Understanding modern carbonate depositional systems gives valuable insights into the interpretation of ancient carbonate systems. Ancient carbonate strand plains have the potential to act as productive hydrocarbon reservoirs because of their relatively high porosity. Unfortunately, they are difficult to identify in the rock record because of the lack of work done on modern analogues. San Salvador Island in the Bahamas hosts a well-exposed and easily accessible Holocene strand plain, ideal as a modern analogue. Sandy Hook, located on the southeast part of the island, consists of approximately 35 ridge-swale features that show signs of four distinct zones of deposition. In this study, 20 sediment samples were collected from one meter in depth, and throughout each zone. The sediment analysis reveals remarkably consistent grain-size distributions across the four zones. Carbon-14 ages were taken from the sediment samples. They revealed ages decreasing from 2617 ± 188 YBP to modern moving seaward through zone 4. The ages reveal depositional rates of 0.08 to 0.29 meters of accretion per year. Four pseudo-3D GPR surveys were acquired in Zones B, C, and D, and a 2D GPR survey was acquired that spanned the three zones. The pseudo-3D surveys revealed consistent reflectors through the width of the survey indicating that the 2D surveys represent more than the single line. The 2D survey reveals semi-parallel seaward-dipping reflectors (representing fair-weather deposits) that are truncated by sigmoidal seaward-dipping reflectors (high-energy storm deposits). Indicating that Sandy Hook was built through both fair-weather deposits and high-energy storm events.

Honey Lake Basin is a large, hydrologically closed valley with two playa lakes that are separated by a low elevation sill. The Basin has a complex hydrogeologic setting, with numerous groundwater flow paths that interact with surface waters and three basic aquifers; shallow, deep, and geothermal. Thirteen flow paths; eleven cold and two thermal, are identified and the geochemical evolution of those paths are characterized by integrating solute chemistry and isotopic data. The chemical flow paths include recharge in either granitoid or volcanic terrains in the Sierra Nevada Range and the Modoc Plateau, respectively. The groundwater then flows through alluvial fan and stream sedimentary environments and eventually flows through lacustrine and playa sediments in the closed basin. This investigating characterizes geochemical evolution of groundwater flow from both mafic and granitic terrains to lacustrine sediments with evaporite minerals, in a closed basin environment. Temperature data reveal that thermal waters circulate to 1.6-3.0 km and 2.8-3.8 km along two major fault zones. Shallow groundwaters above 17°C are determined to have a component of thermal water and mixing ratios are presented. δ18O and δD data show that deep groundwater was recharged by cooler, more humid precipitation from the last ice age, whereas shallow groundwaters reflect current meteoric conditions and show extensive evaporation trends. The two thermal flow paths show exchange with silicate minerals at high temperatures (>100°C). δ13C data show interaction with carbonate minerals in basin fill lacustrine sediments. 3H concentrations and 14C ages show that deep groundwaters throughout the Basin and shallower groundwaters in the center of the basin are not greatly affected by post-1952 recharge. Mean 14C ages range from modern to 23,500 years old. NETPATH was used to model geochemical evolution along the flow paths. Groundwater on the west side of the basin (granitic terrain) is typically low TDS (~150 mg/L) calcium-bicarbonate water and evolves into higher TDS (~300 mg/L) sodium-bicarbonate groundwater as it interacts with granitic rocks and then lacustrine sediments. Groundwater on the east side of the basin (mafic terrain) is typically low TDS (~200 mg/L) sodium-bicarbonate water and evolves into high TDS (~300 mg/L) sodium-bicarbonate water groundwater as it interacts with mafic rocks and then lacustrine sediments. Dissolution of silicate minerals and calcite, and ion exchange with clays is responsible for major chemistry changes. As both of these types of groundwaters come into contact with lacustrine sediments with evaporite minerals on the playas, dissolution of halite and gypsum dominate and the groundwater becomes extremely high in TDS (~ 1100 mg/L on the Honey Lake Playa and ~ 43,000 mg/L on the Fish Spring Playa) and strongly sodium-chloride in character.

A geochemical study of major springs and wells in Spring Valley, Nevada, and Snake Valley, Utah-Nevada was initiated in response to the Clark, Lincoln and White Pine Counties Groundwater Development Project proposed by the South Nevada Water Authority (SNWA). Water budget estimates suggest that interbasin flow accounts for a significant portion (~25%) of the water budgets in Spring and Snake Valleys. Although interbasin flow is possible in some areas, alternative plausible explanations place significant uncertainty on water budget allocations. To examine the plausibility of local and interbasin flow paths the groundwater flow in Spring and Snake Valleys was evaluated using solute and isotopic data. Evidence for local flow paths includes: 1) stable isotope values in local areas which are similar to isotope values in adjacent recharge zones; 2) measurable 3H content and 14C activities ≥ 50 pmc in most samples which suggests short residence times; and 3) plausible geochemical models of local flow paths. Previously defined interbasin flow paths in southern Spring Valley are marked by samples that have low 14C activities (mean = 20.14 pmc), which are consistent with long residence times and can be explained by either interbasin flow from adjacent basins or deep circulation in the basin-fill sediments of Spring Valley. Interbasin flow from southern Spring Valley to southern Snake Valley cannot be confirmed or rejected based on the current data and modeling constraints, which result in plausible models involving both local flow paths and interbasin flow paths. Interbasin flow from northern Spring Valley to northern Snake Valley is unlikely and can be explained by the deep circulation of groundwater that is mixed with modern recharge. The plausibility of alternative explanations to describe previously defined interbasin flow paths suggests that water budget allocations in Spring and Snake Valleys should be redistributed or reevaluated. The use of existing water budgets that allocate large components of water to interbasin flow to determine the distribution of water resources may result in incorrect estimations of available resources.

