Neptunium, with its rich redox chemistry, has a special position in the chemistry of actinides. With a decades-long history of development of aqueous separation methods for used nuclear fuel (UNF), management of neptunium remains an unresolved issue because of its not clearly defined redox speciation. Neptunium is present in two, pentavalent (V) and hexavalent (VI) oxidation states, both in their dioxocation O=Np=O neptunyl form, which differ greatly in their solvent extraction behavior. While the neptunium(VI) dioxocation is being very well extracted, the dioxocation of pentavalent neptunium is practically non-extractable by an organic solvent. As a result, neptunium is not well separated and remains distributed in both organic and aqueous extraction phases. The aim of this study was to develop or enhance the understanding of several key topics governing the redox behavior of neptunium in nitric acid medium, which are of vital importance for the engineering design of industrial-scale liquid-liquid separation systems. In this work, reactions of neptunium(V) and (VI) with vanadium(V) and acetohydroxamic acid - two redox agents envisioned for adjusting the neptunium oxidation state in aqueous separations ��� were studied in order to determine their kinetic characteristics, rate laws and rate constants, as a function of temperature and nitric acid concentration. Further were analyzed the interactions of neptunium(V) and (VI) with nitrous acid, which is formed as a product of radiolytic degradation of nitric acid caused by high levels of radioactivity present in such systems. Once HNO��� is distributed between both the aqueous solutions and organic solvent, nitrous acid is also formed in both phases and has a key influence on redox speciation of neptunium; therefore, the effects of gamma-radiation on the redox speciation of neptunium were investigated. The work also includes the results of examination of scavenging of nitrous acid by hydrogen peroxide, which is generated along with nitrous acid during radiolysis of aqueous solutions of nitric acid, and also by chemical reactions with added scavenging agents (methylurea, acetohydroxamic acid). / Graduation date: 2013

Se compararon dos experiencias de inducción anestésica en seis gatos premedicados con acepromacina y buprenorfina: cámara (exp. 1) o mascarilla (exp. 2). En cada experiencia se empleó isofluorano o sevofluorano vehiculados en oxígeno o en una mezcla de oxígeno y óxido nitroso según grupo. Se valoró la calidad de forma subjetiva y la velocidad de inducción en base a distintos tiempos medidos durante esta fase. Tras un mantenimiento de treinta minutos en el que se registraron distintos parámetros cardiorrespiratorios y la temperatura corporal, se evaluó la calidad y velocidad de recuperación anestésica. No se observaron diferencias en cuanto a los tiempos o calidad de inducción o recuperación anestésica entre isofluorano o sevofluorano con o sin óxido nitroso. Los parámetros cardiorrespiratorios durante el mantenimiento fueron similares entre grupos. En conclusión, a pesar de las mejores propiedades del sevofluorano, el isofluorano sigue siendo un anestésico de elecció n para procedimientos de corta duración en gatos.

Im Rahmen der vorliegenden Arbeit wurde eine neuartige Methode und die entsprechenden Katalysatoren für die heterogen katalysierte Gasphasen-Epoxidation von Propen entwickelt und optimiert. Das Propen wurde an FeOx/SiO2-Katalysatoren mit N2O als Oxidationsmittel epoxidiert. Die Katalysatoren wurden mittels XRD, TEM, XPS, Physi- und Chemisorption, TPR/TPO, TPD und IR untersucht und charakterisiert. Der Einfluß der Reaktionsbedingungen auf die Oxidationsergebnisse wurde bestimmt und Untersuchungen zum Reaktionsablauf durchgeführt. Es wurden Selektivitäten zu Propenoxid von 40-70%, bei Propenumsätzen von 3-12%, erreicht. Die maximalen erzielten PO-Ausbeuten betrugen über 5%, und sind damit den berichteten Ergebnisse aus der Literatur überlegen.

