Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2017-10-04T15:44:46Z No. of bitstreams: 1 tese_renata_maria_completa.pdf: 1532064 bytes, checksum: db3c7a043c5eecc779b264a3e956dea2 (MD5) / Made available in DSpace on 2017-10-04T15:44:46Z (GMT). No. of bitstreams: 1 tese_renata_maria_completa.pdf: 1532064 bytes, checksum: db3c7a043c5eecc779b264a3e956dea2 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geoquímica, Niterói, RJ / Nos últimos anos observa-se um aumento crescente das atividades humanas, tanto científicas quanto turísticas, no ambiente antártico, sendo motivo de preocupação considerando-se que a Antártica é um ambiente de lenta recuperação. Ainda são escassos os estudos sobre o estabelecimento de relações entre a presença de contaminantes e seus efeitos na biota antártica. A contaminação pode ocorrer por processos antrópicos ou naturais e os efeitos destes impactos podem ser detectados e monitorados através da análise das alterações nas comunidades bentônicas. Estas comunidades podem ser consideradas boas indicadoras de impactos ambientais, já que possuem uma relação direta com a origem dos contaminantes acumulados nos sedimentos. Este trabalho avaliou os níveis de metais-traço encontrados no sedimento e em duas espécies circumpolares da megafauna bentônica antártica, a estrela-domar Odontaster validus e o molusco bivalve Laternula elliptica, com a finalidade de determinar se as mesmas podem ser utilizadas como indicadoras de impacto ambiental. Durante o verão austral de 2005/2006 foram realizadas coletas através de diferentes procedimentos, entre 15 e 40m de profundidade, em cinco estações dentro da Área Antártica Especialmente Gerenciada da Baía do Almirantado, Ilha Rei George: 1) Estação Antártica Comandante Ferraz; 2) Botany Point; 3) Punta Ullman; 4) Punta Plaza e 5) Refúgio II. Os seguintes metais foram quantificados tanto para o sedimento quanto para os organismos: Al, V, Cr, Mn, Fe, Ni, Cu, Cd, Ba, Pb e Zn. A concentração de metais variou entre os diferentes compartimentos corpóreos analisados. Para a espécie O. validus, as maiores concentrações de metais-traço (Mn, Ni, Cd, Ba, Pb) e do macronutriente Al, foram encontradas na parede do corpo. Cu, Cr, V e Zn apresentaram maior concentração no estômago, enquanto o macronutriente Fe concentrou-se preferencialmente nos cecos pilóricos. Para a espécie L. elliptica, as maiores concentrações de metais-traço (Mn, V, Ba, Cu) e dos macronutrientes Fe e Al, foram encontradas no sifão. Cd, Ni, Pb e Zn apresentaram maior concentração no rim enquanto o Cr foi mais concentrado no compartimento restos. A concentração de elementostraço nos compartimentos corpóreos de O. validus e L. elliptica não foi influenciada pelo tamanho do organismo (peso total do indivíduo). / Once the Antarctic environment has low recovery rates, the recent growth in the touristic and scientific activities is a serious issue for the scientific community. Few studies have tried to establish the links between the presence of contaminants and the antarctic biota. The contamination may be related to human or natural processes, and be monitored trough the benthic communities. These communities have a direct relation with the contaminants sources in the sediment. The present work analyzed the trace-metals levels found in the sediment and two circumpolar benthic megafauna species in Antarctica, the starfish Odontaster validus and the Antarctic clam Laternula elliptica. The objective was to establish if these species can be used as environmental indicators. Five stations was occupied during the austral summer of 2005/2006, between 15 and 40m deep, in the Antarctic Special Management Area of Admiralty Bay, George King Island: 1) Comandante Ferraz Antarctic Base; 2) Botany Point; 3) Punta Ullman; 4) Punta Plaza and 5) Refúgio II. Analyzes were conducted to quantify the presence of Al, V, Cr, Mn, Fe, Ni, Cu, Cd, Ba, Pb and Zn, both in the sediment and organisms. The metals concentrations vary in the different body compartments. Larger concentrations of (Mn, Ni, Cd, Ba, Pb) trace metals and Al macronutrient were found in the body walls of O. validus. Cu, Cr, V and Zn showed larger concentrations in the stomach and the Fe macronutrient in the caeca pyloric. For L. elliptica, larger trace metals (Mn, V, Ba, Cu) and macronutrients (Fe and Al) concentrations were found in the sifon, while Cd, Ni, Pb and Zn showed larger concentrations in the kidney. Cr presented larger concentrations in the remains compartment. The concentrations of trace elements in both O. validus and L. elliptica were not influenced by the body size (total individual weight).

