[pt] A indústria do petróleo realiza contínuas pesquisas para aperfeiçoar as operações de perfuração, aumentando a taxa de penetração e reduzindo o tempo não produtivo. Diversos estudos analisam o processo de corte em rocha utilizando brocas PDC (Polycrystalline Diamond Compact). Experimentos como o ensaio de cortador único simulam a interação existente entre a rocha e o cortador. Além disso, modelos numéricos têm sido criados para fazer o mesmo tipo de análise obtendo estimativas concordantes com resultados experimentais. No entanto, os ensaios experimentais geram altos custos de investimento, e por sua vez, as simulações numéricas demandam tempo muito alto para realizar análises de boa qualidade. Modelos analíticos procuram eliminar o fator custo e tempo, gerando resultados confiáveis da simulação do processo de corte, similares aos resultados das análises experimentais e numéricas. Os modelos analíticos aqui apresentados permitem estimar as forças medidas pelo cortador no processo de corte, partindo das propriedades mecânicas da rocha. Os modelos levam em conta o equilíbrio de forças no instante do corte e consideram, para o cálculo das forças, a sua geometria e as propriedades de resistência do material. A rocha utilizada no presente trabalho é um evaporito. A aplicação deste tipo de metodologia para corte em halita obriga a considerar no modelo analítico o incremento nas forças devido ao comportamento dúctil do material, à existência de deformações plásticas e à aglomeração de material na face do cortador a fim de obter uma melhor estimativa das forças de corte. Conseguem-se estimativas aceitáveis com dois dos modelos avaliados nas condições de pressões atmosféricas e altas pressões de confinamento. / [en] The oil industry carries out continuous research to improve drilling operations, to increase the penetration rate and to reduce non-productive time. Several studies analyze the rock cutting process using PDC bits (Polycrystalline Diamond Compact). Experiments with a single cutter machine measure the interaction between the rock and the cutter. Furthermore, numerical models aim to simulate the physical process and calculate results as possible consistent with experimental data. However, experimental tests are expensive and robust and numerical simulations are time consuming. Analytical models aim to reduce both cost and time factor, while providing reliable results for simulation of cutting process. The analytical models presented here allow us to estimate the forces measured on the cutter in the rock cutting process. The models take into account the balance of forces acting on the cutter face and these forces are calculated based on geometry and material properties of both cutter and rock. The rock evaluated in this work is an evaporite. The application of such type of methodology to simulate the salt rock drilling requires the analytical model to consider the increase of forces due to rock ductile behavior and the existence of plastic deformation and agglomeration of material on the cutter s face in order to obtain adequate estimation of the cutting forces. Two of the evaluated models in this work presented agreement with experimental results, both under atmospheric and high pressure conditions.

