The oil industry is the richest and most influential industry in the world. The industry has moved the fates of nations. Oil is required to fight wars and exert power, and the restriction of this energy source is paramount to the restriction of movement, control, and in the end, power. Management of this resource and the tax revenue it generates are of serious strategic importance, both domestically and internationally. Understanding the results of taxation for this important commodity is important to international relations as well. The tax system affects tax revenue, government actions, oil company actions, and the oil supply itself. Each of these is important to international relations.

Abstract Purpose: The United States has the highest rate of teen pregnancy of any industrialized nation. Adolescents who have their first sexual intercourse at a young age are at increased risk for teen pregnancies and acquiring a sexually transmitted disease. This study examines predictors of early onset sexual intercourse in male and female residents of the United States. Methods: A nationally representative sample of N=7,643 females and N=4.928 males ages 15-44 was procured from the 2002 National Survey of Family Growth (NSFG), Cycle 6. Age at first sexual intercourse was used to define early onset of sexual debut(<18 years). Socio-demographic and behavioral characteristics of the respondents, demographic and selected reproductive characteristics of the respondent's parents were examined using multiple logistic regression modeling. Results: Non-fispanic black, being raised without both parents, having a mother less than 18 years old at the age of first birth and age difference between partners were significant predictors of early onset of sexual intercourse for both males and females. Maternal education less than high school was a significant protective factor for female respondents [OR=0.72 (95%CI=0.58- 0.90)] and paternal education completed high school only [OR=1.4 (95% CI=l. 1-1.7)] was a significant risk factor for male respondents. Conclusions: Racelethnicity, age difference between partners, not being raised by both parents, having a mother who had her first birth before the age of 18 and parental education are important predictor variables. Further study should be conducted to investigate the protective effect of lack of maternal education for female respondents. Intervention programs for teen pregnancy and sexually transmitted infection prevention should target these at risk groups.

[pt] Por muito tempo, os sistemas de medição dinâmica de petróleo não foram usados para a transferência de custódia. Eles eram utilizados basicamente para fins operacionais, como detectar vazamentos e transferências internas. O aumento progressivo dos preços do barril de petróleo exigiu das medições de petróleo uma incerteza cada vez menor, o que provocou o desenvolvimento de novas tecnologias que resultaram em sistemas dinâmicos de medição de alta precisão a serem utilizados na transferência de custódia. Nesta pesquisa foi avaliada a substituição das medições estáticas por medições dinâmicas no faturamento de exportações marítimas de petróleo, com o objetivo de agilizar as operações de carregamento de navios em píeres diminuindo a indisponibilidade dos recursos logísticos envolvidos, de minimizar a exposição da companhia a perdas financeiras devido a faturamentos errôneos e de verificar que essa diminuição da exposição justifica o investimento em sistemas de medição dinâmica. Foram descritas as medições de tanques de terra, as medições de tanques de navio e os sistemas de medição dinâmica, avaliando procedimentos, equipamentos, além de restrições, problemas e incertezas associadas a cada método. Foi dada atenção especial aos procedimentos de arqueação de tanques para armazenamento de granéis líquidos, comparando procedimentos utilizados no Brasil pelo Inmetro aos requisitos da Norma ISO -7507, e a rastreabilidade metrológica dos equipamentos de medição em relação aos procedimentos utilizados na sua calibração. / [en] For many years, dynamic measurement systems have not been used in the petroleum industry for custody transfer applications, only for operational reasons like detecting leaks and internal transfers. The progressive growth of crude oil prices required measurements with a smaller uncertainty, leading to developing news technologies, resulting in high accuracy flow meters to be used in custody transfer. The main objective of this research was evaluate the replacement of static measurements by dynamic measurements in oil exports sales in order to speed up the loading of vessels, decreasing the unavailability of logistical resources involved, to minimize the company s exposure to economic losses due to erroneous bill of ladings and verify if this justifies the investment in dynamic measurement systems. This research has discussed a number of issues associated with the uncertainty of the shore tanks, vessels tanks and dynamic measurements, evaluating procedures, equipment, and restrictions, problems and accuracy associated with each method. It also included a discussion about the difference between calibration of vertical cylindrical tanks procedures used in Brazil by Inmetro and the requirements of ISO -7507, and about traceability of measuring equipment calibration.

