Esta tese foi dedicada à duas alternativas para tratamento dos lixiviados de aterros sanitários. A primeira delas, o tratamento consorciado do lixiviado com esgoto sanitário em sistemas aeróbios, teve como objetivo principal verificar se a remoção da matéria orgânica do lixiviado seria devida à biodegradação ou à simples diluição no esgoto sanitário. Para responder esse questionamento, propôs-se o método tentativo \"equivalente em ácido húmico\" (Eq.AH). Em ensaios com reatores de lodos ativados (10 L) operados em batelada, avaliaram-se as remoções de matéria orgânica e nitrogênio para diferentes misturas de lixiviado e esgoto sanitários brutos e pré-tratados, com proporções volumétricas de lixiviado de 0, 0,2, 2 e 5%. O tratamento foi mais eficiente para a mistura esgoto bruto e lixiviado pré-tratado por air stripping (para remoção da amônia) na proporção volumétrica de 2%. Essa condição foi avaliada em reatores piloto de lodos ativados (95 L) e biofiltro aerado submerso (178 L), alimentados continuamente com tempo de detenção hidráulica (TDH) de 24 h. O reator piloto de lodos ativados removeu 59% do COD e a eficiência de nitrificação foi de 60%; enquanto que o biofiltro removeu 83% do COD e eficiência de nitrificação foi de 77%. Com o método tentativo Eq.AH, verificou-se que a remoção da matéria orgânica do lixiviado pré-tratado se deu por biodegradação parcial com o esgoto sanitário, resultado confirmado por espectroscopia de infravermelho por transformada de Fourier. As remoções do COD Eq.AH nos reatores piloto de lodos ativados e biofiltro aerado submerso foram de, respectivamente, 47 e 71%. Adicionalmente, o monitoramento da remoção da matéria orgânica pôde ser realizado com eficácia pelo teste de coloração com nanquim, utilizando o método de classificação de tonalidades proposto nesta Tese. A segunda alternativa proposta nesta Tese consistiu no tratamento dos lixiviados bruto e pré-tratado com cal em reatores de lodos ativados. Os resultados, todavia, foram insatisfatórios: indicaram que essa alternativa se mostrou inviável: após 20 dias de aeração nos reatores de bancada alimentados em batelada, a remoção da matéria orgânica foi inferior a 40% e a remoção do nitrogênio foi devida à volatilização da amônia. / This thesis was dedicated to two alternatives for landfill leachate treatment. The first one, the aerobic co-treatment of leachate and domestic wastewater in aerobic systems, aimed to verify if the organic matter of leachate was removed by biodegradation or dilution with domestic wastewater. To answer this questioning, it was proposed the tentative method \"equivalent in humic acid\" (Eq.HA). In the experiments with bench-scale activated sludge reactors (10 L) operated in batch mode, it was evaluated the organic matter and nitrogen removal from mixtures containing raw and pre-treated leachate and domestic wastewater, at the volumetric ratios of 0, 0.2, 2 and 5%. The treatment was mostly efficient when it was used the mixture domestic wastewater and leachate pre-treated by air stripping (for ammonia removal), at a volumetric ratio of 2%. This condition was also evaluated in a pilot-scale activated sludge reactor (95 L) and a submerged aerobic biofilter (178 L), operated under continuous-flow regime with a 24-h hydraulic retention time. The pilot-scale activated sludge reactor removed 59% of DOC and nitrification efficiency was 60%; whereas the submerged aerobic biofilter removed 83% of DOC and nitrification efficiency was 77%. Using the Eq.HA approach, it was determined that pre-treated leachate organic matter removal was due to partial biodegradation with domestic wastewater, which was confirmed by Fourier transform infrared spectroscopy. The removals of COD Eq.HA were 47% for the pilot-scale activated sludge reactor and 71% for the submerged aerobic biofilter. Aditionally, organic matter could be assessed with the India ink reverse stain test, using the proposed method for tonalities classification. The second alternative proposed by this Thesis consisted in the treatment of raw and pre-treated leachate by lime addition, using activated sludge reactors. The results did not indicate the feasibility of this alternative: after 20 days of aeration, the organic matter removal was lesser than 40%, and nitrogen was mostly removed by ammonia volatilization.

