No description available.

Classification of remotely sensed imagery for reliable land use and land cover (LULC) change information remains a challenge in areas where spectrally similar LULC features occur. Dissolved organic matter (DOM) influences the biogeochemistry of aquatic environments and its quantity and quality are due, in large part, to the surrounding LULC. Thus, objectives were to improve the accuracy of LULC classification and quantify seasonal variations of water quality in a watershed dominated by agriculture and determine the controls for the variations in water quality. Support vector machine classification scheme with post classification correction yielded highest accuracy for LULC classifications and four distinct DOM components were found that changed seasonally and were controlled by hydrology and LULC. The microbial component was the main fraction of the DOM pool due in large part to agricultural practices. This DOM can influence the water quality significantly as it moves downstream and causes increased biological activity.

No description available.

No description available.

Les travaux effectués au cours de ce doctorat, en collaboration étroite avec la Direction du Développement et de la Prospective (DDP) du Syndicat Interdépartemental pour l’Assainissement de l’Agglomération Parisienne (SIAAP), s’inscrivent dans le cadre du programme de recherche MOCOPEE (Modélisation, Contrôle et Optimisation des Procédés d’Epuration des Eaux) et s’intéressent aux potentielles applications de la spectrofluorimétrie 3D pour caractériser les quantités et qualités de la matière organique dissoute (MOD) dans les eaux de station d’épuration des eaux usées (STEU) et dans les eaux du milieu naturel. La première partie de ce manuscrit est dédié aux applications de la spectrofluorescence 3D pour caractériser la MOD des eaux de STEU. Une méthodologie de traitement des spectres de fluorescence reposant sur l’utilisation d’un algorithme de déconvolution nommée PARAFAC, a été appliquée pour les eaux usées de la STEU « Seine Centre ». Un fractionnement par hydrophobicité ainsi qu’une étude de biodégradabilité ont permis d’apporter de nouvelles informations sur les propriétés des fluorophores de la MOD des eaux usées de STEU. Des relations entre des indicateurs de fluorescence et les mesures de demandes biologiques en Oxygène (DBO5) soluble ainsi qu’avec les mesures de demande chimiques en oxygène (DCO) soluble ont été mises en évidence pour les eaux usées d’entrée de 6 STEU (n=83) de la région parisienne (SIAAP). Ces modèles de prédiction pourront être utilisés pour optimiser la gestion des filières de traitements épuratoires des eaux usées (ex : ajouts de réactifs). Enfin, les fluorophores identifiés ont été utilisés pour suivre l’évolution de la MOD le long des filières épuratoires des STEU de « Seine Centre » et « Seine Grésillons ». La deuxième partie traite des potentiels d’applications de cette méthodologie dans les eaux du milieu naturel. Grâce au réseau de suivi MeSeine (Mesure en Seine), 373 prélèvements ont été réalisés par le SIAAP, lors d’un suivi hebdomadaire de Juillet 2015 à Juin 2016, dans le bassin versant de la Seine. Ce suivi intègre 12 points de prélèvements de l’amont vers l’aval de Paris et deux des principaux affluents de la Seine (Marne et Oise). De ce suivi, un modèle PARAFAC de 10 composantes a été mis en évidence. Des variations spatio-temporelles de qualité de MOD ont été observées entre les différents cours d’eau étudiés. L’impact de la pression urbaine (rejets de STEU) sur la qualité de la MOD entre l’amont et l’aval de l’agglomération parisienne a également pu être observé. Ainsi, une caractérisation physico-chimique rapide de la MOD et de ses sources en milieu aquatique urbain, peut être effectuée par spectrofluorescence 3D. La mise en place de ce type de suivi in situ apportera des informations rapides sur la qualité et quantité de MOD des milieux aquatiques naturels pour les gestionnaires de stations de potabilisations qui pourront connaitre la qualité de la MOD des eaux de prélèvements et anticiper la formation de sous-produits de désinfections. Les gestionnaires des milieux aquatiques pourront également anticiper la survenue d’épisodes de pollution des eaux de surface. Enfin, un modèle de prédiction de la concentration en carbone organique dissoute par spectrofluorescence 3D combiné à la spectrométrie d’absorbance a été mis en évidence. Les conclusions mises en évidence par ce travail contribueront à une meilleure compréhension de la MOD fluorescente des eaux usées de STEU (optimisation des filières de traitement biologique) et des milieux aquatiques. Ainsi, ce type de travail ne se limite pas à la communauté scientifique, mais s’étend aux gestionnaires et opérationnels du domaine de l’eau / The work carried out during this PhD, in close collaboration with the Development and Prospective Development Department (DDP) of the Interdepartmental Syndicate for the Sanitation of the Paris Metropolitan Area (SIAAP), is part of the research program MOCOPEE (Research Modeling, Control and Optimization of Water Treatment Processes) and are interested in the potential applications of 3D spectrofluorimetry to characterize dissolved organic matter (DOM) quantity and quality in wastewater treatment plant (WWTP) and in natural middle. The first part of