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Análise do aerossol atmosférico em Acra, capital de Gana / Analysis of atmospheric aerosol in Accra, capital of GhanaVerissimo, Thiago Gomes 10 June 2016 (has links)
Cidades dos países da África Subsariana (SSA) têm passado por um intenso processo de urbanização, implicando em crescimento das atividades econômicas em geral e industriais em particular, assim como, o aumento do tráfego de veículos e da produção de lixo, dentre outras mudanças que afetam diretamente o meio ambiente e a saúde dos habitantes. Neste cenário, a identificação de fontes poluidoras do ar é essencial para a fundamentação de políticas públicas que visam assegurar o direito a uma boa qualidade de vida para a população. Esta pesquisa de Mestrado esteve integrada a um projeto internacional denominado Energy, air pollution, and health in developing countries, coordenado pelo Dr. Majid Ezzati, à época professor da Harvard School of Public Health, e integrando também pesquisadores da Universidade de Gana. Este projeto tinha por objetivo fazer avaliações dos níveis de poluição do ar em algumas cidades de países em desenvolvimento, voltando-se, neste caso particular para Acra (capital de Gana e maior cidade da SSA), e duas outras cidades de Gambia, onde até então inexistiam estudos mais substantivos, relacionando-os com as condições socioeconômicas específicas das diferentes áreas estudadas. Contribuímos com as análises de Fluorescência de Raios X (XRF) e de Black Carbon (BC), com as discussões e interpretações dos dados meteorológicos e no emprego dos modelos receptores. Mas do ponto de vista do aprofundamento de estudos da qualidade do ar e do impacto de fontes, este trabalho concentrou-se na região de Nima, bairro da capital de Gana, Acra. A partir da caracterização do aerossol atmosférico local, empregou-se modelos receptores para identificar o perfil e contribuição de fontes majoritárias do Material Particulado Atmosférico Fino MP2,5 e Grosso MP2,5-10. Foram coletadas 791 amostras (de 48 horas) entre novembro de 2006 e agosto de 2008 em dois locais, na principal avenida do bairro, Nima Road, e na área residencial, Sam Road, distantes 250 metros entre si. A concentração anual média em 2007 para MP2,5 encontrada na avenida foi de 61,6 (1,0) ug/m3 e 44,9 (1,1) ug/m3 na área residencial, superando a diretriz de padrão anual máximo de 10 ug/m3 recomendada pela Organização Mundial de Saúde (OMS). A porcentagem de ultrapassagem do padrão diário (OMS) de 25 ug/m3 foi de 66,5% e 92% para a área residencial e avenida, respectivamente, durante todo experimento. As concentrações químicas elementares foram obtidas por XRF e o BC por refletância intercalibrada por Thermal Optical Transmitance (TOT). Neste trabalho desenvolvemos uma metodologia de calibração do XRF e de intercalibração entre refletância e TOT, baseada em Mínimos Quadrados Matricial, o que nos forneceu incerteza dos dados ajustados e boa precisão nos valores absolutos de concentrações medidos. Análise de Fatores (AF) e Positive Matrix Factorization (PMF) foram utilizadas para associação entre fonte e fator, bem como para estimar o perfil destas fontes. A avaliação de parâmetros meteorológicos locais, como direção e intensidade dos ventos e posicionamento de fontes significativas de emissão de MP auxiliaram no processo de associação dos fatores obtidos por esses modelos e fontes reais. No período do inverno em Gana, um vento provindo do deserto do Saara, que está localizado ao nordeste do país, denominado Harmatão, passa por Acra, aumentando de um fator 10 a concentração dos poluentes relacionados à poeira de solo. Assim, as amostras dos dias de ocorrências do Harmatão foram analisadas separadamente, pois dificultavam a identificação de outras fontes por PMF e AF. As fontes majoritárias indicadas por esses dois métodos (AF e PMF), mostraram-se concordantes: Mar (Na, Cl), solo (Fe, Ti, Mn, Si, Al, Ca, Mg), emissões veiculares (BC, Pb, Zn, K), queima de biomassa (K, P, S, BC) e queima de lixo sólido e outros materiais a céu aberto (Br, Pb) . A redução da poluição do ar em cidades da SSA, caso de Acra, requer políticas públicas relacionadas ao uso de energia, saúde, transporte e planejamento urbano, com devida atenção aos impactos nas comunidades pobres. Medidas como pavimentação das vias, cobertura do solo com vegetação, incentivo ao uso de gás de cozinha e incentivo ao transporte público, ajudariam a diminuir os altos índices de poluição do ar ambiental nessas cidades. / Sub-Saharan Africa (SSA) cities have been intense developing process, resulting in generalized economical activities growing, specially industrial, as well as increase in the vehicular traffic and waste generation, among other changes directly affecting the environment and public health. Therefore, identifying the air pollution sources is an essential issue for public decisions