Der Zweck dieser Arbeit ist es, die Beziehung zwischen die Größe des Landes und das Wachstum auf internationaler Ebene und vergleichsweise in der Wirtschafts-und Währungsunion zu untersuchen und erarbeiten ihre Folgen für das Verhalten der wachstumsorientierte Finanzpolitik. Um ein globales Verständnis des Zusammenhangs zwischen Größe des Landes und das Wachstum in der EWU weiter verfolgen wir einen interdisziplinären Ansatz, einschließlich der makroökonomischen Modellierung (DSGE), Ökonometrie und Analyse der politischen Ökonomie. Die Kombination dieser Untersuchungen schließen wir, dass die Größe des Landes einen Einfluss auf die wirtschaftlichen Strukturen der Nationen, die Auswirkungen ihrer Politik und damit auf ihre Wachstumsdynamik hat. Aus diesem Grund ist es notwendig, die Bedeutung der Größe des Landes und ihre Folgen für die WWU wieder. / The purpose of this dissertation is to investigate the relationship between country size and growth at the international level and comparatively in the Economic and Monetary Union, and to draw up its consequences for the conduct of growth-orientated fiscal policies. To further a global understanding of the link between country size and growth in the EMU, we follow an interdisciplinary approach, including macro-economic modelling (DSGE), econometrics and political economy analysis. Combining these analyses, we conclude that country size has an incidence on the economic structures of nations, the effects of their policies and therefore on their pace of growth. For this reason there is a need to reinstate the importance of country size and its consequences for the EMU.

In dieser Arbeit werden zwei wesentliche neue Ergebnisse vorgestellt. Das erste bezieht sich auf die olfaktorische Kodierung und das zweite auf das sensorische Gedaechtnis. Beide Phaenomene werden am Beispiel des Gehirns der Honigbiene untersucht. In Bezug auf die olfaktorische Kodierung zeige ich, dass die neuronale Dynamik waehrend der Stimulation im Antennallobus duftspezifische Trajektorien beschreibt, die in duftspezifischen Attraktoren enden. Das Zeitinterval, in dem diese Attraktoren erreicht werden, betraegt unabhaengig von der Identitaet und der Konzentration des Duftes ungefaehr 800 ms. Darueber hinaus zeige ich, dass Support-Vektor Maschinen, und insbesondere Perzeptronen, ein realistisches und biologisches Model der Wechselwirkung zwischen dem Antennallobus (dem kodierenden Netwerk) und dem Pilzkoerper (dem dekodierenden Netzwerk) darstellen. Dieses Model kann sowohl Reaktionszeiten von ca. 300 ms als auch die Invarianz der Duftwahrnehmung gegenueber der Duftkonzentration erklaeren. In Bezug auf das sensorische Gedaechtnis zeige ich, dass eine einzige Stimulation ohne Belohnung dem Hebbschen Postulat folgend Veraenderungen der paarweisen Korrelationen zwischen Glomeruli induziert. Ich zeige, dass diese Veranderungen der Korrelationen bei 2/3 der Bienen ausreichen, um den letzten Stimulus zu bestimmen. In der zweiten Minute nach der Stimulation ist eine erfolgreiche Bestimmung des Stimulus nur bei 1/3 der Bienen moeglich. Eine Hauptkomponentenanalyse der spontanen Aktivitaet laesst erkennen, dass das dominante Muster des Netzwerks waehrend der spontanen Aktivitaet nach, aber nicht vor der Stimulation das duftinduzierte Aktivitaetsmuster bei 2/3 der Bienen nachbildet. Man kann deshalb die duftinduzierten (Veraenderungen der) Korrelationen als Spuren eines Kurzzeitgedaechtnisses bzw. als Hebbsche "Reverberationen" betrachtet werden. / Two major novel results are reported in this work. The first concerns olfactory coding and the second concerns sensory memory. Both phenomena are investigated in the brain of the honeybee as a model system. Considering olfactory coding I demonstrate that the neural dynamics in the antennal lobe describe odor-specific trajectories during stimulation that converge to odor-specific attractors. The time interval to reach these attractors is, regardless of odor identity and concentration, approximately 800 ms. I show that support-vector machines and, in particular perceptrons provide a realistic and biological model of the interaction between the antennal lobe (coding network) and the mushroom body (decoding network). This model can also account for reaction-times of about 300 ms and for concentration invariance of odor perception. Regarding sensory memory I show that a single stimulation without reward induces changes of pairwise correlation between glomeruli in a Hebbian-like manner. I demonstrate that those changes of correlation suffice to retrieve the last stimulus presented in 2/3 of the bees studied. Succesful retrieval decays to 1/3 of the bees within the second minute after stimulation. In addition, a principal-component analysis of the spontaneous activity reveals that the dominant pattern of the network during the spontaneous activity after, but not before stimulation, reproduces the odor-induced activity pattern in 2/3 of the bees studied. One can therefore consider the odor-induced (changes of) correlation as traces of a short-term memory or as Hebbian reverberations.