this manuscript is devoted to the potential applications of 3D fluorescence spectroscopy to characterize wastewater DOM quality and quality. A methodology for the treatment of 3D fluorescence spectra based on the use of a deconvolution algorithm named PARAFAC has been applied to wastewater from the Seine Center WWTP. Specific MOD fluorophores were observed, allowing a finer approach to the fluorescence characteristics of MOD. Resin fractionation and a biodegradability study yielded new information on raw sewage DOM fluorophores. Relationships between DOM fluorescence indicators and soluble Biological Oxygen Demand (BOD5) measurements as well as soluble Chemical Oxygen Demand (COD) measurements have been demonstrated in raw sewage from 6 Parisian WWTP (SIAAP). Prediction models of soluble BOD5 and soluble COD by 3D spectrofluorimetry can be used to anticipate variations of raw sewage quality and quantity, and to optimize biological treatment processes (eg reagent additions). Finally, DOM fluorescence was analyzed along "Seine Center" and "Seine Grésillons" WWTPs. The second part deals with applications potential of 3D fluorescence spectroscopy in natural middles. Thanks to the MeSeine monitoring network (Mesure en Seine), a total of 373 samples were taken during a weekly monitoring from July 2015 to June 2016 in the Seine catchment area and include 12 sampling points from upstream to downstream of Paris and two of its main tributaries (Marne river and Oise river). From this monitoring, a PARAFAC model with 10 components was highlighted. Variations in DOM quality were observed between the different streams studied. The impact of urban pressure on DOM quality was also observed by fluorescence, between the upstream and downstream of the Parisian agglomeration. We have also been able to monitor WWTP effluent impacts on the Seine during a maintenance operation for its treatment processes. Variations in the quality of MOD between low and high water periods were also observed. Thus, 3D spectrofluorimetry help to provide a rapid physicochemical characterization of DOM and its sources in urban aquatic environments. Theses information will help drinking water plants managers to rapidly know DOM quality to anticipate formation of disinfections by-products. Managers of aquatic environments will also be able to anticipate occurrence of surface water pollution episodes. Finally, 3D fluorescence spectroscopy and absorbance spectroscopy were combined to develop a dissolved organic carbon concentration prediction model. The findings highlighted by this work will contribute, on their scale, to a better understanding of DOM fluorescence in raw sewage water (optimization of biological treatment channels) and in aquatic environments. In this sense, the usefulness of this type of work is not limited to the scientific community, but extends to managers and the operational fields

Les activités anthropiques ont apporté des changements majeurs à notre système global. Par ailleurs, la matière organique dissoute(MOD) du littoral a une grande influence sur le cycle global du carbone et donc sur le changement climatique. L'apport côtier enMOD représente la matière organique terrestre. Les rivières urbanisées sont fortement impactées par la MOD anthropiqueprovenant des usines de traitement des eaux usées. La MOD chromophorique est un sous-groupe de la MOD qui peut absorber lalumière. La MOD fluorescente est à son tour un sous-groupe de la MOD chromophore. Le signal de fluorescence de la MODanthropogénique dans la zone côtière n'est pas bien caractérisé et évalué dans la littérature. Les dégradations induites parphotochimie et les changements au niveau moléculaire sont peuvent de plus influencer la MOD. Dans la présente étude, plusieursexpériences d'irradiation solaire ont été menées avec plusieurs modes de filtration de mélange d’eau de rivière, d’eau de mer et d'uneffluent de station de traitement des eaux usées dans le but de trouver un signal spécifique de fluorescence comme un traceur de laMOD anthropique en utilisant les matrices d'émission d'excitation de la spectroscopie de fluorescence (EEMs) couplées à latechnique statistique chimiométrique de l'analyse factorielle parallèle CP/PARAFAC. Un modèle de régression multilinéaire a étédéveloppé entre la contribution des composantes CP/PARAFAC et la composition du mélange. La cinétique des paramètres derégression multilinéaire a également été étudiée. Des suivis géographiques de l'évolution du signal de fluorescence dans la rivièreGapeau jusqu'à la mer ont été menées ainsi qu’une étude temporelle du signal de fluorescence. Le modèle de régressionmultilinéaire développé a été appliqué pour modéliser les résultats des expériences de champs géographiques et temporelles. Lesrésultats ont montré que le modèle de régression multilinéaire est excellent. Par contre la recherche d'un signal ou d'une signaturede fluorescence spécifique pour l'eau de rivière, les stations d'épuration des eaux usées ou l'eau de mer n'a pas pu être réalisée dansce travail. Dans la zone côtière affectée par l'homme, les matières organiques fluorescentes résiduelles proviennent principalementsinon uniquement de l'usine de traitement des eaux usées, et aucun signal spécifique provenant de l'eau de mer n'a pu être détectéprès de la côte. / Anthropogenic activities have done major