[pt] Dez amostradores de material particulado em suspensão no ar foram instalados em diferentes bairros da cidade do Rio de Janeiro: Gávea, Honório Gurgel, Jacarepaguá, Campo Grande, Tijuca, Ilha do Fundão, Guaratiba, Recreio dos Bandeirantes, Santa Cruz e Realengo, visando contribuir para um maior entendimento a respeito da poluição atmosférica na cidade. Os amostradores empregados foram desenvolvidos pela Universidade de Gent e permitem a coleta das frações inalável (com diâmetro aerodinâmico entre 2,5 e 10µm, MP2,5-10) e respirável (com diâmetro aerodinâmico < 2,5 um, MP2,5). As amostragens foram realizadas, simultaneamente, sempre no meio da semana, durante 24 horas, e compreenderam o período de setembro/2003 a setembro/2004. Ao final deste período, foram obtidas, por ponto de amostragem, trinta amostras de cada fração, totalizando seiscentas amostras. Após a determinação da massa presente em cada filtro, e do teor de carbono elementar no filtro fino (MP2,5), os filtros foram divididos em duas partes. Numa delas foi determinada a concentração de amônio, sódio, potássio, cálcio, magnésio, cloreto, nitrato e sulfato solúvel em água e, na outra parte, a concentração de sódio, potássio, cálcio, magnésio, alumínio, ferro e titânio após dissolução total. A estação de Honório Gurgel foi aquela que apresentou, na média, as maiores concentrações de carbono elementar, particulado grosso e total, refletindo a proximidade com a Avenida Brasil e a presença de indústrias na região. O ponto de coleta com maior concentração de particulado fino e de aerossol de origem secundária correspondeu àquele localizado na Ilha do Fundão, próximo a bairros com uma grande concentração de indústrias, como Bonsucesso e São Cristóvão, além de vias expressas, como a Linha Vermelha e a Avenida Brasil. Por outro lado, as estações de amostragem localizadas no Recreio dos Bandeirantes e em Guaratiba apresentaram as menores concentrações de particulado fino, grosso e de carbono elementar. Os parâmetros analisados permitiram identificar cerca de 70% da origem do material presente nas frações fina e grossa do material particulado em suspensão no ar nas regiões estudadas da cidade do Rio de Janeiro. Como esperado, o particulado grosso é, em grande parte, oriundo da ressuspensão do solo, contendo, ainda, aerossol marinho e compostos de origem secundária, como sulfato e nitrato. O particulado fino, por sua vez, é majoritariamente oriundo da combustão de combustíveis fósseis que dão origem ao aerossol secundário e ao carbono elementar, possuindo uma contribuição de origem terrígena e de aerossol marinho. / [en] The present work intend to be a contribution for the understanding of the air pollution in the Rio de Janeiro city, aerosol sampling was performed at ten different sites of the city: Gávea, Honório Gurgel, Jacarepaguá, Campo Grande, Tijuca, Ilha do Fundão, Guaratiba, Recreio dos Bandeirantes, Santa Cruz and Realengo. Stacked filter units (SFU), developed by Gent University, were used as samplers. These filters separate the particles into two main fractions: the fine mode defined as respirable particles (with aerodynamic diameter < 2.5 um, PM2.5), and coarse mode defined as inhalable particles (with aerodynamic diameter between 2.5 um and 10 um, PM2.5-10). The aerosol monitoring stations were simultaneously operated, always in the middle of the week, during 24 h, from September/2003 to September/2004. At the end of this period, 30 samples of each fraction were obtained from each of the sampling sites (600 filter samples in total). After the determination of the mass concentration, and the elemental carbon amount present in each of the fine filters, the filters were divided into two parts. The first part was used to determine the concentration of ammonium, sodium, potassium, calcium, magnesium, chloride, nitrate and sulfate soluble in water and, the other one, for the determination of the concentration of sodium, potassium, calcium, magnesium, aluminum, iron and titanium. The Honório Gurgel site presented, in average, the highest concentration of elemental carbon, mass concentration of coarse mode and total particle mass concentration, which could be explained by the proximity to the Avenida Brasil and industries of the region. The sampling site of the highest concentration of the fine mode and secondary aerosol was the one localized in Ilha do Fundão, near industrial areas such as Bonsucesso and São Cristóvão, and heavy automobile traffic lines like Linha Vermelha and Avenida Brasil. In other hand, the sites localized at Recreio dos Bandeirantes and at Guaratiba presented in the smallest mass concentration of fine and coarse mode and elemental carbon. Based on these determined parameters, it was possible to identify 70% of the origin of the material present in the fine ad coarse fractions of the particulate matter suspended in the air in the studied areas of Rio de Janeiro city. As expected, the coarse mode particle came from resuspended soil dust, together with marine aerosol and some secondary aerosol, like nitrate and sulfate. The fine mode particle came mainly from fossil fuel combustion that originates secondary aerosol and the elemental carbon, with additional contribution from marine aerosol and terrigineous material.

