Made available in DSpace on 2016-08-10T10:53:33Z (GMT). No. of bitstreams: 1 FRANCISCO EDISON SAMPAIO.pdf: 2658167 bytes, checksum: 58ddae6341c50dac3f47e6293787686a (MD5) Previous issue date: 2012-05-28 / All forms of environmental pollution are potentially harmful to human health, fauna, flora and environment in general. Air pollution, understood as the presence of various substances in the atmosphere, altering its natural composition, making it dangerous for all living beings which depend on it, has received increasing attention. The diversity of pollutants and their concentration in the atmosphere is quite broad and complex. For this reason, and considering other aspects such as the toxicological profile of pollutants and the main sources of atmospheric emissions, several countries have set standards of air quality for specific groups of pollutants. In Brazil, there are standards for seven pollutants (CO, SO2, NO2, O3, PTS, PM10 (all acronyms are in Portuguese), and smoke). This research focus on the characterization of the concentration of PTS in the atmosphere, especially the occurrence of metals associated with these particles and the possible injuries to human health. To fulfill this purpose it was necessary to make the collection of material particles in the central region of Goiania - GO, during the winter of 2011. The analysis was set for metals: Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Ti, Pb, and Zn. The collection of PTS was performed through the Sampler of Great Volume (AGV in Portuguese) method and through the detection of metals, with the application of spectrometry of optical emission with inductively coupled plasma (ICP OES in Portuguese). The results showed a concentration of PTS which at no time exceeded the primary standard for this pollutant, as defined by the CONAMA Resolution 03/90, different reality when the pattern established by the Decree 1.745/79 of the State of Goiás was observed, which demonstrated that for six times the concentrations PTS were above this standard. The average concentration of metals in the twenty-two samples of material particles resulted in values which were considered low in relation to the standards proposed by international agencies and institutions (EPA, ASTDR, and OMS in Portuguese), and, similarly, when compared to the occurrence of metals in material particle in other cities in the country. Human exposure to metals, especially those considered toxic, in high concentrations, or even in low ones but for a long period of time, can cause severe consequences to health, ranging from simple allergic reactions to diseases like cancer that can lead to death. Through the generated, we can conclude that, in general, the air quality in the region observed by the research varies from good to regular, and that the concentrations of metals associated with PTS does not present a significant threat to the health of the population. / Todas as formas de poluição ambiental possuem potencial deletério à saude humana, à fauna, à flora e ao meio ambiente de uma forma geral. A poluição do ar, que se traduz na presença de substancias diversas na atmosfera, alterando sua composição natural, tornando-a perigosa para todos os seres vivos que dela dependem, tem merecido uma atenção crescente. A diversidade de poluentes e a concentração destes na atmosfera é algo bem amplo e complexo. Por essa razão, e considerando outros aspectos como o perfil toxicológico de poluentes e as principais fontes de emissão atmosférica, vários países definem padrões da qualidade do ar para grupos específicos de poluentes. No Brasil, existem padrões para sete poluentes (CO, SO2, NO2, O3, PTS, PM10 e fumaça). Esse trabalho deteve-se na caracterização da concentração de PTS na atmosfera, especialmente a ocorrência de metais associados à essas partículas e os possiveis agravos à saúde humana. Para cumprimento de tal finalidade promoveu-se a coleta de material particulado na região central de Goiânia GO, durante o inverno, no ano de 2011. Os metais definidos para análises foram: Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Ti, Pb e Zn. A coleta de PTS foi realizada pelo método do Amostrador de Grande Volume (AGV) e a detecção dos metais, com aplicação da espectrometria de emissão óptica com plasma indutivamente acoplado (ICP OES). Os resultados demonstraram uma concentração de PTS que em nenhum momento ultrapassou o padrão primário para este poluente, definido pela Resolução CONAMA 03/90, realidade diferenciada quando observado o padrao estabelecido pelo Decreto 1.745/79 do Estado de Goiás, onde por 6 vezes as concentrações de PTS posicionaram-se acima desse padrão. As concentrações médias dos metais nas vinte e duas amostras do material particulado resultaram em valores considerados baixos em relação a padrões propostos por entidades e instituições internacionais (EPA, ASTDR e OMS) e, da mesma forma, quando comparadas a ocorrencia de metais em material particulado em outras cidades do País. A exposição humana a metais, especialmente os considerados tóxicos, em concentrações elevadas ou mesmo baixas, mas de forma prolongada pode provocar sérias consequencias à saúde, variando de simples reações alérgicas até doenças como cancer que pode levar a morte. Pelos resultados gerados, pode-se concluir, em linhas gerais, que a qualidade do ar, na regiao afetada pelo estudo, apresenta-se entre boa e regular e as concentrações de metais associados âs PTS não oferceu ameaças significativas à saúde da população.

