Thin films are used in many energy conversion applications, ranging from photodetectors to solar cells. Accurately predicting the radiative properties of thin films when they possess rough surfaces is critical in many instances, but can be challenging due to the complexity arising from light scattering and interferences at the microscale. This work describes measurements of the spectral transmittance and reflectance of several thin-film materials (including crystalline silicon wafers and a polycrystalline diamond film) in the mid-infrared spectral region (2 20 m) using a Fourier-transform infrared (FT-IR) spectrometer. The transmittance and reflectance were calculated using thin-film optics for the double-side polished samples and scalar scattering theory for the single-side polished samples. The effects of partial coherence are considered using a fringe smoothing technique. The interval used for fringe smoothing was assumed to be linearly dependent on the wavenumber. Good agreement between the predicted and measured transmittance was achieved for the double-side polished silicon wafers and for the diamond film. The disagreement for some single-side polished silicon wafers may be inherently related to their surface microstructures, as suggested from surface topographic data and images obtained from surface profilometry and microscopy. By comparing the intervals used for fringe smoothing with the instrumental resolution, beam divergence in the spectrometer was found to be a major factor contributing to the partial coherence. Future research is proposed to investigate the correlation between the detailed surface characteristics and the conical-conical transmittance and reflectance.

Orientador: Carlos Roberto de Souza Filho / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Geociências / Made available in DSpace on 2018-08-17T09:04:06Z (GMT). No. of bitstreams: 1 Lammoglia_Talita_D.pdf: 27070693 bytes, checksum: 051a8bf03318833e59450c5d128891cf (MD5) Previous issue date: 2010 / Resumo: O petróleo é constituído basicamente por uma mistura de componentes químicos orgânicos (hidrocarbonetos) e pode ser classificado segundo a escala de grau API, viscosidade ou quantidade relativa de seus componentes SARA (i.e. saturados, aromáticos, resinas e asfaltenos). Escapes naturais de hidrocarbonetos para a superfície são denominados de exsudações, que compreendem o objeto principal de estudo desta pesquisa. A investigação remota desses fenômenos foi aqui abordada com base na caracterização espectral de petróleos, bem como por estudos de caso em bacias sedimentares offshore (Campos e Campeche) e onshore (Tucano Norte). Considerando uma oleoteca de 17 amostras de óleo constituída para essa pesquisa, foram efetuadas medidas espectrais de reflectância para o VNIR e SWIR (visível, infravermelho próximo e de ondas curtas), bem como de reflectância total atenuada (ATR), reflectância direcional hemisférica (DHR) e emissividade para o TIR (infravermelho termal). Esses dados foram processados por técnicas quimiométricas. Diversas feições espectrais diagnósticas do petróleo no intervalo do VNIR-SWIR foram discriminadas, permitindo a caracterização espectral dos óleos puros sobre a água ou em emulsão com a água do mar. Ademais, diferentes petróleos (leves e pesados) e sua composição SARA foram qualitativamente distinguidos com base nas suas feições espectrais, mesmo em situações de filme de óleo sobre água. Muitas feições diagnósticas de HCs foram acentuadas em espectros obtidos em emulsões óleoágua, o que pode facilitar o mapeamento de exsudações. A análise quimiométrica desses espectros indicou ser possível a estimativa do tempo de exposição e emulsificação óleo-água na superfície do mar. Os resultados das análises quimiométricas obtidos com espectros do VNIR-SWIR foram também positivos para espectros reamostrados para a resolução espectral dos sensores hiperespectrais (ProspecTIR, Hyperion) ou multiespectrais (ASTER). No intervalo de 3 a 14 ?m, foram observadas feições diagnósticas dos óleos, principalmente entre 2-8 ?m. Entre 