changes to our global system. The coastal dissolved organic matter has great influenceon the global carbon cycle and hence climate change. The riverine input of dissolved organic matter represents the terrestrialorganic matter. Urbanized rivers is greatly impacted by the anthropogenic dissolved organic matter coming from wastewatertreatment plants . Chromophoric dissolved organic matter is a subgroup of the dissolved organic matter which can absorb light.Fluorescent dissolved organic matter in turn is a subgroup of the chromophoric dissolved organic matter .The fluorescence signalof the anthropogenic dissolved organic matter in the coastal zone is not well characterized and evaluated in the literature.Photochemically induced degradations and changes at the molecular level is considered to be a great process which could influencethe dissolved organic matter . In the present study, Laboratory mixing experiments several sunlight irradiation experiments wereconducted with several modes of filtration of three endmember mixing components ( River water, Sea water , wastewater treatmentplant effluent discharge) with the objective of finding a specific signal of fluorescence which could be a tracer of the anthropogenicdissolved organic matter through using the fluorescence spectroscopy excitation emission matrices (EEMs) coupled with thechemometric statistical technique of Parallel Factor analysis CP/PARAFAC. Moreover, multilinear regression model between thecontribution of CP/PARAFAC components and two content fraction of River water and Seawater endmember was developed. Inaddition the kinetics of the multilinear regression parameters were investigated. On top of that , geographical investigations of theevolution of fluorescence signal in the Gapeau river till the sea were conducted. Furthermore, Temporal investigation of thefluorescence signal for four water points in the pathway of Gapeau river were done. The multilinear regression model developedwas applied to model the results of the geographical and temporal field experiments. Results have shown that Multilinearregression model for contribution of CP/PARAFAC components is excellent and could be done for the three endmembers. Inaddition the search for specific fluorescence signal or signature for river water, wastewater treatment plants and sea water couldn’tbe done in this work. In human impacted coastal zone, residual fluorescent organic matter come from wastewater treatment plant,and no specific signal from sea water could be detected near the coast.

A Amazônia representa a maior biodiversidade do mundo e representa um reservatório enorme e dinâmico de carbono, não só na biomassa, mas também no solo. O ciclo do carbono neste bioma é muito importante, principalmente para questões abordadas às mudanças climáticas. Avaliar e compreender a dinâmica do carbono e outros elementos no solo da Amazônia pode ajudar os cientistas a melhorar os modelos e antecipar cenários. Novos métodos, que permitem medições de carbono do solo in situ, são uma abordagem fundamental para este tipo de região, devido aos custos financeiros para a coleta e envio de amostras de solo da floresta para o laboratório, e demanda muito tempo nesta atividade. No presente estudo, uma topossequência de um sistema Latossolo-Espodossolo com caulim associado, desenvolvido a partir de rochas granito gnáissicas do embasamento cristalino, foi estudada. As amostras foram coletadas em São Gabriel da Cachoeira, estado do Amazonas. Dois perfis de solo: Espodossolo Humilúvico (P1) no topo e Latossolo Amarelo (P2) na meia encosta da topossequência foram descritos e amostrados em um total de dezoito amostras. Os objetivos principais foram avaliar e caracterizar através de métodos químicos e espectroscópicos a matéria orgânica e a composição elementar nestes solos arenosos utilizando a análise elementar (CHNS), espectroscopia de emissão ótica com plasma induzido por laser (LIBS), espectrometria de emissão ótica com plasma acoplado indutivamente (ICP OES), espectroscopia de fluorescência induzida por laser (FIL), fluorescência de luz UVVisível e absorção de radiação na região no UV-Visível. Através dos resultados obtidos pela análise elementar foi possível notar que para o Espodossolo Humilúvico houve variações diferenciadas nos teores de carbono, mas para o Latossolo Amarelo, não se pode inferir uma tendência de incremento ou decréscimo do teor de carbono ao longo do perfil, pois o teor de carbono para a maioria das amostras de solo foi inferior a 0,3%, o limite de detecção do CHNS. A espectroscopia de matrizes de fluorescência de excitação-emissão (MEE) foi uma técnica mais seletiva e sensível do que a fluorescência bidimensional para os ácidos húmicos (AH), mostrando informações interessantes, variações estruturais e grande diferença entre os cromóforos que emitem fluorescência nos extratos de ácido fúlvico 2 (EAF2) e AH. A combinação dos espectros de MEE com a análise de fatores paralelos (PARAFAC) permitiu caracterizar qualitativamente os EAF2, podendo identificar e associar com mais clareza os três fluoróforos obtidos, com seus respectivos componentes, ácidos fúlvicos (grupos de fluoróforos simples e complexos) e proteína, com diagnóstico de consistência do tensor núcleo (CORCONDIA) de 85,8%. Esta combinação permitiu caracterizar quantitativamente os AH, identificando