Ce travail permet d'approfondir les connaissances sur l'exposition des voyageurs aux polluants de l'air dans les autobus via des mesures représentatives en fonction du matériel roulant (Agora Long, Agora Standard), le taux de renouvellement de l'air, de la qualité de l'air extérieur et des paramètres du trafic routier. Les expériences ont été réalisées en étudiant la répartition des polluants dans l'habitacle, un sujet peu abordé jusqu'à présent dans la littérature. Sont quantifiées certaines sources de pollution comme le relargage des nouveaux matériaux et le transfert des effluents du bus vers sa cabine (auto-pollution). Dans le cadre de cette démarche, une campagne inédite a été créée pour quantifier l'auto-pollution minimum et maximum pour ces deux types de bus. Dans des conditions réelles de circulation, les concentrations en polluants (NO2, PM2.5, concentration en nombre des particules entre 0,02-1µm) ont été plus élevées dans les habitacles des bus par rapport au fond urbain. De plus il a été constaté des concentrations en NO2 plus faibles à l'avant par rapport à l'arrière du bus, position du pot d'échappement et du moteur. Cette surexposition a été expliquée par une auto-pollution plus importante à l'arrière par rapport à l'avant (0,13% contre 0,05% dans des conditions défavorables). Enfin l'influence du relargage des matériaux, du trafic routier, des ouvertures des portes, de la vitesse du vent sur les concentrations des polluants dans les habitacles des bus a été démontrée / This study can increase knowledge about the travelers' exposure to air pollution inside buses through measures based representative of rolling stock (Agora Long, Agora Standard), the air change rate, air outdoor quality and traffic parameters. The experiments were performed by studying the distribution of pollutants in the cabin, a subject little discussed in the literature. Some sources of pollution such as the material emissions and the transfer of bus exhaust in the cabin are quantified (self-pollution). As part of this approach, an unprecedented campaign was conducted to quantify the maximum and minimum self-pollution for both types of bus. In real traffic conditions, the pollutant concentrations (NO2, PM2.5, particle number concentration between 0.02-1µm) are higher in the instrumented buses compared to outdoors. Moreover the lowest concentrations of NO2 have been measured in the front of the cabin compared to the rear, the localization of exhaust pipe and the engine. This overexposure was explained by a self-pollution higher in the rear of the cabin compared to the front (0.13% against 0.05% in adverse conditions). Finally the influence of the material emissions, traffic, door openings, the wind speed on the pollutant concentrations inside buses have been demonstrated

No description available.

[pt] Este trabalho teve como objetivo caracterizar química e morfologicamente material particulado (PM2.5 e PM10) coletado na zona sul e oeste da cidade de Rio de Janeiro e na região metropolitana, utilizando técnicas como a Cromatografia de íons (CI), Espectrometria de Massas com Plasma Indutivamente Acoplado (ICPMS) e a Microscopia Eletrônica de Varredura acoplada ao Espectrômetro de RaiosX por Dispersão de Energia (MEV-EDX). Além disso, foram realizados ensaios toxicológicos com C. elegans para avaliar os efeitos da exposição ao material particulado (MP), nas diferentes frações de tamanho. Concentrações médias anuais de PM2.5 entre 7,40 +/- 3,96 (micrograma)m-3 e 17,4 +/- 7,38 (micrograma) m-3 foram medidas durante os anos 2015 e 2018, as quais foram inferiores ao padrão intermediário da qualidade do ar, estabelecido pelo CONAMA, registando-se as maiores médias anuais durante o 2016, ano em que foram realizados os Jogos Olímpicos. Resultados das análises químicas mostraram que o MP em todos os pontos de coleta estava constituído principalmente por espécies iônicas como Cl- , NO3 - , Na+ e SO4 2- e elementos como V, Ni, Cu, Cd, Sn e Pb, sendo determinadas apenas variações significativa (p menor que 0,05) nas concentrações de SO4 2- , NO3 - , Na+ , Cu e Sn, entre os períodos estudados. Através