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L’objectif de cette thèse est de démontrer le potentiel de la spectroscopie proche infrarouge multipoints pour suivre en ligne des milieux diffusants et absorbants dont les propriétés physique et chimique varient au cours du temps. Des travaux ont tout d’abord porté sur l’étude d’un milieu où seule la diffusion varie au cours du temps. Le suivi de la réaction de précipitation de la silice a été choisi pour illustrer un tel milieu. Dans un premier temps, des spectres en transmission collimatée ont été mesurés sur des échantillons prélevés au cours du procédé. Grâce à l’application de la loi de Beer-Lambert, il a été possible d'obtenir les coefficients de diffusion de chaque échantillon et ainsi retrouver les différentes étapes de la réaction. Une analyse en composante principale de ces coefficients a montré la présence de deux régimes de diffusion dans le milieu réactionnel. Dans un second temps, une sonde de mesures multipoints, a été immergée dans un réacteur de fabrication. Des spectres ont été mesurés à des angles de 30°, 90°, 150°, 170° et 180° par rapport à la source, tout au long de la précipitation. Une analyse univariée, aux différents angles, a montré des différences et des similitudes entre les positions, en lien avec les interactions lumière matière. Puis une analyse multivariée multi tableaux ACCPS (Analyses en Composantes Communes et Poids Spécifiques) a été appliquée. Elle permet de combiner les informations issues des différents angles et de montrer les informations communes et spécifiques. Cela a permis de valider l’utilisation de la mesure multipoints pour le contrôle du procédé. Grâce à l’analyse des scores globaux, différents types de diffusion et la spécificité de certains angles dans la détection de modifications physiques, ont été identifiés. L’analyse des loadings individuels, a confirmé les différentes étapes réactionnelles identifiées et a révélé des phénomènes relatifs à la diffusion de la lumière comme l’allongement du trajet optique. La même démarche, analyses en laboratoire puis en ligne, a été appliquée à un milieu où la diffusion et l’absorption varient. Le suivi des produits issus des procédés pour l’amélioration de l’extraction du pétrole a été choisi pour illustrer un tel milieu. Dans un premier temps, des microémulsions (eau, huile et tensio-actif) ont été fabriquées de sorte à ce que les propriétés chimiques et physiques soient différentes. Puis chaque phase a été analysée séparément. Une analyse en composantes principales a permis de caractériser les systèmes grâce à l’identification des phases. Elle a également montré que les différences entre elles étaient liées, à la fois à l’absorption et à la diffusion. Pour séparer ces deux phénomènes, une résolution multivariée de courbes par régression alternée a été appliquée. Cela a permis d’expliquer plus en détail les différences entre les phases et d’obtenir des suivis semi-quantitatifs. Enfin dans la dernière partie, les mêmes échantillons ont été analysés en circulation avec une sonde multipoints. Une ACCPS a de nouveau été appliquée et a montré que des phénomènes de diffusion différents avaient lieu entre les classes. De plus elle a mis en lumière une hétérogénéité dans la composition des phases, qui ne pouvait pas être détectée avec des mesures en statique. / The aim of this thesis is to demonstrate the potential of multipoint near infrared spectroscopy to monitor online scattering and absorbing environments, where physical and chemical properties change over time. The work was first based on the study of an environment where scattering was the only parameter varying over time. Monitoring of the silica precipitation reaction has been chosen to illustrate that environment. First of all, spectra in collimated transmittance mode were acquired from samples collected during the process. Thanks to the Beer-Lambert law, scattering coefficients of each sample were obtained and from them the different steps of the reaction were found. A principal component analysis of those coefficients showed the existence of two scattering modes into the reaction environment. In the second phase, a multipoint probe was submerged in an industrial reactor. Spectra were measured during the precipitation with angle of 30°, 90°, 150°, 170° and 180° to the source. A univariate analyse at those different angles showed differences and similarities between the positions, linked to the interaction of light and matter. Then, a multiblock and multivariate analysis, CCSWA (Common Component and Specific Weight Analysis), was applied. It allows the combination of information from different angles and also shows common and specific information, in order to validate the use of multipoint measurement to monitor the process. Thanks to the analysis of global scores, different kind of scattering and the specificity of some angle, in the detection of physical modifications were identified. The analysis of individual loadings confirmed the identification of the different steps of reaction and has revealed some phenomena related to light scattering, such as the extension of the optical path. The same approach, analysis in the laboratory then online, was applied on an environment where scattering and absorption vary. Monitoring of products from the process to improve oil extraction, has been chosen to illustrate that environment. First of all, micro emulsions (water, oil and surfactant) were made so that physical and chemical properties would be different between samples. Then, each phase was analysed separately. A principal component analysis was used to characterize the system by phase identification. It also showed the differences between the phases were linked, both to absorption and scattering. In order to separate those two phenomena, a multivariate resolution by alternate regression has been applied. It has permitted to explain in more details the differences between the phases and to obtain semi-quantitative monitoring. Finally, in the last part, the same samples were analysed in circulation with a multipoint probe. A CCSWA has been applied again and showed that different scattering phenomenon occurred between the categories. Moreover, it highlighted a heterogeneity in the phases' composition that couldn’t be detected in static measurement.

