La partie supérieure de la Formation Khuff est un réservoir représentant le plus grand champ gazier mondial, d'âge Permien supérieur à Trias inférieur. Il est formé de la succession de calcaires, de dolomies et de sulfates. Sa production est principalement contrôlée par des intervalles d'épaisseur généralement inférieure à 10 m, totalement dolomitisés, appelés super-drains ou super-K, connectés sur plusieurs dizaines de kilomètres.Les objectifs de l'étude sont (1) de définir la mise en place et l'extension des super-drains dans un cadre stratigraphique, (2) de comprendre la diagenèse contrôlant leurs propriétés réservoirs et (3) de comparer la mise en place des corps dolomitiques stratiformes précoces ou tardifs liés aux failles à ceux d'un analogue à l'affleurement, à savoir les formations calcaréo-dolomitiques d'âge Jurassique supérieur en Provence.Pour les atteindre, des analyses sédimento-diagénétiques (sédimentologiques, pétrographiques et géochimiques) ont été entreprises sur les deux objets d'études du réservoir de subsurface et de l'analogue réservoir d'affleurement. Pour ce dernier, une modélisation en 3D de corps diagénétiques liés aux failles a été réalisée. Les principaux résultats sont que :- les localisations des super-drains ont été contrôlées par la dynamique sédimentaire de séquences à basse fréquences (SBF) et à haute fréquence (SHF) ;- des super-drains sont localisés au sommet des SBF sous les discontinuités d'émersions et à la limite des fronts de dolomitisation de reflux différé. / The upper part of the Khuff Formation includes the biggest gas reserves in the world, from Upper Permian to Lower Triassic age. It is composed by the succession of limestone, dolomite and sulfate. The gas production is mainly driven by layers typically thinner than 10 m, fully dolomitised, and called super-drains or super-K and connected over several dozen kilometers.The goals of this study are (1) to define the formation and the extension of super-K layers in a stratigraphic framework, (2) to understand the diagenesis controlling their reservoir properties and (3) to compare the creation of early stratabound and late fault-related dolomite bodies with an outcrop analogue, from the limestone and dolomite formations from Provence from Upper Jurassic age.To reach this goal, sedimento-diagenetic analyses (sedimentological, petrographical and geochemical) have been carried out on studied objects, the subsurface reservoir and the outcrop analogue reservoir. For the latter, 3D modelling of fault-related dolomite bodies have been realised. The main results are:- the locations of super-K have been controlled by the sedimentary dynamics of low frequency sequences (SBF) and high frequency sequences (SHF) ;- some super-K are located at the top of SBF under emersion unconformities and at the rim of dolomitisation fronts associated to postponed reflux. The reflux was made of brines, coming from synsedimentary dolomite bodies associated with marine transgressions that followed the emersions. This model is corroborated by an outcrop analogue, which is a dolomite reservoir underlying a long lasting emersion unconformity;

Dados de geoquímica isotópica e elementar foram obtidos em rochas carbonáticas da Fm. Sete Lagoas, Grupo Bambuí, visando contribuir para o entendimento da evolução sedimentar da bacia do São Francisco, assim como decifrar as variações ambientais da água do mar durante o Neoproterozoico. Esta unidade é composta de rochas carbonáticas sobrepostas aos diamictitos da Fm. Carrancas na parte sul do Cráton do São Francisco. As seções Inhaúma (IN), Linha Verde (LV) e Funilândia (FN) são constituídas por carbonatos impuros de cor cinza clara e dolomitos de cor bege, pobres em matéria orgânica, com altos teores de sedimentos detríticos e depositados num ambiente marinho raso com influência de correntes de maré. Os valores de \'\'delta\'\' POT.3\' C mais representativos do ambiente deposicional variam entre -1,0 e 0%o e permitem posicionar estas três seções na primeira sequência deposicional da Formação Sete Lagoas, acima da capa carbonática criogeniana. No entanto, os carbonatos destas seções apresentam baixos teores de Sr, resultando em razões \'ANTPOT.87 Sr\'/\'ANTPOT.86 Sr\' muito radiogênicas entre 0,7111 e 0,7114. As anomalias isotópicas podem estar relacionadas com processos de dolomitização tectônica que ocorreu em uma escala regional na área de influência tectônica da Faixa Araçuaí, na fronteira oriental do cráton. As seções Sete Lagoas (SL) e Haras Veredas (HV) são constituídas por carbonatos puros de cor cinza escuro a preto, ricos