Esta tese interpreta o registro ambiental de um testemunho de gelo antártico pela análise de elementostraço. Esse testemunho de gelo, daqui em diante chamado Mount Johns (MJ), foi coletado no manto de gelo da Antártica Ocidental (79°55’28”S e 94°23’18”W; 91,20 m de comprimento) no verão austral de 2008/09. O testemunho foi descontaminado e subamostrado no Climate Change Institute (University of Maine – Maine /EUA). As primeiras 2137 amostras, correspondentes aos 45 m superiores do testemunho, foram analisadas no espectrômetro de massas Element 2 do CCI para 24 elementos-traço (Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Li, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg e K). Essa parte do testemunho representa 125 anos (1883–2008) de registro, segundo datação relativa baseada na variação sazonal nas concentrações de Na, Sr e S e na identificação dos principais eventos vulcânicos ocorridos no período. A taxa de acumulação média no local de amostragem foi 0,21 m a-1 em eq. H2O no mesmo período de tempo. As concentrações são controladas pelas variações climáticas sazonais (verão/inverno), por mudanças na circulação atmosféricas, por anomalias de temperatura, pela distância de transporte e pelas fontes naturais e antrópicas desses aerossóis. Baseada na análise dos fatores de enriquecimento crustal e marinho e em correlações de Pearson, as concentrações de Al, Ba, Ca, Fe, K, Mg, Mn, Na, S, Sr e Ti são de origem natural. Poeira e solo de fontes continentais, oriundas principalmente de áreas áridas na Austrália, Nova Zelândia e Patagônia, são consideradas importantes fontes de Al, Mg e Ti. Aerossóis marinhos do Pacífico Sul, transportados para o continente antártico pelas massas de ar, são fontes predominantes de Na, Sr, K, S e Ca. Para os elementos Ba, Fe e Mn, tanto fontes crustais como marinhas são significativas. Adicionalmente, Mn e S apresentam um aporte considerável de origem vulcânica (variando de 20–30% na concentração total). Os resultados também mostram enriquecimento significativo nas concentrações de arsênio devido a atividades antrópicas. Foi observado concentrações médias da ordem de 1,92 pg g-1 antes de 1900, aumentando até 7,94 pg g-1 em 1950. Este enriquecimento está diretamente relacionado às emissões da mineração e fundição de metais não-ferrosos na América do Sul, principalmente no Chile. A queda na concentração de arsênio observado no século XXI (concentração média de 1,94 pg g-1 após 1999) é interpretada como uma consequência à introdução de leis ambientais (em 1994) para reduzir emissões desse elemento durante os processos de mineração e fundição de cobre no Chile. O modelo de trajetórias HYSPLIT mostra uma clara variação sazonal no transporte entre os meses de verão/outono e inverno/primavera, onde predomina o transporte de oeste durante o ano todo e um transporte secundário de nordeste durante o verão/outono. As correlações entre as concentrações médias dos elementos-traço estudados e o modelo de reanálises ERA-Interim para o período 1979–2008, indicam que as concentrações de aerossóis marinhos são fortemente influenciadas pelas condições meteorológicas, por exemplo, por anomalias na temperatura da superfície do mar e concentração de gelo marinho. / This thesis interprets the environmental record of an Antarctic ice core by the analysis of trace elements. This ice core, henceforward called Mount Johns (MJ), was collected in the West Antarctica ice sheet (79°55'28"S and 94°23'18"W; 91.20 m long) in the austral summer of 2008/09. The core was decontaminated and subsampled at the Climate Change Institute (CCI, University of Maine - Maine / USA). The first 2137 samples, corresponding to the upper 45 m of the core, were analyzed in the CCI's JRC Element 2 spectrometer for 24 trace elements (Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Li, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg and K). This part of the core represents a 125 years (1883– 2008) record, according to relative dating based on Na, Sr and S seasonal variations and on the identification of major volcanic events in the period. The mean accumulation rate for the sampling site was 0.21 m-1 in eq. H2O in the same time period. The concentrations are controlled by seasonal climatic changes (summer/winter), by changes in atmospheric circulation, temperature anomalies, the transport distance and the natural and anthropogenic sources of these aerosols. Based on analysis of crustal and marine enrichment factors and Pearson correlations, the Al, Ba, Ca, Fe, K, Mg, Mn, Na, S, Sr and Ti concentrations have natural origin. Dust and soil from continental sources, primarily coming from arid areas in Australia, New Zealand and Patagonia, are considered important sources of Al, Mg and Ti. South Pacific marine aerosols, transported to the Antarctic continent by air masses, are predominant sources of Na, Sr, K, S and Ca. For the elements Ba, Fe and Mn, both crustal and marine sources are significant. In addition, Mn and S show a considerable contribution of volcanic origin (ranging from 20-30% of the total concentration). The results also show significant enrichment in arsenic