The swelling properties of Bentonite are highly affected by clay content and the clay-water interactions that arise from the ion distribution in the diffuse double layer formed near the charged montmorillonite (or smectite) surfaces. Existing continuum models describing the electric double layers, such as classical Poisson-Boltzmann and DLVO theory, ignore the ion-ion correlations, which are especially important for multivalent ions at high surface charge and ionic strength. To better understand the clay-water interactions, atomistic models were developed using both density functional theory of fluids (DFT) as well as classical molecular dynamics (MD) methods. In order to increase our understanding of water-saturated, swelling smectite clays, a DFT, technique was initially developed that allowed more accurate predictions of important thermodynamic properties of the diffuse double layers. This DFT approach was then extended to handle systems with mixtures of different sizes and charges. The extended DFT model was verified against experiments and Monte-Carlo simulations. One practical application was to predict the ion exchange equilibria in Bentonite clays, which have wide practical usage in different areas. Nevertheless, in the DFT work it was realized that DFT demands that the particles, ions in this case, which are described as hard spheres, realistically cannot be described as such at low water loadings, when ion specific hydration forces govern the electric double layer properties. To study how the deformation of the hydration shells of Ca2+ influences the properties of compacted smectite clays, MD simulations using the CLAYFF forcefield were employed in order to account for the deformation of the hydration shells. Comparisons of DFT and MD modeling then allowed to demonstrate under which conditions DFT modeling becomes increasingly inaccurate and when it still can give accurate results. / Under senare år har mycket forskning ägnats åt att förstå egenskaperna hos svällande leror som används för att skydda mot läckage av föroreningar från kontaminerade områden och från framtida slutförvar av radionuklider. Den fria svällningen förorsakas av de starka osmotiska krafter som uppstår när vatten tränger in mellan de tunna elektriskt negativt laddade lermineralskikten och löser de laddningskompenserande jonerna i det diffusa dubbelskiktet. I flera arbeten användandes av sk. kontinuum-teori har vattenmolekylens form, specifika orientering och bindning till katjonerna i de nanometerstora utrymmen mellan lerpartiklarna ej beaktats samt ej heller hur de hydratiserade jonerna orienteras på de atomärt ojämna ytorna. Detta möjliggörs dock genom modellering av de enskilda atomernas och jonernas interaktioner med molekyldynamik simuleringar, MD. I detta arbete har programmet Gromacs använts tillsammans med kraftfältet CLAYFF för att studera dessa fenomen i montmorillonitleror med natrium- och kalciumjoner. Simuleringarna visar att natrium bildar transienta innersfärkomplex vilka orienterar sig i bi-triangulära fördjupningar på ytan, ungefär 3.8 Å från mitt-planet mellan lerytorna. Denna orientering observeras ända upp till att avståndet mellan ytorna ökat till större än motsvarande fem lager vattenmolekyler mellan lerpartiklarnas ytor. Detta sker inte med kalcium, oberoende av avståndet mellan ytorna. Natriumjoner koordineras med fyra vattenmolekyler och en syreatom på leran vid ett lager vatten mellan ytorna och med fem till sex vattenmolekyler, ortogonalt orienterade med ökande mängd vatten mellan ytorna, och med en hydratiserad jon-radie av 3.1 Å. Kalcium koordinerar till sju vattenmolekyler vid ett vattenlager mellan ytorna, men ökar till åtta ortogonalt orienterade vattenmolekyler med en jonradie på 3.3 Å vid större avstånd. Generellt visas att när avståndet mellan lerytorna är mindre än ca 10 Å, deformeras de annars symmetriskt hydratiserade jonerna. En jämförelse mellan MD simuleringar och med klassisk täthetsfunktionalteori, DFT, visar att den senare inte kan beskriva hur yttersfärkomplexen samverkar med laddningarna bundna närmast ytan, dvs i Stern-lagret. / <p>QC 20170403</p>

