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

[pt] O objetivo deste estudo foi determinar a concentração de metais, compostos orgânicos e inorgânicos por suspensão aquosa e análise dos metais por abertura ácida presentes nas amostras de PM10 coletadas em áreas urbanas, industrial e rural da Região Metropolitana do Rio de Janeiro. A concentração de PM10 foi determinada por análise gravimétrica. Espécies inorgânicas e orgânicas presentes nos extratos aquosos foram determinadas por cromatografia de íons e carbono orgânico total (TOC). Os extratos ácidos, e também os aquosos, foram analisados por ICP-MS (espectrometria de massa com plasma indutivamente acoplado) e por ICP OES (espectrometria de emissão óptica com plasma indutivamente acoplado) para determinar a concentração de metais. As correlações entre as concentrações de PM10 e de metais foram avaliadas, considerando os dados meteorológicos para cada ponto de coleta e origem das massas de ar. Os resultados mostraram que as concentrações médias de PM10 foram de 36 micrograma m-3 na área rural, 50 micrograma m-3 na área urbana e 74 micrograma m-3 na área industrial. A concentração de PM10 medida na área industrial ultrapassou, em geral, o limite estabelecido pela resolução CONAMA, de 50 micrograma m-3. O teor de metais apresentou maior concentração na área industrial, sendo predominantes ferro, zinco, alumínio, titânio, manganês, cromo, níquel, cádmio e chumbo. Na área de maior tráfego, foi detectada a maior concentração de cobre e vanádio. As espécies iônicas foram maiores na área urbana, devido à proximidade do oceano. Na área rural, menores concentrações de espécies antropogênicas, como sulfato, nitrato e alguns metais (Pb, Cr, V e Ni) foram medidas. Assim, as concentrações das espécies estudadas são influenciadas pelas características locais. Porém, também foi observado a influencia do transporte de poluentes de longa distância, como queimadas e poeiras dos desertos do continente africano. Os percentuais dos extratos ácido/aquoso demonstraram que os metais extraídos de forma mais eficiente foram V e Ni (maior que 45 porcento), enquanto que os menos extraídos foram Al e Fe (menor que 3 porcento), conforme o esperado. A fração aquosa é importante para avaliar a biodisponibilidade de metais associados a danos à saúde. / [en] The scope of this study was to measure the concentration of metals and organic and inorganic anions in aqueous and acid extracts of PM10 samples collected in urban, industrial and rural zones of Rio de Janeiro. PM10 concentration was determined by gravimetric analysis and the organic and inorganic species in the aqueous extracts were determined by ion chromatography and total organic carbon (TOC). The aqueous and acid extracts were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and by ICP OES (inductively coupled plasma optical emission spectrometry), in order to determine metal content. Correlations between PM10 and metal concentrations were evaluated, considering meteorological data for each site. Results showed that the average PM10 concentrations were 36 microgram m-3; 50 microgram m-3 and 74 microgram m-3 at the rural, downtown and industrial sites, respectively. The measured PM10 concentration in the industrial site exceeded the limit allowed by the Brazilian law, which is 50 microgram m-3. While industrial area had the highest concentrations of metals, such as Fe, Zn, Al, Ti, Mn, Cr, Ni, Cd and Pb, the highest concentrations of Cu and V were found in areas with higher traffic densities. Ionic species had higher concentrations in the urban site due to the proximity to the ocean. The lowest concentrations of species from anthropogenic sources, such as sulfate, nitrate and some metals (Pb, Cr, V and Ni) were measured in the rural area. Hence, studied species concentrations are influenced by site locations, but the influence by the transportation of long distance pollutants, such as biomass burning and dust from African deserts was also observed. The acid/aqueous percentiles showed that the most efficiently extracted metals in the aqueous phase were V and Ni (greater than 45 percent) while the less efficiently extracted were Al and Fe (less than 3 percent), as expected. The aqueous fraction is important to evaluate the bioavailability of metals that are associated to damage to the human health.