em matéria orgânica, com baixos teores de sedimentos detríticos e depositados num ambiente relativamente profundo, com pouca influência de correntes de maré. Os valores de \'\'delta\'\' POT.3\' C destas seções são bastante positivos, entre 8,5 e 12,6%o, interpretados como valores primários, o que permite posicionar estas duas seções na segunda sequência deposicional da Formação Sete Lagoas. Os altos valores de \'\'delta\'\' POT.3\' C podem representar alta bioprodutividade com altas taxas de soterramento de matéria orgânica no ambiente marinho, assim como alta produtividade de carbonato autigênico. A deposição dos carbonatos ocorreu em um mar epicontinental restrito com conexões intermitentes com os oceanos contemporâneos, dificultando a homogeneização isotópica do Sr, como demonstrado pela grande variação das razões \'ANTPOT.87 Sr\'/\'ANTPOT.86 Sr\' obtidas nas seções SL e HV, entre 0,7073 e 0,7085. Este cenário é reforçado pela configuração tectônica da bacia, limitada pelas faixas orogênicas Brasília (W) e Araçuaí (E) no final do período Ediacarano. Correlação global por meio de isótopos de Sr não é confiável neste caso. As datações U-Pb obtidas em grãos de zircão detrítico de duas amostras de diamictitos da Formação Carrancas sugerem o Cráton do São Francisco como principal fonte dos sedimentos representados pelas idades de ca. 2800 Ma. Um grão de ca. 1200 Ma, define a idade máxima de deposição desta unidade e a área fonte pode ser rochas do Supergrupo Espinhaço. / Isotope and elemental geochemistry data were obtained on carbonate rocks of the Sete Lagoas Formation in order to contribute to the understanding of the sedimentary evolution of the São Francisco basin in the basal part of the Bambuí Group, as well as to decipher the environmental variations of seawater during the Neoproterozoic. This unit consists of carbonate rocks overlying the diamictites of the Carrancas Formation in southern São Francisco Craton. The Inhaúma (IN), Linha Verde (LV) and Funilândia (FN) sections consist of light gray impure carbonates and beige dolomites, poor in organic matter, with high contents of detrital sediments and deposited in a shallow marine environment with influence of tidal currents. The most representative \'\'delta\'\' POT.3\' C values of the depositional setting range between -1.0 and 0%o, and allow us to correlate these sections with the basal depositional sequence of the Sete Lagoas Formation, above the Cryogenian cap carbonate. However, the carbonates of these sections have low Sr concentrations, resulting in highly radiogenic \'ANTPOT.87 Sr\'/\'ANTPOT.86 Sr\' ratios between 0.7111 and 0.7114. The isotopic anomalies may be related to tectonic dolomitization processes that occurred on a regional scale in the tectonic influenced areas of Araçuaí Belt, on the eastern border of the São Francisco Craton. The Sete Lagoas (SL) and Haras Veredas (HV) sections are composed mainly of dark gray to black pure carbonates, rich in organic matter, with low contents of detrital sediments and deposited in a relatively deep environment with little influence of tidal currents. The \'\'delta\'\' POT.3\' C values of these sections are consistent and very positive, between 8.5 and 12.6%o, being interpreted as representative of the isotopic composition of seawater in the depositional environment, which allow us to correlate these two sections with the second depositional sequence of Sete Lagoas Formation. The very positive \'\'delta\'\' POT.3\' C values may represent high bio-productivity with high burial rates of organic matter in the marine environment, as well as high productivity of authigenic carbonate. The deposition of these carbonates occurred in a restricted epicontinental sea with intermittent connections with contemporary oceans, making difficult the Sr isotopic homogenization with seawater. This explains the large variation on the \'ANTPOT.87 Sr\'/\'ANTPOT.86 Sr\' ratios obtained on carbonates from the SL and HV sections, ranging between 0.7073 and 0.7085. The tectonic setting of the São Francisco Craton, limited by orogenic belts of Brasilia (W) and Araçuaí (E) during the late Ediacaran period, supports this scenario. Global correlation by means of Sr isotope is not reliable in this case. The U- ages of detrital zircon grains from diamictites of the Carrancas Formation are mainly discordant, but ages of ca. 2800 Ma suggest the São Francisco Craton as the main source of sediments. One grain dated at ca. 1200 Ma sets the maximum depositional age for the units, and the source area could be the rocks from the Espinhaço Supergroup.

