Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A comparação entre o Complexo Juiz de Fora e a Unidade Granulítica Ponte de Zinco (Mangaratiba - RJ) revelou que existem diferenças significativas entre essas unidades. Na Unidade Granulítica Ponte de Zinco, são encontrados ortogranulitos de composição granítica e granodiorítica, que representam o embasamento da Unidade, denominada aqui de Ortogranulitos Ribeirão das Lajes. Dois outros litotipos ortoderivados também foram encontrados: (i) um ortognaisse com granada (MAN-JEF-03a), sendo que a granada ocorre de forma subordinada; (ii) ortognaisse leucocrático (MAN-JEF-04), com características miloníticas. Além dessas, rochas metassedimentares também afloram na Unidade Granulítica Ponte de Zinco. Foi interpretado que um ortogranulito (MAN-JEF-01a) de alto-K, com composição monzogranítica, cristalizou em ca. 2653 37 Ma (U-Pb em zircão por LA-ICPMS), afetado por um evento no Neoproterozóico, que gerou os minerais máficos hidratados, observados na análise petrográfica e como mostram as borda de sobrecrescimento em zircão. Sua idade modelo de Nd de 2,7 Ga e seu εNd positivo de +2,1, apontam para uma gênese mantélica, tendo assimilado rochas crustais, pois são encontrados grãos de zircão herdados de aproximadamente 2996 17 Ma e 3343 3.8 Ma. Os dados de litogeoquímica e sua razão 87Sr/86 Sr(t) (0,70529), são compatíveis com uma geração em um arco continental. O ortognaisses com granada do ponto MAN-JEF-03 possui composição granodiorítica. A idade de cristalização interpretada pela análise geocronológica U-Pb em zircão (LA-ICPMS), foi ca. 2117 15 Ma. Esse litotipo foi metamorfizado no Neoproterozóico, sendo a idade obtida pelo intercepto inferior de 631 40 Ma. Seus dados isotópicos apontam para uma rocha juvenil gerada a partir do manto (TDM ≈ de 2,1 Ga e εNd = +3,4). Sua alta razão 87Sr/86 Sr(t) (0,710 ) juntamente com os grãos de zircão herdados (2,6 Ga) e a presença de enclaves, indicam assimilação de rochas crustais. O ortognaisse leucocrático (MAN-JEF-04) classificado como alto-K, possui composição monzogranítica, idade 2132 9,4 Ma U-Pb em zircão (LA-ICPMS). Um único grão relíquiar de ortopiroxênio encontrado em lâmina, , indica que a rocha já foi submetida a metamorfismo de fácies granulito, porém esse evento não deixou registro nos grãos analisados. O retrometamorfismo pode ter ocorrido em dois momentos, 647 11 Ma e 595 38 Ma, calculados através da concordia age, em sobrecrescimentos homogêneos e, pelo intercepto inferior, respectivamente. Sua baixa razão 87Sr/86 Sr(t) (≈ 0,703) associada com εNd positivo (+2,3) e sua idade modelo de aproximadamente 2,1 Ga, revelam que a rocha foi formada por um material mantélico juvenil. Já as análises geocronológicas em U-Pb em zircão (LA-ICPMS) na região de Juiz de Fora (MG), revelaram a existência de dois litotipos Arqueanos: um ortogranulito granodiorítico (MB-JEF-01b), de baixo-K com idade de 2849 11 Ma e com herança de 2975 10 Ma. Seu εNd positivo (+5,9) aponta para uma gênese a partir do manto depletado, já sua alta razão 87Sr/86Sr(t) (≈0,709) indica contaminação de Rb de fontes externas, talvez causada pela assimilação da crosta, como revelam os zircões herdados e/ou fluidos retrometamorficos. Outro litotipo é uma rocha gabróica do tipo E-MORB, cuja idade foi calculada em 2691 14 Ma, com retrometamorfismo ocorrido no intervalo de 604 67 Ma, obtida pelo intercepto inferior. Seu εNd igual a +3,4 e sua razão 87Sr/86 Sr(t) (≈0,701) mostram extração a partir do manto depletado. Novos dados isotópicos do CJF na região de Três Rios (RJ) e Juiz de Fora (MG), sugerem que os ortogranulitos calcioalcalinos podem representar grupos distintos. Rochas com εNd positivos são consequentemente associadas ao manto depletado, porém rochas com εNd negativos devem ter sido geradas por fusão crustal, que podem ser fusão de crosta inferior, devido a razão 87Sr/86 Sr(t) (0,70514) encontrada no amostra MB-JEF-02a (ortogranulito de alto-K) ou tendo a crosta contribuição nas gênese dessas rochas. Os ortogranulitos básicos possuem εNd positivos com baixas razões 87Sr/86 Sr(t) , o que indica extração a partir do manto depletado, porém sua razões La/YbN e La/NbN maiores que 1, revelam alguma contribuição de uma fonte enriquecida, assim também mostram suas razões Pb/Pb, que são maiores do que as razões calculadas para evolução de Pb na Terra. Essas