Uganda is well endowed with economic quantities of mineral salts present in the interstitial brines and evaporite deposits of Lake Katwe, a closed (endorheic) saline lake located in the western branch of the great East African rift valley. Currently, rudimentally and artisanal methods continue to be used for salt extraction from the lake raw materials. These have proved to be risky and unsustainable to the salt miners and the environment and they have a low productivity and poor product quality. This work involves the investigation of the salt raw materials that naturally occur in the brines and evaporites of Lake Katwe. The purpose is to propose strategies for the extraction of improved salt products for the domestic and commercial industry in Uganda. The literature concerning the occurrence of salt and the most common available technologies for salt extraction was documented. Also, field investigations were undertaken to characterize the salt lake deposits and to assess the salt processing methods and practices. The mineral salt raw materials (brines and evaporites) were characterized to assess their quality in terms of the physical, chemical, mineralogical, and morphological composition through field and laboratory analyses. An evaluation of the potential of future sustainable salt extraction from the lake deposits was done through field, experimental, and modeling methods. Moreover, the mineral solubilities in the lake brine systems and dissolution kinetics aspects were investigated. The results reveal that the salt lake raw materials contain substantial amounts of salt, which can be commercialized to enable an optimum production. The brines are highly alkaline and rich in Na+, K+, Cl-, SO42-, CO32-, and HCO3-. Moreover, they contain trace amounts of Mg2+, Ca2+, Br-, and F-. The lake is hydro-chemically of a carbonate type with the brines showing an intermediate transition between Na-Cl and Na-HCO3 water types. Also, the evaporation-crystallization is the main mechanism controlling the lake brine chemistry. These evaporites are composed of halite mixed with other salts such as hanksite, burkeite, trona etc, but with a composition that varies considerably within the same grades. The laboratory isothermal extraction experiments indicate that various types of economic salts such as thenardite, anhydrite, mirabilite, burkeite, hanksite, gypsum, trona, halite, nahcolite, soda ash, and thermonatrite exist in the brine of Lake Katwe. In addition, the salts were found to crystallize in the following the sequence: sulfates, chlorides, and carbonates. A combination of results from the Pitzer’s ion-interaction model in PHREEQC and experimental data provided a valuable insight into the thermodynamic conditions of the brine and the sequence of salt precipitation during an isothermal evaporation. A good agreement between the theoretical and experimental results of the mineral solubilities in the lake brine systems was observed with an average deviation ranging between 8-28%. The understanding of the mineral solubility and sequence of salt precipitation from the brine helps to control its evolution during concentration. Hence, it will lead to an improved operating design scheme of the current extraction processes. The dissolution rate of the salt raw materials was found to increase with an increased temperature, agitation speed and to decrease with an increased particle size and solid-to-liquid ratio. Moreover, the Avrami model provided the best agreement with the obtained experimental data (R2 = 0.9127-0.9731). In addition, the dissolution process was found to be controlled by a diffusion mechanism, with an activation energy of 33.3 kJ/mol. Under natural field conditions, the evaporative-crystallization process at Lake Katwe is influenced by in-situ weather conditions. Especially, the depth of the brine layer in the salt pans and the temperature play a significant role on the brine evaporation rates. With the optimal use of solar energy, it was established that the brine evaporation flux can be speeded up in the salt pans, which could increase the production rates. Moreover, recrystallization can be a viable technique to improve the salt product purity. Overall, it is believed that the current work provides useful information on how to exploit the mineral salts from the salt lake resources in the future. / <p>QC 20151217</p>

