Orientador: Maria Izabel Maretti Silveira Bueno / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-09T19:56:43Z (GMT). No. of bitstreams: 1 Pereira_FabiolaManhasVerbi_D.pdf: 3497538 bytes, checksum: 1fb4f6d6dcc544540876238e76e5b33b (MD5) Previous issue date: 2007 / Resumo: Este trabalho de tese apresenta um procedimento inovador para detectar modificações orgânicas em tintas utilizando Espectroscopia de Raios-X (XRS, X-Ray Spectroscopy) e Análise de Componentes Principais (PCA, Principal Component Analysis). Para esta finalidade foram avaliadas amostras de vernizes, tintas e primers, após serem submetidas a vários testes de exposição, em campo ou em laboratório. Espectros de raios-X foram obtidos utilizando um tubo de raios-X de Rh e a análise de PCA foi efetuada na região de 18 a 24 keV, onde se manifesta o espalhamento de radiação da fonte de Rh. Os gráficos de scores evidenciaram a classificação das amostras conforme a resistência perante aos testes. Esta diferenciação foi promovida pelos Efeitos Compton e Rayleigh, visualizados na região de 18 a 24 keV. Outra parte deste trabalho mostra um método analítico complementar para a avaliação do controle de qualidade. Para o desenvolvimento deste, imagens provenientes das amostras citadas anteriormente, foram digitalizadas com um scanner convencional. As imagens foram convertidas em histogramas de cores em tons de cinza. Os dados foram organizados em uma matriz e analisados com o auxílio da PCA. Com a combinação de informações obtidas com a XRS, as imagens e a PCA foi possível selecionar o melhor produto, evitando interpretações subjetivas. Na parte final do estudo foi desenvolvida a calibração multivariada das propriedades de vernizes e de tintas combinando XRS e Regressão por Mínimos Quadrados Parciais (PLS, Partial Least Squares). As propriedades potenciais para a calibração foram: teor de sólidos/massa (erros entre -14,3 e 17,6%) e massa específica (erros entre -3,29 e 4,42%). Para as tintas, estas propriedades foram: viscosidade Stormer (erros entre -7 e 10%) e brilho especular (erros entre -16,3 e 16,5%) / Abstract: This work presents an unconventional form to detect organic modifications in paints employing X-ray Spectroscopy (XRS) and Principal Component Analysis (PCA). For this purpose, different samples, such as varnishes, paints and primers were submitted to accelerated laboratory and outdoor exposure tests. X-ray fluorescence spectra were obtained using a Rh tube-EDXRF system. PCA was performed using the spectral region from 18 to 24 keV, where X-ray source scattering effects are observed. The scores plots showed a clear paint classification and also a separation according to its performance in the tests. This separation was promoted by Compton and Rayleigh Effects. It is also shown a complementary analytical method for evaluating quality of paints. Digitalized images were obtained from the samples described above using a conventional scanner. The images were converted into gray colour scale histograms and the resulting data were organized into a matrix and analyzed with PCA. It was possible to identify the best performances of varnishes, paints and primers avoiding subjective interpretations. In the last part of this study, analytical methods for multivariate calibration of varnishes and paints properties combining XRS with Partial Least Squares (PLS) data treatment were developed. The potential calibrated properties for varnishes were nonvolatile content (errors from -14.3 to 17.6%) and density (errors from -3.29 to 4.42%). For paints, the potential calibrated properties were Stormer viscosity (errors from -7 to 10%) and specular gloss (errors from -16.3 to 16.5%) / Doutorado / Quimica Analitica / Doutor em Ciências

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.

