Na porção W-SW do lobo Guaxupé, pertencente à Nappe Socorro-Guaxupé, nos arredores da cidade de São José do Rio Pardo, é registrado um evento metamórfico e anatético de fácies granulito, sob condições de desidratação da hornblenda, com T >=850ºC. As rochas diatexíticas, que compõem as suítes São José do Rio Pardo (SJRP) e Pinhal, resultam desse evento de alta temperatura, ocorrido há ~625 Ma. As assinaturas geoquímicas e isotópicas sugerem uma geração a partir da anatexia da crosta continental inferior. Além disso, o enriquecimento em potássio da suíte SJRP indica uma afinidade vaugnerítica, a qual é caracterizada por altos conteúdos de Mg, elementos do tipo LILE (large ion lithophile elements), HFSE (high field strenght elements) e ETR-leves, além de valores negativos de \'épsilon\'Nd e razões de Sr iniciais baixas, ~0.706. O magmatismo vaugnerítico implica em um manto litosférico metassomatizado como fonte, o qual foi enriquecido por eventos de subducção precedentes. A presença de pseudomorfos de fusão nesses diatexitos indicam uma evolução quase isotérmica sob presença de líquido anatético. O transporte sin-magmático ocorreu para NE-E. A fonte de calor para esse metamorfismo pode estar associada à delaminação da base do arco magmático. O processo de fusão parcial gerou leucossomas charno-enderbíticos na Unidade Metatexítica, com assinaturas geoquímicas e isotópicas que indicam uma fonte crustal. Dessas rochas, foram separados cristais de zircão que mostraram duas populações distintas. A primeira, tipicamente com cristais prismáticos e bipiramidados, indicam idades em torno de 620 Ma, enquanto que a segunda, com cristais isométricos típicos de alto grau metamórfico, indicam idades em torno de 610 Ma. Em relação ao pico metamórfico de ~625 Ma, as idades mais jovens obtidas sugerem um período de 15 my em que predominaram altas temperaturas. O transporte tectônico para NW, em estado sólido de alta temperatura, é posterior à cinemática sin-magmática para NE, e deve estar associado à compressão da placa superior convergente, dentro desse período de alta temperatura. Esse regime tectônico é compatível com modelos recentes da tectônica Andina onde é descrita uma subducção horizontal (Pampean flat subduction). Dentre as rochas da Unidade Granulítica Basal, também submetida à fusão parcial por desidratação da hornblenda, ocorrem gnaisses com afinidade adakítica, sugerida pelas altas razões Sr/Y = 72.73, La/Yb = 23.07, \'(La/Yb) IND.N\' = 15.56, e teores de #mg = 51.77, Sr = 1062 ppm, Cr = 197 ppm e Ni = 103 ppm. Tal afinidade sugere magmas resultantes da fusão de um slab em subducção. A Nappe Socorro-Guaxupé admite uma evolução que se inicia, cerca de 670-640 Ma, com uma subducção inclinada para a geração de rochas cálcio-alcalinas com alguns membros adakíticos. É seguido um momento de colisão, entre 625 e 610 Ma, com a geração de rochas diatexíticas e metatexíticas de alto potássio, onde o arco migrou primeiramente para o ante-arco (estado subsólido) e depois em direção ao interior da placa superior (estado sólido). A estabilização da nappe se deu quando da colocação dos maciços sieníticos pós-tectônicos, Capituva e Pedra Branca. / The W-SW portion of the Guaxupé Domain, nearby the São José do Rio Pardo city, records a granulite facies anatetic event under hornblende dehydration-melting conditions, i.e. T >=850ºC. The diatexitic rocks that are comprised within the São José do Rio Pardo and Pinhal suites resulted from this high-T metamorphic event, ca. 625 Ma. Geochemical and isotopic signatures suggest derivation from the lower continental crust. The K-rich SJRP suite also show geochemical affinity with vaugneritic rocks, suggested by high contents of Mg, LILE, HFSE and light-REE in addition to negative ?Nd and low Sr initial ratio (~0.706). Vaugneritic magmatism implies on a derivation from a metasomatized lithospheric mantle source enriched before partial melting in a previous subduction setting. Once both suites contain melt pseudomorphs, it is then suggested and isothermic evolution under the