Les coccolithes, dans les cellules ou détachés, des coccolithophores sont de petites plaquettes de calcite diffusant fortement la lumière. Les efflorescences sont donc très visibles de l’espace et sont couramment quantifiées par l’algorithme Calcite de la NASA appliqué aux données des capteurs de la Couleur de l’Eau.Les coccolithes impactent aussi le produit des matières en suspension non-algales de l’ifremer (MES) largement utilisé sur le plateau continental ouest-européen. Bien que développés indépendamment, ces algorithmes sont basés sur des concepts très proches mais l’algorithme Ifremer est plus souple dans sa modélisation et permet d’établir un lien avec les particules autres que les coccolithes telles les remises en suspension ou les agrégats de particules. L'identification des blooms de coccolithophores sur 18 ans, duGolfe de Gascogne jusqu'au sud de l'Irlande, a été établie par une méthode spectrale, permettant de discriminer la fraction de MES correspondant aux coccolithes. Les blooms suivent le talus au printemps avec une progression vers le nord bien reliée à la variabilité saisonnière de la lumière. La variabilité interannuelle observée indique une légère décroissance globale des blooms, avec une année 2014 aux abondances extrêmement faibles sur toute la région.Les données des campagnes PELGAS en mai dans le Golfe de Gascogne ont mis en évidence la forte corrélation entre le produit MES et la turbidité in situ sur les blooms de coccolithophores. Ce paramètre peut être considéré comme un bon proxy pour le suivi des blooms et pour la description de leur structure verticale.Les données hydrologiques in situ montrent une occurrence plus forte des blooms dans un environnement moins stratifié, des températures plus froides et une salinité plus élevée.La sensibilité de la méthode satellite face à la présence réelle de blooms de coccolithophores a pu être évaluée grâce aux observations in situ de campagnes menées dans le Golfe de Gascogne et en Patagonie.Cette sensibilité reste variable car dépendante de nombreux facteurs intrinsèques aux blooms, liés à la proportion coccolithes/coccosphères et à leur composition taxonomique, qui s’est avérée très riche en mai2016 dans le Golfe de Gascogne. / Coccoliths, in cells or detached, from coccolithophores are calcite plates with highly backscattering signal.Coccolithophore blooms are visible from space and are currently quantified by Calcite algorithm fromNASA applied to Ocean Color data. Coccoliths impact also the Suspended Particulate Matters (SPM) product from Ifremer, well established in the Northwest european continental shelf. Although these algorithms are independent, they are based on the same basic concepts, but Ifremer algorithm is more adaptable and allows to link up with other particles than coccoliths, as the resuspended matters or aggregates.Coccolithophore blooms identification over 18 years, from bay of Biscay to South Irelands has been established by a spectral method, allowing to discriminate coccoliths from SPM. Blooms follow the continental slope northward in connection with the seasonal variability of irradiance. The interannual variability observed indicates a slight decrease of blooms, with a very poor productive year in 2014.Data from PELGAS cruises in May in the Bay of Biscay highlight the strong correlation between SPM product and the in situ turbidity in coccolithophore blooms.This parameter can be considered a a good proxy for the blooms monitoring and for the description of their vertical structure. Hydrological in situ data show a stronger occurrence in less stratified environment, with lower temperatures and higher salinity.The sensitivity of the satellite to the presence of coccoliths has benn evaluated based on in situ observations from cruises in the Bay of Biscay and in Patagonia. This sensitivity is variable due to a lot of inherent factors, to the coccoliths/coccospheres proportion and to the taxonomic composition which has been rich in May 2016 in the Bay of Biscay.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Soil carbon (C) sequestration in agriculture soil is a low cost option to mitigate global climatic change. No-till (NT) associated with good husbandry practices could compensate up to 15% of the anthropogenic CO2 emissions by storing the C from atmosphere as soil organic carbon (SOC). To be fully accepted as a mitigation alternative, research must be conducted to improve the accuracy of soil C sequestration estimates on field experiments as well as those made by mathematical models at regional and local scales. Complementarily, is necessary to improve the knowledge about the SOC stabilization mechanisms, delimiting the real soil´s capacity into accumulate C, quantifying how much of the stored C could be re-emitted to the atmosphere by changes in soil management. The present work is divided in four chapters with the objective to answer these questions. The first chapter has the objective to discuss the importance of sampling depth (0-0.30, 0-0.60, and 0-0.90 m) and the definition of a reliable and adequate baseline for the calculation of the C sequestration rates. Two long-term field experiments from a temperate (Mollisol) and a sub-tropical (Oxisol) climate soil were selected for this research. The experiments tested soil tillage systems (conventional tillage (CT) and NT) (Mollisol and Oxisol) and sources and rates of nitrogen amendment on corn in the Mollisol (control without N, 168 kg N ha-1 as ammonium sulfate, and 168 kg N ha-1 as organic fertilizer) and different crop rotation systems in the Oxisol (R0:soybean-wheat, R1:soybean-wheat-soybean-oat, and R2:soybean-oat-soybean-oat+vetch-corn-radish-wheat). The increase of sampling depth provided limited contribution to the estimates of C sequestration rates due to the increase of the