A região antártica é foco de constante observação por ser uma região de importante monitoramento climático global. Ao sedimento de fundo marinho está associada uma biota que responde aos processos de alterações ambientais e dentre seus representantes os foraminíferos são considerados bons indicadores marinhos. O objetivo do presente estudo é avaliar a fauna de foraminíferos recentes na Baía do Almirantado durante três verões austral consecutivos (2002/2003, 2003/2004 e 2004/2005) e, através da determinação de algumas variáveis ambientais, compreender melhor a ecologia e a distribuição desses organismos na região. Foram coletadas 56 amostras de sedimento de fundo marinho ao longo da Baía do Almirantado para análise e identificação da fauna de foraminíferos e de variáveis abióticas amostradas na água de fundo e no sedimento. Foram encontradas 66 espécies de foraminíferos bentônicos, sendo 36 espécies aglutinantes e 30 espécies calcárias. As espécies mais freqüentes foram as calcárias Bolivina pseudopunctata, Cassidulinoides parkerianus e Globocassidulina biora, e as aglutinantes Portatrochammina antarctica, Pseudobolivina antarctica e Spiroplectammina biformis. As espécies Portatrochammina antarctica e Pseudobolivina antarctica foram as mais abundantes na porção central e em algumas estações das três enseadas da baía. As regiões mais internas das enseadas apresentaram predominância de espécies hialinas principalmente do gênero Globocassidulina e Cassidulinoides. A predominância de espécies hialinas também foi observada nas estações próximas a desembocadura da Baía do Almirantado com as espécies Bolivina pseudopunctata e Fursenkoina fusiformis. / The Antarctic region is focus of constant scientific surveys because of its importance as global climate changing area. The marine bottom sediment has an associated biota that indicates some environmental changes and among them Foraminifera could be considered as one of the best marine biomarkers. The aim of the present study is describe the recent benthic foraminifera fauna from Admiralty Bay collected during three consecutive austral summers (2002/2003, 2003/2004 and 2004/2005) and better understand its ecology and distribution patterns throughout the bay and its relations with some environmental factors. Fifty-six bottom sediment samples were collected along the Admiralty Bay for analysis and identification of the forams fauna and abiotic factors from sediment and bottom water. We found 66 species of benthic foraminifera, 36 agglutinated and 30 calcareous. The most frequent species were the calcareous Bolivina pseudopunctata, Cassidulinoides parkerianus and Globocassidulina biora, and the agglutinated Portatrochammina antarctica, Pseudobolivina antarctica and Spiroplectammina biformis. The species Portatrochammina antarctica and Pseudobolivina antarctica were the most abundant in the central portion of the bay and in some samples of the three inlets of the bay. The inner parts of the inlets there was a predominance of calcareous such as Globocassidulina spp. and Cassidulinoides spp.. The predominance of calcareous species, such as Bolivina pseudopunctata and Fursenkoina fusiformis was also observed at samples near the connection between the Admiralty Bay and the Bransfield Strait.

A Plataforma Oeste da Península Antártica (POPA) é uma região onde a produtividade primária na superfície do oceano apresenta padrões altamente sazonais e considerável variabilidade interanual. A dinâmica do gelo marinho é o principal fator condicionante da produtividade e, por consequência, dos fluxos de matéria orgânica da superfície para o leito marinho. A matéria orgânica particulada depositada, chamada de fitodetrito, forma densas camadas de alimento lábil disponível para os organismos bênticos. Essa relação estreita entre os processos da coluna de água e aqueles que ocorrem no bentos é chamada de acoplamento bento-pelágico. Com o objetivo de avaliar as respostas da macrofauna bêntica aos fluxos e deposição de alimento, foi realizada uma série temporal sazonal de amostragens (novembro/1999 a março/2001) na POPA em três estações de coleta perpendiculares à costa. Cerca de 25.000 indivíduos pertencentes a 22 táxons foram coletados em 15 amostras de box corer (0,25 m2 cada). Mesmo com alguma variação ao largo da plataforma (de 10.886 ind.m-2 (estação A) a 2.326 ind.m-2 (B)), atribuída a diferenças na topografia, a macrofauna apresentou pouca variabilidade em termos de composição e abundância ao longo do período estudado. Além disso, diferenças na composição e abundância entre estratos sedimentares também foram notáveis, sendo que 90% dos indivíduos foram encontrados entre 0 e 5 cm. Dentre as 185 espécies identificadas, Aurospio foodbancsia (Polychaeta, Spionidae), uma espécie típica de regiões de plataforma na Antártica, mas muito próxima da espécie de mar profundo A. dibranchiata, foi a espécie dominante em todos os períodos e estações (2.087 ind.m-2). Além de Polychaeta, outros grupos abundantes na POPA foram Bivalvia, Tanaidacea e Oligochaeta. Picos de abundância foram observados para algumas espécies, provavelmente associados a eventos sazonais de recrutamento, porém nem sempre associados à chegada do alimento ao fundo marinho da região. Os grupo funcionais de Polychaeta também não variaram ao longo do período estudado, o