concentrations due to human activities. Before 1900 the mean concentration was approximately 1.92 pg g-1, rising to 7.94 pg g-1 in 1950. This enrichment is directly related to mining emissions and casting of non-ferrous metals in South America, mainly in Chile. The decrease in the arsenic concentration, observed in the twenty-first century (mean concentration of 1.94 pg g-1 after 1999) is interpreted as a consequence of the introduction of environmental laws (in 1994) to reduce emissions of this element during the cupper mining and smelting in Chile. The HYSPLIT trajectories model show a clear seasonal variation in transport between the summer/autumn all and winter/spring months, where predominates an eastward transport throughout the year and a secondary transport from the northeast during the summer/fall. Correlations between the mean concentrations of the studied trace elements and the ERA-Interim reanalysis models for the 1979-2008 period indicate that marine aerosols concentrations are heavily influenced by weather conditions, for example, by sea surface temperature and sea ice concentration anomalies.

A presente tese trata de analisar, a partir da situação das Regiões Ártica e Antártica, questões ambientais que se inserem no campo das relações e dos estudos de segurança internacionais. Neste sentido, através de uma abordagem comparativa, ajusta-se, metodológica e teoricamente, as relações entre questões ambientais e de segurança e sua intersecção com os estudos sobre regimes internacionais. O objetivo é a partir de uma concepção de que são o Ártico (parcialmente) e a Antártica, áreas internacionais, examinar a relação existente entre a exploração de recursos naturais e questões ambientais (mudanças climáticas) e as possibilidades de conflitos e sua superação ou adiamento, em função do exame intrínseco da competição por recursos naturais (petróleo, gás, hidratos de gás, bioprospecção, recursos marinhos, água doce, turismo e rotas polares, esse último somente para o Ártico) e das mudanças climáticas e dos regimes concebidos nas Regiões Polares. Foram examinadas, ao mesmo tempo, dificuldades econômicas, ambientais, técnicas e políticas (dificuldades intrínsecas) à exploração de recursos ambientais, os efeitos das mudanças climáticas e a força dos regimes das Regiões Polares, verificando-se as respectivas capacidades de adiar ou evitar conflitos. Sendo que a força do regime foi examinada a partir do grau de impacto dos elementos que a formam: 1) efetividade do regime, 2) a resiliência do regime, 3) resistência do regime, 4) a presença do hegemon e outros Estados protagonistas, 5) mecanismos de aquiescência, que incentivem ou obriguem o respeito as regras do regime, e 6) existência de uma organização internacional vinculada. Partiu-se do pressuposto de que quanto maiores as dificuldades para exploração, menor seria a competição e, portanto, menores as possibilidades de ocorrerem conflitos. A possibilidade de ocorrência de conflitos também foi cotejada com o grau de fortalecimento dos regimes instalados nas Regiões Polares. A tese conclui que no Ártico e na Antártica as dificuldades para a exploração dos recursos naturais se equivalem. Especificamente no campo político e econômico, quanto aos minerais (inclusive água) na Antártica a dificuldade é maior na atualidade em função da vedação da exploração até 2048 e porque as pesquisas ainda são insuficientes para comprovar a viabilidade da exploração; em compensação no Ártico a localização dos recursos em áreas sob soberania ou no espaço que compreende a ZEE não enseja dificuldades políticas e jurídicas para exploração em função da aplicação da CNUDM. Por sua vez, em especial, as externalidades dos efeitos das mudanças climáticas nas Regiões Polares podem provocar o aumento do n.m.m. e alterações dos padrões climáticos, contudo conflitos não seriam inevitáveis. Em relação aos Regimes Polares ambos foram considerados fortes, contudo o regime antártico foi considerado mais fortalecido. O exame dos elementos, principalmente, a resiliência e efetividade do STA e cotejamento com o processo de consolidação do regime complexo do Ártico justificam a conclusão. Por fim conclui esta tese que as condições para exploração dos recursos naturais, os efeitos das mudanças climáticas nas e a partir das Regiões Polares e o grau de fortalecimento dos regimes internacionais lá constituídos revelam, que os conflitos, ainda que possíveis não são prováveis. / This thesis analyzes, from Arctic and Antarctic regions, environmental issues which fall within the field of international relations and security studies. In this sense, through a comparative approach sets, intends to, methodological and theoretically, the relationship between environmental and security issues and its intersection with studies on international relations. The goal is, from a design which are the Arctic (in part) and Antarctica, international areas, examining the links between the exploitation of natural resources and environmental issues (climate change) and the potential for conflicts and overcome them or postponement, due to the intrinsic exam competition for natural resources (oil, gas, gas hydrates, bioprospecting, marine resources, freshwater, tourism and polar routes, the latter only for the Arctic) and climate change and regimes in the polar regions. Were examined at the same time, economic, environmental, technical and policy difficulties (intrinsic difficulties) the exploitation of environmental resources, the effects of climate change and the strength of the polar regions regimes, verifying their ability to delay or avoid conflicts. The strength of the system was examined from the degree of impact of the elements that form it: 1) effectiveness of the system, 2) the resilience of the system, 3) regime resistance, 4) the presence of the hegemon and other protagonists States 5) compliance mechanisms that encourage or force respect the rules of the regime, and 6) the existence of a linked international organization. It started with the assumption that the greater the difficulties for exploration, would be less competition and therefore lower the chances of occurrence of conflicts. The possibility of conflict was also checked against the degree of strengthening of systems installed in the polar regions. The thesis concludes that the Arctic and Antarctic difficulties for the exploitation of natural resources are equivalent. Specifically, in the political and economic field, as minerals (including water) in Antarctica the difficulty is greater today due to the operations are prohibited up to 2048 and because the research is still insufficient to prove the viability of the exploitation; in compensation in the Arctic location of resources in areas under the sovereignty or within the EEZ that comprises not entails political and legal difficulties to exploitation due to the implementation of UNCLOS. In turn, in particular, the externalities of the effects of climate change on the polar regions can cause an increase in sea level and changes in weather patterns, however conflicts would not inevitable. Regarding the polar regimes both were considered strong, however the Antarctic regime was considered more strong. Examination of the components, especially the resilience and effectiveness of ATS and mutual comparison with the consolidation of the complex Arctic regime justify the conclusion. Finally, this thesis concludes that the conditions for exploitation of natural resources, the effects of climate change on and from the polar regions and the degree of strengthening international regimes established their reveal that the conflicts, although possible is not probable.

Neste trabalho, duas preparações de lipase imobilizada (EC 3.1.1.3), tipo B (CALB) de Candida antarctica, foram comparadas como biocatalisadores na síntese de ésteres metílicos. CALB imobilizada comercialmente (Novozym 435 - CALB-435) e CALB imobilizada em esferas de estireno-divinilbenzeno (CALB-MCI) foram testadas para as reações de transesterificação. Um delineamento composto central rotacional (DDCR) e metodologia de superfície de resposta (MSR) foram utilizados para otimizar a relação razão molar álcool:óleo, teor de enzimas, e a água adicionada nas reações. As duas preparações de enzimas mostraram diferentes condições ótimas para a produção de ésteres metílicos, com a taxa inicial da reação de 51,47 mmol L-1 h-1 para CALB-435, e 57 mmol L-1 h-1 para CALB-MCI. O estudo do tempo de reação indicou que em 72 h foi possível obter conversões próximas a 100 % para ambos os derivados. Um alto rendimento de conversão foi obtido sob as condições otimizadas, indicando que a RSM pode ser usada para descrever adequadamente a relação entre os parâmetros de reação e da resposta (teor de ésteres metílicos). Sobre a estabilidade operacional durante as experiências de reutilização, ambos preparados enzimáticos mantiveram 70 % de sua atividade inicial após oito bateladas, sugerindo sua aplicabilidade na produção de biodiesel. / In this work two preparations of immobilized lipase (EC 3.1.1.3), type B (CALB) from Candida antarctica, were compared as biocatalysts in the synthesis of esters. Commercial Novozym 435 (CALB-435) and CALB immobilized on styrene-divinylbenzene beads (CALB-MCI) were tested for the transesterification reactions. Central composite design rotational (DCCR) and response surface methodology (RSM) were used to optimize the substrate molar ratio, enzyme content, and the added water. The two enzyme preparations have shown different optimal conditions for the production of methyl esters, with initial rates of reaction 51.47 mmol L-1 h-1 for CALB-435, and 57 mmol L-1 h-1 for CALB-MCI. The study of reaction time indicated that in 72 h it was possible to obtain conversions close to 100 % for both derivatives. A high yield conversion was obtained under the optimized conditions, indicating that RSM can be used to adequately describe the relationship between the reaction parameters and the response (yield conversion) in lipase-catalyzed biodiesel synthesis. Over the operational stability during experiments of batch reuse, both prepared enzymatic maintained 70 % of their initial activity after eight batches, suggesting their potential for economical application on biodiesel production.