Une grande partie du patrimoine bâti provençal a été érigé à l’aide d’un matériau connu sous le nom de « Pierre du Midi ». L’exposition de ces pierres aux intempéries conduit à des dégradations particulières. Parmi celles-ci, la desquamation en plaques a la particularité de se développer en dehors des zones de remontées capillaires ainsi qu’en l’absence des facteurs communs de dégradation. Elle est donc induite par les propriétés intrinsèques du matériau. Ce travail a eu pour objectif d’en comprendre les mécanismes et d’établir le rôle joué par les minéraux argileux. La variabilité du degré de desquamation en plaques a tout d’abord été mise en évidence sur des monuments de périodes de construction équivalentes. Puis, un échantillonnage représentatif de cette variabilité a été mené en carrières. Le cortège argileux de chaque échantillon a été caractérisé en combinant la microscopie électronique en transmission, à la simulation des diffractogrammes de rayons X. La nature et la quantité de chacune des phases argileuses ont ainsi été déterminées et la quantité des feuillets expansifs peut être corrélée au degré de desquamation en plaques. Par ailleurs, les propriétés de stockage et de transfert des fluides de ces matériaux ont été évaluées. Elles ont permis d’appréhender les modalités de transport de l’eau et son impact sur les propriétés mécaniques. La combinaison de la perte de résistance mécanique et d’une forte dilatation au cours de la variation de la teneur en eau semble être à l’origine du processus de desquamation en plaques. Ce travail permet en outre de définir des critères de sélection de pierres de remplacement pertinents du point de vue de leur durabilité. / Most of the Provence built heritage was erected using a material named « Pierre du Midi ». The natural weathering of these limestones leads to specific deterioration patterns. Among these, spalling tends to develop in areas apart from capillary rise and free from the commun decay factors. This phenomenon seems induced by the intrinsic properties of the material. The present study aims to understand the mechanisms at play and to establish the role of the clay minerals. A wide variability of spalling degree has been observed on historical buildings of equivalent construction periods. A representative sampling of the different limestones types has thus been realized in the respective quarries. The clay minerals assemblage of each sample has been defined thanks to an adapted methodological approach combining TEM-EDX characterization to XRD profile modeling. It allowed determining both the nature and the quantity of each clay mineral phase. The link between the expansive layers quantity and the spalling degree has been evidenced. The storage and transport properties of the different types of limestones were also defined. Moreover, the macroscopic behavior upon water content variation was assessed through dilation and compressive strength experiences. The results suggest that the mechanism leading to spalling decay is triggered by the interaction between the expansive clay mineral layers and the water molecules. The hydromechanic behavior of the stone constitutes the macroscopic symptom of this interaction. This behavior is highly controlled by the fluid storage and transport properties that condition the macroscopic transmission of the deformation.

Dans le bassin de Franceville (Gabon), les sédiments détritiques non-métamorphosés d’âge Paléoprotérozoïque (2,15 Ga) des formations FA et FB ont fait l’objet d’une étude faciologique, pétrographique et géochimique. L’objectif était de déterminer l’origine de ces matériaux clastiques et des minéralisations uranifères associées, mais aussi d’en retracer l’histoire diagénétique à travers l’évolution des paléoconditions rédox et des fluides qui les ont percolés.La pétrographie des faciès montre que la minéralogie et la texture initiales de ces sédiments ont été fortement modifiées au cours de la diagenèse précoce. Au toît de la formation FA, les quartz-arénites faiblement granoclassées ont été très tôt cimentées par du quartz, s’opposant ainsi à l’action ultérieure de la diagenèse d’enfouissement. Dans les arènes arkosiques, la séquence paragénétique liée aux ciments authigènes suggère que les interactions fluides-roches ont été polyphasées et que les éléments chimiques nécessaires à leur précipitation trouvent leur origine dans l’altération de minéraux détritiques. Pour un ensemble lithologique donné, les effets de la diagenèse varient peu d’un faciès à l’autre, ce qui indique un fort contrôle des paramètres initiaux tels que la minéralogie, la texture et la composition du fluide poral. Par conséquent, ces faciès sédimentaires nous informent directement sur les propriétés hydrologiques qui régnaient dans le bassin sédimentaire, et sur la nature de la diagenèse précoce qui les a affectés.Les données pétrographiques et géochimiques montrent que la précipitation de l’hématite en lits ferrugineux a débuté juste après le dépôt des sédiments, dont l’altération des minéraux primaires a libéré le fer, plus tard redistribué durant la diagenèse. Ainsi, la mise en évidence d’une corrélation positive