Ce travail présente une étude multi-échelle des relations entre altération et minéralisation en uranium le long de la bordure Sud Est du bassin Méso-Protérozoïque du Thelon, au Nunavut, Canada. Les altérations associées aux minéralisations sont développées dans une série volcano-sédimentaire Archéenne appartenant à la ceinture de roche verte du Woodburn Lake Group (WLG). Elles s'expriment majoritairement par un assemblage à illite (polytypes 1Mcis & 1Mtrans) ± sudoite ± hématite et phosphates sulfates d'aluminium hydratés (APS). De plus des composés carbonés, cogénétiques des minéralisations, ont été identifiés comme des produits des réactions hydrothermales. La signature de l'altération, fortement guidées par les structures Est-Ouest du corridor de Kiggavik-Andrew Lake, apparaît alors très similaire à celle rencontrée dans les roches de socles des parties profondes des autres gisements d'uranium de type discordance du bassin d'Athabasca (Canada) ou de la Kombolgie (Australie). L'étude des marqueurs minéralogiques tels que les APS ont permis de mettre en évidence les transferts élémentaires au cours des processus métallogéniques et de distinguer les caractéristiques pétrographique et chimiques des processus diagénétiques et hydrothermaux. Enfin la compréhension fine de l'expression de marqueurs cristallographiques issus de l'irradiation naturelle des minéraux argileux donne de nouvelles pistes pour le traçage et la compréhension des circulations des radios-éléments à l'échelle géologique. / This work presents a multi-scale study of the relationships between alteration and uranium mineralization along the South Eastern margin of the Meso-Proterozoic Thelon Basin, Nunavut, Canada. The ore associated alterations are hosted in an Archean volcano-sedimentary sequence belonging to the Woodburn Lake Group (WLG). Their main expression is a mineral assemblage composed of dominant illite (1Mcis & 1Mtrans polytypes) together with sudoite ± hematite and aluminum phosphate sulfate minerals. Moreover carbonaceous materials cogenetic with the uranium mineralization have been identified as potential indicators of the hydrothermal conditions. At a regional scale, alteration is strongly controlled via East-West faults forming the main frame of the Kiggavik-Andrew Lake structural trend. Then from the regional to the mineral scale, alterations signatures at Kiggavik are similar to the ones described in deep basement rocks of unconformity type uranium deposits in both Athabasca (Canada) and Kombolgie (Australia) Paleoproterozoic basins. In addition mineralogical markers studies (APS minerals) lead to the distinction between hydrothermal and diagenetic processes as well as elemental transfers during fluid rock interaction. Finally, detailed studies on radiation induced defects on illite revealed new ways to tracing and better understanding the radio elements mobility in such deep seated natural systems.

Les minéraux argileux gonflants sont omniprésents dans tous les compartiments de la surface de la Terre et notamment dans les sols. La structure lamellaire de ces minéraux et leur faible taille leur confèrent une forte réactivité notamment vis à vis des polluants et nutriments qui sont présents dans les eaux porales des sols. Dans ce cadre, cette thèse vise à contribuer à une meilleure compréhension des interactions entre des minéraux argileux gonflants et des cations nutritifs (calcium, strontium) et/ou d'intérêt environnemental (césium). Dans les sols, ces minéraux possèdent de larges distributions de taille et de cristallochimie (charge des feuillets). Par conséquent, pour mieux comprendre le rôle de chacun de ces paramètres sur la réactivité de ces particules naturelles, nous avons travaillé avec des « systèmes modèles », représentatifs des particules argileuses des sols : des particules de vermiculite triées en taille et des saponites synthétiques avec des charges de feuillets contrôlées. Les résultats d'adsorption des cations étudiés (Cs, Sr) en compétition avec les cations majeurs des eaux naturelles (Na, Ca) ont été obtenus en couplant l'analyse chimique des solutions et la modélisation des réflexions 00ℓ des diffractogrammes de rayons X afin d'obtenir la distribution de cations entre les différents sites d'adsorption (interfoliaire vs externes). Une telle approche et l'utilisation des « systèmes modèles » nous ont permis d'obtenir des paramètres quantitatifs décrivant la réactivité des minéraux argileux gonflants des sols. Ces paramètres pourront être pris en compte dans les codes de transport prédisant la migration des cations dans les sols. / The swelling clay minerals are ubiquitous in all areas of the surface of the Earth, particularly in soils. The lamellar structure of these minerals and their small size are at the origin of their high reactivity in particular with respect to pollutants and nutrients that are present in soil pore water. In this context, our work aims to contribute to a better understanding of the interactions between swelling clay minerals and cations of nutritive (calcium) and/or environmental interest (cesium, strontium). In soils, swelling clay minerals have broad size distribution and can have a varied crystal chemistry. Therefore, to better understand the role of each of these parameters on the reactivity of the natural particles, we worked with "model systems", which are yet representative of the swelling clay particles encountered in soil environment. Different particle size fractions of vermiculite and different synthetic saponites characterised by well-controlled layer charge were used as "model systems". Results concerning ion-exchange isotherms for Cs and Sr, in competition with major cations of natural waters (Na, Ca), were obtained by combining chemical analyses and 00ℓ reflection modelling of X-ray diffractograms in order to assess the cation distribution between the different adsorption sites (interlayer vs external) located on swelling clay minerals. Such approach and the use of ‘model systems’ have allowed us to obtain quantitative parameters describing the reactivity of soil swelling clay mineral particles, and should be considered in reactive transport codes devoted to predict the migration of nutritive and polluted cations in soil environments.

The first part of the thesis discuss general characterization of heterogeneous processes in silicates. This part is focused on kinetics of heterogeneous processes and mathematical description of reactions time behavior. The other part describes important technologies in silicate industry such as sintering, solid matter decomposition, transition modification, etc. Another chapter deals mineralogy, structure and properties of eminent silicate raw materials. Emphases is given to characterization of clay minerals and their utilising. The experimental part handle the analytic techniques used for investigation of thermal decompostion, dehydroxylation, crystalization of Al-Si spinel phase and sintering process of washed kaolin Sedlec Ia from the region Carlsbad (Czech Republic). Concluding chapter reports on results of experimental work.

MENVM / Department of Ecology and Resource Management / See the attached abstract below

The objective of the work described in this thesis was to understand sorption reactions of uranium occurring at the water-clay mineral interfaces in the presence and absence of arsenic and other inorganic ligands. Uranium(VI) removal by clay minerals is influenced by a large number of factors including: type of clay mineral, pH, ionic strength, partial pressure of CO2, load of the sorbent, total amount of U present, and the presence of arsenate and other inorganic ligands such as sulfate, carbonate, and phosphate. Both sulfate and carbonate reduced uranium sorption onto IBECO bentonite due to the competition between SO42- or CO32- ions and the uranyl ion for sorption sites, or the formation of uranyl-sulfate or uranyl-carbonate complexes. Phosphate is a successful ligand to promote U(VI) removal from the aqueous solution through formation of ternary surface complexes with a surface site of bentonite. In terms of the type of clay mineral used, KGa-1b and KGa-2 kaolinites showed much greater uranium sorption than the other clay minerals (STx-1b, SWy-2, and IBECO montmorillonites) due to more aluminol sites available, which have higher affinity toward uranium than silanol sites. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. A multisite layer surface complexation model was able to account for U uptake on different clay minerals under a wide range of experimental conditions. The model involved eight surface reactions binding to aluminol and silanol edge sites of montmorillonite and to aluminol and titanol surface sites of kaolinite, respectively. The sorption constants were determined from the experimental data by using the parameter estimation code PEST together with PHREEQC. The PEST- PHREEQC approach indicated an extremely powerful tool compared to FITEQL. In column experiments, U(VI) was also significantly retarded due to adsorptive interaction with the porous media, requiring hundreds of pore volumes to achieve breakthrough. Concerning the U(VI) desorption, columns packed with STx-1b and SWy-2 exhibited irreversible sorption, whereas columns packed with KGa-1b and KGa-2 demonstrated slow, but complete desorption. Furthermore, most phenomena observed in batch experiments were recognized in the column experiments, too. The affinity of uranium to clay minerals was higher than that of arsenate. In systems containing uranium and arsenate, the period required to achieve the breakthrough in all columns was significantly longer when the solution was adjusted to pH 6, due to the formation of the uranyl-arsenate complex. In contrast, when pH was adjusted to 3, competitive sorption for U(VI) and As(V) accelerated the breakthrough for both elements. Finally, experiments without sorbing material conducted for higher concentrations of uranium and arsenic showed no loss of total arsenic and uranium in non-filtered samples. In contrast, significant loss was observed after filtration probably indicating the precipitation of a U/As 1:1 phase.