8-14 ?m, apenas um patamar constante de emissividade foi registrado, sempre inferior ao da água. A análise quimiométrica desses espectros no TIR indicou ser possível a separação dos petróleos de acordo com seu grau API, mesmo quando reamostrados para resolução espectral de sensores hiperespectrais termais (SEBASS). Os resultados de laboratório foram utilizados para caracterização de duas exsudações offshore, ambas registradas pelo sensor ASTER. De modo pioneiro, através dos métodos aqui propostos, foi possível a determinação do grau API, componentes SARA e o tempo de emulsão de exsudações por imagens de satélite. O processamento digital das imagens ASTER, através da aplicação das técnicas spectral mixture analysis (SMA) e redes neurais não supervisionadas, possibilitou a extração de outras informações relevantes, tais como a extensão da mancha de óleo, temperatura, emissividade, indicações de espessura do filme de óleo, além de previsões sobre a aparência de filmes de óleo no mar em relação ao restante da cena. No plano onshore, as exsudações de hidrocarbonetos da Bacia do Tucano Norte (BA) foram estudadas com base na análise estatística de dados geoquímicos regionais e no processamento digital de imagens do sensor ASTER. O modelo teórico de detecção de exsudações aqui estabelecido implica que anomalias gasosas devem coincidir com descoloração de solos e rochas, com marcadores geobotânicos e com a concentração de argilas e carbonatos. Considerando esse modelo, as técnicas de SMA, bem como diferentes sistemas de redes neurais, foram utilizados para mapear áreas mais favoráveis à ocorrência de exsudações. Os produtos da SMA para o VNIR-SWIR e TIR foram combinados e classificados por Lógica Fuzzy e Regressão Logística. Os resultados possibilitaram o mapeamento de locais onde as feições previstas no modelo teórico de detecção coincidem com as anomalias geoquímicas. A experiência em ambas as áreas de estudo nos ambientes onshore e offshore indicam o potencial de modelos quimiométricos, dados ASTER e metodologias de análise e integração espectro-espacial para a exploração de hidrocarbonetos e monitoramento ambiental. / Abstract: Crude oils are a mixture of organic components (hydrocarbons - HCs) which can be classified based on their API gravity or their SARA components (i.e. saturated, aromatics, resins, and asphaltenes). Natural hydrocarbon escapes, known as seepages, are the focus of this research. They were investigated based on laboratory crude oil spectral characterization and considering study cases of seepages recorded on offshore (Campos and Campeche) and onshore (North Tucano) sedimentary basins. Seventeen oil samples with distinct chemical attributes were measured for spectral reflectance ((VNIR-SWIR), Attenuated Total Reflectance (ATR), Directional Hemispherical Reflectance (DHR), and emissivity (TIR). These spectra were processed by chemometric techniques. Crude oil, oil water emulsion and oil films over water were characterized through their diagnostic features in the VNIR-SWIR spectral range. In addition, different oil types (i.e. with different API gravity) and their SARA components were qualitatively distinguished based on these features, including scenarios with oil on water. Several HC diagnostic spectral features were highlighted in stable oil-water emulsions, providing extra evidence for offshore seepage mapping. Chemometric analysis of oil-water emulsion spectra indicates that it is possible to estimate the time of weathering and emulsion of oil over water. Overall VNIR-SWIR chemometric results are also efficient for oil measurements simulated at the spectral resolution of hyperspectral (ProspecTIR and Hyperion) and multispectral (ASTER) sensors. Within TIR wavelengths (3-14 µm), typical HC spectral features were also resolved between 2-8 ?m; Between the 8-14 ?m range, oil emissivity spectra are essentially flat, but always lower than water. Chemometric analysis of TIR spectra shows that oil types can be qualitatively (i.e. API) discriminated, including both full-resolution spectra and spectra