interpretações ainda podem ser estendidas para um ortoanfibolito da série alcalina, encontrado na região de Três Rios (RJ). / The comparison between the Juiz de Fora Complex JFC and the Ponte de Zinco Granulite Unit, (Mangaratiba RJ) has shown that there are some significant differences between those two units. At the Ponte de Zinco Granulite Unit, one can find ortogranulites with a granitic and granodioritic composition, this is embasement of the area, call here as Ribeirão das Lajes Ortogranulites. Two other ortoderived litotypes have also been found: (i) a orthogneiss with garnet, (MAN-JEF-03a), being that the garnet exists in a subordinated form; (ii) leucocratic orthogneiss, (MAN-JEF-04), with mylonitic characteristics. In addition to the latter, Metasedimentary rocks also spring up in the Unit. It has been interpreted that an organulite (MAN-JEF-01a) of a high-K, with a monzogranitic composition, has crystallized into ca. of 2653 37 Ma (U-Pb into zircon by LA-ICPMS), affected by a Neoproterozoic event generated biotite, hornblende and overgrowth rims on zircon grains. Its model age of Nd of 2,7 Ga and its positive εNd of + 2,1, indicates a genesis from the depleted mantle, having assimilated of the crust, as zircon grains have been found of approximately 2996 17 Ma and 3343 3.8 Ma. The data of litogeochemistry and its ratio 87Sr/86Sr(t) (0,70529), are compatible with a generation in a continental arc. The orthogneiss with garnet (MAN-JEF-03a) has a granodioritic composition. Its crystallizing age, as interpreted by geocronological analysis U-Pb on zircon (LA-ICPMS), was ca. of 2117 15 Ma. This litotype has been metamorphized on the Neoproterozoic, with an age of 631 40 Ma being obtained at the lower intercept. Its isotopic data indicates a young rock generated from the mantle (TDM = de 2,1 Ga e εNd = +3,4), its high ratio 87Sr/86Sr(t) (0,710), together with the inherited zircon grains (2,6 Ga) and the presence of an enclave, indicate the assimilation of crusty rocks. The leucocratic orthogneiss, (MAN-JEF-04) classified as high-K, possesses a monzogranitic composition, age 2132 9,4 Ma U-Pb on zircon (LA-ICPMS). One single grain of orthopyroxene found on lamina, which has been practically consumed by retrometamorphism, which might have happened in two moments, 647 18 Ma and 595 38 Ma, calculated through the age concordia, on homogeneous overgrowth and, by the lower intercept, respectively. Its low ratio 87Sr/86Sr(t) (0,0703) associated to the positive εNd (+2,3) and its model age of approximately 2,1 Ga, reveal that the rock was formed by a young mantle material. Now the geochronological analysis in U-Pb on zircon (LA- ICPMS) in the Juiz de Fora (MG) region, revealed the existence of two litotypes (Arqueanos): one ortogranulite granodioritic (MB-EF-01b), of low-K with an age of 2849 11 Ma and a heritage of 2975 10 Ma. Its e Nd positive (+5,9) indicates a genesis from the depleted mantle, but its high ratio 87Sr/86Sr(t) (0,709) indicates contamination of Rb from external sources, maybe caused by the crust assimilation, as the inherited zircons reveal and/or the retrometamorfic fluids. One other lipotype is a gabbroic of the type E-MORB, its age has been calculated in 2691 14 Ma, with a retrometamorphism that occurred in the interval of 604 67 Ma, obtained by the lower intercept. Its εNd equal to +3,4 and its ratio 87Sr/86Sr(t) (0,701) show the extraction from the depleted mantle. New isotopic data of CJF in the Três Rios (RJ) and Juiz de Fora (MG) regions, suggest that the calcium-alkaline ortogranulites may represent distinctive groups. There are rocks with positive εNd, which are associated to the depleted mantle, however rocks with negative εNd must have been generated by crustal fusion, which can be the fusion of the lower crust, due to the ratio 87Sr/86Sr(t) (0,70514) found in the sample MB-JEF-02a (ortogranulite of high-K) or mixture between the mantle and the crust. The basic ortogranulites possess positive εNd with low ratio 87Sr/86Sr(t), which indicates the extraction from the depleted mantle, nevertheless its ratio La/YbN and La/NbN higher than 1, reveal some contribution from an enriched source, as well as its ratio Pb/Pb, which is bigger than the ones calculated for the evolvement of Pb on Earth. These interpretations can still be extended to an alkaline metabasic, found in the Três Rios (RJ) region.