que indicou que animais depositívoros de superfície e subsuperfície se alimentam ao longo de todo o ano, aproveitando o alimento que permanece lábil e disponível, mesmo no inverno, quando o fluxo de matéria orgânica para o bentos é mínimo. Os resultados encontrados neste trabalho confirmam os resultados já encontrados dentro do projeto FOODBANCS, que a macrofauna da POPA age como um filtro, respondendo menos às flutuações sazonais. / The West Antarctic Peninsula shelf (WAP shelf) experiences a high seasonal and interannual variability in surface primary production. Sea ice dynamics is the principal factor controlling productivity and, therefore, the downward particulate organic matter (POM) fluxes. The deposited POM, also called phytodetritus, forms dense layers of available labile food for benthic organisms. This straight relationship between water column and benthic processes is called benthic-pelagic coupling. A seasonal time-series study was conducted between November 1999 through March 2001 in tree sites on WAP shelf, to determine this relationship, specially the benthic macrofauna (> 300 µm) response to the POM flux and its posterior deposition. From a total of 15 box-corer samples (0.25 m2 each), approximately 25,000 macrofaunal individuals were collected, belonging to 22 taxa. Even with some variation along the shelf, ranging from 10,886 ind.m-2 (site A) to 2,326 ind.m-2 (B), the abundance and composition of macrofauna showed only modest seasonal changes. Differences in these parameters were clear between the inner and outer shelves, probably owing to the topography, which was composed of a basin in the innermost region and a flat region, in the offshore area. Differences in abundance and composition between sediment layers were also notable, with 90% of all individuals belonging to the 0-5 cm layer. Among the 185 identified species, Aurospio foodbancsia (Polychaeta, Spionidae), a typical species of Antarctic shelf regions and closely related to the deep-sea species A. dibranchiata, was dominant in all seasons and sites (2,087 ind.m-2). Besides polychaetes, bivalves, tanaids and oligochaetes were also abundant in WAP shelf. Peaks in abundance were observed for some species and this is believed to be related to seasonal recruitment, however not always associated with the availability of food. Polychaete functional groups did not vary along seasons, indicating that surface and subsurface deposit feeders were subsisting on the labile POM along the year, even during the winter, when POM flux to the benthos is extremely low. The results are similar to those obtained in other FOODBANCS works, and indicate that the WAP shelf macrofauna act as a low-pass filter, muting the seasonal water column processes.

Submitted by Diego Santos (diegosantos@unipampa.edu.br) on 2015-04-10T11:49:39Z No. of bitstreams: 1 111010003.pdf: 1306168 bytes, checksum: 65e96979f53ded7b91f629af13358a87 (MD5) / Made available in DSpace on 2015-04-10T11:49:41Z (GMT). No. of bitstreams: 1 111010003.pdf: 1306168 bytes, checksum: 65e96979f53ded7b91f629af13358a87 (MD5) Previous issue date: 2012-08-20 / O metilmercúrio (MeHg) é um agente tóxico que causa importantes prejuízos à saúde humana e ambiental. Parte desses efeitos está relacionado a sua capacidade de induzir estresse oxidativo. Os mecanismos precisos pelos quais o MeHg leva ao estresse oxidativo ainda não estão bem esclarecidos. Dados na literatura apontam para a participação de selenoproteínas como a glutationa peroxidase e a tioredoxina redutase neste processo. Neste estudo, buscou-se investigar o papel de isoformas de glutationa peroxidase (GPx1 e GPx4) e da tioredoxina redutase (TrxR1) na neurotoxicidade induzida por MeHg em camundongos, focando na atividade e expressão destas proteínas. Nossos resultados mostraram, que o tratamento de camundongos Swiss machos adultos com MeHg (40 mg/L na água de beber) durante 21 dias causa uma diminuição significativa na atividade das enzimas GPx e TrxR no córtex e cerebelo dos animais tratados, em comparação com os controles. Observou-se também uma significativa redução na expressão de GPx1, GPx4 e TrxR1 no cerebelo dos animais tratados, enquanto que no córtex apenas GPx4 e TrxR1 foram afetadas. Concomitantemente a estes resultados, observou-se um aumento significativo na atividade das enzimas antioxidantes SOD, CAT, GR e GST no cerebelo e da CAT no cortex. A expressão de HSP70 foi significativamente aumentada no cerebelo dos animais tratados. Estes dados denotam uma clara resposta celular antioxidante frente aos efeitos tóxicos do MeHg em nosso modelo, reforçando dados da literatura que indicam o estresse oxidativo como um importante mecanismos na neurotoxicidade induzida por este organometal. Além disso, nossos resultados apontam para isoformas de glutationa peroxidase e tioredoxina redutase como importantes alvos moleculares do MeHg e, ao menos, em nosso conhecimento, este é o primeiro estudo demonstrando o papel da GPx4 na neurotoxicidade induzida por este agente tóxico ambiental. Outro objetivo deste trabalho foi investigar os efeitos biológicos do extrato da alga Prasiola crispa(PcE), oriunda do continente Antártico, nos modelos de Drosophila melanogaster e Nauphoeta cinérea. Organismos adaptados a ambientes extremos como a Antártica tendem a apresentarem uma constituição única