INTRODUÇÃO: A poluição em centros urbanos é produzida, principalmente, pela queima de combustíveis fósseis. Constitui problema que afeta a saúde da população, provocando doenças tanto no sistema respiratório, como sistemicamente em vários órgãos. Dentre as funções afetadas, realça o impacto da poluição sobre o sistema endócrino, podendo acometer as adrenais, tanto, no ser humano, como em roedores. Todavia, pouco se conhece sobre a ação nesta glândula. Assim, propusemo-nos a analisar os efeitos do ar poluído sobre as adrenais em duas gerações consecutivas de camundongas. OBJETIVOS: Analisar os efeitos do ar concentrado com material particulado (MP) 2,5um sobre as adrenais, avaliando as alterações histomorfométricas; a angiogênese pelo fator de crescimento vascular endotelial (VEGF-A); a pela proliferação celular por meio da proteína Ki-67 e o índice de apoptose pela caspase 3-clivada nas três zonas do córtex da adrenal. MATERIAL E MÉTODOS: Utilizaram-se 20 camundongas alocadas em biotério livre de poluentes, as quais foram acasalados na proporção de um macho para duas fêmeas. Após confirmação da cópula, foram divididas em 2 grupos de 10 animais cada. Acondicionou-se um grupo diariamente em uma câmara, onde as camundongas foram expostas a MP 2,5um à concentração de 600ug/m³ (G0P). O outro grupo, com 10 animais, foi alocado em outra câmara com ar filtrado (G0NP). A exposição ocorreu diariamente durante toda a prenhez das camundongas. Ao nascimento os conceptos, foram amamentados por 30 dias em amamentação, período onde não houve exposição aos poluentes. Após este período, as mães foram eutanasiadas para coleta das adrenais e as filhas sofreram o mesmo protocolo de exposição (G1P e G1NP - submetidas e não submetidas à poluição), não foram acasaladas, sendo eutanasiadas para coleta das adrenais ao fim do protocolo. As adrenais passaram por processamento histológico para coloração de H.E. e imunoistoquímico. RESULTADOS: As adrenais do grupo G0P apresentaram maior espessura da zona glomerulosa e as do G1P apresentaram maior quantidade de espongiócitos na zona fasciculada. As adrenais do grupo G1P tiveram maior imunoexpressão de VEGF-A na zona glomerulosa do que as do G1NP. A imunoexpressão do Ki-67 foi maior na zona reticulada no grupo G0P; no grupo G1P houve maior expressão do Ki-67 na zona glomerulosa do que no grupo G1NP. A imunoexpressão da caspase-3 clivada foi maior nos grupos G0P e G1P do que nos demais. CONCLUSÃO: A exposição ao ar poluído com material particulado 2.5?m determinou alterações histomorfométricas e imunoistoquímicas nas três zonas do córtex da adrenal de duas gerações consecutivas de camundongas. Estas alterações poderiam causar distúrbios endócrinos e cardiovasculares / INTRODUCTION: The pollution in urban centers is produced mainly by the burning of fossil fuels. It\'s a concern of public health, causing diseases in both the respiratory system and the other organs. Among the affected functions, it is important to highlight the impact of pollution on the endocrine system and this effect on the adrenal glands, both in humans and in rodents. However, little is known on the action of pollutants on this gland. Therefore, the aim of this study was to analyze the effects of polluted air on the adrenal in two consecutive generations of female mice. OBJECTIVES: To assess the effects of concentrate air with particulate matter (PM) 2.5um on the adrenal cortex evaluating histomorphometric changes; angiogenesis by vascular endothelial growth factor (VEGF-A); the cell proliferation by Ki-67 index and apoptosis by cleaved caspase-3 in the three zones of the adrenal cortex. MATERIAL AND METHODS: We used 20 female mice in their cages free of pollutants. Those animals were mated at a ratio of one male to two females. After mating confirmation, animals were divided into 2 groups of 10 animals each. A group was daily allocated in a chamber where the female mice were exposed to PM 2.5um at a concentration of 600ug/m³ (G0P). The other group of 10 animals was allocated in another chamber with filtered air (G0NP). The exposure occurred daily throughout pregnancy period. At birth, the fetuses were breastfed for 30 days. During breastfeeding period there was no pollutants exposure. After this period, mothers were euthanized for adrenal collection and daughters suffered the same exposure protocol (G1P and G1NP - exposed and not exposed to pollution), but those were not mated, being euthanized for adrenal collection at the end of the protocol. The adrenal underwent histological processing for H.E. staining and immunohistochemistry. RESULTS: The adrenal of the G0P group had increased thickness of the zona glomerulosa and the G1P presented more espongiocytes in the zona fasciculata. The adrenal of the G1P group had higher immunoreactivity of VEGF-A in the zona glomerulosa than one of the G1NP. The immunoreactivity of Ki-67 in the zona reticularis of G0P group was higher one of G0NP; there was a higher expression of Ki-67 in the zona glomerulosa of the G1P group compared to G1NP group. The immunoreactivity of cleaved caspase-3 in G0P and G1P was higher than ones of other groups. CONCLUSION: Exposure to air pollution with particulate matter 2.5um determined histomorphometric and immunohistochemical changes in the three adrenal cortical zones of the two consecutive generations of mice. These changes could cause endocrine and cardiovascular disorders