entre les valeurs de "delta" 56Fe et les rapports Fe/Mg mesurés sur échantillon total suggère que le fer se répartit entre deux pôles que sont l’hématite authigène et les silicates porteur du fer. En revanche, l’absence de relation entre les rapports Fe3+/FeT et les compositions isotopiques du fer démontre que des oxydes riches en isotopes lourds du fer préexistaient dans les sédiments lorsque la diagenèse précoce a débuté. Le fer présent initialement à l’état réduit dans des faciès sédimentaires verts s’est progressivement oxydé au cours de la diagenèse, processus à l’origine de la formation des lits ferrugineux.Dans la formation FA du Bassin de Franceville, les gisements uranifères résultent de la libération de l’uranium contenu à l’origine dans les grès oxydés des dépôts fluviatiles inférieurs puis de sa migration et de son piégeage dans les grès réduits et les mudstones silteux des formations de deltas de marée supérieures, où il s’est concentré par un mécanisme de type roll-front.L’analyse des éléments chimiques majeurs et traces des formations FA et FB indique que leurs matériaux constitutifs trouvent leur source dans des roches ignées felsiques. Tandis que les diagrammes de terres rares normalisés aux chondrites, les anomalies négatives en Eu et les rapports GdN/YbN plaident plus précisément en faveur des roches archéennes et paléoprotérozoïques. Enfin, des diagrammes discrimants et des rapports en éléments majeurs et traces montrent que, si la plupart des grès de la formation FA se sont déposés sur une marge passive, les mudstones et les grès fins des formations FA et FB ont sédimenté sur une marge continentale active en relation avec la tectonique paléoprotérozoïque de la Ceinture orogénique du Centre-Ouest de l’Afrique. / The FA and FB Formations clastic sediments have been subjected to detailed facies, petrographic, and geochemical analyses in relation to diagenesis, fluid flow, paleo-redox conditions, provenance, and uranium mineralization during the evolution of the unmetamorphosed Paleoproterozoic (ca 2.15 Ga) Franceville Basin, Gabon. Lithofacies analyses in combination with petrographic studies indicate that the original mineralogical and textural properties of the sediments have been greatly modified during diagenesis. The moderately sorted quartz arenite at the top of FA underwent early quartz cementation; thus preventing it from subsequent burial diagenetic processes. The inferred paragenetic sequence of authigenic cements in the arkosic arenites suggest a multiphase of fluid-rock interactions with most of the ions needed for their precipitations likely sourced during alteration of detrital precursors. The observed slight variations in the diagenetic pathways in different lithofacies associations are closely related to primary mineralogy, texture, and nature of pore fluid. This relationship suggests that depositional facies can provide an insight into the diagenetic pathways and hydrologic properties of sediments in sedimentary basins. Petrographic features coupled with whole rock geochemical and iron isotope analyses suggest that hematite precipitation in the red beds started after sediment deposition with the iron internally derived by alteration of iron-bearing minerals and redistributed during late diagenesis. Positive correlation between Fe/Mg ratio and "delta" 56Fe values of bulk samples suggests mixing relationship with end members being authigenic hematite and iron-bearing silicates. The lack of relationship between Fe3+/FeT ratios and iron isotope compositions suggest that the isotopically heavy iron oxide was already present in the sediments during early diagenesis, and was incorporated into green (reduced) facies that likely replaced red facies during diagenesis or burial. Uranium released from the lower, fluvial oxidized sandstones and added to the reduced sandstones and silty mudstones in the upper tidal-deltaic sediments potentially resulted in a uranium mineralization of a roll-front type in the FA Formation of the Franceville Basin. Major and trace element geochemical data for the FA and FB formation are consistent with sediments derived exclusively from felsic igneous source. Chondrite-normalized patterns with high LREE/HREE ratios, negative Eu anomalies, and GdN/YbN ratios favour mixture of Archean and Post-Archean felsic sources. Discriminant diagrams and elemental ratios of major and trace elements suggest deposition of most of the FA sandstone in a passive margin, while the mudstones and fine-grained sandstones of FA and FB were deposited in an active continental margin during Paleoproterozoic tectonic regimes of the West Central African Belt.

