No description available.

No description available.

Descreve-se o método PIXE como uma técnica não destrutiva na análise quantitativa de traços de elementos em amostras de aerossol atmosférico. Fundamenta-se este método através do estudo da ionização de camadas internas de átonos por partículas carregadas e da secção de choque de produção de raios-X consequente do processo de ionização. A seguir são apresentados os conjuntos de impactadores em cascata utilizados pelo Grupo de Estudo de Poluição do Ar - IFUSP e pelo Grupo da FSU, na coleta de amostras de aerossol Atmosférico na cidade de Brasília, D.F.. São dadas. as características geométricas de cada conjunto e suas condições de funcionamento durante as amostragens. Discutem-se os resultados obtidos na análise PIXE das amostras provenientes dos dois conjuntos de impactadores procurando-se estabelecer correlações entre variações nas concentrações de mesmos elementos detectados nos dois conjuntos de impactadores. São discutidas possíveis causas que podem afetar o comportamento de dois conjuntos de impactadores e influir na análise de resultados obtidos pelo método PIXE. Para os casos em que há concordância nos resultados obtidos nas análises das amostras de aerossol atmosférico coletadas com impactadores em cascata e amostrador de filtro sequencial (apêndice 1) procura-se associar possíveis fontes de emissão de particulado na época das amostragens. Na complementação do método PIXE sugere-se a substituição do detector de Si (Li) por um espectrógrafo de cristal convexo. / The PIXE is described as a non destructive technique in the quantitative trace elimental analysis of aerossol atmospheric samples. The method is justified through the investigation of inner-shell ionization of atoms by charged particles and X-ray production cross section due the ionization process. Next are presented the sets of cascade impactors used during the aerossol sampling in Brasilia, Goiás, by the Group of Air Pollution Research - IFUSP and Air Chemistry Group - Oceanography Department - FSU. Dimensions of these two sets of impactors and conditions during the sampling are included in this work The results obtained from the analysis of the two sets of impactors are discussed correlating them with the variations in the amount of elements present in the samples. Possible causes changing the behavior of those impactors and can affect the analysis of results obtained by PIXE method are discussed. Results from impactors that are compatible with STREAKER analysis are interpreted according to possible emission sources of particulate matter in the atmosphere. In the implementation of PIXE apparatus the substitution of Si(Li) detector by a convex crystal X-ray spectrograph is suggested.

No description available.

Descreve-se o método PIXE como uma técnica não destrutiva na análise quantitativa de traços de elementos em amostras de aerossol atmosférico. Fundamenta-se este método através do estudo da ionização de camadas internas de átonos por partículas carregadas e da secção de choque de produção de raios-X consequente do processo de ionização. A seguir são apresentados os conjuntos de impactadores em cascata utilizados pelo Grupo de Estudo de Poluição do Ar - IFUSP e pelo Grupo da FSU, na coleta de amostras de aerossol Atmosférico na cidade de Brasília, D.F.. São dadas. as características geométricas de cada conjunto e suas condições de funcionamento durante as amostragens. Discutem-se os resultados obtidos na análise PIXE das amostras provenientes dos dois conjuntos de impactadores procurando-se estabelecer correlações entre variações nas concentrações de mesmos elementos detectados nos dois conjuntos de impactadores. São discutidas possíveis causas que podem afetar o comportamento de dois conjuntos de impactadores e influir na análise de resultados obtidos pelo método PIXE. Para os casos em que há concordância nos resultados obtidos nas análises das amostras de aerossol atmosférico coletadas com impactadores em cascata e amostrador de filtro sequencial (apêndice 1) procura-se associar possíveis fontes de emissão de particulado na época das amostragens. Na complementação do método PIXE sugere-se a substituição do detector de Si (Li) por um espectrógrafo de cristal convexo. / The PIXE is described as a non destructive technique in the quantitative trace elimental analysis of aerossol atmospheric samples. The method is justified through the investigation of inner-shell ionization of atoms by charged particles and X-ray production cross section due the ionization process. Next are presented the sets of cascade impactors used during the aerossol sampling in Brasilia, Goiás, by the Group of Air Pollution Research - IFUSP and Air Chemistry Group - Oceanography Department - FSU. Dimensions of these two sets of impactors and conditions during the sampling are included in this work The results obtained from the analysis of the two sets of impactors are discussed correlating them with the variations in the amount of elements present in the samples. Possible causes changing the behavior of those impactors and can affect the analysis of results obtained by PIXE method are discussed. Results from impactors that are compatible with STREAKER analysis are interpreted according to possible emission sources of particulate matter in the atmosphere. In the implementation of PIXE apparatus the substitution of Si(Li) detector by a convex crystal X-ray spectrograph is suggested.