Dans le Sud-Est de la France, le département des Alpes-Maritimes, singulier du fait de son relief contrasté, est soumis au jeu des brises et inversions thermiques nocturnes. L’agglomération littorale contribue aux émissions de particules qui sont un des polluants les plus nocifs pour la santé humaine. La pollution de l’air n’est évidemment pas répartie de manière homogène dans le temps et dans l’espace. Les topoclimats sont un protagoniste de la pollution de l’air au sein de cet espace littoral montagneux. La problématique centrale de cette thèse consiste donc à comprendre pourquoi et comment les topoclimats influencent la variabilité spatio-temporelle des concentrations de particules dans le sud-ouest du département, tout en considérant qu’ils ne sont pas seuls à expliquer les concentrations. Afin de répondre à cette question, plusieurs objectifs privilégiant les mesures de terrain, et la modélisation ont été fixés :- exploiter des données de concentrations de particules et de variables météorologiques acquises à l’aide de plusieurs appareils de mesures, de manière fixe et itinérante, en plusieurs endroits et à différentes échelles spatio-temporelles ;- caractériser les écoulements d’air à faible altitude à l’aide de ballons équilibrés (dits CLB) et les mettre en relation avec les niveaux de PM10 mesurés ; - caractériser chimiquement les PM10 pour évaluer la contribution des principales sources d’émissions ;- tester la capacité d’un logiciel de dispersion atmosphérique à simuler en relief contrasté les effets des topoclimats sur la variabilité spatio-temporelle des PM10.L’influence des topoclimats sur la pollution de l’air particulaire a été établie. / In the Southeastern of France, the department of the Alpes-Maritimes is singular by contrasting terrain and is submitted to breezes and temperature inversions. The coastal urbanization contributes to the particulate matters emissions that are part of the most harmful substances to human health. Air pollution is not spread heavenly in time and space, of course. Topoclimates are one of the protagonists of air contamination within this mountainous coastal area. The focus of this thesis work is to understand why and how topoclimates have impact on the spatio-temporal variability of particle concentrations in the Southwest of the department, while considering that they are not alone to explain the concentrations. The researcher identified several objectives to answer this question and he gave priority to ground measures and modeling: - To explore data about the particulate matters and meteorological characteristics that were collected through the use of several measuring tools, in a fixed and travelling way, in different places and on various spatio-temporal scales;- To identify and characterize air flows at low altitude with CLB (Constant Level Balloon) and cross compare them with the measured levels PM10; - To chemically analyse PM10 to assess the contribution of the main sources of emission;- To test the capacity of an atmospheric dispersion software to simulate the impact of topoclimates on the spatio-temporal variety of PM10 on mountainous and uneven landscapes.The influence of topoclimates on the air pollution has been scientifically established.

Non-exhaust PM10 is an issue in the urban environment linked to health issues. Emissions of non-exhaust PM10 is relatable to pavement properties. Also of importance is resuspension of road dust stored from surfaces. This depends on the traffic and metrological conditions. Given this, the purpose of the thesis was to give an overview limited to Sweden and the Nordic countries regarding non-exhaust PM10 emissions and road dust. The overview includes how particles are related to human health. Also included is the principle of how particles are emitted from road surface and tyre interaction, both directly and through resuspension of road dust. This thesis also includes an overview of how the use of studded tyres impact on asphalt surfacings and how the properties of the materials used impact on the abrasion wear. This is then linked to the emissions of non-exhaust particles. Further described is how measurements can be done of ambient particles and road dust, followed on two major models for road abrasion wear and non-exhaust PM prediction. Also included is how road operation, e.g. traction sanding and dust binding, influence the particle emissions together with other options to reduce the emissions through, e.g. limiting the use of studded tyres. One special issue discussed in this thesis is the lack of holistic view regarding the environmental problems in the urban