Os carbonatos continentais vêm sendo bastante estudados nos últimos anos, devido ao seu potencial como arquivo paleoclimáticoe, mais recentemente, como rocha reservatório de hidrocarbonetos. Carbonatos continentais quaternários são registrados na serra da Bodoquena e no platô Corumbá/Ladário, adjacências da Bacia do Pantanal, no Estado de Mato Grosso do Sul,bem como na serra das Araras, Mato Grosso. O estudo desses depósitos é deinteresse científico, uma vez que eles podem contribuir como análogos para ocorrências de carbonatos continentais mais antigos, bem como servir como objeto de análises específicas relacionadas com os fatores que teriam contribuído para sua formação. O objetivo deste trabalho foi investigar carbonatos continentais quaternários expostos nas adjacências do Pantanal Matogrossense, analisando ograu de influência do clima e de atividades tectônicas em sua gênese e evolução. Para isso procedeu-se com seu mapeamento, bem como com seu estudo sedimentológico, petrográfico, isotópico e cronológico. Os depósitos estudados foram depositados nos últimos 525 mil anos, sendo a deposição ainda ativa em algumas áreas. Suagênese ocorreu em ambientes deposicionais lacustres, localmente sujeito à entrada significativa de fluxos de detritos, além de ambientes de canal fluvial, e de nascentes. Os depósitos produzidos por fluxos de detritos são representadospor conglomerados com matriz de lama carbonática, sendo restritos às escarpas doplatô Corumbá/Ladário. Depósitos lacustres consistem em carbonatos finos e/ou fossilíferos, que estão presentes em todas as áreas estudadas; Canais fluviais, caracterizados por tufas maciças e laminadas, presentes nas serras das Araras e Bodoquena; e carbonatos de nascente, que consistem em tufas laminadas em forma de pendentes, presentes na serra das Araras. Os carbonatos das áreas de estudo formam duas sucessões sedimentares, sendo a sucessão 1, basal, caracterizada por depósitos lacustres, inclusive com fluxos de detritos, e em parte, fluviais. Seu topo é uma superfície erosiva marcada por horizonte profundo de calcrete.A sucessão 2 apresenta depósitos lacustres, fluviais e de nascentes, que são pouco alterados em relação à sucessão 1. A presença de calcretes sobre depósitospleistocênicos sugere que após este período pode ter havido incidência de clima semi-árido/árido, que foi seguido por climas relativamente mais úmidos a partir do Holoceno médio. Apesar da possível influência climática, as estruturas pré-cambrianas e a neotectônica regional, condicionaram diretamente a formação desses carbonatos, quanto a localização de lagos alongados paralelamente a planos de falha, e na formação de carbonatos pendentes de nascentes favorecidos por desníveis topográficos e escarpas produzidas por falhamento. / Continental carbonates has been highly studied in the last years due its potential as climatic archive and, recently, as hydrocarbons reservoir. Quaternary continental carbonates are registered at sierra of Bodoquena, Corumbá/Ladário plateau, Pantanal basin surroundings, at Mato Grosso do Sul State, as well at sierra of Araras, Mato Grosso do Sul State. The study of these deposits has scientific interest, because they can be analogues to ancient continental carbonates, as well to be studied in specific ways to understand the factors that contributed to its genesis. The objective of this study was to investigate quaternary continental carbonates exposed at Pantanal Matogrossense surroundings, analyzing the climatic influence and tectonics related to its genesis. To achieve this goal, mapping, sedimentological, petrographical, isotopical and chronological studies were carried out. The studied deposits were formed in the last 525 thousand years, and it\'s still active in some areas. Their genesis occurred in lacustrine depositional systems, locally mixed with debris flows, as well in fluvial channels and spring settings. The debris flows were represented by conglomerates with carbonatic mud matrix, restricted to the borders of Corumbá/Ladário plateau. The lacustrine depositsare composed by fine and/or fossiliferous carbonates, outcropping in all studied regions; Fluvial channels, characterized by massive and laminated tufas, occurring in sierra of Araras and Bodoquena; and spring carbonates, represented by pendant laminated tufas, occurring mainly in sierra of Araras. The carbonates described in the studied area were divided into two sedimentar successions. The succession 1, basal, is characterized by lacustrine deposits, includind presence of debris flows sediments, and in some places, fluvial deposits. Its top is a erosion surface marked by a deep calcrete horizon. The succession 2 presents lacustrine, fluvial and spring deposits, not so changed as succession 1. The occurrence of calcretes over pleistocenic deposits suggests a period of aridity, followed by more humid climates from middle Holocene. Despite the climatic influence, the Precambrian structures and regional tectonics, influenced directly the genesis of thesecarbonates, with lakes elongated according faults and pendants tufas, favored by topographic discontinuity and fault scarps.