Spatial and temporal patterns of semi-volatile organic contaminant (SVOC) concentrations in air and precipitation were investigated at the urban scale in order to improve our understanding of emission sources and factors affecting intra-urban variability. Toronto, Canada was used as a case study. Advances were made in two methods used to examine intra-urban variability, namely passive air sampling and land use regression analysis. The study showed that these methods are useful for assessing local-scale variability, and that passive air sampler concentrations are most reliable when using homologue-specific sampling rates obtained from a co-located low volume sampler. The results of the spatially and temporally distributed sampling demonstrated that the highest atmospheric concentrations of SVOCs were associated with the highest density regions of the urban area. Temporal patterns of elevated concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs) in warm seasons were consistent with temperature-related emission processes such as volatilization and/or ventilation of indoor air. Spatial patterns in air concentrations were influenced by local sources on a scale of <5 km and were explained by factors related to human population activities such as building volume (PBDEs), population density (polycyclic musks, or PCMs), residential, commercial and transportation infrastructure (PAHs), and chemical inventory (PCBs). Industrial activities were not important factors. The link between elevated environmental concentrations and the in-use stock of banned chemicals, such as PCBs and PBDEs, suggest that efforts to control emissions and reduce environmental concentrations must address the removal of current use products, in addition to the bans on new uses of the SVOCs.

Spatial and temporal patterns of semi-volatile organic contaminant (SVOC) concentrations in air and precipitation were investigated at the urban scale in order to improve our understanding of emission sources and factors affecting intra-urban variability. Toronto, Canada was used as a case study. Advances were made in two methods used to examine intra-urban variability, namely passive air sampling and land use regression analysis. The study showed that these methods are useful for assessing local-scale variability, and that passive air sampler concentrations are most reliable when using homologue-specific sampling rates obtained from a co-located low volume sampler. The results of the spatially and temporally distributed sampling demonstrated that the highest atmospheric concentrations of SVOCs were associated with the highest density regions of the urban area. Temporal patterns of elevated concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs) in warm seasons were consistent with temperature-related emission processes such as volatilization and/or ventilation of indoor air. Spatial patterns in air concentrations were influenced by local sources on a scale of <5 km and were explained by factors related to human population activities such as building volume (PBDEs), population density (polycyclic musks, or PCMs), residential, commercial and transportation infrastructure (PAHs), and chemical inventory (PCBs). Industrial activities were not important factors. The link between elevated environmental concentrations and the in-use stock of banned chemicals, such as PCBs and PBDEs, suggest that efforts to control emissions and reduce environmental concentrations must address the removal of current use products, in addition to the bans on new uses of the SVOCs.

