Ces dernières années, la mesure des isotopologues de l'eau est devenue de plus en plus importante pour les sciences de l'atmosphère. A cause de l'influence des conditions climatiques sur les rapports isotopiques, la composition isotopique de l'eau conservée dans la glace en Antarctique et en Arctique peut être utilisée comme un paléothermomètre permettant de comprendre les changements passés du climat. La mesure des variations de la composition isotopique de la vapeur d'eau dans l'atmosphère peut servir à étudier le cycle hydrologique global de la terre et à raffiner les modèles de circulation atmosphérique.Alors que la méthode conventionnelle pour la mesure des isotopes de l'eau, la Spectrométrie de Masse des Rapports Isotopiques (IRMS), n'est pas adaptée aux mesures en continu et in-situ des isotopes de vapeur d'eau, le développement récent des spectromètres laser offre une méthode simple et robuste pour effectuer des recherches sur le terrain avec une bonne résolution temporelle. Pourtant, jusqu'à présent la plupart des instruments optiques exigent des niveaux d'humidité relativement élevés avec des concentrations d'eau supérieures à 1000 ppmv, ce qui exclut les mesures dans quelques unes des régions les plus intéressantes pour l'investigation des variations isotopiques dans l'eau, telles que les couches élevées de l'atmosphère ou les régions centrales de l'Antarctique.Ce travail introduit un nouveau spectromètre laser infrarouge qui est basé sur la technique d'OFCEAS et qui a été conçu spécialement pour la mesure des quatre isotopologues H2_16O, H2_18O, H2_17O et HDO dans un environnement sec avec des concentrations d'eau de quelques centaines à seulement quelques dizaines de ppmv. L'instrument qui a été développé dans le cadre de cette thèse montre une stabilité de mesure supérieure comparée aux instruments OFCEAS précédents, avec des temps d'intégration optimaux pouvant aller jusqu'à plusieurs heures et une longueur de trajet optique effective de plus de 30 km.La performance globale de l'instrument est analysée et le problème de la dépendance des mesures isotopiques vis-à-vis de la concentration d'eau avec laquelle l'expérience est effectuée est investigué en détail. La présence d'un motif fixe spectral est identifiée comme la source principale de bruit et analysée en détail.En outre, un nouveau système de calibration pour des mesures d'isotopes de vapeur d'eau est présenté. Ce système a été développé dans le cadre de cette thèse afin de disposer d'un moyen fiable et stable pour la calibration des mesures des variations isotopiques de la vapeur d'eau. Le système de calibration est basé sur l'injection continue d'eau dans une chambre d'évaporation avec deux pousse-seringue au nanolitre. Il est capable de générer une vapeur d'eau standard entre 5 et 15000 ppmv. Une simulation modélisée de l'injection d'eau, qui est en bon accord avec les expériences, est présentée.Ensuite une première utilisation du spectromètre OFCEAS dans la station de recherche norvégienne (Troll) en Antarctique est exposée en détail. Les données enregistrées pendant une période de trois semaines de Février à Mars 2011 sont présentées et discutées, en particulier relativement aux problèmes de calibration rencontrés avec un système de calibration rudimentaire construit sur place. Pendant cette période le spectromètre a mesuré en continu les isotopologues de vapeur d'eau dans l'atmosphère sur le site de la station.Pour conclure, nous allons présenter le projet Isocloud, un projet international avec pour but d'étudier des effets de (super)saturation en utilisant la chambre à nuages AIDA du KIT en Allemagne. Notre spectromètre et le système de calibration faisaient partie de ce projet. Les données expérimentales de quatre campagnes de mesure sont présentées et des résultats préliminaires sont discutés. Nous concluons avec la discussion d'un protocole de mesure optimal et donnons des perspectives pour le futur. / In recent years, the measurement of water isotopologues has become increasingly important for atmospheric research. Due to the influence of climatic conditions on the isotope ratios, the isotopic composition of water stored in the ice in Antarctica and the Arctic can be used as paleothermometers to reconstruct past climate changes. The measurement of changes of the isotopic composition of water vapor in the atmosphere can be used to study the global hydrolocal cycle and to refine atmospheric circulation models.Whereas the conventional method for water isotope measurements, Isotope Ratio Mass Spectrometry (IRMS), is not adapted for in-situ continuous measurements of water vapor