Esse trabalho trata da análise do transporte de monóxido de carbono no corpo humano. O monóxido de carbono é um gás incolor, inodoro e insípido, sendo a principal causa das mortes acidentais por intoxicação. É o poluente lançado em maior quantidade na atmosfera. Quando inspirado, ocupa lugares destinados ao transporte de oxigênio, com afinidade cerca de 250 vezes maior. O oxigênio é utilizado pelos tecidos no processo de geração de energia. Sua falta pode causar danos à saúde. Concentrações altas de monóxido de carbono podem resultar em acidentes fatais. Para analisar o transporte de monóxido de carbono, foi desenvolvido um modelo matemático do sistema respiratório, considerando as trocas dos gases monóxido de carbono, oxigênio e dióxido de carbono. O modelo possibilita analisar a distribuição de monóxido de carbono no corpo humano, dependendo das condições do ar inspirado, em regime transitório. É definido pela separação dos locais onde os gases estão presentes em compartimentos. São esses os alvéolos, os capilares pulmonares, o sangue arterial, o sangue venoso, os tecidos e os capilares teciduais. No equacionamento, utilizou-se princípios de conservação de massa. O transporte dos gases no sangue e nos tecidos é representado por equações com bases empíricas, incluindo a influência de um gás sobre o outro. No final, alguns resultados de simulações do modelo são apresentados e discutidos. A validação foi feita comparando os resultados do modelo com dados experimentais de exposição controlada ao monóxido de carbono. A coerência entre os resultados foi excelente. Após a validação o modelo foi utilizado para prever a concentração de CO no corpo humano após exposição a alguns ambientes típicos. Entre esses, tem-se a análise dos critérios de qualidade de ar para o monóxido de carbono, que mostraram ser adequados. Outra aplicação são situações típicas de incêndio, onde o aumento de dióxido de carbono e a diminuição de oxigênio mostraram acelerar a absorção de monóxido de carbono pelo corpo humano. / This work is about the transport of carbon monoxide in the human body. The carbon monoxide is a colorless, odourless and tasteless gas and the main cause of accidental deaths for poisoning. It is responsible for the biggest amount of pollutant launched in the atmosphere. When inspired, it occupies places destined to the oxygen transport, with affinity about 250 times bigger. The oxygen is used by the tissues in the process of energy generation. Its lack can cause damages to the health. High concentrations of carbon monoxide can result in fatal accidents. To analyze the transport of carbon monoxide, a mathematical model of the respiratory system was developed, considering the exchanges of the gases carbon monoxide, oxygen and carbon dioxide. With this model, it is possible to analyze the transient distribution of carbon monoxide in the human body, depending on the conditions of the inspired air. It is defined by the separation of the places where the gases are present in compartments. These are the alveoli, the pulmonary capillaries, the arterial blood, the venous blood, the tissues and the tissues capillaries. The equations were defined by principles of mass conservation. The transport of these gases in blood and tissues are represented by empiric based equations, including the influence between them. Some model’s simulation results are presented and discussed at the end. The validation was done comparing the model’s results with experimental data of controlled exposition to carbon monoxide. The agreement between the results was excellent. After that, the model was used to some typical situation. One of them is about the verification of the quality air criteria for carbon monoxide, showing to be adequate. Other application are typical fire situations, where the carbon dioxide rising and oxygen reduction showed to accelerate the absorption of carbon monoxide by the human body.

A compreensão de como a floresta urbana interage com a poluição atmosférica é importante tanto para o planejamento urbano quanto para a saúde pública. A floresta urbana é capaz de reter e absorver os poluentes atmosféricos além de poder ser utilizada como biomonitor de baixo custo em localizações privilegiadas. O Parque Ibirapuera localizado em uma região central da cidade de São Paulo tem uma floresta urbana heterogênea e dentro dele há as principais árvores encontradas nas ruas da cidade. Esse aspecto facilitou o estudo da interação dessas árvores com a poluição atmosférica. Para a realização do estudo foi necessária a coleta das folhas das árvores e sua moagem para a análise dos componentes inorgânicos. Houve a partir desse estudo a determinação dos elementos presentes nas folhas de árvores através da técnica de fluorescência de raio X. Dos componentes encontrados a partir da moagem foram estudados aqueles que possuíam emissão de fontes veiculares para que se fizesse uma relação desses com a interação da vegetação e como essa pode ser utilizada para amenizar os ambientes poluídos e para o biomonitoramento. / The comprehension of the urban forest interaction with atmospheric pollution is important to urban planning and public health. The urban forest is able to held back and absorb the air pollution besides the use as low coast biomonitor and privileges location. The Ibirapuera Park located in a central area of the city of São Paulo has an heterogeneous urban forest and inside of this park there are the mains trees founded in the streets of São Paulo. This aspect has made easier the study of the interaction of those trees with the air pollution. For the realization of this study was need the collection of the foils of the trees and theirs grind for the analyses of the inorganic components. The determination of the elements presents in the leaf of the trees with the technique of x-ray fluorescence allows understand the interaction of these elements with the tree and give the tree the function of ambient biomonitor.