Catalysts based on the first-row (3d) transition metals are commonly seen in chemical and biological reactions. To understand the role of the transition metal in the catalyst, the element specific technique core level spectroscopy is used to probe the electronic structure and geometric properties centered around the metal site. Different types of X-ray spectra can be applied to probe the metal 3d character orbitals involved in reactions, which make it possible to identify and characterize the reactive sites of samples in different forms. A detailed interpretation and understanding of the different X-ray spectra requires a unified method which can be used to model different types of X-ray spectra, e.g., soft and hard X-rays. In this thesis, theoretical investigations of the electronic structures of 3d transition metal complexes through X-ray spectroscopy are presented. The restricted active space method (RAS) is used to successfully reproduce different types of X-ray spectra by including all important spectral effects: multiplet structures, spin-orbit coupling, charge-transfer excitations, ligand field splitting and 3d-4p orbital hybridization. Different prototypes of molecules are adopted to test the applicability of the RAS theory. The metal L edge X-ray absorption (XAS) spectra of low spin complexes [Fe(CN)6]n and [Fe(P)(ImH)2]n in ferrous and ferric oxidation state are discussed. The RAS calculations on iron L edge spectra of these comparing complexes have been performed to fingerprint the oxidation states of metal ion, and different ligand environments. The Fe(P) system has several low-lying spin states in the ground state, which is used as a model to identify unknown species by their spectroscopic fingerprints through RAS spectra simulations. To pave the route of understanding the electronic structure of oxygen evolution complex of Mn4CaO5 cluster, the MnII(acac)2 and MnIII(acac)3 are adopted as prototypical Mn-complexes. The 3d partial fluorescence yield-XAS are employed on the Mn L-edge in solution. Combining experiments and RAS calculations, primary questions related to the oxidation state and spin state are discussed. The first application to simulate the metal K pre-edge XAS of mono-iron complexes and iron dimer using RAS method beyond the electric dipole is completed by implementing the approximate origin independent calculations for the intensities. The K pre-edge spectrum of centrosymmetric complex [FeCl6]n– ferrous state is discussed as s and a donor model systems. The intensity of the K pre-edge increases significantly if the centrosymmetric environment is broken, e:g:, when going from a six-coordinate to the four-coordinate site in [FeCl4]n. Distortions from centrosymmetry allow for 3d-4p orbital hybridization, which gives rise to electric dipole-allowed transitions in the K pre-edge region. In order to deliver ample electronic structure details with high resolution in the hard X-ray energy range, the two-photon 1s2p resonant inelastic X-ray scattering process is employed. Upon the above successful applications of one-photon iron L edge and K pre-edge spectra, the RAS method is extended to simulate and interpret the 1s2p resonant inelastic X-ray scattering spectra of [Fe(CN)6]n in ferrous and ferric oxidation states. The RAS applications on X-ray simulations are not restricted to the presented spectra in the thesis, it can be applied to the photon process of interest by including the corresponding core and valence orbitals of the sample.

>Magister Scientiae - MSc / The ultimate aim of any multiply-charged ion source, like the Electron Cyclotron Resonance Ion Source, ECRIS, is the production of multiply-charged ions, in sufficiently large quantities. These multiplycharged ions, in the case of the ECRIS, are created by a step-by-step ionisation process, whereby neutral atoms are ionised by energetic electrons. The goal of this thesis was to gain an understanding of the relative importance of various ECRIS parameters on the production of these energetic electrons. This was done by measuring the bremsstrahlung continuum emitted by the mirror confined plasma of an ECR ion source. The focus of our study was to investigate the influence of neutral pressure, incident microwave power and magnetic field configuration on spectral temperature and electron density of the warm electron population of the ECRIS plasma. The thesis begins by familiarising the reader with various aspects of plasma physics as it relates to the measurements. The measurements were done with a high-purity germanium detector and processed with the DGF Pixie-4 module. Analyses of the measured spectra were done with subroutines written in Root. From the measured result, it was concluded that by increasing the incident microwave power from 50 W to 300 W, the spectral temperature increases by 14.01% for helium plasma and 7.88% for argon plasma. Evidence of saturation of spectral temperature and electron density with increasing microwave power was also noticed, as reported by other groups investigating plasma bremsstrahlung. The increase of spectral temperature with neutral pressure was found to be considerable, increasing by 20.23% as the neutral pressure in the plasma chamber of the ECRIS was decreased. This increase in spectral temperature was accompanied by a 40.33% decrease in electron density, which led us to conclude that the increase in spectral temperature was most likely due to an increase in the mean free path of the electrons. The influence of the magnetic field configuration on both spectral temperature and electron density was also investigated. During this investigation, one of the solenoid coil currents was increased, whilst keeping the other constant. This amounts to moving the plasma volume around axially in the plasma chamber of the ECRIS. This was found to significantly enhance the spectral temperature and this effect was attributed to more efficient heating of the electrons near the resonance zone. The electron density on the other hand was found to remain relatively constant, if one excludes the electron density as a result of one particularly setting of the solenoid coils. The decrease of electron density as a result of this particular setting of the solenoid coils enhanced the electron losses through the magnetic bottle. This is evidenced by the increase in photon counts as measured by our detector. The influence of neutral pressure, incident microwave power and magnetic field configuration on the extracted ion beam intensities was also investigated. This investigation led us to conclude that the mean charge state extracted increases with spectral temperature. This result was in agreement with those measured by other groups.

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The aim of this thesis is to investigate the methodology of three dimensional chemical imaging of nanoparticles through the use of scanning transmission electron microscope (STEM) – energy dispersive X-ray (EDX) spectroscopy. In this thesis, an absorption correction factor is derived for spherical nanoparticles that can correct X-ray absorption effects. Quantification of EDX spectra of nanoparticles usually neglects X-ray absorption within the nanoparticle but may lead to erroneous results, thus an absorption correction is important for accurate compositional quantification. The absorption correction presented is verified through comparison with experimental data of Au X-ray peaks in spherical Au nanoparticles and is found to agree excellently. This absorption correction allows accurate compositional quantification of large ( > 100 nm) particles with STEM-EDX.Three dimensional chemical mapping is achievable through the use of EDX spectroscopy with electron tomography. Here, the methodology of STEM-EDX tomography is fully explored, with a focus on how to avoid artefacts introduced through detector shadowing and low counts per pixel. A varied-time acquisition scheme is proposed to correct for detector shadowing that is shown to provide a more constant intensity over a series of projections, allowing a higher fidelity reconstruction. The STEM-EDX tomography methodology presented is applied to the study of AgAu nanoparticles synthesized by the galvanic replacement reaction. The elemental distribution as a function of the composition of the as-synthesized nanoparticles is characterised and a reversal in the element segregated to the surface of the nanoparticles is found. The composition at which the reversal takes place is shown to correlate with a peak in the catalytic yield of a three component coupling reaction. It is hypothesized that a continuous Au surface results in the optimum catalytic conditions for the reaction studied, which guides the use of galvanically prepared AgAu nanoparticles as catalysts.