error on SOC stocks estimates at deeper soil depths. To improve the C sequestration rate estimates, SOC temporal dynamic analysis should be preferred rather than the comparison of the SOC stocks of paired plots at a unique time point. The second chapter had the objective to apply simple mathematical equations to describe the SOC dynamics and improve the estimates of C sequestration rates and also to understand the role of the macroaggregate formation on SOC accumulation and saturation. The use of linear and kinetic (exponential growth) equation was adequate to describe the SOC dynamics increasing the accuracy of the C sequestration rate estimates by reducing errors promoted by soil spatial variability. The SOC accumulation was a function of the amount of C input to the soil and the macroaggregate formation to protect SOC. The SOC saturation process occurred from the smaller to the larger aggregate size fraction, limiting the capacity of a given superficial soil layer to accumulate SOC. However, the SOC saturation at superficial soil layers did not indicate the end of C sequestration in the soil, since the SOC accumulation occurred at sub-superficial soil layers. In the third chapter, the mathematical approach to determine changes on SOC stocks and the SOC saturation-induced limitation for C sequestration were applied to improve the accuracy of the Hénin e Dupuís (1945) one- 8 compartmental mathematical model into predict future soil C sequestration rates. The long-term field experiment from the Mollisol was selected for this research because of the better data availability (sampling years) and also by the presence of two treatments under CT and NT with SOC saturated soil layers. The mathematical adjustment (by linear equations) of the SOC dynamic coefficients improved the adjustment of the model‟s predictions. The SOC saturation-induced restriction for SOC accumulation on the mathematical model avoided the overestimation of the soil‟s potential for C sequestration. The predictions of the mathematical models indicate that the Mollisol‟s superficial layer (0-0.05 m) under NT could maintain significant C sequestration rates for up to 50 years as a function of the amount of C input to the soil. For the fourth chapter, a detailed study of the SOC pools in water-stable aggregate size fractions by granulometric and densimetric fractionation was carried out. The objective was to identify the pools where SOC accumulation was occurring and what SOC stabilization mechanisms were present. This will provide estimates of the NT potential to promote long-term C sequestration. SOC accumulation occurred preferentially in the more stable and recalcitrant SOC fractions (Mollisol and Oxisol) or in microaggregate and macroaggregate physically protected fractions (Mollisol). In the Oxisol, the SOC enrichment occurred mostly in the mineral associated-SOC fractions extra-microaggregates occluded within meso- and macroaggregates, while in the Mollisol, the SOC accumulation occurred in both intra- and extra-microaggregate mineral associated-SOC fractions. More than 78 and 92% of the C sequestration verified in the Mollisol and Oxisol, respectively, were considered as long-term by occurring in stable SOC fractions. / O seqüestro de carbono (C) em solos agrícolas é uma opção de baixo custo para mitigação das mudanças climáticas globais. O plantio direto (PD), associado a boas práticas agronômicas, pode compensar até 15% das emissões antrópicas de CO2 ao armazenar o C drenado da atmosfera na forma de carbono orgânico (CO) do solo. Para ser amplamente aceito como alternativa de mitigação, pesquisas devem ser conduzidas a fim de melhorar a precisão das estimativas de taxas de seqüestro de C em experimentos de campo, assim como as previsões feitas por modelos matemáticos em escalas regionais e locais. Complementarmente, é necessário aprimorar o conhecimento sobre os mecanismos de estabilização do CO, delimitando a capacidade real do solo em acumular C e quantificando quanto do C acumulado no solo pode ser re-emitido para atmosfera por mudança no manejo do solo. Desta maneira, o presente trabalho se divide em quatro capítulos com o objetivo de abordar estas questões. O primeiro capítulo tem por objetivo discutir a importância da profundidade de amostragem (0-0,30; 0-0,60; 0-0,90 m) e da definição de situações de linhas-base confiáveis a adequadas para o cálculo das taxas de seqüestro de C. Para isto, foram utilizados dois experimentos de longa duração sobre um solo de clima temperado (Mollisol) e outro de clima sub-tropical (Oxisol). Os experimentos testaram efeitos de sistema de preparo do solo (preparo convencional (PC) e PD) (Mollisol e Oxisol) e fontes e doses de nitrogênio para o milho no Mollisol (testemunha (T), 168 kg N ha-1 na forma de sulfato de amônia (AM) e 168 kg N ha-1 na forma de adubo orgânico (AO)) e diferentes sistemas de rotação de culturas no Oxisol (R0:soja-trigo, R1:soja-trigo-soja-aveia e R2:soja-aveia-soja-aveia+ervilhaca-milho-nabo-trigo). O aumento da profundidade de amostragem não contribuiu com a melhoria das estimativas de taxas de seqüestro de C devido ao aumento do erro nas estimativas dos estoques de CO nas camadas mais profundas de solo. Para melhoria das estimativas das taxas de seqüestro de C devem-se preferir análises temporais da dinâmica do CO no solo ao invés da comparação de estoques de CO em um único momento. O segundo capítulo tem por objetivo aplicar equações matemáticas simples para descrever a dinâmica do CO e melhorar as estimativas taxas de seqüestro de C e também entender o papel da formação de macroagregados no acúmulo e saturação de CO no solo. O uso de equações lineares e cinéticas (crescimento exponencial) foi adequado para descrever a dinâmica do CO, aumentando a precisão das estimativas de taxas de seqüestro de C