Este estudo investigou a aplicação de um AnSBBR com recirculação da fase líquida tratando água residuária a base de glicerina (efluente do processo de produção de biodiesel) para a produção de biohidrogênio, sendo o desempenho do biorreator avaliado de acordo com a influência conjunta do tempo de alimentação, do tempo de ciclo e da concentração afluente. O biorreator teve um volume de meio tratado por ciclo de 1,5 L, volume residual de meio de 2,0 L e volume de suporte inerte com biomassa de 2,1 L, sendo mantido a 30°C durante todo o estudo. O trabalho foi divido em três fases: a Fase I foi realizada para determinar os melhores parâmetros de operação do reator (tipo de inóculo, tipo de glicerina, tipo de suporte, concentração de NaHCO3 e velocidade ascensional) para dar seguimento com a Fase II que estudou apenas o efeito da concentração do afluente, tempo de ciclo e tempo de enchimento. Os parâmetros utilizados na Fase II foram: lodo de abatedouro de aves pré-tratado por HST (Heat Shock Treatment 90°C por 10 minutos) como inóculo, glicerina pura comercial para eliminar interferência de possíveis resíduos, suporte de PEBD (polietileno de baixa densidade) e 100 mg.L-1 de NaHCO3. Na Fase II, foram aplicadas 6 condições experimentais com cargas orgânica volumétrica (COVAS) de 7,7 a 17,1 gDQO.L-1.d-1, combinando diferentes concentrações afluentes (3000, 4000 e 5000 mgDQO.L-1) e tempos de ciclo (4 e 3 h), sendo o tempo de alimentação igual a metade do tempo de ciclo. Os resultados mostraram que houve baixa remoção de DQO (máximo de 38% para amostras filtradas) e que houve predomínio do ácido acético e do ácido butírico em todas as condições. O aumento da XV concentração do afluente e a diminuição do tempo de ciclo favoreceram a produtividade e rendimento molares de hidrogênio nas condições investigadas. O ensaio com melhores resultados foi com carga orgânica de 17,1 gDQO.L-1.d-1 no qual obteve-se 100,8 molH2.m-3.d-1 e 20,0 molH2.kgDQO-1, com 68% de H2 e apenas 3% de CH4 no biogás. Na Fase III, determinou-se a influência do pré-tratamento do inóculo e a viabilidade do sistema tratando glicerina bruta industrial, sendo verificado que o pré-tratamento do lodo por HST melhora ligeiramente a produtividade e rendimento do processo e o uso da glicerina bruta industrial diminuiu consideravelmente a quantidade e qualidade do biogás obtido. / This study investigated the feasibility of an AnSBBR with recirculation of the liquid phase treating glycerin-based wastewater (effluent from biodiesel production process) on biohydrogen production; the performance of the bioreactor was evaluated according the combined influence of fill time, cycle period and influent concentration. The bioreactor had 1.5L of feeding volume per cycle, 2.0 L of residual medium, 2.1 L of inert support and biomass and it was kept at 30°C. This study was divided into three phases. Phase I was conducted to determine the best operational parameters for the reactor (type of inoculum, type of glycerin, type of support for biomass, NaHCO3 concentration and upflow velocity), so Phase II would use these parameters to study only the influence of affluent concentration, cycle time and filling time. The parameters used in Phase II were: sludge from poultry slaughterhouse pretreated by HST (Heat Shock Treatment 90°C for 10 minutes) as inoculum, pure glycerin so there would be no interferences from possible residues, LDPE (low density polyethylene) support, 100 mg.L-1 of NaHCO3 and 10.6 m.h-1 of upflow velocity. Phase II was operated under six conditions with different AOLRS ranging from 7.7 to 17.1 gCOD.L-1.d-1, obtained by the combination of different influent concentrations (3000, 4000 and 5000 mgCOD.L-1) and cycle periods (4 and 3 h), the filling time was equal to half of the cycle lenght. The results showed low COD removal (maximum of 38% for filtrated samples) and high concentrations of acetic acid and butyric acid in all conditions. Increasing the affluent concentration and decreasing the cycle length improved the molar productivy and hydrogen yield in the XVII investigated conditions. The condition with better results was the one operated with 17.1 gCOD.L-1.d-1 of AVOL, it reached 100.8 molH2.m-3.d-1 and 20.0 molH2.kgCOD-1, with 68% of H2 and only 3% of CH4 in its biogas. Phase III determined whether there is a real influence on the pretreatment of the sludge and the feasibility of this system treating industrial glycerin, the results show that the pretreatment of the sludge by HST slightly improves the productivity and the process yield and the wastewater made from industrial glycerin substantially decreased the quantity and the quality of the biogas generated.