environment with focus on particle emissions and road noise emissions, both from the road surface and tyre interaction. Currently the most problematic issue is prioritized and the resulting solution to that specific problem might increase other problems. This thesis shows that much knowledge is available regarding non-exhaust PM10 emissions and road dust, but also that several knowledge gaps exists. Several suggestions on further studies is given together with a brief overview on the continued work forward from this thesis. / Icke-avgasemissioner av PM10 är ett problem i urbana miljöer länkat till flera hälsoaspekter. Dessa emissioner kan relateras till beläggningars egenskaper. Även resuspension av vägdamm från ytor är av betydelse och beror på både trafiken och meterologin. Baserat på detta är syftet med denna avhandling att ge en översikt kring icke-avgas PM10 emissioner och vägdamm, begränsat till Sverige och de övriga nordiska länderna. Denna översikt inkluderar hur partiklar relaterar till människans hälsa. Annat som inkluderas är hur partiklarna emitteras från vägyta-däckinteraktionen, både direkt och genom resuspension av vägdamm. Avhandlingen inkluderar även en översikt kring hur användandet av dubbdäck inverkar på vägbeläggningar och hur dess egenskaper inverkar på nötningsslitage. Detta länkas därefter till partikelemissioner. Vidare beskrivs även hur mätningar kan genomföras av partiklar samt vägdamm vilket följs upp av beskrivningar kring två större modeller kring prediktion av nötningsslitage och prediktion av icke-avgasemissioner. Även hur driftåtgärder inverkar på emissionerna tillsammans med alternativ för att minska emissionerna tas upp. Ett särskilt problem som tas upp i avhandlingen är bristen på helhetssyn beträffande miljöproblem i den urbana miljön med fokus på partikel- och bulleremissioner från vägyta-däckinteraktionen. För närvarande brukar det värsta problemet prioriteras och lösningen till det detta problem kan i sin tur medföra att andra miljöproblem istället förvärras. Denna avhandling visar på att mycket kunskap existerar kring icke-avgasemissioner av PM10 och kring vägdamm, men även att flertalet kunskapsluckor existerar. Flertalet förslag på vidare studier ges tillsammans med en överblick kring det fortsatta arbetet. / <p>QC 20180202</p>

[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.

Atualmente a poluição do ar é um assunto relevante para a população e para os órgãos governamentais, em razão dos efeitos na saúde e no clima. Tão importante quanto a quantidade de material particulado na atmosfera, é também, a sua composição. O objetivo deste estudo foi determinar a concentração de MP10 e espécies orgânicas e inorgânicas em amostras coletadas em ambientes internos e externos de três escolas do Estado de São Paulo, para avaliar a qualidade do ar. As concentrações de MP10 foram determinadas por gravimetria, depois foram submetidas à extração, rotaevaporação, fracionamento em coluna, e os compostos foram determinados através da cromatografia gasosa acoplada ao espectrômetro de massas; o carbono elementar e o carbono orgânico foram determinados pelo método termo-óptico, pelo sistema desenvolvido na Universidade de Aveiro; o carbono grafítico foi determinado por refletometria e os metais por EDXRF e algumas amostras foram analisadas por cromatografia de íons, no instituto de Astronomia, Geofísica e Ciências Atmosféricas da Universidade de São Paulo. As amostras de MP10 foram coletadas nos seguintes sítios: (i) escola de Aplicação, dentro da Cidade Universitária, de área urbana que sofre influência de via de grande movimento de veículos e da vegetação local; (ii) escola Madalena de Almeida do Cais, na cidade de Nova Granada localizada a cerca de 475 quilômetros da cidade de São Paulo, com baixa população e poucos veículos; (iii) escola particular em bairro residencial da zona oeste, que sofre a influência de avenida com grande fluxo de veículos. Os resultados indicaram que a concentração do MP10 foi mais alta em ambiente interno que externo na escola dentro da USP. Na escola particular, a concentração mediana apontou que o ambiente externo apresentou concentração de MP10 superior ao ambiente interno. Para os hidrocarbonetos policíclicos aromáticos, observou-se que tanto na escola do interior quanto na escola do campus, houve maior concentração em ambiente interno, e alguns de maior peso molecular, atribuídos às emissões veiculares, foram mais altos em ambiente externo. As razões diagnósticas indicaram queima de combustíveis fósseis ao redor dos sítios amostrados. As amostras coletadas nas escolas apresentaram baixos riscos à