Les adénovirus sont des virus non enveloppés. Afin de pouvoir se répliquer ils doivent entrer dans leur cellule hôte et être transportés jusqu’au noyau pour pouvoir initier l’expression du génome viral. Pour ce faire le virus utilise les composants de sa capside. Parmi ses composants, la protéine VI, une protéine interne de capside, induit la rupture de l’endosome grâce à son hélice amphipatique en N-terminal de la protéine. Récemment, une autre fonction de cette protéine a été décrite durant l’entrée du virus, impliquant cette fois-ci le motif conservé PPxY de la protéine VI. En effet la mutation de ce motif conservé : mutant M1 (PPxYPGAA), diminue de 20 fois l’infection du virus par rapport au virus sauvage. Cette baisse d’infectiosité est liée à un défaut de transport et d’accumulation du virus au niveau du centre organisateur des microtubules (MTOC). Il se trouve que la mutation du motif PPxY conduit à une perte d’interaction de la protéine VI avec les ubiquitines ligase de la famille Nedd4, mais également à un défaut d’ubiquitylation de la protéine VI. Nous avons ainsi entrepris d’étudier le rôle de cette modification post-traductionnelle lors de l’entrée du virus dans la cellule, mais aussi, de manière plus générale, le rôle de la protéine VI. Ainsi nous avons mis en évidence le rôle de la protéine VI et de son motif PPxY dans l’activation du génome viral. Par ailleurs, nous avons identifié une lysine ubiquitylée de la protéine VI et produit un mutant : mutant M6, pour étudier le rôle de cette ubiquitylation. Nous avons enfin entrepris de caractériser l’entrée du virus en produisant et en utilisant des adénovirus mutants, dont le nouveau mutant M6 / Adenoviruses are non-enveloped viruses. In order to replicate they have to enter their host cell and be transported toward the nucleus to initiate the viral gene expression. This requires the involvement of viral capsids components. Among these components, protein VI, an inner capsid protein, can induce endosomal rupture, thanks to its amphipathic helix located at the N-terminus part of the protein. Recently, the involvement of a conserved PPxY motif in the Protein VI has also been described in viral entry. Indeed, mutation of this motif (PPxY  PGAA) reduced infectivity of the mutant virus (M1 mutant) 20 folds compared to the wild type virus. This reduction of infectivity is related to a defect of transport and accumulation of viruses at the microtubule organizing center (MTOC) during virus entry. The mutation of PPxY motif leads to a loss of interaction between the protein VI and ubiquitin ligases from the Nedd4 family, and to a lack of protein VI ubiquitylation. The aim of this study was therefore to investigate the role of this posttranslational modification during virus entry, but also more generally the role of protein VI. In this work, we highlight the role of protein VI and its PPxY motif in the activation of the viral genome. Moreover, to investigate the ubiquitylation during virus entry we identify a lysine mutant of protein VI that lack ubiquitylation without altering the potential for interaction with ubiquitin ligases: the mutant M6. We then proceed to characterize the entry of the virus by producing and using mutant viruses, including this new mutant.

Ces travaux de thèse ont débuté par la présentation des propriétés physico-chimiques du chrome, ses principaux domaines d'application. On a aussi indiqué les problèmes posés et les risques associés à l'emploi des dérivés chromiques qui s'expriment essentiellement au niveau cutané, respiratoire et même immunologique. Ensuite, on a cité les différents procédés d'élimination tels que les procédés membranaires, procédés chimiques, procédés biologiques et procédés physiques en précisant les avantages et inconvénients de chacun de ces procédés. Après, on a présenté le procédé d'adsorption sur alumine activée, en rappelant brièvement les différents adsorbants utilisés ainsi que les modèles thermodynamiques et cinétiques utilisés pour décrire ce phénomène. Enfin, on a rappelé quelques généralités sur les membranes échangeuses d'ions et sur le procédé de dialyse ionique croisée. Dans une seconde étape, on a étudié la validation de la technique analytique selon la norme Française XPT 90-120, ensuite une étude préliminaire de l'influence des différents paramètres selon le plan d'expérimentation factorielle afin de montrer l'influence de chaque paramètre indépendamment et leurs dépendances aussi. Ces facteurs sont les suivants : pH, quantité de l'adsorbant, concentration du métal initial et de la température. Cette étude a porté sur l'effet du pH mais aussi l'effet de la masse de l'alumine activée et l'effet de la concentration initiale du chrome afin d'optimiser ces paramètres, les résultats expérimentaux ont montré que l'adsorption du chrome dépend essentiellement du pH et de la concentration du chrome initiale. Dans les conditions optimales, les taux d'élimination du chrome VI peuvent attendre 98 % pour une concentration initiale de 10 mg/L en chrome. Les résultats expérimentaux ont été appliqués aux modèles de Freundlich, Langmuir, Dubinin-Redushkevich et Temkin. Des études cinétique et thermodynamiques suivront pour déterminer l'ordre de la réaction d'adsorption des métaux lourds et nature exothermique du mécanisme. La troisième partie a porté sur la Dialyse Ionique Croisée, dans un premier temps on a développé une étude préliminaire de l'influence des différents paramètres selon le plan d'expérimentation effectué afin d'identifier et d'évaluer l'influence de chaque paramètre sur les taux d'élimination de l'ion métallique. Ces facteurs sont la concentration initiale de l'ion métallique, la concentration initiale de l'ion de substitution, le type de la membrane et l'agitation magnétique. Cette démarche est nécessaire afin de fixer les paramètres optimaux et évaluer leurs interactions mutuelles. Cette étude a permis de montrer que le type de membrane échangeuse d'anions est le plus important paramètre influant sur l'élimination du chrome et ceci peut s'expliquer par les valeurs élevées de la capacité d'échange et de la teneur en eau de la membrane AFN. La modélisation du transfert