Os processos de remoção de espécies químicas da atmosfera têm sido estudados atualmente utilizando modelos numéricos, na tentativa de compreender melhor, os processos de transferências de gases e material particulado (sejam elas naturais ou antropogênicas) intra-reservatórios na atmosfera e seus efeitos na dinâmica do tempo e clima. Neste estudo, foi utilizado o modelo RAMS para simular a estrutura vertical das nuvens que se desenvolvem na região amazônica, em conjunto ao modelo de remoção B. V. 2, para os processos de remoção úmida que ocorrem tanto dentro quanto abaixo da nuvem, além das condições atmosféricas locais da região da Bacia Amazônica para, assim, simular a transferência das espécies químicas da atmosfera para a hidrosfera dentro do escopo do projeto LBA. Dentro deste projeto, foram realizadas campanhas intensivas de medições, como a LBA/DRY-TO-WET e LBA/SMOCC (setembro a novembro de 2002) na região de Rondônia. No período das campanhas, foram realizadas medições das concentrações dos gases amônia, ácido nítrico e dióxido de enxofre, além das espécies inorgânicas solúveis em água, como amônio, nitrato e sulfato, entre outros. Estas concentrações de gases e partículas, bem como os parâmetros meteorológicos obtidos durante as campanhas, realizadas durante o período de transição entre as estações seca e chuvosa na região, foram utilizados como dados de entrada para ambos os modelos, onde foram escolhidos alguns eventos específicos. Com intuito de melhor representar o espectro de gotículas de nuvens no modelo de remoção, foram utilizadas a função de distribuição de Levine & Schwartz, 1982 e funções gama ajustadas aos dados observados em distribuição de gotículas de nuvem obtidas em vôos efetuados durante o experimento. Conseqüentemente, este trabalho visou à simulação da concentração na água de chuva de três espécies químicas (SO42-, NO3- e NH4+) removidas da atmosfera pelo evento de precipitação, comparando-as às composições químicas da água de chuva observadas experimentalmente, em dois eventos selecionados (9 e 10 de outubro de 2002). Simulações atmosféricas com o RAMS apresentaram resultados bastante satisfatórios conseguindo representar aspectos microfísicos das nuvens que se desenvolvem na região amazônica com bastante fidelidade. Os resultados da modelagem dos processos de remoção mostraram uma boa concordância com os observados, principalmente para o sulfato (que em alguns casos a quantidade encontrada na água de chuva pela simulação foi 97% da observada) em ambos os eventos, quando a altura da nuvem foi considerada mais realista para região (16 km). Além disso, observou-se que o espectro de gotículas de nuvem utilizado foi um parâmetro importante nos resultados. Os resultados mostraram ainda, uma predominância dos processos que ocorrem dentro da nuvem, sendo estes responsáveis por cerca de 80% a 97% da concentração da espécie química encontrada na água de chuva, corroborando a literatura. Com isso, ficou evidente a complexidade das interações e transferências entre os reservatórios atmosfera / hidrosfera através dos processos de remoção de poluentes, ressaltando assim, a importância dos estudos sobre este assunto. / The scavenging processes of chemical species have been studied using numerical modeling in order to understand the gases and particulate matter intra-reservoir transferences (natural or anthropogenic) which affect weather and climate. In this study RAMS model was used in turn to simulate cloud vertical structure formed over Amazonian area working together to B.V.2 scavenging model. The last model was used to simulate the in- and below-cloud scavenging processes, besides the local atmospheric conditions within the LBA Project. In this Project, there were evaluated many measurements of LBA/DRY-TO-WET and LBA/SMOCC (September to November) Campaigns at Rondonia State. During the Campaigns, ammonia, nitric acid and sulfur dioxide gases were evaluated and their respective particulate matter, ammonium, nitrate and sulfate, among others, as well as rainwater chemistry. These concentrations and meteorological parameters were also obtained, during the transition from dry to wet season, and used as input data to the both modeling, where some events were chosen. With the intention of modeling improvement, cloud droplet spectra were used from Levine & Schwartz, 1982 and gamma functions, according to each case and based on the droplet distribution obtained from flight collected data during the field Campaign. Consequently, this work simulated the rainwater concentrations of three chemical species (SO42-, NO3- e NH4+) scavenged from atmosphere by the precipitation event and compared to the observed data of two selected events (9 and 10 October 2002). RAMS atmospheric simulations presented satisfactory results which showed detailed cloud microphysics processes of Amazonian region. The modeling results show good agreement of observed data, mainly to sulfate, reaching 97% of the observed sulfate for both events, when the cloud height was considered more realistic for the region (16 km). Besides, the cloud droplet spectra were an important parameter to the modeling. The results also showed that the in-cloud process is responsible by 80% to 97% of the chemical species found in rainwater. Additionally, it was clear that the complexity of the interaction and intra-reservoir transferences through the scavenging processes and their importance.