Made available in DSpace on 2016-12-23T14:04:33Z (GMT). No. of bitstreams: 1 Mayana Rigo Alves parte 1.pdf: 1590439 bytes, checksum: 71b9b8c5889a2acb01c01d6378aabf0b (MD5) Previous issue date: 2011-02-28 / A maior parte dos trabalhos científicos sobre a presença de material particulado na atmosfera está relacionada a partículas mais finas (menores que 2,5 μm ou menores que 10 μm), devido a seus efeitos sobre a saúde pulmonar dos seres humanos. Entretanto, partículas maiores podem causar consideráveis incômodos à população, devido a sua deposição sobre as superfícies, e a essas partículas, dá-se o nome de Material Particulado Depositado- MPD. A maior parte dos métodos experimentais para quantificação de partículas é bastante trabalhosa e onerosa, motivando o uso de métodos teóricos ou métodos indiretos de quantificação. O objetivo da aplicação da técnica indireta é reduzir o custo das medições e acelerar o tempo de obtenção dos dados. Nesse contexto, o objetivo geral deste trabalho é avaliar a hipótese da utilização de dados de Partículas Totais em Suspensão - PTS (medidos por equipamento automático) no cálculo do fluxo de deposição, substituindo o uso de medidores de deposição baseados em gravimetria. Dentro desse alvo, o presente trabalho buscou contribuir na implantação da rede de monitoramento de partículas sedimentáveis, bem como agilizar o processo de obtenção dos dados de fluxo de deposição dessas partículas. Os fluxos de deposição foram medidos no período de abril de 2009 a abril de 2010 em algumas das estações pertencentes à Rede Automática de Monitoramento da Qualidade do Ar (RAMQAR) pelo método de coleta baseado na Norma ASTM D1739 (1998). Esse mesmo fluxo foi estimado para uma das estações da rede (RAMQAR), a saber, Jardim Camburi, através de quatro modelos matemáticos. Três deles são baseados em modelos existentes na literatura e um é baseado no ajuste de curva para a obtenção da velocidade de deposição a partir dos dados experimentais de deposição. O último modelo apresentou resultados superiores aos demais. Tendo em vista o bom resultado desse último modelo, ele foi aplicado às demais estações. De forma geral, os resultados obtidos em todas as estações foram bons, conseguindo prever em 93% os valores de fluxo de deposição da região estudada. Demostrando ser uma ferramenta auxiliar para uma rápida estimativa dos fluxos de deposição onde as medições PTS estão disponíveis. No entanto, o modelo é dependente da existência de medidas de fluxo de deposição experimental para a sua calibração / Most scientific studies regarding the atmospheric aerosol is related to fine particles (less than 2.5 μm or less than 10 μm), due to its effects on lung health of humans; however, larger particles can cause considerable annoyance to the population, due to their deposition on surfaces (Settled Particulate Matter SPM). Most experimental methods for the quantification of these particles are laborious and expensive, motivating the use of theoretical methods or indirect methods of quantification. The aim of the indirect methods is to reduce the cost of measurements and time to obtain the data. In this context, the objective of this study is to evaluate the hypothesis using data of TSP concentration (measured by automated equipment) for calculating the deposition flux, replacing the use of experimental methods for direct measurements of deposition based on gravimetry. Within this target, this study sought to contribute in the implementation of the monitoring network of sedimentary particles as well as expedite the process of obtaining the data flow of deposition of