L’objectif de cette thèse est d’étudier le comportement du soufre dans des fluides hydrothermaux soumis à un métamorphisme de bas grade. Elle est séparée en trois études interconnectées couplant étude naturelle et expérimentale : i) une étude du cycle du soufre dans les évaporites carniennes de la "Nappe des Gypses" des Alpes françaises comme cas d’étude naturelle a été réalisée, ii) une étude de la spéciation du soufre dans les inclusions fluides associées à ces évaporites triasiques, et iii) une étude expérimentale du rôle de la spéciation du soufre sur le mécanisme de la Thermo-Réduction des Sulfates (TSR) et l’altération des hydrocarbures associée. La première étude repose sur le couplage d’une approche pétrographique classique et d’une étude détaillée des inclusions fluides, des isotopes stable (δ34S, δ33S, δ36S, Δ33S, Δ36S, δ13C et δ18O) et de la matière organique dans la "Nappe des Gypses". Ces études couplées ont permis d’identifier le processus de TSR comme la réaction contrôlant le comportement du soufre dans cette formation en système fermé. La seconde étude repose sur une nouvelle approche analytique couplant spectroscopie Raman in-situ et platine microthermométrique permettant de réchauffer jusqu’à 300°C les échantillons (naturel et synthétique). Ainsi, à température >100°C la présence de l’ion radicalaire S3- et d’autres espèces polymériques du soufre (Snx) a été mise en évidence dans la “Nappe des Gypses”. Cette étude confirme le rôle indispensable à la TSR de l’ion S3- et des Snx dans les fluides naturels. Cette étude naturelle a été complétée par une étude expérimentale préliminaire qui a permis de mettre en place de nouveaux protocoles expérimentaux en autoclave et en capillaires de silice couplés à des analyses spectroscopiques et isotopiques. Ceci afin de mieux comprendre le rôle de la spéciation du soufre dans les interactions entre une phase aqueuse et un fluide hydrocarboné lors de la TSR. Cette thèse conduit à une meilleure compréhension du rôle de la spéciation du soufre et son lien avec des composés organiques lors de la TSR en condition métamorphique de bas grade. Cela ouvre de nouvelles perspectives de compréhension des formations géologiques basées sur le couplage d’études géologiques classiques et d’études géochimiques plus fines / The aim of this thesis is to study the sulfur behavior in hydrothermal fluids subjected to low grade metamorphism. It is separated into three interconnected studies linking natural and experimental study: i) a study of the sulfur cycle in the Carnian evaporites of the "Nappe des Gypses" from the French Alps as a natural case study is performed, ii) a study of the sulfur speciation in fluid inclusions associated to these Triassic evaporites, and iii) an experimental study of the role of sulfur speciation on the Thermochemical Sulfate Reduction (TSR) mechanisms and the associated hydrocarbons alteration. The first study is based on the coupling of a classical petrographic approach associated to a detailed study of fluid inclusions, stable isotopes (δ34S, δ33S, δ36S, Δ33S, Δ36S, δ13C and δ18O) and organic matter in the “Nappe des Gypses”. The coupling study allows to identify the TSR process as the reaction controlling the behavior of sulfur in this formation in a closed system. The second study is based on a new analytical approach coupling in-situ Raman spectroscopy and microthermometric stage. This technique allows to heat up to 300°C samples (natural and synthetic). Thus, at temperature >100°C, the presence of the radical ion S3- and other polymeric sulfur species (Snx) is demonstrated in the “Nappe des Gypses”. This study confirms the essential role in the TSR process of S3- and Snx species in natural fluids. This study natural was completed by a preliminary experimental study allowed to set up new experimental protocols in autoclave and fused silica capillaries coupled to spectroscopic and isotopic analyses. This to better understood the role of sulfur speciation in the interactions between an aqueous phase and a hydrocarbons fluid during the TSR. This thesis leads to a better understanding of the role of sulfur speciation and its link with organic compounds during TSR under low grade metamorphic conditions. This opens new perspectives to understand geological formations based on coupling of classical geological studies and finer geochemical studies

[pt] O tempo não produtivo (NPT) durante a perfuração de poços de petróleo pode ser responsável pela perda de milhões de dólares em atividades offshore. A má previsão da pressão de poros pode ser uma das responsáveis pelo NPT de um poço ou mesmo sua perda definitiva em campos geologicamente complexos, como em bacias evaporíticas. Nesses campos complexos, os métodos de previsão de pressão de poros convencionais nem sempre são capazes de prever bem a distribuição de pressão de poros, mesmo após a perfuração de número considerável de poços. Este trabalho estuda técnicas alternativas que atendam ao problema de previsão de pressão para esses casos. Para fundamentar os estudos, é apresentada uma revisão sobre os riscos associados à perfuração em bacias evaporíticas e sobre os métodos de previsão de pressão existentes (métodos convencionais, sísmicos, modelagem geológica geomecânica 3D, modelagem pelo método dos elementos finitos e modelagem de bacias). Avaliando os problemas de perfuração nestes campos e as dificuldades de previsão dos métodos convencionais, nota-se que a complexidade imposta pelas consequências da presença do sal pode ser reduzida pelo uso de métodos que considerem a geologia local de forma mais abrangente em seu fluxo de trabalho. Concluiu-se que a modelagem de bacias e a modelagem geológica geomecânica 3D têm forte potencial de aplicação para estes casos. As técnicas, contudo, não tem a previsão