Um estudo petrológico foi realizado em testemunhos e amostras laterais de um poço perfurado na seção pré-sal no Cretáceo Inferior da Bacia de Santos central, margem leste brasileira. As rochas estudadas são constituídas predominantemente por componentes intrabaciais não carbonáticos e carbonáticos, com contribuição extrabacial não carbonática subordinada. Durante a sedimentação rifte inicial da Formação Piçarras no Barremiano, intensa precipitação singenética de argilominerais magnesianos em condições de alta alcalinidade propiciou a deposição de arenitos constituídos principalmente por oóides estevensíticos e pelóides, assim como depósitos híbridos re-sedimentados, com mistura de partículas estevensíticas, bioclastos de ostracodes e bivalves e grãos siliciclásticos e vulcanoclásticos. A diluição da água do lago, provavelmente devido a fatores tectônicos e climáticos, propiciou as condições necessárias para a proliferação dos bivalves e a sedimentação dos depósitos bioclásticos da Formação Itapema. A estrutura maciça dos depósitos, orientação caótica e com a concavidade voltada para cima das conchas de bivalves e sua mistura com partículas estevensíticas indica redeposição por fluxos gravitacionais. Os principais processos diagenéticos nas rochas estevensíticas e híbridas do rifte são a cimentação e a substituição dos grãos por calcita, dolomita, sílica e esmectita. Rochas silici/vulcanoclásticas de granulometria fina apresentam intensa substituição por dolomita. Nos rudstones de bivalves, os principais processos diagenéticos foram a dissolução de conchas e cimentação de poros intrapartícula e interpartícula por calcita e, subordinadamente, por dolomita e sílica. O estudo dos constituintes singenéticos e eodiagenéticos e de suas relações paragenéticas permitiram reconstruir a evolução das condições do sistema lacustre durante o estágio rifte na região central da bacia. Este estudo tem como objetivo prover um melhor entendimento da gênese e evolução diagenética dos depósitos pré-sal do rifte da Bacia de Santos, considerando o contexto de evolução dos sistemas lacustres nos quais estes sedimentos foram depositados. / A petrological study was performed on cores and sidewall samples of a well drilled through the rift pre-salt section of Lower Cretaceous of central Santos Basin, eastern Brazilian coast. The studied rocks are constituted predominantly by carbonate and non-carbonate intrabasinal components, with subordinate extrabasinal non-carbonate contribution. During Barremian early rift sedimentation, intense syngenetic precipitation of magnesium clays under highly alkaline conditions deposited arenites constituted by stevensite ooids and peloids, as well as hybrid, re-sedimented deposits mixed with bivalve and ostracod bioclasts, siliciclastic and volcanoclastic grains of the Piçarras Formation. Freshening of the lacustrine environment provided the conditions required to the proliferation of bivalves and sedimentation of the bioclastic deposits of the Itapema Formation. Massive structure of the deposits, chaotic to concave-up orientation and mixing of the bivalves with stevensitic particles indicates re-deposition by gravitational flows. The main diagenetic processes in rift stevensitic and hybrid rocks are the cementation and replacement of grains by calcite, dolomite, silica and smectite. Silici/volcanoclastic mudrocks present intense replacement by dolomite. In the bivalve rudstones, the main diagenetic processes were dissolution of the shells and cementation of the intraparticle and interparticle pores by calcite and, subordinately, by dolomite and silica. The study of the syngenetic and eodiagenetic constituents and their paragenetic relations allowed reconstructing the evolution of lacustrine environmental conditions during the rift stage in the central area of the basin. This study aimed to provide a better understanding of the genesis and diagenetic evolution of the rift pre-salt deposits of Santos Basin, within the context of evolution of the lake system in which the sediments were deposited

Nenhuma / O Brasil consome enormes quantidades de fertilizantes a base de fósforo devido às características do solo, pobre em nutrientes principais, e à grande produção agrícola. Apesar do grande consumo, a produção de produtos fosfatados é insuficiente para atender a demanda interna. Uma das razões é que os depósitos fosfáticos brasileiros não apresentam a qualidade necessária para a produção de fertilizantes fosfatados. Dentre estes depósitos, está a jazida de Itataia, uma ocorrência ígnea de fósforo e urânio localizada no estado do Ceará. Este depósito apresenta significativas quantidades de carbonatos, principalmente a calcita, o que causa sérios inconvenientes durante a produção do ácido fosfórico. Este trabalho compreendeu a realização de testes de flotação direta com o minério fósforo-uranífero de Itataia realizado com o intuito de obter um concentrado final de P2O5 com teor de 32%, adequado para a produção de ácido fosfórico, e recuperação a mais elevada possível. Foi avaliado em escala de laboratório o desempenho dos depressores inorgânicos (Calgon e silicato de sódio) e dos orgânicos compostos por amidos não modificados (Flotamil 75 e fécula de mandioca) amidos modificados (Filmplus 9002 ACC, EP2031 e dextrina) e a carboximetilcelulose. Foi verificado que, dentre os depressores estudados, a fécula de mandioca apresentou desempenho superior. Estes resultados, obtidos em laboratório, serviram de subsídio para a realização de testes piloto de flotação utilizando coluna. Os resultados do teste rougher-cleaner utilizando circuito aberto (Teste ADP-5) produziram um concentrado final com teor e recuperação de P2O5 de 33,49 e 80,7%, respectivamente. Os teores de CaCO3 e de U3O8 neste produto foram 8,54 e 0,27%. / Brazil consumes huge amounts of phosphorus-based fertilizers due to the characteristics of its soil, poor in major nutrients, and the vast agricultural production. Despite the large consumption, the production of phosphate is insufficient to meet the domestic demand. One reason is that the Brazilian phosphatic deposits do not have the quality needed for producing phosphate fertilizers. Among these deposits is the Itataias deposit, an igneous occurrence of phosphorus and uranium in the state of Ceará. This deposit has significant amounts of carbonates, mainly calcite, which causes serious inconveniences for the phosphoric acid production. This work involved the testing of the direct flotation of Phosphorus-Uraniferous ore from Itataias deposit carried out in order to obtain a final concentrate with a P2O5 content of 32%, suitable for production of phosphoric acid, and the highest possible recovery. The performance of inorganic depressants (Calgon and sodium silicate) and organic compounds including unmodified starches (Flotamil 75 and cassava starch) and modified starches (Filmplus 9002 ACC, EP2031 and dextrin) and carboxymethylcellulose were evaluated on a laboratory scale. It was found that among the studied depressants cassava starch showed the better performance. These results obtained in the laboratory provided subsidies for pilot testing using a flotation column. These tests were carried out using rougher-cleaner open circuit (ADP-5 Test) and produced a final concentrate grade and recovery of P2O5 of 33.49 and 80.7%, respectively. The content of CaCO3 and U3O8 of this product were 8.54 and 0.27%, respectively.