to assure people rights to healthy life. This Master work has been integrated to an international project called Energy, air pollution, and health in developing countries, under coordination of Dr. Majid Ezzati, then at the Harvard School of Public Health, grouping also researchers from the University of Ghana. The aims of this project were to evaluate the air pollution level at some developing countries, by this time devoted to Accra (the capital of Ghana and the main city of SSA), and two other cities of Gambia. Since then, no substantive study was performed there, connecting air pollution to the regional social-economical levels. This Master project, provided the XRF and Black Carbon determination for all samples of the main project, and gave, else, support for meteorological and receptor modeling issues. But concerning the improving of the study of air quality and sources impact, the work focus Nima town, at Accra, the Ghana Capital. The characterization of species in the local atmospheric aerosol was used in Receptor Models to make factor to sources profile association, and respective apportionment in the local PM2.5 and PM10. Between November/2006 and August/2008, 791 filters (sampled for 48 h) collected the local atmospheric aerosol, in two sites separated by 250 m. One was at the main avenue (Nima Road) and other in a residential street (Sam Road). The PM2.5 annual average concentration to 2007 was 61,6 (1,0) ug/m3 near to the avenue and 44,9 (1,1) ug/m3 in the residential area, surpassing ~5 times the Word Health Organization (WHO) guidelines to annual mean (10 ug/m3). Another WHO guideline is not surpass 25 ug/m3 in more than 1% of the samples collected in one year - in each of these sites, 66,5% and 92% of the samples are above this limit. X-Ray Fluorescence (XRF) provided the elemental concentrations, while reflectance, inter calibrated by Thermal Optical Transmittance (TOT), gave the Black Carbon (BC) levels. In this work we performed a methodology for the XRF calibration and for the inter calibration between TOT and reflectance, using Matrix Least Square Fitting that gives the uncertainties of fitted data and improves the precision of the adjusted values. Factor Analysis (FA) and Positive Matrix Factorization (PMF) enabled the association between source and the determined factors, as well as, estimated the sources profile. Local meteorological data, like wind intensity and direction, and the identification of some heavy MP emission sources, helped the process of factors to sources association. During the winter period (January-March), Accra received the Harmattan wind, blowing from Sahara deserts, that increased the concentrations from soil in 10 times. Therefore, the samples from this period were separately analyzed, providing better detection of the other source by PMF and FA. The local main source detected by both methods showed coherency: sea salt (Na, Cl), soil (Fe, Ti, Mn, Si, Al, Ca, Mg), vehicular emissions (BC, Pb, Zn, K) and biomass burning (K, P, S, BC). Reduction of air pollution levels in SSA cities, like Accra, requires public actions providing clean energy sources, health care, public transportation, urban planing and attention to they impact for the poor communities. Relatively simple providences, like roads paving, vegetation covering of the land, use of gas for cooking, public transportation, should decrease the high air pollution level in those cities.
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Fabrication and testing of off-plane gratings for future X-ray spectroscopy missionsDeRoo, Casey T 01 August 2016 (has links)
Soft X-ray spectroscopy is a useful observational tool, offering information about high-temperature (10⁶ -- 10⁷ K) astrophysical plasmas and providing useful characterizations of a number of energetic systems, including accreting young stars, cosmic filaments between galaxies, and supermassive black holes. In order to yield high resolution spectra with good signal-to-noise, however, soft X-ray spectrometers must realize improvements in resolving power and effective area through the development of high performance gratings. Off-plane reflection gratings offer the capability to work at high dispersions with excellent throughput, and are a viable candidate technology for future X-ray spectroscopy missions. The off-plane geometry requires a customizable grating meeting distinct fabrication requirements, and a process for producing gratings meeting these requirements has been developed. These fabricated gratings have been evaluated for performance in terms of resolution and diffraction efficiency. Furthermore, these gratings have been conceptually implemented in a soft X-ray spectrometer, the Off-Plane Grating Rocket Experiment (OGRE), whose optical design provides a template for future missions to achieve high performance within a small payload envelope.