saúde. Os compostos 2- metilantraquinona e benzo(a)antraceno-7,12-diona foram encontrados nas amostras, denotando a influência da exaustão veicular. A fração carbonácea (EC + OC) apresentou maior concentração em ambiente externo, e a razão OC/EC para o ambiente externo apontou para a queima de biomassa. A fonte de carbono grafítico corroborou a influência do tráfego. Para a maioria dos elementos, com exceção do cromo, manganês e ferro, as concentrações obtidas em ambiente interno foram as mais altas, majoritariamente oriundos da ressuspensão do solo. O cromo e o manganês estão relacionados com a emissão dos veículos que utilizaram a mistura gasolina e etanol; o ferro, com a crosta terrestre. Para os íons, a concentração média para ambientes externos apresentou a seguinte tendência: SO42- > NO3- > Ca2+ > NH4+ > Na+ > K+> Mg2+ > Cl- e para ambientes internos foi Ca2+ > SO42- > NO3- > Na+ > NH4+ > K+ > Cl- > Mg2+ > F-. A maioria das espécies apresentou a influência da ressuspensão do solo; o nitrato e o sulfato foram atribuídos à emissão veicular, e o cátion amônio foi formado por reações a partir da degradação da matéria orgânica e dos processos que ocorrem nos catalisadores veiculares. / Nowadays, air pollution is a relevant issue for people and government agencies because of the health and climate effects. As important as the amount of particulate matter in the atmosphere, is also, its composition. The object of this study was to determine the concentration of PM10 and organic and inorganic species in samples collected in indoor and outdoor environment of three schools in the State of São Paulo, to evaluate air quality. The concentrations of PM10 were determined by gravimetry, then the samples were subjected to extraction, rotary evaporation, column fractionation, and the compounds were determined by gas chromatography coupled to the mass spectrometer; elemental carbon and organic carbon were determined by the thermooptical method, by the system developed at the University of Aveiro; the graphitic carbon was determined by reflectometry and the metals by EDXRF and some samples were analyzed by ion chromatography, at the Institute of Astronomy, Geophysics and Atmospheric Sciences of the University of São Paulo. PM10 samples were collected at the following sites: (i) school of Application, within the University City, an urban area that is influenced by a large vehicular route and local vegetation; (ii) Madalena de Almeida do Cais school, in the city of Nova Granada located about 475 kilometers from the city of São Paulo, with low population and few vehicles; (iii) private school in a residential neighborhood in the western zone, which suffers the influence of avenue with a large flow of vehicles. The results indicated that PM10 concentration was higher in indoor than outdoor environment in the school within USP. In the private school, the median concentration indicated that the outdoor environment presented a concentration of PM10 higher than the indoor environment. For the polycyclic aromatic hydrocarbons, it was observed that both countryside school and campus school, a higher concentration of compounds in the indoor environment was found, only some high molecular weight compounds, attributed to vehicular emissions, were higher in the external environment. Diagnostic ratios indicated the burning of fossil fuels around the sites sampled. Samples collected in schools presented low health risks. 2-methylanthraquinone and benzo(a)anthracene-7,12-dione were found in the samples, denoting the influence of vehicle exhaust. The carbonaceous fraction (EC + OC) presented higher concentration in the outdoor environment and OC/EC ratio for the outdoor environment pointed to biomass burning. The graphite carbon source corroborated the traffic influence. For most of the elements, except for chromium, manganese and iron, the concentrations obtained in indoor environment were the highest, mainly derived from soil resuspension. Chromium and manganese are related to the emission of the vehicles that used the mixture gasoline and ethanol; iron is from the terrestrial crust. For the ions, the average concentration for outdoor environments presented the following trend: SO42-> NO3-> Na+> NH4+> Na+> K+> Mg2+> Cl- and for indoor environments was Ca2+> SO42-> NO3-> Na+ > NH4+> K+ > Cl-> Mg2+> F-. Most of the species showed the influence of soil resuspension; nitrate and sulfate were attributed to human activities, i. e., vehicular emission, and, the ammonium cation was formed by reactions from the degradation of the organic matter and the processes that occur in vehicular catalysts.