O câncer de mama vem apresentando considerável aumento nos últimos tempos. A literatura sugere que a poluição atmosférica urbana se associa a neoplasias. Entre os monitores de poluição, o cão se mostra adequado por apresentar grau de exposição à poluição semelhante ao seu dono. Assim, objetivamos estudar o comportamento epidemiológico da neoplasia de mama em cães e sua associação com material particulado atmosférico. Foram incluídos neste estudo observacional transversal, 212 cães de uma clínica veterinária privada de referência para tratamento oncológico em São Paulo. Os dados foram obtidos retrospectivamente de prontuários entre 2008 e 2011 e complementados com ligação telefônica aos proprietários dos animais para coleta de dados sobre tabaco e tempo de moradia no local. A poluição foi estimada pela média do PM10 fornecidos pelos monitores da CETESB. Estratificamos buffers de exposição a poluição por análise espacial dos animais em vias de trânsito rápido, vias arteriais, vias locais e coletoras, como alta, média e baixa exposição respectivamente. Os dados foram analisados por testes de qui-quadrado. A neoplasia de mama incidiu em cadelas de idade avançada (9,58 +- 2,64 anos), não ovariosalpingohisterectomizadas (68,4%) e em estadiamento clínico avançado (41,5%), sendo responsável direta por 67,4% dos óbitos ocorridos. Houve predomínio de raça poodle (22%) e dieta comercial (50,5%). Poucos cães faziam uso de anticoncepcionais (9%) ou apresentaram pseudociese (31,1%). A maioria (65,5%) apresentou os tipos histológicos carcinoma complexo e carcinoma túbulo-papilífero, seguido por carcinoma sólido (14,6%). O MP10 mostrou associação com pior prognóstico (p=0,07). A análise espacial mostrou predomínio de casos na zona Sul da cidade (68,4%), maior concentração em vias de média exposição (51,4%) e tendência a pior prognóstico (p=0,05) nos animais submetidos a alta exposição. Concluímos que na região estudada, o câncer de mama em cães apresenta comportamento agressivo, diagnóstico tardio e a poluição urbana pode estar relacionada ao seu desenvolvimento / Mammary tumors have shown considerable increase in recent times. The literature suggests that urban air pollution is associated with malignancies. Among pollution monitors, the dog has been adequate for presenting level of pollution exposure similar to its owner. Therefore, we aimed to study the epidemiological behavior of breast cancer in dogs at the city of São Paulo and its association with atmospheric particulate matter. This cross-sectional observational study includes 212 dogs from a private veterinary clinic that\'s reference for cancer treatment in São Paulo. Data were obtained retrospectively from medical records between 2008 and 2011, and supplemented with telephone call to animal owners, in order to collect data on tobacco and residence time on location. Exposure of pollution was estimated by average PM10 monitors provided by CETESB. Also stratified buffers of exposure to pollution, by spatial analysis, in large, arterial and side streets as high, medium and low exposure respectively. Data were analyzed for chi-square test. Breast cancer incidence was observed in advanced aged female dogs (9,58?2,64 years), not spayed (68,4%) in advanced clinical staging (41,5), and was directly responsible for 67,4% of death. It was more common in poodle breed (22%) and commercial diet (50,5%). Few dogs were using contraceptives (9%) or showed pseudopregnancy (31,1%). Most of them (65,5%) showed histologic types complex carcinoma and tubule-papillary carcinoma, followed by solid carcinoma (14,6%). PM10 associated with poor prognosis (p=0,07). Spatial analysis showed a predominance of cases in the south zone of the city (68,4%), greater concentration on medium exposure streets (51,4%) and poor prognosis (p=0,005) in animals subjected to high exposure. We concluded that breast cancer in dogs show aggressive behavior at the studied region, mostly of late diagnosis, and that urban air pollution exposure may be correlated to its development

Este trabalho caracteriza os efeitos das condições reais de exposição ao material particulado urbano na espermatogênese por meio de análises histológicas de testículos de duas gerações de camundongos BALB/c durante o período gestacional, pósgestacional ou em ambos os momentos combinados. A geração parental foi exposta à poluição do ar em câmaras com ou sem filtros para PM2,5 (câmaras filtrada e não filtrada, respectivamente) por 4 meses, formando dois grupos: não exposto; e exposto. Estes animais foram acasalados e a freqüência do plug vaginal apresentou tendência de queda nas fêmeas expostas (p>0,05). O número de fêmeas prenhes também foi reduzido (p=0,007) e o número de nativivos foi menor na câmara não filtrada (186) quando comparada com a filtrada (268), contudo, o número de animais por ninhada não foi alterado (p>0,05). Após o acasalamento os machos foram eutanasiados, seus testículos pesados, fixados em solução de Bouin ou paraformaldeído 4% e corados com HE, PCNA, Ki67 ou TUNEL. Metade dos animais produzidos na primeira geração, constituída de animais de 1 dia de vida, foi transferida de uma câmara para outra formando os grupos pré-natal e pós-natal. Os animais remanescentes das câmaras filtrada e não filtrada constituíram os grupos não exposto e pré+pós-natal, respectivamente. Após 90 dias, os animais da primeira geração foram eutanasiados e seus testículos foram retirados, pesados, fixados e