Os efeitos causados pela presença de áreas urbanizadas da Região Metropolitana de São Paulo (RMSP), conhecidos por ilha de calor urbana, são estudados através da modelagem numérica e da análise de alguns dados observacionais, coletados no período de inverno de 1999 durante a 1ª Fase intensiva de medidas de campo do Projeto Temático FAPESP “Meteorologia e Poluição do Ar em São Paulo” e da rede automática da CETESB. Através da utilização de imagens do satélite LANDSAT-5, foi obtido um arquivo de ocupação do solo na RMSP numa resolução de aproximadamente 424 m. Foram definidos dois tipos de ocupação urbana que diferem principalmente na verticalização e espaçamento entre as construções. Simulações realizadas com uma parametrização adequada ao tratamento das propriedades da superfície em áreas urbanas, o modelo RAMS-TEB, mostraram que as fontes antropogênicas de calor de origem veicular são de grande importância no ciclo diurno de temperatura e umidade na RMSP. Uma comparação entre os dados simulados pelo modelo e dados observacionais de superfície apresentou coeficientes de correlações superiores a 0,9 para a temperatura e superiores a 0,8 para a umidade relativa. A interação entre a brisa marítima e a ilha de calor intensifica as zonas de convergência no centro da cidade, podendo ocasionar a re-circulação de poluentes nessa região. Simulações sobre o efeito da urbanização mostram que a ilha de calor urbana faz com que haja uma propagação mais rápida da frente de brisa até o centro da RMSP, que permanece estacionária por algum tempo nessa região. Os efeitos da topografia mostraram-se fundamentais na intensidade da brisa marítima e sua propagação sobre o continente. A presença de grandes corpos d’água, tais como a represa de Guarapiranga e Billings, contribui para a diminuição das amplitudes do ciclo diurno de temperatura na RMSP através das circulações do tipo brisa lacustre geradas pelos mesmos. O uso de um modelo de dispersão mostrou que, com a propagação da frente de brisa para o interior (na direção SE-NW), poluentes emitidos na RMSP são transportados para áreas remotas, diminuindo a concentração dos mesmos nas regiões emissoras. / The effects caused by urbanization in the Metropolitan Area of São Paulo (MASP), known as urban heat island, are studied through the use of numerical modeling and some observed data, collected in the 1999’s winter time during the first phase of intensive field measurements from the Thematic Project FAPESP “Meteorology and Air Pollution in São Paulo” and also from CETESB automatic network. A 424 m resolution land use file was created using LANDSAT-5 satellite pictures where two different kinds of urban regions were identified. The main differences between these regions are the vertical structure and spacing between buildings. Simulations performed with an appropriate parameterization for the treatment of surface properties in urban areas showed that anthropogenic sources due to traffic are of great importance to the temperature and humidity diurnal cycle in MASP. Comparisons between simulated and observed surface data had a correlation coefficient greater than 0.9 for temperature and greater than 0.8 for relative humidity. The interaction between the see breeze and the urban heat island intensify the convergence zones in the center of the city, eventually causing the re-circulation of pollutants in this region. Simulations of the urbanization effects showed that the urban heat island is responsible for a faster propagation of the sea breeze front up to the center of the MASP, remaining stationary in this region for some time. The topographic effects are fundamental in the intensity of the sea breeze and its inland propagation. The presence of large water bodies, as the Guarapiranga and Billings Dams, contribute to a decrease in the temperature diurnal cycle amplitudes because of the lake breeze circulations generated by them. The use of a simple dispersion model showed that with the propagation of the sea breeze front to the countryside (in the direction SE-NW), pollutants emitted in MASP are transported to remote areas, causing a decrease in the concentration of these pollutants in the source region.