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Agricultural systems are known to emit nitrous oxide (N2O)---a potent greenhouse gas. The roving flux tower measuring system of Agriculture and Agri-Food Canada was used to make continuous measurements of N2O fluxes in an edible pea field in Western Quebec in 2003-04 and then in an alfalfa-timothy forage field in Eastern Ontario in 2004-05. The experiment was designed to capture, at the field scale, the expected large N2O emissions occurring as a result of fertilizer application for a year, in relation to both large precipitation events and spring thaw. / Growing season N2O emissions averaged 0.5 to 5 mg N2 O-N m-2 d-1 with peaks following snow melt (between 5 and 8 mg N2O-N m-2 d-1) and manure applications (8 to 37 mg N2O-N m-2 d -1). Although generally small (<0.25 mg N2O-N m -2 d-1), emissions were detectable during the fall and winter, indicating the importance of including them in annual emission totals. / The measurements were used to verify the performance of the simulation model DNDC (DeNitrification-DeComposition) in estimating N2O emissions from legumes and in response to dairy manure application. Sensitivity tests were also carried out in which baseline input values were modified. Results suggest that the current model version (DNDC8.9) requires further modification prior to application for estimating greenhouse gas emissions in national accounting systems.

The purpose of this study was to investigate how farmers in the region of Västerbotten work for a sustainable development according to climate change, and where resources could be put in place to make agriculture even more climate friendly. The method chosen was a qualitative interview study where eight farmers from the county were interviewed. Half of them had an ecological production, and the other half was conventional. All the interviews were recorded, and the raw data was put in a database in Excel and analyzed. The results showed differences between ecological and conventional production systems, such as which agricultural practice that was the most sustainable in the future. Many farmers described several ways of decreasing their own climate burden by changing to LED light bulbs, Eco driving, spring plowing and raising their cattle in an intensive system. The future for agriculture was hard to speculate about, but faith in politicians played a crucial role. There were thoughts about both moving backwards to family-oriented agriculture and to increase the animal units with big industry-like settings. Overall, my own conclusion states that agriculture should be more circular to be sustainable, and that the society should be more involved in this circularity for it to work. Intensively raised cattle fed with less concentrate, and less imported meat, seems like a sustainable production. The agriculture of the future should be close to nature but at the same time modern, and we must protect our countryside if we want to have a sustainable society.

Les sols et les activités agricoles qu’ils supportent, contribueraient à environ 2/3 des émissions globales de protoxyde d’azote (N2O), un puissant gaz à effet de serre. L’objectif de la thèse était la compréhension des déterminismes des émissions de N2O liés aux propriétés hydriques des sols. Des expérimentations de laboratoire permettant le contrôle hydrique fin d’échantillons de sol, en saturation et en désaturation, et la mesure des flux de N₂O ont été menées. Un couplage avec la tomographie par rayons-X a par ailleurs permis de caractériser la connectivité gazeuse. Enfin, une démarche de modélisation a permis de tester les hypothèses de fonctionnement émises, et de poursuivre la démarche de réflexion sur le lien entre les propriétés hydriques des sols et les émissions de N₂O. On a mis en évidence le rôle des propriétés hydriques des sols dans la variabilité des émissions de N₂O couramment observées, et la nécessité de distinguer des périodes de production/consommation de N₂O et de transport. On retiendra ainsi le fort caractère dynamique des émissions de N₂O, en lien avec la phase hydrique (saturation ou désaturation), le fonctionnement hydrodynamique des sols, le transport gazeux et la configuration spatiale de l’air et de l’eau dans le réseau de pores. Afin de décrire l’intensité et le timing des pics de N₂O, il est apparu pertinent d’observer les paramètres potentiel matriciel, coefficient de diffusion gazeuse et connectivité gazeuse, en plus de la teneur en eau. Ces observations ont des implications sur la modélisation des flux de N₂O. On recommande ainsi l’utilisation couplée de modules de transport hydrique, de transport gazeux et en solution de N₂O, en plus de modules de production microbiologique, pour prédire efficacement les émissions de N₂O. / Soils and associated agricultural activities are estimated to account for about 2/3 of the global emissions of nitrous oxide (N₂O), a potent greenhouse gas. The aim of the thesis was to understand the controls linked to soil hydric properties on N₂O emissions. Laboratory experiments were designed to control the hydric status of soil samples during wetting and drying, and to measure N₂O fluxes. Moreover, a coupling with X-ray computed tomography allowed characterizing the gaseous connectivity. Finally, a modeling approach allowed testing the hypotheses of functioning, and to further discuss the links between hydric properties and N₂O emissions. We highlighted the role of soil hydric properties on the variability of N₂O emissions which is often measured, and the need to distinguish N₂O production/consumption and transport phases. The highly dynamic nature of N₂O emissions was linked to the hydric phase (wetting or drying), soil hydrodynamic functioning, gas transport, and spatial configuration of water and air in the pore network, in addition to the water-filled pore space parameter. These observations have implications for N₂O emission modeling. We recommend thus the coupled use of hydric transport, and modules of gas and liquid transport of N₂O, in addition to microbial production modules to efficiently predict N₂O emissions.

