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No. of bitstreams: 1 lima_fg_dr_rcla.pdf: 11693401 bytes, checksum: 59035a53f9dd97177924619aae57fda8 (MD5) Previous issue date: 2017-09-14 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho apresenta os resultados dos estudos petrogenéticos detalhados realizados nos serpentinitos que constituem do Morro do Níquel, maciço ultrabásico mineralizado em níquel laterítico, situado na Faixa Brasília Meridional, ao norte da Zona de Sutura de Alterosa, localizado no Município de Pratápolis (MG), sul/sudoeste do Estado de Minas Gerais, Brasil. Os serpentinitos possuem cor verde escuro a preto, aspecto maciço e é constituído por mais de 95% de lizardita/crisotilo, com ocorrências localizadas de antigorita. O padrão estrutural do maciço é compatível com aqueles gerados pela deformação de em um corpo rígido em matriz dúctil dentro de zona de cisalhamento. Os dados mineralógicos, petrográficos e geoquímicos, em associação com os de campo e de descrição de testemunho de sondagem rotativa, apontam que o protólito destas rochas seria um corpo dunítico de granulação média a grossa e textura granular, suas dimensões seriam superiores a 800 x 400 metros e com mais de 350 metros de espessura. Os dados obtidos indicam que o dunito é mantélico e possibilitou propor um modelo evolutivo desde a exumação do manto até a colocação sobre embasamento TTG e serpentinização. A exumação se inicia com o adelgaçamento da crosta continental durante a instalação de um sistema rifte, que teria evoluído ao ponto de atingir a “super extensão” da crosta e o desenvolvimento de uma crosta oceânica. Com o fechamento do oceano decorrente de colisão continental, no neoproterozóico, o corpo dunítico foi alojado sobre o embasamento cristalino, na margem passiva da placa que contém o Cráton São Francisco. A serpentinização do dunito ocorreu tardi-pós aloctonia, catalisada pela atuação do Cinturão de Cisalhamento do Campo do Meio, em condições de fácies visto verde, fácies prehnita-pumpelyíta, com baixa fugacidade de oxigênio e enxofre e alta atividade de H2(aq.). / This work presents results from detailed petrogenetic studies performed on the Morro do Níquel (Nickel Hill) serpentinites, an ultrabasic massif mineralized in lateritic nickel, located in the Southern Brasília Belt, north of the Alterosa Suture Zone, Municipality of Pratápolis (MG), southwest of the State of Minas Gerais-Brazil. The serpentinite has a dark color, apparently massive aspect and consist of more than 95% lizardite / chrysotile, with localized occurrences of antigorite. The structural pattern of the massif is compatible with those generated by the shear of a rigid body in a ductile matrix within a shear zone. The mineralogical, petrographic and geochemical data, in association with the field and drill hole logs description, indicate that the protolith of these rocks would be a dunitic body of medium to large granulation and granular texture, with dimensions superior to 800 x 400 meters and with more than 350 meters of thickness. The obtained data indicate that the dunite is mantellic and it was possible to propose an evolutionary model from the exhumation of the mantle dunitc body to the emplacement on the TTG basement and serpentinization. The exhumation begins with the thinning of the continental crust during the installation of a rift system, evolving to allow the hyper-extension of the crust until the development of an oceanic crust. With the continental collision, in the Neoproterozoic, the dunite was hosted on the crystalline basement, in the passive margin of the plate that contains the San Francisco Craton. The dunite serpentinization occurred late-post aloctonia, catalyzed by the Campo do Meio Shear Belt, under conditions of green facies, prehnite-pumpelyite facies, with low fugacity of oxygen and sulfur and high H2 (aq.) activity.

L'altération hydrothermale d'une péridotite océanique conduit à une profonde transformation minéralogique qui correspond au « processus de serpentinisation ». Durant ce processus, le Fe2+ initialement contenu dans les olivines et/ou les pyroxènes peut s'oxyder en Fe3+ en incorporant des phases nouvellement formées comme la serpentine et la magnétite. L'hydrolyse de l'eau associée à cette réaction entraine la production de grandes quantités d'hydrogène. Au niveau des dorsales océaniques, de fortes concentrations en hydrogène et hydrocarbures ont été récemment mises en évidence sur quelques sites hydrothermaux d'un genre nouveau, tous situés dans un contexte ultrabasique. Dans le but de comprendre les processus contrôlant l'altération hydrothermale des péridotites, et en particulier la production d'hydrogène dans ce type de contexte, nous avons couplé des expériences de serpentinisation in-situ à des simulations thermodynamiques. Les produits de synthèse obtenus dans nos expériences ont été caractérisés à l'aide de différents outils spectroscopiques, principalement par absorption des rayons X en synchrotron. Nous avons ainsi développé plusieurs protocoles expérimentaux permettant d'une part de quantifier les proportions des phases minérales, mais aussi de déterminer la distribution et la spéciation du fer dans nos échantillons altérés. Nos expériences montrent que la cinétique de serpentinisation est fortement dépendante des conditions physico-chimiques (température, rapport eau/roche, état structurel et composition chimique de protolithe) présentes dans le milieu naturel. Parallèlement, ces travaux indiquent que les rôles joués par la serpentine et la magnétite dans la production d'hydrogène évoluent suivant la température mais changent également fortement au cours de la réaction. Ces résultats, affinés par des modélisations numériques, ont été replacés dans un cadre naturel, dans le but de déterminer les différents processus se produisant le long d'un trajet P-T hydrothermal. Il