presence of melt. A syn-magmatic driven transport occurred towards NE-E, and the heat source for high-T conditions could be assigned to mantle delamination under the margmatic arc. Within the Metatexitic Unit, partial melting resulted in charno-enderbitic leucosomes whose geochemical and isotopic signatures indicate crustal sources. From these leucosomes, two different populations of zircon crystals were separated. The first, comprising bypiramidal-prismatic grains, yield ages around 620 Ma, whereas the second typology of zircons is isometric and soccer-ball type, yielding younger ages around 610 Ma. The latter typology is typical of high-T and melt-bearing rocks. Considering the 625 Ma metamorphic peak, the younger ages suggest a 15 my period when high-T conditions prevailed. Top-to-NW transport, under solid-state high-T conditions, can be associated to the compression of the upper convergent plate within this high-T period. Textural features suggest this transport to have occurred after the crystallization of the syn-magmatic rocks. The compression of the upper plate resembles recent models of the Andean orogenic cycle, where the Pampean flat subduction is described. Among the rocks of the Basal Granulitc Unit, which also underwent hornblende-dehydration partial melting, a gneissic rock shows adakitic affinity, suggested by Sr/Y = 72.73, La/Yb = 23.07, \'(La/Yb) IND.N\' = 15.56, #mg = 51.77, Sr = 1062 ppm, Cr = 197 ppm and Ni = 103 ppm. Adakitic magmas are thought to be slab melts. The Socorro-Guaxupé Nappe was built up between 670 and 640 Ma with a steep subduction and generation of calc-alkaline and subordinate adakitic rocks. A collisional setting, generating high-K diatexites and metatexites, took place between 625 and 610 Ma, where the arc firstly migrated (in subsolidus state) towards the forearc and then migrated (in solid state) towards the interior of the upper plate. Post-tectonic Capituva and Pedra Branca syenitic plutons intruded around 610 Ma, recording the arc migration ceasing.

Na porção W-SW do lobo Guaxupé, pertencente à Nappe Socorro-Guaxupé, nos arredores da cidade de São José do Rio Pardo, é registrado um evento metamórfico e anatético de fácies granulito, sob condições de desidratação da hornblenda, com T >=850ºC. As rochas diatexíticas, que compõem as suítes São José do Rio Pardo (SJRP) e Pinhal, resultam desse evento de alta temperatura, ocorrido há ~625 Ma. As assinaturas geoquímicas e isotópicas sugerem uma geração a partir da anatexia da crosta continental inferior. Além disso, o enriquecimento em potássio da suíte SJRP indica uma afinidade vaugnerítica, a qual é caracterizada por altos conteúdos de Mg, elementos do tipo LILE (large ion lithophile elements), HFSE (high field strenght elements) e ETR-leves, além de valores negativos de \'épsilon\'Nd e razões de Sr iniciais baixas, ~0.706. O magmatismo vaugnerítico implica em um manto litosférico metassomatizado como fonte, o qual foi enriquecido por eventos de subducção precedentes. A presença de pseudomorfos de fusão nesses diatexitos indicam uma evolução quase isotérmica sob presença de líquido anatético. O transporte sin-magmático ocorreu para NE-E. A fonte de calor para esse metamorfismo pode estar associada à delaminação da base do arco magmático. O processo de fusão parcial gerou leucossomas charno-enderbíticos na Unidade Metatexítica, com assinaturas geoquímicas e isotópicas que indicam uma fonte crustal. Dessas rochas, foram separados cristais de zircão que mostraram duas populações distintas. A primeira, tipicamente com cristais prismáticos e bipiramidados, indicam idades em torno de 620 Ma, enquanto que a segunda, com cristais isométricos típicos de alto grau metamórfico, indicam idades em torno de 610 Ma. Em relação ao pico metamórfico de ~625 Ma, as idades mais jovens obtidas sugerem um período de 15 my em que predominaram altas temperaturas. O transporte tectônico para NW, em estado sólido de alta temperatura, é posterior à cinemática sin-magmática para NE, e deve estar associado à compressão da