corados da mesma forma que sua geração parental. Os animais expostos ao PM2,5 da geração parental apresentaram aumento do peso dos testículos (p=0,002), dos epidídimos (p<0,001) e do peso relativo testículo/corpo (p=0,003), epidídimo/corpo (p=0,001). Não houve alteração no número de células germinativas e somáticas e nem na proliferação celular (p>0,05). A apoptose pela coloração de HE foi reduzida no estádio IV (p=0,046) e aumentada no estádio VIII (p=0,019) da espermatogênese. Pela técnica de TUNEL os estádios IV (p=0,017), V (p=0,035) e VIII (p=0,024) mostraram apoptose menor nos animais do grupo exposto. O estádio IV foi identificado como o de maior apoptose espontânea nas duas técnicas empregadas, HE (p<0,001); e TUNEL (p<0,001), entre os animais não expostos. O ciclo do epitélio seminífero foi alterado com freqüência reduzida do estádio IV entre os animais expostos (p=0,005). Os animais da primeira geração expostos no período pré-natal apresentaram redução de peso corpóreo (p<0,001) e dos testículos (p=0,012), bem como, aumento do peso relativo testículos/corpo (p=0,013). O número de células somáticas não foi alterado, mas o de espermatócitos nos grupos pós-natal (p=0,011) e pré+pós-natal foi aumentado (p=0,035) enquanto nos grupos pré-natal e pós-natal houve redução no número de espermátides alongadas (p<0,001). Não houve diferença significativa na taxa de proliferação, apoptose e freqüência dos estádios do ciclo do epitélio seminífero entre os grupos de exposição (p>0,05). O estádio IV mostrou-se o mais sensível para a ocorrência de apoptose espontânea nas duas técnicas empregadas: HE (p<0,001); e TUNEL (p<0,001). A freqüência normal dos estádios entre os animais não expostos mostrou que os estádios finais são os mais freqüentes (VI, VIII e VII, nesta ordem) e os iniciais os menos freqüentes (II e I, nesta ordem) para ambas as gerações. Estes resultados fornecem dados que sugerem que o PM2.5 da poluição atmosférica urbana é capaz de alterar o sistema reprodutivo masculino e a espermatogênese não dependendo do período da vida (durante ou após a gestação) em que os animais são expostos. / The present paper describes the effects of real exposure to urban PM2.5 on spermatogenesis by histological analysis of testes of mice (BALB/c) from two generations during fetal or postnatal phases of development and of mice exposed in both phases of development. Parental generations (BALB/c mice) were exposed to air pollution in chambers with or without filters for PM2.5 for 4 months (filtered and non-filtered chambers, respectively), forming two groups, namely non-exposed and exposed. These animals were mated and a frequency of decrease on vaginal plug in the exposed females was observed (p>0.05). The number of pregnant females was reduced as well (p=0.007) and the number of born alive decreased in the non-filtered chamber (186) when compared to the filtered chamber (268); however, the litter size was not altered (p>0.05). After mating, the male were killed, their testes were weighed and fixed in Bouins solution or 4% paraformaldehyde and stained in H&E, PCNA, Ki67 or TUNEL. Half of 1-day old offspring was crossed over between chambers forming the prenatal and postnatal groups; remaining offspring from filtered and non-filtered chambers comprised the non-exposed and pre+postnatally exposed groups, respectively. After 90 days, the animals from first generation were killed and their testes were removed, weighed, fixed and stained like the parental generation. The animals exposed to PM2.5 from the parental generation showed increased testis weight (p=0.002), epididymis weight (p<0.001), relative testis weight (p=0.003), and relative epididymis weight (p=0.001). The germ and somatic cells number was not reduced, and neither was cell proliferation (p>0.05). The apoptosis labeled by H&E was reduced in stage IV (p=0.046) and increased in stage VIII (p=0.019) of spermatogenesis. By using the TUNEL technique, stages IV (p=0.017), V (p=0.035) and VIII (p=0.024) showed fewer apoptosis in the exposed animal group. Stage IV was identified as the most spontaneous apoptosis in both methods: HE (p<0.001) and TUNEL (p<0.001), among the non-exposed animals. The cycle of the seminiferous epithelium was altered with reduced frequency of stage IV between the exposed animals (p=0.005). The animals from the first generation exposed during the prenatal period had a reduced body (p<0.001) and testis weight (p=0.012) and an increased relative testis weight (p=0.013). Differences in germ cell proliferation, apoptosis, and staging were not significantly different among treatment groups (p>0.05). Nevertheless, germ cell populations of post- (p=0.011) and pre+postnatally (p=0.035) PM-exposed animals contained an increased percentage of spermatocytes, while pre- and postnatal groups (p<0.001) had a reduced number of elongated spermatids. Stage IV was shown to be the most sensitive for the occurrence of spontaneous apoptosis in both methods used: H&E (p<0.001); and TUNEL (p<0.001). The normal frequency of the stages between non-exposed animals showed that the final stages are more frequent (VI, VIII e VII) and the beginning stages less frequent (II e I) to both generations. These results suggest that PM2.5 from urban air pollution is capable of altering the male reproductive system and spermatogenesis independently of the period of life when the animals are exposed to it (during or after pregnancy).