des ions HCrO4- en dialyse ionique croisée a montré la présence de deux phases : la couche limite de diffusion du côté de l'alimentation (solution à traiter contant les ions HCrO4-) et la membrane. En deuxième étape, nous avons effectué une étude du vieillissement des membranes, qui consiste à faire un suivie de l'épaisseur membranaire, de la conductivité membranaire et de leur morphologie par MEB. Nous avons montré que les membranes AMV et AFN se dégradent peu à priori de la même manière. Finalement, nous avons effectué un nouveau montage qui couple les deux procédés et ceci dans le but d'améliorer le taux d'élimination. Ce couplage a permis d'augmenter l'efficacité et la cinétique d'échange de la dialyse, en plus une réduction considérable de la quantité d'alumine activée à régénérer et l'amélioration de la cinétique de transfert transmembranaire / The removal of chromium (VI) from aqueous solutions by activated alumina has been investigated as a function of solution pH, initial chromium concentration, adsorbent dose of activated alumina and temperature. The pH and the adsorbent dose of activated alumina are the most significant parameters affecting chromium (VI) adsorption. The chromium concentrations were analyzed by reaction with 1,5-diphenylcarbazide. This method has been validated according to the French standard XPT-90-210. In order to optimize the effect of the main parameters and their mutual interaction for the adsorption process, a full factor design of the type nk has been used. In this study the removal of chromium (VI) by adsorption on activated alumina was investigated and results were fitted to Langmuir, Freundlich, Dubinin-Redushkevich and Temkin adsorption models, at different temperatures. The constants of each model were evaluated depending on temperature. Thermodynamic parameters for the adsorption system were determined at 10, 25 and 40°C. The obtained values showed that Cr (VI) adsorption is a spontaneous and exothermic process. The kinetic process was evaluated by first–order, second–order and Elovich kinetic models. In second section, the removal of chromium (VI) from aqueous solutions by Donnan dialysis has been investigated. The tows AEMs: Selemion AMV and Neosepta AFN. The amount of chromium removed was determined on the basis of the following parameters: initial chromium concentration, type of anion exchange membranes, co-ion concentration and magnetic stirring. A 24 full factorial design analysis was performed to screen the parameters affecting Cr (VI) removal efficiency were examined. Using the experimental results, a linear mathematical model representing the influence of the different parameters and their interactions was obtained. Analysis of variance (ANOVA), F-test and student's t- test showed that the type of anion exchange membrane is the most significant parameter affecting chromium (VI) removal. The statistical analysis of experimental data assumes that the data come from normal distribution. Then, a modelisation of chromium removal by Donnan dialysis through anion exchange membrane, these results are compared with the theoretical predictions given by the resolution of the corrected Nernst–Planck's equation in the cases of the homogeneous models of ion-exchange membranes. This confrontation confirms the existence of three domains corresponding respectively to a complete diffusion boundary layers (DBLs) control, a mixed control and a complete membrane control of the inter-diffusion process. And finally, the Donnan dialysis and adsorption onto activated alumina has been coupled. The coupling DIC-AAA was successfully achieved with 90% of chromium removed

A preocupação com o desenvolvimento sustentável tem levado a indústria e os órgãos controladores do meio ambiente a reavaliarem o emprego em larga escala de procedimentos industriais que, embora eficientes, são prejudiciais à saúde humana e ao meio ambiente. Em concordância com estas novas tendências, as indústrias de tratamento de superfícies de metais e instituições de pesquisa têm empregado grandes esforços no sentido de encontrar substitutos eficientes para procedimentos de proteção contra a corrosão que contenham íons de cromo hexavalente, os quais são muito eficientes, mas apresentam o inconveniente de não serem ambientalmente corretos devido ao caráter cancerígeno e poluente do íon Cr(VI) já reconhecido por diversas agências de proteção ambiental. Com a finalidade de aumentar a proteção contra a corrosão, em linhas industriais contínuas de eletrogalvanização por eletrodeposição, as peças produzidas são protegidas por uma camada de passivação obtida em banho de conversão contendo sais de Cr(VI) e, na maioria dos casos, não passa pelo processo de enxágue após sua produção. Neste trabalho o comportamento de corrosão do aço eletrogalvanizado protegido com camadas de passivação obtidas a partir de banhos de conversão contendo sais de Cr(III) e Co(II) ou uma emulsão de um copolímero de etileno, sem enxágue, foi avaliado por técnicas eletroquímicas, especificamente, acompanhamento do potencial de circuito aberto, curvas de polarização potenciodinâmica anódicas e catódicas, e espectroscopia de impedância eletroquímica (EIS), em soluções com diferentes concentrações de NaCl. Adicionalmente foi avaliado o comportamento de corrosão por ensaios em câmara de névoa salina, realizados de acordo com a norma ASTM B117-11. Como referência, os resultados foram comparados com aqueles apresentados por amostras protegidas por camada de passivação produzida a partir de banho contendo íons de Cr(VI). Para melhor compreender a influência da microestrutura sobre o mecanismo de corrosão, as amostras foram caracterizadas por microscopia eletrônica de varredura antes e após imersão nos diferentes eletrólitos. A análise microestrutural foi complementada por ensaios de difração de raios-X. 7 Os resultados dos ensaios eletroquímicos realizados após tempos curtos de imersão mostraram melhor desempenho para as amostras protegidas com a camada de passivação produzida a partir de banho contendo íons Cr(VI). Entretanto os ensaios de EIS após tempos mais longos de imersão nos diferentes eletrólitos ensaio, bem como os ensaios