isotopes, the recent development of laser spectrometers offers a comparably easy and robust method to conduct in-the-field research with good time resolution. However, until now, most optical instruments require relative high humidity levels with water concentrations of at least several 1000 ppmv, which excludes measurements in some of the most interesting regions for water isotope research, such as the upper atmosphere and the central regions of Antarctica.In this work, we present a novel infrared laser spectrometer based on the technique OFCEAS, specifically designed to measure the four isotopologues H2_16O, H2_18O, H2_17O and HDO under very dry conditions, at water concentrations of some hundred to only tens of ppmv. The instrument developed during this thesis shows much higher measurement stability over time compared to previous OFCEAS instruments with optimum integration times of up to several hours and a very long effective path length of more than 30 km. At water concentrations around 80 ppmv, a precision of 0.8‰, 0.1‰ and 0.2‰ for d2H, d18O and d17O respectively could be achieved with an integration time of 30 to 60 min and at the optimum water concentration of ~650 ppmv, of 0.28‰, 0.02‰ and 0.07‰ respectively.An investigation of the overall performance of the instrument is presented and we specifically discuss the problem of a dependence of the isotope measurements on the water concentration at which a measurement is carried out. As main source of the concentration dependence, pattern noise is identified and a detailed analysis of the noise sources is given.Furthermore, a new calibration system for water vapor isotope measurements, the Syringe Nanoliter Injection Calibration System (SNICS), is introduced, which was developed in the framework of this thesis to offer a more reliable and stable means for the calibration of water vapor isotope measurements. This calibration system is based on the continuous injection of water into an evaporation chamber with two nanoliter syringe pumps and is able to generate standard water vapor in a range of 5 to 15 000 ppmv. A model simulation of the water injection is presented and shows a good agreement with experimental results.Subsequently, a first employment of the OFCEAS spectrometer at the Norwegian research station of Troll in Antarctica is discussed. Data from a three-week period from February and March 2011, during which the spectrometer continuously measured water vapor isotopologues in the atmosphere at the research station, is shown and problems and possibilities are discussed.Finally, the Isocloud project, an international project to study (super)saturation effects at the AIDA cloud chamber of the Karlsruhe Institute Technology in Germany, is introduced, in which we participated with both the spectrometer and the calibration instrument. Experimental data of the four measurement campaigns is presented, preliminary results are discussed. We conclude with a discussion of the optimum measurement protocol and give an outlook for the future.

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Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Este trabalho foi realizado na regiÃo do Cariri, localizada no sul do Estado do Ceara, onde se encontra a maior e mais importante reserva de agua subterrÃnea do Estado, a Bacia Sedimentar do Araripe. Nessa regiÃo, a principal fonte de agua para o abastecimento publico e privado e o recurso hÃdrico subterrÃneo armazenado no Vale do Cariri, nos aquiÃferos, Rio da Batateira, MissÃo Velha e Mauriti. Dada a importÃncia desta reserva hÃdrica, diversos trabalhos, no decorrer dos anos, tÃm sido feitos para obter informaÃÃes relevantes sobre a Ãgua subterrÃnea da regiÃo. O objetivo deste trabalho foi estudar as aguas subterrÃneas dessa regiÃo e identicar mudanÃas ocorridas durante os Ãltimos 16 anos, utilizando medidas hidroquÃmicas e medidas dos isotopos ambientais oxigÃnio-18, deutÃrio, carbono-13 e carbono-14. Para isso, foram analisadas 17 amostras de Ãgua subterrÃnea coletadas nos municÃpios de Crato, Barbalha, Juazeiro do Norte, Milagres, MissÃo Velha e Nova Olinda. Os resultados isotÃpicos mostraram que na maioria das amostras houve contribuiÃÃo de recargas recentes, caracterizando Ãguas jovens, com valores de O-18 apresentando pequenas flutuaÃÃes em relaÃÃo aos de Ãguas de chuvas atuais e com valores de pMC elevados. Entretanto, 04 amostras apresentaram mistura de aguas modernas com Ãguas nÃo modernas, paleoaguas, devido aos baixos valores de O-18 (< -4 por mil). A idade aparente das amostras de Ãguas subterrÃneas foi calculado pelo metodo de radiocarbono, utilizando um software