these particles. The deposition fluxes were measured from April 2009 to April 2010 at 7 stations of the Regional Air Quality Monitoring Network (RAMQAR), by using ASTM D1739 (1998). The deposition flux was estimated by four mathematical models. Three models are based on models existing literature and one model is based on a curve fit to obtain the deposition rate from the experimental data of deposition. The latter model showed better results than others, given the successful outcome of this last model was applied to the stations. Overall, the results were satisfactory, achieving 93% predict average flux values for the region. Thus, in general, the results indicate the a simple linear fitting can be used as a aiding tool for fast estimating of deposition fluxes where TSP measurements are available. Nonetheless, the model is dependent on the existence of deposition flux measurements for calibration

This study aimed to determine and assess the total concentration of trace elements associated with the total suspended particles (TSP) collected in an urban area of the Aracaju City, Sergipe, Brazil. Forty two samples were collected on glass fiber filters between period August/2009 and September/2010 using a high volume sampler (AGV). The concentration of Fe, Cu, Mn, Ni, V and Ti were determined employing atomic spectrometry techniques in two different work. The first used acid digestion extraction assisted by microwave and analysis by mass spectrometry and optical emission, both inductively coupled plasma (ICP OES and ICP MS). The concentrations of the elements found between <48 and 1620 ± 16 ng.m-3 for Fe; 0.70 ± 0.04 and 322 ± 4 ng.m-3 for Cu;<1,3 and 12.7 ± 6.8 ng.m-3 for Mn; 1.1 ± 0.1 and 16.0 ± 8.4 ng.m-3 for Ni; <15 and 49.3 ± 4.0 ng.m-3 for V and 4,6 ± 0,6 a 129,0 ± 12,5 ng.m-3 for Ti (n=41 samples). The exploratory data analysis results was applied. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) concluded that there are two emitters that contribute to the composition of the PTS that reach the sampling area. Soil resuspension is major contributor in the composition due to correlation between Fe, Mn, Ni and Ti, which are typical elements of the soil. The second emitter, is characteristic of the vehicular traffic. wherein the concentration of Cu, V, SO2 and smoke were likely indicative of action anthropogenic. The enrichment factor calculated for the concentration of the elements identified enrichment for the average concentration of copper found in the urban area, is another indication of anthropogenic inputs. The second study consisted of the Cu and Fe sequential determination in TSP using slurry sampling flame atomic absorption spectrometry and mode fast sequetial (FS-FAAS). The optimization univariate involved the following variables: the concentration of nitric acid used to prepare the slurry, sonication time and the sample mass. The optimized conditions, to about 50 mg of sample were: nitric acid solution 0.5 mol L-1, sonication time of 10 min and a final volume of 25 mL. The calibration curves were obtained using a slurry of a non-filter, the pattern multielement containing Cu and Fe in nitric acid 0.5 mol L-1. This strategy calibration offset the effect observed for the matrix Fe The limit of detection (LOD, 3σ, n = 10) was equal 4 μg.g-1 for Cu and 14 μg.g-1 for Fe , corresponding to 8 ng.m-3 for Cu and 20 ng.m-3 for Fe. The precison was expressed as relative standard deviation (RSD, n = 3) was smaller than 7% for the copper concentration and 8% for iron concentration in the slurries analysis (n=3). The concentrations of both elements determined