Assessments of the anthropogenic threats to savanna ecosystems are primarily focussed on land use change, bush encroachment, and biological invasions. There is, however, very little understanding as to the threats from atmospheric pollution. South Africa is the major emitter of CO2 on the African content while the Mpumalanga region bordering the Kruger National Park (KNP) is among the leading regions for nitrous oxide pollution in the world. It is not only increasing atmospheric pollution, but rainfall intensity is also predicted to increase for southern Africa. As savannas are nutrient limited, an increase in nitrogen deposition will have major consequences for vegetation structure and this can only be exacerbated by increased rainfall amounts. Current research suggests that these predicted increases in water and nutrients will result in increasing grass biomass and decreasing herbaceous species richness. The effects of global change drivers on savanna vegetation are also likely to propagate through to multiple trophic levels, with changes in vegetation structure cascading down to invertebrate assemblages. As invertebrates are ubiquitous, form the bulk of metazoan species diversity and biomass on earth, and play a pivotal role in many ecosystems, I discuss in the introductory chapter of this thesis why the influence of global change on these assemblages should not be ignored. In my first data chapter, Chapter 2, I examine the effect that increases in available nutrients and water may have on vegetation structure, and how this may cascade down to grasshopper and ant assemblages. I do this using a fully factorial experiment in KNP with nutrient and water additions where I assessed both herbaceous (forb and grass) and insect (ant and grasshopper) assemblages five years after resource additions began. My results show that there was a substantial increase in grass biomass while plant and insect species richness declined with water addition alone and that a combination of nutrients and water resulted in the greatest increases in grass biomass and concomitant decreases in plant and insect species richness. The effects of nutrient and water additions on the insect community assembly was primarily driven by a decrease in grasshopper species and ant abundance respectively. An analysis of ant functional traits showed that the rare ant species mediated the impact of the resource additions on the ant assemblage. Fire is inherent to savanna systems with profound effects on vegetation structure. There has, however, been relatively little research on the effects of fire on savanna invertebrate fauna. In Chapter 3 I look at the effect that fire may have on the vegetation and insect community assembly at my study site between five and eight months after the site had been burned. These results show an increase in grass biomass and decrease in plant and insect species richness with a combination of nutrients and water. My results also show that grasshopper biomass, abundance, and species richness decreased as herbaceous biomass decreased. While ant species richness decreased, ant abundance increased post-fire, primarily related to an increase in patches of bare ground. With global change, drought frequency is also expected to increase. The insect and grass assemblages, both on and off Macrotermes mounds, at two sites in the southern section of KNP had been sampled in a separate study in 2012. In Chapter 4 I describe a study where I resampled these mounds during the peak of the most severe drought in 30 years. The two sites differed in drought severity, one where the drought severity was very high and the other where severity was much lower. The objective was to determine the effects that drought may have on the grass and associated insect assemblages both on and off termite mounds. My results show that at the high severity site grass cover and biomass and grasshopper abundance decreased both on and off mounds. The overall reduction in habitat structure resulted in an increase in both ant abundance and species richness but the mound and matrix ant assemblages diverged during drought. Where the drought was less severe there was an increase in large mammal herbivores as animals moved out of the more affected areas. This increase in mammal herbivory was more evident on rather than off mounds resulting in grass biomass being lower on rather than off mounds. The cascading effect saw grasshopper abundance decrease on and increase off mounds. The mound and matrix ant assemblages did not respond to the comparatively smaller change in habitat structure. Finally, in the synthesis chapter I discuss my results in the broader context of how global change drivers such as increased nitrogen deposition may cascade down from plant to insect community assembly. At present there is very little understanding of the amounts of nitrogen being deposited in KNP or the effect that this may have. The results of my study would suggest that this increase in nitrogen deposition will have major consequences for vegetation structure and that this will cascade down to the insect assemblage. In mitigating for this, it is therefore essential that management in KNP adapt a monitoring protocol for nitrogen deposition, especially when considering that where N deposition is really high fire may not volatilise everything to allow the system to reset itself back to its original state. It is not only nitrogen deposition, but drought frequency is also likely to increase. In mitigation for this there should also be monitoring programmes to consider the effects of drought as animals may move from areas of high drought severity to areas where severity is lower. Such movement will increase grazing pressure on both low and high nutrient environments with cascading effects on vegetation structure and insect assemblages.