Neste trabalho foram desenvolvidos métodos eletroanalíticos (redissolução potenciométrica e voltamétrica) para a determinação de metais (mercúrio, cobre, chumbo e zinco) em petróleo, óleo diesel, óleo lubrificante e álcool combustível. Para analisar álcool, foi também desenvolvido um método por eletroforese capilar, que possibilita a determinação de cátions (sódio, potássio e cálcio) e ânions (cloreto, sulfato e nitrato). Procedimentos envolvendo a utilização de fornos de microondas (focalizadas - que opera a pressão atmosférica - e com cavidade, que promove a digestão em frascos pressurizados) para a decomposição de petróleo, óleo diesel e óleo lubrificante são descritos. As determinações de cobre e mercúrio por redissolução potenciométrica apresentaram melhores limites de detecção do que a voltametria de redissolução de onda quadrada nas amostras digeridas, utilizando eletrodos de ouro confeccionados a partir de CDs graváveis (Cdtrodos), como eletrodo de trabalho. Para a determinação de chumbo e zinco nas mesmas amostras digeridas, os melhores resultados foram obtidos com eletrodos de filme de mercúrio e utilizando a voltametria de redissolução potenciométrica. Perdas de mercúrio por volatilização foram verificadas quando as amostras foram digeridas em fornos de microondas focalizadas. Para os demais metais, a utilização deste forno foi vantajosa por proporcionar melhores limites de detecção devido à utilização de maiores massas de amostra no processo de digestão. A utilização de um banho ultrassônico de bancada para promover a extração de cobre e chumbo de óleos lubrificantes na presença da mistura 1:1 (v/v) de HClconc. e H2O2 (30% m/v) mostrou-se eficiente. Trinta minutos de exposição à energia ultrassônica foram necessários para a extração quantitativa de ambos os metais. Nas soluções extratoras, o teor dos metais foi determinado por voltametria de redissolução anódica, usando CDtrodos. Os limites de detecção do método para a determinação de cobre e chumbo foram, respectivamente, de 23 e 67 ng g-1 de óleo, aplicando 120 s de tempo de deposição. A voltametria de redissolução anódica em eletrodo de ouro possibilitou a determinação de cobre e chumbo em álcool combustível, sem qualquer tratamento prévio das amostras. Limites de detecção de 120 e 235 ng L-1 para cobre e chumbo, respectivamente, foram obtidos aplicando 15 min de tempo de deposição. Alternativamente, a evaporação do etanol seguido da redissolução em água desionizada permitiu a determinação dos metais por análise de redissolução. Todos os resultados obtidos utilizando diferentes metodologias de decomposição de amostras foram comparados com os resultados obtidos por análises por espectrometria de absorção atômica com forno de grafite. O método envolvendo a evaporação prévia, seguida da redissolução dos íons em meio aquoso também se mostrou muito favorável para realizar a determinação de cátions e ânions por eletroforese capilar em amostras de etanol hidratado combustível. Os íons Na+, K+ e Ca2+, Cl-, NO3- e SO42- foram encontrados nas amostras analisadas. Os limites de detecção destes íons se encontram na faixa de 0,06 e 0,18 mg L-1. / In this work eletroanalytical methodologies (potentiometric stripping analysis and anodic stripping voltammetry) for the determination of metals (mercury, copper, lead, and zinc) in crude oil, lubricating oil, diesel fuel, and ethanol fuel are proposed. A capillary electrophoresis method for ethanol fuel was developed to determine cations (sodium, potassium, and calcium) and anions (chloride, sulphate, and nitrate). Microwave digestion methods using different ovens (a focused microwave oven – operating at atmospheric pressure, and a cavity microwave oven, which employs pressurized vessels) for crude oil, lubricating oil, and diesel fuel are described. The determination of copper and mercury by potentiometric stripping analysis presents better detection limits than stripping voltammetric determinations for the digested sample analysis. Loss of mercury by volatilization was verified when samples were digested in the focused microwave oven. Otherwise, this oven presented some advantages for the other metals, as the improved detection