de névoa, evidenciaram que as amostras protegidas com a camada passiva obtida a partir do banho contendo íons de Cr(III) e Co(II) podem apresentar desempenho semelhante àquelas protegidas com camada de conversão de Cr(VI). Para esta condição, a análise microestrutural e o ajuste dos diagramas de EIS com circuitos equivalentes indicaram um papel importante dos produtos de corrosão no comportamento anticorrosivo das amostras protegidas com a camada de passivação de Cr(III) e Co(II). Em nenhuma das condições estudadas as amostras protegidas com o copolímero de etileno apresentaram desempenhos comparáveis aos das outras duas camadas de passivação estudadas. / Recent concerns with sustainable development have led industries and environment regulatory agencies to reassess the use at large scale of industrial procedures that, although efficient, are harmful to human health and the environment. In accordance with these new tendencies, surface treatment industries and research institutes have expended great efforts to find efficient substitutes for corrosion protection procedures that employ hexavalent chromium ions (Cr(VI)). They are very effective but have the drawback of not being environmentally friendly due to the carcinogenic and pollutant properties of Cr(VI) ions, already recognized by several environmental protection agencies. Aiming to increase the corrosion protection, in industrial continuous lines of galvanizing by electroplating, the parts produced are protected with a passivation layer obtained from a conversion bath containing Cr(VI). These parts are not rinsed after the final production step. In this work the corrosion behavior of electroplated galvanized steel protected with passivation layers from conversion baths containing Cr(III) and Co(II) ions or an ethylene copolymer emulsion was evaluated by means of electrochemical techniques, specifically, open circuit potential measurements, anodic and cathodic potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The tests were performed in sodium chloride solutions of different concentrations. Additionally, the corrosion behavior was evaluated by salt spray tests performed according the ASTM B117-11 standard. For reference, the results were compared with those presented by samples protected by passivation layers produced from conversion baths containing Cr (VI) ions. Aiming to better understand the influence of microstructure on the corrosion mechanism, the samples were characterized by scanning electron microscopy before and after immersion in the different electrolytes. Microstructure analysis was complemented by X-ray diffraction. The results of electrochemical tests performed after short immersion times showed better corrosion performance for samples protected with the passivation layer produced from conversion baths containing Cr(VI) ions. However, the EIS tests performed after longer immersion times in the different electrolytes, as well as the 9 salt spray tests, showed that samples protected with the passive layer obtained from the bath containing Cr (III) and Co (II) ions may present similar performance to those protected with the Cr (VI) conversion layer. The microstructural analysis and fitting of the EIS diagrams with equivalent circuits indicated an important role of corrosion products in the anti-corrosive performance of the samples protected with the passivation layer of Cr (III) and Co (II). In the studied conditions, the samples protected with the ethylene copolymer did not showed comparable performance to the other two passivation layers investigated in the present study.

The storage of nuclear waste in deep geological formations is discussed worldwide as the main strategy for nuclear waste management. To ensure the confinement of the nuclear waste, a multiple barrier system which consists of engineered, geo-engineered, and geological barriers will be applied. Thereby, in Germany the definition of the isolating rock zone represents an important safety function indicator. Clay rock is internationally investigated as potential host rock for a repository and represents a part of the geological barrier. In the present work, the natural clay rock Opalinus Clay from the Mont Terri rock laboratory, Switzerland, was studied. In Germany, the direct disposal of the spent nuclear fuel without the reprocessing of the spent fuel is preferred. In case of water ingress, radionuclides can be released from the nuclear waste repository into its surroundings, namely the host rock of the repository. Humic acids, ubiquitous in nature, can be found associated with the inorganic components in natural clay rock (1.5×10–3 wt.% in Opalinus Clay). They can be released under certain conditions. Due to their variety of functional groups, humic acids are very strong complexing agents for metal ions. They have inherent redox abilities and a colloidal conformation in solution. Because of these characteristics, humic acids can affect the mobility of metal ions such as actinides. Furthermore, in the near-field of a repository elevated temperatures have to be considered due to the heat production resulting from the radioactive decay of the various radionuclides in the nuclear waste. This work focuses on the interaction of uranium, as main component of spent nuclear fuel, with Opalinus Clay and studies the influence of humic acid and elevated temperature on this interaction. For investigation of the retention behavior of the clay and the mobility of U(VI) in the system, batch sorption and diffusion experiments were performed. To clarify which U(VI) and humic acid species were present under the applied conditions, aqueous speciation modeling was used. Additionally, the U(VI) speciation in solution and on the clay surface was investigated by spectroscopic methods. Prior to the investigation of the ternary system U(VI) / humic acid / clay, the applied batches of Opalinus Clay were characterized (e.g., specific surface area, carbon content, cation exchange capacity, elemental composition, particle size distribution). Leaching studies with Opalinus Clay in synthetic Opalinus Clay pore water (pH 7.6, It = 0.34 mol/L) and in NaClO4 (pH 3 – 10, I = 0.1 