a contribuição das intensidades de dois fluoróforos, associados aos AH, grupos de fluoróforos mais complexos e simples, com CORCONDIA de 84,2%. A partir dos resultados de LIBS, uma forte correlação foi encontrada e os coeficientes de correlação de Pearson\'s obtidos para o ajuste logarítmico foi de R = 0,98 e R = 0,99 para o carbono e o alumínio, respectivamente, entre os valores obtidos por LIBS e as técnicas de referências (CHNS e ICP OES) para o Espodossolo Humilúvico. Nenhuma relação foi observada para o ferro, provavelmente devido aos teores estarem abaixo do limite de detecção. A técnica FIL mostrou para o Espodossolo Humilúvico que o horizonte de transição (Tr) estaria funcionando como uma \"peneira molecular\", acumulando a matéria orgânica pouco humificada, permitindo a passagem para os horizontes de caulim (K1 e K2) de compostos com estruturas mais humificadas, mais complexas, de difícil degradação (mais recalcitrantes), mas de menor tamanho molecular, como anéis aromáticos condensados e/ou conjugação de anéis aromáticos simples, corroborando com a eficiência da extração do AH. Para o Latossolo Amarelo, observou-se um aumento no grau de humificação do horizonte superficial BA em relação ao A2. Logo, estes resultados contribuem para um melhor entendimento sobre a quantificação de carbono, grau de humificação e alterações estruturais da matéria orgânica dos solos arenosos da região de São Gabriel da Cachoeira na Amazônia. / The Amazon represents the world\'s biggest biodiversity, comprehending a large and dynamic carbon pool, considering its biomass and soil, as well. The carbon cycle in this biome is very important, especially in questions regarding climatic changes. To evaluate and to understand the carbon and other elements cycles in Amazonian soil can help scientists to improve models and foresee scenarios. New methods, allowing carbon measurements on site, are a crucial approach for this kind of region, due to the financial costs to collect and ship soil samples from forest to laboratory, and the time spent in this activity. In the present study, it was analyzed a topsequence of an Oxisol-Spodosol system with kaolin associated, generated from granitic-gneiss rocks of crystalline basement. The soil samples were collected in São Gabriel da Cachoeira, Amazonas state, Brazil, considering two different soil profiles: Spodosols (P1), at the top layer, and yellow Oxisols (P2) at the topsequence hillside, representing a total of eighteen samples. The main purpose of this study was to evaluate and characterize the organic matter content and elemental composition by chemical and spectroscopic methods using elemental analysis (CHNS), laserinduced breakdown spectroscopy (LIBS), inductively coupled plasma optical emission spectrometry (ICP OES), laser-induced fluorescence spectroscopy (LIFS), fluorescence spectroscopy and UV-Visible spectroscopy. The CHNS results showed differences in the carbon content for the Spodosol (P1) samples; however, it was not observed any differences for the Oxisol (P2) samples, once the carbon content data obtained for these samples were lower than the equipment detection limit (0.3%). The excitation-emission matrix (EEM) fluorescence spectroscopy was more sensitive for detecting humic acids (HA) than the two-dimensional fluorescence spectroscopy, showing interesting information, structural variations and large difference among chromophores that emit fluorescence in fulvic acid extracts 2 (EAF2) and HA. The EAF2 were qualitatively characterized by combining the EEM spectra with parallel factor analysis (PARAFAC), which allowed to identify clearly the three fluorophores obtained and their respective components, fulvic acids (simple and complex groups of fluorophores) and protein, with core consistency diagnostic (CORCONDIA) of 85.8%. These data also allowed to quantify the HA, identifying contributions of intensities from two fluorophores associated with HA, complex groups and simple fluorophores, presenting CORCONDIA of 84.2%. Regarding the carbon and aluminum content results for the Spodosol samples, a strong correlation was found between the LIBS values and the standard techniques (CHNS and ICP OES). The Pearson\'s coefficients obtained by logarithmic fit were R = 0.98 and R = 0.99 for carbon and aluminum, respectively. It was not observed any differences for the iron contents from the analyzed samples, probably due to the low content observed regarding the detection limit this element presents. The LIFS technique indicated that the transition horizon (Tr) would be acting as a \"molecular sieve\" in the Spodosol soil (P1), accumulating less humified organic matter, and allowing passage to kaolin horizons (K1 and K2) of compounds with more humified, more complex, difficult to degrade (recalcitrant) structures, but with lower molecular size, such as condensed aromatic rings and/or combination of simple aromatic rings. These results were in accordance to the HA extraction efficiency. For the yellow Oxisol (P2) samples, it was observed a humification degree increase in the surface horizon BA compared to the A2 horizon. This way, the data obtained contribute to a better understanding regarding carbon quantification, humification degree and organic matter structural alterations on sandy soils in São Gabriel da Cachoeira, at the Amazonian region.