Microorganisms interact with different soil components, such as varying substrates and soil minerals, to drive soil processes and functionality. They can be influenced by the environment, but they themselves can influence their environment by their activities, for example through the production of extracellular enzymes and extracellular polymeric substances (EPS). The formation and stability of aggregates as the backbone of the soil structure, for instance, are thought to be largely influenced by soil microorganisms, or vice versa. There remain, however, open questions as to whether and how microorganisms can influence soil aggregation. While microbes are influencing their environment their interaction with the soil minerals could also change their responses upon adsorption - affecting their influence on soil aggregation. Therefore, the overarching goal of this thesis was to investigate the effect of soil minerals, in particular clay content, on the composition and activity of soil microbial community, with a specific focus on enzyme activities and EPS. Finally, the microbial control of soil aggregation through the influence of substrate availability was explored. In total, two adsorption experiments and two incubation experiments were conducted using soils manipulated experimentally with increasing clay content. The sandy soil was amended with different amounts of soil minerals (i.e. montmorillonite) to achieve a gradient in clay content. For the first incubation experiment, organic substrates differing in decomposability (i.e., starch and cellulose) were added to the soil to stimulate microbial activities and incubated for 80 days. Soil samples from the first incubation experiment were analysed after 0, 3, 10, 20, 40 and 80 days for enzyme activities, microbial community composition, biomass C, EPS-protein and polysaccharide. Additionally, the geometric mean diameter and mean weight diameter of the soil aggregates were determined as measures of aggregate formation and stability, respectively. The first adsorption experiment examined the effect of soil mineral phases on the activities of extracellular enzymes using commercially available extracellular enzymes (α-glucosidase) added to the soil. The second adsorption and incubation experiment investigated the persistence of extracellular enzyme activities (commercially available α-amylase and cellulase) affected by soil minerals. For further insight into how other soil minerals affect extracellular enzymes, kaolinite and goethite in addition to montmorillonite were included in the second adsorption and incubation experiment. The prepared complexes (enzyme + soil and/or soil minerals) from the second adsorption experiment were incubated for 100 days. Further analytical methods include the determination of enzyme activities, microbial biomass C, extraction and quantification of the soil EPS, protein analyses, DNA isolation, DGGE, qPCR and Illumina sequencing. The adsorption experiment showed that extracellular enzyme activities decreased with increasing clay contents. In contrast, such an inhibitory effect on microbial enzyme activity was only observed directly in the incubation experiment after the stimulation of in-situ microorganisms for extracellular enzyme production through substrate addition. Higher extracellular enzyme activities at later incubation days in soils with high clay content suggested an adaptation of the microbial community in response to soil clay content and/ or persistence of extracellular enzymes by adsorption to mineral surfaces. However, the second adsorption experiment showed that the high specific activity and persistence of the enzymes were constrained by the availability of sorption sites. It is therefore reasonable to assume that soil mineral phases support microorganisms in less-sorptive environments by sparing energy on enzyme production, since even a small enzyme release could already propel sufficient activities to degrade target carbon substrates. Starch amendment accelerated respiration and microbial biomass much more than cellulose. While microbial community differed depending on the C substrate (starch or cellulose) added, clay addition had a stronger influence on alpha diversity than substrate addition. Although the production of EPS-protein was closely linked to the provision of additional substrates, the addition of clay minerals resulted in more EPS production