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Water-Metal Surfaces : Insights from core-level spectroscopy and density functional theorySchiros, Theanne January 2008 (has links)
<p>Computational methods are combined with synchrotron-based techniques to analyze the structure and bonding of water and water plus hydroxyl at metal surfaces under UHV and at near-ambient conditions. Water-metal interaction plays a crucial role in a multitude of cosmic, atmospheric and biological phenomena as well as heterogeneous catalysis, electrochemistry and corrosion. A spotlight of renewed interest has recently been cast on water-metal systems due to their relevance for surface chemical reactions related to the production and utilization of hydrogen as a clean energy carrier. In particular, H2O and OH are essential reaction intermediates in the renewable production of hydrogen from sunlight and water and in fuel cell electrocatalysis.</p><p>Fuel cells are considered one of the most promising power generation technologies for a sustainable energy future. A mechanistic understanding of the oxygen reduction reaction (ORR) pathway, including the role of electronic and geometric structure of the catalyst, is essential to the design of more efficient fuel cell catalysts. This is intimately connected to fundamental factors that affect the ability to form water-metal bonds as well as the site occupation and orientation of the adsorbed H2O and OH at active metal surfaces.</p><p>Key relationships related to critical issues in the fuel cell reaction are illuminated by the synergy of theory and experiment in this thesis. We emerge with a detailed understanding of the structure of the water-metal interface and the factors that rule the wettability of a metal surface, including geometric and electronic structure effects and the influence of coadsorbed species. We show that the preferred microscopic orientation of the water monolayer has consequences for macroscopic properties, and reveal the origin of the hydrophobic water layer. Finally, we identify a cooperativity effect that drives the stability of the mixed water/hydroxyl layer at metal surfaces, an important ORR intermediate.</p>
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Sulfur-Related Conservation Concerns in Marine Archaeological Wood : The Origin, Speciation and Distribution of Accumulated Sulfur with Some Remedies for the <i>Vasa</i>Fors, Yvonne January 2008 (has links)
<p>Synchrotron-based sulfur spectroscopy reveals a common concern for marine archaeological wood from seawater: accumulation of reduced sulfur compounds in two pathways. The distribution of sulfur species in the oak wood cell structure was mapped by scanning x-ray spectro-microscopy (SXM). Organically bound sulfur was found within lignin-rich parts, identified mainly as thiols and disulfides by sulfur K-edge x-ray absorption near edge structure (XANES) spectroscopy. Particles of iron sulfides, which may form in the presence of corroding iron, appeared in wood cavities. Cores scanned by x-ray fluorescence (XRF) show that high sulfur accumulation is restricted to the surface layers for the Swedish shipwreck <i>Vasa</i>, while the distribution is rather uniform throughout the hull timbers of the <i>Mary Rose</i>, U.K. Laboratory experiments, exposing fresh pine to simulated seabed conditions, show that the organically bound sulfur develop in reactions between lignin, exposed by cellulose-degrading erosion bacteria, and hydrogen sulfide produced <i>in situ</i> by scavenging sulfate reducing bacteria. With bacteria inoculated from shipwreck samples also iron sulfides formed. The iron sulfides oxidise in high humidity, and are the probable main cause of the numerous outbreaks on the Vasa’s hull of acidic sulfate salts, which were identified by x-ray powder diffraction (XRD). The iron ions catalyse several wood-degrading oxidative processes. Multi-elemental analyses were performed by scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (ESCA). The present amounts of total S remaining in the <i>Vasa</i> and the <i>Mary Rose</i> are estimated to at least 2 tonnes. After the <i>Vasa´s</i> spray treatment with polyethylene glycol solutions ceased in 1979, the continuing oxidation processes are estimated to have produced 2 tonnes of sulfuric acid in the wood. Laboratory experiments to gently neutralize acidic <i>Vasa</i> wood by ammonia gas have been conducted with promising results.</p>
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Atomic data and plasma spectroscopyOelgoetz, Justin Ryan, January 2006 (has links)
Thesis (Ph. D.)--Ohio State University, 2006. / Title from first page of PDF file. Includes bibliographical references (p. 164-170).