ao reduzir os erros de estimativa por variabilidade espacial do solo. O acúmulo de CO no solo mostrou-se uma função da quantidade de C aportada ao solo por resíduos vegetais e a formação de macroagregados no solo para proteção do CO. O processo de saturação do solo ocorreu das menores para as maiores frações de agregados do solo, limitando a capacidade de uma 6 determinada camada de solo em acumular CO. No entanto, verificou-se que a saturação de camadas superficiais de solo não indica o fim do seqüestro de C neste solo, visto que o acúmulo de CO passa a ocorrer em camadas sub-superficiais. No terceiro capítulo, a aproximação matemática para determinar mudanças nos estoques de CO e a limitação na capacidade do solo em acumular CO promovida pelo processo de saturação dos agregados do solo foram aplicados para melhorar a precisão do modelo matemático uni-compartimental de Hénin e Dupuís (1945) em prever futuras taxas de seqüestro de C. O Mollisol foi escolhido para este estudo em função da maior disponibilidade de dados (anos de amostragem) e também pela presença de dois tratamentos em PC e PD com camada de solo saturada por CO. O ajuste matemático (por equações lineares) dos coeficientes da dinâmica do CO melhorou o ajuste das previsões do modelo com os dados observados. A restrição do modelo matemático quanto à capacidade do solo em acumular CO (saturação de CO) evitou a superestimação do potencial de seqüestro de C deste solo. As previsões do modelo matemático indicam que a camada superficial (0-0,05 m) do solo sob PD pode apresentar taxas significativas de seqüestro de C por até 50 anos, em função da quantidade de C adicionada ao solo. No quarto capítulo, foi realizado um estudo detalhado dos compartimentos do CO em função da sua distribuição em classes de tamanhos de agregados estáveis em água e o fracionamento granulométrico e densimétrico do CO. O objetivo foi identificar em quais compartimentos está ocorrendo o acúmulo de CO no solo, os mecanismos de estabilização do CO, estimando o potencial do PD em promover sequestro de C de longa duração. Verificou-se que o acúmulo de C ocorre preferencialmente em frações mais estáveis e recalcitrantes do CO (Mollisol e Oxisol) ou em frações protegidas fisicamente por micro e macroagregados (Mollisol). No Oxisol, o enriquecimento de CO ocorre principalmente nas frações de CO associadas aos minerais extra-microaggregados oclusas em meso e macroagregados de solo, enquanto que no Mollisol, o acumulo de CO ocorre tanto na fração intra como extra microagregados. Mais de 78 e 92% do seqüestro de C verificado no Mollisol e Oxisol, repectivamente, foi considerado de longa duração por ocorrer em frações estáveis do CO.

Les modèles Eulériens de chimie-transport simulent les phénomènes de formation des polluants atmosphériques dans des mailles de résolution horizontale qui sont généralement de l’ordre de plusieurs kilomètres. Les panaches issus des sources industrielles, de dimensions initiales de l’ordre du mètre, sont donc artificiellement dilués, détériorant alors la représentation de leur impact potentiel sur la qualité de l'air ambiant. Une approche de modèle de panache sous-maille peut-être mise en œuvre pour traiter ce problème. Le modèle de panache sous-maille de Polyphemus traite les émissions des sources ponctuelles industrielles par l'intermédiaire d'un modèle à bouffées gaussiennes qui interagit dynamiquement avec un modèle eulérien. Ceci permet de modéliser la qualité de l’air à grande échelle (régionale à continentale), tout en gardant une bonne représentation des panaches, y compris à l’échelle locale.Les travaux menés dans le cadre de cette thèse ont permis d’améliorer le modèle de panache sous-maille de Polyphemus en intégrant une représentation plus fine de la granulométrie des particules, et d’approfondir les évaluations du modèle à différentes échelles. Ils ont été réalisés selon deux phases principales.La première consiste en l’évaluation à l'échelle continentale du modèle eulérien de Polyphemus dans le cadre de l'exercice d'intercomparaison Eurodelta. La phase actuelle du programme vise à étudier les tendances de pollution à l’échelle de l’Europe sur les vingt dernières années, ainsi que la sensibilité de ces tendances modélisées aux données météorologiques, aux émissions européennes et aux émissions extra-européennes (implicitement représentées par les conditions aux limites). Dans ce contexte, les performances du modèle eulérien de Polyphemus sont évaluées en comparaison à sept autres modèles. Pour cette thèse, l'étude se concentre plus spécifiquement sur l’évaluation de la modélisation des concentrations en aérosols organiques secondaires (AOS), et leurs sensibilités aux différentes paramétrisations utilisées par les modèles participants.La seconde phase présente l’utilisation du modèle de panache sous maille de Polyphemus dans le contexte de différentes campagnes de mesures. En premier lieu, le modèle est appliqué dans le contexte d’une campagne de mesures réalisée en avril 2013 au voisinage de la raffinerie Total de Grandpuits en Seine-et-Marne. Cette étude a permis d'évaluer les performances du modèle à l’échelle de la région Île-de-France et à l'échelle locale. La contribution de la raffinerie aux concentrations en particules inhalables, en interaction avec les autres sources locales, a été analysée. En second lieu, le modèle est appliqué dans le contexte des deux campagnes d'observation du projet TEMMAS (« TEledetection, Measure, Modeling of Atmospherics pollutants on industrial Site »), réalisées au voisinage de la raffinerie Total de La Mède dans les Bouches-du-Rhône en septembre 2015 et février 2016. Les performances du modèle sont évaluées en comparaison à des mesures intensives de concentrations en masse et en nombre et de composition des particules au voisinage de la