Resumo: As indústrias cerâmicas do Pólo de Santa Gertrudes (São Paulo, Brasil) são responsáveis por cerca de 50% da produção nacional de pisos e revestimentos e utilizam, em sua grande maioria, materiais da Formação Corumbataí como base para as massas de revestimentos cerâmicos produzidos na região. Com o objetivo de caracterizar a unidade quanto à petrologia e propriedades tecnológicas na região da atividade mineira, foram realizados levantamentos das frentes de lavras e afloramentos, distribuídas desde a porção basal até o topo da Formação. Para isso, além das atividades cartográficas normais, foram executadas atividades de compilação bibliográfica, caracterização das fácies sedimentares e cerâmicas nas frentes de lavras e afloramentos e correlação entre estas, além de análises mineralógicas, químicas e petrográficas e ensaios tecnológicos. As atividades demonstraram que, praticamente, toda a coluna estratigráfica dessa unidade pode ser utilizada na fabricação de produtos cerâmicos, sendo que a mineralogia e as propriedades tecnológicas apresentam significativa variação tanto na vertical como na horizontal, decorrentes de aspectos sedimentares, diagenéticos e alteração supérgena. A distribuição dos litotipos associada à composição mineralógica, estrutural e textural sugere que o sítio deposicional tratava-se de um extenso mar raso, com indícios de exposições aéreas já nos estratos basais com provável deposição química de carbonatos, sulfatos e outros sais. Os processos de diagênese e circulação de fluídos, principalmente relacionados à colocação e resfriamento dos corpos de diabásio, levaram à geração de illitas, interestratificados, feldspatos, zeólitas, mobilização de carbonato e ferro e o surgimento de fraturamento hidráulico, nos mais diversos litotipos. Do ponto de vista tecnológico, concluiu-se que ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The industries of Santa Gertrudes' Pole (São Paulo, Brazil) are responsible for about 50% of internal production of ceramic tiles and use rocks from Corumbataí Formation as raw materials in the product fabrication in this region. To realize the characterization of the petrology and technological properties of the unit in the mining' area, were made field works in mines and outcrops, distributed from the base to the top of Corumbataí Formation. For that, beyond the normal cartographic activities were carried out activities bibliographic compilation, characterization of sedimentary facies and ceramics on the fronts of mines and outcrops and correlation between them, and mineralogical analysis, chemical and petrographic and technological tests. The activities demonstrated that virtually the entire stratigraphic column of this unit can be used in the manufacture of ceramic products, and the mineralogy and technological properties show significant variation both vertically and horizontally due to aspects of sedimentary, diagenetic and supergene alteration. The distribution of rock types associated with the mineral composition, structural and textural suggests that the depositional site it was an extensive shallow sea, with evidence of exposure companies had basal strata with probable chemical deposition of carbonates, sulfates and other salts. The processes of diagenesis and fluid movement, especially regarding the placement and cooling of bodies of diabase, led to the generation of illite, mixed layer clays, feldspars, zeolites, mobilization of carbonate and iron and the appearance of hydraulic fracturing in many different rock types. From the technological point of view, it was concluded that the properties vary depending on whether the sample (top or bottom of the unit), degree of change, physical and chemical characteristics and influence of hydrothermalism, causing the ... (Complete abstract click electronic access below) / Resumen: Las industrias cerámicas del Polo de Santa Gertrudes (São Paulo, Brasil) son responsables por cerca de 50% de la producción nacional de pavimentos y revestimientos y utilizan, en su gran mayoría, materiales de la Formación Corumbataí como base para las baldosas. Con el objetivo de caracterizar la unidad cuanto a la petrología y propiedades tecnológicas en la región de la actividad minera, fueron realizados trabajos de campo en las canteras y afloramientos, distribuidos desde la base hasta el topo de la Formación. Para esto, fueron realizadas actividades cartográficas usuales y actividades de compilación bibliográfica, caracterización de las facciones sedimentares (descripción de campo, petrografía y litoquímica), cerámicas (ensayos tecnológicos) y correlación entre ellas. Los resultados demostraran que, prácticamente, toda la columna estratigráfica puede ser utilizada en la fabricación de productos cerámicos, siendo que la mineralogía y las propiedades tecnológicas presentan significativa variación tanto en la vertical como en la horizontal, decurrentes de aspectos sedimentares, diagenéticos y alteración supérgena. La distribución de litotipos asociada a la composición mineralógica, estructural y textural sugiere que el sitio deposicional se trataba de un extenso mar raso, con indicios de exposiciones aéreas ya en los estratos basales con probable deposición química de carbonatos, sulfatos e otras sales de sodio, potasio y magnesio. Los procesos de diagénesis y circulación de fluidos, principalmente relacionados a la inyección y resfriamiento de los cuerpos de diabasa, llevaran a la ocurrencia de reacciones químicas que resultaron en la generación de illitas, interestratificados, feldespatos, zeolitas, movimiento de carbonato y hierro en los más diversos litotipos, más allá del fraturamento hidráulico en algunos sitios ... (Resumen completo clicar acceso electrónico abajo) / Orientador: Antenor Zanardo / Coorientador: Anselmo Ortega Boschi / Banca: Maria Margarita Torres Moreno / Banca: Fábio Ramos Dias de Andrade / Banca: Angélica Fortes Drummond Chicarino Varajão / Banca: Emilia García Romero / Doutor

O método de decoração metálica com ouro, desenvolvido por Bassett, em 1958, é de muito interesse no estudo de cristais por microscopia eletrônica de transmissão. Desde aquela época, o método vem sendo aplicado ao estudo de vários fenômenos físicos relacionados à nucleação e epitaxia de filmes finos, bem como em estudos de crescimento e evaporação de cristais. Neste trabalho o método de réplica de decoração foi utilizado para investigar a microtopografia superficial de cristais inorgânicos, de interesse tecnológico e industrial. Nos vários experimentos de decoração, obtivemos adsorção bem localizada dos núcleos de ouro, ao longo de orientações definidas. Nos argilominerais caulinita e diquita, foram marcadas figuras poligonais que seguem os contemos pseudo-hexagonais da própria partícula cristalina. Nos cristais iônicos usados, brometo de potássio e cloreto de sódio, observaram-se degraus monoatômicos em formas variadas, inclusive em espirais originadas por discordâncias em parafuso. Outros sítios da superfície com diferentes energias de adsorção puderam ser identificados em todas as amostras estudadas, através desta metodologia. Nos cristais de calcita não logramos obter figuras de decoração bem definidas, mas sim áreas alternadas com ouro condensado e áreas de interdição, causadas provavelmente pela hidratação natural do mineral. Defeitos pontuais como vacâncias, ilhas ou depressões monoatômicas foram reconhecidos nas figuras de decoração, assim como degraus lineares causados por clivagem. / The gold decoration method originally developed by Bassett in 1958, still is of great interest for unraveling microtopographic details of crystal surfaces in the transmission electron microscope. It is of interest also for studies relating to nucleation and epitaxial growth of thin films, as well as in the study of crystal growth and evaporation itself. The present study was intended to investigate the surface morphologies and defects of some selected inorganic crystals, having technological applications. Ali the different samples prepared by this replica method, presented a clear localization of the gold clusters, along very specific sites. The clay minerais kaolinite and dickite exhibited polygonal figures with a pseudo hexagonal arrangement, parallel to the crystal\'s edges. Growth steps having two different spacings were seen to interlace at 120°. Bromine and sodium halides have monoatomic steps aligned along linear or curved paths; these gold decorated steps could be followed for ample extents in the replicas; among them, other less usual patterns of gold decorated imperfections forming loops, waves and circles were located. The only exception was represented by calcite, in which the decoration was at random. Despite this, some images of deep steps caused by cleavage of the crystals could be clearly recognized. Control images obtained by scanning electron microscopy of cleaved crystals and direct transmission electron microscopy of clay mineral particles, were helpful in the interpretation of the results.