resampled to hyperspectral thermal sensors (SEBASS). The spectral libraries here built for a number of oils at diverse status were used to characterize two offshore seepages, both recorded by the ASTER sensor. Using the methodology presented in this research, it was possible, for the first time, to estimate the API gravity, SARA components and seepage exposition to the ocean surface environment using orbital remote sensing data. By means of spectral mixture analysis and unsupervised neural network algorithms, relevant additional information was extracted from ASTER data, including seepage extension, temperature, emissivity and oil thickness. The appearance of oil films as relatively lighter or darker patches on ASTER imagery was predicted by yielding radiance data through the mean square slope of ocean waves. On onshore settings, microseepages at the Tucano Norte basin were evaluated using geostatistical analysis of regional hydrocarbon geochemical data yielded from soil samples and digital processing of ASTER data. A theoretical detection model was devised in which gas anomalies indicated by hydrocarbon geochemistry should spatially match a number of surface expressions such as the presence of bleached soil and rocks, geobotanical markers and concentration of specific clays and carbonates. Based on this detection model, VNIR-SWIR and TIR ASTER data were processed through spectral mixing analysis and neural network systems. These results were also combined by Fuzzy logic and Logistic Regression in order to locate sites more favorable to host hydrocarbon seeps. The outcomes showed that several sites where the features predicted in the detection model concurred with geochemical anomalies were mapped. This research demonstrated the outstanding potential of spectroscopy, chemometric analysis, ASTER data and methodologies of spectra-spatial analysis and integration for exploration of hydrocarbons and environmental monitoring. / Doutorado / Geologia e Recursos Naturais / Doutor em Ciências

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / A ConBr à uma proteÃna tetramÃrica presente em sementes de Canavalia brasiliensis e que possui afinidade para os aÃÃcares D-mannose e D-glucose. à vasto o uso desta lectina em ensaios biotecnolÃgicos devido as suas propriedades biolÃgicas. à comumente utilizada conjugada ao FITC, um fluorÃforo amplamente utilizado nas diversas Ãreas da biotecnologia para anexar um marcador fluorescente a proteÃnas atravÃs do grupamento amina. No entanto, a influÃncia deste fluorÃforo na atividade de tais proteÃnas precisa ser mais bem evidenciada. Essa pesquisa visou obter informaÃÃes sobre as alteraÃÃes na estrutura secundÃria da proteÃna ConBr nativa e conjugada com FITC, alÃm de iniciar um estudo desta lectina tambÃm conjugada com pontos quÃnticos. Amostras de ConBr nativa, conjugada com o FITC (ConBr-FITC (2%)), misturada com FITC na proporÃÃo de 2% em massa (ConBr/FITC (2%)), misturada com FITC na proporÃÃo de 20% em massa (ConBr/FITC (20%)) e processada mas nÃo conjugada com o FITC (ConBr-), foram analisadas por espectroscopia de infravermelho com transformada de Fourier (FTIR) atravÃs da tÃcnica de reflectÃncia total atenuada (ATR). Foram realizados testes de atividade hemaglutinante especÃfica com ConBr nativa, ConBr-FITC (2%), ConBr/FITC (2%), ConBr- e ConBr conjugada com pontos quÃnticos (ConBr-QD Zn/Cd). A atividade hemaglutinante especÃfica nos extratos foi determinada usando-se suspensÃes de hemÃcias de coelho a 3% em placas de microtitulaÃÃo. Os dados obtidos nos ensaios de atividade especÃfica foram submetidos ao teste estatÃstico de Mann-Whitney. Quando os espectros de ConBr nativa e ConBr-FITC (2%) foram comparados, observou-se que o pico da lectina nativa referente Ãs estruturas de folhas β, nÃo sofreu qualquer modificaÃÃo quando a proteÃna foi conjugada com FITC, entreteanto, notou-se uma diminuiÃÃo da intensidade na regiÃo do espectro referente Ãs estruturas em α-hÃlice, o que permite inferir uma reduÃÃo da quantidade destas estruturas. Houve tambÃm um aumento de