A high-volume air sampler (PS-1) was used to measure the concentrations of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of Kaohsiung coast, PAHs diagnostic ratios,Hierarchical Cluster Analysis (HCA) and Principal Component Analysis (PCA) were employed to determine the potential sources of PAHs. The results show that the lowest concentrations of PAHs occurred in May (2.62 ngm-3), while the highest occurred in December (36.4 ngm-3). The nighttime concentrations of PAHs are higher than daytime with average night / day ratio of 1.65. The PAHs was more distributed in gas phase with proportions between 64.1 to 93.7 %. The 2, 3-Ring PAHs were mostly present in the gaseous phase (96.2 and 96.5 % respectively), 4-Ring also present dominantly in the gaseous phase (73.0 %), 5-Ring present mostly in the particle phase (80.2 %), 6, 7-Ring PAHs were mostly present in particulate phase (97.4 and 97.7 % respectively). During the Ghost Festiva and Asian dust storm events, atmospheric concentrations of PAHs and PAHs/TSP ratios were both found increased. It is found that gaseous and particulate PAHs correlate negatively with ambient temperature(r=-0.62, -0.57). Results from analyses of diagnostic ratios, HCA and PCA, the major sources of pollution include gasoline, diesel exhaust and industrial emission.

Fours sets of PM10 samples were collected in three sites in SEQ from December 2002 to August 2004. Three of these sets of samples were collected by QLD EPA as a part of their regular air monitoring program at Woolloongabba, Rocklea and Eagle Farm. Half of the samples were used in this study for the analysis of water-soluble ions, which are Na+, K+, Mg2+, Ca2+, NH4 +, Cl-, NO3 -, SO4 2-, F-, Br-, NO2 -, PO4 -3 and the other half was retained by QLD EPA. The fourth set of samples was collected at Rocklea, specifically for this study. A quarter of the samples obtained from this set of samples were used to analyse water-soluble ions; a quarter of the sample was used to analyse Pb, Cu, Al, Fe, Mn and Zn; and the rests were used to analyse US EPA 16 priority PAHs. The water-soluble ions were extracted ultrasonically with water and the major watersoluble anions as well as NH4 + were analysed using IC. Na+, K+, Mg2+, Ca2+ Pb, Cu, Al, Fe, Mn and Zn were analysed using ICP-AES while PAHs were extracted by acetonitrile and analysed using HPLC. Of the analysed water-soluble ions, Cl-, NO3 -, SO4 2-, Na+, K+, Mg2+ and Ca2+ were high in concentration and determined in all the samples. F-, Br-, NO2 -, PO4 -3 and NH4 + ions were lower in concentration and determined only in some samples. Na+ and Cl- were high in all samples indicating the importance of a marine source. Principal Component Analysis (PCA) was used to examine the temporal variations of the water-soluble ions at the three sites. The results indicated that there was no major difference between the three sites. However, comparing the average concentrations of ions and Cl-/Na+ it was concluded that Woolloongabba had more marine influence than the other sites. Al, Fe and Zn were detected in all samples. Al and Fe were high in all samples indicating the significance of a source of crustal matter. Cu, Mn and Pb were in low concentrations and were determined only in some samples. The lower Pb concentrations observed in the study than in previous studies indicate that the phasing-out of leaded petrol had an appreciable impact on Pb levels in SEQ. This study reports for the first time, simultaneous data on the water-soluble, metal ion and PAH levels of PM10 aerosols in Brisbane, and provides information on the most likely sources of these chemical species. Such information can be used alongside those that already exist to formulate PM10 pollution reduction strategies for SEQ in order to protect the community from the adverse effects of PM pollution.

In this work the organic markers that serve for identification of sources of aerosols are monitored. Theoretic part deals with detailed survey of organic markers emitted from the most significant sources of atmospheric aerosols (biomass combustion, combustion of fossil fuels and traffic) as well as with sampling of aerosols and analysis of organic markers by analytical techniques. Monosaccharide anhydrides (emissions from biomass combustion) and polyaromatic hydrocarbons (emissions from traffic and incomplete combustion) were observed especially. Hopanes and steranes (traffic, coal combustion) and fatty acids (cooking) were next groups of monitored organic markers. Markers were studied mainly in size fraction PM1 because this fraction of aerosols is the most harmful to human health. Aerosols were sampled in two seasons (winter and summer) in two towns in 2009. Higher concentrations of aerosols and organic compounds were found in winter season, which resulted from increased combustion of biomass, coal and other organic material while traffic was the most significant source of aerosols in summer.