Subglacial hydrology is known to influence the flow of ice. However, difficulty in accessing the base of large ice sheets has made determining the interaction between ice streams, basal sediment and water difficult to discern. The aim of this thesis is to determine the influence of subglacial hydrology on the flow of the West Antarctic ice streams. This is achieved through development of a numerical flowline model, the Hydrology, Ice and Till (HIT) model. Ice thermodynamics are coupled to a till layer of Coulomb plastic rheology. The porosity of the till changes with basal melt and freeze and can be augmented by water transported through a subglacial conduit system. Water availability strongly affects ice flow, as till porosity influences the till failure strength and thereby the basal resistance of the ice. The model was developed in four stages and a number of sensitivity tests were performed. It was then applied to Kamb Ice Stream (Ice Stream C) and Whillians Ice Stream (Ice Stream B), West Antarctica. Results confirm that ice streams are capable of oscillating between fast and slow velocity states. Cycles are generated at the grounding line of an ice stream and the speed of the transition from slow to fast flow is governed by water availability. The period of oscillation of the cycles for the West Antarctic ice streams was found to be several hundred years, which is in line with observations of stagnation and reactivation of these ice streams. This shows that subglacial hydrology has a role in modulating the flow variability of ice streams and that rather large changes in the flow of the West Antarctic ice streams are likely to occur this century.

L'ion nitrate (NO3-) présent dans les neiges Antarctiques est issus de l'oxydation des oxydes d'azote (NOx = NO + NO2) dans l'atmosphère. Aux sites de faible accumulation de neige tels que Vostok et Dôme C sur le plateau de l'Est de l'Antarctique, le nitrate n'est pas piégé de manière ultime dans la neige, ce qui limite fortement l'interprétation des enregistrements en nitrate dans les carottes de glace. Des mesures récentes de la composition isotopique en azote du nitrate (δ15N) montrent des valeurs extrêmement élevées (+339‰) dans les premiers décimètres de la neige de Dôme C. Ces valeurs ont été attribuées à la photolyse du nitrate et au recyclage important qui en résulte. Le nitrate possède, par ailleurs, une anomalie isotopique en oxygène (Δ17O) qui permet de tracer l'activité de l'ozone (O3) au cours de sa formation. Ce travail de thèse présente le premier enregistrement de la composition isotopique complète du nitrate (δ15N, Δ17O et δ18O) dans une carotte de glace : la carotte de glace de Vostok dont les 64 échantillons analysés couvrent une période de 150 000 ans. Ce jeu de données a été complété par 313 échantillons collectés entre 2007 et 2010 dans le continuum atmosphère/givre/neige au Dôme C ainsi que dans 21 puits de neige prélevés dans une zone couvrant l'essentiel de l'Est de l'Antarctique. L'analyse isotopique de ces échantillons modernes a permis de contraindre le modèle conceptuel TRANSITS développé au cours de cette thèse et dont le but est de représenter le recyclage du nitrate à l'interface entre l'atmosphère et la neige ainsi que son impact sur la composition isotopique du nitrate archivé. Les valeurs positives et élevées du δ15N du nitrate piégé dans la carotte de glace de Vostok montrent que le recyclage du nitrate a toujours eu lieu sur le plateau Antarctique au cours de la période étudiée. Les variations du flux primaire de nitrate reçu au site de Vostok estimées à l'aide du modèle TRANSITS montrent, en périodes glaciaires, un flux primaire plus important qui pourrait être lié à une dénitrification stratosphérique plus conséquente. Les valeurs de Δ17O du nitrate montrent que l'incursion d'ozone d'origine stratosphérique dans la troposphère était plus fréquente en périodes glaciaires. Nous proposons enfin que les résultats acquis dans le cadre de cette thèse pourraient permettre de mieux contraindre le cycle de l'azote sur la côte Antarctique et d'apporter des éléments d'interprétation des enregistrements en nitrate