A forma isomórfica predominante nos biominerais (casca de ostra, coral, madrepérola e concha) estudados foi a aragonita. Contudo, o surgimento da fase calcita deu-se à temperatura de 500°C a uma taxa de aquecimento de 10°C/s para todas as amostras; e para a amostra de coral, à temperatura de 400°C, independente da taxa de aquecimento. O elemento mais abundante nas amostras de biominerais foi o Ca na forma de CaO e para os silicatos (tremolita, diopsídio e rodonita), o Si na forma de SiO. O elemento traço mais presente nas amostras de biominerais foi o Fe. A análise de ressonância paramagnética eletrônica mostrou as linhas de Mn2+ nas amostras de coral e madrepérola, antes da irradiação. Para amostras irradiadas, os defeitos encontrados foram os radicais CO2-, CO33-, CO3-, SO2-, SO3-, e num intervalo de g entre 2,0010 e 2,0062. Na análise por absorção óptica dos biominerais foram encontradas transições devido à presença de Mn nas amostras. Foi observado um pico termoluminescente (TL) em aproximadamente 140°C para os biominerais e em 180°C para os silicatos, cuja intensidade depende diretamente da dose. Para amostras expostas a diferentes tipos de radiações, o pico TL ocorre em temperaturas mais baixas. Para as curvas dose-resposta obtidas para esses materiais, foi possível determinar um intervalo de linearidade para o qual a sua aplicação em dosimetria de doses altas se torna possível. Levando-se em consideração o tipo de radiação, dentre os biominerais e os silicatos, obteve-se a menor dose detectável (40mGy), para a radiação gama em amostra de casca de ostra utilizando-se a técnica de medição de luminescência opticamente estimulada (LOE). Para radiação beta, as amostras de tremolita e diopsídio obtiveram a menor dose detectável (60mGy). No geral, obteve-se uma boa reprodutibilidade para as amostras, utilizando-se as técnicas TL, LOE e emissão exoeletrônica termicamente estimulada (TSEE) para as radiações alfa, beta e gama. Portanto, pode-se concluir que as amostras caracterizadas neste trabalho podem ser utilizadas como detectores/dosímetros de doses altas. / The predominant isomorphous form in the biominerals studied in this work (oyster shell, coral, mother of pearl and shell) was aragonite. The appearence of the calcite phase occurred at 500°C at a heating rate of 10°C/s for all samples except for the coral sample, which was 400°C, independent of the heating rate. The most abundant element in the biominerals samples was Ca in the CaO form, and in the silicates (tremolite, diopside and rhodonite) Si in the SiO form. The most common trace element observed in the biominerals samples was Fe. The analyses of electron paramagnetic resonance showed lines of Mn2+ in the coral and mother-of-pearl samples before irradiation. In the case of the irradiated samples, the defects found were CO2-, CO33-, CO3- and SO2-, in the g range between 2.0010 and 2.0062. In the analyses by optical absorption of biominerals, transitions due to the presence of Mn in the samples were found. A thermoluminescent (TL) peak at approximately 140°C was found for the biominerals and at 180°C for silicates, which intensity depends directly on the dose. For samples exposed to different types of radiation, the TL peak occurred at lower temperatures. From the dose-response curves obtained for these materials, it was possible to determine a linear range for which their application in high dose dosimetry becomes possible. Taking into account the radiation type, among biominerals and silicates, the lowest detectable dose (40mGy) to gamma radiation was achieved for oyster shell samples using the measuring technique of optically stimulated luminescence (OSL). Using beta radiation, for diopside and tremolite samples the lowest detectable dose of 60mGy was obtained. For all samples, using the TL, OSL and thermally stimulated exoelectron emission (TSEE) techniques in alpha, beta and gamma radiation beans a good response reproducibility was obtained. Therefore, the samples characterized in this work are suitable to be used as high dose detectors/dosimeters.