Le Sud du Brésil est une région où l'agriculture est très intensive et la pression sur les sols est beaucoup plus importante que dans la région amazonienne. Ainsi, il est important d'étudier les processus d'altération des roches qui constituent des étapes clés du développement des sols et de leurs fonctions environnementales.Dans ce contexte, ce travail vise à : (i) caractériser la morphologie, les propriétés physiques et chimiques de profils d'altération développés en l'absence ou avec une intervention humaine minimale : (ii) établir les évolutions géochimiques et minéralogiques des sols dans un environnement subtropical ; et (iii) évaluer l'impact des actions anthropiques sur la minéralogie des horizons de surface. Cette étude concerne des sols du Rio Grande do Sul dont le climat subtropical (T ~17°C et P ~1800 mm/an) favorise l'accumulation de matière organique ainsi que la formation de minéraux argileux 2:1 en faible proportion. Les indices d'altération (Weathering Intensity Scale – WIS, Chemical Index of Alteration - CIA) permettent de classer les profils selon leur degré d'altération et de leur composition minéralogique différente (smectite, smectite + kaolinite, kaolinite). Dans la dernière partie les résultats montrent qu'après 12 ans de culture des sols avec un système intégré culture-élevage les surfaces non pâturées présentent une proportion moins importante de minéraux 2:1. Les surfaces sous pâturage intensif et modéré présentent une aluminisation plus élevée de la couche interfoliaire des minéraux 2:1. La fixation d'une partie de l'aluminium dans la phase solide du sol, ce qui pourrait le rendre moins disponible pour les plantes et diminuer sa phytotoxicité. / Southern Brazil is a region with a very intensive agriculture and the pressure on soil is considerably more intense than in the Amazonian region. Thus, it is necessary to study weathering processes as they control soil development and their environmental functions.In this context, this work aims to: (i) characterize the morphological, physical and chemical properties of weathering profiles developed in the absence, or with minimal human action; (ii) establish the geochemical and mineralogical evolution of soils in a subtropical environment; and (iii) assess the impact of anthropogenic actions on on the mineralogy of surface horizons. This study concerns soils of Rio Grande do Sul where the subtropical climate (T ~17°C and P ~1800mm/yr) favored the accumulation of organic matter and occurrence of 2:1 clay minerals in low proportion. The weathering indices (Weathering Intensity Scale - WIS and Chemical Index of Alteration - CIA) make it possible to classify the profiles according to their weathering intensity and their different mineralogical compositions (smectite, smectite + kaolinite, kaolinite).In the last chapter, the results show that after 12 years of cultivation under an integrated soybean–beef cattle production system, the ungrazed areas presented lower proportion of 2:1 minerals. The areas under intensive grazing and moderate grazing presented higher aluminization of the interlayer of 2:1 minerals. The higher aluminization under intensive and moderate grazing managements may be a drain of aluminum in the soil solid phase and possibly making it less available to plants and decreasing its phytotoxicity. / O sul do Brasil é uma região com uma agricultura muito intensa e com grande pressão de uso do solo, consideravelmente mais intenso do que na região da Amazônia. Assim, é necessário desenvolver estudos que relacionem o desenvolvimento do solo com seu respectivo material de origem, detalhando as transformações na zona de transição solo-rocha e suas implicações para as atividades ambientais e humanas. Neste contexto, este trabalho tem como objetivo: (i) caracterizar os aspectos mineralógicos, pedoquimicos e geoquimicos dos perfis de alteração desenvolvidos na ausência ou mínima ação humana; (ii) caracterizar qualitativa e semi-quantitativamente os minerais primários e os minerais pedogênicos em solos inseridos em regiões ecossistêmicas importantes do Rio Grande do Sul; e (iii) avaliar o impacto de diferentes intensidades de pastejo na mineralogia de um Latossolo, sob sistema de produção integrada soja-bovinos de corte no sul do Brasil. Este estudo foi realizado em solos do Rio Grande do Sul, onde o clima subtropical (temperatura média anual ~ 17°C, precipitação anual média de 1800mm/ano) favorece o acúmulo de matéria orgânica ea ocorrência de argilominerais 2:1.Os índices de intemperismo (Weathering Intensity Scale - WIS e Chemical Index of Alteration - CIA), considerando a composição mineralógica dos perfis de alteração, indicaram a seguinte sequência crescente do grau de intemperismo: esmectita < caulinita - esmectita < caulinita. O estudo mostrou diferenças importantes nos solos, mesmo entre aqueles formados a partir do mesmo material de origem, devido às diferenças climáticas e de relevo. Por fim, após 12 anos sob um sistema integrado de produção de soja-bovinos de corte, as áreas não pastejadas apresentaram menor intensidade para os argilominerais 2:1. Por outro lado, as áreas sob pastejo intensivo e pastejo moderado apresentaram comportamento semelhante, devido à maior aluminização da entrecamada dos argilominerais 2:1. A maior aluminização sob pastejo intensivo e moderado pode ser um dreno de alumínio na fase sólida do solo, tornando-o menos disponível para as plantas e diminuindo sua fitotoxicidade.

