Submitted by Bruna Rodrigues (bruna92rodrigues@yahoo.com.br) on 2016-09-15T20:31:27Z No. of bitstreams: 1 DissECA.pdf: 4704364 bytes, checksum: 1909457a146bdb29a74ad65130ca2bd9 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-16T19:58:59Z (GMT) No. of bitstreams: 1 DissECA.pdf: 4704364 bytes, checksum: 1909457a146bdb29a74ad65130ca2bd9 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-16T19:59:07Z (GMT) No. of bitstreams: 1 DissECA.pdf: 4704364 bytes, checksum: 1909457a146bdb29a74ad65130ca2bd9 (MD5) / Made available in DSpace on 2016-09-16T19:59:13Z (GMT). No. of bitstreams: 1 DissECA.pdf: 4704364 bytes, checksum: 1909457a146bdb29a74ad65130ca2bd9 (MD5) Previous issue date: 2015-03-27 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coarse particulate matter with aerodynamic diameter smaller than 10μm (PM10) have long been considered as air pollutants associated with health issues. They penetrate into the upper respiratory tract, causing respiratory problems such as worsening of asthma. The aim of this study was to determine and quantify the distribution of chemical elements in the PM10 particulate matter present in the atmosphere of the city of Sao Carlos (Sao Paulo). Samples were collected daily for a period of 23h and 30 minutes, from April 16, 2014 to April 16, 2015. A high-volume sampler (AGV-PM10) with micro quartz and fiber glass filters were used. The filters were subjected to gravimetric analysis to obtain the mass of PM10 and were then analyzed by energy dispersive X-ray fluorescence and Laser Induced Breakdown Spectroscopy to identify and quantify the chemical composition of the samples. The highest average concentration during twelve-month period was 70.41μg/m³ (August, 2014) and the smallest was 22.59μg/m³ (January, 2015). The annual arithmetic average found for the twelve months period was 42.71μg/m³. If compared with annual arithmetic average limit of 40μg/m³, established by CETESB, the value is slightly above and below 50 μg/m³ (CONAMA). If we consider the limit established by the World Health Organization (WHO), which is 20μg/m³, this value is much higher than recommended. The chemicals elements found were characteristic of urban areas / O material particulado, cujo diâmetro aerodinâmico é menor do que 10μm vem sendo considerado como poluente atmosférico muito associado a questões de saúde, uma vez que são os que penetram em vias respiratórias, agravando problemas como o da asma, por exemplo. O objetivo deste trabalho foi avaliar os níveis de concentração de material particulado (MP10) e determinar a distribuição dos elementos químicos deste material particulado presente no ar atmosférico do centro da cidade de São Carlos (São Paulo). As amostras foram coletadas diariamente, por um período de 23h e 30 minutos, entre 16 de abril de 2014 a 16 de abril de 2015. Foi utilizado um amostrador de grandes volumes (AGV-MP10), submetendo os filtros, de fibra de vidro e de micro quartzo, à análise gravimétrica para obtenção de massa de MP10, Fluorescência de Raios-X de Energia Dispersiva de (EDX) e a Espectroscopia de ruptura induzida por laser (LIBS) para identificação e quantificação da composição química elementar das amostras. A maior concentração média do período de doze meses amostrado foi de 70,41μg/m³ em agosto/2014 e a menor de 22,59μg/m³ em janeiro/2015. A média aritmética anual encontrada para o período de doze meses foi de 42,71μg/m³. Se comparada com a média aritmética anual do limite estabelecido pela CETESB, de 40μg/m³, o valor está um pouco acima e um pouco abaixo de 50 μg/m³(CONAMA). Se for considerado o limite estabelecido pela Organização Mundial da Saúde (OMS), que é de 20 μg/m³, este valor encontra-se muito acima do recomendado. Os elementos químicos encontrados são característicos de áreas urbanas e apresentam resultados semelhantes a estudos anteriores na cidade.