Les missions océanographiques Carambar (2010), Carambar 1.5 (2014) et Carambar 2 (2016-2017) menées au large de la pente nord du Petit Banc des Bahamas (PBB) ont permis d’étudier les processus d’export sédimentaire quaternaires sur ce système carbonaté. Les 24 270 km² de données bathymétriques couplées aux 6398 km de lignes sismiques très haute-résolution et aux 42 carottes sédimentaires reparties entre – 177 m et – 4873 m de profondeur ont permis de caractériser ce système depuis la pente supérieure jusqu’à la plaine abyssale.Le travail présenté ici s’intéresse aux résultats obtenus sur les carottes sédimentaires prélevées sur le haut de pente supérieur du PBB (Carambar 1.5) et celles obtenues sur le bas de pente et dans la zone du canyon du Great connecté à la plaine abyssale (Carambar 2). Ils viennent compléter les résultats obtenus précédemment par Tournadour (2015) et Chabaud (2016) sur les pentes inférieures et moyennes.Un prisme de haut niveau marin se dépose haut de pente supérieure. Actuellement, ce prisme daté de l’holocène s’étend de - 177 m à – 360 m. Les dépôts sédimentaires sont principalement engendrés parle density cascading et le passage d’ouragans. Son alimentation La formation du prisme a débuté il y a13,6 ± 3,5 ka cal BP, après le Meltwater Pulse 1A. Les Meltwater Pulses ont engendré la formation de terrasses qui correspondent alors à des environnements peu profonds et qui induisent une production carbonatée qui peut être exportée vers le prisme. La principale phase de développement du prisme est datée à 6,5 ± 0,9 ka cal BP, quand le niveau marin a finalement atteint le rebord de plate-forme. La sédimentation du bas de pente suggère une alimentation principalement pélagique et liée aux passages des courants plutôt qu’aux apports de plate-forme. Les variations dans les faciès dans ces dépôts sont donc issues de variations climatiques (intensification des courants, apports arctiques). La sédimentation de cette zone semble similaire à celle retrouvé sur la Blake Outer Ridge à 400 km au nord.Entre -1300 et -4800 m, la pente se caractérise par le canyon géant du Great Abaco. L’alimentation peu fréquente de ce canyon contrôlé structuralement a lieu principalement par le biais de tributaires, la tête du canyon ne semble pas être le lieu préférentiel de passage de courants de turbidité fréquents. / Over the past decade, the Little Bahamas Bank (LBB) in the Caribbean has been at the heart of oceanographic cruises Carambar (2010), Caramba 1.5 (2014) and Carambar 2 (2016-2017). These scientific expeditions were carried out with the aim of improving our knowledge of the processes tha controlled sediment export during the Quaternary in this tropical setting. Thus, bathymetric datacovering some 24,270 km² of seabed, high-resolution seismic lines running over 6,398 km and 42sediment cores ranging from 177 to 4,873 m water depth were collected in the upper slope through tothe abyssal plane of the LBB system.This study focusses on those sediment cores retrieved in the upper (Carambar 1.5) and lower slope ofthe LBB and those from the Great Canyon (Carambar 2) which is connected to the abyssal plane. These results are complementary to previous studies led on the middle and lower northern slope of the LBB (Tournadour, 2015; Chabaud, 2016).A highstand accretion wedge, currently dated to the Holocene, expands at water depths of 177-360 m. Sediment deposition in the prism is mainly the result of hurricanes and density cascading. Its initiation is dated at 13. 6 ± 3.5 ka cal BP, following Meltwater Pulse 1A. Melwater Pulses led to the formationof shallow terraces that enhanced carbonate production and ultimately supplied the prism with sediment through the export of said carbonate. The height of the development of the prism occurred at 6.56 ± 0.9ka cal BP when the sea level reached the shelf-break.Sedimentation in the lower slope is indicative of more pelagic processes, since currents play a greater part in the deposition of sediment than the shelf. Variability in the facies of theses deposits are thus the result of climatic variations (e.g strengthening of currents, influxes of Arctic water). Sediments in this are a share similarities with those in Blake Outer Ridge, 400 km north of the LLB. At water depth of1,300-4,800 m, the slope is scored by a giant canyon, namely the Great Abaco. The morphology of this canyon attests to a structural control of sediment supply: rather than the head of the canyon, tributaries appear to supply the majority of sediment within this system.