estatÃstico de tratamento de dados, desenvolvido nesse trabalho; e as idades foram corrigidas pelos modelos de Pearson, Tamers e Vogel. Quanto aos resultados dos parÃmetros hidroquÃmicos, predominam Ãguas do tipo bicarbonatada quanto aos Ãnions e mista quanto aos cÃtions, numa relaÃÃo: rHCO3- > rCl- > rSO4 2- e rCa2+ rMg2+ > rNa+. As Ãguas amostradas enquadram-se nos padrÃes de potabilidade do CONAMA, com exceÃÃo de duas amostras. / This work was performed in the Cariri, located in the south of the state of Ceara, where is found the largest and most important groundwater reserves of the state, the Araripe Sedimentary Basin. In this region, the main source of water for public and private supply is groundwater stored in the Cariri Valley, in the aquifers, Rio da Batateira, MissÃo Velha and Mauriti. Given the importance of these water reserves, several research projects have been made to obtain relevant information about the groundwater in the region. The objective of this work was to study groundwaters samples this region and to identify changes occurred during the last 16 years, using hydrochemical measures and measures of environmental isotopes oxygen-18, deuterium, carbon-13 and carbon-14. For this, we analyzed 17 samples of groundwater collected in the municipalities of Crato, Barbalha,Juazeiro, Milagres, MissÃo Velha and Nova Olinda. The isotope results showed that in most samples were found contributions of recent recharge, featuring young waters, with values of O-18 with minor fluctuations with respect to modern rain water and high values PMC. However, 04 samples showed a mixture of modern waters with paleowater, with low values of O-18 (<-4 permil). The apparent age of groundwater samples was calculated by the method of radiocarbon using software processing statistical data, developed in this work, and ages were corrected by the methods of Pearson, Tamers and Vogel. Regarding the results of hydrochemical parameters, bicarbonate type waters predominate for anions and the mixed type for cations: rHCO3- > rCl- > rSO4 2- e rCa2+ rMg2+ > rNa+. The waters comply with the standards of potability of CONAMA, regarding major ions, except two samples.

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D.Ing. / An optimal laser pulser topology for employment in a future commercial molecular laser isotope separation (MLIS) plant is proposed by this thesis. It is pointed out in the introduction that power modulator research and development were performed without much regard to economic constraints in the past. These conditions were mainly caused by international strategic initiatives and spawned a wealth of different circuit topologies and techniques. Many more can be devised by using the various subsystems of these topologies and techniques in different combinations. However, under the paradigm of a modern day commercial application, the luxury of trying yet another new topology, merely on the merits of personal preference, does not exist. Therefore, it is proposed that a laser pulser topology be formally selected by using suitable criteria derived from the application. Formal definitions are provided for the general subsystems found in all laser excitation systems, as a foundation for the selection process. The available options for each subsystem type, as well as the options for combining them into various topologies are described. Many examples are quoted from the literature to corroborate the basic descriptions. Practical circuit issues are dealt with in an appendix. Selection criteria are determined by contemplating the theory and practical issues of pulse power technology, transversely excited atmospheric carbon dioxide lasers as well as molecular laser isotope separation. It is argued that all of these criteria can be combined into a single economic criterion, namely life cycle cost. This argument is supported by the commercial requirement of economic viability of the future plant. The author formulates a life cycle cost calculation model (LCCCM) from all the technical and economic issues previously mentioned. It includes a flexible design section that can accommodate any of the possible topology options. Cost functions, which include reliability analysis, are used to calculate capital and operating costs from the design parameters, throughout the life cycle of the plant. Probability theory is used to model parameters with indeterminate values. The use of the LCCCM and its subtleties are demonstrated by comparing two basic options in a case study. It is finally used in a reasoned process of elimination to find the best topology option for the application.