intensidade na regiÃo referente Ãs estruturas irregulares. Os espectros de ConBr nativa, ConBr- e ConBr/FITC (2%) nÃo sugeriram alteraÃÃes na estrutura secundÃria. Nos testes de atividade hemaglutinante especÃfica de ConBr nativa e ConBr-FITC (2%) houve uma diminuiÃÃo da atividade especÃfica para esta Ãltima em relaÃÃo a primeira e estes resultados demonstraram diferenÃa estatisticamente significativa entre si. ConBr nativa e ConBr- nÃo apresentaram diferenÃas estatÃsticas significativas entre si. A atividade de ConBr/FITC (2%) tambÃm nÃo apresentou diferenÃas estatÃsticas em relaÃÃo à ConBr nativa. Em conjunto, estes resultados contribuem e reforÃam a proposiÃÃo de que à a ligaÃÃo do FITC à proteÃna que promove a alteraÃÃo estrutural na regiÃo de α-hÃlice. A atividade especÃfica de ConBr-QD Zn/Cd diminuiu drasticamente quando comparada com a atividade de ConBr nativa, apresentando diferenÃa estatisticamente significativa entre estas amostras. AnÃlises estatÃsticas realizadas com os dados obtidos no teste de atividade especÃfica e anÃlise dos espectros de infravermelho sugerem alteraÃÃes na estrutura secundÃria da lectina ConBr conjugada ao FITC. PorÃm, ainda à necessÃria a elucidaÃÃo da natureza dessa alteraÃÃo e se essa à realmente devida à ligaÃÃo da proteÃna ao fluorÃforo. / ConBr is a tetrameric protein found in Canavalia brasiliensis seeds and has affinity for D-mannose and D-glucose carbohydrates. It is vast use of this lectin in biotechnological assays due their biological properties, and itâs used commonly linked to FITC, a fluorophore widely used in various fields of biotechnology to attach to proteins a fluorescent marker through amine grouping. However, the fluorophore influence in proteins activity must be further highlighted. This research aimed obtain informations about native ConBr secondary structure and FITC-conjugated changes and start a study of this lectin conjugated quantum dots also. Samples of native ConBr, ConBr-FITC conjugated (FITC-ConBr (2%)), ConBr mixed with the FITC proportion of 2% by mass (ConBr/FITC (2%)), ConBr mixed with FITC at 20 mass% (ConBr/FITC (20%)) and processed but not conjugated with FITC ConBr (ConBr-) were analyzed by Fourier Transform Infrared spectroscopy (FTIR), mode ATR (Attenuated Total Refectance). The native ConBr, ConBr-FITC (2%), ConBr/FITC (2%), ConBr-, and conjugated quantum dots ConBr (QD ConBr-Zn / Cd) specific haemagglutinating activity were performed. The specific haemagglutinating activity in the extracts was determined using the rabbit erythrocytes suspensions at 3% in microtiter plates. The specific activity data were tested using the Mann-Whitney test. When the native ConBr and FITC-ConBr (2%) spectra were compared, it was found the peak of the native lectin relating to β-sheet structures not suffered modification when the protein was conjugated with FITC, but there was a intensity reduction in the spectrum region relating to α-helix structures, which allows a reduction in the amount these structures. There was an intensity increase of irregular structures also. Native ConBr, ConBr- e ConBr/FITC (2%) spectra suggested no changes in secondary structure. There was a ConBr-FITC (2%) hemagglutinating activity decrease and that result showed statistically significant difference to native ConBr. Native ConBr and ConBr- do not have significantly differences. The ConBr/FITC (2%) activity didnât showed statistical differences regarding native ConBr. These results contribute and reinforce the proposition that is the FITC binding to protein promotes the structural change in the α-helix region. The ConBr-QD Zn/Cd specific activity decreased compared with the activity of native ConBr, demonstrating statistically significant differences between these samples. Statistical analyzes using the data obtained in the specific activity test and infrared spectra analysis suggest lectin ConBr FITC-conjugated secondary structure changes. However, itâs still necessary elucidate the nature of this change, and whether this is really due to the protein-fluorophore binding.