Esta tese foi dedicada à duas alternativas para tratamento dos lixiviados de aterros sanitários. A primeira delas, o tratamento consorciado do lixiviado com esgoto sanitário em sistemas aeróbios, teve como objetivo principal verificar se a remoção da matéria orgânica do lixiviado seria devida à biodegradação ou à simples diluição no esgoto sanitário. Para responder esse questionamento, propôs-se o método tentativo \"equivalente em ácido húmico\" (Eq.AH). Em ensaios com reatores de lodos ativados (10 L) operados em batelada, avaliaram-se as remoções de matéria orgânica e nitrogênio para diferentes misturas de lixiviado e esgoto sanitários brutos e pré-tratados, com proporções volumétricas de lixiviado de 0, 0,2, 2 e 5%. O tratamento foi mais eficiente para a mistura esgoto bruto e lixiviado pré-tratado por air stripping (para remoção da amônia) na proporção volumétrica de 2%. Essa condição foi avaliada em reatores piloto de lodos ativados (95 L) e biofiltro aerado submerso (178 L), alimentados continuamente com tempo de detenção hidráulica (TDH) de 24 h. O reator piloto de lodos ativados removeu 59% do COD e a eficiência de nitrificação foi de 60%; enquanto que o biofiltro removeu 83% do COD e eficiência de nitrificação foi de 77%. Com o método tentativo Eq.AH, verificou-se que a remoção da matéria orgânica do lixiviado pré-tratado se deu por biodegradação parcial com o esgoto sanitário, resultado confirmado por espectroscopia de infravermelho por transformada de Fourier. As remoções do COD Eq.AH nos reatores piloto de lodos ativados e biofiltro aerado submerso foram de, respectivamente, 47 e 71%. Adicionalmente, o monitoramento da remoção da matéria orgânica pôde ser realizado com eficácia pelo teste de coloração com nanquim, utilizando o método de classificação de tonalidades proposto nesta Tese. A segunda alternativa proposta nesta Tese consistiu no tratamento dos lixiviados bruto e pré-tratado com cal em reatores de lodos ativados. Os resultados, todavia, foram insatisfatórios: indicaram que essa alternativa se mostrou inviável: após 20 dias de aeração nos reatores de bancada alimentados em batelada, a remoção da matéria orgânica foi inferior a 40% e a remoção do nitrogênio foi devida à volatilização da amônia. / This thesis was dedicated to two alternatives for landfill leachate treatment. The first one, the aerobic co-treatment of leachate and domestic wastewater in aerobic systems, aimed to verify if the organic matter of leachate was removed by biodegradation or dilution with domestic wastewater. To answer this questioning, it was proposed the tentative method \"equivalent in humic acid\" (Eq.HA). In the experiments with bench-scale activated sludge reactors (10 L) operated in batch mode, it was evaluated the organic matter and nitrogen removal from mixtures containing raw and pre-treated leachate and domestic wastewater, at the volumetric ratios of 0, 0.2, 2 and 5%. The treatment was mostly efficient when it was used the mixture domestic wastewater and leachate pre-treated by air stripping (for ammonia removal), at a volumetric ratio of 2%. This condition was also evaluated in a pilot-scale activated sludge reactor (95 L) and a submerged aerobic biofilter (178 L), operated under continuous-flow regime with a 24-h hydraulic retention time. The pilot-scale activated sludge reactor removed 59% of DOC and nitrification efficiency was 60%; whereas the submerged aerobic biofilter removed 83% of DOC and nitrification efficiency was 77%. Using the Eq.HA approach, it was determined that pre-treated leachate organic matter removal was due to partial biodegradation with domestic wastewater, which was confirmed by Fourier transform infrared spectroscopy. The removals of COD Eq.HA were 47% for the pilot-scale activated sludge reactor and 71% for the submerged aerobic biofilter. Aditionally, organic matter could be assessed with the India ink reverse stain test, using the proposed method for tonalities classification. The second alternative proposed by this Thesis consisted in the treatment of raw and pre-treated leachate by lime addition, using activated sludge reactors. The results did not indicate the feasibility of this alternative: after 20 days of aeration, the organic matter removal was lesser than 40%, and nitrogen was mostly removed by ammonia volatilization.