Atualmente a poluição do ar é um assunto relevante para a população e para os órgãos governamentais, em razão dos efeitos na saúde e no clima. Tão importante quanto a quantidade de material particulado na atmosfera, é também, a sua composição. O objetivo deste estudo foi determinar a concentração de MP10 e espécies orgânicas e inorgânicas em amostras coletadas em ambientes internos e externos de três escolas do Estado de São Paulo, para avaliar a qualidade do ar. As concentrações de MP10 foram determinadas por gravimetria, depois foram submetidas à extração, rotaevaporação, fracionamento em coluna, e os compostos foram determinados através da cromatografia gasosa acoplada ao espectrômetro de massas; o carbono elementar e o carbono orgânico foram determinados pelo método termo-óptico, pelo sistema desenvolvido na Universidade de Aveiro; o carbono grafítico foi determinado por refletometria e os metais por EDXRF e algumas amostras foram analisadas por cromatografia de íons, no instituto de Astronomia, Geofísica e Ciências Atmosféricas da Universidade de São Paulo. As amostras de MP10 foram coletadas nos seguintes sítios: (i) escola de Aplicação, dentro da Cidade Universitária, de área urbana que sofre influência de via de grande movimento de veículos e da vegetação local; (ii) escola Madalena de Almeida do Cais, na cidade de Nova Granada localizada a cerca de 475 quilômetros da cidade de São Paulo, com baixa população e poucos veículos; (iii) escola particular em bairro residencial da zona oeste, que sofre a influência de avenida com grande fluxo de veículos. Os resultados indicaram que a concentração do MP10 foi mais alta em ambiente interno que externo na escola dentro da USP. Na escola particular, a concentração mediana apontou que o ambiente externo apresentou concentração de MP10 superior ao ambiente interno. Para os hidrocarbonetos policíclicos aromáticos, observou-se que tanto na escola do interior quanto na escola do campus, houve maior concentração em ambiente interno, e alguns de maior peso molecular, atribuídos às emissões veiculares, foram mais altos em ambiente externo. As razões diagnósticas indicaram queima de combustíveis fósseis ao redor dos sítios amostrados. As amostras coletadas nas escolas apresentaram baixos riscos à saúde. Os compostos 2- metilantraquinona e benzo(a)antraceno-7,12-diona foram encontrados nas amostras, denotando a influência da exaustão veicular. A fração carbonácea (EC + OC) apresentou maior concentração em ambiente externo, e a razão OC/EC para o ambiente externo apontou para a queima de biomassa. A fonte de carbono grafítico corroborou a influência do tráfego. Para a maioria dos elementos, com exceção do cromo, manganês e ferro, as concentrações obtidas em ambiente interno foram as mais altas, majoritariamente oriundos da ressuspensão do solo. O cromo e o manganês estão relacionados com a emissão dos veículos que utilizaram a mistura gasolina e etanol; o ferro, com a crosta terrestre. Para os íons, a concentração média para ambientes externos apresentou a seguinte tendência: SO42- > NO3- > Ca2+ > NH4+ > Na+ > K+> Mg2+ > Cl- e para ambientes internos foi Ca2+ > SO42- > NO3- > Na+ > NH4+ > K+ > Cl- > Mg2+ > F-. A maioria das espécies apresentou a influência da ressuspensão do solo; o nitrato e o sulfato foram atribuídos à emissão veicular, e o cátion amônio foi formado por reações a partir da degradação da matéria orgânica e dos processos que ocorrem nos catalisadores veiculares. / Nowadays, air pollution is a relevant issue for people and government agencies because of the health and climate effects. As important as the amount of particulate matter in the atmosphere, is also, its composition. The object of this study was to determine the concentration of PM10 and organic and inorganic species in samples collected in indoor and outdoor environment of three schools in the State of São Paulo, to evaluate air quality. The concentrations of PM10 were determined by gravimetry, then the samples were subjected to extraction, rotary evaporation, column fractionation, and the compounds were determined by gas chromatography coupled to the mass spectrometer; elemental carbon and organic carbon were determined by the thermooptical method, by the system developed at the University of Aveiro; the graphitic carbon was determined by reflectometry and the metals by EDXRF and some samples were analyzed by ion chromatography, at the Institute of Astronomy, Geophysics and Atmospheric Sciences of the University of São Paulo. PM10 samples were collected at the following sites: (i) school of Application, within the University City, an urban area that is influenced by a large vehicular route and local vegetation; (ii) Madalena de Almeida do Cais school, in the city of Nova Granada located about 475 kilometers from the city of São Paulo, with low population and few vehicles; (iii) private school in a residential neighborhood in the western zone, which suffers the influence of avenue with a large flow of vehicles. The results indicated that PM10 concentration was higher in indoor than outdoor environment in the school within USP. In the private school, the median concentration indicated that the outdoor environment presented a concentration of PM10 higher than the indoor environment. For the polycyclic aromatic hydrocarbons, it was observed that both countryside school and campus school, a higher concentration of compounds in the indoor environment was found, only some high molecular weight compounds, attributed to vehicular emissions, were higher in the external environment. Diagnostic ratios indicated the burning of fossil fuels around the sites sampled. Samples collected in schools presented low health risks. 2-methylanthraquinone and benzo(a)anthracene-7,12-dione were found in the samples, denoting the influence of vehicle exhaust. The carbonaceous fraction (EC + OC) presented higher concentration in the outdoor environment and OC/EC ratio for the outdoor environment pointed to biomass burning. The graphite carbon source corroborated the traffic influence. For most of the elements, except for chromium, manganese and iron, the concentrations obtained in indoor environment were the highest, mainly derived from soil resuspension. Chromium and manganese are related to the emission of the vehicles that used the mixture gasoline and ethanol; iron is from the terrestrial crust. For the ions, the average concentration for outdoor environments presented the following trend: SO42-> NO3-> Na+> NH4+> Na+> K+> Mg2+> Cl- and for indoor environments was Ca2+> SO42-> NO3-> Na+ > NH4+> K+ > Cl-> Mg2+> F-. Most of the species showed the influence of soil resuspension; nitrate and sulfate were attributed to human activities, i. e., vehicular emission, and, the ammonium cation was formed by reactions from the degradation of the organic matter and the processes that occur in vehicular catalysts.