Medidas in situ na Bacia Amazônica mostraram uma grande variedade de partículas de aerossol provenientes principalmente de fontes biogênicas e de queimadas. Partículas de queimadas foram estudadas em detalhe e são compostas de misturas de partículas esféricas e não esféricas, e aglomerados de até milhares de esferas nanométricas de \"black carbon\" PC). A forma e a estrutura macroscópica das partículas de queimadas são determinadas pelo tipo de combustíve1 queimado, pel0 tipo de combustição e pela \"idade\" das partículas. A estrutura macroscópica das partículas muda em função de suas interações com vapor d\'água, gotas de nuvens e devido à condensação de gases em sua superfície (e.g. gases orgânicos e dióxido de enxofre). Partículas não esféricas e grandes aglomerados tornam-se mais compactos e esféricos em função de seu envelhecimento. Estes aglomerados foram encontrados apenas perto das fontes de queimadas em fase \"flaming\", o que sugere que a compactação dos aglomerados ocorre numa escala de tempo relativamente pequena após sua emissão (minutos até horas). Esta mudança de morfologia produz alterações significativas nas propriedades ópticas das partículas aumentando suas eficiências de absorção e espalhamento de radiação. Micrografias obtidas com microscopia eletrônica de varredura em filtros amostrados em paralelo com diversas outras medidas sugerem o efeito da morfologia nas propriedades ópticas das partículas. Propriedades intensivas das partículas foram medidas neste trabalho para partículas de queimadas e biogênicas. Apesar serem emitidas por fontes bastante distintas, as partículas de queimadas e biogênicas apresentaram importantes similaridades em composição química, tamanho, coeficientes de Angström e rações de retroespalhamento. Por outro lado, as eficiências de absorção e espalhamento assim como o albedo simples apresentaram diferenças significativas entre partículas provenientes das duas fontes. Uma nova metodologia foi desenvolvida neste trabalho para a obtenção da forçante radiativa direta (FRD) por partículas de aerossol usando imagens de sensoriamento remoto. Novos parâmetros das partículas de aerossol foram também definidos neste trabalho para o estudo de seu impacto radiativo. Medidas espectrais com o sensor AVIRIS (224 comprimentos de onda entre 0,38 e 2,5 µm) a bordo do avião ER2 da NASA durante o experimento SCAR-B (Smoke Clouds and Radiation-Brazil) foram utilizadas para a derivação do albedo simples, da espessura óptica e da FRD. Valores significativos da FRD foram obtidos entre 0,25 e 1,6 µm com pico de aproximadamente -200 W m-2µm-1 para um comprimento de onda da ordem de 0,5 µm, por unidade de espessura óptica (valores de em = 0.66 µm). A integral da FRD ao longo do espectro solar é da ordem de -60 w m-2 em média para uma região de superfície heterogênea (incluindo áreas urbanas e vegetação) em Cuiabá. A FRD sobre áreas urbanas se mostrou significativamente menor que em áreas de vegetação devido à sua maior reflectância de superfície. / In situ measurements in the Amazon Basin showed a large variety of aerosol particles in the atmosphere due mainly to biogenic and biomass burning sources. Particles from biomass burning are generally composed of a mixture of spherical and non-spherical particles, and chain aggregates of thousands of tiny black carbon (BC) spherules. The morphology and structure of smoke particles from biomass burning are determined by the type of fuel, the phase of combustion, and the age of the smoke. This structure changes due to interactions with water vapor, cloud droplets and due to condensation of gases on its surface (eg. sulfates and organic gases). Non-spherical and large (tens of micrometers) fluffy aggregates become more compacted and increasingly spherical with age. They are generally found only near the source of flaming-phase combustion, which suggests that particle compaction occurs in a relatively short time (likely, few hours) after release from a biomass fire. This change