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Les zones de subduction sont les plus grands systèmes de recyclage de notre planète. Elles permettent le recyclage de l'eau contenue dans la croûte océanique hydratée et de la lithosphère du manteau supérieur. L'eau joue un rôle clé dans de nombreux processus associés aux zones de subduction, comme la tectonique des plaques, la production de magma, le transport élémentaire et la génération de tremblement de terre. La composition chimique, le contenu H2O de la lithosphère océanique, l'âge et la géométrie de la plaque océanique sont les principaux facteurs contrôlant les processus de subduction, y compris la déshydratation.L'objectif principal de cette thèse est d'étudier le régime de la libération de l'eau depuis la plaque océanique subductante et le comportement du Fe et du S en contenus dans les serpentinites, qui représentent la principale lithologie de roche hydratées océaniques. L'approche expérimentale de ce travail permet d’étudier les changements chimiques et minéralogiques associés lors la déshydratation des serpentinites de différentes compositions. Un certain nombre de techniques d'analyse ont été utilisées pour étudier l’influence de la composition de la roche totale sur la composition des assemblages produits. Les intervalles de pression de température expérimentalement étudiés, à savoir 2 GPa et 450-900C, représentent des zones de subduction chaudes. L'extrapolation à d'autres gradients géothermiques communs a été faite par thermodynamique. Les compositions de serpentinite étudiées correspondent aux péridotites serpentinisées naturelles décrites pour la lithosphère océanique.Mon travail indique que la teneur en Fer contrôle a stabilité thermique d’antigorite. Déshydratation de serpentinites avec Fe, par conséquent, pasee à des températures plus basses par rapport aux assemblages Fe-libres. La déshydratation observée dans les systèmes sans Fer se fait le long d'une réaction univariante, alors que dans les systèmes contenant du Fer, la déshydratation se fait sur un domaine de température (réactions de déshydratation divariantes). De plus, la présence de Al dans serpentinite stabilise clinochlore, qui conserve 15% de l'eau initiale jusqu'à ~ 120 km (820°C/2 GPa) dans subduction chaud. Cette dépendance sur Fe et Al apporte importance de considérer non seulement la géométrie et l'âge de la plaque océanique, mais aussi une composition de lithologies lors de la modélisation et d’interprétation de subduction. Une comparaison entre la profondeur des séismes et la profondeur de déshydratation des serpentinites indique une possible contribution de la libération de l'eau à la sismicité dans les zones de subduction chaudes et à pente faible.La spectroscopie d'absorption des rayons X montre une réduction progressive de Fe et de S dans des serpentinites. Le rapport Fe3+/ Fetotal, de la roche totale, élevé dans la serpentinite, diminue dans les assemblages anhydres de haute température par décomposition de la magnétite (< 550°C) et de l’antigorite (700°C). La pyrite des serpentinites se transforme en pyrrhotite en-dessous de 450°C et induit une libération de ¼ de soufre initial, probablement sous forme de H2S. La magnétite et la pyrite présentes dans des serpentinites, sont des phases cruciales pour la production de fluides très oxydés et d’espèces volatiles soufrées qui peuvent être transportés depuis la plaque subductée vers le coin mantellique. Application des résultats montre que les fluides s’élevant de la plaque océanique sont responsables de l'oxydation du manteau; et décomposition de la magnétite et l’antigorite avec au moins 100°C différence peut provoquer une libération de fluides chimiquement différents à peu profond (basse-T) et profondes (T-élevé) parties de subduction. / Subduction zones are the largest recycling systems of our planet. Subduction zones involve recycling of water from hydrated oceanic crust and lithosphere to the upper mantle. Water plays a key role in subduction zone processes, including plate tectonics, magma generation, elemental transport and earthquake generation. The chemical composition, H2O content of oceanic lithosphere sinking to the mantle, age and geometry of subducting oceanic slab are the main factors controlling subduction zone processes including dehydration.The principle aim of this dissertation is to investigate the regime of water release from subducting oceanic plate and the associated behavior of Fe and S in serpentinites, which are the main carriers of water into the slab. The experimental approach of my work allows one to compare chemical and mineral changes occurred during dehydration of serpentinites with different composition. A number of analytical techniques were applied to study the influence of bulk rock composition on the mineral chemistry of produced assemblages. The experimentally investigated pressure-temperature ranges, i.e. 2 GPa and 450-900C, are representative for hot subduction zones. The extrapolation to other common geothermal gradients was done through thermodynamic modeling. The