limits due to the employment of higher sample mass for the digestion process. The use of a ultrasonic bath to promote the extraction of copper and lead from lubricating oils in the presence of 1:1 (v/v) HClconc and H2O2 (30% m/v) was efficient. Thirty minutes of ultrasonic exposure were necessary for quantitative exctraction of copper and lead. Anodic stripping voltammetry using gold CDtrodes was applied for metal determination in the extracted solutions. The detection limits of the proposed method for copper and lead were 23 and 67 ng g-1, respectively, under application of 120 seconds as deposition time. Anodic stripping voltammetry at a gold electrode was used for the determination of copper and lead in ethanol fuel, without any prior sample treatment. Detection limits of 120 and 235 ng L-1 for copper and lead, respectively, were attained applying 900 s as deposition time. Alternatively, the ethanol evaporation followed by re-suspension in deionised water allowed the metals determination by stripping analysis. All results obtained for sample decomposition methods were compared with the ones obtained by electrothermal atomic absorption spectrometric determinations. The method, which employs prior ethanol evaporation followed by re-suspension in deionised water, was applied for the determination of cations and anions by capillary electrophoresis in the hydrated ethanol fuel (automotive fuel). Na+, K+, Ca2+, Cl-, NO3-, and SO42- ions were found in the analyzed samples. The detection limits for these ions were situated between 0.06 and 0.18 mg L-1.

Die zunehmend kritische Betrachtung von Tierhaltungssystemen durch den Verbraucher erfordert eine wissenschaftliche Bewertung der Tiergerechtheit und der arteigenen Bedürfnisse von Nutztieren. Konventionelle ballaststoffarme Schweinemastfutter entsprechen nicht den ethologischen und ernährungsphysiologischen Ansprüchen der Tiere. Verhaltensstörungen sind daher bei Schweinen verbreitet. Der gewählte Forschungsansatz geht davon aus, dass eine erhöhte Befriedigung der Fressmotivation durch rohfaserreiche Futtermittel hier Abhilfe schaffen kann. Daher wurden je 14 Börge über eine Mastperiode mit einer lignocellulosehaltigen Ration gefüttert und mit einer konventionell gemästeten Tiergruppe verglichen. Die Futteraufnahme der Tiere wurde am Fressplatz mit RFID-Respondern registriert. Dabei zeigte sich, dass rohfaserreich gefütterte Schweine langsamer, länger und seltener fraßen und insgesamt weniger Futter aufnahmen. Das lässt auf ein erhöhtes Sättigungsgefühl der Tiere schließen. Das Aktivitäts- und Erkundungsverhalten wurde durch eine Kombination verschiedener Methoden gemessen. Videoanalysen belegten, dass die Tiere beider Gruppen etwa gleich lang ruhten. Die Rohfasertiere zeigten sich dabei weniger empfindlich gegenüber der Umgebungstemperatur. Die Erkundungsintensität, die mittels Respondern gemessen wurde, war ebenfalls nicht durch das Futter beeinflusst. Rohfaserreich gefütterte Schweine zeigten allerdings weniger Interesse an einem Spielzeug und weniger agonistische Auseinandersetzungen. Die Konkurrenz am Futterautomaten war wegen der längeren Fresszeit jedoch erhöht. Vermutlich war die Haltungsumwelt nicht geeignet, bestimmte Unterschiede im Verhalten der Schweine festzustellen. Die Rohfasertiere wuchsen langsamer als die Kontrolltiere, hatten jedoch Schlachtkörper mit erhöhtem Muskelfleischanteil. Die Futterverwertung unterschied sich nicht. Rohfaserreiches Futter verbessert offensichtlich beim Mastschwein die Sättigung und erhöht das Tierwohl. / Animal welfare is of growing importance to consumers of animal products. The development of animal-friendly housing systems and the research on the animal’s requirements are thus aspects of interest. Conventional feeds for fattening pigs are poor in dietary fibre and do not meet the ethologic and nutritional physiologic needs of pigs. This presumably this leads to misdirected behaviour and behavioural disorders, which are widespread in growing pigs. Numerous studies indicate that fibrous feed causes a higher satiation. The thesis on hand is based on the approach that a high level of crude fibre for fattening pigs leads to a reduced