apparait ainsi que l'essentiel de la réaction de serpentinisation s'effectue sur le trajet « prograde » avec une production maximale d'hydrogène située autour de 275°C. Enfin, et grâce aux gradients de température estimés dans ce type de contexte, nous avons pu déterminer la taille et la géométrie probable d'un site hydrothermal comme celui de « Rainbow ». / The hydrothermal alteration of a natural peridotite leads to a strong mineralogical change, the so-called “serpentinization process”. During this process, the Fe2+ initially contained in olivines and/or pyroxenes is partially oxidized in Fe3+ incorporated in new mineral phases like serpentine or magnetite. This reaction conducts to the hydrolysis of water and therefore produces high amount of hydrogen. In the mid-ocean ridges, high concentrations of hydrogen and hydrocarbons have recently been measured on a new type of hydrothermal fields, always located on on ultramafic rocks. With the aim to better understand the processes controlling the hydrothermal alteration of peridodites, and in particular the related hydrogen production, numerous in-situ experiments of serpentinization were coupled with thermodynamic calculations. The altered products were characterized using different spectroscopic tools, particularly by X-ray absorption analysis in 3rd generation synchrotrons. Several experimental protocols were thus developed allowing to accurately quantify the phase proportions, the iron distribution, and the iron speciation in the altered samples. Experiments display that the serpentinization kinetic is highly dependent from the physico-chemical conditions (temperature, water-to-rock ratio, structural state and chemical composition of the protolith) inferred in the natural environment. In parallel, our work shows that the roles play by both serpentine and magnetite mineral phases evolve as function of temperature but as well change during the alteration process. These results were coupled with the numerical simulations to be replaced in a natural context determining the different processes encountered along a P-T hydrothermal pathway. As a result, the serpentinization reaction is mainly effective during the “prograde” pathway and the maximum hydrogen production occurs around 275°C. Finally and based on the thermal gradients inferred in such contexts, the size and the geometry of the “Rainbow” hydrothermal field were defined.

abstract: Evaluations of chemical energy supplies for redox reactions used by chemotrophs in water-rock hosted ecosystems are often done separately from evaluations of chemotroph diversity. However, given that energy is a fundamental and unifying parameter for life, much can be gained by evaluating chemical energy as an ecological parameter of water-rock hosted ecosystems. Therefore, I developed an approach that combines evaluation of chemical energy supplies with 16S and 18S rRNA gene amplicon sequencing. I used this approach to assess drivers of microbial distribution, diversity and activity in serpentinized fluids of the Samail Ophiolite of Oman and in hot springs in Yellowstone National Park. Through the application of the approach, microbiological interactions in serpentinized fluids were found to be more complex than anticipated. Serpentinized fluids are hyperalkaline and pH is often considered the driving parameter of microbial diversity, however hydrogenotrophic community composition varies in hyperalkaline fluids with similar pH. The composition of hydrogenotrophic communities in serpentinized fluids were found to correspond to the availability of the electron acceptor for hydrogenotrophic redox reactions. Specifically, hydrogenotrophic community composition transitions from being dominated by the hydrogenotrophic methanogen genus, Methanobacterium, when the concentration of sulfate is less than ~10 μm. Above ~10 μm, sulfate reducers are most abundant. Additionally, Methanobacterium was found to co-occur with the protist genus, Cyclidium, in serpentinized fluids. Species of Cyclidium are anaerobic and known to have methanogen endosymbionts. Therefore, Cyclidium may supply inorganic carbon evolved from fermentation to Methanobacterium, thereby mitigating pH dependent inorganic carbon limitation. This approach also revealed possible biological mechanisms for methane oxidation in Yellowstone hot springs. Measurable rates of biological methane oxidation in hot spring sediments are likely associated with methanotrophs of the phylum, Verrucomicrobia, and the class, Alphaproteobacteria. Additionally, rates were measurable where known methanotrophs were not detected. At some of these sites, archaeal ammonia oxidizer taxa were detected. Ammonia oxidizers have been shown to be capable of methane oxidation in other systems and may be an alternative mechanism for methanotrophy in Yellowstone hot springs. At the remaining sites, uncharacterized microbial lineages may be capable of carrying out methane oxidation in Yellowstone hot springs. / Dissertation/Thesis / Doctoral Dissertation Microbiology 2020