placa superior convergente, dentro desse período de alta temperatura. Esse regime tectônico é compatível com modelos recentes da tectônica Andina onde é descrita uma subducção horizontal (Pampean flat subduction). Dentre as rochas da Unidade Granulítica Basal, também submetida à fusão parcial por desidratação da hornblenda, ocorrem gnaisses com afinidade adakítica, sugerida pelas altas razões Sr/Y = 72.73, La/Yb = 23.07, \'(La/Yb) IND.N\' = 15.56, e teores de #mg = 51.77, Sr = 1062 ppm, Cr = 197 ppm e Ni = 103 ppm. Tal afinidade sugere magmas resultantes da fusão de um slab em subducção. A Nappe Socorro-Guaxupé admite uma evolução que se inicia, cerca de 670-640 Ma, com uma subducção inclinada para a geração de rochas cálcio-alcalinas com alguns membros adakíticos. É seguido um momento de colisão, entre 625 e 610 Ma, com a geração de rochas diatexíticas e metatexíticas de alto potássio, onde o arco migrou primeiramente para o ante-arco (estado subsólido) e depois em direção ao interior da placa superior (estado sólido). A estabilização da nappe se deu quando da colocação dos maciços sieníticos pós-tectônicos, Capituva e Pedra Branca. / The W-SW portion of the Guaxupé Domain, nearby the São José do Rio Pardo city, records a granulite facies anatetic event under hornblende dehydration-melting conditions, i.e. T >=850ºC. The diatexitic rocks that are comprised within the São José do Rio Pardo and Pinhal suites resulted from this high-T metamorphic event, ca. 625 Ma. Geochemical and isotopic signatures suggest derivation from the lower continental crust. The K-rich SJRP suite also show geochemical affinity with vaugneritic rocks, suggested by high contents of Mg, LILE, HFSE and light-REE in addition to negative ?Nd and low Sr initial ratio (~0.706). Vaugneritic magmatism implies on a derivation from a metasomatized lithospheric mantle source enriched before partial melting in a previous subduction setting. Once both suites contain melt pseudomorphs, it is then suggested and isothermic evolution under the presence of melt. A syn-magmatic driven transport occurred towards NE-E, and the heat source for high-T conditions could be assigned to mantle delamination under the margmatic arc. Within the Metatexitic Unit, partial melting resulted in charno-enderbitic leucosomes whose geochemical and isotopic signatures indicate crustal sources. From these leucosomes, two different populations of zircon crystals were separated. The first, comprising bypiramidal-prismatic grains, yield ages around 620 Ma, whereas the second typology of zircons is isometric and soccer-ball type, yielding younger ages around 610 Ma. The latter typology is typical of high-T and melt-bearing rocks. Considering the 625 Ma metamorphic peak, the younger ages suggest a 15 my period when high-T conditions prevailed. Top-to-NW transport, under solid-state high-T conditions, can be associated to the compression of the upper convergent plate within this high-T period. Textural features suggest this transport to have occurred after the crystallization of the syn-magmatic rocks. The compression of the upper plate resembles recent models of the Andean orogenic cycle, where the Pampean flat subduction is described. Among the rocks of the Basal Granulitc Unit, which also underwent hornblende-dehydration partial melting, a gneissic rock shows adakitic affinity, suggested by Sr/Y = 72.73, La/Yb = 23.07, \'(La/Yb) IND.N\' = 15.56, #mg = 51.77, Sr = 1062 ppm, Cr = 197 ppm and Ni = 103 ppm. Adakitic magmas are thought to be slab melts. The Socorro-Guaxupé Nappe was built up between 670 and 640 Ma with a steep subduction and generation of calc-alkaline and subordinate adakitic rocks. A collisional setting, generating high-K diatexites and metatexites, took place between 625 and 610 Ma, where the arc firstly migrated (in subsolidus state) towards the forearc and then migrated (in solid state) towards the interior of the upper plate. Post-tectonic Capituva and Pedra Branca syenitic plutons intruded around 610 Ma, recording the arc migration ceasing.