em termos de metabólitos secundários. Desta forma, estudos que visem à elucidação de efeitos biológicos de organismos oriundos destas regiões tendem a apresentarem relevância do ponto de vista biotecnológico. Nossos dados apontam para um potencial biocida de PcE nos modelos de mosca-da-fruta (Drosophila melanogaster) e barata cinerea (Nauphoeta cinerea), visto que a administração do extrato induziu toxicidade nos dois modelos. A toxicidade em D. melanogaster foi avaliada como percentagem de mortalidade, atividade locomotora (geotaxia negativa) e alterações bioquímicas incluindo atividade acetilcolinesterase (AChE) e marcadores de estresse oxidativo.Também foi investigada a ação cardiotóxica do extrato no modelo de coração semi-isolado de barata cinerea. A administração do extrato(2mg/ml) foi feita por 24 horas e, nas moscas, causou um aumento massivo na mortalidade (aumento de 7,6 vezes em relação ao controle). Também foi observado um aumento significativo na atividade locomotora, indicando uma ação neurotóxica do extrato. A atividade AChE, os níveis de glutationa e formação de hidroperóxido manteve-se inalterada. A atividade da glutationa S-transferase aumentou significativamente após a administração de PcE, já a atividade da catalase diminuiu significativamente em moscas que receberam o extrato. No modelo de coração semi-isolado de barata, foi observado uma diminuição da freqüência cardíaca. A incubação do extrato com DTNB, um forte agente oxidante, bloqueou significativamente o efeito cardiotóxico do extrato, sugerindo que compostos redutores podem ser responsáveis pelo efeito observado. Desta forma, este estudo demonstrou os efeitos tóxicos de PcE, em dois modelos de inseto, sugerindo seu potencial como bioinseticida. Os mecanismos precisos relacionados a este efeito ainda necessitam de esclarecimentos, entretanto, alterações em sistemas antioxidantes vitais podem estar envolvidos. / Methylmercury (MeHg) is a toxic agent that causes severe damage to human health and the environment. These effects are related to its ability to induce oxidative stress. The precise mechanisms by which MeHg leads to oxidative stress are not well understood. Data from literature point to the involvement of selenoproteins such as glutathione peroxidase and thioredoxin reductase in this process. In this study, we sought to investigate the role of isoforms of glutathione peroxidase (GPx4 and GPx1) and thioredoxin reductase (TrxR1) in MeHg-induced neurotoxicity in mice, focusing on activity and expression of these proteins. Our results showed that treatment of adult male mice Swiss with MeHg (40 mg / L in drinking water) for 21 days causes a significant decrease in GPx and TrxR enzyme activity in the cerebral cortex and cerebellum of treated animals when compared to controls. We also observed a significant reduction in the expression of GPx1, GPx4 and TrxR1 in the cerebellum of the treated animals, whereas in the cortex only GPx4 and TrxR1 are affected..In parallel, we observed a significant increase in antioxidant enzymes SOD, CAT, GR and GST in the cerebellum and CAT in cortex. HSP70 expression was significantly increased in the cerebellum of the treated animals. These results show a clear antioxidant cell response against the toxic effects of MeHg in our model, reinforcing the literature data indicating oxidative stress as an important mechanism in the neurotoxicity induced by this organometal. Furthermore, our results point to isoforms of glutathione peroxidase and thioredoxin reductase as important molecular targets of MeHg and, at least, to our knowledge, this is the first study demonstrating the role of GPx4 in the neurotoxicity induced by this toxic environmental agent. Another objective of this study was to investigate the biological effects of the extract of the alga Prasiola crispa (PcE), from the Antarctic continent, in the insect models Drosophila melanogaster and Nauphoeta cinerea. Organisms adapted to extreme environments such as Antarctica tend to present a unique composition in terms of secondary metabolites. Thus, studies aimed at elucidating the biological effects of organisms from these areas tend to be relevant in a biotechnological point of view. Our data demonstrates a potential biocide PcE effect in the fruit fly (Drosophila melanogaster) and lobster cockroach (Nauphoeta cinerea), since the administration of the extract induced toxicity in both models. Toxicity in D. melanogaster was assessed as percentage of mortality, locomotor activity (negative geotaxis) and biochemical measurements including acetylcholinesterase (AChE) and markers of oxidative stress. We also investigated the cardiotoxic action of the extract in a cockroach semi-isolated heart model. The administration of the extract (2 mg / ml) for 24 hours toflies, caused a massive increase in mortality (7.6-fold increase compared to control). We also observed a significant increase in locomotor activity, indicating a neurotoxic action of the extract. AChE activity, glutathione levels and the formation of hydroperoxide remained unchanged. The activity of glutathione S-transferase significantly increased after administration of PcE while catalase activity was significantly decreased in flies that received the extract. A significant decrease in heart rate in the cockroach semi-isolated heart model was observed after PcE administration. The incubation of the extract with DTNB, a strong oxidizing agent, significantly blocked the cardiotoxic effect of the extract, suggesting that reducing compounds may be responsible for the observed effect. Thus, this study demonstrated, for the first time, the toxic effects of PcE, in two insect models, suggesting its potential as a bioinsecticide. The precise mechanisms related to this effect still need clarification, however, changes in vital antioxidant systems may be involved.