Thesis advisor: Ethan Baxter / Serpentinites assume a critical role in geochemical and geophysical cycles, from recycling fluid into the sub-arc mantle to facilitating exhumation within subduction zones. Rodingite dikes can be used as a lens to investigate the hydration of the oceanic lithosphere as their development is synchronous with serpentinization, and while serpentinites lack sufficient mineral phases for geochronology, rodingite dikes are rich in andradite and grossular garnet which are potentially amenable for geochronology. This research seeks to constrain the timescales and duration of hydration of the oceanic lithosphere within the Alpine Tethys ocean basin, and associated serpentinization, by examining Apennines rodingites from the Internal Ligurides (Italy). These rodingites experienced seafloor hydrothermal alteration and were obducted onto the continental margin during Alpine orogenesis. As a result, they are ideal for studying seafloor metasomatism as they were not affected by prograde subduction zone metamorphism and dehydration. Sr isotopic and trace element profiles were constructed across two rodingite-serpentinite transects, revealing a complex, multi-stage hydration history consisting of 1) Widespread serpentinization, 2) Gabbroic intrusions, 3) Rodingitization, and 4) Localized, late-stage advective fluid flow. Serpentinizing fluids locally display strong continental crustal isotopic signatures, while rodingitization fluids are characterized by seawater-like values. U-Pb geochronology on rodingite garnets produced an age of 96.1 ± 8.9 Ma, which could represent either the main rodingitization phase or the late-stage advective alteration. / Thesis (MS) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

La réaction de serpentinisation résulte de l’interaction de l’eau de mer, ou de fluides hydrothermaux avec les roches mantelliques. Elle engendre des changements des propriétés chimiques de la lithosphère océanique, avec notamment un enrichissement en éléments mobiles (ex. As, Sb, Li, Cs, Pb, et B). Ces éléments sont importants en sciences de la terre car ce sont des traceurs géochimiques des interactions fluides-roches depuis la ride océanique jusqu’aux zones de subduction. Ce travail de thèse a pour but de caractériser le partitionnement de certains éléments mobiles entre un fluide et la serpentine de manière expérimentale. Pour cela, j’ai développé deux protocoles expérimentaux en condition alcaline. Le premier, consiste en la synthèse de chrysotile à partir d’un gel à la stoechiométrie de la serpentine, à 300 °C et Psat. Pour le second protocole, la serpentine est obtenue par altération de grains d’olivine San Carlos (granulométrie : <30 µm, 30-56 µm, >56 µm) à 200 °C (Psat) pour 1M de NaOH et en présence de carbonate (HCO3-). La minéralogie des produits expérimentaux ainsi que leurs abondances ont été déterminées par diffraction des rayons-X, spectroscopie infrarouge et analyse thermogravimétrique. Les propriétés texturales ont été caractérisées par microscopie électronique à balayage et à transmission haute résolution. La composition du produit solide a été mesurée par spectrométrie de masse et analyse par microsonde-électronique et l’état d’oxydo-réduction du fer a été déterminé par analyses Mössbauer. Des analyses d’absorption des rayons-X (XAS) ont été effectuées afin d’analyser la structure locale de l’antimoine et de l’arsenic. La combinaison de ces techniques analytiques a permis de montrer que la synthèse de chrysotile est effective après seulement 8 heures de réaction. A 200°C, l’olivine est remplacée (pseudomorphose) par le chrysotile et la brucite. Le remplacement est total après 1 mois (<30 µm) et 3 mois (30 et 56 µm). En présence de carbonate, l’altération de l’olivine est caractérisée par une cinétique plus lente et est contrôlée par la précipitation de la magnésite et de la lizardite.En reprenant les 2 protocoles expérimentaux de synthèse de chrysotile (1M NaOH), et en dopant le fluide en un élément trace (Li, As, Cs, Sb et B) le partitionnement des éléments mobiles a pu être étudié. Le coefficient de partage solide-fluide (KD) a pu être défini pour chaque élément durant la synthèse du chrysotile à 300 °C en modélisant nos résultats suivant l’équation de Langmuir (concentrations en solution de 5 à 1000 µg g-1). La séquence obtenue pour les coefficients de partage est la suivante : 0.5<B < As < Li < Cs < Sb<9. En présence de lithium, d’arsenic et d’antimoine, la morphologie du chrysotile atteste d’une croissance radiale. En revanche, le bore favorise une croissance en longueur du chrysotile perpendiculaire à l’axe c. Un mécanisme d’adsorption contrôle principalement la séquestration des éléments mobiles par le chrysotile comme l’indiquent les résultats d’absorption des rayons-X sur l’arsenic et l’antimoine. Lors de l’altération des olivines, la séquestration des éléments trace est hétérogène et le changement des conditions d’oxydo-réduction du système durant la réaction de serpentinisation explique les changements dans la séquestration de l’antimoine d’abord adsorbé sous sa forme pentavalente puis incorporé sous sa forme trivalente par des phases secondaires. Même en faible concentration en solution (200 µg g-1), le lithium a un fort pouvoir catalytique sur la réaction de serpentinisation de l’olivine à 200 °C.En perspective plusieurs expériences haute pression et température (450 °C et 1-4 kbar) ont été réalisées afin de mieux comprendre le comportement des éléments traces durant les transitions de phase et la déstabilisation de la serpentine en contexte de subduction. Les résultats préliminaires indiquent que la présence de ces éléments traces a un rôle très important sur la stabilité du chrysotile. / Serpentinization reaction is the result of the interaction of seawater with mantle rocks especially at slow-spreading ridges. The formation of serpentinite during this alteration reaction changes the physico-chemical properties of the oceanic lithosphere and induces an enrichment in Fluid-mobile elements (FME: e.g. As, Sb, Li, Cs, Pb and B) compared to primary minerals. These elements are efficient geochemical tracers reflecting mantle hydration from the oceanic ridge to subduction environments. In this context, there is a lack of data concerning the partitioning and sequestration processes of FME between serpentine and fluids. The aim of this thesis is to determine fluid/serpentine partition coefficients of these elements as well as their effects on serpentine formation (reaction mechanism and kinetics, textural properties etc.). To achieve this goal, serpentine has been synthesized under highly alkaline hydrothermal conditions using two distinct protocols. Experimental-products