Les gisements de type roll-front du Kazakhstan représentent près de 13% des réserves mondiales en uranium en 2015. Les minéraux argileux, présents à chaque étape du cycle minier, ont récemment suscité l’intérêt des exploitants. L’étude de la distribution et des proportions de ces minéraux dans les sédiments à l’échelle d’un gisement permettraient d’améliorer à la fois l’exploration, l’exploitation et la réhabilitation de ce type de gisement.Différentes méthodes ont été développées pour identifier et quantifier les minéraux d’intérêt à partir de la spectrométrie infrarouge (IR), une technique instrumentale rapide, adaptée à une utilisation sur le terrain. Ces méthodes ont été calibrées à l’aide d’une large base de données de spectres IR et la préparation de sables artificiels.Il est possible d’obtenir, à partir d’une seule mesure spectrale, la teneur en argiles des sables et particulièrement celle en smectite afin d’identifier les zones les plus riches et adapter l’extraction de l’uranium. L’ensemble de ces méthodes permettent de réaliser des cartographies de la répartition des minéraux argileux à l’échelle du gisement pour comprendre sa géométrie et sa mise en place.La migration des corps minéralisés à l’échelle régionale a été mise en évidence par spectrométrie de résonance paramagnétique, avec l’étude des défauts structuraux engendrés par la proximité des minéraux argileux avec les minéraux uranifères. / Uranium roll-front type sandstone-hosted deposits from Kazakhstan account for about 13% of the worldwide uranium reserve in 2015. Clay minerals occur at every step of the mining cycle and recently begun to be considered by mining companies.The proportions and distribution of these clay minerals in the sediments at the roll-front deposit scale could improve the exploration, exploitation and rehabilitation of such uranium deposits.Several methods were developed to identify and quantify minerals using a portable near-infrared spectrometer, a convenient and fast analytical tool for use in the field. These methods were calibrated with the help of a wide spectral database and the conception of artificial sands.The clay mineral content, and more importantly, the smectite content can be obtained from a single spectral measurement. It enables the detection of smectite-rich areas to optimise the uranium extraction process where they occur. Combination of the methods provide a mapping tool for clay minerals at the ore deposit scale, yielding information about its actual geometry and formation.Uranium ore bodies migration was observed at the ore deposit scale with the use of the electron paramagnetic resonance spectroscopy. Crystalline radiation induced defects in clay minerals that were in close contact with uranium showed records of the past migration.

Le projet de thèse s’inscrit dans le Projet Investissement d’Avenir (PIA) DEMETERRES, dont l’objectif est le développement de méthodes et de technologies pour la décontamination et la remédiation des sols et effluents contaminés après un accident nucléaire. L’objectif de cette thèse est de mieux appréhender les interactions de 137Cs et 90Sr avec les différentes composantes des terres agricoles et ainsi être capable de prédire l’état chimique dans lequel ces éléments se trouveraient dans les sols en cas d’accident nucléaire. Une base de données dans le formalisme des échangeurs d’ions multi-sites a été mise en place, représentant les comportements d’adsorption de Cs+ et Sr2+ dans les illites et smectites (deux des principaux minéraux argileux) vis-à-vis des cations majeurs environnementaux H+, Na+ et Ca2+. Cette base de données a par la suite été utilisée pour tenter de prédire le comportement d’adsorption de Cs+ et Sr2+ dans des échantillons de sols agricoles français (Pusignan, Etoile-sur-Rhône et Herqueville). De bonnes simulations du comportement d’adsorption de Cs+ et Sr2+ ont été obtenues sur Pusignan et Etoile-sur-Rhône. Dans le cas d’Herqueville, la suppression de la MON n’a pas amélioré l’accord entre les simulations et les expériences, tandis que l’élimination de l’aluminium échangeable a lui permis une meilleure simulation de l’adsorption de Sr2+, mais pas de Cs+. Ces travaux permettent de simuler efficacement le comportement d’adsorption de Cs et Sr dans des sols et ainsi d’appuyer les stratégies de décontamination et remédiation après un accident nucléaire / This study is part of the DEMETERRES project, which aims to develop new methods and technologies in the field of decontamination and remediation