A Plataforma Oeste da Península Antártica (POPA) é uma região onde a produtividade primária na superfície do oceano apresenta padrões altamente sazonais e considerável variabilidade interanual. A dinâmica do gelo marinho é o principal fator condicionante da produtividade e, por consequência, dos fluxos de matéria orgânica da superfície para o leito marinho. A matéria orgânica particulada depositada, chamada de fitodetrito, forma densas camadas de alimento lábil disponível para os organismos bênticos. Essa relação estreita entre os processos da coluna de água e aqueles que ocorrem no bentos é chamada de acoplamento bento-pelágico. Com o objetivo de avaliar as respostas da macrofauna bêntica aos fluxos e deposição de alimento, foi realizada uma série temporal sazonal de amostragens (novembro/1999 a março/2001) na POPA em três estações de coleta perpendiculares à costa. Cerca de 25.000 indivíduos pertencentes a 22 táxons foram coletados em 15 amostras de box corer (0,25 m2 cada). Mesmo com alguma variação ao largo da plataforma (de 10.886 ind.m-2 (estação A) a 2.326 ind.m-2 (B)), atribuída a diferenças na topografia, a macrofauna apresentou pouca variabilidade em termos de composição e abundância ao longo do período estudado. Além disso, diferenças na composição e abundância entre estratos sedimentares também foram notáveis, sendo que 90% dos indivíduos foram encontrados entre 0 e 5 cm. Dentre as 185 espécies identificadas, Aurospio foodbancsia (Polychaeta, Spionidae), uma espécie típica de regiões de plataforma na Antártica, mas muito próxima da espécie de mar profundo A. dibranchiata, foi a espécie dominante em todos os períodos e estações (2.087 ind.m-2). Além de Polychaeta, outros grupos abundantes na POPA foram Bivalvia, Tanaidacea e Oligochaeta. Picos de abundância foram observados para algumas espécies, provavelmente associados a eventos sazonais de recrutamento, porém nem sempre associados à chegada do alimento ao fundo marinho da região. Os grupo funcionais de Polychaeta também não variaram ao longo do período estudado, o que indicou que animais depositívoros de superfície e subsuperfície se alimentam ao longo de todo o ano, aproveitando o alimento que permanece lábil e disponível, mesmo no inverno, quando o fluxo de matéria orgânica para o bentos é mínimo. Os resultados encontrados neste trabalho confirmam os resultados já encontrados dentro do projeto FOODBANCS, que a macrofauna da POPA age como um filtro, respondendo menos às flutuações sazonais. / The West Antarctic Peninsula shelf (WAP shelf) experiences a high seasonal and interannual variability in surface primary production. Sea ice dynamics is the principal factor controlling productivity and, therefore, the downward particulate organic matter (POM) fluxes. The deposited POM, also called phytodetritus, forms dense layers of available labile food for benthic organisms. This straight relationship between water column and benthic processes is called benthic-pelagic coupling. A seasonal time-series study was conducted between November 1999 through March 2001 in tree sites on WAP shelf, to determine this relationship, specially the benthic macrofauna (> 300 µm) response to the POM flux and its posterior deposition. From a total of 15 box-corer samples (0.25 m2 each), approximately 25,000 macrofaunal individuals were collected, belonging to 22 taxa. Even with some variation along the shelf, ranging from 10,886 ind.m-2 (site A) to 2,326 ind.m-2 (B), the abundance and composition of macrofauna showed only modest seasonal changes. Differences in these parameters were clear between the inner and outer shelves, probably owing to the topography, which was composed of a basin in the innermost region and a flat region, in the offshore area. Differences in abundance and composition between sediment layers were also notable, with 90% of all individuals belonging to the 0-5 cm layer. Among the 185 identified species, Aurospio foodbancsia (Polychaeta, Spionidae), a typical species of Antarctic shelf regions and closely related to the deep-sea species A. dibranchiata, was dominant in all seasons and sites (2,087 ind.m-2). Besides polychaetes, bivalves, tanaids and oligochaetes were also abundant in WAP shelf. Peaks in abundance were observed for some species and this is believed to be related to seasonal recruitment, however not always associated with the availability of food. Polychaete functional groups did not vary along seasons, indicating that surface and subsurface deposit feeders were subsisting on the labile POM along the year, even during the winter, when POM flux to the benthos is extremely low. The results are similar to those obtained in other FOODBANCS works, and indicate that the WAP shelf macrofauna act as a low-pass filter, muting the seasonal water column processes.