A poluição atmosférica é hoje uma questão que afeta as megacidades por todo o mundo. As partículas de aerossol participam do balanço radiativo, da formação de nuvens, da química atmosférica, e são prejudiciais à saúde da população exposta. A extensão e o rápido crescimento das megacidades têm levado à necessidade do desenvolvimento de ferramentas para o monitoramento da poluição do ar, urbana e regional, por sensoriamento remoto via satélites. Foram analisadas as propriedades ópticas dos aerossóis da região metropolitana de São Paulo com medidas obtidas por fotômetros da rede mundial AERONET (Aerosol Robotic Network) operada pela NASA. Foi desenvolvida uma nova metodologia para a determinação da espessura óptica das partículas de aerossol com alta resolução espacial de 1x1 km, sobre a região metropolitana de São Paulo, por satélite. Cinco modelos ópticos de aerossol, representativos da região, foram definidos como função do albedo simples. No comprimento de onda de 550 nm, os modelos possuem valores de albedo simples que variam de 0,83 a 0,93. Foram utilizadas medidas de radiâncias obtidas com o sensor MODIS (Moderate-Resolution Imaging Spectroradiometer), a bordo dos satélites Terra e Aqua da NASA. Extensos testes de sensibilidade foram realizados, analisando o papel do albedo simples, parâmetro de assimetria, refletância de superfície, vapor de água e outras propriedades na espessura óptica derivada. O algoritmo desenvolvido utiliza a propriedade de refletância crítica, que pode ser obtida pelo próprio sensor, para determinar o modelo de aerossol a ser empregado. Este procedimento permitiu a identificação mais precisa do modelo de aerossol, de forma dinâmica e interativa, reduzindo a incerteza na determinação da espessura óptica em alta resolução com o sensor MODIS. Os resultados de validação mostraram uma melhora significativa na comparação entre os produtos de espessura óptica obtidos com o sensor MODIS, quando comparado com as medidas de referência obtidas com radiômetros em superfície. Foram obtidos com esta metodologia mapas com a distribuição espacial de aerossóis com resolução de 1x1 km. Os estudos de casos também apresentaram a potencialidade do método em identificar o modelo de aerossol mais adequado, seja em eventos de poluição local, seja de transporte de poluentes de longa distância. Os modelos e procedimentos desenvolvidos podem ser aplicados a outras regiões urbanas, após as devidas validações. Como ferramenta complementar ao monitoramento ambiental de estações de superfície o produto apresentado pode-se tornar operacional e ser utilizado em rotina por órgãos de controle ambiental em megacidades, como, por exemplo, pela CETESB em São Paulo / Urban air pollution is a public concern in all megacities around the world. Aerosol particles are active participants in the atmospheric energy budget, cloud properties, atmospheric chemistry and have adverse effects on human health. The spatial extension and the high growth rate of the megacities show the need of the use of remote sensing technologies on urban air pollution monitoring. Optical properties of São Paulo aerosol particles were analyzed using global sun photometer measurements from the AERONET (Aerosol Robotic Network) operated by NASA. A new methodology was developed to retrieve aerosol optical thickness in 1x1 km resolution over São Paulo metropolitan area from satelites measurements. Five aerosol optical models representative of the region were defined as a function of the single scattering albedo. The single scattering albedo in 550 nm varied from 0,83 to 0,93 in the models. Radiances were used from MODIS (Moderate-Resolution Imaging Spectroradiometer) sensor on Terra and Aqua NASA platforms. Sensitivities studies have shown the importance of the single scattering albedo, assymmetry parameter, surface reflectance, water vapor and other properties in the aerosol optical thickness retrieval from space. The developed algorithm uses the critical reflectance aerosol property, that is obtainable from the sensor measurements, to identify the aerosol model to be used. This procedure allow a more precise and dynamic definition of the aerosol model, reducing the uncertainties in the aerosol optical thickness retrieved from the MODIS sensor. Validation results have shown a significant improvement in a comparison between aerosol optical thickness obtained from MODIS and from surface radiometers measurements. Aerosol optical thickness images with 1x1 km resolution were obtained with this methodology and shows that the increase in the resolution of the aerosol optical thickness provides a more effective monitoring of the aerosol distribution in São Paulo. The case studies have shown the potentiality of this methodology to identify an adequate aerosol model, for both local aerosol pollution and in the long distance transport of pollutants. The models and procedures developed in this work can be applied in other urban regions with the appropriate validation. The presented product can be operational and used as routine measurement by environmental agencies in megacities, as an example, for CETESB in São Paulo, as a complementary tool to the regular ground based particulate matter monitoring.

