Dinitrous oxide (N2O) is a potent greenhouse gas some 354 times stronger than carbon dioxide (CO2) in the atmosphere. Recent studies show that lake denitrification contributes to a considerable part of the global N2O emissions. Despite this, lake-N2O emissions are not being accounted for in global greenhouse gas modeling because it has not yet been accurately understood and quantified. The aim of this study was to assess how denitrification varies between and within boreal lakes and how it is controlled by nitrate- (NO3) and carbon (C) availability and temperature. Studies on denitrification were performed using the acetylene inhibition technique on sediments from three lakes in northern Sweden (February to August, 2014). Results showed that denitrification was correlated (linear regression, r2=0.71) with NO3 concentrations in the hypolimnion water at ambient conditions and that additions of NO3 up to a concentration of 50 µg NO3-N L-1 increased denitrification. Temperature increased denitrification in all lakes, at all sites except in one lake in July, when nutrient concentrations were at its lowest. The spatial and temporal variation in denitrification was small at ambient conditions (1-3 µmol N2O m-2 h-1)but the variation in the response to nutrient additions and temperature increase was very high. This was in part attributed to differences in dissolved organic C (DOC). These findings have important implications for future denitrification research and how lake-N2O production is included in greenhouse gas modeling and contributes to our knowledge on how northern boreal lakes may respond to enhanced nutrient loadings and global warming.

The thesis presents the research results obtained while studying novel chemical strategies for preparing Si(100)-based electrochemical platforms suitable for aqueous environments. A primary research aim was the preparation of well-passivated Si(100) surfaces amenable to further chemical derivatization. The preparation and functionalization of alkyne-terminated alkyl monolayers on Si(100) surfaces using the Huisgen 1,3-dipolar ???click??? cycloaddition of azides with surface-bound acetylenes is reported and shown to be a versatile, experimentally simple, chemically unambiguous modular approach to modified silicon surfaces. Covalently immobilized, structurally well-defined acetylenyl organic monolayers are prepared from a commercially available ??,??-diyne (1,8-nonadiyne) species using a one-step thermal hydrosilylation procedure. Subsequent derivatization of the alkyne-terminated monolayers in aqueous environments with representative azide species affords disubstituted surface-bound [1,2,3]-triazole species. Neither activation procedures nor protection/deprotection schemes are required, as is the case with more established grafting approaches for silicon surfaces. The described surface modification scheme has been used in preparing modified Si(100) electrode surfaces, where modular components such as ferrocene derivatives or electrochemically ???switchable??? linker molecules are introduced onto the passivated silicon surface. An implementation study to prepare modified light-addressable ???switchable??? Si(100) electrodes is also reported. Negligible oxidation of the substrate was generally observed after exposure to aqueous systems for extended periods (tens of hours), and the electroactive monolayers showed a robust and reversible behaviour. The proposed concept of modular components and high-yielding coupling procedures has been shown on Si(100) surfaces and also extended to illustrate the functionalization of porous silicon rugate filters.

Thesis (Ph.D.)--McMaster University (Canada), 1991. / Source: Dissertation Abstracts International, Volume: 54-02, Section: B, page: 0820.

Thesis (M. Phil.)--University of Hong Kong, 2009. / Includes bibliographical references (leaves 59-60) Also available in print.

Thesis (doctoral)--Ludwig-Maximilians-Universität München, 1960. / Vita. Includes bibliographical references (p. 79-80).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliography.

Made available in DSpace on 2014-10-09T12:55:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:00Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Orientador: Celso Aparecido Bertran / Tese (doutorado) - Universidade Estadual de Campinas. Instituto de Quimica / Made available in DSpace on 2018-07-27T07:22:09Z (GMT). No. of bitstreams: 1 Marques_CarlaSimoneTafuri_D.pdf: 16927683 bytes, checksum: b7e62e3886759d4afb629fa31db9ec66 (MD5) Previous issue date: 2000 / Resumo: Neste trabalho, realizou-se o estudo da cinética de formação de radicais produzidos no estado eletrônico excitado e o estudo da formação das partículas de fuligem, durante a combustão de misturas de C2H2/O2 e C2H2/O2/Ar produzidas em uma câmara fechada. Na metodologia utilizada, o processo de combustão é turbulento e ocorre na ausência do ar atmosférico. Desta forma, é possível obter uma correlação entre a pressão e composição da mistura que queima, e a formação e reação das espécies presentes na chama. A cinética de formação dos radicais excitados OH*, CHO*, CH* e C2*, principais emissores em chamas de hidrocarbonetos, foi estudada pela determinação de suas intensidades de emissão em função do tempo. A evolução das partículas de fuligem, durante a combustão das misturas ricas em acetileno, foi observada através do espalhamento e absorção da luz de um laser por essas partículas, em função do tempo. Realizou-se também a análise morfológica das partículas formadas por microscopia eletrônica de varredura. As medidas espectroscópicas de emissão dos radicais excitados foram associadas à simulação computacional da cinética de combustão, permitindo se estabelecer um mecanismo reacional para o processo de combustão turbulento da mistura de C2H2/O2 e identificando-se as principais rotas de reação para a formação dos radicais excitados: H + O2 = OH* + O CH + O = CHO* C2H + O2 = CH* + CO2 CH2 + C = C2* + H2 / Abstract: In this work, a kinetic study of radicals in the excited electronic state and a study of soot particles evolution from C2H2/O2 and C2H2/O2/Ar flames in a closed chamber was carry out. In the methodology used the combustion process is turbulent and occurs in the atmospheric air absence. Therefore, we can correlate mixture pressure and composition that burning to species formation and reactions in the flame. The formation kinetic of OH*, CHO*, CH* and C2* excited radicals, which are the main emitters in the hydrocarbon flames was studied by emission intensities as a function of time determination. The soot particle evolution from fuel-rich flames was observed through laser light scattering and absorption. The morphology analysis of these soot particles was executed by scanning electronic microscope. The spectroscopic measurements of emission of excited radicals was associated to computational simulation of combustion kinetics allowing to establish a mechanism of reactions to the turbulent combustion process of C2H2/O2 and to identify the predominant reactions for the formation of excited radicals: H + O2 = OH* + O CH + O = CHO* C2H + O2 = CH* + CO2 CH2 + C = C2* + H2 / Doutorado / Físico-Química / Doutora em Química