raffinerie de la Mède / Eulerian Chemical-Transport Models (CTM) simulate the formation of atmospheric pollutants in gridded domain with horizontal resolutions that are usually of the order of several kilometers. Industrial plumes emitted from elevated stacks with initial dimensions of a few meters are, therefore, artificially diluted in those grid cells, thereby deteriorating the representation of their potential impact on local air quality. A Plume-in-Grid modeling approach may be used to improve the representation of industrial plumes. The Polyphemus Plume-in-Grid model treats point source emissions with a Gaussian puff model, dynamically interacting with an Eulerian model. This approach allows one to model air quality at several scales (regional to continental) while ensuring a good representation of industrial plumes from local to continental scales.In this thesis, the Polyphemus Plume-in-Grid model has been improved by integrating a finer representation of the particle size distribution. Several studies were also conducted in order to further the model performance evaluation at various scales. This thesis consists of two main parts.The first part covers the evaluation of the Polyphemus Eulerian model at the continental scale, in the context of the Eurodelta model intercomparison project. The current phase of Eurodelta consists in studying pollution trends at the European scale over the past two decades and the sensitivity of those trends to meteorology, European emissions, and extra-European emissions (represented in the models by the boundary conditions). In this context, the performance statistics of the Polyphemus Eulerian model are evaluated in comparison to seven other CTM. This thesis focuses principally on secondary organic aerosol (SOA) modeling, and their sensitivity to various parameterizations used in the participating CTM.The second part presents applications of the Polyphemus Plume-in-Grid modelto different field measurement campaigns. The first campaign focuses on the month of April 2013, in the vicinity of the Total refinery of Grandpuits, Seine-et-Marne. Model performance is evaluated at the regional scale, with the refinery sources treated with the Plume-in-Grid representation. The refinery contribution to local respirable particle concentrations, in interaction with local sources, is analyzed. Next, the model is applied to two measurement campaigns of the TEMMAS project (“TEledetection, Measure, Modeling of Atmospheric pollutants on industrial sites”), conducted in the vicinity of the Total refinery at La Mède, Bouches-du-Rhône, in September 2015 and February 2016. The performance of the Polyphemus Plume-in-Grid model is evaluated with intensive measurements of mass concentrations, number concentrations, and chemical composition of particles in the vicinity of the refinery

Abstract The results of the comparison of various dissolution methods for sulphur showed, that HNO3 together with H2O2 gave more complete decomposition of organic components than HNO3 alone. The acid procedure with a mixture of HNO3+H2O2 slightly underestimated the S concentrations of plant material. The losses of sulphur were the highest in the dry ashing digestion procedure (HF(DAC)). The Leco combustion technique with infrared (IR) detection gave good precision and accuracy for sulphur. For the determination of heavy metals in plant materials, both the HNO3 and HNO3+H2O2 procedures were especially effective for determining Cr. However, the HNO3+HClO4 procedure gave lower results, and HF and HF(DAC) procedures greater values for Cr. Sulphur accumulation in pine needles around the pulp and paper mills was clearly higher than other points in the Kemi area. For example, within a radius of about 1-1.5 km around the mills of Oy Metsä-Botnia Ab Kemi Mills, the sulphur concentrations for (C) and (C+1) needles were 28 % and 26 % higher than those in the corresponding background samples collected in Kuivaniemi at a distance about 25 km from Kemi. Pine needles do not appeared to be appropriate a method for monitoring the accumulation of Fe, Zn, V and Pb emitted from pulp and paper mills. However, the Ca concentrations in (C+1) needles in the vicinity of the Oy Metsä-Botnia Ab Kemi Mills was 48 % higher than the average Ca concentration calculated from all (C+1) needles; thus it is likely that part of the Ca in the needles is derived from the mills. The regional distribution pattern of Cr and Ni in mosses in the Kemi-Tornio area in 2000 showed clearly that the most polluted area (Cr > 200 μg/g and Ni > 20 μg/g) appeared to lie within a few kilometres of the ferrochrome and stainless steel works of AvestaPolarit Stainless Oy. Within this area, the Cr concentrations in mosses were 4-13 times higher than those outside the urban area of Tornio. The area most polluted by the opencast chromium mining complex (Cr > 200 μg/g and Ni &lt; 20 μg/g) appeared to be in the immediate vicinity of complex. All the 95th percentile values for TSP (total suspended particles) in the mine area of AvestaPolarit Chrome Oy Kemi Mine were below the current Finnish air quality limit value of 300 μg/m3. However, the 98th percentile value exceeded the Finnish air quality guideline value of 120 μg/m3 at one monitoring site. According to leaching studies, the sum of calculated annual airborne pollution impact of water-soluble fraction (H2O) and environmentally mobile (CH3COONH4) fraction from the AvestaPolarit Chrome Oy Kemi Mine was Cr 1.2 kg, Fe 29 kg, Cu 63 kg, Ni 2.5 kg and Cd &lt; 100 mg. According to the homogeneity studies of heavy metal deposition on TSP filters, Cr, Ni, Cu and Fe were non-uniformly distributed over the glass fibre filters. The rsd values varied between 5.4-33.9 % for Cr, between 7.5-35.0 % for Ni, between 3.6-25.9 % for Cu, and between 6.6-19.9 % for Fe.