L’utilisation du glucose exogène est un déterminant de la performance sportive, particulièrement lors d’épreuves de plus d’une heure. Les caractéristiques des sujets, les conditions d’exercice et d’ingestion du glucose sont tous des facteurs pouvant affecter l’oxydation de glucose exogène (OGE). De plus, la co-ingestion d’autres substrats et l’environnement dans lequel l’activité est pratiquée peuvent également avoir un impact sur l’OGE et sa contribution à la fourniture d’énergie. Il est souvent difficile, voire impossible, de comparer les résultats des études qui ont examiné l’OGE due au manque d’uniformité dans la méthodologie. Afin de clarifier l’effet de ces facteurs sur le taux d’OGE, ainsi que sa contribution à la fourniture d’énergie lors de l’exercice prolongé, une revue de littérature et une méta-analyse ont été effectuées. Le sexe, l’âge, la masse corporelle, le VO2max des participants, le moment d’ingestion, le taux d’ingestion, la concentration de la solution, la puissance absolue et relative de l’exercice, et la durée de l’exercice ont été utilisés comme modérateurs. Les facteurs pouvant influencer le taux d’OGE et sa contribution à la fourniture d’énergie pendant l’exercice prolongé rapportés dans cette méta-analyse confirment une relation dose-réponse curvilinéaire. D’autres facteurs, tels le VO2 et le %VO2max de l’exercice, ainsi que le moment d’ingestion, permettent également d’expliquer la relation observée dans le taux d’oxydation exogène et sa contribution à la fourniture d’énergie. La grande majorité des études ayant été effectuées sur une population restreinte (hommes sportifs ou en santé, âgés entre 20 et 30 ans), davantage de travaux sont nécessaires chez les femmes et les sujets d’âge et de masse corporelle différents afin d’éviter les biais d’interprétation dus à au sexe ou aux caractéristiques physiques. Les résultats de cette méta-analyse pourront aider à améliorer les recommandations sur l’ingestion de glucides au cours de l’exercice prolongé. / Exogenous glucose oxidation is a determinant of sports performance especially in activities lasting over 1 hour. Many factors concerning the subjects, the substrate and the exercise itself could influence the capacity of the human body to oxidize exogenous glucose. Furthermore, the co-ingestion of other substrates, as well as the environment in which the activity is performed, could also influence the rate of exogenous glucose oxidation (EGO) and its contribution to the energy yield. The lack of uniformity in methodologies used to investigate EGO makes it very difficult, and in some cases even impossible, to make direct comparisons between study results. In an attempt to shed some light on the impact of those various factors on the rate of EGO and its contribution to the energy yield, the literature was reviewed and a meta-analysis was done. The sex, age, body mass, VO2max, timing of ingestion, rate of ingestion, solution concentration, exercise’s absolute and relative intensity, and exercise duration were used as moderators. Many factors can contribute to EGO and its contribution to the energy yield and the results from this meta-analysis confirm a dose-response relationship. Additional factors, such as exercise VO2 or %VO2max, and ingestion timing also have a significant effect. Further studies might be needed with women and subjects with different age and body mass to avoid bias due to an unbalanced number of studies when comparing subject characteristics. These results should help improve nutritional recommendations for carbohydrate ingestion during prolonged exercise.