by the proposed method were compared to concentrations obtained by ICP-MS after acid extraction assisted by microwave and showed no significant differences, applying the t test for a confidence level of 95%. The proposed procedure was simple, fast and reliable suitable for the sequential determination of Cu and Fe in PTS samples by FS-FAAS. / Este trabalho teve como objetivo determinar e avaliar a concentração total de elementos traço associados as partículas totais em suspensão (PTS) coletadas em uma área urbana da cidade de Aracaju, Sergipe, Brasil. Quarenta e duas amostras foram coletadas em filtros de fibra de vidro no período entre agosto/2009 e setembro/2010 utilizando um amostrador de grande volume (AGV). As concentrações de Fe, Cu, Mn, Ni, V e Ti foram determinadas empregando-se técnicas de espectrometria atômica em dois trabalhos distintos. O primeiro usou a digestão ácida assistida por micro-ondas e análise por espectrometria de massa e de emissão óptica, ambas com plasma indutivamente acoplado (ICP-MS e ICP OES). Foram encontradas as concentrações entre <48 a 1620 ± 16 ng g-1 para Fe; 0,70 ± 0,04 a 322 ± 4 ng.m-3 para Cu; 1,3 a 12,7 ± 6,8 ng.m-3 para Mn; 1,1 ± 0,1 a 16,0 ± 8,4 ng.m-3 para Ni, <15 a 49,3 ± 4,0 ng.m-3para V e 4,6 ± 0,6 a 129,0 ± 12,5 ng.m-3. Foi aplicada a análise exploratória de dados aos resultados. A partir da análise de componentes principais (PCA) e a análise de agrupamentos hierárquicos (HCA) concluiu-se que há dois emissores que contribuem na composição do PTS que atingem a área amostral. A ressuspensão do solo é o maior contribuidor na composição química, devido correlação encontrada entre Fe, Mn, Ni e Ti, que são elementos tipicos do solo. O segundo emissor é caracteristico do trafego veicular, onde a concentração de Cu, V, SO2 e Fumaça foram prováveis indicativos de ação antropogênica. O fator de enriquecimento calculado para a concentração dos elementos identificou o enriquecimento para a concentração de cobre encontrada na área urbana, sendo outro indicativo da ação antropogênica. O segundo trabalho consistiu da determinação sequencial de Cu e Fe no PTS usando amostragem em suspensão e espectrometria de absorção atômica com chama no modo seqüencial rápido ( fast sequential ) multi-elementar (FS-FAAS). A otimização univariada envolveu as seguintes variáveis: concentração da solução de ácido nítrico usada no preparo da suspensão, tempo de sonicação e massa da amostra. As condições otimizadas, para cerca de 50 mg de amostra, foram: solução de ácido nítrico 0,5 mol.L-1, tempo de sonicação de 10 min e um volume final de 25 mL. As curvas de calibrações foram obtidas, usando-se uma suspensão de um filtro não utilizado, contendo o padrão multielementar de Cu e Fe em meio de ácido nítrico 0,5 mol.L-1. Esta estratégia de calibração compensou o efeito de matriz verificado para o Fe. O limite de detecção (LD, 3σ, n=10) do método proposto foi igual a 4 μg.g-1 para Cu e igual a 14 μg.g-1 para Fe, que corresponde a 8 ng.m-3 para Cu e a 20 ng.m-3 para Fe. A precisão, expressa como o desvio padrão relativo (RSD, n=3), foi menor do que 7% para a concentração de Cu e a 8% para a concentração de Fe na análise das suspensões. As concentrações de ambos os elementos determinados pelo método proposto foram comparadas com as concentrações obtidas por ICP-MS após extração ácida assistida por micro-ondas e não apresentaram diferenças significativas, aplicando-se o teste t para um nível de confiança de 95%. O procedimento proposto é simples, rápido e confiável, adequado para a determinação sequencial de Cu e Fe em amostras de PTS por FS-FAAS.