This study is focused on the identification of the sources and processes affecting levels and composition of PM10 and PM2.5 from air quality monitoring networks in Eastern Spain. This is a multidisciplinary study. Time series of TSP and PM10 recorded from 1996 to 2000 are interpreted to assess the role of local, regional and distant sources in PM levels in this region. To this is end, the influence of the meteorology on PM levels recorded at nineteen rural, urban and industrial monitoring stations is studied by means of synoptic charts, back-trajectories and local meteorological variables. The impact of African dust transport on PM levels is investigated by means of simulations in the SKIRON forecast system and by TOMS satellite observations. Moreover, a chemical characterisation of PM10, PM2.5 and TSP size segregated fractions and a daily PM10 and PM2.5 source apportionment by two receptor modelling techniques are performed. For this purpose, 24-hour samples of PM10 were collected for 16, 12 and 5 months at rural, urban and industrial sites, respectively. PM2.5 was sampled at the urban site simultaneously with PM10. The results showed that day-to-day variations in PM levels are highly influenced by the meteorology. From March to October, PM levels at rural, urban and industrial sites vary as a function of the concatenation of Atlantic air mass advections (Atlantic episodes with low PM levels) and regional circulations (Regional events with high PM and O3 levels) which induce the PM transport from urban/industrial to rural sites and the ageing of polluted air masses in the Western Mediterranean. From November to February low PM levels are recorded at rural sites, and variations in PM levels at urban/industrial sites are governed by the successive occurrence of Atlantic episodes and Local urban/industrial pollution events (with high PM, NOx and CO levels). The African dust events mainly occur from January to October and induce very high PM levels in all sites. As a result of the frequency and intensity of the Regional episodes, PM levels at rural sites undergo a seasonal evolution with a summer maximum. The difference between PM levels at urban and rural sites presents an autumn-winter maximum owing to the occurrence of intensive Local urban pollution events. The meteorological context in which the aforementioned episodes occur is discussed, with special emphasis on the synoptic scenarios giving rise to the African dust outbreaks in the different seasons. Levels of PM components at the different study sites were compared. The seasonal evolution and the grain size distribution of these components was studied and the form of occurrence was determined. The chemical characterisation shows that high levels of natural mineral dust components (e.g. Al, Fe, Mg, Ti, Sr, Ca) are simultaneously recorded in PM10 and PM2.5 at all sites during African episodes. Other interesting findings are: 1) a marked seasonal evolution of nitrate levels and grain size distribution due to the occurrence of ammonium-nitrate in autumn-winter, 2) an excess of Na with respect to the Na/Cl marine ratio in summer owing to reactions of acids with sea salt, and 3) high background levels of ammonium-sulphate in summer. Moreover, the levels of elemental, organic and mineral carbon were determined. At the rural site, the PM10 annual mean reaches 22µg/m3, the main contributions being secondary particles from industrial emissions (27% of PM10), vehicle exhausts (14-23%), natural mineral dust (23%) and sea spray (5-9%). At the urban kerbside station, the PM10 annual mean reaches 49µg/m3, the main contributions being vehicle exhausts (35-45% of PM10), secondary particles from industrial emissions (24-31%), natural + road dust (25%) and sea spray (4-6%). At the urban kerbside station, the PM2.5 annual mean reaches 34µg/m3, the main contributions being vehicle exhausts (41-53% of PM2.5), secondary particles from industrial emissions (29-35%) and mineral dust (9-11%). These results