Le démantèlement des réacteurs Uranium Naturel Graphite Gaz génèrera en France environ 23 000 tonnes de déchets radioactifs graphités. La gestion appropriée de ces déchets nécessite de déterminer leur inventaire radiologique et de disposer de données fiables sur la localisation et la spéciation des radionucléides (RN). Le 14C a été identifié comme RN d'intérêt pour le stockage en raison de son inventaire initial important et du risque de présence d'une fraction organique mobile dans l'environnement, lors de la phase de stockage. A ce titre, l'objectif de cette thèse CIFRE, réalisée en partenariat avec EDF, est de mettre en œuvre des études expérimentales permettant de simuler et d'évaluer l'impact de la température, de l'irradiation et de la corrosion radiolytique du graphite sur le comportement migratoire en réacteur du 14C et de son précurseur azote. Les données ainsi acquises sont intégrées dans la deuxième partie de ce travail consacrée à l'étude d'un procédé de décontamination thermique du graphite en présence de vapeur d'eau. La démarche expérimentale consiste à simuler respectivement la présence de 14C et de 14N par implantation ionique de 13C et d'azote (14N ou 15N) dans un graphite de rondin SLA2 vierge. Cette étude montre que dans la gamme de températures du graphite en réacteur (100 - 500°C) et en absence de corrosion radiolytique, le 13C est stable thermiquement quel que soit l'état de structure du graphite. En revanche, les expériences d'irradiation du graphite chauffé à 500°C au contact d'un gaz représentatif du caloporteur radiolysé montrent le rôle synergique joué par les espèces oxydantes et l'endommagement du graphite favorisant la mobilité du 13C par gazéification des surfaces et/ou oxydation sélective du 13C plus faiblement lié. En ce qui concerne l'azote constitutif, il a tout d'abord été démontré que sa concentration en surface atteint plusieurs centaines de ppm (< 500 ppm at.) et décroît en profondeur jusqu'à environ 160 ppm at.. Contrairement au 13C implanté, l'azote implanté migre à 500°C lorsque le graphite est fortement déstructuré (environ 8 dpa) alors qu'il reste stable pour un taux de déstructuration moindre (0,14 dpa). Les expériences montrent également le rôle synergique des excitations électroniques et de la température qui accélèrent le transport de l'azote vers la surface du graphite. Cette migration de l'azote semble se faire sous forme moléculaire d'espèces C-N, C=N voire C N. Après huit heures d'irradiation ces espèces ne sont toutefois pas ou peu relâchées et restent bloquées à la surface. L'étude du procédé de décontamination thermique en présence de vapeur d'eau a nécessité la mise en place d'un dispositif de thermogravimétrie couplé à un générateur de vapeur d'eau ainsi que l'optimisation des paramètres de l'étude. Les influences de la température (700°C et 900°C) et de l'humidité relative (50 % HR et 90 % HR) ont été testées à un débit de gaz humide fixe de 50 mL/min. Dans ces conditions, l'oxydation sélective du carbone implanté a été confirmée / The dismantling of UNGG reactors in France will generate about 23 000 tons of radioactive graphite wastes. To manage these wastes, the radiological inventory and data on radionuclides (RN) location and speciation should be determined. 14C was identified as an important RN for disposal due to its high initial activity and the risk of release of a mobile organic fraction in environment, after water ingress into the disposal. Hence, the objective of this thesis, carried out in partnership with EDF, is to implement experimental studies to simulate and evaluate the impact of temperature, irradiation and graphite radiolytic corrosion on the in reactor behavior of 14C and its precursor, 14N. The obtained data are then used to study the thermal decontamination of graphite in presence of water vapor. The experimental approach aims at simulating the presence of 14C and 14N by the respective ion implantation of 13C and 14N or 15N in virgin graphite. This study shows that, in the temperature range reached during reactor operation, (100-500°C) and without radiolytic corrosion, 13C is thermally stable whatever the initial graphite structure. Moreover, irradiation experiments were performed on heated graphite (500°C) put in contact with a gas representative of the radiolysed coolant gas. They show the synergistic role played by the oxidative species and the graphite structure disorder on the enhancement of 13C mobility resulting in the gasification of the graphite surface and/or the selective oxidation of 13C more weakly bound than 12C. Concerning the pristine nitrogen, we showed first that the surface concentration reaches several hundred ppm (<500 ppm at) and decreases at deeper depths to about 160 ppm at.. Unlike implanted 13C, implanted nitrogen migrates at 500 ° C when the graphite is highly disordered (about 8 dpa) while remaining stable for a lower disorder rate (0.14 dpa). Experiments also show the synergistic role by electronic excitations and temperature that accelerate the transport of nitrogen to the surface of the graphite. Nitrogen seems to migrate in the form of molecular species (CN, C = N or C N). After eight hours of irradiation these species are, however, little or not released and blocked at the surface. The study of the thermal decontamination of graphite in presence of water vapor was performed with a thermogravimetric device coupled to a steam water generator device. The influence of temperature (700 ° C and 900 ° C) and of the relative humidity (50% RH and 90% RH) was tested with a wet gas fixed flow rate of 50 ml/min. Under these conditions, the selective oxidation of implanted carbon was confirmed