Critical water resources, such as groundwater, are undergoing a period of intense and global environmental change, driven by climate change, anthropogenic impacts and exploitation, and perturbations to interactions of fundamental processes that are affected by hydrological, mineralogical and biogeochemical factors. Arsenic contamination is a significant threat to these water resources and the populations who depend on them, yet there are few studies directly linking water quality with changes in hydrology and geochemistry in sediments on varying scales. My research explores environmental variability in hydrology and redox processes that regulate soluble arsenic concentrations at the pore scale (µm to mm), and develops methods of upscaling these mechanistic studies to understand heterogeneity in groundwater arsenic levels and their impacts on public health at larger scales (a couple of meters to hundreds of kilometers). Specifically, my research examines the interaction of redox processes in the Earth’s subsurface that drive the release of arsenic into groundwater. Naturally-occurring, or geogenic, arsenic contamination is the main source of arsenic release into groundwater that affects human health, with possible anthropogenic exacerbation of this natural contamination. Throughout this dissertation, I have developed a suite of data-driven approaches to understand and quantify the highly variable factors that underlie the mechanisms of geogenic arsenic release into groundwater and its migration in the environment. In Chapter 1, I investigate the effects of hydrologic perturbations on formerly uncontaminated aquifers that release arsenic due to increased groundwater pumping in the Red River Delta, Vietnam. To compare the effect of hydrologic processes to measured groundwater arsenic concentrations, I used Monte Carlo simulations in an end-member mixing model and quantified fraction of different recharge sources into an aquifer based on stable water isotopes. I find that changing flow patterns due to groundwater abstraction have increased the extent of arsenic release into groundwater and also changed the location of where arsenic contamination originates. In Chapter 2, I characterize iron mineralogy associated with arsenic release through sampling of sediment cores across a lateral redox gradient in Vietnam with extensive spectroscopy measurements. Through hierarchical cluster analysis on this data set of X-ray absorption spectroscopy (XAS) measurements of borehole cuttings paired with dissolved groundwater measurements, I reveal signatures of iron mineral reduction that could cause or exacerbate arsenic release. This was upscaled to other deltaic aquifers in South and Southeast Asia based on groundwater data to identify aquifers at risk of arsenic release. I showed that the extent of older and previously pristine aquifers that have been contaminated may have been misclassified and thus underrepresented in deltaic aquifers throughout South and Southeast Asia, disrupting the assumption that older and deeper aquifers are oxidized and thus guarded against arsenic release. In Chapter 3, I use process-based reactive transport modeling of a laboratory-scale experiment to mechanistically explain the infiltration of contaminated water into uncontaminated aquifers and find that arsenic contamination cannot be explained by the commonly invoked mechanism of iron reducing bacteria only, but instead relies on sulfate reduction and complexation of aqueous arsenic in solution. The role of sulfate reduction in mobilizing arsenic in groundwater is in stark contrast to and undermines the previous use of sulfate reduction as strategy for arsenic remediation. Finally, in Chapter 4, I quantitatively examine the processes that release arsenic across different arsenic-impacted aquifers, based on the relationships between redox status of iron and arsenic mineralogy and groundwater concentrations. Synthesis of X-ray absorption spectra of the deltaic aquifers of Southeast Asia and the glacial aquifer system in the Northern United States shows that arsenic release occurs in similar geochemical environments in both systems, and is highly generalizable via statistical and unsupervised machine learning approaches. This dissertation demonstrates that common assumptions behind geogenic arsenic release must be tested: from which aquifers are low in arsenic to the commonly assumed mechanism of arsenic release by iron reducing bacteria. These findings also reveal that the extent of anthropogenic impact on geogenic arsenic contamination is detectable: from changes in recharge sources to changes in mineralogy that affect arsenic concentrations and human health. The next step is to use these data driven and machine learning approaches to quantify the vulnerability of affected aquifers, to mitigate the risk of those currently reliant on contaminated groundwater, to reduce the risks of future contamination and, ultimately, to protect human health.

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第19817号 / 人博第788号 / 新制||人||189(附属図書館) / 27||人博||788(吉田南総合図書館) / 32853 / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 田部 勢津久, 教授 吉田 寿雄 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

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