were characterized using X-ray powder diffraction (XRPD), Fourier Transform Infra-Red spectroscopy (FTIR), N2 sorption isotherms, ThermoGravimetric Analyses (TGA), Field Emission gun Scanning Electron Microscopy (FESEM), High Resolution Transmission Electron Microscopy (HRTEM), X-ray Absorption Spectroscopy (XAS) and Mössbauer Spectroscopy. The first protocol consists in chrysotile synthesis from H2SiO3 and MgCl2 at 300 °C using batch and semi-continuous experiments. With this approach, we were able to chrarcterized chrysotile nanotubes nucleation and growth processes. In the second protocol, we investigated olivine serpentinization reaction under high hydroxyl-alkalinity or high carbonate-alkalinity at 200 °C. We note the efficiency of serpentine formation under high alkaline conditions in the both protocols and the significant effect of the carbonate component on the serpentinization processes and crystal growth rates. The serpentinization of olivine under alkaline conditions induces the oxidation of a large part of iron trapped by brucite.Replacement is total after 1 month (<30 µm) and 3 month (30-56 µm). The presence of a carbonate component induces a lower reaction kinetic and is characterized by the co-precipitation of magnesite and lizardite.Based on these results, we chose favorable conditions in order to study FME (Li, As, Cs, Sb and B) sequestration. Solid-liquid partitioning for each FME was investigated during chrysotile synthesis at 300°C. Experimental results were modeled using the Langmuir equation and the role of each element on chrysotile textural properties was investigated. In addition, we report new results concerning the sequestration and the distribution of the trace elements during olivine replacement by serpentine and brucite. We highlight that Li act as a catalyst during olivine serpentinisation. Moreover, from XAS measurements, we indicate that Sb and As sequestration is dominated by adsorption mechanism. The precipitation of secondary As- and Sb-bearing phases was also revealed by Electron Microprobe X-ray mapping. Finally, Sb-trapping within chrysotile tubes was also suspected by HRTEM measurements. The changes of redox conditions during serpentinisation induce a change of Sb sequestration mechanism and the precipitation of Sb-bearing phases. In addition, we investigate the partitioning of FME at higher pressure (1-4 kbar) and temperature (450 °C). This pilot study brings promising results regarding the behavior of trace elements during serpentine destabilization (deep lithosphere or subduction contexts) and on the non-negligible role of trace elements on the stability of chrysotile.

Afin de mieux comprendre la serpentinisation des roches mantelliques au niveau des dorsales océaniques lentes, diverses séries d’expériences ont été réalisées à 50 MPa et 250, 300 et 350 ℃ pour quantifier l’H₂ produit et clarifier les liens entre la production d’ H₂, les phases minéralogiques produites et les propriétés rédox dues à la présence d’ H₂. Les résultats, qui constituent un effort cohérent de prise en compte des paramètres et conditions rédox lors de la serpentinisation, sont les suivants : – Une nouvelle méthode expérimentale de mesure in situ de la \fH a été mise au point à 250 et 300 ℃, 50 MPa. Les deux variables exprimant la concentration d’H2 dans le fluide, \molalHydAq et \fH, ont été reliées quantitativement. Ces résultats permettent le calcul de la \fO dans les systèmes hydrothermaux océaniques à partir de la concentration en hydrogène dissout. La production d’ H₂ commence précocement, augmente rapidement et est continue au cours de la serpentinisation. – Les expériences d’interaction harzburgite-eau de mer montrent que la serpentinisation est une dissolution irréversible de l’olivine et de l’orthopyroxene et qu’elle se décompose en une succession d’étapes impliquant des assemblages de phases hors d’équilibre et métastables. – Les mécanismes de la serpentinisation et les assemblages de phases produits (en particulier les oxydes de fer) dépendent de la \fH laquelle est étroitement contrôlée par les régimes de circulation des fluides dans la croûte océanique. – La modélisation thermodynamique des fluides hydrothermaux riches en H₂ souligne le besoin de connaître précisément \yHydAq , le coefficient d’activité de \hydAq. / To better understand serpentinization of mantle rocks at slow-spreading ridges, several series of experiments have been conducted at 50 MPa and 250, 300 et 350 ℃ to quantify the H₂ production associated with the serpentinization process, and to clarify the relations between the H₂ generation, the nature of product mineral phases and the redox properties of H₂ bearing hydrothermal systems. The main results of this work, which represents a significant effort toward the consideration of redox parameters and processes during serpentinisation, are the following: – A new experimental method of in situ monitoring of the \fH has been set up at 250 and 300 ℃, 50 MPa. The two variables expressing the H₂ production, \molalHydAq; aq and \fH , have been related quantitatively. Results enable the \fO of hydrothermal oceanic systems to be computed from the dissolved hydrogen concentration. H₂ production starts early, increases rapidly and is continuous in our serpentinization experiments. – Harzburgite-seawater interaction experiments show that serpentinisation is an irreversible dissolution reaction of olivine and orthopyroxene and that it consists of a sequence of discrete steps involving metastable and disequilibrium phase assemblages. – Serpentinisation mechanisms and phase assemblages (especially Fe oxides) depend on \fH, the latter being closely controlled by processes of fluid circulation in the oceanic crust. – Thermodynamic modelling of H₂ rich hydrothermal fluids stresses the need to know precisely \yHydAq, the activity coefficient of \hydAq.