de pressão de poros por objetivo principal, mas podem ser aplicadas ou adaptadas para tal fim. Este estudo apresenta adaptações de metodologia e/ou aplicações direcionadas de ambas para fins de previsão de pressão de poros. Para validar as propostas apresentadas, estudos de caso foram desenvolvidos e apresentaram resultados considerados bastante satisfatórios. / [en] The non-productive time (NPT) while drilling oil and gas wells may be responsible for losing millions of dollars, especially in offshore activities. Bad pore pressure predictions may be responsible for large NPT or even the definitive loss of well in geologically complex fields, such as evaporate basins. On these complex fields, the conventional pore pressure prediction methods sometimes are not capable of providing good predictions, even if a considerable number of wells has been already drilled. This thesis studies alternative techniques which may attend for pore pressure prediction in these cases. In order to develop a consistent knowledge about the case, a literature review has been conducted in two ways: to understand what are the risks associated to drilling in evaporate basins; to review what are the available methods for pore pressure prediction (conventional methods, seismic methods, 3D geological and geomechanical modeling, finite element methods and basin modeling). During analyzing geomechanical drilling risks in these sites, and the difficulties found by conventional methods to predict it, it was noted that the complexity imposed by the presence of salt bodies can be reduced by using methods that make a strong use of geological knowledge on their workflow. It has been concluded that basin modeling and 3D geological and geomechanical modeling have a good potential to be applied for this goal. The techniques, nevertheless, do not have pore pressure prediction as their main goal, but can be applied to or adapted for such finality. This work presents some methodology adaptations and/or applications of both of techniques directed to pore pressure prediction goals. In order to validate the presented proposals, case studies has been developed, and their results were considered satisfactory.

La thèse cherche à caractériser les types de fluides à différents niveaux structuraux et types de déformation. Les résultats de la Sierra Bédar indiquent le rôle d'une saumure enrichie en métaux lors des derniers stades de circulation au sein de la croûte ductile dans un domaine encore isolé des fluides de surface. Cette saumure est plus diluée à l'est dans la Sierra Almagrera et où l'impact du système décrochant va devenir de plus en plus important avec du volcanisme et de nombreux gisements. Dans le domaine fragile, des veines de quartz enregistrent des fluides de surface. Suivent des veines de quartz indiquant la réapparition des fluides métamorphiques sous-jacent. La formation de veines de sidérite-pyrite-galène-barytine montre de plus forte salinité et des rapports Cl/Br indiquant la contribution d'une autre source de saumures secondaires issues cette fois des évaporites messiniennes. Le décrochement a modifié le compartimentage de part et d'autre de la transition fragile-ductile / This thesis aim at characterizing the types of fluids concerned structural levels and style of deformation. Results from Sierra Bedar point out the role played by metal-rich brines during late stages of fluid flows within the ductile crust within a domain was still isolated from surficial fluids. Brine concentration drop in the eastern Sierra Almagrera which was progressively more impacted by the major transcurrent system with volcanism and metal ore deposits. At reaching the brittle domain, quartz veins trapped surficial fluids. Soon after, quartz veins indicating the return of metamorphic fluids. Following siderite-pyrite-galena-barite veins display higher salinities and Cl/Br ratios indicate the contribution of another secondary brine coming from early Messinian evaporites. This major transcurrent tectonics clearly modified the partitioning on both sides of the brittle-ductile transition

Triple oxygen and hydrogen isotope analysis of the structurally-bound water in gypsum can provide a direct measure of past hydrologic variability. This thesis presents the development of the water extraction and isotopic measurement procedures, the calculation of the gypsum-water isotope fractionation factors, and the application of the method to constrain the palaeohydrologic conditions in two temporally and geographically disparate sites. Measurement of the isotopic composition of gypsum hydration water is used to examine the hydrological changes that occurred during the Terminal Classic Drought of the Maya lowlands (~800-1000 CE), coincident with the period when the Classic Maya Civilization of Mesoamerica collapsed. The data provide a complete and direct archive of hydrological conditions that have previously been limited to ice core records. Mean annual rainfall is shown to have decreased by between 41% and 54%, with intervals of up to 70%, compared to present-day conditions. This