than when no additional clay was present. By correlating soil aggregation (stability and formation) with the recorded microbial parameters (that is biomass C, EPS-protein and EPS-polysaccharide), both EPS-protein and EPS-polysaccharide exhibited a significant control on aggregate formation and microbial processes, though, surprisingly, more strongly with high clay content. It was observed that EPS is only a transient compound, which initiates aggregate formation, but clay content plays a more significant role in long-term aggregate stabilization. Overall, this thesis contributed to our knowledge about the interaction of microorganisms with the soil mineral phase and their influence on soil structural stability. The findings established that soil minerals shape the composition and activity of microbial communities. In turn, the microbial production of EPS seems to be more significant for aggregate formation than stability. The results on the effect of soil minerals on extracellular activities provided a paradigm that the persistence of enzyme activities by adsorption does not always hold. Producing EPS might contribute to microbial adaptation that mitigates the negative effect of adsorption on extracellular enzymes. It might also be probable that the EPS become a substance of degradation for the extracellular enzymes. Overall, the results indicated that in clay-rich soils the process leading to extracellular enzyme persistence can be stochastic, depending on multiple factors including sorption sites and substrate availability. Labile organic C clearly plays a role in aggregate formation by supporting EPS production. However, increasing clay content enhanced aggregate stability, promoted the development of distinct microbial communities and increased EPS production. The discrepancy so observed in the contribution of the two EPS parameters, EPS polysaccharide and protein, on soil aggregation points to the need for inclusion of different EPS compositions in future studies relating to soil aggregation.

No description available.

PhDENV (Geology) / Department of Mining and Environmental Geology / The Cretaceous period marked the breaking up of Gondwana, giving rise to the separation of the African and South American continents with the subsequent emergence of the South Atlantic Ocean. Most correlation studies between the two continents with respect to paleoenvironmental conditions and tectonic settings during the Cretaceous- Tertiary periods have been concentrated more on the use of flora and fauna as indicators with less application of kaolinite as paleoenviromental proxies, hence, this study. The research involved the evaluation of paleoenvironmental conditions and tectonic settings of four (4) selected Cretaceous-Tertiary kaolin deposits with two (2) each from the Eastern Dahomey (Eruku and Lakiri) and Niger Delta (Awo-Omama and Ubulu-Uku) Basins in Nigeria. Representative kaolin samples collected from the selected deposits were analysed for physico-chemical, mineralogical, geochemical, isotopic, and geochronological data. The geochemical data obtained by x-ray fluorescence (XRF) spectroscopy and laser ablation inductively coupled plasma mass spectrometry (LAICPMS) were used in unraveling the provenance and tectonic settings of the kaolins. The kaolinite stable isotopic data for oxygen and hydrogen determined using a Finnigan Delta XP Mass Spectrometer were used to assess the paleoenvironmental and paleoclimatic conditions under which the kaolins were formed. The detrital zircon geochronological data acquired by laser ablation – single collector – magnetic sectorfield – inductively coupled plasma – mass spectrometry (LA-SFICP-MS) as well as kaolinite stable isotopic data were employed in constraining the probable timing of kaolinisation. The industrial applications of the kaolins were assessed based on the physico-chemical (Colour, particle size distribution (PSD), pH, electrical conductivity, and Atterberg limits), mineralogical, and geochemical data. The mineralogical data were obtained through x-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, Thermogravimetric analysis and differential scanning calorimetry, and scanning electron microscopy (SEM). Correlative studies between selected Cretaceous African and South American kaolins were conducted. The results showed that the dominant colour in the studied kaolins was pale red (39 %) followed