La gestion et la conservation des pêcheries sont problématiques pour la plupart des chondrichthiens; cela tient principalement au manque de données scientifiques causé par les défis logistiques impliqués par les prélèvements par grandes profondeurs. De plus, plusieurs les techniques analytiques, à l’exemple du contenu stomacal et des mesures morphologiques, demandent des quantités d’échantillons importantes difficilement obtenues. De nouvelles techniques exigent moins d'échantillons, en particulier celles mettant en oeuvre la biochimie qui sont de plus en plus utilisées pour résoudre des questions écologiques et biologiques complexes au niveau individuel et démographique des populations. Cette thèse a testé plusieurs techniques biochimiques (analyses de lipide, mercure, et isotope de carbone et azote) pour mieux comprendre les aspects de la reproduction, de l'écologie trophique, de l'amplification du mercure et de la physiologie de chondrichthiens des profondeurs. La plupart des espèces font partie de l'Ordre des Squaliformes. D'autres espèces appartiennent à différentes Familles: Chimaeridae, Rhinochimaeridae, Scyliorhinidae et Hexanchidae. Tous les échantillons ont été capturés dans les filets de pêcheurs dans les eaux du plateau continental et des marges du sud-est de l'Australie. L’analyse de la composition en lipides de différents tissus révèlent que le foie des chondrichthiens est riche en lipides (38 à 70% de la masse des tissus humides), en majeure partie des lipides neutres et des acides gras mono-saturés. Le foie est un tissu multifonctionnel, qui joue un rôle essentiel dans la distribution de la biosynthèse lipidique, le stockage de l’énergie et la régulation de la flottaison. A l’inverse, le tissu musculaire est un organe structurel, à faible concentration en lipide (<2 %) qui se compose essentiellement de lipides polaires. La composition des lipides rénaux et pancréatiques montre que leur fonctionnement métabolique est complexe. L'analyse des lipides des organes reproducteurs a révélé que l’énergie utile à la gestation chez les adultes chondrichthiens en pré-ovulation nécessite un pourcentage important de lipide (follicule ovarien 18 à 34 %). Les variations de triacylglycérols (8 à 48 %), des éthers diacylglycéryls (0,2 à 28 %) et des cires (0,5 à 20 %) ont été observées dans tous les échantillons. Ces variations impliquent l'utilisation de classes lipidiques multiples pour favoriser le développement embryonnaire. Les réserves maternelles sont différentes entre espèces ovipares et vivipares et entre les élasmobranches et les holocéphales. L’allocation la plus important de lipides est trouvée chez les requins vivant dans les environnements les plus profonds. Cette observation suggère que leur fécondité est plus faible et que leur vulnérabilité face à la pêche est plus importante. Le régime alimentaire des requins a été déterminé par des techniques complémentaires: traceurs lipidiques et analyses du contenu stomacal. 41 taxons de proie ont été identifiés. Ils étaient surtout composés de poissons et de céphalopodes du domaine demersal. En utilisant les profils des acides gras, la variabilité de la composition de nourriture a été établie pour chaque espèce en associant la signature de ces profils dans les tissus des chondrichthiens aux profils de plusieurs proies. Les deux techniques ont montré que les chondrichthiens sont des prédateurs opportunistes qui consomment une large gamme de proie. Les concentrations en mercure et sa distribution des tissus ont été examinés pour accéder à sa bioamplification dans ce type d’organisme et de déterminer des niveaux de contamination pour la consommation publique. Le mercure total (THg : toutes formes chimiques confondues) et le méthylmercure (MeHg : la forme la plus toxique et bioaccumulable) ont été dosées. Pour la plupart des espèces, les niveaux de THg étaient supérieurs au seuil maximal recommandé par les législations en vigueur dans plusieurs pays dont l’Australie (>0,1 mg kg-1 pois humide, ph) et une concentration aussi forte que 6,6 mg kg-1 (ph) a été enregistrée. L' / Analyse de spéciation a montré que le mercure est présent à plus de 91 % sous forme de MeHg, et même avec des taux supérieurs à 95 % chez les espèces des environnements les plus profonds. Les concentrations maximales en THg ont été trouvés dans les tissus musculaires (59 à 82 % de charge corporelle). Les reins et le foie possèdent aussi des taux élevés, respectivement de 0,3 à 4,2 et 0,5 à 1,5 mg kg-1 (ph), tandis que la peau enregistre les concentrations les plus faibles (> 0,3 mg kg-1, ph). Cette