dos resultados das análises de MEV-EDX as partículas atmosféricas se classificaram segundo sua morfologia – Fuligem, esféricas, biológica e minerais- e segundo sua composição elementar – partículas com teor de enxofre, de cloro e de ferro -. Finalmente, efeitos tóxicos foram observados pela exposição ao PM10 e PM2.5 em organismos C. elegans, alterando parâmetros fisiológicos (e.g. crescimento e reprodução) e promovendo respostas dos mecanismos antioxidantes, como resultado do estresse oxidativo gerado por espécies presentes no MP. / [en] This work aimed to characterize chemically and morphologically particulate matter (PM2.5 and PM10) collected in the south and west zones of the city of Rio de Janeiro and in the metropolitan region, using techniques such as ion chromatography (IC), inductively coupled plasma mass spectrometry (ICP-MS) and Scanning electron microscopy- energy dispersive spectrometry (SEM-EDX). Annual mean concentrations of PM2.5 between 7,40 +/- 3,96 microgram m-3 e 17,4 +/- 7,38 microgram m-3 were measured during the years 2015 and 2018, which were lower than the intermediateair quality standard established by CONAMA, with the highest annual averages recorded during 2016, the year in which the Olympic Games were held. In addition, toxicological tests were performed with C. elegans to evaluate the effects of exposure to particulate matter (PM) in the different size fractions. Results of the chemical analysis showed that PM at all collection sites consists mainly of ionic species such Cl- , NO3 - , Na+ and SO4 2- and elements such as V, Ni, Cu, Cd, Sn and Pb, being determined only significant variations (p less than 0,05) in the concentrations of SO4 2- , NO3 - , Na+ , Cu, and Sn, between the studied periods. Based on the results of the SEM-EDX analysis, atmospheric particles were classified according to their morphology – Soot, spherical, biological and minerals- and according to their elemental composition – particles with sulfur, chlorine and iron content. Finally, toxic effects were observed by exposure C. elegans organisms to PM10 and PM2.5, altering physiological parameters (e.g growth and reproduction) and promoting antioxidant mechanisms responses, as a result of oxidative stress generated by compounds present in the PM.

[pt] Este trabalho tem como finalidade determinar a concentração em massa, caracterizar quimicamente as espécies presentes e identificar as possíveis fontes das amostras de material particulado (MP10 e MP2,5) coletados em locais com (Gericinó, Lagoa e Copacabana) e sem (Botafogo) a influência dos Jogos Olímpicos, no Rio de Janeiro. As amostras de MP foram disponibilizadas pelo Instituto Estadual do Ambiente (INEA) referente ao ano de 2016, sendo os meses de julho a setembro considerados como a temporada Olímpica. A caracterização química das amostras foi realizada por ICP-MS e Cromatografia de Íons (CI). Durante a temporada Olímpica, em 2016, foram reduzidos cerca de 26 porcento de MP10, quando comparados aos anos anteriores na mesma época do ano, por outro lado, o MP2,5 não foi reduzido. De todos os íons solúveis em água analisados, as maiores concentrações foram obtidas para o NO3-, SO4 2- e Na positivo nas duas frações de MP. As altas concentrações dos íons NO3 - e SO4 2- sugerem a presença de fontes antropogênicas. A partir do cálculo de nss (non-sea salt) foi possível observar que os íons Ca2 positivo, K positivo e SO4 2- tiveram uma contribuição marinha baixa. Os metais Fe, Cu e Ti foram os majoritários em todas as amostras nas duas frações de MP, enquanto que elementos como Mn, Pb, V e Ni foram detectados como minoritários. Correlações acima de 0,90 foram observadas entre Ti-Mn e Ti-Fe, sugerindo emissões de ressuspensão do solo e fortes correlações entre V-Ni e VPb mostram a influencia veicular como principal fonte. Finalmente, foi possível observar que houve uma influência dos Jogos Olímpicos na concentração em massa e de algumas espécies no MP2,5, enquanto que no MP10 não foi observada qualquer correlação. / [en] The main aim of this work was to determine the mass concentration, chemically characterize the