dans les carottes de glace de sites de plus forte accumulation de neige (au Groenland par exemple). / Nitrate ions (NO3-) found in Antarctic snows stem from the degradation of nitrogen oxydes (NOx = NO + NO2) in the atmosphere. At sites with low snow accumulation rates such as Vostok or Dome C (East Antarctic plateau), nitrate deposition to the snow is not irreversible and this strongly hampers the interpretation of nitrate concentration records in ice cores. Nitrogen stable isotopic (δ15N) as high as +339‰ were measured in nitrate in the upper firn at Dome C and have been attributed to nitrate photolysis initiating a strong recycling at the snow surface. The oxygen isotopic anomaly (Δ17O) reflects the activity of ozone (O3) in nitrate formation. We present the first comprehensive isotopic analysis of nitrate (δ15N, Δ17O and δ18O) in a deep ice core. 64 samples of nitrate from the Vostok ice core have been analyzed and cover the last 150 000 years. This dataset has been completed with 313 samples recently collected in the atmosphere/surface hoar/snow continuum at Dome C as well as in several snowpits from various sites covering most of the East Antarctica. Those present-day samples are used to evaluate a conceptual model (named TRANSITS) developped during this PhD and which aims at representing nitrate recycling at the snow/atmosphere interface and at modelling its impact on the isotopic composition of the archived nitrate. High positive δ15N values measured in the Vostok ice core reveal that nitrate recycling has always occurred at the surface of the Antarctic plateau over this period. Past variations of the primary flux of nitrate to the Vostok site have been estimated using the TRANSITS model. They show that glacials are characterized by higher inputs which may be linked to a greater stratospheric denitrification. The Δ17O values indicate that intrusions of stratospheric air masses to the troposphere may have been more frequent in glacials thus incorporating significant amounts of stratospheric ozone to the lower atmosphere. Last, we suggest that this study may have some relevance to the coastal nitrogen budget in Antarctica and to the interpretation of ice cores retrieved from high accumulation sites (e.g. in Greenland).

L'augmentation de l'accumulation de neige simulée en Antarctique de l'Est pour le siècle à venir est une contribution négative à la hausse du niveau moyen des mers. Les modèles climatiques simulant cette augmentation ne possèdent pas de paramétrisation du transport éolien de neige or ce dernier joue un rôle primordial sur l'accumulation d'après les observations. Les modèles climatiques régionaux possédant une paramétrisation du transport éolien permettent d'estimer l'incertitude des modèles climatiques sur la hausse du niveau moyen des mers en ne représentant pas ce processus. Cependant aucune donnée de transport ne permet une validation précise de ces modèles en Antarctique. Dans ce contexte, cette thèse décrit la constitution d'une base de données de transport éolien de neige en Antarctique ainsi qu'une validation d'un modèle climatique régional incluant le transport éolien de neige. Un instrument acoustique, le FlowCapt, a été choisi pour acquérir les données. Une comparaison avec un appareil de mesure optique du transport, le Snow Particle Counter, a été menée dans les Alpes françaises. Cette comparaison a permis de déterminer les limites des deux générations de FlowCapt existantes pour la détection des événements de transport et la quantification du flux de neige. Une base de données de trois années a été acquise en Terre Adélie, Antarctique, pour permettre une comparaison avec un modèle climatique régional. Elle a permis de calculer la hauteur de rugosité et la vitesse de frottement seuil avec leurs incertitudes. Les épisodes de transport éolien de neige et une borne inférieure de la quantité de neige déplacée en un point ont été estimés. Deux comparaisons ont été menées avec le Modèle Atmosphérique Régional, un modèle climatique régional incluant de nombreuses rétroactions du transport sur l'écoulement. Les deux simulations utilisées pour les comparaisons ont été