mol/L) were performed to identify the competing ions and their concentrations in the background electrolytes. These data were used to calculate the U(VI) and humic acid speciation in solution. Calcium and carbonate ions are present under pore water conditions as well as in 0.1 mol/L NaClO4 from pH 7 to 8.5, due to dissolution of calcite (mineral fraction in Opalinus Clay). Thus, the U(VI) speciation is dominated by the aquatic Ca2UO2(CO3)3 complex. In the case of pore water, Ca2UO2(CO3)3(aq) is also the dominant U(VI) species in the presence of humic acid, which was corroborated by time-resolved laser-induced fluorescence spectroscopic measurements. A significantly changed speciation was found in 0.1 mol/L NaClO4 in the presence of humic acid. At pH > 7, the negatively charged UO2(CO3)2HA(II)4– complex determines the U(VI) speciation, thus repressing the Ca2UO2(CO3)3(aq) complex. In addition, the speciation of humic acid is influenced from ions leached out from Opalinus Clay. The CaHA(II) complex is the dominating humic acid species in solution. Batch sorption experiments in 0.1 mol/L NaClO4 showed that Opalinus Clay has the strongest retardation effect on U(VI) in the pH range from pH 4.5 to 7. However, under environmentally relevant conditions (pH > 7), the sorption of U(VI) onto Opalinus Clay is very weak. Under pore water conditions, a distribution coefficient (Kd) of 0.0222 ± 0.0004 m3/kg was determined, which was shown to be independent of solid-to-liquid ratios ≥ 60 g/L. In addition, in pore water, the U(VI) sorption onto Opalinus Clay is not influenced by humic acid, which is supported by the speciation results. Extended X ray absorption fine-structure investigations confirmed this batch sorption result. The U(VI) diffusion experiments performed in pore water at 25 °C with Opalinus Clay bore core samples confirmed the Kd value obtained by batch sorption experiments. In the diffusion experiments at 60 °C, a change in the U(VI) speciation occurred. Beside Ca2UO2(CO3)3(aq), a colloidal U(VI) species was formed. Almost equivalent apparent diffusion coefficient (Da) values were determined for the diffusion of the aqueous U(VI) species at 25 and 60 °C through Opalinus Clay. Thus, based on the investigations in the present study the breakthrough of U(VI) through Opalinus Clay is expected to be independent of the temperature and should occur nearly at the same time. Modeling calculations showed that it would take about 10 years until a detectable amount of 233U(VI) (1×10–9 mol/L) migrates through an 11 mm thick Opalinus Clay sample. Two distinct humic acid size fractions – a large- and a small-sized colloid fraction – diffused through the Opalinus Clay samples. Within three months, the high molecular size humic acid colloids migrated only about 500 µm into the clay, whereas the low molecular size fraction diffused through the entire Opalinus Clay samples and were consequently detected in the receiving reservoirs. These findings demonstrate a filtration effect of the compacted clay. The diffusion experiments revealed that the effect of humic acid on U(VI) diffusion is negligible and, under the studied conditions, independent of temperature. The obtained results contribute to data bases used for modeling of interaction and migration processes in uranium / clay rock systems. Thus, the collected sorption and diffusion data are not only relevant for safety assessment of nuclear waste repositories but also for any clay-containing system present in the environment, where the geochemical interaction with uranium contaminated water plays a role. Concerning the suitability of Opalinus Clay as host rock for a nuclear waste repository, it can be concluded, that Opalinus Clay has a relatively high retardation potential for U(VI). In case of water ingress U(VI) as part of the nuclear waste is released into the clay formation. Under near-neutral pH conditions, it will be complexed by calcium and carbonate ions leached out from Opalinus Clay, whereby Ca2UO2(CO3)3(aq) is formed. This complex is only weakly retarded by sorption onto the clay, which can contribute to an enhanced mobility of U(VI) in the host rock. However, the U(VI) migration through the clay rock is governed by molecular diffusion. This decelerates the migration of Ca2UO2(CO3)3(aq) through Opalinus Clay and thus it represents the decisive retardation process in the investigated system. Additionally, under environmentally relevant conditions, humic acid has no significant influence on U(VI) / Opalinus Clay interaction even at an elevated temperature of 60 °C. This was shown by speciation, sorption, as well as diffusion experiments. / Eine weltweit diskutierte Strategie zum Umgang mit radioaktiven Abfällen ist deren Endlagerung in tiefen geologischen Formationen. Zur Abschirmung der Umwelt vor den schädlichen Einflüssen des radioaktiven Abfalls soll ein Multibarrierensystem bestehend aus technischen, geotechnischen und geologischen Barrieren im Endlager dienen. Dabei ist in Deutschland die Definition des einschlusswirksamen Gebirgsbereichs ein wichtiger sicherheitstechnischer Indikator. Tongestein wird als potentielles Endlagerwirtsgestein und Teil der geologischen Barriere international erforscht. In der vorliegenden Arbeit wurde das natürliche Tongestein Opalinuston aus dem Mont Terri Felslabor, Schweiz, untersucht. In Deutschland wird die direkte Endlagerung des abgebrannten Kernbrennstoffes ohne Wiederaufarbeitung des Brennstoffs favorisiert. Bei Wassereinbruch können Radionuklide aus dem Abfall in die Umgebung des Endlagers freigesetzt werden, d. h. sie können in Kontakt mit dem Wirtsgestein kommen. Ubiquitär in der Natur vorkommende Huminsäuren können mit den anorganischen Komponenten des natürlichen Tongesteins vergesellschaftet sein (1.5×10–3 Gew.