The biodegradability and when functionalised biocompatibility of aliphatic polycarbonates (APCs) makes them an attractive class of materials for biomedical applications such as tissue engineering scaffolds and drug-delivery carriers. One route to accessing a wide-range of well-defined and functional APCs is the controlled ring-opening polymerisation (ROP) of cyclic carbonates. In turn, these would ideally be prepared by the direct coupling of CO2 with diols to give water as the only by-product. In this way, the combination of CO2 and sugar-derived diols draws upon two natural renewable building blocks for the construction of polycarbonates that are anticipated to show good biocompatibility properties. Chapter 2 develops a simple and mild alternative to the traditional use of phosgene derivatives for the synthesis of six-membered cyclic carbonates from 1,3-diols and CO2. DFT calculations highlighted the need to lower both the CO2-insertion and ring-closing kinetic barriers to cyclic carbonate formation. Organic superbase, 1,8- diazabicyclo[5.4.0]undec-7-ene (DBU) enabled the formation of carbonate species at 1 atm CO2 pressure whereas, the introduction of a leaving group strategy lowered the cyclisation barrier. Mechanistic considerations suggested a kinetic preference for ring- closing via a nucleophilic addition-elimination pathway rather than a SN2-like intramolecular cyclisation. Chapter 3 applies the procedure with CO2 to the preparation of a novel monomer from natural sugar, ᴅ-mannose. ROP was carried out via an organocatalytic approach and a preference for head-tail linkages in the polycarbonate backbone indicated by NMR spectroscopy and supported by DFT calculations. Chapter 4 utilises CO2 to invert the natural stereochemistry of sugars and create a thymidine-based monomer. The thermodynamic parameters of the ROP with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyst are determined and the properties of the polycarbonates investigated to include preliminary cell attachment studies. Finally, chapter 5 details the synthesis of cyclic carbonates from 2- deoxy-ᴅ-ribose and the investigation into the different ROP behaviour of the α- and β- anomers. The ability to tune the polymer properties through copolymerisation with trimethylene carbonate (TMC) is also discussed.

Le stockage géologique du carbone est l’une des techniques les plus prometteuses pour réduire le taux de CO₂ dans l’atmosphère. La séquestration géologique possède la capacité et la longévité potentielles pour diminuer les émissions de CO₂ vers l’atmosphère. Dans le cadre d’injections à l’échelle industrielle, les réservoirs carbonatés peuvent faire partie des sites aptes à stocker du CO₂. Toutefois, ces injections à grandes profondeurs sont sujettes à des risques de fuites du piège géologique lui-même ou des infrastructures liés à l’exploitation du site de stockage. Ainsi, il existe principalement deux types de fuite : brutale et diffuse. Dans les deux cas, elles sont susceptibles d’entrainer des risques pour l’environnement et de mettre en danger les populations. Il est ainsi nécessaire de développer des outils capables de prévenir une fuite de CO₂ quel que soit son type. Par ailleurs, il est particulièrement indispensable de comprendre les mécanismes de transport réactif qui rentrent en jeu lors de l’arrivée de cette fuite en contexte de proche surface (zone vadose) et ainsi d’essayer d’étudier comment cette fuite peut s’amortir. Ces travaux de thèse traitent donc de la caractérisation, de la quantification et de la modélisation des processus de transferts et des interactions CO₂-H₂O-CaCO₃ dans la zone vadose en contexte de fuite à partir d’un puits de forage. Cette problématique a été d’abord abordée par une approche expérimentale sur un site pilote à Saint-Emilion. Puis, les interactions CO₂-H₂O-CaCO₃ ont été étudiées au travers d’une approche expérimentale à l’échelle de la carotte en laboratoire. L’approche expérimentale a conduit à la réalisation de deux fuites dans la zone vadose du site pilote : une fuite diffuse et une fuite ultra diffuse. Elles furent réalisées dans la continuité des expériences qui avaient déjà eu lieu auparavant. Une comparaison de l’ensemble des fuites a montré la nécessité d’utiliser des gaz nobles comme précurseurs de l’arrivée en surface du CO₂. Selon le type de fuite, l’hélium peut servir de précurseur temporel du CO₂, tandis que le krypton prévient de l’étendue du panache de gaz durant la fuite. Plus la pression d’injection du CO₂ est importante et plus le gaz migre par advection. Par ailleurs, une pression d’injection importante favorise l’existence de passage préférentiel dans la zone vadose. L’utilisation d’isotopes tels que ceux de l’hélium et du carbone permet de mettre en évidence la présence locale de phases aqueuses dans le massif et de déterminer l’origine biologique ou anthropique du CO₂. Les expériences à l’échelle de la carotte permettent d’estimer le pouvoir tampon des calcaires oligocènes en fonction du faciès de la roche. La perméabilité et la porosité de celle-ci conditionnent la dissolution des calcaires. De même, la réactivité des carbonates en contexte de fuite dépend du pH de la phase aqueuse, du débit qui traverse le réseau poreux, de la saturation en eau et des caractéristiques pétro-physiques des carbonates. / Carbon storage is one of the most encouraging methods to decrease CO₂ concentration into the atmosphere. Carbon storage provides the