L'Antarctique est encore un continent à explorer pour comprendre le climat terrestre, passé, présent et futur. Grâce à l'analyse des carottages, on peut remonter l'histoire du climat terrestre sur plusieurs centaines de milliers d'années. Grâce à l'étude de sa topographie, on peut remonter à la variabilité de son climat, connaître sa dynamique : écoulement de la glace, vêlages d'icebergs. . . Grâce au suivi de la topographie, c'est-à-dire la variation de la hauteur de glace, on peut estimer les pertes et les gains de masses ainsi que la contribution à la hausse du niveau de la mer, pour déduire l'impact sur les océans et les littoraux. Pour explorer ce continent, nous utilisons dans cette thèse l'instrument embarqué sur satellite qu'est l'altimètre. Une onde radar ou laser est envoyée sur le sol et la réflexion de ce signal est enregistrée permettant d'extraire des paramètres pertinents et la hauteur de glace. Les satellites ont pris le relais des expéditions célèbres du XIXème siècle, notamment depuis le lancement du premier altimètre couvrant jusqu'à 82æ S ce continent, embarqué sur la mission ERS-1. Depuis 2013, SARAL marque un changement dans les caractéristiques instrumentales par rapport aux missions précédentes, car elle émet dans une fréquence appartenant à la bande Ka (36.75 Ghz) au lieu des bandes Ku (13.6 Ghz) et S (3.2 Ghz) ce qui implique une interaction avec la surface différente qu'il faut pouvoir comprendre. Avec près de trois ans d'observations, ce manuscrit regroupe les travaux sur le traitement des données altimétriques dans un but de valorisation de la mission SARAL. Nous présentons le contexte géographique et le contexte technique pour montrer les difficultés du traitement des données . En utilisant la méthode des points de croisement que nous expliciterons, nous présentons l'importance de la comparaison de deux missions concomitantes, ENVISAT et ICESat afin d'estimer la profondeur de pénétration en bande Ku de l'onde radar et corriger de cet effet, étude que l'on pourra répéter avec SARAL une fois la mission ICESat-2 lancée. Nous avons adapté une chaîne de calibration et de validation des données sur glace continentale qui nous permet d'établir des diagnostics, des statistiques et des suivis temporels. La pente de la surface joue un rôle prépondérant dans la dégradation de la précision des données. Nous mettons en place un processus de sélection des données altimétriques afin d'augmenter cette précision. Grâce à cette sélection et l'application de la correction de marée océanique, nous quantifions avec des métriques aux points de croisement la performance de la mesure de SARAL sur glace continentale, et nous réduisons l'imprécision de la mesure de plus de 90%. Enfin, grâce aux sorties de notre chaîne de validation, nous décrivons les observations de SARAL sur près de trois ans afin d'apporter une analyse préliminaire cohérente avec la mission précédente qu'est ENVISAT. Nous soulevons les améliorations à apporter pour aller plus loin dans la physique de la mesure. Que ce soit la comparaison avec d'autres missions, l'utilisation de modèles ou des modifications dans l'algorithme d'extraction des paramètres du signal appelé retracking, SARAL apporte de nouvelles perspectives afin que l'évolution de la calotte Antarctique soit connue avec une précision toujours croissante. / Antarctica still remains a fascinating place to be explored. With ice corings, the past Earth climate can be retraced. Studying its surface, its climate variability and its dynamic are better known : ice velocity, iceberg calvings. . . Through the height variations monitoring, ice gains and losses are estimated, leading to the contribution to the sea-level rise, from which is deduced the impact over coastal areas or the oceans. To explore this continent, we use the sensor called altimeter : a radar or laser wave is sent from the satellite to the surface and the reflected signal is recorded. From this signal we extract relevant parameters and the height. The satellites have observed this area, notably since the altimetric mission ERS-1 launching, until 82æ S in 1991, following the still famous explorations from the beginning of the twentieth century. SARAL, launched in February 2013, innovates because of the major change in the frequency used, the Ka-band (36.75 Ghz) instead of the Ku-band (13.6Ghz) and the S-band (3.2 Ghz) implying a different interaction between the radar wave and the snowpack that needs to be investigated. Using almost three years of observations, we focus on the altimetric signal processing and its validation. The geographic and the technical aspects are introduced and we show the limitations in the altimetric data processing. Using the crossover method (explained in greater detail later), we compare two simultaneous missions, ENVISAT and ICESat in order to better constrain the penetration effect of the radar-wave into the snowpack and correct it. The method that is used will be of great interest to compare SARAL with the future mission ICESat- 2. A new calibration and validation tool has been implemented, allowing a long-term survey of the Antarctic area, providing statistics, diagnostics and temporal series. The slope effect is the major limitation in the precision assessment of the mission. Thanks to a new way of selecting the data and the oceanic tide correction, we quantify with metrics computed at crossover points the accuracy of altimetric data over the Antarctic ice sheet. We describe in the last part the SARAL observations to give a preliminary analysis in agreement with the former mission ENVISAT. Other ways of improvement are presented, like future altimetric missions, modifications in the so-called retracking algorithm that extracts the relevant parameters or even the use of models. SARAL raises perspectives to estimate with a growing precision the evolution of the Antarctic continent, and this thesis is a state of the art about the different possible processings needed to do so.