La datation de l’âge de génération des hydrocarbures et de la déposition de la roche mère fournit des informations importantes dans la prospection pétrolière. Dans ce travail, différentes stratégies ont été étudiées pour la détermination des métaux traces, et des rapports isotopiques du plomb dans des produits pétroliers par des techniques de spectrométrie de masse. Les stratégies d’analyses développées dans ce travail ont été utilisées pour estimer l’âge de génération du pétrole, ainsi que l’âge de déposition de la roche mère âge du « New Albany shales » dans le basin d’Illinois, en utilisant les géochronomètres U-Th-Pb. Les ages déterminés par la méthode U-Th-Pb sont en très bon accord avec ceux prédits par les modèles numériques géologiques, ce qui démontre le potentiel de cette approche pour étudier l’histoire de la formation des hydrocarbures et dans la recherche de nouvelles sources d'hydrocarbures. / Timing crude oil generation and source rock deposition provides important clues in petroleum prospection. In this work, different analytical procedures were developed for trace metals and Pb isotope ratio were determination crude oils and related products. These analytical strategies were then used, for the first time, to assess the applicability of the U-Th-Pb geochronometers for timing source rock deposition age and crude oil generation in the Illinois Basin. Ages determined are in good agreement with those predicted by geological numerical models, demonstrating the potential of these geochronometers to study the history of hydrocarbons formation and to find new hydrocarbon sources.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21583号 / 理博第4490号 / 新制||理||1645(附属図書館) / 京都大学大学院理学研究科地球惑星科学専攻 / (主査)准教授 伊藤 正一, 教授 生形 貴男, 教授 山路 敦 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

L’acidification des océans provoquée par l’absorption du CO2 atmosphérique par l’eau de merest devenue une préoccupation écologique majeure et menace déjà les organismes calcifiants. Suiteà la révolution industrielle, le pH de l’océan de surface a diminué de 0,1 unité-pH. En revanche, celuides eaux profondes reste peu documenté. Les isotopes du bore (11B) dans les carbonatesbiogéniques se sont révélés être un puissant outil géochimique pour la reconstitution du pH, mais n’apas encore été appliqué aux coraux profonds. Un travail analytique sur MC-ICPMS Neptune et uneanalyse géochimique de ces coraux ont été effectués afin de reconstituer et quantifier l’acidificationdes océans. De même, la valeur 11B de l’eau de mer utilisée pour calculer les paléo-pH a étérevisitée et l’homogénéité des océans vérifiée.L’analyse de deux colonies modernes de Lophelia pertusa et Madrepora oculata a permis dequantifier un taux d’acidification pendant la fin du XXème siècle pour les eaux de sub-surface en mer deNorvège et cela après établissement d’une calibration expérimentale à partir de coraux de culture.L’analyse géochimique des coraux profonds a mis en évidence un effet vital lié à la physiologie quidoit être considéré pour quantifier avec précision la variabilité du pH. Celui-ci peut être en partiecorrigé par une analyse statistique des isotopes stables B, C et O. Cette étude a aussi révélél’influence de l’hydrodynamique régionale. Enfin les variations naturelles du pH pendant l’Holocène etle Dernier Maximum Glaciaire sur des coraux profonds fossiles méditerranéens ont été établies etcelles pendant l’aube de l’explosion de la diversité biologique. / Ocean acidification is caused by the absorption of rising atmospheric CO2 by seawater andrepresents a major environmental issue. Since the beginning of the industrial era, seawater pH hasdecreased by 0.1 pH units and is already threatening calcifying organisms. Boron isotopes (11B) haveproved to be a powerful geochemical tool for the reconstruction of pH variations, but has not yet beenapplied to deep-sea corals (DSC). Accurate and precise measurements of boron isotopes in coralsand seawaters were performed in order to measure small pH variations.The technique of pH reconstruction based on boron isotopes (pH-11B) was used on two specimens of the DSC Madrepora oculata and Lophelia pertusa collected alive in the Norwegian Sea and spanning an age of 40 (3) and 67 (3) years, respectively. Acidification rates were calculated by applying a new pH-11B calibration obtained from the geochemical analysis M. oculata and L. pertusa samples cultured under different pCO2 conditions. The contribution of a biological-related vital effect on d11B was observed at macrometer scale, and a correction was finally suggested based on oxygen and carbon isotopes. Overall, the coral δ 11B-based reconstructions show a pH decrease in the Norwegian Sea since the 1940s, which seems to be related to the local hydrodynamics. The pH-11B technique was also applied to fossil DSC fragments from two “on-mound sediment cores” retrieved in the Siculo-Tunisian Strait with the aim to reconstruct the pH during the Last Glacial Maximum and the Holocene periods. Finally, well-preserved limestone samples from the stratigraphic sequence Nama (551-543 Ma) in Namibia were investigated for 11B to study the pH variations at the beginning of the Cambrian evolutive radiation.