Para o presente trabalho, três testemunhos foram amostrados nos manguezais João Cardoso (JC), Ipaneminha (IPA) e Perequê (PE), localizados na face norte da llha do Cardoso. Estudo interdisciplinar envonveldo descrições faciológica, análise granulométrica, datação 14C, análises isotópicas e elementares de C e N e palinologia foram realizados com o objetivo de descrever a evolução sedimentar e da vegetação, com inferâncias climáticas. Entre 250 a 166 cm, o testemunho JC é composto de areia média creme-acinzentada base gradando para areia muito-fina cinza, com idades de 33.000 (198cm) e 29.400 anos cal. A.P. (166cm), carbono orgânico total (COT) de 0,044 a 0,633%, nitrogênio total (NT) de 0,002 a 0,017%, C/N de 7 a 30, \'delta\'13C de -18,49 a -24,46%o e \'delta\'15N de 2,48 a 8,13%o), indicativos de matéria orgânica terrestre de plantas C3 e C4 e algas/fitoplâncton. A palinologia mostra predomínio de elementos arbóreos dos táxons Alchornea, Drymis, Ilex, Myrsine, Myrtaceae, Podocarpus e Weinmannia (até 10%, cada) e esporos de Cyathea e Polypodiaceae (30%), característico de clima frio e úmido. De 166 a 70 cm a fácies apresenta areia média com estratificação cruzada plano-paralela marcada por areia/argila cinza escura, indicando ambiente praial de inframaré. Esta camada representa um hiato de ~27.000 anos cal. A.P. de sedimentação original, provavelmente erodidos durante transgresão Santos. Os testemunhos IPA e PE apresentam camada semelhante, iniciando na base (170 e 140cm, respectivamente), até aprox. 60 cm. A 163 cm no testemunho IPA foi obtida idade de ~2200 anos AP e ausência de palinomorfos. Sobre a camada da areia, nos três testemunhos, depositam-se sedimentos arenosos/argilosos bioturbados, com abundantes fragmentos/raízes vegetais e conchas. A partir de ~850 anos cal. A.P. (testemunho IPA - 50cm), a variação nos valores elementares e isotópicos de C e N indicam a substituição do predomínio de M.O. fitoplanctônica para M.O. de plantas C3, ainda com influência do fitoplâncton (COT: 0,15 a 12,8%; NT: 0,01 a 0,48%; \'delta\'13C: - 21,00 até - 29,00%o; \'delta\'15N: 8,00 a 3,40%o). A palinologia mostra um padrão semelhante nos três testemunhos. Os táxons Alchornea, Arecaceae, Fabaceae, Hedyosmum, Myrsine, Myrtaceae, Podocarpus, Sloanea, Weinmannia são os mais representativos entre os arbóreos (até 10%). Esporos de Cyathea e Polypodium e grãos de pólen de Poaceae e Cyperaceae correspondem a aprox. 30% da soma total, pouco variando. Estes valores indicam a presença das formações da Floresta Atlântica e da Restinga na região durante todo o período. O táxon Rhizophora sofre aumento neste período de 5 para até 22% nos dias atuais. Infere-se presença de manguezal na região e seu subsequente estabelecimento no local. Palinoforaminíferos e dinocistos são abundantes (até 15%) na base da camada, diminuindo em frequência para o topo (4%). Estes dados mostram uma progressiva diminuição na influência marinha, evoluindo de ambientes intermaré para ambiente de supramaré, devido à redução do nível marinho local durante o Holoceno tardio. Estes dados contribuem para o entendimento da evolução paleoambiental no litoral sul do Estado de São Paulo desde o Pleistoceno Tardio / For the present work, three cores where sampled on the \"João Cardoso (JC)\", \"Ipaneminha (IPA)\" and \"Perequê (PE)\" mangroves, located at the northern face of the Cardoso Island. A interdisciplinary study involving facies, radiocarbon dating, elementary and isotopic carbon and nitrogen, granulometric and palynological analysis were carried with the objective of describing the vegetation and sedimentary evolution, with climatic inferences. Between 250 and 166 cm, the JC core is primarily constituted by grayish medium sand progressing to very fine sand, with ages of ~33.000 (198cm) and ~29.450 (166) cal yr AP. Total Organic Carbon (TOC) of 0,044% to 0,633%, Total Nitrogen (NT) of 0,001 to 0,017%, C/N ratios of 7 to 30, \'delta\'13C of -18,49 to -24,46%o and \'delta\'15N of 2,48 to 8,13%o indicates mixture of C3and C4 terrestrial plants and phytoplantonic sources. Palynology show predominance of the arboreal elements Alchornea, Drymis, Ilex, Myrsine, Myrtaceae, Podocarpus e Weinmannia (up to 10% of total, each) , Cyathea and Polypodium spores (up to 20%), caracteristic of humid and cold climate. From 166 to 70 cm the facies show plane-paralell cross-bedded stratification marked by dark gray medium sand, indicating an inter-tidal environment. This layer represents a hiatus of ca. ~27.000 yr of original sedimentation, probably eroded on the Santos marine transgression. Cores IPA and PE presents similar facies at their bases (170 and 140 cm, respectively) up to near 60 cm. At 163 cm, the IPA core shows age of ~2.000 cal yr AP, and no palynomorphs. On top of this sandy facies are layers of sandy/silty/clayey bioturbated sediments, with an abundance of root, shells and plant debris. Since . ~850 cal yr AP, the isotopic and elementary values show a gradual substitution of the phytoplanctonic source of the sedimentary organic matter to a terrestrial C3 plant source on the three cores. Palynology also shows a similar pattern between the three records?, with Alchornea, Arecaceae, Fabaceae, Hedyosmum, Myrsine, Myrtaceae, Podocarpus, Sloanea, Weinmannia taxons the most well represented between the trees, with Cyathea e Polypodium, Poaceae e Cyperaceae with up to 30% of the total. These are characteristic of the Pluvial and sandbank forests. Rhizophora show an increase in this period from 5 to 22%, indicating the establishment and evolution of the mangrove vegetation on the area since ~850 cal yr AP. Palinoforaminifera and dinocyst show a diminishing pattern (from 15 to 4%) through this period, indicating a progressive decrease of the marine influence at the area, evolving an intertidal to a supratidal zone, following a decrease of local sea level during the late Holocene. This data contributes to a better understanding of the late Pleistocene environment evolution in the southeastern Brazilian coast