faites sur un petit domaine à fine échelle sur une période d'un mois. Le modèle simule bien les épisodes de transport sauf lorsque de la fonte s'est produite juste avant un épisode ou lorsque les épisodes ont une hauteur maximale de transport inférieure à cinquante centimètres. Le modèle sous-estime les quantités de neige transportée. / Predicted accumulation by global numerical climate models for the next century increases in East Antarctica and negatively contributes to the mean sea level rise. None of the climate models integrates a blowing snow parametrisation. However few smaller scale regional climate models include a blowing snow parametrisation and thus can assess the climate models uncertainty on the mean sea level rise by not representing this process. Yet none of the blowing snow data available in Antarctica allows for a precise validation of a regional climate model. In this context, this PhD described the establishment of an Antarctica blowing snow database and the validation of a regional climate model including a blowing snow parametrisation. An acoustic blowing snow sensor, the FlowCapt, has been chosen to collect data in Antarctica. A comparison with an optic blowing snow sensor, the Snow Particle Counter, has been conducted in the French Alps. The capacity of the two existing FlowCapt generation has been determined on the blowing snow event and the flux quantification. A three years blowing snow model-oriented database is now available in Adélie Land, Antarctica. The threshold friction velocity and the roughness height have been calculated with their uncertainty. Blowing snow variability has been determined as well as the minimum transport rate at one field point. Two comparisons have been done with the Modèle Atmosphérique Regional (MAR), a regional climate model including a blowing snow parametrisation. Both simulations represent a small domain with a high vertical and horizontal resolution over one month. The model is able to reproduce the blowing snow event except when melting occurs or when the blowing snow height is encompassed within the first fifty centimetres above the ground. The model underestimate the snow quantity transported at the field measurement point.

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.

Durante o Eoceno e o Oligoceno (55 a 23 Ma) a Terra esteve sujeita a período de grandes mudanças climáticas. Registros geológicos, reforçados por modelos climáticos, indicam que o clima global durante esse período passou de estágio praticamente livre de calotas polares para situacao climática próxima a que hoje podemos encontrar na Antártica. Grande parte desses registros são indiretos, retirados de sedimentos de fundo marinho ou de material fóssil. Evidência terrestre clara da variação climática (greenhouse-icehouse) para o Eoceno-Oligoceno pode ser encontrada em Wesele Cove, ilha Rei Jorge, Antártica Ocidental. Tais evidências correspondem a uma sucessão de cerca de 60m com pelo menos 13 derrames de lava basáltica, de alguns metros de espessura cada, sobreposta, em contato erosivo, por diamictito e arenito. A sucessão basáltica é correlacionada com a Formação Mazurek Point/Hennequin, datada radiometricamente como do Eoceno, e o diamictito e arenito correspondem ao Membro Krakowiak Glacier da Formação Polonez Cove, datada, paleontológica e radiométricamente como pertencente ao Oligoceno inferior. Cada camada de basalto toleítico exibe uma zona inferior, mais espessa (1 a poucos metros), de rocha fresca, que é seguida transicionalmente por uma zona de alteração, variando de alguns decímetros a 1-1,5 m de espessura. O pacote de basalto está inclinado 25º para leste, provavelmente por tectonismo. A sucessão foi recentemente exposta devido ao rápido recuo da atual geleira Wyspianski. A evidência inicial de campo sugere que a sucessão representa um registro geológico de variação paleoclimática de condições mais amenas para condições glaciais, que pode ser correlacionada com a mudança do ótimo climático do final do Eoceno (greenhouse) para as condições de icehouse do Oligoceno, registradas na curva de paleotemperatura cenozóica estabelecida pela determinação de 