En France, des minéralisations stratiformes de fluorine spatialement liées à une discordance socle/couverture sont localisées à la base de la série sédimentaire mésozoïque du bassin de Paris autour du Morvan cristallin, avec des réserves estimées à environ 5.5 Mt de fluorine. Ce travail concerne principalement quatre gisements de fluorine développés au sein de grès/conglomérats à Antully, de calcaires à Courcelles-Frémoy et de dolomies à Pierre-Perthuis et Marigny-sur-Yonne. L’objectif est d’apporter des contraintes sur l’âge et l’origine de ces minéralisations à l’aide d’une approche pluri-disciplinaire combinant géochronologie, pétrographie, géochimie élémentaire et isotopique afin d’élaborer un modèle métallogénique. Une première étude géochronologique permet de déterminer l’âge de mise en place des minéralisations de la génération géodique de fluorine de Pierre-Perthuis à 130 ± 15 Ma. L’élaboration d’une paragenèse générale détaillée révèle deux séquences minérales de type « fluorine-barytine-quartz », précédées par un événement de dissolution/karstification affectant les phases carbonatées des roches encaissantes. Au cours de ces phases de dissolution, le fluide s’enrichit en calcium et joue un rôle majeur pour la minéralisation en fluorine. Une étude microthermométrique des inclusions fluides piégées dans les cristaux géodiques de fluorine montre la présence de fluides particulièrement riches en CaCl₂ avec des températures entre 80-100°C, et des températures ponctuellement plus élevées. L’ensemble de ces données a été confronté à l’histoire thermique du sud-est du bassin de Paris et permet d’évoquer une remontée de fluides hydrothermaux au Crétacé inférieur jusqu’à la discontinuité entre le socle et la base du bassin sédimentaire. L’origine météorique de l’eau a été identifiée par les isotopes stables de l’oxygène sur les générations de quartz. L’implication d’une source granitique a été démontrée par les rapports isotopiques ²⁰⁶Pb/²⁰⁴Pb très radiogéniques dans la galène et l’étude des minéraux constituants du socle granitique, avec l’implication de la biotite en tant que source potentielle du fluor. Au cours du Crétacé inférieur, le soulèvement des bordures du bassin de Paris génère un gradient hydraulique susceptible de provoquer la mise en charge de fluides météoriques dans les massifs cristallins, percolant à travers le socle en profondeur (2 à 5 km). La dissolution des carbonates par les fluides ascendants hydrothermaux contenant du fluor va permettre la formation de la fluorine au cours de l’enrichissement du fluide en calcium dans le bassin au niveau de la discontinuité socle/couverture. / In France, unconformity-related stratabound fluorite deposits occurred at the base of Mesozoic sedimentary units from the Paris Basin around the Morvan Massif, and reserves are estimated to about 5.5 Mt. This work mainly concerns four fluorite deposits in sandstones at Antully, in limestones at Courcelles-Frémoy and in dolomite at Pierre-Perthuis and Marigny-sur-Yonne. The aim of this study is to constrain the age and origin of mineralizations inferred from a multi-disciplinary approach including geochronoly, petrography, elementary and isotopic geochemistry in order to produce a metallogenic model. Firstly, the geochronological study allows to determine the age of the geodic fluorite stage at Pierre-Perthuis at 130 ± 15 Ma. The detailed paragenetic sequence displays two major mineral successions of “fluorite-barite-quartz”, occurring after two dissolution or karstification events that affect the carbonate phases in host-rocks. During the dissolution event, the fluid is enriched in calcium and plays a key role for the fluorite mineralization. The microthermometric study of fluid inclusions in geodic fluorite crystals shows CaCl₂-rich fluids with temperature around 80-100°C, with sporadic higher temperatures. All these data has been confronted to the thermal history of southeastern part of Paris Basin and allows to evoke deep ascendant hydrothermal brine circulation during the Early Cretaceous at the basement/basin unconformity. The meteoritic origin of fluid is determined by the oxygen isotopic compositions in the quartz stages. The implication of basement source has been demonstrated by the radiogenic lead isotopic compositions added to the study of major minerals in basement with the involvement of biotite as a potential source of fluor. During the Early Cretaceous, it is proposed that flows of meteoric waters percolated downwards to depths of 2-5 km, driven by a hydraulic gradient due to the flexural deformation of the Paris Basin. The carbonate dissolution by the fluor-bearing ascendant hydrothermal fluids will allows the deposition of fluorite mineralization during the Ca enrichment of fluids in the basin at the basement/cover unconformity.