-% in Opalinuston). Unter bestimmten Bedingungen können die Huminsäuren freigesetzt werden. Ihre Struktur enthält eine Vielzahl von funktionellen Gruppen, was sie zu starken Komplexbildnern für Metallionen macht. Sie besitzen Redoxeigenschaften und bilden in Lösung eine kolloidale Konformation aus. Aufgrund dieser Charakteristika können sie die Mobilität von Metallionen wie den Actinoiden beeinflussen. Weiterhin sind im Nahfeld eines Endlagers erhöhte Temperaturen zu erwarten, welche aus der Wärmefreisetzung beim radioaktiven Zerfall der verschiedenen Radionuklide im radioaktiven Abfall resultieren. Die vorliegende Studie konzentriert sich auf die Untersuchung der Wechselwirkung von Uran, als Hauptkomponente des endgelagerten abgebrannten Kernbrennstoffs, mit Opalinuston und untersucht dabei den Einfluss von Huminsäure und erhöhter Temperatur. Um das Rückhaltevermögen des Tongesteins gegenüber U(VI) und die U(VI)-Mobilität im System zu ermitteln, wurden Sorptions- und Diffusionsversuche durchgeführt. Zur Klärung, welche U(VI)- und Huminsäurespezies unter den untersuchten Bedingungen vorliegen, wurde die aquatische Speziation berechnet. Zusätzlich wurde die U(VI)-Speziation in Lösung und an der Tonoberfläche mit spektroskopischen Methoden untersucht. Vor der Untersuchung des ternären Systems U(VI) / Huminsäure / Ton wurden die eingesetzten Opalinuston-Chargen charakterisiert (z. B. spezifische Oberfläche, Kohlenstoffgehalt, Kationenaustauschkapazität, elementare Zusammensetzung, Partikelgrößenverteilung). Anschließend wurden Auslaugungsversuche mit Opalinuston in synthetischem Opalinustonporenwasser (pH 7.6, It = 0.34 mol/L) und in NaClO4 (pH 3 – 10, I = 0.1 mol/L) durchgeführt, um relevante Konkurrenzionen zu identifizieren und deren Konzentration in den Hintergrundelektrolyten zu bestimmen. Die erhaltenen Daten wurden zur Berechnung der U(VI)- und Huminsäurespeziation in Lösung verwendet. Unter Porenwasserbedingungen sowie in 0.1 mol/L NaClO4 von pH 7 bis 8.5 liegen, durch die Auflösung von Calcit (Mineralphase im Opalinuston), Calcium- und Carbonationen in Lösung vor. Dadurch wird die U(VI)-Speziation von dem aquatischen Ca2UO2(CO3)3-Komplex dominiert. Im Falle des Porenwassers ist Ca2UO2(CO3)3(aq) auch in Gegenwart von Huminsäure die dominierende U(VI)-Spezies. Dies wurde durch zeitaufgelöste laserinduzierte fluoreszenzspektroskopische Messungen nachgewiesen. Eine signifikante Änderung der U(VI)-Speziation tritt in 0.1 mol/L NaClO4 in Gegenwart von Huminsäure auf. Bei pH > 7 bestimmt der negativ geladene UO2(CO3)2HA(II)4–-Komplex die U(VI)-Speziation, wobei der Anteil von Ca2UO2(CO3)3(aq) zurückgedrängt wird. Auch die Huminsäurespeziation wird durch die vom Opalinuston ausgelaugten Ionen beeinflusst. So ist der CaHA(II)-Komplex die dominierende Huminsäurespezies in Lösung. Sorptionsversuche in 0.1 mol/L NaClO4 zeigten, dass Opalinuston gegenüber U(VI) den stärksten Retardationseffekt im pH-Bereich 4.5 bis 7 aufweist. Unter umweltrelevanten Bedingungen hingegen (pH > 7) ist die U(VI)-Sorption an Opalinuston sehr schwach. Unter Porenwasserbedingungen wurde ein Verteilungskoeffizient (Kd) von 0.0222 ± 0.0004 m3/kg ermittelt, der von Fest-Flüssig-Verhältnissen ≥ 60 g/L unabhängig ist. Außerdem wird die U(VI)-Sorption an Opalinuston in Porenwasser nicht von Huminsäure beeinflusst. Dies wird durch die Ergebnisse aus den Speziations-rechnungen unterstützt. Röntgenabsorptionsspektroskopische Untersuchungen bestätigten ebenfalls dieses Sorptionsergebnis. Die U(VI)-Diffusionsexperimente in Porenwasser bei 25 °C unter Verwendung von Opalinustonbohrkernstücken bestätigten den Kd-Wert der Sorptionsexperimente. In den Diffusionsexperimenten bei 60 °C trat eine Änderung in der U(VI)-Speziation auf. Neben Ca2UO2(CO3)3(aq) wurde eine kolloidale U(VI)-Spezies gebildet. Für die Diffusion der aquatischen U(VI)-Spezies durch Opalinuston bei 25 und 60 °C wurden annähernd gleiche scheinbare (apparente) Diffusionskoeffizienten (Da) bestimmt. Das bedeutet, der Durchbruch von U(VI) durch Opalinuston ist unabhängig von den hier untersuchten Temperaturen und wird deshalb etwa zum gleichen Zeitpunkt erwartet. Modellierungen zeigten, dass es etwa zehn Jahre dauern würde, bis eine detektierbare Menge an 233U(VI) (1×10–9 mol/L) durch ein 11 mm-dickes Opalinustonbohrkernstück migrieren würde. Zwei verschiedene Huminsäuregrößenfraktionen diffundierten durch die Opalinustonproben – eine große und eine kleine kolloidale Größenfraktion. Innerhalb von drei Monaten migrierten die hochmolekularen Huminsäurekolloide nur 500 µm in den Ton, während die niedermolekularen Huminsäurekolloide durch die gesamten Opalinustonproben diffundierten und dadurch im Auffangreservoir detektiert werden konnten. Diese Resultate demonstrieren den Filtrationseffekt des Tongesteins. Die Diffusionsversuche zeigten, dass der Einfluss von Huminsäure auf die U(VI)-Diffusion, unabhängig von der in dieser Arbeit verwendeten Temperatur, vernachlässigbar ist. Die erhaltenen Ergebnisse tragen zu Datenbanken bei, die für die Modellierung von Wechselwirkungs- und Migrationsprozessen in Uran / Tongestein-Systemen genutzt werden. Das bedeutet, die gesammelten Sorptions- und Diffusionsdaten sind nicht nur für den Langzeitsicherheitsnachweis eines Endlagers für radioaktive Abfälle von Relevanz, sondern auch für jedes tonhaltige System in der Umwelt, bei dem die geochemische Wechselwirkung mit urankontaminierten Wässern eine Rolle spielt. Bezüglich der Eignung von Opalinuston als Wirtsgestein für ein Endlager radioaktiver Abfälle lässt sich schlussfolgern, dass Opalinuston ein relativ hohes Retardationspotential bezüglich U(VI) aufweist. Wenn U(VI) als Bestandteil des radioaktiven Abfalls bei Wassereinbruch im Endlager in die Umgebung freigesetzt wird, wird es unter umweltrelevanten Bedingungen von Calcium- und Carbonationen, welche aus dem Opalinuston herausgelöst werden, komplexiert. Dabei bildet sich Ca2UO2(CO3)3(aq). Dieser Komplex wird nur schwach durch Sorption am Tongestein zurückgehalten, was zu einer erhöhten U(VI)-Mobilität im Wirtsgestein führen kann. Im untersuchten System wird die U(VI)-Migration durch das Tongestein jedoch durch molekulare Diffusion bestimmt. Sie verzögert die Migration von Ca2UO2(CO3)3(aq) durch Opalinuston und stellt somit den maßgeblichen Retardationsprozess im System dar. Huminsäure hat keinen signifikanten Einfluss auf die U(VI) / Opalinuston-Wechselwirkung, sogar bei einer erhöhten Temperatur von 60 °C. Dies wurde mittels Speziationsmodellierungen sowie durch Sorptions- und Diffusionsversuche gezeigt.