Ainda que a invenção do automóvel tenha gerado diversos benefícios para a sociedade, atualmente, podem ser identificadas várias externalidades negativas associadas ao seu consumo, como congestionamentos, poluição sonora, visual e atmosférica, e, geração de resíduos sólidos. No que se refere às emissões de gases poluentes, foco deste estudo, as repercussões são visivelmente imediatas na saúde da população, principalmente no aumento de problemas respiratórios. Assim, dado o crescente aumento da frota de veículos e o fato de, em 2014, 33,40% da frota nacional de autoveículos (automóveis, comerciais leves, caminhões e ônibus) e 21,44% das motocicletas estarem concentradas no estado de São Paulo, a presente pesquisa objetiva mensurar as emissões de gases poluentes de escapamento, por veículos automotores rodoviários nos 645 municípios paulistas, para o período de 2006 a 2015. A metodologia adotada neste estudo é a mesma utilizada pela CETESB e consiste numa abordagem do tipo bottom-up. Nessa abordagem, além da quantidade consumida de combustíveis, também no cálculo das estimativas empregam-se o fator de emissão segundo o tipo de veículo, de poluente e de combustível utilizado, a intensidade de uso ou quilometragem média percorrida anualmente por tipo de veículo e a quantidade da frota circulante, segundo sua idade e categoria de veículo. Os gases poluentes estimados foram os seguintes: monóxido de carbono (CO), hidrocarbonetos (HC), hidrocarbonetos não-metano (NMHC), metano (CH4), óxidos de nitrogênio (NOX), aldeídos totais - acetaldeído + formaldeído (RCHO), dióxido de carbono (CO2) e material particulado (MP). A análise destas estimativas foi do tipo descritiva, incluindo também a construção de mapas para melhor identificação das cidades mais emissoras. Na sequência, busca-se relacionar estas emissões com a saúde da população, via análise do número de internações hospitalares devido a problemas respiratórios. Ainda que as emissões estejam concentradas na região conhecida como macrometrópole paulista, três municípios não pertencentes a ela apresentaram altas emissões, dependendo do tipo de gás considerado, a saber, São José do Rio Preto, Bauru e Franca. Tanto na cidade de São Paulo, maior emissora de gases poluentes do estado, como nas demais, ainda se observa uma contribuição expressiva dos veículos com mais de 20 anos para as emissões veiculares totais de monóxido de carbono. Assim, pode-se concluir que uma política de renovação da frota pode reduzir substancialmente tais emissões. Na cidade de São Paulo, em 2015, estes veículos foram responsáveis por 41,5% das emissões de CO, mesmo representando tão somente 6,96% do total da frota de veículos. A partir da vasta e detalhada fonte de dados gerada nesta pesquisa outros estudos podem ser realizados ensejando a implementação de políticas referentes à mobilidade urbana. No que se refere à relação destas emissões com a saúde da população, observando os dados de internações hospitalares por problemas respiratórios nos municípios paulistas, não foi possível estabelecer uma relação direta. O uso de outros métodos para aprofundar o exame dessa questão é particularmente recomendável tendo em vista que diversos outros fatores podem influenciar essas internações, tais como emissões de outras fontes que não as veiculares, clima, assistência médica preventiva, entre outros. / Although the invention of the automobile has generated several benefits for society, several negative externalities associated with its consumption, such as congestion, noise, visual and atmospheric pollution, and solid waste generation can be identified. Regarding the emission of pollutant gases, which consists on the focus of this study, its consequences are immediately noticeable in the health of the population, mainly the increase of respiratory problems. Thus, given the growing fleet of vehicles, and that 33.40% of the national fleet of motor vehicles (automobiles, light commercial vehicles, trucks and buses) and 21.44% of the motorcycles were concentrated in São Paulo state, in 2014, this research aims to measure emissions of pollutant gases by road vehicles, for the 645 municipalities of this state, between 2006 and 2015. The methodology applied is the same used by CETESB and consists of a bottom-up approach. In addition to the volume of fuel consumed, we also consider the emission factor according to the vehicle category, the pollutant emitted and the type of fuel consumed, the intensity of use or average mileage traveled by each vehicle category and the total active fleet, categorized by its age and type of vehicle. The gaseous pollutants estimated were carbon monoxide (CO), hydrocarbons (HC), non-methane hydrocarbons (NMHC), methane (CH4), nitrogen oxides (NOX), total aldehydes - acetaldehyde + formaldehyde (RCHO), Carbon dioxide (CO2) and particulate matter (PM). We conducted a descriptive analysis of these estimates, also including the construction of maps for better identification of the major emitting cities. The aim is to relate these emissions to the population´s health, by analyzing the number of hospital admissions due to respiratory problems. Although emissions are concentrated in the region known as São Paulo metropolitan area, three outside municipalities also presented high emissions for some of the examined gases, namely São José do Rio Preto, Bauru and Franca. In São Paulo city, the largest emitter in the state, as in those cities just listed, an expressive contribution of vehicles older than 20 years was found in the total vehicular emissions of carbon monoxide. Therefore we conclude that a policy of fleet´s renewal can substantially reduce such emissions. In the city of São Paulo, in 2015, these vehicles accounted for 41.5% of CO emissions, although they represent only 6.96% of the total fleet of vehicles. In addition, the vast and detailed data source generated by this research allows carrying out other studies focusing on the implementation of policies related to urban mobility. Regarding the relation between emissions and the population health, we could not establish a direct causality only by examining the data of hospitalizations due to respiratory problems in the São Paulo´s municipalities. The use of other methods to deepen the analysis is particularly advisable for this issue in view of the fact that several other factors can influence hospitalizations for respiratory problems, such as emissions from other sources than vehicles, weather, and preventive medical care, among others.