investigated serpentinite compositions correspond to natural serpentinized peridotites described for oceanic lithosphere.Bulk Fe content was demonstrated to decrease thermal stability of antigorite by 25C on average. Dehydration of Fe-bearing serpentinites, consequently, occurs at lower temperatures compared to Fe-free assemblages. Dehydration reactions observed in Fe-free systems are univariant reactions, while in Fe-bearing systems, serpentinites dehydration appears over a range of temperature through divariant reactions. Moreover, the presence of Al in serpentinite stabilized clinochlore, which retains 15% water initial contain in serpentinite down to ~120km (820°C/2 GPa) within hot subduction. Such a dependence of serpentinite dehydration on bulk Fe and Al brings importance of considering not only geometry and the age of the slab, but also a composition of slab lithologies while modeling and interpreting processes in subduction zone. A comparison of the depths of serpentinite dehydration and seismicity revealed a strong correlation and therefore a potential contribution of water release to seismicity in the case of hot subduction zones (i.e., Chili type subduction).X-ray absorption spectroscopy measurements revealed a progressive reduction of Fe and S in investigated serpentinites. The bulk Fe3+/Fetotal ratio initially high in serpentinite is shown to decrease in anhydrous and higher temperature assemblages due to magnetite and Fe3+-bearing antigorite breakdown at <550°C and 700°C, respectively. The presence of pyrite in serpentinite, which transforms to pyrrhotite below 450°C, imposes a release of ¼ of initial sulfur, in H2S form. The presence of magnetite and pyrite in serpentinite, is crucial and responsible for the production of highly oxidized fluids and volatile sulfur species, which can be transported from the subducting slab into the mantle wedge. Application of results, obtained in the present study, to nature demonstrates that fluids rising from subducting slab are responsible for oxidation of overlying mantle, and in addition, magnetite and antigorite breakdown which occurs with at least 100°C difference may cause a release of chemically different fluids at shallow (low-T) and deep (high-T) parts of subduction.

Apart from the concentrations of chromite in layers within the Great Dyke and other ultramafic complexes, chromite also occurs as interstitial grains throughout the olivine-bearing rock-types. These olivine-bearing rocks include no rites, gabbros, dunites and pyroxenites. Chromite concentration in these rocks varies from 0.48 to 3.09 per cent of the rock, usually in the form of chromite (Ahrens, 1965; Worst, 1960). A small fraction of this chromite settled to form chromitite layers whilst the remainder is retained within the rock mass as finely disseminated chromite and chromite interstitial to olivine. This retained chromite is much finer grained than layer chromite and is the primary source of eluvial chromite (Cotterill, 1981). During weathering of the serpentine rock and transportation by rainwater, the heavier chromite and magnetite grains are re-deposited along watercourses and vleis or valleys as the speed of the water is retarded sufficiently for the heavier particles to settle. The lighter serpentine material is removed and the chromite concentration in the soil is increased, thus resulting in eluvial chromite (Keech et ai, 1961; Worst, 1960; Prendergast, 1978). The concentration of chromite particles in soil can be up to 15 (or more) Cr₂O₃ %, resulting in economic and exploitable deposits, located primarily along the Great Dyke fiacks. A preliminary evaluation of the eluvials indicate that the Great Dyke could be host to up to 10 million tonnes of potential chromite concentrates which could be processed from such eluvial concentrates. These chromite-rich soils can be mined more cheaply than the traditional seams mining and processed into chromite concentrates through simple mechanical processing techniques of spirals, jigs and heavy media separators. The resultant chromite concentrates are of high quality and can be used to manufacture chromite ore briquettes, which are an alternative to lumpy chromite smelter feed. The main challenges to eluvial mining are the inevitable environmental degradation and coming up with methods that could possibly mitigate against such environmental damage. The distribution of these eluvials over vast plains as thin soil horizons, necessitate use of mobile concentrator plants and hence establishment of extensive infrastructure. These challenges, however, are not insurmountable and test mining and previous production runs have proved profitable. The eluvials are also associated with some lateritic nickel concentrations. The nickel occurs in close association with some oxide such as goethite and garnierite and is associated with iron-manganiferous soil pisolites. The analyses of these pisolites indicate high nickel grades of generally above 1.00 %Ni. Such high nickel-content of Great Dyke laterites warrant, further investigations.