L’objectif de cette thèse est d’utiliser la géochimie des spéléothèmes à travers une étude multi-proxy afin de reconstituer des changements environnementaux et climatiques dans le Sud-Ouest de l’Europe au cours de l’Holocène. Ce travail basé sur trois sites répartis entre l’Espagne et la France couvre les 14 000 dernières années. Cette région du sud-ouest de l’Europe, située à la confluence des hautes et des basses latitudes en fait une région particulièrement sensible à la fois à l’influence climatique de la région Nord-Atlantique mais également des régions Méditerranéenne et subtropicales Africaines et Asiatiques. Ce contexte particulier permet d’étudier idéalement l’impact des différents mécanismes climatiques agissant sur les modifications de son environnement. La répartition des sites d’étude a pour but de comparer les sites sous influence majeure Atlantique (Candamo, Nord Espagne), Méditerranéenne (Salamandre, SE France) ou sous influence mixte (Nerjà, sud Espagne). La compréhension des comportements géochimiques d’éléments clés, a constitué la première partie de cette étude. Après avoir établi un cadre temporel bien contraint (14C, U/Th), la géochimie élémentaire (éléments traces et terres rares) a été couplée à l’étude isotopique (87Sr/86Sr, d18O, d13C). Le rapport 87Sr/86Sr traditionnellement utilisé comme traceur de sources du Sr a été couplé à l’étude des variations élémentaires des éléments alcalins (Li, Rb, Cs) afin de déterminer des changements de sources des éléments (roche-mère ou de sol) dans les spéléothèmes. Le comportement de ces alcalins s’est également révélé lié à des modes de transports différents (particulaire, dissous ou liés à des complexes organiques) et l’utilisation du d13C et des terres rares (fractionnement terres rares légères et terres rares lourdes et anomalie en cerium) a permis de confirmer ou non ces hypothèses. La deuxième partie de ce travail a été d’appliquer ces mécanismes géochimiques à la détermination des processus hydrologiques et environnementaux et de les replacer dans le cadre climatique propre à chaque site d’étude. Ainsi, les éléments alcalins (Li, Rb, Cs) se sont révélés de bons indicateurs de phénomènes d'altération pouvant être liés à des changements climatiques (comme la transition entre le Bölling-Alleröd et le Younger-Dryas dans le site de la Salamandre), et/ou environnementaux (période de déforestation ou de mise en place de végétation à l’Holocène moyen dans le cas du site de Nerjà ou de Candamo). Ces événements pouvant donc se dérouler en contexte très différents (climat sec, déforestation, apports détritiques en climat humide par lessivage), le couplage à d’autres proxis est alors nécessaire pour préciser les conditions d'enrichissement de ces éléments alcalins. / The purpose of this thesis is to use speleothem geochemistry through a multi-proxy study to reconstruct environmental and climatic variations in southwestern Europe during the Holocene. This work, based on three sites distributed between Spain and France, covers the last 14,000 years. Due to its location at the confluence of the high and low latitudes, this region of south-western Europe is especially sensitive to both the influence of the North Atlantic climate but also the Mediterranean and subtropical African and Asian climate. This particular context allows to study ideally the impact of the different climatic mechanisms driving the modifications of its environment. The choice of the study sites’ distribution aims to compare sites with main Atlantic influence (Candamo, N Spain), Mediterranean (Salamandre cave, SE France) and mixt one (Nerjà, S Spain). The understanding of geochemical behavior was the first part of this study. After the establishment of a chronological frame (14C, U/Th), elemental geochemistry (trace elements and rare earth elements) and isotopic (87Sr/86Sr, d18O, d13C) was coupled. The 87Sr/86Sr isotope ratio, traditionally used as a source tracer for Sr, has been coupled to the study of elementary variations of alkali elements (Li, Rb, Cs) in order to determine changes in the contribution of bedrock and soil in speleothems. The behavior of these alkalis has also been shown to be related to different modes of transport (particulate dissolved or bound to organic complexes) and the use of d13C and rare earths (light rare earth and heavy