of contaminated soils and effluents after a nuclear accident. The objective of this PhD is to obtain a better knowledge of 137Cs and 90Sr interactions onto agricultural soils and to better predict the chemical state of these elements in soils after a nuclear accident. A database in the multi-sites ion exchanger formalism has been built, reflecting the adsorption behaviours of Cs+ and Sr2+ onto illite and smectite (two major clay minerals) with regards to major environmental cations: i.e. H+, Na+, and Ca2+. It was used to predict the adsorption of Cs+ and Sr2+ onto French agricultural soil samples (Pusignan, Etoile-sur-Rhône and Herqueville). Good simulations of the adsorption of Cs+ and Sr2+ onto Pusignan and Etoile-sur-Rhône are obtained. In the case of Herqueville, the removal of NOM does not improve the agreement between experimental results and simulations, but the removal of exchangeable aluminum allows a better representation of the adsorption results of Sr2+ onto Herqueville, but not for Cs+. This work allows efficiently simulating the adsorption of Cs and Sr onto soils and support decontamination and remediation strategies after a nuclear accident

Expansive clay mineral contamination of road aggregate materials in Texas is a persistent problem. Hydrous layer silicate minerals - particularly smectites - in concretes are associated with decreased strength and durability in Portland cement and asphalt concretes. The Texas Department of Transportation (TXDOT) and Texas A&M Transportation Institute (TTI) evaluated the methylene blue adsorption test for its potential to identify and estimate quantities of expansive clays in aggregate stockpiles. Clay mineral quantification was completed for 27 geologically-diverse aggregate materials from Texas, Oklahoma, and Arkansas. X-ray diffraction analysis (XRD) of separated clays on glass was conducted, and NEWMOD was utilized to model the resulting diffraction patterns. Methylene blue adsorption (MBA) and cation exchange capacity (CEC) of clay fractions (< 2µm) and -40 mesh screenings (< 400 µm) were determined for most aggregates. Many of the aggregates exhibited significant quantities of expansive clay minerals such as smectite, which are linked to deleterious performance properties in concretes. While the majority of aggregates were derived from crushed limestone or calcareous river gravel parent materials, severalexhibited uncommon origins and unusual clay mineralogy. Due to the relatively low number of aggregates tested and diverse geological origins of the different aggregates,it proved difficult to formalize any conclusions abouttrendsbetweenthedifferent aggregate performance properties.

The major purpose of this study is to evaluate the paleoenvironmental and paleoclimatological conditions during the Middle Miocene-Early Pliocene in Kalecik-Ankara by using mineralogical and geochemical proxies from Han&ccedil / ili Formation. To achieve a high-resolution paleoclimate data, 2 stratigraphic sectioning and 1 continous core drilling were examined. Field studies were followed by analytical techniques on the selected representative samples. The mineralogical compositions of the bulk samples and the minerals of the clay fractions were determined by X-ray diffractometer. Scanning electron microscopic analyses were also carried on the specific samples which have the potential to define the important microstructural units. The major and trace elemental compositions were determined by X-ray fluoresence spectrometer. Additionally, the stable isotope compositions of the samples selected from the continous core drilling on Han&ccedil / ili formation were among the major proxies to gather a paleoenvironmental and paleoclimatrological approach. All the proxies employed for this study clearly indicate that mineralogical and geochemical signatures are consistent with each other and can be used for paleoclimatic interpretations. The stable isotope values point that C4 plants were dominant during the deposition of Han&ccedil / ili Formation, while evaporation caused the development of alkaline environment which is seasonally dry with depositional temperature approximately between 25-30&deg / C. During deposition, lava flowand tuff were deposited due to the volcanic activity in the vicinity of the lake. Based on this volcanism, economical bentonite deposits were originated. The lake at which the Han&ccedil / ili formation was deposited, completed its development in a time to time silicate rich and salty-alkaline anvironment.