Estudos epidemiológicos estabelecem uma associação evidente entre poluição do ar e o aumento de morbimortalidade cardiovascular e respiratória. No entanto, os mecanismos moleculares subjacentes aos efeitos do material particulado fino (MP2,5) sobre o organismo ainda estão pouco esclarecidos. O objetivo deste trabalho foi caracterizar o impacto da exposição ao MP2,5 sobre a biologia do endotélio pulmonar e do coração, através da avaliação do perfil de expressão gênica por microarray. Camundongos adultos fêmeas foram anestesiados e submetidos à instilação intratraqueal de MP2,5 (grupo exposto) ou veículo (grupo controle). Os animais foram sacrificados 12 a 18 horas após a instilação e pulmão, coração e sangue da veia cava inferior foram coletados. Os pulmões foram dissociados com colagenase tipo I e células endoteliais foram positivamente selecionadas por captura imuno-magnética através de micro-ímãs acoplados a anti-CD31. O cRNA derivado de endotélio pulmonar e de coração total foi hibridizado em membrana de microarray de baixa densidade desenhada para representar genes relevantes à biologia endotelial. Os genes encontrados diferencialmente expressos no pulmão foram Itgb1, Cxcl1, Tnf, Ecgf1 e Tnfaip3 (hiper-expressos em expostos a MP2,5) e Enpep, Pdgfra, Gzmb, Birc2, Npr1, Angpt1, Cxcl5 e Il7 (hipo-expressos). Não foi possível realizar análise de inferência estatística de membranas do coração neste trabalho. Não houve diferença estatisticamente significativa entre os grupos exposto e controle na contagem sangüínea de neutrófilos, linfócitos ou plaquetas, apesar dos dois grupos apresentarem plaquetose. Os achados indicam que MP2,5 altera a transcrição de genes envolvidos não só na inflamação e estresse oxidativo, mas também no tônus e remodelamento vascular, que podem ser os responsáveis pelos efeitos cardiovasculares agudos do MP2,5 / Epidemiological studies establish a clear association between air pollution and increased cardiovascular and respiratory morbidity and mortality. However, the molecular mechanisms underlying the effect of fine particulate matter (PM2,5) are still poorly understood. The aim of this study was to characterize the impact of exposure to PM2,5 on the biology of pulmonary endothelium and the heart, through the assessment of gene expression profiling by microarray. Adult female mice were anesthetized and submitted to intratracheal instillation of either PM2,5 (challenged group) or vehicle (control group). The animals were sacrificed 12 to 18 hours after instillation and lung, heart and blood samples from the inferior vena cava were collected. The lungs were dissociated with collagenase type I and endothelial cells were positively selected by immuno-magnetic capture through microbeads coupled to anti-CD31. The cRNA derived from the pulmonary endothelial cells and heart were hybridized to low-density microarray designed specifically to represent genes relevant to endothelial biology. Genes found differentially expressed in the lung were Itgb1, Cxcl1, Tnf, Ecgf1, and Tnfaip3 (over-expressed in challenged group) and Enpep, Pdgfra, Gzmb, Birc2, Npr1, Angpt1, Cxcl5 and IL7 (under-expressed). It was not possible to perform statistical inference of heart samples in this study. There was no statistically significant difference between challenged and control groups in blood counts of neutrophils, lymphocytes or platelets, despite both groups presented increased number of platelets. The findings indicate that PM2,5 alters transcription of genes involved not only in inflammation and oxidative stress, but also in vascular tonus and remodeling, which may be responsible for the acute cardiovascular effects of PM2,5

Há poucos estudos relacionados com a caracterização dos componentes biológicos presentes no material particulado atmosférico, chamados bioaerossóis. Esses componentes biológicos podem assumir uma relação direta com a deflagração de doenças e também estão relacionados com os processos climáticos, em especial como núcleos de formação de gelo. Dentre os bioaerossóis, foram estudados, neste trabalho, os fungos anemófilos, sendo os principais os Basidiomycota, Ascomycota e os Fungos mitospóricos. O objetivo desse trabalho foi estimar a contribuição dos aerossóis fúngicos para a composição biogênica do material particulado atmosférico da Região Metropolitana de São Paulo. Foram realizadas medidas em dois sítios: na Cidade Universitária e no Pico do Jaguará. Para isso, foram caracterizados os tipos fúngicos utilizando-se um microscópio ótico e estimada a massa dos aerossóis de origem fúngica utilizando-se biomarcadores. Foram realizadas coletas durante 2013, 2014 e 2015 com o amostrador Burkard 7-day Recording Sampler, sendo que em 2015 também foram realizadas coletas com filtros de quartzo com o amostrador Airmetrics MiniVol portable Sampler. Foram identificados e obtida a concentração dos tipos fúngicos observados na atmosfera da RMSP, sendo encontrados 39 grupos principais de fungos, sendo os principais os Basidiomycotas. A concentração média total foi de 5736 (± 2459) esporos/m³ por dia. Os Ascomycota, Basidiomycota e os fungos mitospóricos se correlacionaram com as variáveis meteorológicas de forma diferente. Observou-se variação da concentração de esporos durante os diferentes períodos do dia, sendo que a maior concentração de esporos ocorreu na madrugada, possivelmente