Made available in DSpace on 2014-10-09T12:55:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:00Z (GMT). No. of bitstreams: 0 / O estudo do comportamento de materiais poliméricos em relação ao intemperismo (calor, luz UV, umidade, radiação de alta energia, ataque químico e poluentes) é de fundamental importância para se avaliar a estabilidade do material. Os termoplásticos avaliados foram os HMS-PPs sintetizados, a partir do iPP estabilizado e não estabilizado, por meio de irradiação gama (g) em atmosfera de acetileno. A caracterização das amostras degradadas foi estabelecida por ensaios mecânicos, espectroscopia no infravermelho por transformada de Fourrier (FTIR), análise termogravimétrica (TGA), calorimetria exploratória diferencial (DSC), microscopia óptica (MO), microscopia eletrônica de varredura (MEV) e reometria de placas paralelas. O HMSPP, obtido a partir de esferas, nas condições de envelhecimento natural e acelerado sob radiação UV, evidencia a formação de cristais defeituosos que se organizam em diferentes estruturas. Na condição de termooxidação em estufa, apesar da cisão de cadeias, a fase cristalina diminui. O HMSPP 20 kGy parece ser mais estável às reações de cisão de cadeia nos testes que envolvem a radiação UV. A reologia indica que as ramificações com acetileno são mais estáveis à radiação ultravioleta. No HMSPP, obtido a partir de grãos, devido à eficiência dos aditivos como capturadores de espécies oxidadas e supressores de peróxido radicais, foram propiciadas mais as reações de cisão que a formação de cristais irregulares e isso conduziu ao aumento da cristalinidade tanto sob envelhecimento natural quanto térmico ou sob radiação ultravioleta (UV). As propriedades físicas sob tração mostraram que a diferença superior da tensão de ruptura inicial do HMS 20 kGy é perdida durante exposição a diversos envelhecimentos. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Afin de progresser dans la compréhension de la structure de vibration-rotation de l'acétylène dans son état électronique fondamental, un modèle global a été développé avec succès pour trois de ses isotopologues, permettant d'attribuer de nouvelles données de spectres enregistrés sous diverses conditions expérimentales. L'ensemble des programmes d'analyse rovibrationnelle globale conçus à l'Université Catholique de Louvain par le Pr. A. Fayt et al. ont été utilisés pour répondre aux demandes de collaborateurs tels que les Prs. A. Campargue, A. Jolly ou encore R. Georges dans le cadre de plusieurs problèmes de type spectroscopique, notamment pour des applications astrophysiques. Le modèle global et son pouvoir prédictif mis ainsi à l'épreuve, nous avons démontré la validité de nos jeux de paramètres pour ces trois molécules.<p><p>Concernant l'isotopologue principal, $H^{12}C^{12}CH$, 14 nouvelles bandes ont été mises à jour à partir de spectres enregistrés en CRDS à Grenoble par A. Campargue et al. Une analyse rovibrationnelle globale a été effectuée jusqu'à une énergie de 8600 cm$^{-1}$. 10750 raies ont été ajustées simultanément sur les 12137 attribuées dans la littérature. 266 paramètres ont été déterminés par la méthode de moindres-carrés. La déviation standard sans dimension du fit est de 0.92. La bande $u_{5}$-$u_{4}$, centrée vers 117 cm$^{-1}$ a été simulée. La valeur du moment de transition associé, $ / Doctorat en Sciences / info:eu-repo/semantics/nonPublished