motivation to feed and to explore and thus provides relief to the animals. To investigate this, groups of 14 castrated male pigs were fed with a ration containing lignocelluloses during an entire fattening period and were compared to conventionally fed pigs. The feeding pattern of the animals was recorded using RFID responders. Pigs receiving high-fibre feed ate slower, longer and less often and consumed less feed than control pigs. This indicated an improved satiation. Activity and explorative behaviour was measured using various methods. Video analysis showed that both groups performed the same amount of resting behaviour. When choosing a place to rest, high-fibre pigs were less sensitive to their ambient temperature. The intensity of exploration, which was RFID-recorded, was not influenced by the feed. However, high-fibre pigs showed less interest in a toy and less agonistic behaviour. The competition at the feeders was higher, probably because of the prolonged feeding time. Presumably the housing conditions were not suitable for the detection of differences in explorative behaviour between high-fibre and control groups. High-fibre pigs fattened less than control pigs, but delivered better carcasses. The feed conversion was the same for both groups. Fibrous feed apparently enhances satiety in growing pigs and improves animal welfare.

Cette thèse étudie des systèmes locaux de gestion de transfert de pétrole ayant une architecture de réseau de canalisation. Pour leur représentativité, deux systèmes localisés au Venezuela et appartenant à l'entreprise PDVSA (Pétroles du Venezuela) ont été retenus pour illustrer les méthodes proposées et les valider : le Terminal Maritime de Pétrole de Guaraguao et le Centre de Stockage de Punta de Palmas. Dans ces réseaux des connexions, appelées « alignements », sont établies en ouvrant/fermant des vannes à travers d'un système SCADA (Supervisory Control and Data Acquisition). Le choix d'un alignement doit tenir compte de critères d'optimisation. La minimisation des interférences avec d'autres alignements, liée à la notion de capacité opérative, a été identifiée comme le critère de choix le plus important. Les contributions de cette thèse reposent sur une modélisation sous forme de graphes, et sur des algorithmes appartenant au domaine de la recherche opérationnelle. Elles contribuent à fournir aux opérateurs de supervision des outils d'analyse permettant d'optimiser le choix des alignements. Des indicateurs permettant de quantifier l'impact des opérations d'alignement ou des défaillances, sur la capacité opérative du système, sont proposés. La minimisation de l'impact sur la capacité opérative, va correspondre à la minimisation des interférences avec des alignements potentiels. Un algorithme de calcul de ces indicateurs, est présenté, ainsi que des algorithmes de recherche de chemin, de détermination d'éléments critiques, et de recherche d'alignements utilisant des pompes. Ces algorithmes sont basés sur des algorithmes classiques s'adressant au problème du plus court chemin, du flot maximum et du nombre maximum de chemins disjoints. Cependant, ils utilisent des méthodes innovantes, comme l'ajout de contraintes considérant l'existence de sous-types d'alignements, le calcul dynamique des coûts des chemins à partir de son impact sur la capacité opérative, et la recherche de chemins via un point intermédiaire obligatoire. Les contributions sont potentiellement applicables dans des domaines autres que le transport de pétrole. Les algorithmes ont été mis en œuvre en utilisant le langage Python et ont été testés en utilisant les données réelles des réseaux étudiés. L'objectif à moyen terme de ces travaux est le développement d'un logiciel d'assistance à la prise de décision. / This thesis studies local crude oil transportation systems with a pipe network architecture. Two representative systems, belonging to PDVSA (Venezuelan oil company), have been studied: the Guaraguao Crude Oil Seaport and the Punta de Palmas Tanks Yard. In this systems, connections, called "alignments", are established by opening/closing valves using a SCADA(Supervisory Control and Data Acquisition) system. Alignment choice is