<p>This thesis contributes to the understanding of glacier response to climate change by ice dynamical studies on Storglaciären, Sweden, and Bonnevie-Svendsenbreen, Kibergbreen and Plogbreen in Dronning Maud Land, Antarctica. Ice surface velocities, ice geometry and temperature information is fed through a force budget model to calculate ice mass outflux of these glacial systems via three-dimensional stress distributions for a flux-gate. </p><p>Field data were collected through repeated DGPS and GPR observations on Storglaciären between July 2000 to September 2001 and on Kibergbreen and Plobreen during the SWEDARP 2002/03 expedition to Antarctica. The work was strongly supported by remotely-sensed information.</p><p>The results from Storglaciären show a strength in the force budget model to discern both spatial and temporal variability in ice dynamical patterns. It highlights the influence of seasonality and bedrock topography upon glacier flow. A modeling experiment on Bonnevie-Svendsenbreen suggested that ice temperature increases substantially under conditions of high stress (≥0.4 MPa) due to strain-heating. This provides a positive feedback loop, increasing ice deformation, as long as it overcomes the advection of cool ice from the surface. These results explain, to some extent, the mechanism behind fast flowing ice streams. Mass flux caclulations from Bonnevie-Svendsenbreen suggest that the outflux given from force budget calculations can be used as a gauge for influx assuming steady state conditions. Plogbreen receives an influx of 0.48±0.1 km³ a^-1 and expedites a discharge volume of 0.55±0.05 km³ a^-1. This indicative negative mass balance is explained by a falling trend in upstream accumulation and the recent rise in global sea level, as it is likely to induce glacier acceleration due to a reduction in resistive forces at the site of the gate. This result is comparable with other Antarctic studies reporting negative mass balances, e.g. from WAIS, as caused by changes in the global atmospheric circulation pattern.</p>

This thesis describes the use of rational redesign to modify the properties of the enzyme Candida antarctica lipase B. Through carefully selected single-point mutations, we were able to introduce substrate-assisted catalysis and to alter the reaction specificity. Other single-point mutations afforded variants with greatly changed substrate selectivity and enantioselectivity. Mutation of the catalytic serine changed the hydrolase activity into an aldolase activity. The mutation decreased the activation energy for aldol addition by 4 kJ×mol-1, while the activation energy increased so much for hydrolysis that no hydrolysis activity could be detected. This mutant can catalyze aldol additions that no natural aldolases can catalyze. Mutation of the threonine in the oxyanion hole proved the great importance of its hydroxyl group in the transition-state stabilization. The lost transition-state stabilization was partly replaced through substrate-assisted catalysis with substrates carrying a hydroxyl group. The poor selectivity of the wild-type lipase for ethyl 2-hydroxypropanoate (E=1.6) was greatly improved in the mutant (E=22), since only one enantiomer could perform substrate-assisted catalysis. The redesign of the size of the stereospecificity pocket was very successful. Mutation of the tryptophan at the bottom of this pocket removed steric interactions with secondary alcohols that have to position a substituent larger than an ethyl in this pocket. This mutation increased the activity 5 500 times towards 5-nonanol and 130 000 times towards (S)-1-phenylethanol. The acceptance of such large substituents (butyl and phenyl) in the redesigned stereospecificity pocket increases the utility of lipases in biocatalysis. The improved activity with (S)-1-phenylethanol strongly contributed to the 8 300 000 times change in enantioselectivity towards 1-phenylethanol; example of such a large change was not found in the literature. The S-selectivity of the mutant is unique for lipases. Its enantioselectivity increases strongly with temperature reaching a useful S-selectivity (E=44) at 69 °C. Thermodynamics analysis of the enantioselectivity showed that the mutation in the stereospecificity pocket mainly changed the entropic term, while the enthalpic term was only slightly affected. This pinpoints the importance of entropy in enzyme catalysis and entropy should not be neglected in rational redesign.