A Região Metropolitana de São Paulo (RMSP) enfrenta sérios problemas relacionados à degradação da qualidade do ar devido às emissões de sua intensa frota veicular, apresentando constantes ultrapassagens dos Padrões de Qualidade do Ar de poluentes como o ozônio (PQAr ~80ppbv). O Ozônio é formado na atmosfera em condições complexas em presença de intensa radiação solar, altas temperaturas, baixa umidade relativa, ventos fracos e altas concentrações dos precursores, óxidos de nitrogênio (NOx = NO + NO2) e compostos orgânicos voláteis (COVs). Assim, o problema da poluição do ar em centros urbanos precisa ser tratado com metodologias mais modernas para que possam ser estabelecidos novos critérios para redução de seus precursores e o conhecimento das condições mais adequadas (relação entre os COVs e os NOx, além da especiação destes COVs) para a redução do ozônio troposférico. Neste contexto, modelos fotoquímicos de qualidade do ar têm sido usados para auxiliar na tomada de decisões ambientais estratégicas. O módulo químico SAPRC Statewide Air Pollution Research Center é um mecanismo detalhado para simular reações entre COVs e NOX, desenvolvido para ser aplicado para atmosferas urbanas e regionais dos Estados Unidos. Porém, devido características específicas do combustível (aproximadamente 30% da frota usa etanol), no Brasil a poluição urbana apresenta características próprias. Dessa forma, baseado em campanhas anteriores de amostragem de COVs, no presente estudo foram modificados o inventário de emissões e o módulo químico (SAPRC99) do modelo fotoquímico CIT a fim de melhorar a representação do ozônio quanto a sua formação e consumo na atmosfera da RMSP. Para isso, alguns COVs como xilenos, 1-buteno e trimetilbenzenos foram explicitados. As simulações para os dias 30 e 31 de outubro de 2006 mostraram aumentos de espécies como peroxiacetilnitrato e ozônio de aproximadamente 10% para o centro de formação de pluma sobre a RMSP. / The Metropolitan Area of São Paulo (MASP) suffers severe problems related to air quality degradation presenting constant air quality standard overpasses for pollutants like ozone (QSAir ~80ppbv), due to its intense vehicular fleet. Ozone is formed in the atmosphere under complex conditions in the presence of strong solar radiation, high temperatures, low relative humidity, weak winds and also high precursor concentrations, such as nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs). Therefore, the problem of air pollution in urban centers has to be treated using modern methodologies in order to establish new criteria for reduction of precursors and to know more adequate conditions (relation between VOCs and NOx, as well as speciation of these VOCs) in order to reduce tropospheric ozone. In this context, air quality photochemical models have been used to support strategic environmental decisions. SAPRC chemical mechanism Statewide Air Pollution Research Center developed to be applied in the United States urban atmospheres, consists of a detailed mechanism to simulate reactions between VOCs and NOx. However, due to specific fuel properties (about 30% of vehicular fleet uses ethanol), urban air pollution in Brazil presents its own characteristics, such as higher level of the oxygenated compounds. Hence, based on previous campaigns where VOCs had been sampled, the emission inventory and the chemical module (SAPRC99) were modified in order to improve ozone consumption and formation representation in the MASP atmosphere. As a result, some VOCs like xylenes, 1-butene and trimethilbenzens were explicated. Simulations for 30 and 31 of October 2006 presented increases in species formation like peroxyacetylnitrate and ozone about 10% in the centre of the MASP plume.

Globalmente, os problemas de poluição são mais severos em regiões densamente povoadas ou industrializadas. A Região Metropolitana de São Paulo (RMSP) é um exemplo de megalópole com um conjunto único de emissões, insolação e condições meteorológicas que determinam sua elevada poluição atmosférica. Entre os compostos mais tóxicos presentes nesta atmosfera estão os aldeídos, moléculas de grande potencial mutagênico e carcinogênico que podem ser originados da oxidação de combustíveis fósseis e etanol, além de possuir fontes endógenas. Sua adição covalente em biomoléculas como DNA e proteínas é estudada como mecanismo de sua ação mutagênica e carcinogênica. Desenvolvemos um método ultrassensível de HPLC acoplado à espectrometria de massas para análise simultânea de vários adutos de DNA com aldeídos presentes na atmosfera urbana como formaldeído, acetaldeído, crotonaldeído e acroleína, além de modificações oxidativas. Foram utilizados para validação da metodologia células modelo de Anemia Fanconi e tecido de músculo de ratos modelo para ELA (Esclerose Lateral Amiotrófica), os quais apresentaram níveis basais dos adutos de formaldeído, acetaldeído, acroleína e crotonaldeído. Outros modelos de exposição aos aldeídos foram utilizados na validação desta metodologia, como a fumaça de cigarro de tabaco e de cannabis sendo que a formação desses adutos também foi verificada em DNA de timo de bezerro. Pela primeira vez, foi mostrada a formação inequívoca do aduto de acetaldeído (1,N2-propanodGuo) em pulmões e cérebros de ratos Wistar expostos à 10 ppb de acetaldeído isotopicamente marcado e sua estrutura