made based on optimization criteria. Interferences minimization with other alignments, related to the notion of operative capacity, has been identified as the most important criterion. The contributions of this thesis are based on graph modelling and algorithms from operational research. The main goal is to provide analysis tools allowing alignment choice optimization. Indexes permitting the quantification of alignments or failures impact on the operative capacity of the system are proposed. Minimizing the impact on the operative capacity will correspond to minimizing interferences with potential alignments. An algorithm computing these indexes is presented, as well as complementary developments such as a path search algorithm, an algorithm for critical elements determination, and algorithm for alignments using pumps. These algorithms are based on classical algorithms for the shortest path problem, the maximum flow problem and the maximum disjoint paths problem. However, they use innovative methods such as adding constraints when considering alignment sub-types, the dynamic computation of path costs based on their impact on operative capacity, and path search considering an obligatory intermediate node. These contributions can potentially be applied in areas other than oil transportation. The algorithms had been implemented in Python and had been tested using real data from the studied systems. The middle term goal of these works is the development of assistance software for decision making.

Le Pb est omniprésent dans les échantillons terrestres et sa relation avec ses ascendants radioactifs, l’U et le Th, en fait un marqueur de choix des processus géodynamiques.L’équipe lyonnaise de Janne Blichert-Toft et Francis Albarède a démontré, à travers une vaste compilation de données bibliographiques accompagnée de la production de nouvelles mesures, une correspondance entre la répartition des valeurs de composition isotopique du Pb dans la croûte continentale et la localisation de figures tectoniques majeures sur plusieurs continents (Bouchet et al., 2014 ; Blichert-Toft et al., 2016 ; Delile et al., 2014). L’existence de ces "provinces géochimiques" démontre l’intérêt des isotopes du Pb comme outil pour mieux comprendre comment l’histoire tectonique d’une région façonne la géochimie de ses continents. Un premier volet de ces travaux de thèse visait à compléter la base de données existante des compositions isotopiques du Pb dans la croûte continentale européenne, grâce à l’analyse de 104 échantillons de feldspaths potassiques issus de granites principalement originaires de Catalogne, de Corse, de Galice et de Kabylie, jusqu’ici restées en blanc sur les cartes précédemment établies. Les cartes ainsi obtenues, illustrant la répartition à travers l’Europe et le bassin méditerranéen des valeurs des "paramètres géochimiques" définis par Albarède et al. (2012), exprimant à partir des rapports isotopiques du Pb mesurés l’âge modèle de la roche et les fractionnements entre l’U, le Th et le Pb enregistrés en son sein, confirment le potentiel des isotopes du Pb comme traceurs robustes de l’héritage tectonique d’une région.Mais le cœur de cette thèse a été d’appliquer cet outil reliant chimie et histoire géodynamique que sont les isotopes du Pb à un type d’échantillon géologique pour lequel des analyses de haute précision de la compositions isotopique en Pb n’avaient jamais été entreprises jusqu’à maintenant : les pétroles bruts. Pour cela, il a fallu développer une méthode analytique novatrice permettant d’extraire le Pb de quelques millilitres de pétrole brut vers une solution aqueuse adaptée aux protocoles habituels de purification indispensables à des analyses isotopiques du Pb à haute précision par MC-ICP-MS (Fetter et al., 2019). Cette méthode a ensuite été appliquée à un total de 211 échantillons de pétrole brut issus de partout dans le monde. Des échantillons de roches mères d’hydrocarbures (schistes noirs) ont également été analysés afin de compléter les premières interprétations des résultats. Ce jeu de données unique met en évidence que le Pb contenu dans les pétroles bruts résultait du mélange d’au moins trois composantes d’âges