devido às condições meteorológicas (elevada umidade e temperaturas mais amenas), contudo a concentração dos fungos mitospóricos foi maior durante o período da tarde, principalmente devido aos mecanismos de liberação de esporos. No verão e na primavera foram obtidas as maiores concentrações de Ascósporos e Basidiósporos e no inverno e outono foram obtidas as maiores concentrações dos fungos mitospóricos. Além disso, observou-se uma correlação positiva e significativa entre a concentração de esporos totais e o material particulado inalável (MP10), indicando que ambos são influenciados da mesma forma pelas variáveis meteorológicas e/ou tem uma fonte em comum, como por exemplo a ressuspensão da poeira do solo. O Arabitol, Manitol, Treitol e os esporos de fungos são positivamente correlacionados, indicando que os três açucares podem ser traçadores de esporos de fungos na atmosfera. Utilizando-se um fator de conversão proposto na literatura foi possível estimar que 2% da concentração do MP10 e 8% da concentração do OC estão associados aos esporos de fungos, indicando a importância dos esporos fúngicos. Com o uso de modelos receptores foram observadas 6 fontes para o MP10: queima de biomassa resultante de processos industriais; queima de biomassa resultante da queima da vegetação; aerossóis fúngicos; formação de aerossol secundário; ressuspensão do solo e emissão veicular. Esses resultados constituem um avanço para a pesquisa em bioaerossóis no Brasil, já que muitas dessas análises ainda não haviam sido realizadas em áreas urbanas no Brasil / Although the biogenic components of Particulate Matter (PM) can have a direct relationship with the outbreak of respiratory diseases and can be linked to changes in climate processes there are very few studies related to its characterization in the atmospheric aerosols. Among the bioaerosols, the airborne fungi were studied, and the Basidiomycota, Ascomycota and Mitosporic fungi were the main characterized. The goal of this work was to estimate the contribution of the fungal aerosol to the RMSP atmosphere, with samplings in two sites: Cidade universitária (USP) and Pico do Jaraguá (PJ). For that, the fungi types were characterized using an optical microscope and it was estimated the mass of the fungal aerosol using biomarkers. Sampling was carried out during 2013, 2014 and 2015 with the \"Burkard 7-day Recording Sampler\", and in 2015, filters were sampled with the \"Airmetrics MiniVol portable Sampler. It was identified and determined the concentration of the fungi types observed in the RMSP atmosphere, and were found 39 main groups of fungi. The main group was the Basidiomycota. The mean concentration of the total fungi was 5736 (± 2459) spores/m³ per day. The Ascomycota, Basidiomycota and the mitosporic fungi correlated in different ways with the meteorological variables. A variation of the spores concentration during different times of the day was observed, with the occurrence of the highest concentration of spores at dawn, possibly due to weather conditions (high humidity and cooler temperatures), but the concentration of the mitosporic fungi was higher during the afternoon, mainly due to the spores release mechanisms. In the summer and spring were observed higher concentrations of Ascospores and Basidiospores and in the autumn and winter were obtained higher concentration of Mitospores. Besides that, it was also observed a positive and significant correlation between the fungal spore with the particulate matter, indicating that both are influenced in the same way by weather variables and/or has a common source such as soil resuspension. Arabitol, Mannitol, Threitol and the fungi spores are positive correlated, indicating that these three sugar alcohols can be a tracer for fungi spores in the atmosphere. Using the conversion factor proposed in the literature was possible to estimate that 2% of the PM10 concentration and 8% of the OC concentration it is due to fungi spores, indicating its importance. Using receptor modeling it was identified six sources for PM10, the biomass burning resulting from industrial processes, the biomass burning resulting from vegetation burning, the fungal aerosol, the secondary formation aerosol, the soil resuspension and vehicular emission. These results are a breakthrough for research on bioaerosols in Brazil, since many of this analyzes had never been performed in urban areas in Brazil

A preocupação com a qualidade do ar é crescente. Nos últimos anos, as emissões industriais e veiculares acarretam em muitos casos, especialmente em áreas urbanas, condições inadequadas para a saúde da população. Diversos estudos relacionam aumento em internações hospitalares, especialmente por problemas respiratórios, durante episódios de altas concentrações de material particulado. O objetivo deste estudo foi coletar dados diários de concentração de MP10 e compará-los com uma série de dados de quase 10 anos de coleta disponíveis para a cidade de São Carlos-SP. Além disso, ambas as séries de dados foram utilizadas para criar modelos de previsão da concentração de material particulado utilizando como ferramenta as redes neurais artificiais. O local escolhido para aquisição dos dados foi a Praça Voluntários da Pátria, no centro de São Carlos, em função da grande circulação de pessoas e veículos. As duas séries de dados foram coletadas