Os locais de estudo estão situados no PETAR – Parque Estadual Turístico do Alto Ribeira e PEI – Parque Estadual Intervales, na região do sudeste do Brasil. A área é caracterizada pela presença de vegetação nativa de Floresta Atlântica e dois lagos naturais conhecidos por Lagoa Grande E Lagoa Vermelha, onde foram coletados três testemunhos sedimentares. Análises químicas (C, N, mineralogia), isotópicas (12C, 13C e 14C) e biológicas (palinologia) foram usadas nesse estudo para entender a história da paleovegetação da região durante o Pleistoceno tardio e o Holoceno, assim como suas relações com as mudanças climáticas. Amostras de solo foram coletadas a partir de trincheiras e tradagens em dez locais sob vegetação de floresta natural no PETAR e no PEI. Os dados isotópicos (&#948;13C) da matéria orgânica do solo em dois pontos do PETAR mostraram valores de &#948;13C mais enriquecidos ( -17,1%0 e -20,1%0) nas camadas mais profundas, indicando a presença de uma vegetação menos densa que a atual, com uma provável mistura de plantas C3, e C4, no período de ~30.000 a 16.000 anos AP, sugerindo a presença de um clima mais seco. De ~16.000 anos AP até o presente um empobrecimento isotópico significativo (até -28,3 %0) foi observado em todos os locais, indicativo de expansão da floresta, provavelmente associada à presença de um clima mais úmido que no período anterior. Os dados isotópicos (&#948;13C) dos solos de PEI indicam a presença de vegetação de floresta desde ~14.000 anos AP, exceto em um local (SAI) onde valores de &#948;13C mais enriquecidos (-21,8 %0) foram observados, relacionados provavelmente à mistura de plantas C3 e C4 e/ou à presença de uma vegetação de floresta menos densa em ~14.000 anos AP. A partir dos resultados da matéria orgânica sedimentar do testemunho da Lagoa Grande foi verificado que as condições ambientais foram relativamente estáveis durante os últimos 1000 anos, caracterizados pela presença de plantas C3, e fitoplâncton, sugerindo condições climáticas úmidas e que o lago provavelmente não se apresentou seco durante o último milênio. Condições ambientais para a Lagoa Vermelha também foram relativamente estáveis durante os últimos 4500 anos, caracterizadas pela presença significativa de plantas C3 na matéria orgânica sedimentar indicando condições climáticas úmidas. Mudanças na composição da vegetação foram registradas pela palinologia durante o período de ~1400 a 1100 anos AP, relacionadas a presença de um provável clima frio que o atual. / The study sites are in the PETAR - Parque Estadual Turístico do Alto Ribeira and PEI - Parque Estadual Intervales, in the southeastern region of Brazil. The area is characterized by the presence of the native vegetation of Atlantic forest and two natural lakes called LAgoa Grande and Lagoa Vermelha, where three sediment cores were collected. Chemical (C, N and mineralogy), isotope (12C, 13C and 14C), and biological (pollen analyses) tools were used in the study to understand the palaeovegetation history of the region during the late Pleistocene and Holocene and its relation to climate changes. Soils samples were collected from trenches and by drilling at five locations under natural forest vegetation in the PETAR and PEI study sites.The isotope data (&#948;13C)collected in soil at two locations in the PETAR area showed much more enriched &#948;13C values ( -17,1%0 and -20,1%0)in the deeper horizons, indicating the presence of a less dense vegetation than the present modern day, with a probable mixture of C3 and C4 plants, in the period of ~30.000 to ~16.000 years BP. This pattern suggested the presence of a drier climate. From ~16.000 years BP to the present, a significant isotopic depletion (up to -28,3 %0)was observed in all sites indicating an expansion of the forest, probable associated to the presence of a more humid climate than the previous period. The isotope results (&#948;13C) collected at the PEI soils indicated the presence of forest vegetation since ~14.000 years BP, except in one location (SAI), where more enriched &#948;13C values (-21,8 %0) were observed probable related to mixture of C3 e C4 plants, and/or a presence of a less dense forest vegetation around ~14.000 years BP. From the results of the sediment organic matter compositions of LAgoa Grande, it was verified that the environmental conditions were relatively stable during the last 1000 years, characterized by the presence of C3 plants and phytoplankton, suggesting humid climaticconditions and the lake probable wasn't dry during the last millennium. Environmental conditions for the Lagoa Vermelha were also relatively stable during the last 4500 years, characterized by the significant presence of C3 plants in the sediment organic matter indicating humid climatic conditions. The changes in vegetation composition recorded by palynology during the period of ~1400 to 1100 years BP can be related to existence of a probable colder climate than today.