étude de l’organotropisme permet de conclure que les reins et le foie sont associés au métabolisme du métal, à l'élimination et au stockage à court terme, alors que le muscle est le sites le plus important du stockage du mercure à long terme. Les isotopes stables de carbone et d’azote ont été utilisés pour évaluer l'influence de la position trophique (d15N) et de la source de carbone (d13C) sur l'accumulation du THg chez les chondrichthiens. Le d15N varie entre 12,4 à 16,6 ‰ démontrant la large gamme de positions trophiques occupées par ces espèces. La variation interspécifique du d13C est quant à elle minimale (–18,7 à –17,1 ‰). Les concentrations en mercure notées chez la plupart des requins augmentent en fonction de la taille, de la position trophique (d15N) et du stade de maturité de l’animal. Dans la communauté des chondrichthiens des profondeurs on observe des taux modérés de bioamplification du mercure, ceci est révélé par la faible pente de la relation, log (THg mg kg-1 ww) = 0,2 (d15N) – 2,4 (R2 = 0,35 ; P <0,05). Le THg et les acides gras de 61 espèces appartenant aux niveaux trophiques intermédiaires ont été analysés dans le but d’étudier les régimes alimentaires des proies et la bioaccumulation de ce métal à travers la chaîne alimentaire démersale. L'utilisation intégrée de ces techniques biochimiques a fourni des données fondamentales sur la reproduction, l'accumulation en mercure et l'écologie trophique des chondrichthiens des profondeurs. La compréhension de ces fonctions est impérative non seulement pour la mise en place d’une gestion durable des pêcheries, mais aussi pour la protection des habitats des chondrichthiens et leurs écosystèmes associés. / For most deepwater chondrichthyans, fisheries and conservation management is problematic, largely due to the lack of scientific data resulting from inherent logistical challenges working within deep-sea environments. Furthermore, many conventional analytical techniques (stomach content analysis and morphometrics) require large sample sizes and are often quantitatively inadequate. Thus, new and more robust methods requiring fewer specimens are needed. Biochemical ‘tracer’ techniques are increasingly being used to resolve complex ecological and biological questions at individual species and population levels. This research explored the integrated use of multiple biochemical techniques (lipid and fatty acid profiling, stable nitrogen and carbon isotope and mercury analysis) to understand aspects of the reproduction, feeding ecology, metal accumulation and physiology of deepwater chondrichthyans. Most were from the Order Squaliformes. Other species include those from the Families: Chimaeridae, Rhinochimaeridae, Scyliorhinidae and Hexanchidae. All specimens were caught as fisheries bycatch from the continental slope waters off southeast Australia. The examination of lipid composition and partitioning revealed that deepwater chondrichthyans have large, lipid rich (38–70 % wet weight, ww) livers high in neutral lipids and monounsaturated fatty acids. Liver is a multifunctional tissue, playing a vital role in lipid distribution and biosynthesis, buoyancy regulation and storage. In contrast, muscle is a structural organ, low in lipid (<2 %) and consisting primarily of polar lipids. Lipid composition of kidney and pancreas show that they, too, have complex roles in lipid metabolism and storage. Lipid analysis of reproductive tissues revealed high maternal investment in deepwater chondrichthyans as indicated by high lipid content in mature pre-ovulated ovarian follicles (18–34 %). Variable levels of triacylglycerols (8–48 %), diacylglyceryl ethers (0.2–28 %) and wax esters (0.5–20 %) were observed in all specimens, demonstrating the use of multiple lipid classes to fuel embryonic development. The maternal provisions differed between oviparous and viviparous species and between elasmobranchs and holocephalans. Greater lipid investment was displayed by sharks living in deeper environments, suggesting lower fecundity and increased vulnerability to fishing. Diet was examined by complementary lipid biomarker and traditional stomach content techniques. A total of 41 prey taxa were identified using stomach content analysis and consisted mainly of bathyal-demersal fish and cephalopods. Using multidimensional scaling analysis, the extent of variability in composition within each species was determined by grouping the signature fatty acid profiles of shark tissues with profiles for demersal fish, squid and crustaceans. Both techniques showed that deepwater chondrichthyans are