Soils in the vicinity of Křemže in the Southern Bohemia are developed on altered ultrabasic rocks. The occurrence of Ni-hydrosilicate and Fe-rich ores in this area lead to their mining mainly during 19th century, then during the World War II. This thesis is focused on distribution and availability of Ni, Cr and Co and accompanying elements in soils at former mine and prospection sites (2 soil profiles and 32 topsoil samples at historical surface mine area). In all soil samples, physico-chemical parameters (pH, TOC, TS) and bulk concentrations of Al, Ca, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb and Zn were measured. In addition, deionised water, DTPA and EDTA extracts were used to determine the (bio)availability and mobility of these elements. Some of trace elements were found in elevated concentrations in the mining area topsoils; mean Ni: 1175 mg/kg (range 545-2849 mg/kg), mean Cr: 416 mg/kg (240-849 mg/kg), mean Co: 127 mg/kg (65-238 mg/kg), mean Fe: 49155 mg/kg (30460-113800 mg/kg), mean Mg: 12648 mg/kg (8795-18770 mg/kg) and mean Mn: 1480 mg/kg (1028-2319 mg/kg). In soil profiles the Ni availability decreased with depth. In the uppermost organic O horizon in forest soil profile, 19.5 % and 23.8 % of total Ni was extracted by DTPA and EDTA, respectively. The extractabilities are decreasing down to mineral...

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Etude minéralogique et pétrographique du massif du Chenaillet entre briançon et Cesana-Torinese ( Italie)

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O Design, sendo uma atividade responsável pela criação de bens materiais, vem incorporando características culturais e saberes locais no desenvolvimento de produtos. O interesse por produtos culturais acarreta em desenvolvimento para as regiões produtoras, refletindo em diversos âmbitos da vida em sociedade, impulsionando e aumentando a competitividade do mercado local. Para isso, as tecnologias são fundamentais na promoção de inovações em produtos, facilitando o processo de produção e permitindo novas aplicações. Desta forma, a união destes dois fatores, tecnologias e valorização de produtos culturais, podem acarretar em ganhos, tanto para a região produtora, como para o país, no oferecimento de produtos com maior valor agregado. O serpentinito, considerado uma gema ornamental rara do Rio Grande do Sul, não possui atualmente uso comercial. O principal mineral constituinte dessa rocha são minerais do grupo das serpentinas, que podem ocorrer como agregados maciços e lamelares (antigorita e lizardita) e como cristais fibrosos (crisotilo). Assim, este trabalho tem como objetivo estudar as técnicas de beneficiamento em serpentinito, a fim de valorizar sua utilização como material gemológico para aplicação em joalheria. Para a caracterização mineralógica do serpentinito, utilizou-se lupa binocular, difratometria de raios X e microscópio petrográfico. As técnicas testadas para seu beneficiamento foram: corte por jato d’água, gravação a laser, polimento e resinagem. Para análise das interações das técnicas empregadas com o material, utilizou-se a lupa estereoscópica, microscópio eletrônico de varredura (MEV) e medidor de brilho (Gloss meter). Obteve-se resultados satisfatórios quanto a aplicação das técnicas no serpentinito, mas estes variam, conforme a textura da rocha. Em rochas com predominância de antigorita e lizardita, recomenda-se o uso da técnica de corte por jato d’água e a gravação a laser de preenchimento para obtenção de texturas superficiais. Em rochas com crisotilo, recomenda- se a realização de cortes com serra diamantada de precisão e o uso da gravação a laser de linhas e preenchimentos, para criação de elementos gráficos de média complexidade. Para o polimento, recomenda-se o uso de lixas de carbeto de silício (carborundum), partindo da faixa de grão 180 até 2000, para rochas com predominância da serpentina antigorita, e da faixa de grão 320 até 2000, para rochas com predominância da serpentina crisotilo. O tempo de cada etapa de lixamento é de 2 minutos e velocidade em torno de 300 rpm. Para proteção do material e obtenção de um brilho mais intenso, recomenda-se a aplicação de resina acrílica como etapa final do processo de beneficiamento. / Design as an activity for developing material goods, has been adding cultural characteristics and local knowledge in the development of products. The interest in cultural products brings progress for the producing regions, reflecting in different areas of social life, promoting and increasing the