La caractérisation isotopique des éléments présents dans les combustibles nucléaires irradiés est d'une importance majeure pour la qualification et la validation des codes de calculs neutroniques ainsi que la gestion des déchets nucléaires. Le protocole conventionnel pour l'analyse de ces échantillons nécessite plusieurs étapes de séparation par chromatographie liquide. L'uranium (U), le plutonium (Pu) et une fraction contenant les produits de fission et les actinides mineurs, sont séparés par chromatographie sur résine échangeuse d'ions puis les fractions purifiées d'U et de Pu sont analysées par spectrométrie de masse. L'objectif de cette thèse consiste à étudier et développer un protocole analytique applicable sur des échantillons de type combustibles irradiés et employant une technique séparative transposable sur plateforme miniaturisée qui devra pouvoir être couplée à un spectromètre de masse à source plasma et à système multicollection (ICPMS-MC) afin de réaliser en ligne l'analyse isotopique et élémentaire des éléments présents dans le combustible irradié. Une méthode de séparation de l'U, du thorium (Th) et des lanthanides par électrophorèse capillaire (EC) avec préconcentration de l'échantillon a été développée en utilisant le Th(IV) comme analogue chimique du Pu(IV). L'électrolyte de séparation se compose d'acide acétique 0,25M comme complexant ainsi que de sel d'ammonium 0,1M, pour ajuster la force ionique et permettre la préconcentration. Le montage d'EC a été adapté afin d'être intégré en boite à gants et couplé à un ICPMS-MC. La séparation de l'Am de l'U et du Pu a été réalisée sur quelques nL d'une solution de combustible irradié. / Precise isotopic and elemental characterization of nuclear spent fuel is a major concern for the validation of the neutronic calculation codes and waste management in the nuclear industry. The conventional protocol for the analysis of nuclear fuel samples uses several purification steps by liquid chromatography. Uranium (U) and plutonium (Pu) and a fraction containing fission products and minor actinides are separated using ion exchange chromatography prior to the isotopic characterization of the U and Pu fractions by multi-collector mass spectrometry techniques. The objective of the work presented is to develop a new analytical approach based on miniaturized separation techniques like capillary and microfluidic electrophoresis coupled with a multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) detection for online isotopic ratio measurements. An electrophoretic separation method of U, Pu and fission products with a stacking step was developed using thorium (Th) as a chemical analog for Pu(IV). The separation electrolyte is composed of acetic acid (0.25M) as complexing agent for the separation and 0.1M of ammonium salt to realize the stacking step. The instrumentation was adapted to be used in glove box and directly coupled to a MC-ICPMS. The separation of Am, Pu and U was realized with few nL of a spent nuclear fuel solution. The reproducibilities obtained on the isotope ratios were in the order of few ‰ and comparable with those obtained with the conventional analytical protocol. This new protocol will help to reduce the quantities analyzed from µg to ng, the liquid waste volume scale from mL to µL and the sample volumes form µL to nL.