Orientador: Alexandre César Rodrigues da Silva / Resumo: O reconhecimento de atividades humanas abrange diversas técnicas de classificação que permitem identificar padrões específicos do comportamento humano no momento da ocorrência. A identificação é realizada analisando dados gerados por diversos sensores corporais, entre os quais destaca-se o acelerômetro, pois responde tanto à frequência como à intensidade dos movimentos. A identificação de atividades é uma área bastante explorada. Porém, existem desafios que necessitam ser superados, podendo-se mencionar a necessidade de sistemas leves, de fácil uso e aceitação por parte dos usuários e que cumpram com requerimentos de consumo de energia e de processamento de grandes quantidades de dados. Neste trabalho apresenta-se o desenvolvimento do Sistema de Reconhecimento de atividades Humanas e Avaliação do Equilíbrio Postural, denominado SIRAH. O sistema está baseado no uso de um acelerômetro localizado na cintura do usuário. As duas fases do reconhecimento de atividades são apresentadas, fase Offline e fase Online. A fase Offline trata do treinamento de uma rede neural artificial do tipo perceptron de três camadas. No treinamento foram avaliados três estudos de caso com conjuntos de atributos diferentes, visando medir o desempenho do classificador na diferenciação de 3 posturas e 4 atividades. No primeiro caso o treinamento foi realizado com 15 atributos, gerados no domínio do tempo, com os que a rede neural artificial alcançou uma precisão de 94,40%. No segundo caso foram gerados 34 ... (Resumo completo, clicar acesso eletrônico abaixo) / Doutor

La thèse se concentre sur une recherche méthodologique sur l'optimisation structurelle catégorielle au moyen d'un apprentissage multiple. Dans cette thèse, les variables catégorielles non ordinales sont traitées comme des variables discrètes multidimensionnelles. Afin de réduire la dimensionnalité, les nombreuses techniques d'apprentissage sont introduites pour trouver la dimensionnalité intrinsèque et mapper l'espace de conception d'origine sur un espace d'ordre réduit. Les mécanismes des techniques d'apprentissage à la fois linéaires et non linéaires sont d'abord étudiés. Ensuite, des exemples numériques sont testés pour comparer les performances de nombreuses techniques d’apprentissage. Sur la base de la représentation d'ordre réduit obtenue par Isomap, les opérateurs de mutation et de croisement évolutifs basés sur les graphes sont proposés pour traiter des problèmes d'optimisation structurelle catégoriels, notamment la conception du dôme, du cadre rigide de six étages et des structures en forme de dame. Ensuite, la méthode de recherche continue consistant à déplacer des asymptotes est exécutée et fournit une solution compétitive, mais inadmissible, en quelques rares itérations. Ensuite, lors de la deuxième étape, une stratégie de recherche discrète est proposée pour rechercher de meilleures solutions basées sur la recherche de voisins. Afin de traiter le cas dans lequel les instances de conception catégorielles sont réparties sur plusieurs variétés, nous proposons une méthode d'apprentissage des variétés k-variétés basée sur l'analyse en composantes principales pondérées. / The thesis concentrates on a methodological research on categorical structural optimizationby means of manifold learning. The main difficulty of handling the categorical optimization problems lies in the description of the categorical variables: they are presented in a category and do not have any orders. Thus the treatment of the design space is a key issue. In this thesis, the non-ordinal categorical variables are treated as multi-dimensional discrete variables, thus the dimensionality of corresponding design space becomes high. In order to reduce the dimensionality, the manifold learning techniques are introduced to find the intrinsic dimensionality and map the original design space to a reduced-order space. The mechanisms of both linear and non-linear manifold learning techniques are firstly studied. Then numerical examples are tested to compare the performance of manifold learning techniques mentioned above. It is found that the PCA and MDS can only deal with linear or globally approximately linear cases. Isomap preserves the geodesic distances for non-linear manifold however, its time consuming is the most. LLE preserves the neighbour weights and can yield good results in a short time. KPCA works like a non-linear classifier and we proves why it cannot preserve distances or angles in some cases. Based on the reduced-order representation obtained by Isomap, the graph-based evolutionary crossover and mutation operators are proposed to deal with categorical structural optimization problems, including the design of dome, six-story rigid frame and dame-like structures. The results show that the proposed graph-based evolutionary approach constructed on the reduced-order space performs more efficiently than traditional methods including simplex approach or evolutionary approach without reduced-order space. In chapter 5, the LLE is applied to reduce the data dimensionality and a polynomial interpolation helps to construct the responding surface from lower dimensional representation to original data. Then the continuous search method of moving asymptotes is executed and yields a competitively good but inadmissible solution within only a few of iteration numbers. Then in the second stage, a discrete search strategy is proposed to find out better solutions based on a neighbour search. The ten-bar truss and dome structural design problems are tested to show the validity of the method. In the end, this method is compared to the Simulated Annealing algorithm and Covariance Matrix Adaptation Evolutionary Strategy, showing its better optimization efficiency. In chapter 6, in order to deal with the case in which the categorical design instances are distributed on several manifolds, we propose a k-manifolds learning method based on the Weighted Principal Component Analysis. And the obtained manifolds are integrated in the lower dimensional design space. Then the method introduced in chapter 4 is applied to solve the ten-bar truss, the dome and the dame-like structural design problems.