com um equipamento amostrador de grande volume &#40;AGV-MP10&#41;. A série 1 &#40;1997-2006&#41; foi obtida para caracterizar o MP de São Carlos. As coletas eram realizadas alternando-se os dias na semana. Para a série 2 &#40;2014-2015&#41; foram realizadas coletas diárias, com o mesmo equipamento e no mesmo local de amostragem da série 1. Para a criação dos modelos de previsão foram utilizados dados do Banco de Dados Meteorológicos para Ensino e Pesquisa &#40;BDMEP&#41; do Instituto Nacional de Meteorologia &#40;INMET&#41;, de temperatura &#40;&#176;C&#41;, umidade relativa &#40;&#37;&#41;, velocidade do vento &#40;m&#47;s&#41; e o acumulado de precipitação &#40;mm&#41;. Os modelos foram desenvolvidos no softwareMatLab, utilizando duas arquiteturas de redes neurais, uma do tipo MLP &#40;Multilayer Percetron&#41; e outra do tipo NARX &#40;nonlinear autoregressive network with exogenous inputs&#41;. Comparando os dados de MP10 da série 1 e da série 2, foi observado que houve uma redução nos índices de concentração de MP10 ao longo do tempo. Isto se deve à implantação de leis mais rigorosas e o desenvolvimento de tecnologias menos poluentes. Em relação aos modelos de previsão, para os dados da série 1, a utilização do modelo para previsão de médias mensais de concentração de MP10 foi mais eficiente do que o modelo para previsão de médias diárias, ambos tiveram como neurônios de entrada apenas variáveis climáticas, compostas de médias diárias e médias mensais, respectivamente. Para a previsão da série 2, o modelo utilizando a rede neural NARX, que utilizou como neurônios de entrada as variáveis climáticas e o MP10 do dia anterior, apresentou o maior erro absoluto médio &#40;7,13&#41;, no entanto, o modelo NARX apresentou a convergência mais rápida. O menor erro absoluto &#40;6,00&#41; foi obtido pelo modelo em que foi utilizada a rede do tipo MLP, que apresentava como neurônios de entrada as médias diárias das variáveis climáticas e da concentração de MP10 do dia anterior. A rede MLP também foi utilizada para criação de um modelo em que apenas as variáveis climáticas eram utilizadas, para este modelo foi encontrado o valor de 6,52 como erro absoluto. A apresentação do dado de concentração de MP10 do dia anterior torna o desempenho dos modelos de previsão mais eficiente. / Concern about air quality is growing. In recent years, industrial and vehicular emissions have in many cases, especially in urban areas, resulted in inadequate conditions for the health of the population. Several studies have reported an increase in hospital admissions, especially due to respiratory problems, during episodes of high concentrations of particulate matter. The objective of this study was to collect daily PM10 concentration data and compare them with a series of data of almost 10 years of collection available for the city of São Carlos-SP. In addition, both sets of data were used to create forecasting models of the concentration of particulate material using artificial neural networks as a tool. The place chosen for data collect was Praça Voluntários da Pátria, in the center of São Carlos, due to the great circulation of people and vehicles. The two data series were collected with a high volume air sampler. The series 1 &#40;1997-2006&#41; was obtained to characterize the PM of São Carlos. The collections were carried out alternating the days in the week. For the series 2 &#40;2014-2015&#41; daily collections were carried out with the same equipment and in the same sampling site of the series 1. For the creation of the forecast models we used data from the Banco de Dados Meteorológicos para Ensino e Pesquisa &#40;BDMEP&#41; do do Instituto Nacional de Meteorologia &#40;INMET&#41;, de temperature &#40;&#176;C&#41;, relative humidity &#40;&#37;&#41;, wind speed &#40;m&#47;s&#41; and precipitation &#40;mm&#41;. The models were developed in the MatLab software, using two neural network architectures, one of the MLP &#40;Multilayer Percetron&#41; type and another of the NARX &#40;nonlinear autoregressive network with exogenous inputs&#41; type. Comparing PM10 data from series 1 and series 2, it was observed that there was a reduction in PM10 concentration indices over time. This is due to the implementation of stricter laws and the development of cleaner technologies. In relation to the prediction models, for the data of the series 1, the use of the model to predict monthly means of concentration of PM10 was more efficient than the model for prediction of daily means, both had as input neurons only climatic variables, daily averages and monthly averages, respectively. For the prediction of series 2, the model using the NARX neural network, which used as input neurons the climatic variables and PM10 of the previous day, presented the highest mean absolute error &#40;7,13&#41;, however, the NARX model presented the better convergence. The lowest absolute error &#40;6.00&#41; was obtained by the model in which the MLP type network was used, which presented as input neurons the daily averages of the climatic variables and PM10 concentration of the previous day. The MLP network was also used to create a model in which only the climatic variables were used, for this model was found the value of 6.52 as absolute error. Presenting an PM10 concentration data from the previous day improves the performance of forecast models.