This thesis is the result of nine weeks fieldwork in Babati and Bukoba districts in Northern Tanzania during spring 2012. The purpose of this thesis is to study why development projects on fuel-efficient stoves have had a limited adoption in these two regions and what obstacles and opportunities there are for further spread of fuel-efficient cooking stoves. Semi-structured interviews were the main method used for collecting the empirical data, which was then analysed from a socio-economic perspective with help from the framework of Sustainable Rural Livelihoods. The Results showed that people’s perceptions of fuel-efficient stoves are positive but that projects face many obstacles connected to socio-economic conditions. Knowledge on how to get stoves and access to financial capital is main obstacles for further spreading. Social networks and organisations are channels for information, but to spread outside these networks will need complementing strategies from organisations promoting fuel-efficient stoves. Important are also finding ways of making the financial aspect of adopting stoves less, like using materials with lower costs, using stove-models with low costs and training people in building stoves so re-investments are unnecessary and dependency of funding from organisations less. Gender is a factor affecting the adoption of fuel-efficient stoves, regarding access to assets and generated benefits. There is therefore an importance of involving gender throughout the different stages of the projects.

I denna uppsats gör jag en textanalys av tre årgångar av tidskriften Vi föräldrar: 1968, 1983 och 1994. Jag ställer frågan vilka bilder av föräldraskap, framförallt faderskap, som framkommer i tidskriften och hur jämställd relationen mellan pappa och mamma är. Avspeglar sig tankar om ”den dubbla emancipationen” – det vill säga att både kvinnor och män ska delta i såväl yrkesarbete som i arbetet med hem och barn – i tidskriften och sker det några förändringar över tid? Som inramning till min analys beskriver jag det samhälleliga och politiska sammanhanget när det gäller föräldraskap och jämställdhet under den tid då respektive årgång gavs ut. Jag använder mig av teoretiska resonemang om bland annat barnorienterad maskulinitet och diskursen om det olika föräldraskapet i min analys. Min beskrivning och analys av de tre årgångarna visar att tidskriften genomgår stora förändringar över tid. Bilden av föräldraskapet och jämställdheten i tidskriften motsvarar väl det sammanhang i vilket den ges ut. Pappa är 1968 en relativt frånvarande familjeförsörjare men har 1994 blivit en delaktig familjefar. Samtidigt har han, fortfarande 1994, långt större möjlighet än mamma att välja nivå på sitt engagemang i barnen och hemmet. Att pappa spenderar tid med barnen och tar ut en större del av föräldraledigheten är något som i alla fall i de två senare årgångarna ses som positivt, även om det i årgång 1983 ofta betonas att papparollen inte får bli för lik mammarollen. Mamma har dock alltid huvudansvaret för barnen och hemmet och pappas delaktighet lyfts inte fram som viktig för hennes skull utan som något som i första hand är bra för barnen och för hans egen personliga utveckling. Min slutsats är att tidskriften Vi föräldrar under denna period inte kan sägas ha varit en tydlig förespråkare för den dubbla emancipationen. / In this essay, I carry out a text analysis of three volumes of the Swedish monthly magazine Vi föräldrar: 1968, 1983 and 1994. I examine what kind of images of parenthood, particularly fatherhood, the magazine reflects, and the relationship between mum and dad in terms of gender equality. Does the idea of so-called double emancipation – that both men and women are to participate in working life as well as in childcare and housework – manifest itself in the magazine and are there changes over time? As a contextual framework for my analysis, I use a separate section of the essay to describe the societal and political context as regards family and equal opportunities policy in the periods during which each of the three analysed volumes were originally published. Theoretically, the analysis utilises discussions and research on child-oriented masculinity, and the gender differentiated parenthood discourse. My description and analysis of the three volumes makes apparent that the magazine undergoes major changes over time. The images of parenthood and gender equality in each volume correspond to the social and political context in which it was published. In 1968, dad is a relatively absent breadwinner, whereas in 1994 he has become more of a family man. However, even in the 1994 volume, he retains the privilege of being able to choose the level of his commitment to the family in a way that mum never can. The fact that dad spends more time with the children and takes a greater share of parental leave is something that, at least in the two later volumes, is seen as something positive , even though the importance of differentiating fatherhood from motherhood is frequently stressed in the 1983 volume. Still, throughout the period mom is the primary carer as well as the one responsible for the housework, and dad’s involvement is not primarily seen as beneficial for her, but rather as something that is good for the children and for his personal growth. My conclusion is that the magazine Vi föräldrar cannot be said to be a strong advocate for double emancipation.Key

The dissertation takes the modern business technique/concept of brands and branding, applies them to a historic case study, the creation by James VI and I of Great Britain from 1603 to 1625, and by doing so throws new light on both. It compares two distinct approaches to branding, unidirectional and social interactionist, postulating that the latter would prove better at explaining the success of the brand Great Britain/British. The case study reveals that neither approach is supported by the evidence. Content analysis shows that there was a lack of awareness of the brand Great Britain/British and an inconsistency in its use, hence neither approach can be sustained. However, the same analysis does show that an alternative brand, England/English, existed in the same time and that this brand provides some limited support for the social interactionist view of brands and branding. The lack of success of the brand Great Britain/British during his reign does not appear to have prevented James VI and I from establishing himself as the legitimate King of England in addition to Scotland although the contribution of the brand to this was marginal at best.