Face à l’émergence de l’imagerie multi et hyperspectrale, il existe une demande croissante de connaissance fine de la réponse spectrale des détecteurs infrarouge. Dans ce travail de thèse, nous proposons une démarche de modélisation optique des réponses spectrales des plans focaux infrarouge HgCdTe. L’objectif est de mieux maîtriser les origines physiques des oscillations observées sur les réponses spectrales des pixels d’une matrice de détection, ainsi que des disparités de longueurs d’onde de coupure. Ces phénomènes étaient peu étudiés dans la littérature; pourtant, ils sont responsables en partie du bruit spatial fixe qui limite les performances des détecteurs. Nous proposons une description qui conserve l’interprétation physique des phénomènes observés (absorption, interférences,…), tout en permettant d’extraire les paramètres technologiques (responsables de ces non-uniformités) de la façon la plus indépendante possible. Le principe repose sur la décomposition du comportement global du détecteur, qui peut sembler complexe, en une multitude de briques élémentaires, simples à modéliser. L’étude a été appliquée au cas particulier d’un micro-spectromètre infrarouge intégré au plan de détection. Une analyse de sensibilité sur le modèle proposé a alors permis d’évaluer la précision nécessaire sur les paramètres technologique afin d’obtenir une bonne qualité de restitution de spectres. Cette démarche est généralisable à d’autres architectures de détecteurs et d’autres technologies de fabrication, à condition de maîtriser les propriétés optiques des matériaux mis en jeu. / Due to the emergence of multi and hyperspectral imaging, there is an increasing demand for the control of the spectral response of infrared detectors. In this thesis, we propose an optical modelling approach of the spectral response of HgCdTe focal plane arrays. The aim is to better identify the physical origins of the oscillations observed on the spectral responses of the pixels belonging to the same detector array, as well as the cutoff wavelength disparities. These phenomena were not studied in the literature; though, they are partly responsible for the fixed pattern noise that limits the performance of the detectors. We propose a description that takes account of the physical interpretation of the observed phenomena (absorption, interference…), while allowing the extraction of the technological parameters (that are responsible for such non-uniformities) in the most independent way possible. The principle is based on the decomposition of the global behaviour of the detector, which may seem complex, as a multitude of elementary phenomena, which are easy to model. The study was applied to the particular case of a micro-spectrometer integrated to an infrared detection array. A sensitivity analysis of the proposed model was then performed to deduce the necessary precision on the technological parameters to obtain good quality spectra restitution. This approach can be generalized to other architectures detectors and other manufacturing technologies, provided that the optical properties of the materials involved are well known.

Results of ab initio and density functional theory calculations on the structure and vibrational frequencies of hypophosphite anion indicate earlier experimental assignments of the fundamental vibrational modes are correct while the recent reassignments of several modes proposed by Bickley et al. are inconsistent with the calculated results.

L'Angélique (Dicorynia guianensis Amsh.) est une espèce forestière de Guyane très exploitée pour son bois mais ce dernier est connu pour présenter une durabilité naturelle variable, dont les conséquences peuvent être très lourdes pour l'utilisateur. Dans le cadre de cette thèse nous avons souhaité comprendre l'origine de la durabilité naturelle du duramen se l'Angélique afin d'appréhender sa variabilité pour mieux la prédire. Dans un premier temps, nous avons mis en oeuvre une stratégie d'échantillonnage basée sur l'étude architecturale de l'arbre pour appréhender la variabilité de la durabilité naturelle, ce qui a été confirmé par les essais biologiques réalisés. Nous avons par la suite évalué l'influence de potentiels facteurs mesurés dans le bois sur la durabilité naturelle. A ce titre, le rôle des extractibles a été évalué par des approches métaboliques ciblées et non ciblées, couplées à une stratégie de déréplication. La lignine et l'infradensité ont également été retenues comme facteurs de durabilité naturelle de l'Angélique. Enfin, ses caractéristiques propres à l'ontogénie se l'arbre ont été pris en compte et les résultats mettent en lumière l'importance du stade de développement de l'arbre ainsi que son environnement. Enfin, nous avons proposé ses outils spectroscopiques (moyen et proche infrarouge) simples, rapides et fiables pour prédire la durabilité naturelle. Ces résultats sont encourageants et suggèrent leur utilisation potentielle pour la filière bois pour prédire la durabilité naturelle du bois de l'Angélique. / Angélique (Dicorynia guianensis Amsh.) is a tree species in French Guiana that is heavily exploited for its wood, but it is known to have variable natural durability, which can be of severe consequences for the user. In this thesis we wanted to understand the origin of the natural durability of Angelique heartwood in order to understand its variability, to beter predict it. This multidisciplinary work combines wood sciences, natural products chemistry and microbiology. First, we implemented a sampling strategy based on the architectural profile of tree individuals to understand the variability of natural durabilityn which was confirmed by biological assays. We then assessed the influence of potential natural durability factors that we measured in the wood samples. As such, the role of metabolies was investigated using targeted and untargeted metabolomics, coupled with a dereplication strategy. Lignin and infradensity have also been tested as factors of durability for Angelique heartwood. Finally, factors that are related to tree ontogeny have been taken into account and the results highlight the importance of the stage development and the environment of tree individuals. Lastly, we have proposez esasy, fast and reliable spectroscopie tools (medium and near infrared) to predict the nartural durability. These results are encouraging and suggest their potential use by the timber industry to predict durability of Angélique heartwood.