Ce travail de thèse porte sur le devenir du N2 récemment fixé par les diazotrophes dans l’océan oligotrophe de surface.Il apparaît que le N2 récemment fixé est excrété dans le compartiment dissous par tous les diazotrophes marins étudiés et que l'amplitude de cette excrétion dépend d'abord des contraintes environnementales que des diazotrophes impliqués dans la fixation.Le transfert de N2 fixé vers le plancton non-diazotrophe a été quantifié en utilisant une méthodologie innovante (couplage de la spectrométrie de masse à ionisation secondaire à l’échelle nanoscopique (nanoSIMS) et du tri cellulaire par cytométrie en flux). En conditions naturelles, 5 à 20 % du N2 récemment fixé est transféré vers les communautés non diazotrophes, principalement via l’excrétion de NH4+. Ce transfert est deux fois plus efficace lorsque le N2 est fixé par le diazotrophe Trichodesmium que lorsqu’il est fixé par les diazotrophes unicellulaires Crocosphaera ou Cyanothece.L’export du N2 récemment fixé a été évalué en utilisant des larges mésocosmes équipés de pièges à sédiments, déployés dans le lagon de Nouvelle Calédonie, et enrichis en PO43- pour stimuler la fixation de N2. Lors de cette expérience, il a été démontré que la fixation de N2 a alimenté une grande partie de la production primaire nouvelle (>90 %) et que le N2 fixé par les diazotrophes a rapidement été exporté. Cet export a été direct, par la sédimentation des diazotrophes eux-mêmes (représentant ~20 % de la matière particulaire retrouvée dans les pièges au plus fort de l’efflorescence de diazotrophes), et indirect, par le transfert de ~20 % du N2 fixé vers les communautés non diazotrophes qui, à leur tour, ont sédimenté. / This PhD thesis, achieved within the framework of the VAHINE project, focuses on the fate of the recently fixed N2 by diazotrophes in the oligotrophic surface ocean.It appears that the release of the recently fixed N2 in the dissolved pool is a process shared between all diazotrophs tested and that the magnitude of this release depend on the environmental contrains rather than on diazotroph involved in fixation.The transfer of the N2 fixed toward non-diazotroph plankton has been investigated using an innovative methodology (coupling of nano-scale mass spectrometry (nanoSIMS) and cell sorting flow cytometry). It appeared that 5 to 20 % of the recently fixed N2 is transferred toward non-diazotroph plankton, mainly through NH4+ release. This transfer is twice more efficient when the N2 is fixed by the filamentous Trichodesmium compared to Crocosphaera and Cyanothece.Particulate export of the fixed N2 has been investigate in large in-situ mesocosms equipped with sediment traps, deployed in the New Caledonian lagoon and enriched with PO43- in order to stimulate N2 fixation. During this experiment, N2 fixation fueled a large part of the new primary production (>90 %) and that fixed N2 was quickly exported. The export has been direct, through the sedimentation of the diazotrophs themselves, and indirect, through the transfer of ~20 % of the recently fixed N2 toward non-diazotrophic plankton that have, in turn, sedimented.

The purpose of this research was to evaluate the capability and performance of the University of South Florida’s (USF) Human Exposure Chamber (HEC) using aerosols in the thoracic range. The goals of this research were two-fold: to obtain an average particle size of 10 µm (thoracic-size range) inside the chamber during dust production and to test for evenness of dust concentration within the chamber. The USF HEC can be used for studies using gases and/or particulates. The chamber measurements are 4.16 ft x 2.67 ft x 6.75 ft, for a total volume of 75 ft3 or 2.13 m3. This research has public health significance since outdoor air pollution is found most commonly in the thoracic size range; future studies with the HEC could focus on the impact of outdoor air pollution on human subjects under various exposure conditions, and various particle size ranges. Soda lime glass beads were used in this study due to their uniformity in shape and size. A Wright Dust Feeder (WDF) was used to generate the glass beads aerosol in the chamber. Nitrogen gas and HEPA-filtered fresh air were used to transport the aerosol through the system and into the chamber. A total of nine different chamber configurations were made in order to increase the average particle size closer to the goal of 10 µm. Chamber reconfiguration provided statistically significant effect on increasing particle size with the exception of two intermediate settings. It was concluded that aerosol distribution within the chamber was even during operation of the chamber, and modification steps utilized in the study provided size distribution within +/- 6% of the target particle size.