This thesis contributes to the understanding of glacier response to climate change by ice dynamical studies on Storglaciären, Sweden, and Bonnevie-Svendsenbreen, Kibergbreen and Plogbreen in Dronning Maud Land, Antarctica. Ice surface velocities, ice geometry and temperature information is fed through a force budget model to calculate ice mass outflux of these glacial systems via three-dimensional stress distributions for a flux-gate. Field data were collected through repeated DGPS and GPR observations on Storglaciären between July 2000 to September 2001 and on Kibergbreen and Plobreen during the SWEDARP 2002/03 expedition to Antarctica. The work was strongly supported by remotely-sensed information. The results from Storglaciären show a strength in the force budget model to discern both spatial and temporal variability in ice dynamical patterns. It highlights the influence of seasonality and bedrock topography upon glacier flow. A modeling experiment on Bonnevie-Svendsenbreen suggested that ice temperature increases substantially under conditions of high stress (≥0.4 MPa) due to strain-heating. This provides a positive feedback loop, increasing ice deformation, as long as it overcomes the advection of cool ice from the surface. These results explain, to some extent, the mechanism behind fast flowing ice streams. Mass flux caclulations from Bonnevie-Svendsenbreen suggest that the outflux given from force budget calculations can be used as a gauge for influx assuming steady state conditions. Plogbreen receives an influx of 0.48±0.1 km3 a-1 and expedites a discharge volume of 0.55±0.05 km3 a-1. This indicative negative mass balance is explained by a falling trend in upstream accumulation and the recent rise in global sea level, as it is likely to induce glacier acceleration due to a reduction in resistive forces at the site of the gate. This result is comparable with other Antarctic studies reporting negative mass balances, e.g. from WAIS, as caused by changes in the global atmospheric circulation pattern.

Les céramides sont des lipides de la classe des sphingolipides issus de la N-acylation d'une base sphingoide par un acide gras. Ces lipides et leurs analogues suscitent un grand intérêt comme composants actifs dans les industries pharmaceutique et cosmétique. Parmi les biocatalyseurs capables de réaliser la synthèse de ce type de lipide, la lipase B de Candida antarctica semble être l'enzyme la plus adaptée à la production de " pseudo-céramides " à partir d'amino-polyols. Dans ce contexte, nous avons abordé l'étude de l'acylation de composés de type " amino-alcool "catalysée par la lipase B de Candida antarctica, en gardant à l'esprit une approche fondamentale afin d'élargir les connaissances actuelles sur ce sujet. La première partie de notre travail a ainsi traité de l'étude cinétique de l'acylation de composés monofonctionnels afin de déterminer les mécanismes réactionnels et l'énantio sélectivité de la lipase B de Candida antarctica pour les réactions de N-acylation et de O-acylation. Les parties suivantes de notre travail ont porté sur une étude structure-réactivité du substrat accepteur d'acyle et sur l'étude de l'influence du solvant utilisé (solvant organique ou liquide ionique) afin de déterminer les facteurs clés influençant la chimio sélectivité et la régio sélectivité de la lipase B de Candida antarctica lors de l'acylation de composés multifonctionnels de type " amino-alcool ". Finalement, à partir des connaissances acquises dans les différentes parties, nous avons développé et optimisé un procédé de synthèse enzymatique de " pseudo-céramides " (O,N-diacyl aminopropanediols) mis en oeuvre en réacteur continu à " lit fixe ".