Les argiles sont des minéraux complexes présentant une porosité multi-échelles et une aptitude à gonfler sous atmosphère humide. Ces matériaux ont diverses applications en catalyse, dans le stockage des déchets, dans le bâtiment… Pourtant, les propriétés de l'eau confinées sont encore mal comprises, notamment en raison de la complexité de l'eau elle-même. Le but de ce travail est, en utilisant principalement les simulations moléculaires et les spectrométries vibrationnelles, de comprendre la structure et la dynamique de l'eau confinée dans les argiles.Afin d'évaluer la précision des modèles numériques pour décrire l'eau confinée dans les argiles, et pour comprendre l'origine de ses propriétés structurales et dynamiques, un large part de ce travail est consacrée aux briques constitutives de l'argile : l'eau pure, l'eau interfaciale et l'eau salée. A ce titre, on étudie les propriétés viscoélastiques de l'eau du domaine surfondu jusqu'à la température d'ébullition par dynamique moléculaire classique. On analyse aussi les propriétés de frottement près d'une surface type, et la précision des approches ab initio et des modèles de sels.Dans une seconde partie, on confronte ces résultats aux propriétés de l'eau confinée dans les argiles à basse température et à température ambiante, expérimentalement et numériquement. Les expériences consistent en des mesures exhaustives par spectrométrie d'absorption dans l'infrarouge moyen et lointain, tandis que les calculs sont des simulations de dynamique moléculaire classique. En particulier, on s'intéresse à l'existence de transitions de phases induites par le confinement ou les variations de température / Clay are complex minerals with a multiscale porosity and a remarkable ability to swell under humid atmosphere. These materials have many applications in catalysis, waste management, construction industry... However, the properties of confined water are still not fully understood, due in particular to the complexity of water itself. The aim of this work is, using mainly molecular simulations and vibrational spectroscopy, to understand the structure and the dynamics of water confined in clay minerals. To evaluate the accuracy of numerical models to describe water confined in clay minerals, and to understand the origin of its structural and dynamical properties, a large part of the work was devoted to the building blocks of clays: pure bulk water, water at the surface of a solid, and salt water. To this extent, the viscoelastic properties of water from the deeply supercooled regime to the boiling temperature were investigated using classical molecular dynamics. The evolution of the friction properties of water on a prototypical solid surface was also analyzed, and the accuracy of ab initio approaches and empirical salt models was studied.In a second part, those results were confronted to the properties of water confined in clay minerals at low and room temperature, studied both experimentally and numerically. Experimental work consisted mostly in extensive far- and -mid infrared absorption spectrometry measurements, whereas numerical work mainly consisted in empirical molecular dynamics simulations. Especially, the existence of confinement- or temperature-induced phase transitions of confined water was investigated