It is a challenge to assess the toxicity of environmental air particulate matter (PM) because PM composition is complex and variable, due to source contribution and atmospheric transformation. The goal of this study is to establish an in vitro model that can fingerprint the cytotoxic effects of airborne PM and their associated toxicity mechanisms. For this purpose, the cytotoxic effects of different reference and environmental particles on A549 human lung epithelial cells were characterized using multiple endpoint assays (cytokine release, LDH release, BrdU incorporation, cellular ATP and resazurin reduction) and proteomic analyses (2D-GE and MALDI-TOF-TOF-MS/MS). The results of this study demonstrated that proteomic analyses can distinguish the influences of different (carbon black and titanium dioxide) and similar (cristobalite and α-quartz) particles on various pathways in A549 cells (e.g., cell death and cell proliferation); and the cytotoxicity assays were capable of differentiating the phenotypic outcomes of the particles, which were complementary and supportive to pathway analyses. The ability of in vitro toxicoproteomics to differentiate the toxicity of environmental particles was tested on Ottawa urban dust (EHC-93) and its water-insoluble and soluble fractions. Findings from both cytotoxicity assays and proteomic analyses consistently indicated that the insoluble materials explained most of the toxic effects of the total PM. Interestingly, the toxic potency of EHC-93 total was not equal to the sum of its insoluble and soluble fractions, implying inter-component interactions between insoluble and soluble materials that may be reflected through synergistic or antagonistic in vitro responses. The insoluble and soluble fractions uniquely altered the expression patterns of the proteins involved in pathways such as cell death, cell proliferation and inflammation. For example, the insoluble and soluble fractions oppositely altered the expression of the proteins (e.g., TREM1, PDIA3, PKM and ENO1) involved in an inflammatory response pathway in A549 cells, and the insoluble fraction was more potent than the soluble fraction in increasing secretion of pro-inflammatory cytokines MCP-1 and IL-8 from A549 cells. In essence, in vitro toxicoproteomics is a valuable tool in relating the physicochemical characteristics of ambient air particles to their biological reactivity through understanding their mechanisms of toxicity.

L’objectif de cette étude était de développer une nouvelle génération de catalyseurs, dits électrochimiques, capables d’abaisser la température de régénération des filtres à particules, et de diminuer les coûts du post-traitement des moteurs Diesel, en évitant notamment une surconsommation en carburant. Pour cela, un banc de mesure a été développé où de forts moyens analytiques pour les phases gazeuses (GC et analyseur de NOx), particulaires (spectromètre de masse à aérosols AMS) et de caractérisations physiques des aérosols (SMPS, Scanning Mobility Particle Sizer) ont été couplés. Le catalyseur électrochimique développé est composé d’un catalyseur oxyde de type pérovskite La0.5Sr0.23Ag0.27MnO3±δ (noté LSAM), en contact avec un électrolyte solide conducteur par les ions O2-, la zircone dopée à l’oxyde d’yttrium (YSZ). L’enduction de ce catalyseur électrochimique directement dans les canaux d’un filtre à particule (FAP) en céramique (SiC) a montré des performances permettant d’abaisser la température de régénération des FAP de 100°C voire de 260°C selon le flux de régénération. Ces performances sont le résultat d’un effet de synergie entre les phases de la pérovskite LSAM et du conducteur ionique YSZ / The aim of this study was to develop a new generation of catalysts, called electrochemical, which can lower the regeneration temperature of the particulate filter, and reduce post-treatment costs of Diesel engines, especially avoiding over-consumption of fuel. For this, a test bench has been developed where strong analytical analyzer for gas phases (GC and Nox analyzer), for particles (aerosol mass spectrometer AMS) and for physical characterization of aerosols (SMPS, Scanning Mobility Particle Sizer) have been coupled. The electrochemical catalyst developed is composed of a perovskite catalyst La0.5Sr0.23Ag0.27MnO3±δ (denoted LSAM), in contact with a solid electrolyte conductor by O2-ions, yttria stabilised zirconia (YSZ). The coating of the electrochemical catalyst directly into the channels of a particulate filter (DPF) showed performance to lower the DPF regeneration temperature of 100°C or even 260°C depending of the regeneration flow. These performances are the result of a synergistic effect between the phases of the perovskite LSAM and YSZ ionic conductor