species present and identify the possible sources of samples of particulate matter (PM10 e PM2.5) collected at sites with (Gericinó, Lagoa e Copacabana) and without (Botafogo) the influence of the Olympic Games in Rio de Janeiro. The PM samples were obtained from the Instituto Estadual do Ambiente (INEA) relative to the year 2016. The Olympic seasons considered were July to September of 2016. The chemical characterization of the samples was performed by ICP-MS and ion chromatography (IC). PM10 during the Olympic period were reduced 26 percent, when compared to previous years at the same time of the year. On the other hand, PM2.5 was not reduced during the Olympic period. Of all the water-soluble ions analyzed, the highest concentrations were obtained for NO3-, SO42- and Na plus in both fractions of PM. High concentrations of NO3 - and SO4 2- suggest the presence of anthropogenic sources. From calculation of non-sea salt was possible to observe that Ca2 plus, K plus and SO4 2- had a low marine contribution. Fe, Cu and Ti were the majority metals of all samples in both fractions of PM, while Mn, Pb, V and Ni were detected as minorities. Correlations above 0.90 are observed between Ti-Mn and Ti-Fe, suggested soil resuspension emissions. Strong correlations coefficients between V-Ni and V-Pb show the vehicular influence as the main source. Finally, it was possible to observe an influence of the Olympic Games in mass concentration and some species in PM2.5, while in PM10 no correlation was observed.

[pt] As partículas finas (PM2.5) são um dos principais poluentes atmosféricos associados a problemas de saúde. Estas partículas penetram no sistema respiratório, carreando desde metais traços a substâncias orgânicas. Apesar disso, a legislação ambiental brasileira ainda não tem estabelecido padrões para este poluente. Entretanto, Agencia Ambiental dos Estados Unidos (US.EPA) já tem adotado limites para exposições de curto (25 (micro)g m-3/diário) e longo (15 (micro)g m-3/anual) prazo. Esta tese teve quatro principais objetivos: (1) investigar a relação das condições meteorológicas, sazonalidade e bacias aéreas sobre as concentrações de PM2.5 na atmosfera; (2) avaliar modelos de previsão de qualidade do ar inovadores para estimar concentração de PM2.5 em locais com diferentes fontes de emissão; (3) validar método de extração e determinação pseudototal de metais traços presentes no material particulado, com espectrômetro de emissão ótica por plasma indutivamente acoplado (ICP-OES) de acordo com critérios estabelecidos pelo INMETRO; (4) quantificar carbono orgânico e metais traços presentes no material particulado fino para entender melhor como a atmosfera do estado do Rio de Janeiro tem sido afetada, devido aos vários tipos de emissão e condições meteorológicas. Amostradores de grandes volumes coletaram todas as amostras de PM2.5. Estes amostradores foram operados por 24 h, a cada seis dias, em locais com diferentes fontes de emissão (industrial, veicular, poeira do solo, etc.), no estado do Rio de Janeiro. As amostras foram coletadas pelo Instituto Estadual do Ambiente (INEA), no período de janeiro/11 até dezembro/13. Variáveis meteorológicas próximas (d(menor que)2 km) aos pontos de monitoramento de PM2.5 também foram obtidas na mesma frequência e período de amostragem. Em relação a este estudo, quatro resultados podem ser destacados. O primeiro, as concentrações médias diárias de PM2.5 variaram de 1-65 (micro)g m-3, ultrapassando em alguns pontos os limites adotados pela US.EPA. Estes resultados mostraram que concentrações de PM2.5 no RJ não é influenciada, em expressão, pela sazonalidade. Além disso, foi observado que as bacias aéreas definidas no Rio de Janeiro não têm sido confirmadas, e os locais mostraram uma semelhança de comportamento em função da sua fonte de emissão. O segundo, a aplicação do modelo Holt-Winters para previsão de PM2.5 simulou melhor a zona industrial, com RMSE (raiz do erro quadrático médio) entre 5,8-14,9 (micro)g m-3. Em contrapartida, a rede neural artificial associada a variáveis meteorológicas estimou melhor os resultados das zonas urbanas e