competitiveness of the local market. For this reason technologies are very important, to promote innovations in products, to enable the production process and new applications. So, the union of these two factors, technologies and valorization of cultural products, providing products with a bigger added value, may result in improvement for the producing region and also for its Country. Serpentinite, a rock used as a rare ornamental gemstone occurs in Rio Grande do Sul State (Brazil) and currently does not have commercial use. The main mineral of this rocks are of serpentine group, that may occur as massive and lamelar aggregates (antigorite and lizardite) and as fibrous crystals (chrysotile). This research aims to study processing techniques to apply in this serpentinite, in order to increase its use as gemological material for use in jewelry. The mineralogical characterization of serpentinite were done with a stereoscopic loupe, X-ray diffraction and with petrographic microscopy. The processing techniques tested were cut by water jet, laser engraving, polishing and resin coating. To analyze the interactions of this techniques with the serpentinite, it was used a stereoscopic loupe, a Scanning Electron Microscope (SEM) and a gloss meter. The results obtained with the application of the processing techniques in serpentinite are good, but vary according to the texture of the rock. In rocks with predominance of antigorite and lizardite, is recommend the use of cutting by water jet and the use of filled shapes laser engraving to obtain surface textures. In rocks with chrysotile, it is recommended to use precision cut diamond saw and the use of laser engraving lines and fill shapes to create graphics of medium complexity. To obtain a good polishment, the use of silicon carbide (carborundum) sandpaper is recommended, with the grit of 180 until 2000, for rocks with predominance of antigorite, and the grit of 320 until 2000, for rocks with predominance of chrysotile. The sanding time for each step is 2 minutes with a speed around 300 rpm. To protect the material and to obtain a better luster, is recommend the application of an acrylic resin as a final step of the improvemente process.

Ce travail est consacré aux études cinétiques et thermodynamique des processus qui produisent les magmas basaltiques (basalte de dorsale océanique ou MORB et basalte de l'île océaniques ou OIB) dans la lithosphère, notamment lors de l'interaction du magma avec la lithosphère serpentinisée. Dans ce travail, nous avons testé l'hypothèse selon laquelle la genèse des chromitites de la zone de transition entre le manteau et la croute peut être la conséquence de l'interaction du magma basaltique avec le protolite du manteau serpentinisé. Une étude détaillée du corps de chromitites nodulaires dans les dunites hôtes de la région Maqsad de l'ophiolite d'Oman a été réalisée. Dans l'étude pétrologique, nous avons démontré une relation génétique étroite entre les dunites hôtes et les chromitites nodulaires et disséminées lors de la cristallisation sans équilibre des cristaux de chromite à partir de l'étude des inclusions piégées dans la chromite. Les expériences d'équilibre sur la saturation des liquides basaltiques et haplobasaltiques en chromite et en magnesiochromite comme la fonction de la fugacité d'oxygène (de ΔFMQ (-2) à ΔFMQ (+2)) ont été effectuées à une température constante de 1450 ° C et une pression de 0,1 MPa. Pour la première fois, les concentrations de chrome dans les liquides basaltiques saturés en magnesiochromite ont été mesurées. Les teneurs en Cr lors de la saturation en magnesiochromitre est de ~ 6800 ppm à ΔFMQ (-2), ~ 4500 ppm à ΔFMQ et 3500 ppm à ΔFMQ (+2), qui sont plus élevés par rapport à ceux (~ 6300 ppm à ΔFMQ (-2), 2900 ppm à ΔFMQ et 2000 ppm à ΔFMQ (+2)) de saturation en chromite (système contenant du Fe). Ce fait a une implication importante pour l'assimilation du manteau serpentinisé par des magmas basaltiques. Sur la base de toutes les données disponibles sur la saturation des liquides mafiques et ultramafiques en chromite, nous avons créé un nouveau modèle prévisible de solubilité de chromite et magnéstochromite dans les liquides en fonction de la température, de la fugacité d'oxygène et de la basicité optique du liquide : [X liq Cr tot]/[X Chr Cr2O3] = exp(a+b*lambda+c/T)*(1+fO2^(-0.25)*exp(d+k/T+g*lambda)), où [X liq Cr tot] est la fraction molaire du chrome dans le liquide silicaté, [X Chr Cr2O3] est la fraction molaire de l'oxyde de chrome dans le chromite, T est la température en Kelvins