18O em carapaças de foraminíferos. Este estudo teve como foco central a análise estratigráfica e geoquímica da ocorrência, a fim de interpretar a sucessão de eventos paleoclimáticos documentados no afloramento e analisá-los, no contexto da história paleoclimática da Antártica. Os dados obtidos mostraram que a transição de zonas não alteradas para alteradas observada em cada derrame de basalto pode de fato ser atribuídas à ação moderada de processos intempéricos no topo de cada derrame. Eles também demonstram uma origem glacial, em parte subglacial com contribuição marinha, dos diamictitos sobrepostos, que apresentam feições, tais como, clastos de litologias e tamanhos variados, facetados e estriados, clastos tipo bullet shaped, clastos partidos por congelamento, estrias intraformacionais e fósseis marinhos encontrados na matriz do diamictito. As condições climáticas amenas responsáveis pelo intemperismo do basalto durou até o surgimento do último horizonte de lava, seguida por movimentação tectônica que inclinou o pacote. Esses eventos indicam condições paleoclimáticas menos rigorosas relativamente longas durante o Eoceno, precedendo o estabelecimento do manto de gelo oligocênico nesta parte da Antártica. / During the Eocene and Oligocene (55 23 Ma) the Earth was undergoing a period of great climatic changes. Geological records, reinforced by climate models indicate that global climate during this period went from a stage in which the Earth was virtually free of polar ice caps to a stage close to what we find today in Antarctica. Most of these records are indirect, taken from the deep-sea cores or fossil material. Clear terrestrial evidence of climate change (greenhouse-icehouse) for the Eocene-Oligocene transition is found in Wesele Cove, King George Island, West Antarctica. This evidence includes a succession of at least thirteen, few meters thick, basaltic lava flows overlain disconformably by diamictite and sandstone. The basaltic section is correlated with the Mazurek Point/Hennequin Formation, radiometric dated as Eocene, and the diamictite and sandstone correspond to the Krakowiak Glacier Member of the Polonez Cove Formation, dated as Early Oligocene, on paleontological and radiometric basis. Each tholeiitic basalt layer exhibits a lower, thicker (1 to few meters) fresh zone, transitionally followed up by a zone of saprolith, varying from decimeters to 1-1.5 m in thickness. The entire basalt package of around 60 m, is tilted 25º to the east. The succession has been recently exposed due to fast retreat of the present Wyspianski Glacier. The initial field evidence suggests that the succession represents the geological record of paleoclimatic variation from mild to glacial conditions, that could correlate with the change from the late Eocene optimum climatic (greenhouse) to icehouse conditions in the Oligocene, as recorded on the Cenozoic paleotemperature curve established by 18O determinations on calcareous foram tests. This study had focus on the stratigraphy and geochemistry analysis of the occurrence, in order to interpret the succession of palaeoclimatic events documented in outcrop and analyze them in the context of paleoclimatic history of Antarctica. Data obtained consistently showed that the supposed transition from unaltered to altered zones observed in each basalt layer may in fact be assigned to the moderated action of weathering processes on top of each flow. They also demonstrate a glacial, in partly subglacial with marine contribution, origin for the overlying diamictites, which has features such clasts of diverse lithologies and sizes, faceted and striated clasts, bullet shaped clasts, clasts broken by freezing and thaw, intraformational striae and marine fossils found in the matrix of the diamictite. The mild paleoclimatic conditions responsible for weathering of the basalt lasted until the emplacement of the highest lava horizon, followed by tectonic movement that tilted the package. These events indicate a relatively long paleoclimatic mild conditions during the Eocene, preceding the establishment and displacement of the Oligocene ice-sheet in this part of Antarctica.