rurais, com RMSE entre 4,2-9,3 (micro)g m-3. O terceiro, o método de extração e determinação pseudototal de metais por ICP-OES atendeu aos critérios de validação estabelecidos pelo INMETRO. Além disso, mostrou-se ser equivalente ao método US.EPA IO-3.1. Finalmente, as concentrações de carbono orgânico solúvel em água variaram de 0,8-4,9 (micro)g m-3. Os principais metais determinados foram: Na (5,8-13,6 (micro)g m-3), Al (1,6-6,7 (micro)g m-3) e Zn (1,9-6,6 (micro)g m-3). Foi verificado também que os fenômenos meteorológicos de superfície aumentam em 30 por cento a explicação da variância do modelo receptor (PCA), quando adicionados aos dados das substâncias químicas analisadas do PM2.5. Contudo, é crucial a aplicação de ferramentas quimiométricas para ajudar na caracterização e estimava das concentrações de poluentes atmosféricos. / [en] Fine particulate matters (PM2.5) are one of the primary air pollutants associated with health problems. These particles penetrate in the respiratory system, loading from trace metals to organic compounds. Neverthelere4ss, the Brazilian environmental legislation has not yet established standards for this pollutant. However, the US Environmental Agency (US.EPA) has already adopted limits for short-term (25 (micro)g m-3/daily) and long-term (15 (micro)g m-3/annual) exposures. This thesis had four main objectives: (1) to investigate the relation of weather conditions, seasonality and air basins on PM2.5 concentrations in the atmosphere; (2) to evaluate innovative air quality forecast models to estimate PM2.5 concentration in sites with different emission sources; (3) to validate method to extract and pseudo total determinate trace metals present in the particulate matter by inductively coupled plasma optical emission spectrometer (ICP-OES) according to criteria established by INMETRO; (4) to quantify organic carbon and trace metals present in fine particulate matter to better understand how the Rio de Janeiro State (RJ) atmosphere has been affected due to the various types of emission and weather conditions. High volumes samplers PM2.5 collected all PM2.5 samples. These samplers were operated for 24 h, every six days, in places with different emission sources (industrial, vehicular, soil dust, et caetera), in the Rio de Janeiro State. The samples were collected by the State Environmental Institute (INEA) during the period from January/2011 still December/2013. Meteorological variables nearby (d(less than)2 km) to PM2.5 monitoring points were also obtained at the same frequency and sampling period. Regarding this study, four results can be highlighted. The first one, the PM2.5 dailly concentrations average ranged from 1-65 (micro)g m-3, exceeding in some sites the limits adopted by US.EPA. These results showed that PM2.5 concentrations in RJ is not influenced, in expression, by the seasonality. In addition, it was observed that the defined RJ air basins have not been confirmed, and the local showed a similar performance according to their emission sources. The second one, the application of the Holt-Winters model for PM2.5 forecast simulated best industrial zone, with RMSE (root mean square error) between 5.8 to 14.9 (micro)g m-3. On the others hand, the artificial neural network associated with meteorological variables estimated best results from urban and rural areas, with RMSE between 4.2 to 9.3 (micro)g m-3. The third one, the method to extract and determine pseudo total metals by ICP-OES followed the validation criteria established by INMETRO. Furthermore, it was shown to be equivalent to US.EPA IO-3.1 method. Finally, the water-soluble organic carbon concentrations ranged from 0.8 to 4.9 (micro)g m-3. The principal metals determined were: Na (5.8-13.6 (micro)g m-3), Al (1.6-6.7 (micro)g m-3) and Zn (1.9-6.6 (micro)g m-3). It was also found that the surface meteorological phenomena increase at 30 percent the explicated variance of the receiver model (PCA) when added to PM2.5 chemical analysis data. Therefore, it is crucial the application of chemometric tools to help in the characterization and estimated air pollutant concentrations.