confirmada por espectrometria de massas de alta resolução. Esse resultado comprova o mecanismo de formação do aduto por meio da adição de duas moléculas de acetaldeído in vivo por inalação e em baixa concentração, sendo crucial para formulação de políticas públicas por agências ambientais. / Globally, air pollution problems are more severe in densely populated or industrialized regions. The Metropolitan Region of São Paulo (RMSP) is an example of a megalopolis with a unique set of emissions, insolation and meteorological conditions that determinates its high atmospheric pollution. Among the most toxic compounds present in this atmosphere are aldehydes, molecules of great mutagenic and carcinogenic potential that can be originated from the oxidation of fossil fuels and ethanol, besides having endogenous sources. Its covalent addition in biomolecules like DNA and proteins is studied as a mechanism of its mutagenic and carcinogenic action. We developed an ultra-sensitive HPLC method coupled with mass spectrometry for the simultaneous analysis of several DNA adducts with aldehydes present in the urban atmosphere as formaldehyde, acetaldehyde, crotonaldehyde and acrolein and oxidative lesions as well. To validate the method, we used a cell model of Fanconi Anemia and muscle tissue from a rat model for ALS (Amyotrophic Lateral Sclerosis) which presented basal levels of the adducts of formaldehyde, acetaldehyde, acrolein and crotonaldehyde. Other models of exposure to aldehydes were used to validate the method, such as tobacco and cannabis smoke and the formation of these adducts was also verified in Calf Thymus DNA. For the first time, the unequivocal formation of the acetaldehyde (1, N2-propanodGuo) adduct was shown in lungs and brains of Wistar rats exposed to 10 ppb of isotopically labeled acetaldehyde and its structure was confirmed by high resolution mass spectrometry. This result confirms the mechanism of adduct formation by the addition of two molecules of acetaldehyde in vivo by inhalation of a low concentration of acetaldehyde, being crucial for the formulation of public policies by environmental agencies.

L'objectif de cette thèse est le développement et la validation d'un modèle numérique de la dynamique des particules en mélange externe et résolu en taille. Afin de suivre plusieurs compositions chimiques par classe de tailles, une nouvelle approche est présentée dans laquelle la composition chimique des particules est elle-même discrétisée suivant la fraction d'un ou plusieurs des constituants chimiques (e.g. suie, sulfate). Cette approche a pour but de mieux simuler l'évolution d'une population de particules à l'échelle locale et de particulariser des compositions chimiques typiques de certaines sources. Dans l'atmosphère, les particules interagissent essentiellement entre elles et avec les polluants gazeux par coagulation et condensation/évaporation. La première partie de la thèse a été consacrée à l'élaboration du modèle pour la coagulation, processus physique qui s'avère le plus complexe à modéliser selon notre approche du mélange externe. Dans un premier temps, les équations de la coagulation en mélange externe sont présentées et discrétisées suivant un nombre arbitraire de classe de tailles et de compositions chimiques. Plusieurs simulations numériques ont ensuite été effectuées avec ce modèle sur un même cas d'étude, en utilisant deux, trois et quatre composants chimiques. On vérifie à chaque fois que les résultats de la simulation numérique en mélange externe sont cohérents avec ceux du mélange interne du cas d'étude. Les résultats de ces simulations permettent d'apprécier l'effet de mélange de la coagulation qui produit, à partir de particules monocomposées, des particules bicomposées et tricomposées. Étant donné la complexité croissante d'un tel modèle, une attention toute particulière a été portée à l'implémentation numérique et à l'optimisation des algorithmes choisis. L'extension de cette approche à la condensation/évaporation constitue le prochain développement de ce modèle, nous en posons les bases théoriques en annexe. S'il existe aujourd'hui des données de mesure résolues en taille (SMPS), il n'y en a pas encore qui puissent être réellement validantes pour ce modèle de mélange externe, c'est-à-dire qui distinguent quantitativement plusieurs compositions chimiques par classe de taille. Aussi, dans la seconde partie de la thèse, nous avons envisagé le protocole d'une expérience en chambre permettant de mettre en évidence le mélange par coagulation de deux populations de particules de compositions différentes et d'apporter des données validantes pour le modèle développé. Deux séries d'expériences ont été menées, la première dans la chambre de grand volume CESAM et la seconde, dans le réacteur de petit volume de l'INERIS. La première série a mis en évidence l'homococagulation de chaque distribution polydispersée prise séparément et dans une moindre mesure, l'hétérocoagulation des deux distributions de nature différentes (NaBr et KBr) entre elles. La seconde série a montré la possibilité d'observer simultanément deux distributions monodispersées de particules de compositions différentes (CaSO4 et KBr), prérequis pour ce cas. Au final, les résultats de mesure se sont avérés insuffisants pour produire des données validantes pour le modèle, à cause du trop