L'Imagerie par Résonance Magnétique pondérée en Diffusion (IRM-D) permet l'accès à l'information structurelle des tissus au travers de la lecture du mouvement brownien des molécules d'eau. Ses applications sont nombreuses en imagerie cérébrale, tant en milieu clinique qu'en recherche. Néanmoins le mouvement physiologique créé une perte de signal supplémentaire au cours de l'encodage de la diffusion. Cette perte de signal liée au mouvement limite les applications de l'IRM-D quant à l'imagerie cardiaque. L'utilisation de faibles valeurs de pondération (b) réduit cette sensibilité mais permet seulement l'imagerie du mouvement incohérent intra-voxel (IVIM) qui contient la circulation sanguine et la diffusion des molécules d'eau. L'imagerie IVIM possède pourtant de nombreuses applications en IRM de l'abdomen, depuis la caractérisation tissulaire à la quantification de la perfusion, mais reste inexplorée pour l'imagerie du coeur. Mon travail de thèse correspond à l'évaluation des conditions d'application de l'IRM-D à faibles valeurs de b pour le coeur humain, afin de proposer des contributions méthodologiques et d'appliquer les techniques développées expérimentalement. Nous avons identifié le mouvement cardiaque comme une des sources majeures de perte de signal. Bien que le mouvement global puisse être corrigé par un recalage non-rigide, la perte de signal induite par le mouvement perdure et empêche l'analyse précise par IRM-D du myocarde. L'étude de cette perte de signal chez un volontaire a fourni une fenêtre temporelle durable où le mouvement cardiaque est au minimum en diastole. Au sein de cette fenêtre optimale, la fluctuation de l'intensité atteste d'un mouvement variable résiduel. Une solution de répéter les acquisitions avec un déclenchement décalé dans le temps permet la capture des minimas du mouvement, c.-à-d. des maximas d'intensité en IRM-D. La projection du maximum d'intensité dans le temps (TMIP) permet ensuite de récupérer des images pondérées en diffusion avec un minimum de perte de signal lié au mouvement. Nous avons développé et évalué différentes séquences d'acquisition combinées avec TMIP : la séquence d'imagerie écho-planaire classique par écho de spin (SE-EPI) peut être adaptée mais souffre du repliement d'image ; une séquence Carr-Purcell-Meiboom-Gill combinée avec une préparation d'encodage de diffusion est plus robuste aux distorsions spatiales mais des artefacts de bandes noires empêchent son applicabilité ; finalement une séquence double-SE-EPI compensant les courants de Foucault et pleinement optimisée produit des images IRM-D moins artefactées. Avec cette séquence, l'IRM-D-TMIP permet la réduction significative de la perte de signal liée au mouvement pour l'imagerie cardiaque pondérée en diffusion. L'inconvénient avec TMIP vient de l'amplification du bruit positif d'intensité. Afin de compenser cette sensibilité du TMIP, nous séparons le bruit d'intensité des fluctuations lentes liées au mouvement grâce à une nouvelle approche basée sur l'analyse en composantes principales (PCA). La décomposition préserve les détails anatomiques tout en augmentant les rapports signal et contraste-à-bruit (SNR, CNR). Avec l'IRM-D-PCATMIP, nous augmentons à la fois l'intensité finale et la qualité d'image (SNR) en théorie et expérimentalement. Les bénéfices ont été quantifiés en simulation avant d'être validés sur des volontaires. De plus la technique a montré des résultats reproductibles sur des patients post-infarctus aigue du myocarde, avec un contraste cohérent avec la position et l'étendue de la zone pathologique. Contrairement à l'imagerie cérébrale, l'imagerie IRM-D par faibles valeurs de pondération in vivo doit être différentiée des analyses IRM-D ex-vivo. Ainsi l'IRM-D-PCATMIP offre une technique sans injection pour l'exploration du myocarde par imagerie IVIM. Les premiers résultats sont encourageants pour envisager l'application sur un modèle expérimental d'une maladie cardiovasculaire [etc...] / Diffusion weighted magnetic resonance imaging (DW-MRI, or DWI) enables the access to the structural information of body tissues through the reading of water molecules Brownian motion. Its applications are many in brain imaging, from clinical practice to research. However physiological motion induces an additional signal-loss when diffusion encoding is applied. This motion-induced signal-loss limits greatly its applications in cardiac imaging. Using low diffusion-weighting values (b) DWI reduces this sensitivity but permits only the imaging of intravoxel incoherent motion (IVIM), which combines both water diffusion and perfusion. IVIM imaging has many applications in body MRI, from tissue characterization to perfusion quantification but remains unexplored for the imaging of the heart. The purpose of this work was to evaluate the context of low b-values DWI imaging of the heart, propose methodological contributions and then apply the developed techniques experimentally. We identified cardiac motion as one of the major sources of motion-induced signal loss. Although bulk motion can be corrected with a non-rigid registration algorithm, additional signal-loss remains uncorrected for and prevents accurate DWI of the myocardium. The study of diffusion-weighted signal-loss induced by cardiac motion in a volunteer provided a time-window when motion is at minimum in diastole. Within this optimal time-window, fluctuation of intensity attests of variable remaining physiological motion. A solution to repeat acquisition with shifted trigger-times ease the capture of motion amplitude minima, i.e. DWI-intensity maxima. Temporal maximum intensity projection (TMIP) finally retrieves diffusion weighted images of minimal motion-induced signal-loss. We evaluated various attempts of sequence development with TMIP: usual spin-echo echo-planar