As nanopartículas atmosféricas podem causar diversos efeitos à saúde já que durante a inalação podem penetrar mais profundamente no sistema respiratório humano, atingindo inclusive os alvéolos e a corrente sanguínea, e, desta forma, aumentar os efeitos toxicológicos prejudiciais. Estas partículas podem ser emitidas diretamente para a atmosfera (partículas primárias) ou ser formadas por conversão gás-partícula (partículas secundárias). Durante a última década, estudos têm sido realizados para uma melhor compreensão sobre as concentrações de nanopartículas, avaliando sua emissão, formação, dispersão, exposição e os efeitos à saúde. No entanto, poucos estudos foram realizados no Brasil e desta forma ainda há pouca informação em relação a esta temática. A Região Metropolitana de Porto Alegre - RMPA (Brasil) possui forte tráfego veicular, cerca de 1,8 milhões de veículos e, apesar das fontes móveis impactarem fortemente a qualidade do ar nesta região e ser a principal fonte de nanopartículas, não há estudos que avaliem em profundidade os níveis deste importante poluente ambiental. Desta forma, no presente estudo foram avaliadas as concentrações de nanopartículas em diferentes pontos da RMPA. Além disso, foram avaliadas as concentrações ambientais de partículas <1 μm (MP1) e metais associados, bem como foram identificadas e quantificadas as contribuições de fontes utilizando o modelo receptor Positive Matrix Factorization (PMF). Em adição, foi realizada uma análise das assinaturas espectrais no infravermelho de nitro-hidrocarbonetos policíclicos aromáticos (nitro-HPAs) associados ao MP1. Este grupo de compostos orgânicos possui uma ampla distribuição no ambiente e, por possuírem propriedades mutagênicas e carcinogênicas, seus riscos ambientais foram calculados. Desta forma, considerando os resultados obtidos, verificou-se uma forte contribuição antropogênica dos poluentes avaliados na RMPA. Esta degradação da qualidade do ar está em geral associada ao tráfego veicular, especialmente no que se refere aos níveis de nanopartículas e nitro-HPAs associados ao MP1. Além disso, as emissões industriais, a queima de carvão, biomassa e óleo combustível, bem como a queima de combustíveis veiculares apresentaram forte influência nos níveis de metais observados em MP1. / Atmospheric nanoparticles can cause health effects, as during inhalation penetrate more deeply into the human respiratory system, including the alveoli and reaching the bloodstream, and thereby increase the damaging toxicological effects. These particles can be emitted directly to the atmosphere (primary particles) or be formed by gas-to-particle conversion (secondary particle). Over the last decade, studies have been conducted for a better understanding of the nanoparticles, assessing the emission, formation, dispersion, exposure and health effects. However, few studies have been conducted in Brazil and thus there is little information regarding this subject. The Metropolitan Area of Porto Alegre - MAPA (Brazil) has a strong vehicular traffic, about 1.8 million vehicles and, despite mobile sources strongly impact the air quality in this region and be the main source of nanoparticles, there are no studies that evaluate in depth the levels of this important environmental pollutant. Thus, considering this knowledge gap, the present study evaluated the nanoparticle concentrations in different sites of the MAPA. In addition, environmental concentrations of particles <1 μm (MP1) and associated metals were evaluated and the sources were identified and quantified using the receptor model Positive Matrix Factorization (PMF). In addition, an analysis of the infrared spectral signatures of nitro polycyclic aromatic hydrocarbons (nitro-PAHs) associated with PM1 was performed. This group of organic compounds has a wide distribution in the environment, and because they have mutagenic and carcinogenic properties, their environmental risks were calculated. Thus, considering the obtained results, a strong anthropogenic contribution of the evaluated pollutants in the MAPA was observed. This degradation of the air quality in general is associated with vehicular traffic, especially regarding the levels of nanoparticles and nitro-PAHs associated with PM1. In addition, industrial emissions, coal, biomass and fuel oil combustion, as well as vehicle fuels combustion had a strong influence on the metal levels observed in PM1.