FERREIRA, Tatiane Morais. Efeito da massa e dos constituintes químicos do material particulado inalável sobre admissões hospitalares por doenças respiratórias e circulatórias em cidade de porte médio, 2015. 112f. Dissertação (Mestrado) Programa de Pós-Graduação em Ciência Ambiental (PROCAM) Universidade de São Paulo, São Paulo, 2015. Segundo a Organização Mundial da Saúde, a poluição atmosférica é atualmente o principal fator de risco ambiental para a saúde no mundo, principalmente aos grupos mais vulneráveis como crianças e idosos. Em relação ao material particulado inalável (MP10) ainda há incertezas quanto às características físico-químicas que são determinantes de sua toxicidade na saúde. Diversos estudos vêm correlacionando níveis de poluentes com o estado de saúde populacional. Entretanto, tais correlações têm sido feitas principalmente em cidades de grande porte. Assim, é de grande importância estender as avaliações para outras cidades, como as de médio porte, a fim de conhecer os níveis de concentração a qual a população está sendo exposta, para que medidas preventivas possam ser tomadas. O objetivo deste estudo foi analisar a associação entre as concentrações de MP<2, MP2-10 e MP10 e seus constituintes químicos (Cl-, NO3-, SO42-, Na+, NH4+, K+, Ca2+e Mg2+) com as admissões hospitalares por doenças respiratórias e circulatórias em crianças e idosos. Para isso, realizou-se um estudo ecológico de séries temporais a partir de dados de internação por doenças respiratórias em crianças (5 anos) e idosos (60 anos) e por doenças cardiovasculares em idosos, residentes em São José dos Campos, São Paulo, entre março/2010 e fevereiro/2011. Para a análise utilizou-se regressão de Poisson em Modelo Aditivo Generalizado, com ajuste para tendência temporal, variáveis meteorológicas (temperatura e umidade), dias da semana e feriados. Foi encontrada associação estatisticamente significativa entre MP10 e MP2-10 apenas com as doenças respiratórias em crianças e idosos. A cada 10 g/m3 de MP2-10 o aumento no risco de internações para crianças e idosos foi de 20% (IC95%: 11;30) e 23% (IC95%: 13;34), respectivamente, e para MP10 o risco foi cerca de 13% em ambos os grupos. Para o MP<2 observou-se associação estatisticamente significativa para as doenças respiratórias em crianças e circulatórias em idosos. A cada 10 g/m3 de MP<2 o aumento no risco de internação foi de 26% (IC95%: 9;45) para doenças respiratórias em crianças e 20% (IC95%: 6;35) para doenças circulatórias em idosos. Quanto às espécies químicas observaram-se riscos específicos para cada constituinte sobre cada causa analisada. De modo geral, o SO42- no MP2-10 e o K+ no MP<2 foram os constituintes associados ao aumento no risco de internação por todas as causas e em todos os grupos avaliados. Esses resultados estão em acordo com as evidências de que os riscos para diferentes causas variam em relação à fração do MP10 e sua composição química. Porém, para valer-se de estimativas de maior confiabilidade, há necessidade da disponibilização de dados para os demais constituintes químicos de ambas as frações do MP10 e por um período de tempo maior. / FERREIRA, Tatiane Morais. Mass and the chemical constituents effect of inhalable particulate matter on hospital admissions for respiratory and circulatory diseases in medium-sized city, 2015. 112f. Thesis Masters Dissertation - Graduate Program of Environmental Science, Universidade de São Paulo, São Paulo, 2015. According to the World Health Organization, air pollution is currently the main environmental risk factor for health in the world, especially to the most vulnerable groups such as children and the elderly. Regarding the inhalable particulate matter (PM10) there is still uncertainty about the physical and chemical characteristics that are determinants for toxicity in health. Several studies have correlated pollutant levels with the health status of the population. However, these correlations were performed mainly in large cities. Therefore, it is very important to extend the evaluation for other cities, such as medium-sized, in order to know the concentration levels to which the population is being exposed so that preventive measures can be taken. The objective of this study was to analyze the association between PM<2, PM2-10 and PM10 concentrations and its chemical constituents (Cl-, NO3-, SO42-, Na+, NH4+, K+, Ca2+ and Mg2+) with hospital admissions for respiratory and circulatory diseases in children and the elderly. To do so, we carried out an ecological time-series study using hospitalization data for respiratory diseases in children (5 years) and elderly (60 years) and cardiovascular disease among elderly people living in São José dos Campos, São Paulo, between March 2010 and February 2011. For the analysis we used Poisson Regression in Generalized Additive Model, adjusted for temporal trends, meteorological variables (temperature and humidity), day of week and holidays. A statistically significant association between PM10 and PM2-10 was found only with respiratory diseases in children and elderly. The increase in hospitalization risk for children and the elderly was 20% (CI95%: 11;30) and 23% (CI95%: 13;34) for every 10 µg/m3 of PM2-10, respectively, and for the PM10 the risk was about 13% in both groups. For the PM<2 there was a statistically significant association for respiratory diseases in children and circulatory in the elderly. The increase in hospitalization risk was 26% (CI95%: 9;45) for respiratory diseases in children and 20% (CI95%: 6;35) for circulatory diseases in the elderly, for every 10 g/m3 of PM<2. For chemical species we observed risks specific to each constituent and for each cause of hospitalization analyzed. In general, the SO42- in the PM2-10 and the K+ in PM<2 were the constituents associated with an increase in the hospitalization risk for all causes and for all study groups. These results are in accordance with the evidence that the risks for different causes vary according to different fractions of PM10 and its chemical composition. However, to obtain more reliable estimates, one needs data on other chemical constituents of both PM10 fractions and over a longer period of time.