longevity and the capacity needed to decrease CO₂ emissions toward the atmosphere. When dealing with storage on an industrial scale, carbonated reservoirs can be among the most suitable storage sites. However, these high depth injections are subject to leakage risks from the geologic trap itself or from the framework created by the establishment of the site. Two main types of leakage exist: brutal and diffusive leakage. In both cases, they are likely to endanger the environment and the population. Therefore, it is essential to develop tools that are able to anticipate any types of CO₂ leakage. Furthermore, it is also necessary to understand the reactive transport mechanism that take place when the leakage arrives in the shallow subsurface (vadose zone)and to see how the leakage can be buffered. This work deals with the characterization, the quantification and the modelling of transfer processes and CO₂-H₂O-CaCO₃ interactions into the vadose zone in a context of a leakage from a drilling well. This issue was first dealt through field experiment on the site of Saint Emilion. Then, the CO₂-H₂O-CaCO₃ interactions were studied through an experimental approach in laboratory. Two leakage experiments were performed on the site: a diffusive leakage and an ultra-diffusive leakage. They were performed as a sequel of former experiments carried on the pilot site. A comparison of all the leakage experiments revealed the necessity to use noble gases as precursor of the CO₂ arrival at the surface. Depending of the type of the leakage, helium can be a temporal precursor while krypton can anticipate the spread of the CO₂ gas plume. The higher the injection pressure, the more the gas migrates through advective flux. Moreover, a high injection pressure favors the existence of preferential paths in the vadose zone. The use of helium and carbon isotopes makes it possible to reveal the presence of a local aqueous phase within the porous media and to identify the origin of CO₂. The core scale experiments lead to the estimation of the buffering power of Oligocene limestone according to the rock facies. The permeability and the porosity influence the dissolution of the limestone. The reactivity of carbonates during a leakage depends on the pH of the aqueous phase, the flow rate that goes through the porous media, the water saturation and petrophysical characteristics of the carbonates.

Orientador: José Alexandre Matelli / Banca: Eliana Vieira Canettieri / Banca: Carlos Manuael Romero Luna / Resumo: Os modelos energéticos atuais são baseados majoritariamente na utilização de combustíveis fósseis, os quais, além de serem fontes finitas, ainda geram gases poluentes que contribuem para o efeito estufa e, consequentemente, para o aquecimento global. As células a combustível, por possuírem alta eficiência de conversão, baixa emissão, simplicidade de operação e flexibilidade em sua utilização, vêm sendo estudadas como opção mais limpa de geração. A célula a combustível de carbonato fundido, em particular, além de ter vantagens estruturais por operar a alta temperatura, possui calor residual que pode ser aproveitado para cogeração. O presente trabalho propõe uma configuração de ciclo combinado de uma célula a combustível de carbonato fundido de 10 MW, que possui reforma interna de gás natural, com um ciclo a vapor que aproveita o calor residual da célula. A reforma a vapor do gás natural, simulada pelo software STANJAN Chemical Equilibrium Solver, apresentou valores satisfatórios de produção de H2 na temperatura de operação da célula. As análises energética e exergética, simuladas através do software Engineering Equation Solver (EES), apontaram aumentos nas respectivas eficiências globais de 4,8 e 4,6%, respectivamente. A análise exergoeconômica indicou custo de geração de 0,4679 USD/kWh, valor acima das tarifas nacionais. Entretanto, a análise de sensibilidade mostrou que plantas de grande porte com essa configuração podem ser economicamente competitivas em diferentes cenários... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Current researches point to a significant increase in energy demand over the next few years. Energy models are mostly based on fossil fuels, which generates greenhouse gases that contribute to global warming. Thus, it becomes necessary to develop equipment and cycles that operate with greater efficiency, as well as new technologies of energy generation with both fossil and renewable sources. Fuel cells are being widely investigated due to their high conversion efficiency, low emissions, structural simplicity and flexibility. Among several fuel cell types, molten carbonate fuel cell has advantages such as fuel flexibility and high operating temperature, which leads to high thermal energy residue. This residue can be used for cogeneration and combined cycles, in order to enhance the global efficiency. This study aimed to introduce a 10 MW internal reforming molten carbonate fuel cell and steam turbine combined cycle. Steam reforming of natural gas was simulated by STANJAN Chemical Equilibrium Solver and presented satisfactory H2 production at MCFC operating temperature. Simulation in Engineering Equation Solver (EES) of energetic and exergetic analysis showed efficiency increases of 4,8 and 4,6%, respectively. Exergoeconomic analysis pointed to a 0,4679 USD/kWh power cost. However, sensitivity analysis showed that higher plants can achieve economic viability in different scenarios / Mestre