As nanopartículas atmosféricas podem causar diversos efeitos à saúde já que durante a inalação podem penetrar mais profundamente no sistema respiratório humano, atingindo inclusive os alvéolos e a corrente sanguínea, e, desta forma, aumentar os efeitos toxicológicos prejudiciais. Estas partículas podem ser emitidas diretamente para a atmosfera (partículas primárias) ou ser formadas por conversão gás-partícula (partículas secundárias). Durante a última década, estudos têm sido realizados para uma melhor compreensão sobre as concentrações de nanopartículas, avaliando sua emissão, formação, dispersão, exposição e os efeitos à saúde. No entanto, poucos estudos foram realizados no Brasil e desta forma ainda há pouca informação em relação a esta temática. A Região Metropolitana de Porto Alegre - RMPA (Brasil) possui forte tráfego veicular, cerca de 1,8 milhões de veículos e, apesar das fontes móveis impactarem fortemente a qualidade do ar nesta região e ser a principal fonte de nanopartículas, não há estudos que avaliem em profundidade os níveis deste importante poluente ambiental. Desta forma, no presente estudo foram avaliadas as concentrações de nanopartículas em diferentes pontos da RMPA. Além disso, foram avaliadas as concentrações ambientais de partículas <1 μm (MP1) e metais associados, bem como foram identificadas e quantificadas as contribuições de fontes utilizando o modelo receptor Positive Matrix Factorization (PMF). Em adição, foi realizada uma análise das assinaturas espectrais no infravermelho de nitro-hidrocarbonetos policíclicos aromáticos (nitro-HPAs) associados ao MP1. Este grupo de compostos orgânicos possui uma ampla distribuição no ambiente e, por possuírem propriedades mutagênicas e carcinogênicas, seus riscos ambientais foram calculados. Desta forma, considerando os resultados obtidos, verificou-se uma forte contribuição antropogênica dos poluentes avaliados na RMPA. Esta degradação da qualidade do ar está em geral associada ao tráfego veicular, especialmente no que se refere aos níveis de nanopartículas e nitro-HPAs associados ao MP1. Além disso, as emissões industriais, a queima de carvão, biomassa e óleo combustível, bem como a queima de combustíveis veiculares apresentaram forte influência nos níveis de metais observados em MP1. / Atmospheric nanoparticles can cause health effects, as during inhalation penetrate more deeply into the human respiratory system, including the alveoli and reaching the bloodstream, and thereby increase the damaging toxicological effects. These particles can be emitted directly to the atmosphere (primary particles) or be formed by gas-to-particle conversion (secondary particle). Over the last decade, studies have been conducted for a better understanding of the nanoparticles, assessing the emission, formation, dispersion, exposure and health effects. However, few studies have been conducted in Brazil and thus there is little information regarding this subject. The Metropolitan Area of Porto Alegre - MAPA (Brazil) has a strong vehicular traffic, about 1.8 million vehicles and, despite mobile sources strongly impact the air quality in this region and be the main source of nanoparticles, there are no studies that evaluate in depth the levels of this important environmental pollutant. Thus, considering this knowledge gap, the present study evaluated the nanoparticle concentrations in different sites of the MAPA. In addition, environmental concentrations of particles <1 μm (MP1) and associated metals were evaluated and the sources were identified and quantified using the receptor model Positive Matrix Factorization (PMF). In addition, an analysis of the infrared spectral signatures of nitro polycyclic aromatic hydrocarbons (nitro-PAHs) associated with PM1 was performed. This group of organic compounds has a wide distribution in the environment, and because they have mutagenic and carcinogenic properties, their environmental risks were calculated. Thus, considering the obtained results, a strong anthropogenic contribution of the evaluated pollutants in the MAPA was observed. This degradation of the air quality in general is associated with vehicular traffic, especially regarding the levels of nanoparticles and nitro-PAHs associated with PM1. In addition, industrial emissions, coal, biomass and fuel oil combustion, as well as vehicle fuels combustion had a strong influence on the metal levels observed in PM1.

This diploma thesis deals with the ongoing research under the auspices of the Department of Applied Physics and Technics Faculty of Education, University of South Bohemia in České Budějovice, in which the author of the work was actively participated. The thesis is divided into theoretical and experimental part. The theoretical part contains information from natural polymers, especially cellulose, plasma technology and infrared spectrometry. The subject of the experimental part of the thesis is research that deals with the functionalization of cellulose using a microwave plasma discharge on the apparatus CX-22. In the present research was also conducted to process optimization of functionalization with the liquid precursor hexamethyldisiloxane (HMDSO).