Made available in DSpace on 2015-05-07T14:49:30Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 971027 bytes, checksum: d7b9e301ff511c4ffe34d7076926030e (MD5) Previous issue date: 2006-02-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The industry is a section of the contemporary society with great pollutant potential of the environment, especially of the aquatic ecosystems. The tanning industries are big producing of dejections with significant amounts of organic matter and of chrome. The conventional processes of treatment applied those dejections, not always they possess good effectiveness. Actuality, the Advanced Oxidation Processes represent an excellent alternative of tertiary treatment. In the present study, the application of the heterogeneous photocatalysis was evaluated, being used a photocatalyst (TiO2) immobilized, in the tertiary treatment of synthetic liquid effluents representative of tanning industries. It was aimed at to remove Cr(VI) and organic matter. The photocatalytic reactor was of the type Fixed Bed of Fine Film, built with a plate of glass arrayed for the fixation of TiO2. It was adopted as radiation sources, the sun and lamps issuing of UV radiation (λ= 250 nm). The smallest values of removal effectiveness for Cr(VI) they were of 62% and 51% and of DOC they were from 60% and 53% to the experiments done with radiation UV originating from of the sun and of lamps, respectively. The results of the parameters related to the reduction phases and oxidation of the heterogeneous photocatalysis, they showed that the exhibition in the sun, he/she has effectiveness of larger relative removal than the exhibition to UV lamps. The data of relative removal of Cr(VI) and of DOC and the constants kinetics of these parameters, they indicated that the adopted experimental configurations optimized the phase of reduction of the heterogeneous photocatalysis. / A indústria é um setor da sociedade contemporânea com grande potencial poluidor do meio ambiente, especialmente dos ecossistemas aquáticos. As indústrias de curtume são grandes produtoras de dejetos com significativas quantidades de material orgânico e de cromo. Os processos convencionais de tratamento aplicados a esses dejetos, nem sempre possuem boa eficácia. Atualmente, os Processos Oxidativos Avançados representam uma excelente alternativa de tratamento terciário. No presente estudo, avaliou-se a aplicação da fotocatálise heterogênea, usando-se um fotocatalisador (TiO2) imobilizado, no tratamento final de efluentes líquidos sintéticos representativos de indústrias de curtume. Objetivou-se remover Cr(VI) e matéria orgânica. O fotorreator foi do tipo Leito Fixo de Filme Fino, construído com uma placa de vidro jateado para a fixação do TiO2. Adotou-se como fontes de radiação, o sol e lâmpadas germicidas emissoras de radiação UV (λ= 250 nm). Os menores valores de eficácia de remoção para Cr(VI) foram de 62% e 51% e de DQO foram de 60% e 53% para os experimentos feitos com radiação UV oriundas do sol e de lâmpadas, respectivamente. Os resultados dos parâmetros relacionados às fases de redução e oxidação da fotocatálise heterogênea, mostraram que a exposição ao sol, tem eficácia de remoção relativa maior do que a exposição à lâmpadas UV. Os dados de remoção relativa de Cr(VI) e de DQO e as constantes cinéticas destes parâmetros, indicaram que as configurações experimentais adotadas otimizaram a fase de redução da fotocatálise heterogênea.