have important implications for the implementation of the PM10 EU standards. The natural load in ambient PM10 levels in Eastern Spain accounts for 30-40% of the 2010 EU annual PM10 limit value (20µg/m3). In this region it will not be easy to meet this limit value given that the annual PM10 levels are in the range 17-20µg/m3 at rural, 30-45µg/m3 at urban and 45-60µg/m3 at industrial sites. The high background levels of PM10 in this region are favoured by the specific orographic and meteorological context of the Mediterranean and by the high load of mineral dust caused by the soil re-suspension and the frequent occurrence of African dust events. At rural sites, 2-5 exceedances of the EU daily PM10 limit value (50µg/m3) are recorded every year during African dust outbreaks. On average, 15 African induced and 40-80 non-African induced exceedances of the EU daily PM10 limit value are recorded every year at the urban kerbside stations. The parameter selected for PM monitoring is a key factor. Most of the PM species resulting from combustion and vehicle exhaust emissions have a fine size distribution (<2.5µm), with exception of nitrate in summer, whereas sea spray and mineral dust present a coarse size distribution. The interference of African dust in the PM monitoring is significantly reduced when PM2.5 instead of PM10 is monitored. Natural mineral dust concentrations during African episodes are in the ranges 20-30µg/m3 in PM10 and 10-15µg/m3 in PM2.5. However, PM2.5 is not a suitable parameter for PM monitoring in all environments. The selection of PM10 or PM2.5 should be conditioned by the type of anthropogenic activity. At urban sites, PM2.5 contains mainly vehicle exhaust products, whereas the road traffic dust principally occurs in the 2.5-10µm fraction. PM2.5 is not a suitable parameter for monitoring some industrial activities (e.g. ceramics, cement production or mining) with primary PM emissions in the 2.5-10µm range.

Masters Research - Master of Medical Science / Numerous overseas studies have linked both short and long-term exposures to outdoor air pollution to a range of health effects. The differences in air pollution sources, climate and geography in Australia challenged the generalisability of these overseas findings to the Australian setting. In response, the Hunter Illawarra Study of Airways and Air Pollution (HISAAP) was undertaken. The aim of Phase II of HISAAP was to assess the short-term effects of particulates on respiratory health amongst symptomatic children. This thesis presents the results of an analysis of the 345 primary school children eligible for Phase II of the Hunter component of HISAAP. There were multiple daily diary measures on each child, different types of outcomes such as continuous, dichotomous and count variables, as well as several sources of exposure data on pollutants. Because of the complex and hierarchical nature of data, there are several possible methods of analyses that could be used. The thesis begins with a description of the sampling methods used in the study. Next, an overview of the literature on the relationship between air pollution and respiratory health, followed by a review of the methods of analyses appropriate for longitudinal diary studies of this nature. The methods and results are then presented for the analyses of the association between the three main outcomes of interest – evening peak flow, day cough and bronchodilator use – and air quality variables: particulates (PM10 and TSP), sulphur dioxide, pollens and fungi, using three modelling approaches. These include a representative of data reduction methods (Aggregate analysis), subject-specific or mixed-model methods (Korn-Whittemore analysis) and marginal methods (Generalised Estimating Equations). All estimates were adjusted for climate-related covariates and trend. The final chapter discusses the advantages and disadvantages of the various methods of analyses, and a recommendation for analytic techniques for further studies.