by pinkish and light grey (35 %) as well as reddish yellow, light pink, light brown, vii reddish brown, and pinkish white. The pH and EC values generally ranged from 4.27 to 5.29 and 0.2 to 13.1 μS/cm, respectively. The kaolins predominantly have clay to sandy clay textures with plasticity indices between 10 and 22 wt %. Bulk mineralogical quantitative results indicated that the Cretaceous kaolins have kaolinite, quartz, and muscovite present in that decreasing order with anatase, goethite, and hematite in traces whereas Tertiary kaolins have kaolinite and quartz present in that decreasing order with anatase and goethite in traces. In the silt fractions, kaolinite and quartz were the dominant mineral constituents, whereas in the clay fractions, the dominant clay mineral was kaolinite accounting for 69 to 99 wt % with the non-clay minerals like quartz, anatase, hematite and goethite accounting for percentages between 1 to 28 wt % in the Cretaceous – Tertiary kaolins. Morphologically, the studied kaolins were characterised by pseudohexagonal stacks to books and thin platy kaolinite particles with moderate structural order. The chemical compositions of the Cretaceous-Tertiary kaolin deposits were identical to hydrated alumino-silicates based on the dominance of SiO2, Al2O3 and LOI. The chemical index of alteration (CIA) and chemical index of weathering (CIW) values varied between 96.98 to 99.39 % and 98.95 to 99.89 %, respectively. The clay fractions were enriched in Cr, Nb, Sc, Th, U, V, Zr, and LREE and depleted in Ba, Co, Rb, Sr, and HREE, respectively, relative to the average Upper Continental Crust (UCC). The Th/Sc, La/Sc, Th/Cr, and Eu/Eu* ratios were within the range of sediments derived from felsic rocks. The TiO2 versus Al2O3 and La-Th-Sc plots indicated source rocks with granitic – granodioritic - gabbroic compositions. Geochemical discrimination plots showed that the Cretaceous and Tertiary kaolins were deposited in passive margin tectonic settings. The stable isotopic results indicated that the values of the Cretaceous kaolins ranged from – 47 to – 57 ‰ and 19.1 to 19.8 ‰, respectively, with paleotemperatures between 29.0 and 32.2 ˚C, whereas the δD and δ18O corresponding values for the Tertiary kaolins ranged from – 54 to – 66 ‰ and 20 to 21.5 ‰, respectively, with paleotemperatures between 17.0 and 23.9 ˚C. viii The U-Pb dating of the detrital zircons showed that the Cretaceous - Tertiary kaolins have inputs from rocks of Eburnean (2500 – 2000 Ma) and Pan African (750 – 450 Ma) ages. The age of maximum deposition determined from the least to statistically robust approach corresponds to the Ediacaran Period (645 – 541 Ma) of the Neoproterozoic Era (1000 – 541 Ma). The Cretaceous – Tertiary kaolins were formed under intense anoxic chemical paleoweathering conditions of predominantly felsic rocks in addition to contributions from intermediate and mafic rocks in passive margin tectonic settings. The Cretaceous kaolins were formed under warmer conditions relative to the Tertiary kaolins. The West African Massif rocks were the main sediment sources for the Cretaceous kaolins, whereas both the West African and Northern Nigerian Massif rocks were the major sediment sources for the Tertiary kaolins. The most probable timing of kaolinisation for the Cretaceous – Tertiary kaolins occurred between the Ediacaran (645 – 541 Ma) and Early Cretaceous Periods for the Cretaceous kaolins and between the Ediacaran Period (645 – 541 Ma) and Oligo – Miocene age for the Tertiary kaolins. The Nigerian and Brazilian Cretaceous kaolins formed under similar warm tropical paleoclimate. The study corroborated the occurrence of the Eburnean (Transamazonian) and Pan African (Brasiliano) orogenic events across the African and South American continents. Beneficiation of the Cretaceous – Tertiary kaolins will allow large scale industrial applications in paper coating, ceramics, pharmaceutical, and cosmetics industries. The major contributions from this study have been: the better understanding of the past environmental conditions and tectonic settings, the dating of the possible timing of kaolinisation, and improvement on the potential industrial applications of the Cretaceous – Tertiary kaolins. / NRF