Le démantèlement des réacteurs Uranium Naturel Graphite-Gaz (UNGG), tous arrêtés depuis 1994, génèrera 23 000 tonnes de déchets de graphite de Faible Activité et Vie Longue (FAVL), contenant notamment du 14C. Le but de ce travail de thèse est d’étudier un procédé original d’extraction sélective de ce radionucléide par carboxy-gazéification. L’organisation multi-échelle des graphites vierge et irradié a été étudiée par un couplage entre microspectrométrie Raman et microscopie électronique à transmission. Avec la fluence neutronique, la structure se dégrade et la nanostructure peut être fortement modifiée. Dans les cas extrêmes, la nanostructure lamellaire du graphite nucléaire est devenue nanoporeuse. En outre, ces dégâts sont systématiquement hétérogènes. Un effet d’orientation des « cristallites », mis en évidence expérimentalement par implantation ionique, pourrait être une cause de ces hétérogénéités. Cette étude a également montré qu’à partir d’une certaine fluence, l'apparition importante de zones nanoporeuses coïncide avec une augmentation spectaculaire de la concentration en 14C. Ce radionucléide pourrait donc être préférentiellement concentré dans ces zones nanoporeuses qui sont potentiellement plus réactives que les zones restées lamellaires et a priori moins riches en 14C.Ce procédé par carboxy-gazéification a d'abord été testé sur des matériaux « analogues » non radioactifs (graphites broyés mécaniquement). Ces essais ont confirmé, pour des températures entre 950 et 1000 °C, l’élimination sélective et complète des zones nanoporeuses. Des tests ont alors été réalisés sur des déchets de graphite provenant des réacteurs Saint-Laurent-des-Eaux A2 et G2. Les résultats sont prometteurs avec notamment un quart du 14C extrait pour seulement quelques pourcents de perte de masse. Jusqu’à 68 % du 14C a pu être extrait, mais au prix d’une gazéification plus importante. Ce traitement permettrait donc d’extraire sélectivement une part du 14C (mobile ou lié à des zones nanoporeuses) et d’imaginer des scénarios alternatifs de gestion de ces déchets de graphite. / The decommissioning of French gas cooled nuclear reactors (UNGG), all arrested since 1994, will generate 23,000 tons of graphite waste classified Low Level and Long Lived and notably containing 14C. The aim of this thesis is to study a new method for selective extraction of this radionuclide by CO2 gasification.The multiscale organization of virgin and irradiated graphite has been studied by a coupling between microspectrometry Raman and transmission electron microscopy. With the neutron fluence, the structure degrades and the nanostructure can be greatly changed. In extreme cases, the lamellar nanostructure nuclear graphite has become nanoporous. Furthermore, these damages are systematically heterogeneous. An orientation effect of "crystallites", shown experimentally by ion implantation, could be a cause of these heterogeneities.This study also showed that from a specific fluence, there is an important development of nanoporous zones coinciding with a dramatic 14C concentration increase. This radionuclide could be preferentially concentrated in the nanoporous areas which are potentially more reactive than the remaining laminar areas which could be less rich in 14CThis process by CO2 gasification was firstly tested on "analogous" non-radioactive materials (mechanically milled graphite). These tests confirmed, for temperatures between 950 and 1000 °C, the selective and complete elimination of nanoporous areas.Tests were then carried out on graphite waste from Saint-Laurent-des-Eaux A2 and G2 reactors. The results are promising with notably the quarter of 14C inventory extracted for a weight loss of only few percent. Up to 68 % of 14C inventory was extracted, but with an important gasification. Thus, this treatment could allow extracting selectively a share of 14C inventory (mobile or linked to nanoporous areas) and allows imagining alternative scenarios for graphite waste managing.