A Amazônia representa a maior biodiversidade do mundo e representa um reservatório enorme e dinâmico de carbono, não só na biomassa, mas também no solo. O ciclo do carbono neste bioma é muito importante, principalmente para questões abordadas às mudanças climáticas. Avaliar e compreender a dinâmica do carbono e outros elementos no solo da Amazônia pode ajudar os cientistas a melhorar os modelos e antecipar cenários. Novos métodos, que permitem medições de carbono do solo in situ, são uma abordagem fundamental para este tipo de região, devido aos custos financeiros para a coleta e envio de amostras de solo da floresta para o laboratório, e demanda muito tempo nesta atividade. No presente estudo, uma topossequência de um sistema Latossolo-Espodossolo com caulim associado, desenvolvido a partir de rochas granito gnáissicas do embasamento cristalino, foi estudada. As amostras foram coletadas em São Gabriel da Cachoeira, estado do Amazonas. Dois perfis de solo: Espodossolo Humilúvico (P1) no topo e Latossolo Amarelo (P2) na meia encosta da topossequência foram descritos e amostrados em um total de dezoito amostras. Os objetivos principais foram avaliar e caracterizar através de métodos químicos e espectroscópicos a matéria orgânica e a composição elementar nestes solos arenosos utilizando a análise elementar (CHNS), espectroscopia de emissão ótica com plasma induzido por laser (LIBS), espectrometria de emissão ótica com plasma acoplado indutivamente (ICP OES), espectroscopia de fluorescência induzida por laser (FIL), fluorescência de luz UVVisível e absorção de radiação na região no UV-Visível. Através dos resultados obtidos pela análise elementar foi possível notar que para o Espodossolo Humilúvico houve variações diferenciadas nos teores de carbono, mas para o Latossolo Amarelo, não se pode inferir uma tendência de incremento ou decréscimo do teor de carbono ao longo do perfil, pois o teor de carbono para a maioria das amostras de solo foi inferior a 0,3%, o limite de detecção do CHNS. A espectroscopia de matrizes de fluorescência de excitação-emissão (MEE) foi uma técnica mais seletiva e sensível do que a fluorescência bidimensional para os ácidos húmicos (AH), mostrando informações interessantes, variações estruturais e grande diferença entre os cromóforos que emitem fluorescência nos extratos de ácido fúlvico 2 (EAF2) e AH. A combinação dos espectros de MEE com a análise de fatores paralelos (PARAFAC) permitiu caracterizar qualitativamente os EAF2, podendo identificar e associar com mais clareza os três fluoróforos obtidos, com seus respectivos componentes, ácidos fúlvicos (grupos de fluoróforos simples e complexos) e proteína, com diagnóstico de consistência do tensor núcleo (CORCONDIA) de 85,8%. Esta combinação permitiu caracterizar quantitativamente os AH, identificando a contribuição das intensidades de dois fluoróforos, associados aos AH, grupos de fluoróforos mais complexos e simples, com CORCONDIA de 84,2%. A partir dos resultados de LIBS, uma forte correlação foi encontrada e os coeficientes de correlação de Pearson\'s obtidos para o ajuste logarítmico foi de R = 0,98 e R = 0,99 para o carbono e o alumínio, respectivamente, entre os valores obtidos por LIBS e as técnicas de referências (CHNS e ICP OES) para o Espodossolo Humilúvico. Nenhuma relação foi observada para o ferro, provavelmente devido aos teores estarem abaixo do limite de detecção. A técnica FIL mostrou para o Espodossolo Humilúvico que o horizonte de transição (Tr) estaria funcionando como uma \"peneira molecular\", acumulando a matéria orgânica pouco humificada, permitindo a passagem para os horizontes de caulim (K1 e K2) de compostos com estruturas mais humificadas, mais complexas, de difícil degradação (mais recalcitrantes), mas de menor tamanho molecular, como anéis aromáticos condensados e/ou conjugação de anéis aromáticos simples, corroborando com a eficiência da extração do AH. Para o Latossolo Amarelo, observou-se um aumento no grau de humificação do horizonte superficial BA em relação ao A2. Logo, estes resultados contribuem para um melhor entendimento sobre a quantificação de carbono, grau de humificação e alterações estruturais da matéria orgânica dos solos arenosos da região de São Gabriel da Cachoeira na Amazônia. / The Amazon represents the world\'s biggest biodiversity, comprehending a large and dynamic carbon pool, considering its biomass and soil, as well. The carbon cycle in this biome is very important, especially in questions regarding climatic changes. To evaluate and to understand the carbon and other elements cycles in Amazonian soil can help scientists to improve models and foresee scenarios. New methods, allowing carbon measurements on site, are a crucial approach for this kind of region, due to the financial costs to collect and ship soil samples from forest to laboratory, and the time spent in this activity. In the present study, it was analyzed a topsequence of an Oxisol-Spodosol system with kaolin associated, generated from granitic-gneiss rocks of crystalline basement. The