grand écart-type des distributions polydispersées dans la chambre de grand volume et à cause du dépôt au paroi qui domine dans le réacteur de petit volume. Des analyses au microscope électronique ont cependant attesté de la présence de particules issues de la coagulation entre les deux natures. A la suite des différentes expériences menées, nous revenons sur le protocole envisagé et proposons quelques pistes d'améliorations / The objective of this thesis is the development and validation of a numerical size resolved and externally mixed model of the particle dynamics. In order to trace several chemical compositions for each size class, a new approach is presented in which the particle chemical composition is itself discretized according to the mass fraction of one or several of its components (e.g. soot, sulfate). This approach aims to improve the simulation of the particle population evolution at local scale and to emphasize chemical compositions which are specific to some sources. In atmosphere, particles interacts essentially between themselves and gaseous pollutants through coagulation and condensation/evaporation. The first part of this thesis is dedicated to the model development for the coagulation process, which happens to be the most complex to model with our external mixing approach. First, coagulation equations in external mixing were set up and discretized with an arbitrary number of size and chemical composition classes. Several numerical simulations were then performed with this model according to the same case 6 study, using two, three and four chemical components. We checked each time that the simulation results in external mixing agreed well with those of the case study internal mixing. The results of these simulations are useful to understand how coagulation mix particles and produces, from monocomposed ones, bicomposed and tricomposed particles. Given the growing complexity of such a model, the numerical implementation has been carried out with carefullness and algorithms have been optimized. The extension of this approach to condensation/evaporation is the next development step of this model, the theoretical basis are adressed in appendix. Size resolved particle measurements (SMPS) do exist nowadays, but truely suitable data to validate the external mixing model still lack, that is to say measurements which would quantitatively distinguish several chemical compositions per size class. That is why, in the second part of this thesis, we considered the protocol of a chamber experiment allowing to highlight the mixing by coagulation of two particle populations with distinct compositions and to bring validating data for the model developed. Two series of experiments were conducted, the first one with the CESAM large volume chamber and the second, with the small reactor of INERIS. The first serie underlined the homocoagulation of each polydispersed distribution taken separately and to a lower extent, the heterocoagulation of the two distributions of different kinds (NaBr et KBr) between themselves. The second serie showed the possibility to observe simultaneously two monodispersed distributions of particles with different compositions (CaSO4 et KBr), which was required in this case. Finally, measurement results happened to be insufficiant to produce validating data for the model, because of the great deviation of polydispersed distributions in the large volume chamber and because of the dominating wall losses in the small reactor. However, some microscope electronic analysis showed evidences of particles produced from coagulation between both kind of particles. Further to these experiments, we come back to the planed protocol and propose some improvements

Ce travail de thèse a porte sur l’évaluation de la qualité de l’air sur l’aéroport Paris-Charles- De-Gaulle. L’objectif était d’évaluer l’impact de l’activité aéroportuaire à l’échelle locale et régionale. Cette étude s’est centrée sur les observations à long terme des concentrations des oxydes d’azote (NOx), d’ozone (O3) et des hydrocarbures. Nous avons quantifié la contribution de l’activité aéroportuaire sur les concentrations des NOx observées sur les stations CDG-nord et CDG-sud. Les résultats ont montré que cette contribution était de 18% (12 μ g.m−3) sous un vent du sud et de 47% (25 μ g.m−3) sous un vent du nord. Cette analyse a été réalisée à partir de 3 ans de mesures (2005-2007). Les concentrations des NOx ont également été analysées à l’aide d’un modèle neuronal. Ce modèle a été construit pour estimer les concentrations des NOx en fonction de paramètres météorologiques (direction du vent, vitesse du vent, température, hauteur de la couche limite) et temporels (jour de l’année, heure du jour et la différence entre les jours de la semaine et du week-end). Le modèle a permis d’estimer les concentrations des NOx pour des scénarios ponctuels. Des campagnes de mesures ciblées sur les hydrocarbures ont été mises en oeuvre au cours de cette thèse. Elles ont permis de caractériser la spéciation des hydrocarbures émis par les moteurs d’avion. Les résultats ont montré que cette spéciation était similaire de celle observée pour les véhicules diesel. Ceci ne permet pas d’établir clairement un profil caractéristique permettant de distinguer les émissions des avions de celles de véhicules. La spéciation