Para o presente trabalho, três testemunhos foram amostrados nos manguezais João Cardoso (JC), Ipaneminha (IPA) e Perequê (PE), localizados na face norte da llha do Cardoso. Estudo interdisciplinar envonveldo descrições faciológica, análise granulométrica, datação 14C, análises isotópicas e elementares de C e N e palinologia foram realizados com o objetivo de descrever a evolução sedimentar e da vegetação, com inferâncias climáticas. Entre 250 a 166 cm, o testemunho JC é composto de areia média creme-acinzentada base gradando para areia muito-fina cinza, com idades de 33.000 (198cm) e 29.400 anos cal. A.P. (166cm), carbono orgânico total (COT) de 0,044 a 0,633%, nitrogênio total (NT) de 0,002 a 0,017%, C/N de 7 a 30, \'delta\'13C de -18,49 a -24,46%o e \'delta\'15N de 2,48 a 8,13%o), indicativos de matéria orgânica terrestre de plantas C3 e C4 e algas/fitoplâncton. A palinologia mostra predomínio de elementos arbóreos dos táxons Alchornea, Drymis, Ilex, Myrsine, Myrtaceae, Podocarpus e Weinmannia (até 10%, cada) e esporos de Cyathea e Polypodiaceae (30%), característico de clima frio e úmido. De 166 a 70 cm a fácies apresenta areia média com estratificação cruzada plano-paralela marcada por areia/argila cinza escura, indicando ambiente praial de inframaré. Esta camada representa um hiato de ~27.000 anos cal. A.P. de sedimentação original, provavelmente erodidos durante transgresão Santos. Os testemunhos IPA e PE apresentam camada semelhante, iniciando na base (170 e 140cm, respectivamente), até aprox. 60 cm. A 163 cm no testemunho IPA foi obtida idade de ~2200 anos AP e ausência de palinomorfos. Sobre a camada da areia, nos três testemunhos, depositam-se sedimentos arenosos/argilosos bioturbados, com abundantes fragmentos/raízes vegetais e conchas. A partir de ~850 anos cal. A.P. (testemunho IPA - 50cm), a variação nos valores elementares e isotópicos de C e N indicam a substituição do predomínio de M.O. fitoplanctônica para M.O. de plantas C3, ainda com influência do fitoplâncton (COT: 0,15 a 12,8%; NT: 0,01 a 0,48%; \'delta\'13C: - 21,00 até - 29,00%o; \'delta\'15N: 8,00 a 3,40%o). A palinologia mostra um padrão semelhante nos três testemunhos. Os táxons Alchornea, Arecaceae, Fabaceae, Hedyosmum, Myrsine, Myrtaceae, Podocarpus, Sloanea, Weinmannia são os mais representativos entre os arbóreos (até 10%). Esporos de Cyathea e Polypodium e grãos de pólen de Poaceae e Cyperaceae correspondem a aprox. 30% da soma total, pouco variando. Estes valores indicam a presença das formações da Floresta Atlântica e da Restinga na região durante todo o período. O táxon Rhizophora sofre aumento neste período de 5 para até 22% nos dias atuais. Infere-se presença de manguezal na região e seu subsequente estabelecimento no local. Palinoforaminíferos e dinocistos são abundantes (até 15%) na base da camada, diminuindo em frequência para o topo (4%). Estes dados mostram uma progressiva diminuição na influência marinha, evoluindo de ambientes intermaré para ambiente de supramaré, devido à redução do nível marinho local durante o Holoceno tardio. Estes dados contribuem para o entendimento da evolução paleoambiental no litoral sul do Estado de São Paulo desde o Pleistoceno Tardio / For the present work, three cores where sampled on the \"João Cardoso (JC)\", \"Ipaneminha (IPA)\" and \"Perequê (PE)\" mangroves, located at the northern face of the Cardoso Island. A interdisciplinary study involving facies, radiocarbon dating, elementary and isotopic carbon and nitrogen, granulometric and palynological analysis were carried with the objective of describing the vegetation and sedimentary evolution, with climatic inferences. Between 250 and 166 cm, the JC core is primarily constituted by grayish medium sand progressing to very fine sand, with ages of ~33.000 (198cm) and ~29.450 (166) cal yr AP. Total Organic Carbon (TOC) of 0,044% to 0,633%, Total Nitrogen (NT) of 0,001 to 0,017%, C/N ratios of 7 to 30, \'delta\'13C of -18,49 to -24,46%o and \'delta\'15N of 2,48 to 8,13%o indicates mixture of C3and C4 terrestrial plants and phytoplantonic sources. Palynology show predominance of the arboreal elements Alchornea, Drymis, Ilex, Myrsine, Myrtaceae, Podocarpus e Weinmannia (up to 10% of total, each) , Cyathea and Polypodium spores (up to 20%), caracteristic of humid and cold climate. From 166 to 70 cm the facies show plane-paralell cross-bedded stratification marked by dark gray medium sand, indicating an inter-tidal environment. This layer represents a hiatus of ca. ~27.000 yr of original sedimentation, probably eroded on the Santos marine transgression. Cores IPA and PE presents similar facies at their bases (170 and 140 cm, respectively) up to near 60 cm. At 163 cm, the IPA core shows age of ~2.000 cal yr AP, and no palynomorphs. On top of this sandy facies are layers of sandy/silty/clayey bioturbated sediments, with an abundance of root, shells and plant debris. Since . ~850 cal yr AP, the isotopic and elementary values show a gradual substitution of the phytoplanctonic source of the sedimentary organic matter to a terrestrial C3 plant source on the three cores. Palynology also shows a similar pattern between the three records?, with Alchornea, Arecaceae, Fabaceae, Hedyosmum, Myrsine, Myrtaceae, Podocarpus, Sloanea, Weinmannia taxons the most well represented between the trees, with Cyathea e Polypodium, Poaceae e Cyperaceae with up to 30% of the total. These are characteristic of the Pluvial and sandbank forests. Rhizophora show an increase in this period from 5 to 22%, indicating the establishment and evolution of the mangrove vegetation on the area since ~850 cal yr AP. Palinoforaminifera and dinocyst show a diminishing pattern (from 15 to 4%) through this period, indicating a progressive decrease of the marine influence at the area, evolving an intertidal to a supratidal zone, following a decrease of local sea level during the late Holocene. This data contributes to a better understanding of the late Pleistocene environment evolution in the southeastern Brazilian coast