Spatial distribution of diurnal variations of aerosol properties in South Korea, both long term and short term, is studied by using 9 AERONET sites from 1999 to 2017 for long-term averages and from an additional 10 sites during the KORUS-AQ field campaign. The extent to which WRF-Chem model and the GOCI satellite retrieval can describe these variations is also analyzed. In daily average, Aerosol Optical Depth (AOD) at 550 nm is 0.386 and shows a diurnal variation of +20 to -30% in inland sites, respectively larger than the counterparts of 0.308 and ± 20% in coastal sites. Both the inland and coastal sites have their diurnal variation peaks in the early morning and in the evening with noontime and early afternoon valleys. In contrast, Angstrom exponent values in all sites are between 1.2 and 1.4 with the exception of the inland rural sites having smaller values near 1.0 during the early morning hours. All inland sites experience a pronounced increase of Angström Exponent from morning to evening, reflecting overall decrease of particle size in daytime. To statistically obtain the climatology of diurnal variation of AOD, a minimum of requirement of ~2 years of observation is needed in coastal rural sites, twice more than the urban sites, which suggests that diurnal variation of AOD in urban setting is distinct and persistent. AERONET, GOCI, WRF-Chem, and observed PM2.5 data consistently show dual peaks for both AOD and PM2.5, one at ~ 10 KST and another ~14 KST. While Korean GOCI satellite is able to consistently capture the diurnal variation of AOD, WRF-Chem clearly has the deficiency to describe the relatively change of peaks and variations between the morning and afternoon, suggesting further studies for the diurnal profile of emissions. Overall, the relative small diurnal variation of PM2.5 is in high contrast with large AOD diurnal variation, which suggests the need to use AOD from geostationary satellites for constrain either modeling or analysis of surface PM2.5 for air quality application.

Atmospheric aerosols deteriorate visibility and pose a significant risk to human health. The global fluxes of secondary organic aerosols (SOA) that form in the atmosphere from aromatic hydrocarbons are poorly constrained and highly uncertain. The lack of molecular tracers to quantify anthropogenic SOA (ASOA) in part limits the understanding of its abundance and variability, and results in a systematic underestimation of the role of ASOA in the atmosphere. The research presented in this thesis advances the knowledge about ASOA through the i) development of new and advanced methods to quantify potential ASOA tracers, ii) evaluation of their suitability as tracers for ASOA, and iii) application of the validated tracers to assess the spatial, diurnal and seasonal variation of ASOA in three urban environments. In this research, a greater understanding of the role of ASOA is gained through the expansion of tracers for SOA from aromatic hydrocarbons. An analytical method to quantify furandiones, which are produced in high yields from the photooxidation of aromatic hydrocarbons, was developed and enabled the first ambient measurements of furandiones. The optimized method allows for the simultaneous extraction of primary source tracers (e.g., polycyclic aromatic hydrocarbons, hopanes, levoglucosan) and other potential ASOA tracers (e.g., 2,3-dihydroxy-4-oxopentanoic acid [DHOPA], benzene dicarboxylic acids, and nitromonoaromatics). The systematic evaluation of potential ASOA tracers by their detectability, gas-particle partitioning, and specificity revealed that DHOPA, phthalic acid, 4-methylphthalic acids, and some nitromonoaromatics are good ASOA tracers because they are specific to aromatic hydrocarbon photooxidation, readily detected in ambient air, and substantially partition to the particle phase under ambient conditions. These tracers are thus recommended for use in field studies to estimate ASOA contributions to atmospheric aerosol relative to other sources. ASOA was determined to be a significant contributor to PM2.5 organic carbon (OC) in three urban environments. In the industrial Houston Ship Channel area in Houston, TX, ASOA contributed 28% of OC, while biogenic SOA (BSOA) contributed 11%. Diurnally, ASOA peaked during daytime and was largely associated with motor vehicle emissions. In Shenzhen, a megacity in China, 13-23% of OC mass was attributed to ASOA, three folds higher than BSOA. When China controlled the emissions from fossil fuel-related sources, the ASOA contribution to OC reduced by 42-75% and visibility remarkably improved. In downtown Atlanta, GA, ASOA contributed 29% and 16% of OC during summer and winter, respectively. ASOA dominates over BSOA during winter, while high biogenic VOC fluxes made BSOA the major SOA source in Atlanta, GA during summertime. These results indicate the high abundance of ASOA in urban air that has potential to be reduced by modification of anthropogenic activities. Overall, the work presented in this dissertation advances the knowledge about the abundance and variation of ASOA in urban atmospheres through the development of quantification methods and expansion of ASOA tracers. These tracers improve source apportionment of ASOA in receptor based models, which can ultimately aid in developing and implementing effective strategies for air quality management.