La glace de H2O est présente dans de nombreux environnements planétaires, et notamment sous forme de polymorphe de haute pression au sein des satellites de glaces ainsi que dans le manteau des planètes extrasolaires, dites planètes océan. La diversité des conditions thermodynamiques prédite au sein de ces corps planétaires a souligné le besoin de nouvelles données de laboratoire et de calculs sur les glaces de H2O afin de pouvoir modéliser leur évolution et leur structure interne.Si les propriétés structurales et spectroscopiques des pôles purs de ces glaces sont déjà relativement bien connues, une description pétrologique plus réaliste des solutions solides et des phases riches en impureté, manque encore à la communauté. Ce travail de thèse s’est concentré sur l’étude de la fusion des glaces VI et VII dans le binaire H2O-NaCl grâce aux techniques de cellules à enclumes en diamants et la spectroscopie vibrationelle Raman. Ces données ont été complétées par des mesures du fractionnement du sel analogue RbI entre les glace VI et VII et le fluide aqueux en utilisant la cartographie de fluorescence X et de diffraction des rayons X réalisées à l’European Synchrotron Research Facility (Grenoble). Ceci as permis de mettre en évidence une inversion de densité entre le fluide riche en sel et la glace VI et de révéler une forte différence de partage du sel entre la glace VI et la glace VII avec un coefficient de partage du RbI estimé à Kd(VI-VII)=4.5(±2.7)10-2.Au sein des plus gros corps riches en H2O appelés planète océan, le manteau de glace potentiellement épais de plus de 1000 km abrite un type de glace de ultra haute pression appelé glace X. Cette phase de la glace d’eau est unique de part sa structure cristallographique ionique, contrairement aux autres glaces de plus basse pression, toutes de structure moléculaire. Cette caractéristique structurale et l’absence de données concernant ses propriétés mécaniques ont motivé l’étude de ses propriétés élastiques et plastiques. Ainsi à partir de calcul ab initio et du modèle de Peierls Nabarro, j’ai pu déterminer une forte variation de l’anisotropie élastique avec la pression, les différentes structures de cœurs des dislocations vis et coin et les systèmes de glissement préférentiels au sein de la glace X dans son champ de stabilité de 100 à 350 GPa. Nos calculs suggèrent que la déformation de la glace X est toujours localisée sur le plan {110} et que le système <110>{110} contrôle la déformation plastique en dessous de 250 GPa et que le système <100>{110} est dominant à plus haute pression. Nos résultats montrent aussi que si l’anisotropie élastique augmente rapidement avec la pression, la plasticité de la glace X devient quasi-isotrope à 350 GPa. / H2O ice is found in a variety of planetary environments, notably in the form of high pressure polymorphs inside icy moons and extrasolar ocean planets. The great diversity of thermodynamic conditions predicted inside such planetary bodies, reveals the need for new experimental and computational data to allow modeling of their internal structure and dynamics.Structural and spectral properties of H2O pure ices have been intensively studied, but surprisingly there is a lack of petrological data on impurities rich ice solid solutions. This Ph.D. thesis work focused on the study of ice VI and ice VII fusion curves in the H2O-NaCl binary, using diamond anvil cell and Raman spectroscopy. We later determined the partitioning of the NaCl analog salt, RbI, between ice VI and VII and the aqueous fluid using X- ray fluorescence and X-ray diffraction techniques at the European Synchrotron Research Facility (Grenoble). Our results enable us to observe a density inversion between ice VI and the salty fluid, and to measure a strong difference in salt partitioning between ice VI and ice VII with a partition coefficient of Kd(VI-VII)=4.5(±2.7)10-2. Inside the largest H2O rich planetary bodies, called ocean planets, the icy mantle, putatively more than 1000 km thick, shelters an ultra high pressure ice form called ice X. This H2O ice phase is unique because of its ionic crystallographic structure, in contrast with lower pressure ices polymorphs, all being molecular solids. This characteristic coupled with the fact that no data are available yet on its mechanical properties, encouraged us to study its elastic and plastic properties. Using ab initio calculations and the Peierls Nabarro model, I showed the strong variation of elastic anisotropy with increasing pressure and determined the dominant slip system inside the structure of ice X over its entire pressure stability range from 100 to 350 GPa. Our calculations suggest that plasticity in ice X is dominated by displacement always occurring on the {110} glide plane. Also, it reveals that the <110>{110} glide system is dominant below 250 GPa and that the <100>{110} slip system controls the plasticity of ice X. Our results also show that, if elastic anisotropy of ice X is strongly increasing with increasing pressure, the plasticity becomes almost isotropic at 350 GPa.