study has also shown for the first time that relative humidity was 2%-7% lower during the Terminal Classic Drought compared to today. The methodology is also applied to the massive gypsum deposits in the marginal and deep basins of the Mediterranean to interpret the chemical evolution of parent water bodies during the Messinian Salinity Crisis (5.97-5.3 Ma). By combining the measurement of gypsum hydration water with other traditional (e.g. strontium) and novel (e.g. calcium and barium) isotope tracers, the hydrological changes during the deposition of Primary Lower Gypsum units of the Sorbas Basin in southeastern Spain, the Upper Gypsum units of Sicily, and deep basin deposits have been constrained. The results indicate that all deposits experienced a significant freshwater contribution to the mother fluids from which they formed. It is proposed that obliquity-controlled sea level and eccentricity-modulated precession, superimposed on longer-term tectonic restriction of the Mediterranean-Atlantic exchange, together controlled the varying depositional environments during the formation of the Messinian Salt Giant. This thesis demonstrates that the analysis of gypsum hydration water is a powerful tool for palaeoclimate reconstruction. The methodology can be applied to gypsum (and other hydrated minerals) in a wide range of settings across geological space and time, providing a rich source of information about the environmental conditions under which they formed.

[pt] A perfuração de poços de petróleo em ambientes adversos requer especialistas dedicados a estuda-la a fim de garantir que ela ocorra de forma rápida, segura e com qualidade. Dentro desse contexto, há estudos experimentais e numéricos que avaliam a ação de corte feita por um cortador individual objetivando quantificar as forças de contato, propor soluções para aumentar o seu tempo de vida útil e a sua taxa de penetração, e entender o mecanismo de corte. Seguindo esta linha de pesquisa, a presente Tese visa oferecer uma melhor compreensão para o problema de interação rocha/cortador PDC (Polycrystalline Diamond Compact) ao longo da perfuração de depósitos evaporíticos de halita e de reservatórios de carbonatos. O estudo foi abordado através da modelagem numérica do ensaio de cortador único e da modelagem numérica de corte por múltiplos cortadores através do método dos elementos discretos. Resultados experimentais aferiram a calibração da amostra sintética e dos modelos numéricos de corte em rocha. Um estudo numérico paramétrico do ensaio de cortador único foi feito objetivando identificar parâmetros que controlam a ação de corte. Em seguida, foi desenvolvida uma equação analítica que quantifica a energia específica mecânica global resultante da ação de múltiplos cortadores, a fim de entender e quantificar qual a contribuição de cada cortador na eficiência global. A equação foi aplicada usando os resultados das modelagens numéricas de múltiplos cortadores. Constatou-se que o bom ajuste entre as previsões numéricas e os resultados experimentais validou o uso do método dos elementos discretos para modelar o processo de corte em diferentes tipos de rochas. A modelagem numérica desenvolvida neste estudo pode ser considerada uma ferramenta útil para projeto e otimização do desempenho de brocas de perfuração. / [en] Oil wells drilling in adverse environments requires specialists dedicated to study the drilling process to ensure a quickly, safely and quality performance. In this context, experimental and numerical studies can be find in technical literature that evaluate the cutting action done by a single cutter aiming to quantify the contact forces, proposing solutions to increase its useful life time and its rate of penetration, and to understand the cutting mechanism. Following this line of research, this Thesis aims to provide a better understanding regarding the rock / polycrystalline diamond compact cutter interaction during the halite deposits and carbonate reservoirs drilling. The study was approached through numerical modeling of the single cutter test and through numerical modeling of the cutting action by multiple cutters using the discrete element method. Experimental results were used to calibrate the synthetic sample and the rock cutting numerical models. A parametric numerical study of the single cutter test was done aiming to identify parameters that control the cutting action. Then, an analytical equation was developed that quantifies the global mechanical specific energy resulting from the cutting action of multiple cutters, in order to understand and quantify the contribution of each cutter to overall efficiency. The equation was applied using the results of numerical modeling of multiple cutters developed in this work. It was verified that the good agreement between numerical predictions and experimental results validated the use of the discrete element method to model the cutting process in different rock types. The numerical modeling developed in this study can be considered a useful tool for design and optimizing the performance of drill bits.