modèles distincts : le pôle le plus radiogénique a été identifié comme associé aux roches mères des pétroles, tandis que les deux autres, d’âges modèles paléozoïque et protérozoïque, suggèrent des interactions conséquentes entre le pétrole et les roches encaissantes et sous-jacentes. Un nouveau modèle de migration du pétrole depuis sa roche mère a donc été proposé (Fetter et al., soumis), prenant en compte la forte implication des eaux circulant en profondeur dans les bassins sédimentaires en faisant intervenir un phénomène grandement négligé jusqu’à maintenant : la solubilité mutuelle de l’eau et du pétrole à haute température.La mise en évidence d’une dynamique complexe du Pb dans les pétroles bruts invalide une utilisation de ces derniers comme alternative aux feldspaths potassiques pour obtenir des données isotopiques en Pb fiables sur la croûte continentale européenne située sous les bassins sédimentaires. Cependant, elle ouvre de nouvelles portes quant à l’utilisation jusqu’ici inexplorée des isotopes du Pb comme traceurs de phénomènes de pollution associés à une prospection pétrolière peu responsable. / Lead is ubiquitous in terrestrial samples and its relationship to its radioactive ascendants, U and Th, makes it a prime tracer of geodynamic processes.The team of Janne Blichert-Toft and Francis Albarède, based in Lyon (France), has demonstrated on several continents, through large compilations of literature data supplemented by new measurements, a correspondence between the distribution of Pb isotopic compositions in the continental crust and major tectonic features (Bouchet et al., 2014 ; Blichert-Toft et al., 2016 ; Delile et al., 2014). The existence of these "geochemical provinces" has firmly established the potential of Pb isotopes as a tool for understanding how the tectonic history of a given region shaped its geochemistry. A first aspect of this PhD aimed at complementing the existing database of Pb isotopic compositions of the European continental crust through the analysis of 104 K-feldspar samples separated from granites originating mainly from Catalonia, Corsica, Galicia, and Kabylie, up until this PhD blank areas on the compiled map. The resulting updated maps showing the distribution throughout Europe and the circum-Mediterranean area of the "geochemical parameters" defined by Albarède et al. (2012), which derive a model age and fractionations between U, Th, and Pb from measured Pb isotopic ratios, confirm the potential of Pb isotopes as powerful tracers of the tectonic heritage of a given region.The core of this PhD, however, was to apply this tool connecting chemistry and geodynamic history to a type of geological sample so far never analyzed for high-precision Pb isotopic compositions: crude oil. To achieve this goal, a novel analytical method was developed which allows the extraction of Pb from a few milliliters of crude oil into an aqueous solution suitable for the standard Pb purification protocol essential for high-precision Pb isotope analysis by MC-ICPMS (Fetter et al., 2019). This method was then applied to a total of 211 crude oil samples from around the world. Hydrocarbon source rocks (black shales) also were analyzed. This unique data set reveals that Pb in crude oil results from the mixing of at least three endmembers of distinct model ages: the more radiogenic endmember is identified as the oil source rocks, while the other two components, of Paleozoic and Proterozoic ages, suggest considerable interactions between crude oil and the surrounding and underlying rocks. A new model was hence proposed for oil migration (Fetter et al., submitted), taking into account the key role of deep-seated waters circulating through the sedimentary basin by calling on a long-neglected phenomenon: mutual solubility of water and oil at high temperatures.Bringing to light the complex dynamics of Pb in crude oil invalidates the use of crude oil as an alternative to K-feldspars to obtain the Pb isotopic signature of the continental crust underlying sedimentary basins. However, it opens up new promising avenues for the yet unexplored use of Pb isotopes as tracers of irresponsible oil prospection related pollution.