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Water-Metal Surfaces : Insights from core-level spectroscopy and density functional theorySchiros, Theanne January 2008 (has links)
Computational methods are combined with synchrotron-based techniques to analyze the structure and bonding of water and water plus hydroxyl at metal surfaces under UHV and at near-ambient conditions. Water-metal interaction plays a crucial role in a multitude of cosmic, atmospheric and biological phenomena as well as heterogeneous catalysis, electrochemistry and corrosion. A spotlight of renewed interest has recently been cast on water-metal systems due to their relevance for surface chemical reactions related to the production and utilization of hydrogen as a clean energy carrier. In particular, H2O and OH are essential reaction intermediates in the renewable production of hydrogen from sunlight and water and in fuel cell electrocatalysis. Fuel cells are considered one of the most promising power generation technologies for a sustainable energy future. A mechanistic understanding of the oxygen reduction reaction (ORR) pathway, including the role of electronic and geometric structure of the catalyst, is essential to the design of more efficient fuel cell catalysts. This is intimately connected to fundamental factors that affect the ability to form water-metal bonds as well as the site occupation and orientation of the adsorbed H2O and OH at active metal surfaces. Key relationships related to critical issues in the fuel cell reaction are illuminated by the synergy of theory and experiment in this thesis. We emerge with a detailed understanding of the structure of the water-metal interface and the factors that rule the wettability of a metal surface, including geometric and electronic structure effects and the influence of coadsorbed species. We show that the preferred microscopic orientation of the water monolayer has consequences for macroscopic properties, and reveal the origin of the hydrophobic water layer. Finally, we identify a cooperativity effect that drives the stability of the mixed water/hydroxyl layer at metal surfaces, an important ORR intermediate.
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Time-dependent molecular properties in the optical and x-ray regionsEkström, Ulf January 2007 (has links)
Time-dependent molecular properties are important for the experimental characterization of molecular materials. We show how these properties can be calculated, for optical and x-ray frequencies, using novel quantum chemical methods. For xray absorption there are important relativistic effects appearing, due to the high velocity electrons near the atomic nuclei. These effects are treated rigorously within the four-component static exchange approximation. We also show how electron correlation can be taken into account in the calculation of x-ray absorption spectra, in time-dependent density functional theory based on the complex polarization propagator approach. The methods developed have been applied to systems of experimental interest|molecules in the gas phase and adsorbed on metal surfaces. The effects of molecular vibrations have been take into account both within and beyond the harmonic approximation.
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Dynamics of multiphoton processes in nonlinear optics and x-ray spectroscopyLiu, Ji-Cai January 2009 (has links)
New generations of ultrashort and intense laser pulses as well ashigh power synchrotron radiation sources and x-ray free electronlasers have promoted fast developments in nonlinear optics andx-ray spectroscopy.The new experimental achievements and the appearance of varieties of novelnonlinear phenomena call for further development of theories. The objective of this thesis is to develop and apply thetheories to explain existing experimental data and to suggest new experiments. The first part of the thesis is devoted to nonlinear propagation of optical pulses. It is shown that the vibrational levels can be selectively populated by varying the duration, shape and intensity of the pump pulse. We obtained a strict analytical solution for the resonant two-photon interaction in a multilevel system beyond rotating wave approximation. Simulations show that the polarization anisotropy of the two-photon excitation affects strongly the anisotropy of photobleaching.The two-photon area theorem is reformulated with taking into account the dynamical Stark shift and the contribution from the permanent dipole moments. In general the dynamical Stark shift does not allow complete population of the excited state, but it can be compensated by detunings in atoms. A dynamical theory of the sequential two-photon absorption of microsecond pulses is developed to explore the role of transverse inhomogeneity of the light beam on optical limiting properties. The propagation of ultrashort laser pulses in nondipolar and dipolar media is investigated with special attention to the generation of superfluorescence and supercontinuum and the formation of attosecond pulses. The second part of the thesis addresses the interaction of molecules with x-ray radiation. We explore here the role of