rare earth fractionation and cerium anomaly) made it possible to confirm or not these hypotheses. The second part of this work was to apply these geochemical mechanisms to the determination of the hydrological and environmental processes and to place them in the specific climatic context of each study site. Thus, the alkali elements (Li, Rb, Cs) have proved to be good indicators of weathering phenomena that may be related to climate change (such as the transition between Bölling-Alleröd and Younger-Dryas in the Salamandre site), and/or environmental changes (period of deforestation or establishment of vegetation in the Middle Holocene in the case of the sites of Nerjà or Candamo). These events can thus take place in very different contexts (dry climate, deforestation, detrital inputs during wet climate by leaching) the coupling to other proxis is then necessary to specify the conditions of enrichment of these alkali elements.

Surface manifestations of hydrothermal fluids such as fumaroles and hot springs provide valuable information about the level of activity of a volcano during quiescent period. Geochemical study of gas and spring waters is useful to elaborate geochemical model for magmatic-hydrothermal system. Furthermore, temporal geochemical monitoring of these fluids with time provides a better understanding in processes occurring inside the volcano and can be useful to detect any changes in the activity of the magmatic-hydrothermal system. This thesis investigates two hydrothermal systems at Kelud and Papandayan volcanoes that are located at Java Island in Indonesia. Kelud is considered as one of the most dangerous volcanoes of Java because of its frequent eruptions. After the last eruption that occurred in 1990, a new lake rapidly filled the crater of Kelud volcano. Water samples collected since 1993 are near neutral Na-K chloride fluids and are typical of aged hydrothermal system where the acidity has been completely neutralized by fluid-rock interaction and where the emission of acid magmatic gases has stopped. Two sudden increases in lake temperature in 1996 and 2001 were accompanied by rapid changes in lake water compositions and suggest the existence of two hydrothermal systems feeding the lake: a shallow hydrothermal system dominated by Ca-Mg sulfate waters and a deepest aquifer with neutral alkali chloride waters. From 2001 to 2005, measurements of CO2 emitted by the surface of the lake were performed by using the accumulation chamber method modified in order to work at the surface of a crater lake. Two statistical methods were used to process data: the graphical statistical and stochastic simulation methods. The results of graphical statistical approach showed that two different degassing processes are acting at the lake surface: one corresponding to CO2 fluxes resulting from rising bubbles and the other corresponding to equilibrium diffusion of dissolved CO2 at the water-air surface. Total CO2 emission rate estimated by stochastic simulation ranges from 105 t/day for 2001 to 32 t/day for 2005. Thermal energy released by the lake was also estimated by using an energy balance model with a new constraint using the CO2 flux. The thermal flux decreased from 200 MW (2001) to 100 MW (2002) and then remained stable. Correlation between the chemical data of waters, the fluxes of CO2 and energy show that a constant decrease in the level of activity of the volcano since 1993 occurred although the lake temperature has been stable since 2003. Since the last magmatic eruption that occurred in 1772, phreatic eruptions occur on Papandayan volcano with the last one in 2002. The volcanic material ejected during this eruption is essentially made of altered rocks from within the hydrothermal system. The interaction of acid waters with the host rocks corresponds to an advanced argilic alteration. The chemical compositions of waters from Papandayan volcano and Kelud lake waters are contrasting. Indeed, the spring waters sampled since 1994 are acid sulfate-chloride waters and acid sulfate waters. The chemical and isotopic analyses of gases and waters suggest a significant magmatic contribution in SO2, HCl and HF to the hydrothermal system. The chemical composition of waters sampled after the 2002 eruption have provided information about origin of this eruption. Decrease in chloride concentration and in delta 34S of dissolved sulfates showed that the magmatic contribution in these fluids are less important and that the waters are likely to be formed by the condensation of steam (H2O, H2S) rising from a boiling aquifer.