des hydrocarbures sur la plate-forme a également été évaluée. Les résultats ont montré que la spéciation des hydrocarbures observée sur la plate-forme est comparable à celle observée en milieu urbain et dans d’autres milieux aéroportuaires. Par ailleurs, les concentrations moyennes observées étaient typiquement de l’ordre de celles observées dans une atmosphère urbaine. L’estimation de l’impact des activités aéroportuaires à l’échelle régionale a fait l’objet d’une étude préliminaire à l’aide d’un modèle de chimie-transport, CHIMERE. Cette étude a permis d’évaluer l’étendue spatiale de l’impact de l’activité aéroportuaire pour deux épisodes. Ces épisodes correspondent à un épisode de pollution estival à l’ozone et hivernal au NO2. Les simulations ont indiqué une contribution inférieure à 5μ g.m−3 à une quinzaine de kilomètres sous le vent de l’aéroport / The work presented here deals with the evaluation of air quality at Paris-Charles-de-Gaulle airport. The objective was to evaluate the local and regional impact of airport activity. This study is centered on long term measurements of nitrogen oxides (NOx), ozone (O3) and hydrocarbons concentrations. We calculated the contribution of airport activity to NOx concentrations in north and south stations. Results showed this contribution was 18% (12 μ g.m−3) from southern wind and 47 % (25 μ g.m−3) from northern wind. This analysis had been performed from 3 years data (2005-2007). NOx concentrations had been also analyzed with a neuronal model. This model was built in order to estimate concentrations according to meteorological (wind direction, wind velocity, temperature, boundary layers) and temporal parameters (day, hour, difference between week-day and week-end). The neuronal model allowed to estimate NOx concentrations for punctual scenarios. Field campaigns targeting hydrocarbons were conducted during this thesis. The speciation of hydrocarbons emitted by engine aircraft was characterized. These results showed engine aircraft hydrocarbon speciation was similar to motor diesel hydrocarbon speciation. This does not allow for the clear establishment of a characteristic profile that differentiates aircraft emissions from those of vehicles. Hydrocarbon speciation observed at the airport was also evaluated. Results showed that the hydrocarbon speciation detected at the airport was comparable to that observed within an urban environment as well as at other airports. Moreover, average concentrations were akin to those observed within an urban environment. The estimation of regional impact of airport activity was preliminary studied with a chemicaltransport model, CHIMERE. This study permitted the evaluation of the spatial extent of the impact of airport activity for two episodes. These episodes correspond to summer pollution by ozone and winter pollution by NO2. Simulations showed the contribution downwind of the airport was lower than 5 μ g.m−3 for 15 km

L'objectif de cette thèse est d'étudier les phénomènes d'import et d'export de la pollution gazeuse et particulaire au-dessus du Bassin Méditerranéen (BM). Ce travail consiste dans un premier temps à étudier l'évolution de l'ozone (O3) de surface dans un contexte de changement climatique au-dessus du BM entre 2000 et 2100, en exploitant les sorties issues de 13 modèles participant à l'exercice ACCMIP (Atmospheric Chemistry and Climate Model Intercomparison Project). Nous avons montré que l'ozone de surface diminue entre 2000 et 2030 (2100) pour 3 RCPs (Representative Concentration Pathway) : -14% (-38%) pour le RCP2.6, -9% (-24%) pour le RCP4.5 et -10% (-29%) pour le RCP6.0, alors que pour le scénario RCP8.5, l'ozone de surface reste stable au cours du XXIème siècle. Dans un second temps, nous avons identifié les sources et les chemins de transport de l'O3 et du monoxyde de carbone (CO) représentatifs des différentes régions du BM : l'Est, l'Ouest et le Centre entre 2012 et 2014, en utilisant une approche statistique qui combine des observations de surface et des rétro-trajectoires issues du modèle HYSPLIT (Hybrid Single Particle Lagrangian Trajectory). En général, l'O3 et le CO sont transportés, respectivement, depuis l'Europe continentale et l'Europe de l'Est vers le BM. Finalement, nous avons étudié les phénomènes d'import et d'export de la pollution au-dessus du BM, en utilisant le modèle MOCAGE (Modèle de Chimie Atmosphérique à Grande Échelle) et le modèle HYSPLIT, et en exploitant les observations récoltées lors des deux campagnes de mesures TRAQA (TRAnsport à longue distance et Qualité de l'Air) (été 2012) et GLAM (Gradient in Longitude of Atmospheric constituents above the Mediterranean basin) (août 2014) réalisées dans le cadre du programme ChArMEx (The Chemistry-Aerosol Mediterranean Experiment). Nous avons mis en évidence le transport à longue distance des masses d'air enrichies en O3 et l'impact du Mistral sur le mélange des masses d'air. Le bilan d'O3 et de CO a été aussi réalisé sur le BM pour l'année 2012 à partir des simulations du modèle MOCAGE. Les résultats montrent que le CO est importé vers le BM pendant le printemps et l'été alors que l'O3 est importé vers le BM durant la période janvier-juin puis exporté le reste de l'année. / The objective of this thesis is to study the import and the export processes of gaseous and particulate air pollution over the