L'altération hydrothermale du manteau lithosphérique dans les dorsales médio-océaniques fournit un mécanisme de transfert de chaleur et de masse entre la terre profonde et l'océan recouvrant. Le manteau lithosphérique est constituée de roches ultramafiques, également appelées péridotites. Ils comprennent plus de 70% d'olivine, de pyroxènes associés et de phases minérales mineures. La percolation de l'eau de mer dans le socle ultramafique produit l'altération de l'olivine et des pyroxènes en serpentine par le processus de serpentinisation et il est associé à des réactions d'oxydation et de carbonatation (lorsque le CO2 est présent dans le fluide). Le processus de serpentinisation présente un intérêt particulier pour la production de H2, le stockage du CO2, le développement de la vie et la production de gisements de minerai économiquement intéressants concentrés dans les fumeroles hydrothermaux. La durabilité et l'efficacité des réactions nécessitent la pénétration et le renouvellement des fluides à l'interface fluide-minéral. Les failles et les fractures des détachements océaniques sont les zones hautement perméables qui permettent à l'eau de mer de pénétrer profondément dans le manteau lithosphérique. Cependant, le processus de serpentinisation conduit à la précipitation de minéraux de faible densité qui peuvent remplir le réseau poreux, colmatant les chemins d'écoulement qui peuvent modifier les propriétés hydrodynamiques et la réactivité des roches réagi.Ces travaux de thèse visent à améliorer la compréhension des effets en retour des réactions sur les propriétés hydrodynamique du milieu dans les zones hautement perméables au cours des premières étapes de l'altération du socle ultramafique. Il se concentre en particulier sur les changements de texture et les réactions chimiques des roches ultramafiques en évaluant les effets du (i) débit et (ii) des fluides salins riches en CO2. Deux séries d'expériences de percolation réactive ont été réalisées à T = 170-190°C et P = 25MPa. La première série d'expériences consistait à injecter de l'eau de mer dans des échantillonnes de poudre d'olivine compressé sur une large gamme de débits constants. La tomographie par rayons X de haute résolution a été acquise avant et après l'expérience avec des débits élevés; afin d'évaluer les changements dans la microstructure de la roche lors de la réaction de serpentinisation. La deuxième série d'expériences consistait à injecter des fluides salins riches en CO2 dans des échantillonnes de péridotite fracturés mécaniquement.Les résultats ont permis de différencier: (1) un contrôle du débit du flux à l'échelle du pore peut contrôler la composition du fluide local et le développement de différents chemins de réaction à l'échelle de l'échantillon. (2) Le développement de différentes chemins réactifs et les changements de texture dans la roche dépend de la concentration de CO2 dissous dans la solution. (3) La formation de minéraux carbonatés (MgCO3) peut stocker du CO2 sous forme stable de minéral à long terme. (4) Un contrôle de la concentration de CO2 dissous dans le fluide et du réseau de fractures peut améliorer / limiter l'efficacité du stockage de CO2 dans les réservoirs de péridotite fracturés.Ces nouvelles données suggèrent un contrôle complexe de la structure des roches ultramafiques dans le processus de serpentinisation et fournissent de nouvelles perspectives pour le stockage potentiel du CO2 dans les réservoirs fracturés à la péridotite. / The hydrothermal alteration of the mantle lithosphere at mid-ocean ridges provides a mechanism for transferring heat and mass between the deep Earth and the overlaying ocean. The mantle lithosphere is constituted by ultramafic rocks, also called Peridotites. They comprise more than 70% of olivine, associated pyroxenes and minor mineral phases. The percolation of seawater into the ultramafic basement produces the alteration of olivine and pyroxenes to serpentine through the so-called serpentinization process and is associated to oxidation and carbonation reactions, the later when CO2 is present. The serpentinization process has special interest on H2 production, CO2 storage, development of life, and the production of economically valuable ore-deposits concentrated at hydrothermal vents. The sustainability and efficiency of the reactions requires penetration and renewal of fluids at the mineral-fluid interface. Oceanic detachment faults and fractures are the highly permeable zones allowing seawater derived fluids to penetrate deeply into the mantle lithosphere. However, the serpentinization process lead to the precipitation of low density minerals that can fill the porous network, clogging flow paths efficiently that may in turn modify the hydrodynamic properties and the reactivity of the reacted rocks.This PhD thesis aims at better understanding the feedback effects of chemical reactions on the hydrodynamic rock properties occurred on highly permeable zones during the earliest stages of alteration of the ultramafic basement. It focuses in particular on the changes in texture and chemical reaction paths of ultramafic rocks by assessing the effects of (i) flow rate and (ii) CO2-rich saline fluids. Two suite of reactive percolation experiments were performed at T=170-190°C and P=25MPa. The first suite of experiments consisted in injecting artificial seawater into porous compressed olivine powder cores over a wide range of constant flow rates. X-Ray µ-tomography of high resolution was acquired before and after the experiment run with high flow rates; in order to evaluate the micro-structural changes of the rock occurred during the serpentinization reaction. The second suite of experiments consisted in injecting CO2-rich saline fluids into peridotite cores mechanically fractured.The results allowed us to differentiate: (1) That, a control of flow infiltration rate at the pore-scale can control the local fluid compositions and the development of different reaction paths at the sample-scale. (2) The development of different reaction paths and textural changes in the rock depends on the concentration of CO2 dissolved in solution. (3) The formation of carbonate minerals (MgCO3) can store CO2 in a form of stable mineral at long-term. (4) A control of the concentration of dissolved CO2(g) and the fracture network can enhance/limit the efficiency of CO2-storage in peridotite fractured reservoirs.These new supporting data suggest a complex control of the structure of the ultramafic rocks in serpentinization process and provides new insights for the potential CO2-storage in peridotite fractured reservoirs.