et fO2 est la fugacité de l'oxygène (en bars), lambda est la basicité optique du liquide, a (-7.01), b (13.72 ), c (-12404.92), d (24.46), k (24394.65), g (-23.59) sont des constantes. Des expériences cinétiques sur l'interaction serpentinite-basalte ont été effectuées à des températures entre 1200 et 1300 C et la pression de 0,2 à 1,0 GPa. Les données impliquent que la réaction est contrôlée par un mécanisme à plusieurs étapes: (i) une transformation métamorphique prograde de la serpentinite en harzdurgite (Fo92-95 mol. %) à spinelles riches en Cr (ii) la dissolution progressive de l'assemblage de harzburgite avec la formation des liquides basaltique à andésitique et (iii) l'assimilation finale de l'association de harzburgite par le basalte avec la formation du liquide basique hydraté appauvri ('depleted' et enrichi en Mg, Cr) à 0,5 - 1,0 GPa (51% pds de SiO2, 12 à 13% pds de MgO). / This work is devoted to kinetic and thermodynamic investigation of processes happening during basaltic (mid-ocean ridge basalt, MORB and ocean island basalt, OIB) magma genesis and evolution in the lithosphere, in particular, during the magma interaction with the serpentinized lithosphere. In this work, we tested hypothesis that the chromitite genesis at the Moho transition zone may be consequence of interaction of basaltic magma with serpentinized mantle protolith. Detailed field investigation of the nodular chromitites ore body in the host dunite at Maqsad area of the Oman ophiolite has been performed. In the petrologic investigation, we have demonstrated close genetic relationship between the host dunites and the nodular and disseminated chromitites during non-equilibrium crystallization of chromites based on investigation of chromite-hosted inclusions. Equilibrium experiments on chromite and magnesiochromite saturation in basaltic and haplobasaltic melts as function of oxygen fugacity (from ΔFMQ(-2) to ΔFMQ(+2)) were performed at a constant temperature of 1450 C and pressure of 0.1 MPa. For the first time, chromium concentrations in basaltic melts at magnesiochromite saturation were determined. The Cr contents at magnesiochromitre saturation are from ~6800 ppm at FMQ(-2), ~4500 ppm at FMQ and 3500 ppm at ΔFMQ(+2), that are higher compared to those (~ 6300 ppm at ΔFMQ(-2), 2900 ppm at ΔFMQ and 2000 ppm at ΔFMQ(+2)) of chromite saturation in Fe-bearing system. This fact has an important implication for serpentinized mantle assimilation by basaltic magmas. Based on all available data on chromite saturation in mafic and ultramafic melts, we created a new predictable model of chromite and magnesiochromite solubility depending on temperature, oxygen fugacity and the melt optical basicity: [X liq Cr tot]/[X Chr Cr2O3] = exp(a+b*lambda+c/T)*(1+fO2^(-0.25)*exp(d+k/T+g*lambda)), where [X liq Cr tot] is molar fraction of chromium in the silicate liquid, [X Chr Cr2O3] is molar fraction of the chromium oxide in the chromite, T is temperature in Kelvins and fO2 is oxygen fugacity (in bars), lambda is optical basicity, a (-7.01), b (13.72), c (-12404.92), d (24.46), k (24394.65), g (-23.59) are constants. Kinetic experiments on serpentinite-basalt interaction have been performed at temperatures of 1200 - 1300 C and pressure range from 0.2 to 1.0 GPa. The data imply that the reaction is controlled by multi-stage mechanism: (i) prograde metamorphic transformation of serpentinite to Cr-rich spinel-bearing harzdurgite (Fo92-95 mol.%) (ii) progressive dissolution of harzburgite assemblage with formation of hydrous basaltic to andesite melts and (iii) the final assimilation of the harzburgite association by basalt with formation of hydrous depleted basaltic melts at 0.5 - 1.0 GPa (51 wt% of SiO2, 12 - 13 wt.% of MgO contents). We experimentally demonstrate that serpentinite assimilation by basaltic melt at 0.5 - 1.0 GPa happening at average rate of 4.3 × 10-10 m2/s at 1300°C is controlled by silica diffusion in hydrous basaltic melt. Our experimental work provides incontestable evidence that depleted MORB melts, depleted high-Mg-Cr cumulates, and oceanic andesites can be routinely produced from "normal" mid-ocean ridge melts by chemical reaction with serpentinized lithospheric mantle. Our study prevents routine interpretation of depleted and primitive oceanic melts (MORB and OIB) as uniquely derived from a deep mantle. The data obtained in this work confirm that serpentinites, which may have been important constituents of the Hadean crust as a whole were possibly involved in the generation of the first continental crust.