opportunistic predators, and that there is some degree of specialisation and overlap between them. Total (THg) and inorganic (monomethyl, MeHg) mercury concentrations and tissue distribution were examined to determine the extent of biomagnification and evaluate levels for human consumption. Mean THg levels for most species were above the regulatory threshold (>0.1 mg kg-1 ww) and levels as high as 6.6 mg kg-1 ww were recorded. Speciation analysis demonstrated that 91% mercury was bound as MeHg with higher percentages (>95%) observed in species occupying deeper environments. Higher levels of THg were stored in muscle which accounted for between 59–82% of the total body burden of mercury. High levels were also found in kidney (0.3–4.2 mg kg-1 ww) and liver (0.5–1.5) with lower levels observed in skin (>0.3). Both the kidney and liver are likely to be associated in metal metabolism, short term storage and elimination procedures, while the muscle is the major site for long term storage. Stable isotopes were used as natural dietary tracers, to further evaluate dietary relationships and to assess the influence of trophic position (d15N) and carbon sources (d13C) on THg accumu / lation. Isotopic nitrogen (d15N) values ranged from 12.4 to 16.6 ‰ demonstrating a broad range of trophic positions. Minor variation in carbon (d13C) enrichment was observed between species (–18.7 to –17.1‰). In most shark species, mercury concentrations increased with size, trophic position (d15N), and maturity stage, but not between location or collection period. As a community, deepwater sharks demonstrated moderate rates of THg biomagnification, as indicated by the regression slope (log (THg) = 0.2 d15N – 2.4, R2 = 0·35, P < 0·05). THg and fatty acid analyses of 61 mid-trophic species were measured for their usage in studies of diet in high-order predators and mercury bioaccumulation in the extended demersal food chain. The integrated use of these biochemical techniques has provided fundamental data on the reproduction, metal accumulation and trophic ecology of deepwater chondrichthyans. Understanding these parameters is imperative not only for the implementation of sustainable management but for habitat protection of deepwater chondrichthyans and their associated ecosystems.

Long term management plans for restoration of natural flow conditions through the Everglades increase the importance of understanding potential nutrient impacts of increased freshwater delivery on coastal biogeochemistry. The present study sought to increase understanding of the coastal marine system of South Florida under modern conditions and through the anthropogenic changes in the last century, on scales ranging from individual nutrient cycle processes to seasonal patterns in organic material (OM) under varying hydrodynamic regime, to century scale analysis of sedimentary records. In all applications, carbon and nitrogen stable isotopic compositions of OM were examined as natural recorders of change and nutrient cycling in the coastal system. High spatial and temporal variability in stable isotopic compositions were observed on all time scales. During a transient phytoplankton bloom, ä15N values suggested nitrogen fixation as a nutrient source supporting enhanced productivity. Seasonally, particulate organic material (POM) from ten sites along the Florida Reef Tract and in Florida Bay demonstrated variable fluctuations dependent on hydrodynamic setting. Three separate intra-annual patterns were observed, yet statistical differences were observed between groupings of Florida Bay and Atlantic Ocean sites. The POM ä15N values ranged on a quarterly basis by 7‰, while ä13C varied by 22‰. From a sediment history perspective, four cores collected from Florida Bay further demonstrated the spatial and temporal variability of the system in isotopic composition of bulk OM over time. Source inputs of OM varied with location, with terrestrial inputs dominating proximal to Everglades freshwater discharge, seagrasses dominating in open estuary cores, and a marine mixture of phytoplankton and seagrass in a core from the boundary zone between Florida Bay and the Gulf of Mexico. Significant shifts in OM geochemistry were observed coincident with anthropogenic events of the 20th century, including railroad and road construction in the Florida Keys and Everglades, and also the extensive drainage changes in Everglades hydrology. The sediment record also preserved evidence of the major hurricanes of the last century, with excursions in geochemical composition coincident with Category 4-5 storms.