The number concentration and size distribution of particles in Brisbane have been studied extensively by the researchers at The International Laboratory for Air Quality and Health, Queensland University of Technology (Morawska et al., 1998, 1999a, 1999b). However, the comprehensive studies of chemical compositions of atmospheric particles, especially with regard to the two main classes of pollutants (polycyclic aromatic hydrocarbons and trace elements), that are usually of environmental and health interest, have not been fully undertaken. Therefore, this thesis presents detailed information on polycyclic aromatic hydrocarbons (PAHs) and elemental compositions of vehicle exhausts and of urban air in Brisbane. The levels of polycyclic aromatic hydrocarbons (PAHs) and elements in three of Brisbane's urban sites (Queensland University of Technology, Woolloongabba and ANZ stadium sites) were measured. The most common PAHs found in all sites were naphthalene, phenanthrene, anthracene, fluoranthene, pyrene and chrysene while Al, Cd, Co, Cr, Cu, Fe, Mn, Mo, Si, Sn, Sr and Zn were the most common elements detected in the total suspended particles and fine particle (PM2.5). With the aid of multivariate analysis techniques, several outcomes were obtained. For example: -- Major human activities such as vehicular and industrial sources were the most contributing pollution sources in Brisbane. However, these two sources have different influential strength on the compositions of the polycyclic aromatic hydrocarbons and trace inorganic elements found in the urban air. -- Woolloongabba bus platform was the most polluted site on the basis of the elemental and PAH compositions in its air samples while QUT site was the worst polluted site in terms of PM2.5 elemental contents. These results demonstrated that the impact of traffic related pollutants on Brisbane's urban air is significant. This led to the investigations of the direct emissions of pollutants from exhaust vehicular source in the second part of this research work. The exhaust studies included the investigations of PAHs, trace inorganic elements and particles. At the time of the study, the majority of vehicles in Brisbane used low sulfur diesel (LSD) fuel or unleaded petrol (ULP). However, the importance of vehicles using ultra low sulfur diesel (ULSD) and liquefied petroleum gas (LPG) is constantly growing. Therefore, the exhaust emission studies on chassis dynamometer from heavy duty non-catalyst-equipped buses powered by LSD and ULSD with 500 ppm and 50 ppm sulfur contents respectively as well as passenger cars powered by ULP and LPG were explored. The outcomes of such studies are summarized as follows: -- Naphthalene, acenaphthene, acenaphthylene, anthracene, phenanthrene, fluorene, fluoranthene and pyrene were frequently emitted by the buses powered by LSD and ULSD. However, buses powered by ULSD emitted 91% less PAHs than those powered by LSD. On the other hand, Mg, Ca, Cr, Fe, Cu, Zn, Ti, Ni, Pb, Be, P, Se, Ti and Ge were found in measurable quantities in the exhaust of the buses. The emissions of the elements were found to be strongly influenced by the engine driving conditions of the buses and fuel parameters such as sulfur content, fuel density and cetane index. -- Naphthalene, fluorene, phenanthrene, anthracene, pyrene, chrysene, benzo(a)anthracene and benzo(b)fluoranthene were predominantly emitted by ULP and LPG cars. On the average, the total emission factors of PAHs from LPG cars were generally lower than those of ULP cars, but given the large variations in the emission factors of cars powered by the same type of fuel, differences in the emission factors from both car types were statistically insignificant. In general, platinum group elements and many other elements were found in the exhausts of cars powered by both fuels. Emissions of inorganic elements from the cars were dependent on the type and the mileage of the cars. For example, ULP cars generally emitted higher levels of Cu, Mg, Al and Zn while LPG cars emitted higher level of V. In addition, cars with higher mileages were associated with higher emissions of the major elements (Zn, Al, Fe, V and Cu). -- Buses powered by ULSD usually emitted fewer particles, which were generally 31% to 59% lower than those emitted by LSD powered buses. Similarly, cars powered by LPG emitted less particles from those powered by ULP fuel. However, more nanoparticles (those with aerodynamic diameters of less than 50 nm) were emitted by LPG powered cars than their ULP counterparts. Health effect assessment of the exhaust PAHs was evaluated in terms of benzo(a)pyrene toxicity equivalent (BAPeq). The potential toxicities of PAHs emitted by ULSD powered buses were generally lower than those emitted by their LSD counterparts. A similar trend with lower emissions of PAHs from LPG cars than from ULP cars was observed when otherwise identical passenger cars were powered by LPG and ULP fuels. In summary, this thesis has shown that the majority of airborne particles found around Brisbane have anthropogenic origins, particularly vehicle emissions, and that fuel or lubricant formulations and engine operating conditions play important roles in the physical and chemical characteristics of pollutants emitted by vehicles. The implications of these results on worldwide strategies to reduce the environmental and health effects of particles emitted by motor vehicles were discussed. In this regard, direct emission measurements from vehicles powered by LSD, ULSD, ULP and LPG unveiled the relative environmental benefits associated with the use of ULSD in place of LSD to power diesel engines, and of LPG in place of ULP to power passenger cars.