148f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-03-22T17:35:21Z No. of bitstreams: 1 TESE VERSÃO FINAL_Rogete.pdf: 3403393 bytes, checksum: 8ad0a12697759237a2a80d8d5568a3c8 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-04-19T14:20:42Z (GMT) No. of bitstreams: 1 TESE VERSÃO FINAL_Rogete.pdf: 3403393 bytes, checksum: 8ad0a12697759237a2a80d8d5568a3c8 (MD5) / Made available in DSpace on 2013-04-19T14:20:43Z (GMT). No. of bitstreams: 1 TESE VERSÃO FINAL_Rogete.pdf: 3403393 bytes, checksum: 8ad0a12697759237a2a80d8d5568a3c8 (MD5) Previous issue date: 2013 / CAPES / O material particulado atmosférico (MP) é um dos principais poluentes do ar, este pode ser emitido por fontes naturais e antrópicas. Em ambientes urbanos o tráfego de veículos é um dos grandes responsáveis por sua emissão. Em sua composição estão associadas inúmeras espécies químicas, dentre as quais se destacam metais e metalóides. A origem destas espécies através do tráfego está relacionada a várias fontes, tais como, produtos de combustão do combustível e óleo; produtos de desgaste de pneus, lonas de freio, rolamentos; materiais de construção das vias de tráfego; e ainda a ressuspensão da poeira do solo. As frações mais finas do MP são as mais nocivas e a exposição a estas partículas é responsável por vários efeitos à saúde e estão associadas ao aumento de riscos de doenças respiratórias e cardiovasculares e problemas reprodutivos. Especialmente os metais podem causar câncer, mutações e problemas neurológicos. Neste trabalho, as concentrações de partículas em suspensão foram determinadas por meio de técnica gravimétrica; e as concentrações atmosféricas dos elementos traço As, Ba, Ca, Cd, Co, Cu, Fe, Hg, Mg, Mn, Ni, Pb, Sb, Sn, V e Zn, nas frações MP10 e MP2,5 coletadas no Terminal Rodoviário da Lapa, foram determinadas usando as técnicas de ICP-MS e ICP OES. As amostras de MP10 e MP2,5 do ano de 2010, foram coletadas sobre filtros de microfibra de quartzo em amostradores de grande volume (Hi-Vol). As amostras de MP10 coletadas em 2005 em outro estudo, foram utilizadas neste trabalho com a finalidade principal de se investigar a composição elementar do MP no período de transição B0 (2005) para B5 (2010). Para a seleção do procedimento de extração, com vistas ao tratamento das amostras de MP, foram realizados alguns experimentos e dentre estes, a mistura de 2 mL HNO3, 1 mL de H2O2 e 5 mL H2O, se mostrou adequada produzindo respostas satisfatórias. A validação do método garantiu recuperações na faixa de 83% a 114%. Os limites de quantificação do método nas determinações realizadas por ICP-MS foram estabelecidos entre 0,02 e 1,82 ng m-3 e nas determinações por ICP OES entre 1,9 e 896 ng m-3. Os resultados da concentração de partículas em suspensão para MP10 e MP2,5, apresentaram valor médio, respectivamente, de 134 μg m-3 e 83,2 μg m-3. Entre os elementos traço minoritários, as maiores concentrações médias encontradas em 2010, foram para Hg, Ni, Pb, Sn e V cujos valores para MP10 foram, respectivamente, 4,52; 4,53; 7,33; 4,41 e 5,68 ng m-3; e para MP2,5 foram, respectivamente, 2,68; 3,01; 4,57; 1,32 e 2,96 ng m-3. Entre os elementos majoritários as maiores concentrações encontradas em 2010, foram para Ba, Ca, Fe e Mg, cujos valores médios foram, respectivamente, para MP10, 587; 5260; 5190 e 1907 ng m-3 e MP2,5, 165; 2759; 2101; 947 ng m-3. A avaliação das concentrações dos elementos traço por turno em 2010 mostrou que nos turnos da manhã e tarde em conjunto, a concentração dos elementos traço compreendeu aproximadamente entre 58% a 87% do total emitido na fração MP10; e entre 62% a 85% na fração MP2,5. Os cálculos do fator de enriquecimento revelaram que os elementos de origem antrópica no MP em suspensão, portanto considerados enriquecidos, foram As, Ba, Cd, Cu, Hg, Pb, Sb, Sn e Zn. A análise multivariada permitiu identificar os elementos que caracterizaram as emissões do MP e a influência do tráfego conforme os turnos de amostragem. E ainda indicou que as diferenças entre as frações MP10 de 2005 e 2010, correspondentes ao período de transição de B0 para B5, foram relacionadas às concentrações de Cd, Mn, Cu e Hg. / Salvador