Este trabalho tem como objetivo investigar os processos controladores da mobilidade e concentração de níquel (Ni) em rochas ultramáficas serpentinizadas no Escudo Sul-Riograndense (ESrg), Rio Grande do Sul (RS), Brasil. A composição primária das rochas ultramáficas hospedeiras de Ni constitui um parâmetro relevante, mas os processos secundários são os controladores mais importantes dessas mineralizações, principalmente a serpentinização, pressupondo-se que o Ni possa migrar da olivina ou metamórfica para os minerais do grupo das serpentinas. Para a caracterização mineralógica e textural das rochas ultramáficas serpentinizadas da porção oeste do ESrg, foram aplicadas técnicas de petrografia e Microscopia Eletrônica de Varredura. Para a análise química dos elementos em rocha total foi realizada fluorescência de Raios-X, ICP e ICP-MS. Estas técnicas permitiram classificar quimicamente as rochas e relacionar a variação da intensidade dos eventos metassomáticos, metamórficos e hidrotermais que modificaram a mineralogia dos protólitos. No entanto, foram necessárias estudos de detalhe dos minerais individuais, notadamente olivinas e serpentinas com o uso da microssonda eletrônica para determinar as concentrações de Ni e suas variações nos diferentes corpos ultramáficos investigados. Dessa forma, foi possível quantificar e identificar os minerais concentradores de Ni e a relação dos eventos com a mobilidade e concentração dos elementos. Os resultados de microssonda indicam que as olivinas dos peridotitos do Maciço Pedras Pretas possuem baixos teores de níquel que variam de 0,13% a 0,21% e a média é 0,17%, enquanto que as olivinas dos harzburgitos da Sequência Cerro Mantiqueiras possuem teores mais elevados na média de 0,31%. As olivinas do Pedras Pretas possuem composição homogênea enquanto que aquelas do Cerro Mantiqueiras mostram variações composicionais importantes com conteúdo de Fo 92-98 e teores de níquel entre 0,3% e 0,4%. Tais variações no Cerro Mantiqueiras podem estar relacionadas a diferenças na composição do protólito ou a outro fator desconhecido que necessita futuras investigações. As olivinas e serpentinas no Cambaizinho e Serrinha mostram valores de níquel entre 0,19% a 0,3%, comparáveis ao Cerro Mantiqueiras, porém bem mais elevados que o Pedras Pretas. Este estudo mostra que os corpos ultramáficos do Cambaizinho- Serrinha e Cerro Mantiqueiras possuem potencial para desenvolver depósitos de Ni não sulfetado devido as concentrações relativamente elevadas de Ni nas olivinas. Entretanto, tais depósitos não se desenvolveram devido a dois fatores principais: o primeiro está ligado à superposição de eventos de metamorfismo e deformação recorrentes no tempo e no espaço que propiciaram a mobilização do Ni; o segundo fator é atribuído a ausência de agentes supergênicos favoráveis para a formação de depósitos lateríticos como os observados na região norte do Brasil. / This paper investigates the processes controlling the mobility and concentration of nickel (Ni) in serpentinized ultramafic rocks in the Sul- Riograndense Shield (ESrg), Rio Grande do Sul (RS), Brazil. The primary composition of the ultramafic Ni host is a relevant parameter, but the secondary processes are the almost important controllers of these mineralizations, mainly serpentinization, assuming that Ni may migrate from igneous or metamorphic olivine minerals to the group of serpentine this phase. For the mineralogical and textural characterization of the serpentinized ultramafic rocks of the western portion of ESrg, were applied techniques of petrographic and scanning electron microscopy. For chemical analysis of elements in rock whole was performed X-ray fluorescence, ICP and ICP-MS. Although these techniques allow chemically classification of rocks and relate the variation of intensity in which metasomatics, metamorphic and hydrothermal events, changed the that mineralogy of the rock, however analysis of individual mineral detail, notably olivine and serpentine minerals using the electron microprobe detail, were necessary to determine the concentrations of Ni and variations in different ultramafic bodies investigated. Thus, it was possible to quantify and identify the Ni concentrators minerals and the relationship of events with the mobility and concentration of the elements. The microprobe results indicate that the olivine of peridotite Pedras Pretas have low contents of NiO ranging from 0.13% to 0.21% and averaged 0.17%, while the olivine harzburgites Cerro Mantiqueiras have higher levels of NiO averaging 0.31%. The olivine of Pedras Pretas have a homogeneous composition as those of Cerro Mantiqueiras show important compositional variations with a content of forsterite the Fo 92-98 and NiO contents of between 0.20% and 0.40%. Such variations in Cerro Mantiqueiras may be related to differences in the composition of the protolith or another unknown factor that needs further investigation. The olivine and serpentine in Cambaizinho and Serrinha, show NiO values between 0.19 % to 0.3 %, values comparable to the Cerro Mantiqueiras, but higher than the Pedras Pretas. This study shows that the Cambaizinho, Serrinha and Cerro Mantiqueiras have the potential to develop non- sulphide Ni deposits, due high Ni concentrations in olivine. However, these deposits are not developed due two main factors: the first is linked to the superposition of events the metamorphism and deformation applicants in time and space, that enabled the Ni mobilization; the second factor is attributed to lack preservation of profiles suitable for the Ni concentration, due to uplift and erosion lateritic subsequent.