nuclear dynamics in resonant Auger scattering. Multimode simulations of the Auger spectra of ethylene molecule explain the main spectral features of the experimental spectra and show that the spectral profiles are formed mainly due to six vibrational modes. We predict the Doppler splitting of the atomic peak in resonant Auger scattering from SF6 molecule for circularly polarized x-rays. This effect is confirmed by the recent experiment. A new scheme of x-ray pump-probe spectroscopy, namely, resonant inelastic x-ray scattering accompanied by core-hole hopping induced by strong laser fields is suggested. The laser-induced promotion of core holes opens the symmetry forbidden scattering channels and gives rise to new spectral lines in the x-ray scattering spectrum. The strength of the symmetry forbidden lines becomes strong when the time of Rabi flopping is shorter than the lifetime of the core-excited state. We study the role of propagation of femtosecond x-ray free-electron pulses on the Auger process. Simulations show that there exists a strong competition between Auger decay and stimulated emission. The Auger yield and Auger branching ratio are strongly suppressed in the course of pulse propagation. / QC 20100729
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Sulfur-Related Conservation Concerns in Marine Archaeological Wood : The Origin, Speciation and Distribution of Accumulated Sulfur with Some Remedies for the VasaFors, Yvonne January 2008 (has links)
Synchrotron-based sulfur spectroscopy reveals a common concern for marine archaeological wood from seawater: accumulation of reduced sulfur compounds in two pathways. The distribution of sulfur species in the oak wood cell structure was mapped by scanning x-ray spectro-microscopy (SXM). Organically bound sulfur was found within lignin-rich parts, identified mainly as thiols and disulfides by sulfur K-edge x-ray absorption near edge structure (XANES) spectroscopy. Particles of iron sulfides, which may form in the presence of corroding iron, appeared in wood cavities. Cores scanned by x-ray fluorescence (XRF) show that high sulfur accumulation is restricted to the surface layers for the Swedish shipwreck Vasa, while the distribution is rather uniform throughout the hull timbers of the Mary Rose, U.K. Laboratory experiments, exposing fresh pine to simulated seabed conditions, show that the organically bound sulfur develop in reactions between lignin, exposed by cellulose-degrading erosion bacteria, and hydrogen sulfide produced in situ by scavenging sulfate reducing bacteria. With bacteria inoculated from shipwreck samples also iron sulfides formed. The iron sulfides oxidise in high humidity, and are the probable main cause of the numerous outbreaks on the Vasa’s hull of acidic sulfate salts, which were identified by x-ray powder diffraction (XRD). The iron ions catalyse several wood-degrading oxidative processes. Multi-elemental analyses were performed by scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (ESCA). The present amounts of total S remaining in the Vasa and the Mary Rose are estimated to at least 2 tonnes. After the Vasa´s spray treatment with polyethylene glycol solutions ceased in 1979, the continuing oxidation processes are estimated to have produced 2 tonnes of sulfuric acid in the wood. Laboratory experiments to gently neutralize acidic Vasa wood by ammonia gas have been conducted with promising results.
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Spectroscopic analysis of selected silicon ceramicsLeitch, Sam Anthony 17 June 2005
<p>Silicon ceramics are popular in both commercial applications and material research. The purpose of this thesis is to present measurements and analysis of four different silicon ceramics: á, â and ã phases of silicon nitride and silicon oxynitride using soft x-ray spectroscopy, which analyses the electronic structure of materials by measuring the absorption and emission of x-ray radiation. Absorption and emission spectra of these materials are presented, many of which have not be previously documented. The results are compared to model spectra and together they provide information about the electronic structure of the material.</p><p>Assignments of emission features to element, orbital, and site symmetry are performed for each material. Combinations of silicon and nitrogen emission spectra provide insight into the strained bonding structure of nitrogen. It is concluded that p-dð interaction plays a role in the bonding arrangement of nitrogen and oxygen sites within these structures. The emission features of non-equivalent silicon sites within ã-Si3N4 are identified, which represents some of the first analysis of same element, non-equivalent sites in a material.</p><p>Silicon absorption and emission spectra were plotted on the same energy scale to facilitate measurement of the band gap. Since previously measured band gaps are not well represented in literature, the measured band gaps were compared to values predicted using DFT calculations. The band gap values are in reasonable agreement to calculated values, but do not vary as widely as predicted.</p>
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