Analytical Characterization of complex mixtures, such as crude oil, environmental samples, and biological mixtures, is challenging because of the large diversity of molecular components. Mass spectrometry based techniques are among the most powerful tools for the separation of molecules based on their molecular composition, and the coupling of ion mobility spectrometry has enabled the separation and structural elucidation using the tridimensional structure of the molecule. The present work expands the ability of analytical chemists by furthering the development of IMS-MS instrumentation by coupling Trapped Ion Mobility Spectrometry to Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (TIMS-FT-ICR MS). The TIMS-FT-ICR MS platform combines the high-resolution separation of TIMS, which has mobility resolving powers up to 400, and ultra-high mass resolution of FT-ICR MS, with mass resolving power over 1,000,000. This instrumentation allows the assignment of exact chemical composition for compounds in a complex mixture, as well as measurement of the collision cross-section of the molecule. Herein, the principles of the TIMS separation and its coupling to FT-ICR MS are described, as well as how the platform can be applied to targeted analysis of molecules, and untargeted characterization of complex mixtures. Molecular standards were analyzed by TIMS-MS in order to develop a computational workflow that can be utilized to elucidate molecular structure, using the measured collision cross-section of the ion. This workflow enabled identification of structural, cis/trans isomers, and chelated molecules and provides the basis for unsupervised structural elucidation of a complex mixture, and in particular for the elucidation of hydrocarbons from fossil fuels. In summary, this work presents the coupling of TIMS-FT-ICR MS and provides examples of applications as a proof of concept of the potential of this platform for solving complex analytical challenges.

When plants are exposed to multiple environmental stress factors, one form of stress can affect the response to another stress. This study used seedlings of a new cultivar of wheat(Triticum aestivum L. cv. 1862), grown under factorial combinations of two levels of ultraviolet-B (UV-B)radiation, two salinity regimes and two levels of iron treatment in chelator-buffered nutrient solutions in a growth chamber. A number of morphological and physiological measurements were made. The accumulation of chlorophyll, UVabsorbing compounds and proline in shoots, as well as phytosiderophores (PSs) in root exudates were measured. Feed value measurements included crude protein, water-soluble carbohydrates, acid detergent fibre and Fe in shoots and roots. After 21 days of stress exposure, results showed that Fe deficiency and NaCl stress generally decreased plant growth and function as well as nutritive value, but increased plant biochemical protection traits such as proline accumulation (16.3 fold under salinity stress) and release of PSs (2.4 fold under Fe deficiency). Interestingly, UV-B radiation affected belowground parameters, inducing a 47% reduction in PS release, together with decreasing root DM by 9% and Fe concentration in roots by 7%. When Fe deficiency and NaCl stress were combined, the results showed a decrease in PS release by 3.5 fold compared to unstressed plants. UV-B radiation synergistically increased UV-absorbing compound levels in combination with Fe deficiency, compared to plants grown under optimal Fe levels. This stress combination also resulted in a cumulative effect by decreasing Fe concentration in shoots and roots. However, salt stress did not interact with UV-B radiation for any of the traits measured. In addition, some three-way interactions were noted, with the Fe x NaCl x UV-B stress combination slightly decreasing PS release and resulting in a cumulative effect by decreasing Fe concentration in roots. In conclusion, this study found that aboveground stress factors such as UV-B can affect important aspects of belowground plant function, and that Fe deficiency can interact with UV-B and salinity stress in modifying plant responses to either stress alone.