imaging (se-EPI) sequence can be improved but suffers aliasing issues; a balanced steady-state free-precession (b-SSFP) combined with a diffusion preparation is more robust to spatial distortions but typical banding artifacts prevent its applicability; finally a state-of-the-art double-spin-echo EPI sequence produces less artifacted DWI results. With this sequence, TMIP-DWI proves to significantly reduce motion-induced signal-loss in the imaging of the myocardium. The drawback with TMIP comes from noise spikes that can easily be highlighted. To compensate for TMIP noise sensitivity, we separated noise spikes from smooth fluctuation of intensity using a novel approach based on localized principal component analysis (PCA). The decomposition was made so as to preserve anatomical features while increasing signal and contrast to noise ratios (SNR, CNR). With PCATMIP-DWI, both signal-intensity and SNR are increased theoretically and experimentally. Benefits were quantified in a simulation before being validated in volunteers. Additionally the technique showed reproducible results in a sample of acute myocardial infarction (AMI) patients, with a contrast matching the extent and location of the injured area. Contrarily to brain imaging, in vivo low b-values DWI should be differentiated from ex vivo DWI pure diffusion measurements. Thus PCATMIP-DWI might provide an injection-free technique for exploring cardiac IVIM imaging. Early results encourage the exploration of PCATMIP-DWI in an experimental model of cardiac diseases. Moreover the access to higher b values would permit the study of the full IVIM model for the human heart that retrieves and separates both perfusion and diffusion information

Made available in DSpace on 2014-12-17T15:42:31Z (GMT). No. of bitstreams: 1 MariaFGM.pdf: 2684798 bytes, checksum: 4d672e17bab00bdd5d88eb70b9c57edf (MD5) Previous issue date: 2007-03-30 / Petr?leo Brasileiro SA - PETROBRAS / Many studies on environmental ecosystems quality related to polycyclic aromatic hydrocarbons (PAH) have been carried out routinely due to their ubiquotus presence worldwide and to their potential toxicity after its biotransformation. PAH may be introduced into the environmet by natural and anthropogenic processes from direct runoff and discharges and indirect atmospheric deposition. Sources of naturally occurring PAHs include natural fires, natural oil seepage and recent biological or diagenetic processes. Anthropogenic sources of PAHs, acute or chronic, are combustion of organic matter (petroleum, coal, wood), waste and releases/spills of petroleum and derivatives (river runoff, sewage outfalls, maritime transport, pipelines). Besides the co-existence of multiples sources of PAH in the environmental samples, these compounds are subject to many processes that lead to geochemical fates (physical-chemical transformation, biodegradation and photo-oxidation), which leads to an alteration of their composition. All these facts make the identification of the hydrocarbons sources, if petrogenic, pyrolytic or natural, a challenge. One of the objectives of this study is to establish tools to identify the origin of hydrocarbons in environmental samples. PAH diagnostic ratios and PAH principal component analysis were tested on a critical area: Guanabara Bay sediments. Guanabara Bay is located in a complex urban area of Rio de Janeiro with a high anthropogenic influence, being an endpoint of chronic pollution from the Greater Rio and it was the scenario of an acute event of oil release in January 2000. It were quantified 38 compounds, parental and alkylated PAH, in 21 sediment samples collected in two surveys: 2000 and 2003. The PAH levels varied from 400 to 58439 ng g-1. Both tested techniques for origin identification of hydrocarbons have shown their applicability, being able to discriminate the PAH sources for the majority of the samples analysed. The bay sediments were separated into two big clusters: sediments with a clear pattern of petrogenic introduction of hydrocarbons (from intertidal area) and sediments with combustion characteristics (from subtidal region). Only a minority of the samples could not display a clear contribution of petrogenic or pyrolytic input. The diagnostic ratios that have exhibited high ability to distinguish combustion- and petroleum-derived PAH inputs for Guanabara Bay sediments were Phenanthrene+Anthracene/(Phenanthrene+Anthracene+C1Phenanthrene); Fluorantene/(Fluorantene+Pyrene); Σ (other 3-6 ring PAHs)/ Σ (5 alkylated PAH series). The PCA results prooved to be a useful tool for PAH source identification in the environment, corroborating the diagnostic indexes. In relation to the temporal evaluation carried out in this study, it was not verified significant changes on the class of predominant source of the samples. This result indicates that the hydrocarbons present in the Guanabara Bay sediments are mainly related to the long-term anthropogenic input and not directly related to acute events such as the oil spill of January 2000. This findings were similar to various international estuarine sites. Finally, this work had a complementary objective of evaluating the level of hydrocarbons exposure of the aquatic organisms of Guanabara Bay. It was a preliminary study in which a quantification of 12 individual biliar metabolites of PAH was performed in four demersal fish representing three different families. The analysed metabolites were 1-hydroxynaphtalene, 2-hidroxinaphtalene, 1hydroxyphenanthrene, 9-hydroxyphenanthrene, 2-hydroxyphenanthrene, 1hydroxypyrene, 3-hidroxibiphenil, 3- hydroxyphenanthrene, 1-hydroxychrysene, 9hydroxyfluorene, 4-hydroxyphenanthrene, 3-hydroxybenz(a)pyrene. The metabolites concentrations were found to be high, ranging from 13 to 177 ?g g-1, however they were similar to worldwide