Mediterranean Basin (MB). Firstly, we investiga- ted the evolution of surface ozone (O3) over the MB over the time period 2000-2100 in a context of climate change, using the Atmospheric Chemistry and Climate Model In- tercomparison Project (ACCMIP) outputs from 13 models. Compared to the reference period (2000), we found a net decrease in the ensemble mean surface O3 over the MB in 2030 (2100) for 3 RCPs (Representative Concentration Pathway) : -14% (-38%) for RCP2.6, -9% (-24%) for RCP4.5 and -10% (-29%) for RCP6.0. For the RCP8.5 scenario, the ensemble mean surface O3 is almost constant over the MB from 2000 to 2100. Se- condly, we identified the geographical sources and the transport pathways of polluted air masses inducing high levels of surface O3 and carbon monoxide (CO) concentrations in di erent regions of the MB, representative of the west, the center and the east of the MB between 2012 and 2014, using several backward trajectory statistical analyses combining in situ measurements and back trajectories obtained from the HYSPLIT (HYbrid Single- Particle Lagrangian Integrated Trajectory) model. In general, O3 and CO are transported to the MB from continental Europe and Eastern Europe, respectively. Finally, we studied the import and export processes of pollution over the MB using the chemical transport model MOCAGE (MOdele de Chimie Atmosphérique à Grande Échelle) and the HYS- PLIT model. We also investigated in situ measurements carried out during both TRAQA (TRAnsport à longue distance et Qualité de l'Air) (2012) and GLAM (Gradient in Longi- tude of Atmospheric constituents above the Mediterranean basin) (2014) field campaigns performed within the framework of the ChArMEx (The Chemistry-Aerosol Mediterranean Experiment) program. We highlighted the long-range transport of air masses rich in O3 and the impact of the Mistral wind on the air mass mixing. The budget of O3 and CO was also performed over the MB for the year 2012 using the MOCAGE model simulations. We found that the MB is an import area for CO during the spring-summer period, whilst tropospheric O3 is imported to the MB during the January-June period and exported the rest of the year.

Les objectifs de cette thèse sont d'étudier les effets respiratoires de la pollution atmosphérique en prenant en compte 3 niveaux d'exposition: les niveaux macroscopique, semi-individuel et individuel.Pour le niveau macroscopique, nous avons étudié les effets sanitaires des émissions des feux de forêts dans une étude de type écologique. Au travers d'une revue de la littérature, nous avons observé que plusieurs études épidémiologiques avaient mis en évidence l'association entre l'exposition aux émissions des feux et l'augmentation des maladies cardiopulmonaires et la mortalité pour les individus habitant à proximité. La principale limite à ces études est donnée par l'évaluation de l'exposition. Dans une étude de cas sur les incendies de Marseille de 2009, nous avons observé des effets à la limite de la signification 8 et 9 jours après l'exposition entre les concentrations des particules fines(PM2.5 ) issues des incendies et les effets respiratoires.Pour le niveau semi-individuel, nous avons étudié le lien entre la pollution domestique et professionnelle et les maladies respiratoires chez des agriculteurs auvergnats dans le cadre d'une étude de type transversale. Nous avons observé que les dérivés halogénés et l'étyl-butoxyacetate étaient associés de façon significative aux maladies des petites voies aériennes. La concentration de benzène dans la pièce de vie principale de la ferme était significativement associée à une augmentation du risque d'asthme. Enfin, l'utilisation de l'acide mercapturique, dans le cadre d'une étude de type cas témoin nichée nous a permis de mesurer la dose interne d'exposition du benzène parmi des enfants de l'étude et son lien avec l'asthme. / The objectives of this thesis were to study the respiratory effects of air pollution by taking into account three levels of exposure: the macroscopic, semi-individual and individual levels. For the macroscopic level, we studied the health effects of emissions from forest fires in an ecological study. Through a literature review, we found that several epidemiological studies have shown the association between exposure to wildfire emissions and increase cardiopulmonary disease and mortality for the people living nearby. The main limitation of these studies is given by the exposure assessment. In a case study of the wildfire occurred in Marseille in the summer 2009, we observed effects at the limit of significance 8 and 9 days after exposure between concentrations of fine particles (PM2.5) from fire and respiratory effects .For semi-individual level, we have studied the link between domestic and occupational pollution and respiratory diseases among farmers from Auvergne using a cross-sectional study. We observed that the halogenated hydrocarbons and Etyl-butoxyacetate were significantly associated with the small airways disease. Benzene concentration in the living room of the farm was significantly associated with an increased risk of asthma. Finally, the use of a biomarker (the mercapturic acid) in the context of a case-control study allowed us to measure the internal dose of the exposure to benzene and its link with asthma among children included the study.