Este trabalho tem como objetivo investigar os processos controladores da mobilidade e concentração de níquel (Ni) em rochas ultramáficas serpentinizadas no Escudo Sul-Riograndense (ESrg), Rio Grande do Sul (RS), Brasil. A composição primária das rochas ultramáficas hospedeiras de Ni constitui um parâmetro relevante, mas os processos secundários são os controladores mais importantes dessas mineralizações, principalmente a serpentinização, pressupondo-se que o Ni possa migrar da olivina ou metamórfica para os minerais do grupo das serpentinas. Para a caracterização mineralógica e textural das rochas ultramáficas serpentinizadas da porção oeste do ESrg, foram aplicadas técnicas de petrografia e Microscopia Eletrônica de Varredura. Para a análise química dos elementos em rocha total foi realizada fluorescência de Raios-X, ICP e ICP-MS. Estas técnicas permitiram classificar quimicamente as rochas e relacionar a variação da intensidade dos eventos metassomáticos, metamórficos e hidrotermais que modificaram a mineralogia dos protólitos. No entanto, foram necessárias estudos de detalhe dos minerais individuais, notadamente olivinas e serpentinas com o uso da microssonda eletrônica para determinar as concentrações de Ni e suas variações nos diferentes corpos ultramáficos investigados. Dessa forma, foi possível quantificar e identificar os minerais concentradores de Ni e a relação dos eventos com a mobilidade e concentração dos elementos. Os resultados de microssonda indicam que as olivinas dos peridotitos do Maciço Pedras Pretas possuem baixos teores de níquel que variam de 0,13% a 0,21% e a média é 0,17%, enquanto que as olivinas dos harzburgitos da Sequência Cerro Mantiqueiras possuem teores mais elevados na média de 0,31%. As olivinas do Pedras Pretas possuem composição homogênea enquanto que aquelas do Cerro Mantiqueiras mostram variações composicionais importantes com conteúdo de Fo 92-98 e teores de níquel entre 0,3% e 0,4%. Tais variações no Cerro Mantiqueiras podem estar relacionadas a diferenças na composição do protólito ou a outro fator desconhecido que necessita futuras investigações. As olivinas e serpentinas no Cambaizinho e Serrinha mostram valores de níquel entre 0,19% a 0,3%, comparáveis ao Cerro Mantiqueiras, porém bem mais elevados que o Pedras Pretas. Este estudo mostra que os corpos ultramáficos do Cambaizinho- Serrinha e Cerro Mantiqueiras possuem potencial para desenvolver depósitos de Ni não sulfetado devido as concentrações relativamente elevadas de Ni nas olivinas. Entretanto, tais depósitos não se desenvolveram devido a dois fatores principais: o primeiro está ligado à superposição de eventos de metamorfismo e deformação recorrentes no tempo e no espaço que propiciaram a mobilização do Ni; o segundo fator é atribuído a ausência de agentes supergênicos favoráveis para a formação de depósitos lateríticos como os observados na região norte do Brasil. / This paper investigates the processes controlling the mobility and concentration of nickel (Ni) in serpentinized ultramafic rocks in the Sul- Riograndense Shield (ESrg), Rio Grande do Sul (RS), Brazil. The primary composition of the ultramafic Ni host is a relevant parameter, but the secondary processes are the almost important controllers of these mineralizations, mainly serpentinization, assuming that Ni may migrate from igneous or metamorphic olivine minerals to the group of serpentine this phase. For the mineralogical and textural characterization of the serpentinized ultramafic rocks of the western portion of ESrg, were applied techniques of petrographic and scanning electron microscopy. For chemical analysis of elements in rock whole was performed X-ray fluorescence, ICP and ICP-MS. Although these techniques allow chemically classification of rocks and relate the variation of intensity in which metasomatics, metamorphic and hydrothermal events, changed the that mineralogy of the rock, however analysis of individual mineral detail, notably olivine and serpentine minerals using the electron microprobe detail, were necessary to determine the concentrations of Ni and variations in different ultramafic bodies investigated. Thus, it was possible to quantify and identify the Ni concentrators minerals and the relationship of events with the mobility and concentration of the elements. The microprobe results indicate that the olivine of peridotite Pedras Pretas have low contents of NiO ranging from 0.13% to 0.21% and averaged 0.17%, while the olivine harzburgites Cerro Mantiqueiras have higher levels of NiO averaging 0.31%. The olivine of Pedras Pretas have a homogeneous composition as those of Cerro Mantiqueiras show important compositional variations with a content of forsterite the Fo 92-98 and NiO contents of between 0.20% and 0.40%. Such variations in Cerro Mantiqueiras may be related to differences in the composition of the protolith or another unknown factor that needs further investigation. The olivine and serpentine in Cambaizinho and Serrinha, show NiO values between 0.19 % to 0.3 %, values comparable to the Cerro Mantiqueiras, but higher than the Pedras Pretas. This study shows that the Cambaizinho, Serrinha and Cerro Mantiqueiras have the potential to develop non- sulphide Ni deposits, due high Ni concentrations in olivine. However, these deposits are not developed due two main factors: the first is linked to the superposition of events the metamorphism and deformation applicants in time and space, that enabled the Ni mobilization; the second factor is attributed to lack preservation of profiles suitable for the Ni concentration, due to uplift and erosion lateritic subsequent.