soil samples were collected in São Gabriel da Cachoeira, Amazonas state, Brazil, considering two different soil profiles: Spodosols (P1), at the top layer, and yellow Oxisols (P2) at the topsequence hillside, representing a total of eighteen samples. The main purpose of this study was to evaluate and characterize the organic matter content and elemental composition by chemical and spectroscopic methods using elemental analysis (CHNS), laserinduced breakdown spectroscopy (LIBS), inductively coupled plasma optical emission spectrometry (ICP OES), laser-induced fluorescence spectroscopy (LIFS), fluorescence spectroscopy and UV-Visible spectroscopy. The CHNS results showed differences in the carbon content for the Spodosol (P1) samples; however, it was not observed any differences for the Oxisol (P2) samples, once the carbon content data obtained for these samples were lower than the equipment detection limit (0.3%). The excitation-emission matrix (EEM) fluorescence spectroscopy was more sensitive for detecting humic acids (HA) than the two-dimensional fluorescence spectroscopy, showing interesting information, structural variations and large difference among chromophores that emit fluorescence in fulvic acid extracts 2 (EAF2) and HA. The EAF2 were qualitatively characterized by combining the EEM spectra with parallel factor analysis (PARAFAC), which allowed to identify clearly the three fluorophores obtained and their respective components, fulvic acids (simple and complex groups of fluorophores) and protein, with core consistency diagnostic (CORCONDIA) of 85.8%. These data also allowed to quantify the HA, identifying contributions of intensities from two fluorophores associated with HA, complex groups and simple fluorophores, presenting CORCONDIA of 84.2%. Regarding the carbon and aluminum content results for the Spodosol samples, a strong correlation was found between the LIBS values and the standard techniques (CHNS and ICP OES). The Pearson\'s coefficients obtained by logarithmic fit were R = 0.98 and R = 0.99 for carbon and aluminum, respectively. It was not observed any differences for the iron contents from the analyzed samples, probably due to the low content observed regarding the detection limit this element presents. The LIFS technique indicated that the transition horizon (Tr) would be acting as a \"molecular sieve\" in the Spodosol soil (P1), accumulating less humified organic matter, and allowing passage to kaolin horizons (K1 and K2) of compounds with more humified, more complex, difficult to degrade (recalcitrant) structures, but with lower molecular size, such as condensed aromatic rings and/or combination of simple aromatic rings. These results were in accordance to the HA extraction efficiency. For the yellow Oxisol (P2) samples, it was observed a humification degree increase in the surface horizon BA compared to the A2 horizon. This way, the data obtained contribute to a better understanding regarding carbon quantification, humification degree and organic matter structural alterations on sandy soils in São Gabriel da Cachoeira, at the Amazonian region.

Le recyclage des déchets organiques est une préoccupation environnementaleimportante tant du point de vue énergétique que du point de vue du réchauffement climatique.Le compostage permet la transformation d'un déchet en produit, le compost, mais permetaussi d'augmenter le stockage du carbone dans les sols. Parmi les déchets, les boues de stationd'épuration sont un type de déchet urbain organique problématique et grandissant. La teneurélevée en matières organiques des boues peut ainsi être valorisée grâce au co-compostageavec des déchets verts. En effet, de nombreuses modifications chimiques se produisent aucours du processus de maturation d’un compost transformant les molécules simples ensubstances humiques bénéfiques aux sols. Cependant, il n'existe pas encore, à ce jour, detechniques rapides et universelles permettant de prédire la stabilité et la maturité du compost.Il est, en effet, nécessaire, pour suivre l'évolution d'un compost, de mesurer un nombreimportant de paramètres biologiques (test de respirométrie, test de germination), physiques(pH, température,…) et chimiques (potentiel d'oxydo-réduction, capacité d’échange de cations(CEC),…). Ceci n'est pas économiquement viable et rarement fait sur les plates-formes decompostage.L’objectif de cette étude a donc été d’identifier quel(s) paramètre(s) pourrai(en)t êtreutilisé(s) pour suivre aisément, sur une plate-forme de compostage, l’évolution du compostsur le terrain. Pour cela, nous avons suivi un co-compostage de boues de station d’épurationau cours du processus de maturation dans des composteurs de particuliers (sur place et enserre) et dans l’andain (sur place) afin d’observer l’effet de la taille mais aussi l’effet desconditions climatiques sur le processus de compostage. Une méthode d’extraction simple etpeu coûteuse de la matière organique extractible à l’eau (WEOM) utilisant un percolateur àeau à température ambiante est proposée. Ces