Une période intéressante de l'histoire précoce du système solaire est celle du disque, i.e. la période pendant laquelle se déroule la plupart des processus qui vont conduire du mélange de gaz et de poussières nébulaires à des grains et des planétésimaux, qui seront à un stade ultérieur le matériel de départ pour la formation des embryons planétaires et des planètes. Les témoins de cette époque sont les constituants des météorites primitives (chondrites), principalement les inclusions réfractaires (CAIs) et les chondres. Une des questions centrales dans la compréhension des processus à l'origine des CAIs et des chondres est celle du temps. Les travaux récents de Johan Villeneuve ont permis de démontrer que l'26Al et les isotopes du Mg étaient distribués dans le disque d'accrétion à un niveau d'homogénéité permettant d'utiliser le système 26Al-26Mg comme le chronomètre le plus précis qui soit des évènements qui se sont déroulés lors des 2 ou 3 premiers millions d'années du disque. Le but de cette thèse a été de reprendre toute l'étude de l'26Al avec des mesures de plus haute précision que les mesures existantes, en associant les mesures in-situ (sonde ionique) et en roche totale (HR-MC-ICPMS). Les développements analytiques mis en place pour mesurer les compositions isotopiques en Mg ont été appliqués à l'étude d'olivines réfractaires et de chondres de la météorite Allende, et d'olivines de la pallasite Eagle Station. L'ensemble des données a permis d'apporter des éléments de réponse sur les âges de formation des chondres et de leurs précurseurs, et sur l'origine des olivines réfractaires riches en Mg et la possibilité que celles-ci figurent parmi les précurseurs des chondres / The disk history is a very interesting period of the early Solar System history, i.e. the period during which occurred most of the processes leading from the mixing of nebular gas and dust to grains, and then planetesimals, which will then constitute the starting material for formation of planetary embryos and terrestrial planets. The witnesses of this period that we have in the laboratory are the chondrite constituents, mostly refractory inclusions (CAIs) and chondrules. One of the central questions regarding the processes leading to the formation of CAIs and chondrules is the timing. Villeneuve et al. (2009, 2011) have shown that 26Al and Mg isotopes were homogeneously distributed in the accretion disk, at a level allowing the use of the 26Al-26Mg system as the most precise short-lived chronometer to constrain the 2 or 3 first million years of the disk history. My PhD project aimed at reconsidering the 26Al study with more precise measurements, and by combining in-situ (by MC-SIMS) and bulk (by HR-MC-ICPMS) analyses. The analytical developments we set for Mg-isotope measurements (because of the high precision needed) were then applied to a set of extraterrestrial materials, including Mg-rich isolated olivines and Mg-rich olivines in porphyritic type I chondrules from the Allende CV3 meteorite, as well as chondrules from the same meteorite, and olivines from the Eagle Station pallasite. The whole data set allowed to answer questions such as (i) the origin of chondrule precursor materials and the time of chondrule formation, as well as (ii) the origin of Mg-rich refractory olivines, and the possibility that the latters were part of chondrule precursors

Ce travail de thèse est essentiellement consacré à l'investigation des populations de zircons et de l'âge des protolithes des formations varisques grâce à une datation U-Pb in situ systématique par le couplage Laser/MC-ICPMS, dans des formations orthodérivées, métasédimentaires et magmatiques tardi-orogéniques du Massif Central français et du domaine Sud armoricain. Cette étude a montré que les populations de zircons sont largement héritées, s'étalant de l'Archéen au Paléozoïque inférieur. L'ensemble des pics d'âges obtenus, ainsi que l'absence d'âge mésoprotérozoïque (1.7-1.1 Ga) accréditent l'affinité gondwanienne de ces formations. Des âges maximum de dépôt sont proposés pour les métasédiments des principales unités définies dans le Massif Central. Ces âges maximum de dépôt sont décroissants suivant l'empilement lithotectonique reconnu. En marge de ce travail, nous avons pu déterminer que les âges de mise en place des granitoïdes du Sillon Houiller (Massif Central) et du golfe du Morbihan se situent aux alentours de 300 Ma. Des âges plus anciens, principalement obtenus sur monazite lors d'études antérieures, ont été réinterprétés comme des âges hérités. L'abondance de zircons hérités d'âge ordovicien et néoprotérozoïque met en évidence la large contribution des métagranites et métasédiments fertiles de ces périodes dans la source des granites tardi-orogéniques varisques. Le granite de Sarzeau expose de plus les traces d'un protolithe silurien. Le recyclage de la croûte continentale est caractérisé par une évolution polycyclique au cours de l'orogénèse varisque, avec tout d'abord l'érosion de formations du craton africain, majoritairement d'âge néoprotérozoïque, puis la superposition des événements magmatiques cambro-ordoviciens et syn-orogéniques varisques.