regions under high anthropogenic input. Besides the metabolites established by the used protocol, it was possible to verified high concentrations of three other compounds not yet reported in the literature. They were related to pyrolytic PAH contribution to Guanabara Bay aquatic biota: 1-hydroxypyrine and 3-hydroxybenz(a)pyrine isomers / In?meros estudos da qualidade de ecossistemas naturais em rela??o a contamina??o de hidrocarbonetos polic?ciclos arom?ticos (HPA) t?m sido desenvolvidos continuadamente face a sua presen?a ub?quoa em todo o planeta e ao seu potencial t?xico ap?s a biotransforma??o. A introdu??o dos HPA no meio ambiente pode ocorrer atrav?s de processos naturais e antropog?nicos, atrav?s de despejos e/ou drenagens e deposi??o atmosf?rica indireta. Fontes naturais de HPA incluem queimadas naturais, exsuda??es de ?leo e processos biog?nicos recentes. Fontes antropog?nicas de HPA, advindas de eventos cr?nicos ou agudos, s?o a combust?o incompleta de ?leo combust?vel automotivo e industrial, a queima intencional de madeira e planta??es, os despejos dom?sticos e industriais, as drenagens pluviais urbanas, os efluentes da ind?stria petrol?fera, os derrames acidentais de ?leo e derivados. Al?m da coexist?ncia de m?ltiplas fontes destes hidrocarbonetos nas amostras ambientais, os HPA est?o sujeitos a v?rios processos geoqu?micos que conduzem ? altera??o de sua composi??o qu?mica ao longo do tempo, tornando a identifica??o das fontes contaminantes, se petrog?nica, pirol?tica ou natural, um verdadeiro desafio. Desta forma, um dos objetivos deste estudo foi estabelecer ferramentas que possibilitem a determina??o das fontes de hidrocarbonetos no meio ambiente. Foram utilizadas raz?es diagn?sticas e an?lise de componentes principais de HPA, tendo sido quantificados 38 compostos, incluindo os HPA parentais e alquilados, em 21 amostras de sedimento da Ba?a de Guanabara, coletadas nos anos de 2000 e 2003. A Ba?a de Guanabara ? um ecossistema estuarino com elevada influ?ncia antropog?nica, que recebe polui??o cr?nica da regi?o metropolitana do Rio de Janeiro e que foi cen?rio de um derrame de ?leo em janeiro de 2000. As concentra??es de HPA nos sedimentos estudados apresentaram-se na faixa de 400 a 58439 ng g-1. Ambas as t?cnicas de diferencia??o de fontes de HPA testadas, raz?es diagn?sticas e an?lise de componentes principais, demonstraram sua aplicabilidade, permitindo a diferencia??o das fontes de HPA para a maioria dos sedimentos da ba?a, que foram divididos em dois grandes grupos: sedimentos com padr?es de introdu??o de hidrocarbonetos predominantemente petrog?nicos e sedimentos com caracter?sticas de combust?o. Apenas uma minoria de amostras n?o apresentou com nitidez a natureza de sua contamina??o. As raz?es que apresentaram maior capacidade em diferenciar as fontes de HPA foram Fluoranteno / (Fluoranteno + Pireno), (Fenantreno + Antraceno) / (Fenantreno + Antraceno + C1Fenantreno) e o ?ndice pirol?tico, Σ (HPA parentais de 3-6 an?is) /Σ (5 s?ries de HPA alquilados). Na avalia??o temporal realizada neste estudo n?o foram verificadas varia??es significativas na natureza das fontes contaminantes predominantes na ba?a, revelando que os hidrocarbonetos presentes est?o correlacionados principalmente com os aportes cr?nicos e n?o diretamente com eventos agudos como o derrame de ?leo ocorrido em janeiro de 2000. Este estudo teve como segundo objetivo a avalia??o preliminar do n?vel de exposi??o a que os organismos aqu?ticos da Ba?a de Guanabara est?o submetidos, atrav?s da quantifica??o de 12 metab?litos individuais de HPA presentes em bile de peixe de quatro esp?cies demersais representativas de tr?s fam?lias diferentes. Os metab?litos analisados foram 1-hidroxinaftaleno, 1-hidroxifenantreno, 9hidroxifenantreno, 2-hidroxinaftaleno, 2-hidroxifenantreno, 1-hidroxipireno, 3hidroxibifenila, 3-hidroxifenantreno, 1-hidroxicriseno, 9-hidroxifluoreno, 4hidroxifenantreno, 3-hidroxibenzo(a)pireno. As concentra??es encontradas nas esp?cies de peixes analisadas mostraram-se elevadas, na faixa de 13 a 177 ?g g1, por?m similares ?s encontradas em algumas regi?es de grande influ?ncia antropog?nica, tanto no Brasil quanto no exterior. Al?m dos metab?litos estabelecidos pela metodologia utilizada, foi poss?vel quantificar tr?s compostos, ainda n?o reportados na literatura, em concentra??es relevantes. Estes metab?litos, relacionados a contribui??o pirol?tica de HPA aos organismos aqu?ticos da Ba?a de Guanabara, s?o is?meros de 1-hidroxipireno e de 3-hidroxibenzo(a)pireno

The Ceratitis capitata is a very important agricultural pest, whose reproduction behaviour is controled by chemical signals. Males initiate mating by creating leks, where they release sexual pheromones to attract females. The main goal of this diploma thesis was to determine the influence of host plants on the composition of male sex-pheromones C. capitata and to compare emanations of wild males with those originating from laboratory population. We studied the chemical composition of volatiles, released by calling males C. capitata from laboratory and two wild populations, using two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC×GC-TOFMS), gas chromatography with electroantennographic and flame ionization detection (GC-EAD-FID). All data were statistically analyzed by multivariate data analyses. Significant differences were observed in the quantitative and qualitative composition of the chemical emanations among males from the three populations. The GC-EAD-FID analyses revealed fourteen antenally active compounds with a possible behavioral function. Isomenthone, geraniol, bornyl acetate, geranyl acetone and ethyl octanoate were newly identified antenally active compounds of C. capitata male sex pheromone. Statistical analyses indicated that males and females of...