extraits à l'eau ont été caractérisés par différentsparamètres, tels que le carbone organique dissous (CODWEOM) et l’azote total (NTWEOM) oules acides gras volatils (AGVWEOM) mais aussi par différentes techniques spectrométriquesd'absorption UV-Visible et de fluorescence. Pour l’absorption, des indices nous informent surl'aromaticité (SUVA254 WEOM), la taille moléculaire (E2/E3 WEOM), le poids moléculaire (E4/E6WEOM) et sur les substitutions des composés organiques (EET/EBZ WEOM) de la matièreorganique. En ce qui concerne la fluorescence, les indices d'humification HLIF, Kalbitz WEOM,Milori WEOM, Ra,c WEOM et Zsolnay WEOM ont été utilisés pour étudier les propriétés de laWEOM. De plus, à partir des matrices d'excitation-émission de fluorescence, les composantsCP/PARAFAC ont été déterminés. Au total, ce sont 23 paramètres qui ont été suivis au coursdu compostage.Les résultats permettent de discriminer les indices les plus pertinents pouvant êtreutilisés sur le terrain. Ces indices sont le SUVA254 WEOM, ainsi que les indices de Kalbitz WEOMet de Milori WEOM. La spectrométrie est une technique pertinente pour le suivi du compost surle terrain. Il n'a pas été décelé d'influence de la météorologie pour les composteursparticuliers, mais bien un effet de taille pour certains paramètres. / The recycling of organic waste is a major environmental concern both from anenergetic perspective and the global warming. The composting allows the conversion of wasteinto a product, the compost, and also the increase of carbon storage in soils. Among thedifferent wastes, sewage sludges are a problematic and increasing organic urban waste. Thehigh level of organic matter in sludges can be valorized by co-composting with green waste.Indeed, many chemical changes occur in the compost maturation process, transforming thesimple molecules in humic substances which are beneficial for soils. However, there are notyet, rapid and universal techniques which could predict the stability and the maturity ofcompost. It is necessary to measure a large number of biological (respirometric test, test ofgermination), physical (pH, temperature,…) and chemical (redox potential, cation exchangecapacity (CEC),…) parameters in order to follow the compost evolution. These measurementsare expensive and are rarely done on the composting platforms.Our objective was therefore to determine which parameter(s) could be used to easilymonitor the compost on the platform. For that, we followed a co-composting of sewagesludges during the maturation process in private compost bins (platform and greenhouse) andin swath (platform) in order to observe the size effect and the climatic condition effect on thecomposting process. An easy and little expensive extraction method of the water extractibleorganic matter (WEOM), using a percolator with water at room temperature was proposed.These water extracts were characterized by various parameters, such as dissolved organiccarbon (DOC WEOM) and total nitrogen (TN WEOM) or the content of volatile fatty acids, butalso, by various spectroscopic technics such as UV-Visible absorption and fluorescence. ForUV-Visible absorption, indices provide data on the aromaticity (SUVA254 WEOM), themolecular size (E2/E3 WEOM), the molecular weight (E4/E6 WEOM) and the substitutions oforganic compounds (EET/EBZ WEOM) of organic matter. Regarding fluorescence, humificationindexes such as HLIF, Kalbitz WEOM, Milori WEOM, Ra,c WEOM and Zsolnay WEOM were used tostudy the properties of WEOM. In addition, from the excitation-emission fluorescencematrices, CP/PARAFAC components were determined. All in all, 23 parameters werefollowed during the composting.We were thus able to distiguish the most relevant indices that can be used on theplatform. These indices are the SUVA254 WEOM and indices of Kalbitz WEOM and Milori WEOM.The spectroscopy is a relevant technique for monitoring the compost in the field. No impactof climatic conditions was revealed for the private compost bins, but a size effect for someparameters was observed.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2016-02-01T07:36:16Z No. of bitstreams: 2 Tese - Mariana da Silva Godinho - 2014.pdf: 11659350 bytes, checksum: 36a0ea84b6d0c992d5629322e89390a3 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-02-01T07:42:02Z (GMT) No. of bitstreams: 2 Tese - Mariana da Silva Godinho - 2014.pdf: 11659350 bytes, checksum: 36a0ea84b6d0c992d5629322e89390a3 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2016-02-01T07:42:02Z (GMT). No. of bitstreams: 2 Tese - Mariana da Silva Godinho - 2014.pdf: 11659350 bytes, checksum: 36a0ea84b6d0c992d5629322e89390a3 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-06-27 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / The lifetime of a power transformer is determined by the state of degradation of its insulation system. This system consists of Kraft paper immersed in insulating oil (IMO). In order to prevent an abrupt crash transformer its oxidation state should be monitored. This monitoring is performed