Une calibration orbitale du Valanginien et d’une partie de l’Hauterivien (Crétacé inférieur) est présentée au cours de ce travail. Celles-ci sont basées sur l’identification des cycles de l’excentricité à partir d’analyses spectrales menées sur des proxies climatiques mesurés à haute résolution sur des alternances marne/calcaire hémipélagiques.Cinq coupes de référence sont analysées dans le Bassin Vocontien (Sud-Est de la France), couvrant l’ensemble de l’étage du Valanginien. Une durée de 5,08 Ma est proposée pour cet étage à partir de l’identification du cycle de l’excentricité de 405 ka. Le cadre temporel proposé, combiné aux âges radioisotopiques disponibles, montre que la perturbation en 13C du Valanginien moyen (événement Weissert) est antérieure à la mise en place des trapps du Paraná-Etendeka. La forte expression de l’obliquité dans la partie supérieure du Valanginien pourrait refléter la mise en place de calottes polaires de faible extension.La transition Hauterivien-Barrémien de Río Argos (Sud-Est de l’Espagne) est traitée par une analyse multi-proxies (cortèges argileux et susceptibilité magnétique ou SM). Par comparaison avec les bancs calcaires, les interbancs marneux sont enrichis en kaolinite et en illite, appauvries en smectite et possèdent de fortes valeurs de SM. Cela reflète des conditions tropicales humides lors du dépôt des marnes tandis que les calcaires se déposent en climat semi-aride. Les durées des zones d’ammonite à P. ohmi et à T. hugii sont respectivement estimées à 0,78 Ma et 0,54 Ma. L’événement anoxique Faraoni a une durée comprise entre 100 et 150 ka. Par corrélation avec d’autres coupes, Río Argos apparaît être le meilleur candidat GSSP / Orbital floating time scales are proposed for the Valanginian Stage and part of the Hauterivian Stage (Early Cretaceous). These are based on the identification of the eccentricity cycles from spectral analyses performed on high-resolution climatic proxies measured on hemipelagic marl-limestone alternations. Five reference sections were analysed in the Vocontian Basin (SE France), spanning the entire Valanginian. A duration of 5,08 myr is proposed for the Valanginian Stage from the identification of the 405-kyr eccentricity cycle. The time frame proposed, combined with available radiometric ages, shows that the mid-Valanginian 13C positive excursion (namely the Weissert Event) occurs prior to the onset of the Paraná-Etendeka traps. The stronger expression of the obliquity cycles in the upper part of the Valanginian Stage may be caused by the onset of low-extension polar ice. The Hauterivian-Barremian transition of the Río Argos section (SE Spain) was studied by a multi-proxies analysis (clay minerals, magnetic susceptibility or MS). Compared to limestone beds, marl interbeds are enriched in kaolinite and illite, impoverished in smectite and show stronger MS values. This reflect tropical humid conditions during marl deposits while limestone were deposited under semi arid conditions. The durations of the P. ohmi and T. hugii ammonite zones are assessed at 0.78 myr and 0.54 myr, respectively. The duration of the Faraoni anoxic event ranges from 100 to 150 kyr. By correlation with other sections, the Río Argos section appears to be the most valuable candidate for GSSP.

Ph.D. thesis represents summary of multidiciplinary palaeoenvironmental and palaeoclimatic research of the most significant Late Pennsylvanian lacustrine horizon of the central and western Bohemian basins - the Malesice Member of the Slaný Formation. Two cores from new shallow drills, situated 80 km apart, were analysed. Multidisciplinary approach is based on description of lamination structure and periodicity; mineral and isotopic composition of autigennic carbonates, namely siderite; compositiona of detrital minerals including clay mineral assemblages; and composition of autochthonous and allochthonous organic particles including palynospectra. Detailed analysis of drill cores lead to the identification of individual phases of lake development linked with lake-level fluctuation and water-column stratification, which were driven by a sume of precipitation and its seasonal distribution. Changes in precipitation also affected compostion and density of vegetational cover in the lake surroundings, weathering intesity of source rocks and degradation of organic matter in the drainage basin, and so precipitation affected final grain-size and composition of detrital material deposited in the lake. Beside common environmental signatures at both studied sites, there are also significant...