Cette thèse est consacrée aux grottes et aux dépôts souterrains du grand bassin karstique charentais de la Touvre, la deuxième source de France qui alimente Angoulême. Le premier objectif est de montrer que la série calcaire jurassique est affectée dans sa masse par le processus de fantômisation (altération isovolume) qui s'est produit pendant le Crétacé inférieur durant 45 millions d'années. Les preuves ont été apportées dans les carrières, les grottes et à partir des forages. La fantômisation de la roche explique la genèse des grottes labyrinthiques et permet d'expliquer que les grandes réserves aquifères sont contenues principalement dans la roche devenue poreuse (circulation très lente) et secondairement dans des conduits karstiques (circulation rapide). Cette conclusion est confirmée par l'analyse des courbes de tarissement de la résurgence qui suggère une mauvaise karstification. Le deuxième objectif est l'étude de deux grands remplissages détritiques situés dans les grottes de la Fuie et du Bois du Clos. L'étude géochimique, sédimentologique et minéralogique des dépôts a permis de caractériser les dynamiques hydro-sédimentaires et les conditions aléoenvironnementales, notamment entre les stades isotopiques marins 6 et 3, obtenus à partir des datations 14C et U/Th sur les stalagmites de la grotte du Bois du Clos. L'imagerie chimique par fluorescence X met en évidence des niveaux carbonatés, apportant une preuve supplémentaire de la spéléogenèse par fantômisation. Enfin l'étude comparée des séquences spéléologiques et archéologiques régionales rend compte du rôle des paramètres locaux et régionaux, mais aussi des facteurs globaux au niveau paléoclimatique.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-06-28T21:49:04Z No. of bitstreams: 1 KARINE CASTRO NÓBREGA – DISSERTAÇÃO (UAEMa) 2015.pdf: 1849613 bytes, checksum: c5a145f0dd677d54aab0ed55f6ccc4e9 (MD5) / Made available in DSpace on 2018-06-28T21:49:04Z (GMT). No. of bitstreams: 1 KARINE CASTRO NÓBREGA – DISSERTAÇÃO (UAEMa) 2015.pdf: 1849613 bytes, checksum: c5a145f0dd677d54aab0ed55f6ccc4e9 (MD5) Previous issue date: 2015-02-23 / CNPq / A perfuração de poços de petróleo pode danificar fortemente a formação, incluindo a região de interesse: o reservatório. Perfurar sem que se danifique o reservatório caracteriza-se como um grande desafio, e por isso, tem sido estimulado o desenvolvimento de tecnologias de fluidos e otimização de processos de perfuração, incluindo, por exemplo, o uso de fluidos argilosos com vistas à minimização de perdas excessivas de filtrado para as formações permeáveis. Desta forma, este trabalho teve como objetivo avaliar a influência dos aditivos carboximetilcelulose (CMC) e calcita (CaCO3) e suas interações nas propriedades de filtração de fluidos de perfuração argilosos. Para tanto, foi utilizada uma amostra de argila bentonítica, comercialmente conhecida por Volclay, duas amostras de CMC com diferentes massas molares (CMC 1 (9,0 x 104g/mol) e CMC 2 (2,5 x 105g/mol)) e mesmo grau de substituição (DS = 0,7) e, duas amostras de calcita (CaCO3), com diferentes diâmetros médios de partículas e curvas de distribuição em tamanho. Foram realizadas a caracterização física e mineralógica da amostra de argila e a caracterização granulométrica das amostras de calcita, em seguida determinadas as propriedades reológicas (viscosidades aparente (VA) e plástica (VP), limite de escoamento (LE) e força gel (FG)) e de filtração (volume de filtrado (VF), volume de filtrado corrigido (VFcorr), spurt loss (SPL), espessura (h) e permeabilidade (k) do reboco e poder de retenção (R)) dos fluidos argilosos estudados. Os resultados evidenciaram que os fluidos estudados apresentaram comportamento pseudoplástico e os fluidos argilosos preparados com elevada concentração de CMC 2 (2g/350mL de água) apresentaram melhores valores de propriedades reológicas, pois estas propriedades são fortemente influenciadas pelo grau médio de polimerização dos aditivos poliméricos. A aditivação de fluidos argilosos com carboximetilcelulose de baixa massa molar e com calcita de granulometria fina conferiu aos fluidos melhor desempenho na melhoria das propriedades de filtração. Isto aconteceu, porque no meio aquoso a CMC 1 em elevada concentração associada a calcita 1 conduziu a menores valores de VF, h e k e, elevados valores de R. / The drilling of oil wells can greatly damage the formation, including the region of interest: the reservoir. Drilling without damaging the reservoir is characterized as a big challenge, and therefore, has been stimulated the development of fluid technologies and optimization of drilling processes, including, for example, the clay fluids use aiming at minimization excessive losses of the filtrate into the permeable formations. Thus, this study aimed to evaluate the influence of additives carboxymethylcellulose (CMC) and calcite (CaCO3) and their interactions in the filtration properties of clay drilling fluids. For this, it was used a sample of bentonite clay, commercially known by Volclay, two samples of CMC with different molecular weight (CMC 1 (9,0 x 104g/mol) and CMC 2 (2,5 x 105g/mol) ) and the same degree of substitution (DS = 0,7) and two samples of calcite (CaCO3) with different average diameters of particles and size distribution curves. It was done the physical and mineralogical characterization of the clay sample and the particle size characterization of the calcite samples it was also determined the rheological properties (apparent viscosity (AV) and plastic (PV), yield limit (YL) and gel strength (GS)) and of filtration (filtrate volume (FV), filtrate volume corrected (FVcorr), spurt loss (SPL), cake thickness (h) and permeability (k) and retaining power (R)) of the studied clay fluids. The results showed that the studied fluids showed pseudoplastic behavior and clay fluids prepared with high concentration of CMC 2 (2g/350mL of water) showed better values of rheological properties, because these properties are strongly influenced by the average degree of polymerization of polymeric additives. The additived clay fluids with low molecular weight carboxymethylcellulose and with fine granulometry calcite gave the fluids best performance in improving the filtration properties. This happened because in the aqueous medium the CMC 1 in high concentration associated at calcite 1 led at lower values of FV, h and k and high values of R.