Made available in DSpace on 2014-12-17T14:20:27Z (GMT). No. of bitstreams: 1 Betania MFM_TESE.pdf: 5735783 bytes, checksum: aa96656543e594bd12ee70db21dd8194 (MD5) Previous issue date: 2012-12-20 / This study was elaborated based on our research of the work Mithologiques by the anthropologist Claude L?vi-Strauss (1908-2009), which affirms that languages, indigenous myths and music are related. He proposes that the understanding of myths occurs in a similar manner as with an orchestral score. In the course of his tetralogy we investigated the musical terms used in the analysis and in the division of the chapters, especially in the first volume of his work. Several compositional procedures and forms are named. Composers in pairs are categorized: Sebastian Bach for the code, Ludwig van Beethoven for the message, and Richard Wagner for the myths. In this deduction, we structured in parts: theme and variations, sonata and fugue with the aforementioned composers. Within the greatness of anthropological study, from among over 800 myths, we selected the first five of the indigenous tribe Bororo to discuss within the Theme and Variation segment. In the Sonata part there are two myths with the same theme: The wife of the jaguar which relates to the compositional structure, and four myths about The origin of women. Finally, in the segment related to the Fugue, we collected four myths that address The shortness of life. Honoring the many terms expressed in opposition, contrast, or symmetry under consideration in Levi-Strauss work, we entitled this thesis emphasizing the migration between the tempos Largo and Prest?ssimo as these are oppositional presentations in music. Fifteen musical myths accompany the work supported by selected narratives. In light of this we questioned, we questioned: how are incest, murder and other events part of a society that elevates nature as an extension of life itself? And how did L?vi-Strauss think that anthropology harmonized with music? In the preparation of this study, philosophers like Peter Sloterdijk discuss the circular territory of Mythology / Este estudo foi elaborado com base em nossas pesquisas na obra Mitol?gicas do antrop?logo Claude L?vi-Strauss (1908-2009), na qual afirma que linguagens, mitos ind?genas e m?sica est?o relacionados. Ele prop?e que a compreens?o dos mitos ocorre de maneira similar com a partitura orquestral. No decorrer da sua tetralogia, investigamos termos da m?sica usados na an?lise e na divis?o dos cap?tulos, principalmente do primeiro volume da obra. V?rios procedimentos de composi??o e formas est?o nomeados. Compositores em pares s?o categorizados: Sebastian Bach para o c?digo, Ludwig van Beethoven para a mensagem e Richard Wagner para os mitos. Nesta dedu??o, estruturamos em partes: tema e varia??es, sonata e fuga com os compositores citados. Na grandeza do estudo antropol?gico, entre mais de 800 mitos, selecionamos os cinco primeiros da tribo ind?gena Bororo para discutir na parte Tema e Varia??o. Na parte Sonata h?: dois mitos com mesmo tema, A esposa do jaguar, para relacionar ? estrutura composicional e quatro mitos sobre A origem das mulheres. Por ?ltimo, na Fuga recolhemos quatro mitos que abordam A vida breve. Diante dos termos dados em oposi??o, contrastes ou simetria presentes na obra, demos o t?tulo a este trabalho migrando os andamentos largo e prest?ssimo por se apresentarem na m?sica tamb?m em opostos. Quinze mitos musicais acompanham o trabalho apoiados nas narrativas selecionadas. Para tanto, questionamos como incesto, assassinato e outros acontecimentos fazem parte da sociedade ind?gena que eleva a natureza como extens?o da pr?pria vida? E como L?vi- Strauss pensou a antropologia harmonizada ? m?sica? Na elabora??o deste estudo, pensadores como Peter Sloterdijk dialogam o territ?rio redondo da Mitologia

Ces travaux de thèse, effectués dans le cadre des études sur le retraitement des combustibles nucléaires usés par extraction-liquide-liquide, concernent l’étude cinétique d’extraction de l’uranium(VI) et du plutonium(IV) en milieu acide nitrique par un mélange d’extractants de type monoamide. Trois techniques ont été utilisées pour étudier les cinétiques d’extraction et identifier les régimes de transfert : la méthode de la goutte unique, la cellule d’extraction de Nitsch et la cellule à membrane tournante (RMC). Les résultats obtenus avec la goutte unique indiquent que les cinétiques de transfert d’U(VI) et Pu(IV) sont proches. Une étude hydrodynamique des gouttes et la modélisation du transfert de l’U(VI) ont montré que la présence d’une circulation interne à la goutte diminue les résistances diffusionnelles pour des tailles de goutte croissantes. L’influence de la concentration d’U(VI) dans le solvant sur la cinétique d’extraction a montré que le transfert d’U(VI) et Pu(IV) ralentit lorsque la concentration d’U(VI) en phase organique et la viscosité augmentent. L’ensemble de ces résultats couplé à l’étude du transfert de l’U(VI) par la cellule de Nitsch conduisent à supposer une cinétique gouvernée par la diffusion principalement localisée dans la phase organique. Les études réalisées avec la RMC ont permis de déterminer la constante chimique d’extraction de l’U(VI), du même ordre de grandeur que les cinétiques obtenues par la goutte unique et de confirmer la présence d’une réaction chimique interfaciale. Enfin, le transfert d’U(VI) et Pu(IV) s’avère 3 fois plus lent que celui par le TBP mais reste adapté pour un procédé d’extraction à l’échelle industrielle. / This thesis was conducted in the framework of the reprocessing of spent nuclear fuels. The kinetics extraction of uranium(VI) and plutonium(IV) by N,N-dialkylamides or monoamides in an aliphatic diluent were studied from an aqueous nitric solution using 3 different techniques: “single drop technique”, Nitsch cell and Rotating Membrane Cell (RMC). All these experiments were useful to attempt the identification of the transfer process between the phases which can be controlled by kinetic or diffusional regime. The kinetics of extraction of U(VI) by monoamides solvent seems to be similar to that of the Pu(IV). In general, molecular diffusion in organic phase slows down the extraction process and the limiting thickness of organic phase increases with solvent viscosity. The process in “single drop technique” seems to be controlled not only by diffusion but also by the chemical reaction. Then the extraction kinetics of U(VI) has been carried out by Nitsch cell and the RMC. Diffusionnal regime is the limiting step in Nitsch cell and the results confirm that molecular diffusion in organic phase should mainly control the kinetics transfer. Then experiments performed by the RMC indicate that the kinetics is in the same order as transfer coefficient obtained by “single drop” and the chemical reaction occurs at the interface. Finally, these results were compared with data obtained with a TBP solvent (tributyl phosphate) currently used in the PUREX process in order to estimate the interest of such a new solvent. The kinetics of extraction of U(VI) by this monoamide-based solvent is three times lower that of the TBP 30 % but remains fast and suitable for a future industrial process.