Depuis la révolution industrielle en Europe (XIXe siècle), les nombreuses activités anthropiques ont provoqué des changements environnementaux globaux considérables. La composition de l'atmosphère terrestre en particulier, a été fortement modifiée par l'émission de polluants gazeux et particulaires. Actuellement, l'industrie métallurgique de seconde fusion contribue de façon significative aux émissions atmosphériques de métaux. C'est pourquoi ce travail de thèse s'est focalisé sur l'étude des transferts et impacts sur les sols, les végétaux et l'homme, des particules émises par le procédé de recyclage du plomb en relation avec leurs propriétés physico-chimiques. Trois sources principales d'émissions de particules ont été identifiées dans le procédé du recyclage du plomb et caractérisées en vue d'étudier les impacts potentiels sur les cibles végétales et humaines. Les particules échantillonnées (postes de travail et émissions canalisées) et ségréguées en fonction de leur taille (PMtot, PM10 et PM2,5) sont principalement composées de métaux (jusqu'à 50% en masse de la composition totale en métaux de transition, alcalins et alcalino-terreux), avec une majeur partie de plomb (25-45 %). Les spéciations majoritaires du plomb sont la galène (PbS), le sulfate du plomb (PbSO4) ou dérivés (xPbO.PbSO4 x=1,2 ou 3). L'étude du transfert des particules dans le sytème sol-plante a montré que, lorsque la taille des particules de process présentes dans le sol diminue (de 10µm à 2.5µm), le tranfert du plomb vers les parties aériennes des salades augmente de 20%. Le transfert foliaire de plomb issu des particules de process a été mis en évidence et des mécanismes d'absorption.ont été proposés. Enfin, l'étude exploratoire des particules riches en plomb sur la santé humaine a permis de montrer que la diminition de la taille des particules ingérées augmentait la bioaccessibilité gastrique du plomb. Dans le cas de l'inhalation, il a été démontré que les particules n'induisaient pas de cytotoxicité jusqu'à 50µg/cm2, mais provoquaient une réponse inflammatoire dose-dépendante des cellules épithéliales pulmonaires. / Since the Industrial Revolution in Europe (XIXe century), human activities have caused significant global environmental changes. The composition of the atmosphere in particular, has been extensively modified by the emission of gaseous and particulate pollutants. Currently, the secondary (or recycling) metallurgical industry contributes significantly to air emissions of metals. Therefore, this thesis focused on the study of transfers and impacts on soils, plants and humans, of particles from the recycling process of lead in relation to their physicochemical properties. Three main sources of particulate emissions have been identified in the process of recycling lead and characterized, to study the potential impacts on plant and human targets. The particles sampled (workstations and channelled emissions), and segregated according to their size (PMtot, PM10 and PM2, 5), are mainly composed of metals (up to 50% by weight of the total composition in transition metals alkaline and alkaline), with a major part of lead (25-45%). The major speciations of lead are galena (PbS), lead sulfate (PbSO4) or derivatives (xPbO.PbSO4 x = 1,2 or 3). The study of transfer of particles in the soil-plant system has shown that when the particle size of processes in the soil decreases (from 2.5µm to 10µm), the transfer of lead into the aerial parts of lettuce growing at 20 %. The uptake of lead from particles process by leaves has been demonstrated and mechanisms of absorption have been proposed. Finally, exploratory study of lead-rich particles on human health has shown that diminution of the size of particles ingested increased gastric bioaccessibility of lead. In the case of inhalation, it was shown that the particles did not induce cytotoxicity up 50µg/cm2, but caused a dose-dependent inflammatory response of lung epithelial cells