Este trabalho tem como objetivo investigar os processos controladores da mobilidade e concentração de níquel (Ni) em rochas ultramáficas serpentinizadas no Escudo Sul-Riograndense (ESrg), Rio Grande do Sul (RS), Brasil. A composição primária das rochas ultramáficas hospedeiras de Ni constitui um parâmetro relevante, mas os processos secundários são os controladores mais importantes dessas mineralizações, principalmente a serpentinização, pressupondo-se que o Ni possa migrar da olivina ou metamórfica para os minerais do grupo das serpentinas. Para a caracterização mineralógica e textural das rochas ultramáficas serpentinizadas da porção oeste do ESrg, foram aplicadas técnicas de petrografia e Microscopia Eletrônica de Varredura. Para a análise química dos elementos em rocha total foi realizada fluorescência de Raios-X, ICP e ICP-MS. Estas técnicas permitiram classificar quimicamente as rochas e relacionar a variação da intensidade dos eventos metassomáticos, metamórficos e hidrotermais que modificaram a mineralogia dos protólitos. No entanto, foram necessárias estudos de detalhe dos minerais individuais, notadamente olivinas e serpentinas com o uso da microssonda eletrônica para determinar as concentrações de Ni e suas variações nos diferentes corpos ultramáficos investigados. Dessa forma, foi possível quantificar e identificar os minerais concentradores de Ni e a relação dos eventos com a mobilidade e concentração dos elementos. Os resultados de microssonda indicam que as olivinas dos peridotitos do Maciço Pedras Pretas possuem baixos teores de níquel que variam de 0,13% a 0,21% e a média é 0,17%, enquanto que as olivinas dos harzburgitos da Sequência Cerro Mantiqueiras possuem teores mais elevados na média de 0,31%. As olivinas do Pedras Pretas possuem composição homogênea enquanto que aquelas do Cerro Mantiqueiras mostram variações composicionais importantes com conteúdo de Fo 92-98 e teores de níquel entre 0,3% e 0,4%. Tais variações no Cerro Mantiqueiras podem estar relacionadas a diferenças na composição do protólito ou a outro fator desconhecido que necessita futuras investigações. As olivinas e serpentinas no Cambaizinho e Serrinha mostram valores de níquel entre 0,19% a 0,3%, comparáveis ao Cerro Mantiqueiras, porém bem mais elevados que o Pedras Pretas. Este estudo mostra que os corpos ultramáficos do Cambaizinho- Serrinha e Cerro Mantiqueiras possuem potencial para desenvolver depósitos de Ni não sulfetado devido as concentrações relativamente elevadas de Ni nas olivinas. Entretanto, tais depósitos não se desenvolveram devido a dois fatores principais: o primeiro está ligado à superposição de eventos de metamorfismo e deformação recorrentes no tempo e no espaço que propiciaram a mobilização do Ni; o segundo fator é atribuído a ausência de agentes supergênicos favoráveis para a formação de depósitos lateríticos como os observados na região norte do Brasil. / This paper investigates the processes controlling the mobility and concentration of nickel (Ni) in serpentinized ultramafic rocks in the Sul- Riograndense Shield (ESrg), Rio Grande do Sul (RS), Brazil. The primary composition of the ultramafic Ni host is a relevant parameter, but the secondary processes are the almost important controllers of these mineralizations, mainly serpentinization, assuming that Ni may migrate from igneous or metamorphic olivine minerals to the group of serpentine this phase. For the mineralogical and textural characterization of the serpentinized ultramafic rocks of the western portion of ESrg, were applied techniques of petrographic and scanning electron microscopy. For chemical analysis of elements in rock whole was performed X-ray fluorescence, ICP and ICP-MS. Although these techniques allow chemically classification of rocks and relate the variation of intensity in which metasomatics, metamorphic and hydrothermal events, changed the that mineralogy of the rock, however analysis of individual mineral detail, notably olivine and serpentine minerals using the electron microprobe detail, were necessary to determine the concentrations of Ni and variations in different ultramafic bodies investigated. Thus, it was possible to quantify and identify the Ni concentrators minerals and the relationship of events with the mobility and concentration of the elements. The microprobe results indicate that the olivine of peridotite Pedras Pretas have low contents of NiO ranging from 0.13% to 0.21% and averaged 0.17%, while the olivine harzburgites Cerro Mantiqueiras have higher levels of NiO averaging 0.31%. The olivine of Pedras Pretas have a homogeneous composition as those of Cerro Mantiqueiras show important compositional variations with a content of forsterite the Fo 92-98 and NiO contents of between 0.20% and 0.40%. Such variations in Cerro Mantiqueiras may be related to differences in the composition of the protolith or another unknown factor that needs further investigation. The olivine and serpentine in Cambaizinho and Serrinha, show NiO values between 0.19 % to 0.3 %, values comparable to the Cerro Mantiqueiras, but higher than the Pedras Pretas. This study shows that the Cambaizinho, Serrinha and Cerro Mantiqueiras have the potential to develop non- sulphide Ni deposits, due high Ni concentrations in olivine. However, these deposits are not developed due two main factors: the first is linked to the superposition of events the metamorphism and deformation applicants in time and space, that enabled the Ni mobilization; the second factor is attributed to lack preservation of profiles suitable for the Ni concentration, due to uplift and erosion lateritic subsequent.