Surface manifestations of hydrothermal fluids such as fumaroles and hot springs provide valuable information about the level of activity of a volcano during quiescent period. Geochemical study of gas and spring waters is useful to elaborate geochemical model for magmatic-hydrothermal system. Furthermore, temporal geochemical monitoring of these fluids with time provides a better understanding in processes occurring inside the volcano and can be useful to detect any changes in the activity of the magmatic-hydrothermal system. This thesis investigates two hydrothermal systems at Kelud and Papandayan volcanoes that are located at Java Island in Indonesia. Kelud is considered as one of the most dangerous volcanoes of Java because of its frequent eruptions. After the last eruption that occurred in 1990, a new lake rapidly filled the crater of Kelud volcano. Water samples collected since 1993 are near neutral Na-K chloride fluids and are typical of aged hydrothermal system where the acidity has been completely neutralized by fluid-rock interaction and where the emission of acid magmatic gases has stopped. Two sudden increases in lake temperature in 1996 and 2001 were accompanied by rapid changes in lake water compositions and suggest the existence of two hydrothermal systems feeding the lake: a shallow hydrothermal system dominated by Ca-Mg sulfate waters and a deepest aquifer with neutral alkali chloride waters. From 2001 to 2005, measurements of CO2 emitted by the surface of the lake were performed by using the accumulation chamber method modified in order to work at the surface of a crater lake. Two statistical methods were used to process data: the graphical statistical and stochastic simulation methods. The results of graphical statistical approach showed that two different degassing processes are acting at the lake surface: one corresponding to CO2 fluxes resulting from rising bubbles and the other corresponding to equilibrium diffusion of dissolved CO2 at the water-air surface. Total CO2 emission rate estimated by stochastic simulation ranges from 105 t/day for 2001 to 32 t/day for 2005. Thermal energy released by the lake was also estimated by using an energy balance model with a new constraint using the CO2 flux. The thermal flux decreased from 200 MW (2001) to 100 MW (2002) and then remained stable. Correlation between the chemical data of waters, the fluxes of CO2 and energy show that a constant decrease in the level of activity of the volcano since 1993 occurred although the lake temperature has been stable since 2003. Since the last magmatic eruption that occurred in 1772, phreatic eruptions occur on Papandayan volcano with the last one in 2002. The volcanic material ejected during this eruption is essentially made of altered rocks from within the hydrothermal system. The interaction of acid waters with the host rocks corresponds to an advanced argilic alteration. The chemical compositions of waters from Papandayan volcano and Kelud lake waters are contrasting. Indeed, the spring waters sampled since 1994 are acid sulfate-chloride waters and acid sulfate waters. The chemical and isotopic analyses of gases and waters suggest a significant magmatic contribution in SO2, HCl and HF to the hydrothermal system. The chemical composition of waters sampled after the 2002 eruption have provided information about origin of this eruption. Decrease in chloride concentration and in delta 34S of dissolved sulfates showed that the magmatic contribution in these fluids are less important and that the waters are likely to be formed by the condensation of steam (H2O, H2S) rising from a boiling aquifer.<p><p> / Doctorat en sciences, Spécialisation géologie / info:eu-repo/semantics/nonPublished