La tsavorite, grossulaire vert à V-Cr-Mn, est contenue dans des gneiss et roches calco-silicatées graphiteux, souvent associés à des marbres dolomitiques, et appartenant à la ceinture métamorphique néoprotérozoïque mozambicaine. La tsavorite se trouve soit dans des nodules ou des veines de quartz (gisements primaires), soit dans des placers (gisements secondaires). L'étude minéralogique des tsavorites propose un nouveau protocole de certification de leur origine géographique, à partir du rapport V/Cr, de la teneur en Mn et du [delta]18 O. L'étude des gisements de Lemshuku et Namalulu en Tanzanie montre que le métamorphisme des protolithes sédimentaires riches en matière organique et évaporites s'est effectué à P = 7,0 ± 0,4 kbar et T = 677 ± 14°C, à 634 ± 22 Ma (datation U-Th-Pb sur monazite). Le bâti métamorphique s'est refroidi vers 500 Ma (datation 40Ar-39Ar sur muscovite). Deux stades de métasomatose sont reliés à la formation de la tsavorite : (i) une métasomatose de diffusion formant les nodules à P = 5,0-7,4 kbar et T = 580-691°C; (ii) une métasomatose calcique d'infiltration contemporaine de la formation des veines de quartz à P = 3,6-4,9 kbar et T = 505-587°C. Ces dernières sont datées in situ par la méthode Sm-Nd à 606 ± 36 Ma. Les évaporites continentales, déposées dans une sabkha de côte marine avec des sédiments silico-calcaires, sont transformées en tsavorite dans le cas des nodules, alors que les sels fondus sont associés à la formation des veines de quartz. Les minéralisations sont contrôlées par la lithostratigraphie et la tectonique / Tsavorite, a (V, Cr, Mn)-bearing green grossular, is hosted by graphitic gneisses or calc-silicates, often asssociated with dolomitic marbles, and belonging to the Metamorphic Neoproterozoic Mozambique Belt. Tsavorite is found either as nodules or in quartz veins (primary deposits), or in placers (secondary deposits). The mineralogical study of tsavorites suggests a new protocol to certificate their geographical origin, based on the V/Cr ratio, Mn content and delta18O. The study of the Lemshuku and Namalulu deposits in Tanzania has shown that the metamorphism of organic matter-rich and evaporites-rich sedimentary protoliths occurred at P = 7.0 ± 0.4 kbar and T = 677 ± 14°C, at 634 ± 22 Ma (U-Th-Pb dating on monazite). The metamorphic series cooled down at around 500 Ma (40Ar-39Ar dating on muscovite). Two metasomatic stages are linked to the formation of tsavorite : (i) diffusion metasomatism forming nodules at P = 5.0-7.4 kbar and T = 580-691°C; (ii) calcitic infiltration metasomatism forming quartz veins at P = 3.6-4.9 kbar and T = 505-587°C. These last have been dated in situ with Sm-Nd dating at 606 ± 36 Ma. Continental evaporites, deposited in a coastal marine sabkha with (Si, Ca)-bearing sediments, transformed into tsavorite in the case of the nodules, while the molten salts are associated with the formation of the quartz veins. The mineralisations are controlled by lithostratigraphy and structure