using physico-chemical and chromatographic assays. The physico-chemical parameter of greatest importance is the interfacial tension (IT), which is a measure for assessing indirectly the oxidation state of the Kraft paper. The objective of this thesis to propose analytical methodologies to evaluate the oxidation process of the insulation system, both in naturally and accelerated degraded oil samples, using Image Analysis and spectroscopic techniques combined with methods of Multivariate Calibration (Partial Least Squares - PLS), Resolution Multivariate Curve and Data Fusion. Spectra of Moleculular Fluorescence (MF), Nuclear Magnetic Resonance of 1H (1H NMR), Fourier Transform Near Infrared (FT-NIR) and RGB images were obtained for a set of 268 oil samples provided by CELG Distribuição S.A. (CELG D). Subsequently, spectra in the Ultraviolet-Visible (UV-Vis) region, FM and RGB images were obtained for a set of 24 oil samples subjected to an accelerated degradation. PLS models were obtained in order to predict the IT and color parameters for the set of samples provided by CELG D. For the set of degraded samples PLS models were obtained for prediction of degradation time. PARAFAC and MCR-ALS models were obtained to evaluate the oxidation process of the insulating system and too identify the pure spectra of possible compounds formed during this process. Furthermore, low level data fusion combined with variable selection using the Variables Importance in the Projection (VIPs) was used in this study to obtain PLS models. The best PLS model for the set of samples provided by CELG D was obtained for the fused spectroscopic data using variable selection by VIPS. This model provided a mean square error of prediction (RMSEP) of 2.9 mN/m for IT and 0.3 for the color parameter (dimensionless units). PARAFAC and MCR-ALS models allowed to assess the process of system degradation. The proposed methodologies are fast and non-destructive, showing great advantages over traditional methods, which take a long time, and generate a lot of waste. This work opens perspectives for an online monitoring to assess the degradation of the insulating system besides having permitted a more detailed study on the compounds formed during the degradation process. / A vida útil de um transformador de potência é determinada pelo estado de degradação de seu sistema isolante. Esse sistema é constituído pelo papel tipo Kraft imerso em óleo mineral isolante (OMI). Para evitar que um transformador chegue ao seu fim de vida de forma abrupta é necessário que seja realizado o monitoramento do seu estado de oxidação. Esse monitoramento é feito através de ensaios físico-químicos e cromatográficos. O parâmetro físico-químico de maior importância é a tensão interfacial (TI), pois é uma medida que avalia indiretamente o estado de oxidação do papel. O objetivo deste trabalho foi propor metodologias analíticas para avaliar o processo de degradação do sistema isolante tanto em amostras degradadas naturalmente quanto em amostras degradadas aceleradamente, usando Análise de Imagens e técnicas espectroscópicas aliadas a métodos de Calibração Multivariada (Mínimos Quadrados Parciais - PLS), Resolução de Curva Multivariada e Fusão de Dados. Foram obtidos espectros de Fluorescência Molecular (FM), Ressonância Magnética Nuclear de 1H (RMN de 1H), Infravermelho na região do próximo (FT-NIR) e imagens RGB de um conjunto de 268 amostras de OMI fornecidas pela CELG Distribuição S.A. (CELG D). Posteriormente, foram obtidos espectros de UV-Vis, FM e imagens RGB de um conjunto de 24 amostras degradadas aceleradamente. Modelos PLS foram construídos para prever os parâmetros TI e cor para o conjunto de amostras fornecidas pela CELG D. Para as amostras degradadas aceleradamente modelos PLS foram obtidos para previsão do tempo de degradação. Modelos PARAFAC e MCR-ALS foram construídos com objetivo de avaliar o processo de oxidação do sistema isolante e identificar os espectros puros de possíveis compostos formados durante esse processo. Além disso, Fusão de Dados de baixo nível aliada à seleção de variáveis usando as Variáveis de Importância na Projeção (VIPs) foram utilizadas neste trabalho para a obtenção de modelos PLS. O melhor modelo PLS para o conjunto de amostras fornecidas pela CELG D foi obtido para os dados espectroscópicos fundidos usando seleção de variáveis por VIPS. Esse modelo forneceu um erro médio quadrático de previsão (RMSEP) de 2,9 mN/m para previsão da TI e 0,3 para o parâmetro cor (unidade adimensional). Os modelos PARAFAC e MCR-ALS permitiram avaliar o processo de degradação do sistema isolante. As metodologias propostas são rápidas e não destrutivas, mostrando grandes vantagens sobre os métodos tradicionais, os quais demandam muito tempo, além de gerar uma grande quantidade de resíduos. Este trabalho abre perspectivas para um monitoramento direto (on-line) para avaliar a degradação do sistema isolante, além de ter permitido um estudo mais aprofundado a respeito dos compostos formados durante o processo de degradação.