralisation et halo d'altération) permettant de préciser le modèle génétique de ce gisement profond. La localisation des différentes zones minéralisées dépend non seulement des phénomènes d'altération liés aux circulations hydrothermales contrôlées par la tectonique, mais aussi de la nature du remplissage sédimentaire et de son évolution diagénétique. L'architecture de la zone minéralisée de Shea Creek montre que les corps minéralisés sont localisés dans des structures en grabben remplies par des alternances de grès propres et de grès argileux souvent préservés de la compaction et de l'altération. La signature minéralogique et géochimique de ces grès suggère un apport provenant de l'érosion de paléo-altérites continentales (régolithe). La très forte concentration en défauts d'ir / Shea Creek is an unconformity-type uranium deposit located in the west part of Atabaska basin. It is related to an unconformity between a metamorphic basement and sedimentary rocks of fluvial origin, of paleoproterozoic age. Shea Creek's particularity is to be the deepest ore deposit ever known in the basin (between 680 m and 1000 m deep). It gathers all types of unconformity hosted mineralization known. More than 1200 samples, taken from halo alteration around the deposit, were analyzed and mining exploration data were used for this study. First, the aim was to determine the markers for prospection of mineral elements in deep area: sedimentological, petrographical, geochemical and mineralogical types. Then, it was to build a simple three-dimensional model (mineralization and alteration halo) using these criteria in order to precise the genetic pattern of this deep deposit. The location of mineralized areas depends on tectonic deformation, on sedimentary filling and diagenetic development. The morphology of Shea Creek’s ore deposit shows clearly that mineralization is located in the grabbens composed by clean sandstones and clay sandstones, often preserved from compaction and alteration phenomena. The mineralogical and geochemical signature of these clay sandstones suggests a contribution from the erosion of continental paleo-alterite (regolith). Beside, the great concentration of radiation induced defects suggests the presence in abundance of uranium in the grabbens from sedimentary state.

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