Os locais de estudo estão situados no PETAR – Parque Estadual Turístico do Alto Ribeira e PEI – Parque Estadual Intervales, na região do sudeste do Brasil. A área é caracterizada pela presença de vegetação nativa de Floresta Atlântica e dois lagos naturais conhecidos por Lagoa Grande E Lagoa Vermelha, onde foram coletados três testemunhos sedimentares. Análises químicas (C, N, mineralogia), isotópicas (12C, 13C e 14C) e biológicas (palinologia) foram usadas nesse estudo para entender a história da paleovegetação da região durante o Pleistoceno tardio e o Holoceno, assim como suas relações com as mudanças climáticas. Amostras de solo foram coletadas a partir de trincheiras e tradagens em dez locais sob vegetação de floresta natural no PETAR e no PEI. Os dados isotópicos (&#948;13C) da matéria orgânica do solo em dois pontos do PETAR mostraram valores de &#948;13C mais enriquecidos ( -17,1%0 e -20,1%0) nas camadas mais profundas, indicando a presença de uma vegetação menos densa que a atual, com uma provável mistura de plantas C3, e C4, no período de ~30.000 a 16.000 anos AP, sugerindo a presença de um clima mais seco. De ~16.000 anos AP até o presente um empobrecimento isotópico significativo (até -28,3 %0) foi observado em todos os locais, indicativo de expansão da floresta, provavelmente associada à presença de um clima mais úmido que no período anterior. Os dados isotópicos (&#948;13C) dos solos de PEI indicam a presença de vegetação de floresta desde ~14.000 anos AP, exceto em um local (SAI) onde valores de &#948;13C mais enriquecidos (-21,8 %0) foram observados, relacionados provavelmente à mistura de plantas C3 e C4 e/ou à presença de uma vegetação de floresta menos densa em ~14.000 anos AP. A partir dos resultados da matéria orgânica sedimentar do testemunho da Lagoa Grande foi verificado que as condições ambientais foram relativamente estáveis durante os últimos 1000 anos, caracterizados pela presença de plantas C3, e fitoplâncton, sugerindo condições climáticas úmidas e que o lago provavelmente não se apresentou seco durante o último milênio. Condições ambientais para a Lagoa Vermelha também foram relativamente estáveis durante os últimos 4500 anos, caracterizadas pela presença significativa de plantas C3 na matéria orgânica sedimentar indicando condições climáticas úmidas. Mudanças na composição da vegetação foram registradas pela palinologia durante o período de ~1400 a 1100 anos AP, relacionadas a presença de um provável clima frio que o atual. / The study sites are in the PETAR - Parque Estadual Turístico do Alto Ribeira and PEI - Parque Estadual Intervales, in the southeastern region of Brazil. The area is characterized by the presence of the native vegetation of Atlantic forest and two natural lakes called LAgoa Grande and Lagoa Vermelha, where three sediment cores were collected. Chemical (C, N and mineralogy), isotope (12C, 13C and 14C), and biological (pollen analyses) tools were used in the study to understand the palaeovegetation history of the region during the late Pleistocene and Holocene and its relation to climate changes. Soils samples were collected from trenches and by drilling at five locations under natural forest vegetation in the PETAR and PEI study sites.The isotope data (&#948;13C)collected in soil at two locations in the PETAR area showed much more enriched &#948;13C values ( -17,1%0 and -20,1%0)in the deeper horizons, indicating the presence of a less dense vegetation than the present modern day, with a probable mixture of C3 and C4 plants, in the period of ~30.000 to ~16.000 years BP. This pattern suggested the presence of a drier climate. From ~16.000 years BP to the present, a significant isotopic depletion (up to -28,3 %0)was observed in all sites indicating an expansion of the forest, probable associated to the presence of a more humid climate than the previous period. The isotope results (&#948;13C) collected at the PEI soils indicated the presence of forest vegetation since ~14.000 years BP, except in one location (SAI), where more enriched &#948;13C values (-21,8 %0) were observed probable related to mixture of C3 e C4 plants, and/or a presence of a less dense forest vegetation around ~14.000 years BP. From the results of the sediment organic matter compositions of LAgoa Grande, it was verified that the environmental conditions were relatively stable during the last 1000 years, characterized by the presence of C3 plants and phytoplankton, suggesting humid climaticconditions and the lake probable wasn't dry during the last millennium. Environmental conditions for the Lagoa Vermelha were also relatively stable during the last 4500 years, characterized by the significant presence of C3 plants in the sediment organic matter indicating humid climatic conditions. The changes in vegetation composition recorded by palynology during the period of ~1400 to 1100 years BP can be related to existence of a probable colder climate than today.