La SCR (Selective Catalytic Reduction) permet de réduire les oxydes d'azote (NOx) à l'intérieur d'une ligne d'échappement d'un véhicule Diesel à l’aide d’une solution réductrice à base d’urée injectée en amont d’un catalyseur. L'urée est convertie en NH3 par pyrolyse et hydrolyse, et NH3 réduit les NOx enN2 sur le catalyseur. Cependant, comme cette technique met en jeu un ensemble de réactions très complexes, beaucoup de réactions parasites peuvent entraîner la formation de produits secondaires contenant de l'azote et perturber le bon déroulement du procédé. Par conséquent, l’élaboration d’une étude sur la mesure de ces produits secondaires et de leurs conditions de formation est donc essentielle pour la bonne calibration de la SCR. Si pour certains composés, les techniques de mesures sont encore à développer, dans tous les cas, on se trouve confronté à des problèmes liés au prélèvement des espèces. L'objectif de la thèse est d'identifier, de comprendre et de quantifier les phénomènes qui entrent en jeu et qui perturbent l'analyse des composés azotés dans la ligne d'échappement et dans la ligne de prélèvement. Le travail a été mené selon différents axes de recherche : la comparaison des méthodes de mesure de composés azotés en situation réelles dans les gaz d‘échappement d'un moteur Diesel muni d’un catalyseur SCR, l'étude du prélèvement des composés azotés et notamment NH3 dans une ligne de prélèvement standard et la modélisation des pertes dans une ligne de prélèvement. A la fin de ce travail, nous avons évalué l’impact des conditions de prélèvements : température des gaz, composition et/ou longueur des lignes de prélèvement, sur les résultats de la mesure. Ce travail nous permet d'apporter des suggestions pour améliorer le prélèvement et les mesures des composés azotés présents à l'échappement d'un véhicule Diesel équipé d'une SCR. / SCR (Selective Catalytic Reduction) reduces nitrous oxides (NOx) in the exhaust line of a Diesel vehicle using a reducing solution containing urea injected upstream of a catalyst. Urea is converted by pyrolysis and hydrolysis in NH3, NH3 reduces NOx in N2 on the catalyst. However, as this technique involves a very complex set of reactions, many side reactions can lead to the formation of secondary products containing nitrogen and disturb the process. Therefore, the study of the measurement of these secondary products and the conditions of their formation is essential for the proper calibration of the SCR technology. If for some compounds, the measurement techniques are already on the market, for other devices they are still developing, but in all cases, we are faced with problems related to the collection of species that disturb measurement. The objective of this thesis is to identify, understandand quantify the phenomena that disturb the analysis of nitrogen compounds in the exhaust and the sampling line. The work was carried out in different areas of research: comparison of methods for measuring nitrogen compounds in real situations in the exhaust gas of a Diesel engine equipped with an SCR catalyst, study of the sampling of nitrogen compounds and particularly NH3 in a standard sampling line and modelling of losses in the sampling line. At the end of this work, we evaluated the impact of sampling conditions: temperature, gas composition and / or length of the sample lines on the measurement results. This work allows us to make suggestions to improve the sampling and the measurement of nitrogen compounds present in the exhaust of a Diesel vehicle equipped with an SCR.

Made available in DSpace on 2014-10-09T12:42:16Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:20Z (GMT). No. of bitstreams: 0 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP / FAPESP:11/04051-3