This thesis presents the use of data assimilation with optimal interpolation (OI) to develop atmospheric aerosol concentration estimates for the United States at high spatial and temporal resolutions. Concentration estimates are highly desirable for a wide range of applications, including visibility, climate, and human health. OI is a viable data assimilation method that can be used to improve Community Multiscale Air Quality (CMAQ) model fine particulate matter (PM2.5) estimates. PM2.5 is the mass of solid and liquid particles with diameters less than or equal to 2.5 μm suspended in the gas phase. OI was employed by combining model estimates with satellite and surface measurements. The satellite data assimilation combined 36 x 36 km aerosol concentrations from CMAQ with aerosol optical depth (AOD) measured by MODIS and AERONET over the continental United States for 2002. Posterior model concentrations generated by the OI algorithm were compared with surface PM2.5 measurements to evaluate a number of possible data assimilation parameters, including model error, observation error, and temporal averaging assumptions. Evaluation was conducted separately for six geographic U.S. regions in 2002. Variability in model error and MODIS biases limited the effectiveness of a single data assimilation system for the entire continental domain. The best combinations of four settings and three averaging schemes led to a domain-averaged improvement in fractional error from 1.2 to 0.97 and from 0.99 to 0.89 at respective IMPROVE and STN monitoring sites. For 38% of OI results, MODIS OI degraded the forward model skill due to biases and outliers in MODIS AOD. Surface data assimilation combined 36 × 36 km aerosol concentrations from the CMAQ model with surface PM2.5 measurements over the continental United States for 2002. The model error covariance matrix was constructed by using the observational method. The observation error covariance matrix included site representation that scaled the observation error by land use (i.e. urban or rural locations). In theory, urban locations should have less effect on surrounding areas than rural sites, which can be controlled using site representation error. The annual evaluations showed substantial improvements in model performance with increases in the correlation coefficient from 0.36 (prior) to 0.76 (posterior), and decreases in the fractional error from 0.43 (prior) to 0.15 (posterior). In addition, the normalized mean error decreased from 0.36 (prior) to 0.13 (posterior), and the RMSE decreased from 5.39 μg m-3 (prior) to 2.32 μg m-3 (posterior). OI decreased model bias for both large spatial areas and point locations, and could be extended to more advanced data assimilation methods. The current work will be applied to a five year (2000-2004) CMAQ simulation aimed at improving aerosol model estimates. The posterior model concentrations will be used to inform exposure studies over the U.S. that relate aerosol exposure to mortality and morbidity rates. Future improvements for the OI techniques used in the current study will include combining both surface and satellite data to improve posterior model estimates. Satellite data have high spatial and temporal resolutions in comparison to surface measurements, which are scarce but more accurate than model estimates. The satellite data are subject to noise affected by location and season of retrieval. The implementation of OI to combine satellite and surface data sets has the potential to improve posterior model estimates for locations that have no direct measurements.

Understanding the composition of atmospheric organic particulate matter (OPM) is essential for predicting its effects on climate, air quality, and health. However, the polar oxygenated fraction (PO-OPM), which includes a significant mass contribution from carboxylic acids, is difficult to speciate and quantitatively determine by current analytical methods such as gas chromatography-mass spectrometry (GC-MS). The method of chemical derivatization and two-dimensional GC with time of flight MS (GC×GC/TOF-MS) was examined in this study for its efficacy in: 1) quantifying a high percentage of the total organic carbon (TOC) mass of a sample containing PO-OPM; 2) quantitatively determining PO-OPM components including carboxylic acids at atmospherically relevant concentrations; and 3) tentatively identifying PO-OPM components. Two derivatization reagent systems were used in this study: BF₃/butanol for the butylation of carboxylic acids, aldehydes, and acidic ketones, and BSTFA for the trimethylsilylation (TMS) of carboxylic acids and alcohols. Three α-pinene ozonolysis OPM filter samples and a set of background filter samples were collected by collaborators in a University of California, Riverside environmental chamber. Derivatization/GC×GC TOF-MS was used to tentatively identify some previously unidentified α-pinene ozonolysis products, and also to show the characteristics of all oxidation products determined. Derivatization efficiencies as measured were 40-70% for most butyl derivatives, and 50-58% for most trimethylsilyl derivatives. A thermal optical method was used to measure the TOC on each filter, and a value of the quantifiable TOC mass using a gas chromatograph was calculated for each sample using GC×GC separation and the mass-sensitive response of a flame ionization detector (FID). The TOC quantified using TMS and GC×GC-FID (TMS/TOCGC×GC FID) accounted for 15-23% of the TOC measured by the thermal-optical method. Using TMS and GC×GC/TOF-MS, 8.85% of the thermal optical TOC was measured and 48.2% of the TMS/TOCGC×GC-FID was semi-quantified using a surrogate standard. The carboxylic acids tentatively identified using TMS and GC×GC/TOF-MS accounted for 8.28% of the TOC measured by thermal optical means. GC×GC TOF-MS chromatograms of derivatized analytes showed reduced peak tailing due in part to the lesser interactions of the derivatized analytes with the stationary phase of the chromatography column as compared to the chromatograms of underivatized samples. The improved peak shape made possible the greater separation, quantification, and identification of high polarity analytes. Limits of detection using derivatization and GC×GC/TOF-MS were μL injected for a series of C2-C6 di-acids, cis-pinonic acid, and dodecanoic acid using both butylation and TMS. Derivatization with GC×GC/TOF-MS was therefore effective for determining polar oxygenated compounds at low concentrations, for determining specific oxidation products not previously identified in OPM, and also for characterizing the probable functional groups and structures of α-pinene ozonolysis products.