O continente Antártico é considerado um ambiente pouco impactado, porém com o aumento das atividades humanas e do número de estações de pesquisa, há uma tendência de aumento dos níveis de alguns contaminantes. Neste estudo estabeleceram-se os níveis de arsênio, cádmio, chumbo, cobre, cromo, mercúrio, níquel, zinco, e a razão isotópica de nitrogênio, em sedimentos e na biota, coletados em 2003, na Baía do Almirantado, Ilha Rei George, Antártica. Os metais pesados foram quantificados por Espectrometria de Emissão Ótica com Plasma Indutivamente Acoplado (ICP-OES). Os resultados demonstraram elevadas concentrações de cobre e zinco nos sedimentos, atribuídas à composição geológica da região. Verificou-se bioacumulação de arsênio na biota da Baía do Almirantado, e bioacumulação de cádmio e zinco na biota da Enseada Martel. Somente cobre apresentou tendência de biomagnificação na teia trófica estudada. O molusco Laternula elliptica se apresentou como um bom biomonitor das concentrações de metais pesados para o ambiente Antártico. Além disso, os resultados foram úteis para o conhecimento dos níveis de metais pesados nas condições pré-acidente da Estação Antártica Comandante Ferraz (EACF), que ocorreu em 2012, e para comparação com as atuais condições, dentro dos trabalhos de monitoramento que estão sendo realizados pelo INCT-APA (Instituto Nacional de Ciência e Tecnologia Antártico de Pesquisas Ambientais). / The Antarctic continent is considered a slightly affected environment, but as the human activities and the number of research stations are increasing, there is a tendency of a higher level of some contaminants. This study established the levels of arsenic, cadmium, lead, copper, chromium, mercury, nickel, zinc, and nitrogen isotope ratios in sediments and biota collected in 2003, in Almirantado Bay, Rei George Island, Antarctica. Heavy metals were quantified by Optical Emission Spectrometry with Inductively Coupled Plasma (ICP-OES). The results showed high concentrations of copper and zinc in sediments attributed to the geological composition of the region. There was arsenic bioaccumulation in biota of Almirantado Bay, and bioaccumulation of cadmium and zinc in the biota of Martel Bay. Only copper tended to biomagnification in the trophic web studied. The clam Laternula elliptica presented itself as a good biomonitor of heavy concentrations of metals for Antarctic environment. Moreover, the results were useful for the acknowledge of the levels of heavy metals in pre-accident conditions of Comandante Ferraz Antarctic Station (EACF), which occurred in 2012, and for comparison with current conditions within the monitoring work now performed by INCT-APA (National Antartic Institute of Science and Technology Environmental Research).

Bifenilos policlorados (PCBs) e pesticidas organoclorados são compostos que não ocorrem naturalmente no ambiente e não são facilmente degradados química ou microbiologicamente. Seu estudo no ambiente é importante devido à sua persistência, toxicidade, lipossolubilidade e conseqüente biomagnificação. Por isso, representam a maioria dos poluentes orgânicos persistentes (POPs) considerados prioritários pela UNEP (United Nations Environmental Programme) e banidos ou restritos pela Convenção de Estocolmo, de maio de 2001. Tais poluentes podem ser facilmente emitidos para a atmosfera, atingindo áreas remotas como a Antártida, integrando um processo cíclico de contaminação conhecido como destilação global. No presente trabalho otimizou-se uma metodologia analítica capaz de detectá-los em ovos gorados de pingüins e indivíduos de krill coletados na Baía do Almirantado, Ilha Rei Jorge, Antártida. Tal metodologia foi avaliada e enquadrou-se em critérios internacionais de controle de qualidade. Os compostos mais presentes foram, de um modo geral, os PCBs, DDTs e o HCB e a ocorrência pareceu ser espécie-específica dentro do gênero Pygoscelis. Em todos os casos, o teor dos compostos não foi superior ao de aves árticas em nível trófico semelhante. A análise do krill permitiu estimar a biomagnificação dos compostos encontrados nos ovos, cuja única fonte de contaminação é a transferência fêmea-filhote. / Polychlorinated biphenyls (PCBs) and organochlorine pesticides are compounds that do not occur naturally in the environment and are not easily degraded by chemical or microbiological action. Their study in the environment is important due to persistence, toxicity, liposolubility and consequent biomagnification. For these reasons, they represent the majority of the persistent organic pollutants (POPs), considered to have priority by the UNEP (United Nations Environmental Programme) and banished and/or restricted by the Stockholm Convention of May, 2001. Such pollutants can be easily ejected into the atmosphere and reach areas as remote as Antarctica, integrating a cyclical contamination process known as ?global distillation?. In the present work an analytical methodology capable of detecting such compounds in unhatched penguin eggs and whole krill was optimized. The samples were collected in Admiralty Bay, King George Island, Antarctica. This methodology was evaluated and fitted international quality control criteria. The compounds found in higher levels were, in most of the samples, the PCBs, DDTs and HCB and the occurrence seemed to be species-specific for the Pygoscelis genus. In all of the cases, the levels found were not higher than the ones in arctic birds in a similar trophic level.The krill samples analysis made it possible to estimate the biomagnification of the compounds found in eggs, whose only source of contamination is the female-offspring transfer.