in morphology produces a significant change in the optical properties of these particles, enhancing its absorption and scattering cross sections. Scanning electron microscope photographs of aerosol particles from biomass burning taken in parallel with other physical measurements show correlation between morphology and the absorption coefficients suggesting the effect of the particle shape on optical properties. Intensive microphysical properties of the particles were measured and modeled in this work for biomass burning and biogenic aerosols. Despite of completely distinct sources, biogenic and biomass burning aerosols show some important similarities in chemical composition and particle sizes. Angström coefficients and backscattering ratios of biogenic aerosols were also found in the same range as biomass burning particles, but the scattering and absorption efficiencies, as well as single scattering albedo showed significantly different values. A new methodology was developed to obtain the spectral direct radiative forcing (DRF) by aerosol particles using remote sensing images and new parameters were defined in this work to access the radiative impact of the aerosols. Spectral measurements with the AVIRIS spectrometer (224 wavelengths between 0.38 and 2.5 µm) onboard the NASA-ER2 aircraft during the SCAR-B experiment (Smoke Clouds and Radiation -Brazil) have been used in this work to derive the spectral single scattering albedo of the aerosol particles, the aerosol optical thickness, and .the DRF.Significant values of spectral direct radiative forcing were found between 0,25 and 1.6 µm with a peak about -200 W m-2 µm-1 for a wavelength around 0.5 µm, per unity of optical depth (optical depth values at 0.66 µm). The integral over the whole solar spectrum averaged over heterogeneous surfaces (urban areas and vegetation) is about -60 W m-2 for the studied region (Cuiabá). The DRF over urban areas is smaller than over vegetation due to its brighter surface reflectance.

Medidas in situ na Bacia Amazônica mostraram uma grande variedade de partículas de aerossol provenientes principalmente de fontes biogênicas e de queimadas. Partículas de queimadas foram estudadas em detalhe e são compostas de misturas de partículas esféricas e não esféricas, e aglomerados de até milhares de esferas nanométricas de \"black carbon\" PC). A forma e a estrutura macroscópica das partículas de queimadas são determinadas pelo tipo de combustíve1 queimado, pel0 tipo de combustição e pela \"idade\" das partículas. A estrutura macroscópica das partículas muda em função de suas interações com vapor d\'água, gotas de nuvens e devido à condensação de gases em sua superfície (e.g. gases orgânicos e dióxido de enxofre). Partículas não esféricas e grandes aglomerados tornam-se mais compactos e esféricos em função de seu envelhecimento. Estes aglomerados foram encontrados apenas perto das fontes de queimadas em fase \"flaming\", o que sugere que a compactação dos aglomerados ocorre numa escala de tempo relativamente pequena após sua emissão (minutos até horas). Esta mudança de morfologia produz alterações significativas nas propriedades ópticas das partículas aumentando suas eficiências de absorção e espalhamento de radiação. Micrografias obtidas com microscopia eletrônica de varredura em filtros amostrados em paralelo com diversas outras medidas sugerem o efeito da morfologia nas propriedades ópticas das partículas. Propriedades intensivas das partículas foram medidas neste trabalho para partículas de queimadas e biogênicas. Apesar serem emitidas por fontes bastante distintas, as partículas de queimadas e biogênicas apresentaram importantes similaridades em composição química, tamanho, coeficientes de Angström e rações de retroespalhamento. Por outro lado, as eficiências de absorção e espalhamento assim como o albedo simples apresentaram diferenças significativas entre partículas provenientes das duas fontes. Uma nova metodologia foi desenvolvida neste trabalho para