[pt] As descargas atmosféricas são de grande importância para o setor elétrico, sendo frequentemente responsáveis por desligamentos de linhas de transmissão, que podem desencadear uma sequência de eventos que levem o sistema elétrico interligado ao colapso. As longas extensões de linhas de transmissão, expostas a intemperes climáticas, determinam uma probabilidade significativa de incidência direta de descargas atmosféricas nestes equipamentos. Devido ao caráter estratégico das linhas para o fornecimento de energia e a constatação de que descargas atmosféricas estão entre as principais causas de desligamentos, torna-se importante o estudo do comportamento das descargas atmosféricas, antes do instante da ocorrência do desligamento das linhas de transmissão, para compreender os padrões característicos potenciais causadores destes desligamentos. Os estudos encontrados atualmente estão orientados na eficiência das redes de detecção de descargas atmosféricas e na identificação de condições climáticas que indiquem a ocorrência de raios de forma preditiva, sem correlação a ocorrências em linhas de transmissão. Assim, essa dissertação consiste na determinação do risco de desligamentos de linhas de transmissão por descargas atmosféricas, visando fornecer informações antecipadas e possibilitar ações operativas para manter a segurança do sistema elétrico. O modelo desenvolvido nesse estudo, denominado Risco de Desligamentos de Linhas de Transmissão por Raios (RDLR), é composto de dois módulos principais, sendo o primeiro o agrupamento do conjunto amostral de descargas atmosféricas, realizado através de um método baseado em densidade. Nesse módulo, os ruídos são eliminados de forma eficiente e são formados grupos representativos de descargas atmosféricas. O segundo módulo consiste em uma etapa classificatória, baseado em redes neurais artificiais para identificar padrões de grupos de descargas que representem riscos de desligamentos de linhas de transmissão. Visando a otimização do modelo, foi aplicado um método de seleção das variáveis, através de componentes principais, para determinar aquelas que mais contribuem na caracterização desses eventos. O modelo RDLR foi testado com dados reais dos registros de desligamentos de linhas de transmissão, associado a outro banco com dados reais contendo milhões de registros de descargas atmosféricas oriundos das redes de detecção de raios, sendo obtidos excelentes resultados na determinação dos riscos de desligamentos de linhas de transmissão por descargas atmosféricas. / [en] Atmospheric discharges are of great importance to power systems, and are often responsible for outages of transmission lines, which can trigger a sequence of events that leads to a system collapse. The long extensions of transmission lines, exposed to climatic conditions, create significant probability of direct incidence of atmospheric discharges in these equipments. Due to the strategic nature of power supply lines and the fact that atmospheric discharges are among the main causes of outages, it is important to study atmospheric discharges characteristics before failure of transmission lines and understand patterns that are responsible for interruptions. Current studies focus on efficiency of lightning detection networks and on identification of climatic conditions that indicate lightning occurrence in a predictive approach, without any correlation with transmission lines outages. Therefore, this thesis consists on real-time risk determination of transmission lines outage by lightning, providing early information to enabling operational procedures for power system safety. The proposed model, named Transmission Lines Outage Risk by Lightning (TLORL) is composed of two main modules: Atmospheric Discharge Data Clustering and Classification. In the atmospheric discharges data-clustering module, performed by a density-based method, the outages are efficiently eliminated and representative groups of atmospheric discharges are formed. The second module consists of a classification step, based on artificial neural networks, to identify patterns of discharges groups that represent risks to cause transmission lines outages. Aiming at improving the proposed model, principal components analysis (PCA) was applied to determine the input variables that most contribute to the events characterization. The TLORL model was tested with real data transmission line outages, associated to another database with millions lightning records from the detection networks, producing excellent results of transmission lines outages caused by atmospheric discharges.