a obtenção da forçante radiativa direta (FRD) por partículas de aerossol usando imagens de sensoriamento remoto. Novos parâmetros das partículas de aerossol foram também definidos neste trabalho para o estudo de seu impacto radiativo. Medidas espectrais com o sensor AVIRIS (224 comprimentos de onda entre 0,38 e 2,5 µm) a bordo do avião ER2 da NASA durante o experimento SCAR-B (Smoke Clouds and Radiation-Brazil) foram utilizadas para a derivação do albedo simples, da espessura óptica e da FRD. Valores significativos da FRD foram obtidos entre 0,25 e 1,6 µm com pico de aproximadamente -200 W m-2µm-1 para um comprimento de onda da ordem de 0,5 µm, por unidade de espessura óptica (valores de em = 0.66 µm). A integral da FRD ao longo do espectro solar é da ordem de -60 w m-2 em média para uma região de superfície heterogênea (incluindo áreas urbanas e vegetação) em Cuiabá. A FRD sobre áreas urbanas se mostrou significativamente menor que em áreas de vegetação devido à sua maior reflectância de superfície. / In situ measurements in the Amazon Basin showed a large variety of aerosol particles in the atmosphere due mainly to biogenic and biomass burning sources. Particles from biomass burning are generally composed of a mixture of spherical and non-spherical particles, and chain aggregates of thousands of tiny black carbon (BC) spherules. The morphology and structure of smoke particles from biomass burning are determined by the type of fuel, the phase of combustion, and the age of the smoke. This structure changes due to interactions with water vapor, cloud droplets and due to condensation of gases on its surface (eg. sulfates and organic gases). Non-spherical and large (tens of micrometers) fluffy aggregates become more compacted and increasingly spherical with age. They are generally found only near the source of flaming-phase combustion, which suggests that particle compaction occurs in a relatively short time (likely, few hours) after release from a biomass fire. This change in morphology produces a significant change in the optical properties of these particles, enhancing its absorption and scattering cross sections. Scanning electron microscope photographs of aerosol particles from biomass burning taken in parallel with other physical measurements show correlation between morphology and the absorption coefficients suggesting the effect of the particle shape on optical properties. Intensive microphysical properties of the particles were measured and modeled in this work for biomass burning and biogenic aerosols. Despite of completely distinct sources, biogenic and biomass burning aerosols show some important similarities in chemical composition and particle sizes. Angström coefficients and backscattering ratios of biogenic aerosols were also found in the same range as biomass burning particles, but the scattering and absorption efficiencies, as well as single scattering albedo showed significantly different values. A new methodology was developed to obtain the spectral direct radiative forcing (DRF) by aerosol particles using remote sensing images and new parameters were defined in this work to access the radiative impact of the aerosols. Spectral measurements with the AVIRIS spectrometer (224 wavelengths between 0.38 and 2.5 µm) onboard the NASA-ER2 aircraft during the SCAR-B experiment (Smoke Clouds and Radiation -Brazil) have been used in this work to derive the spectral single scattering albedo of the aerosol particles, the aerosol optical thickness, and .the DRF.Significant values of spectral direct radiative forcing were found between 0,25 and 1.6 µm with a peak about -200 W m-2 µm-1 for a wavelength around 0.5 µm, per unity of optical depth (optical depth values at 0.66 µm). The integral over the whole solar spectrum averaged over heterogeneous surfaces (urban areas and vegetation) is about -60 W m-2 for the studied region (Cuiabá). The DRF over urban areas is smaller than over vegetation due to its brighter surface reflectance.