Made available in DSpace on 2014-12-17T14:08:43Z (GMT). No. of bitstreams: 1 MariaSMQ_DISSERT_1-36.pdf: 5283210 bytes, checksum: e75f1aa1d6f8e40607338226667f1b0d (MD5) Previous issue date: 2011-02-07 / Estuaries are environments prone to the input of chemical pollutants of various kinds and origins, including polycyclic aromatic hydrocarbons (PAHs). Anthropogenic PAHs may have two possible sources: pyrolytic (with four or more aromatic rings and low degree of alkylation) and petrogenic (with two and three aromatic rings and high degree of alkylation). This study aimed to evaluate the levels, distribution and possible sources of polycyclic aromatic hydrocarbons in the estuary of the Potengi river, Natal, Brazil. Samples of bottom sediments were collected in the final 12 km of the estuary until its mouth to the sea, where the urbanization of the Great Natal is more concentrated. Sampling was performed on 12 cross sections, with three stations each, totaling 36 samples, identified as T1 to T36. The non alkylated and alkylated PAHs were analyzed by gas chromatography coupled to mass spectrometry (GC / MS). PAHs were detected in all 36 stations with total concentration on each varying 174-109407 ng g-1. These values are comparable to those of several estuarine regions worldwide with high anthropogenic influence, suggesting the record of diffuse contamination installed in the estuary. PAHs profiles were similar for most stations. In 32 of the 36 stations, low molecular weight PAHs (with 2 and 3 ring: naphthalene, phenanthrene and their alkylated homologues) prevailed, which ranged from 54% to 100% of the total PAH, indicating that leaks, spills and combustion fuels are the dominant source of PAH pollution in the estuary. The level of contamination by PAHs in most stations suggests that there is potential risk of occasional adverse biological effects, but in some stations adverse impacts on the biota may occur frequently. The diagnostic ratios could differentiate sources of PAHs in sediments of the estuary, which were divided into three groups: petrogenic, pyrolytic and mixing of sources. The urban concentration of the Great Natal and the various industrial activities associated with it can be blamed as potential sources of PAHs in bottom sediments of the estuary studied. The data presented highlight the need to control the causes of existing pollution in the estuary / Os estu?rios s?o ambientes prop?cios ao aporte de poluentes qu?micos de diversas naturezas e origens, incluindo Hidrocarbonetos Polic?clicos Arom?ticos (HPA). Os HPA antr?picos s?o de duas fontes poss?veis: pirol?tica (com quatro ou mais an?is arom?ticos e baixo grau de alquila??o) e petrog?nica (com dois e tr?s an?is arom?ticos e alto grau de alquila??o). O presente trabalho teve como objetivo avaliar os n?veis, distribui??o e poss?veis fontes de Hidrocarbonetos Polic?clicos Arom?ticos no estu?rio do rio Potengi, Natal-RN. Amostras de sedimentos de fundo foram coletadas nos 12 km finais do estu?rio at? a sua foz, onde a urbaniza??o da Grande Natal ? mais concentrada. A amostragem foi realizada em 12 se??es transversais, com tr?s esta??es em cada uma, totalizando 36 amostras, identificadas de T1 a T36. Os HPA alquilados e n?o alquilados foram analisados por cromatografia gasosa acoplada a um detector seletivo de massas (CG/EM). Foram detectados HPA em todas as 36 esta??es, com concentra??o total em cada uma variando de 174 a 109407 ng g-1. Esses valores s?o compar?veis aos de v?rias regi?es estuarinas mundiais com grande influ?ncia antr?pica, o que sugere o registro de contamina??es difusas instaladas no estu?rio. O perfil de HPA foi similar para a maioria das esta??es. Em 32 das 36 esta??es predominaram HPA de baixo peso molecular (com 2 e 3 an?is: naftaleno, fenantreno e seus hom?logos alquilados), que variaram de 54% a 100% em rela??o ao total de HPA, indicando que vazamentos, derramamentos e queima de combust?veis s?o a fonte dominante de polui??o por HPA no estu?rio. O n?vel de contamina??o por HPA na maioria das esta??es sugere que h? risco potencial de ocasionais efeitos biol?gicos adversos serem observados, por?m em algumas esta??es se confirmam que impactos adversos sobre a biota ocorrem com freq??ncia. As raz?es diagn?sticas permitiram diferenciar as fontes de HPA nos sedimentos do estu?rio, que foram divididos em tr?s grupos: sedimentos com padr?es de introdu??o de hidrocarbonetos petrog?nicos, pirol?ticos e de mistura de fontes. A concentra??o urbana da Grande Natal e as atividades industriais diversas a ela associadas podem ser responsabilizadas como fontes potenciais dos HPA nos sedimentos de fundo do estu?rio estudado. Os dados apresentados evidenciam a necessidade de se controlar as causas da polui??o existente no estu?rio

Submitted by Biblioteca de Pós-Graduação em Geoquímica BGQ (bgq@ndc.uff.br) on 2016-05-02T17:58:54Z No. of bitstreams: 1 GALLOTTA_30_06_14.pdf: 62695484 bytes, checksum: 33335ee3affc2bcffb11fc10caf9ae3f (MD5) / Made available in DSpace on 2016-05-02T17:58:54Z (GMT). No. of bitstreams: 1 GALLOTTA_30_06_14.pdf: 62695484 bytes, checksum: 33335ee3affc2bcffb11fc10caf9ae3f (MD5) / Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ / Os hidrocarbonetos presentes no ambiente consistem em misturas complexas de compostos derivados de múltiplas fontes. Os combustíveis fósseis representam a principal contribuição, devido à taxa e escala espacial, em que o petróleo tem sido usado como fonte de energia e matéria-prima para a indústria química. O objetivo deste estudo foi avaliar os níveis de concentração e identificar fontes de hidrocarbonetos na Bacia do Alto Iguaçu e, em especial, na área de influência da Refinaria Presidente Getúlio Vargas (REPAR). Além dos fatores de poluição crônica, a área de estudo foi alvo de um derrame acidental de petróleo em julho de 2000. Diversos indicadores em diferentes compartimentos ambientais (água superficial, sedimento, solo e água subterrânea) foram avaliados na fase pós-derrame e no monitoramento ambiental ao longo de várias campanhas por mais de uma década. Os esforços de avaliação foram concentrados nos seguintes indicadores: os nalcanos, os alcanos isoprenoides, os hidrocarbonetos policíclicos aromáticos (HPA), os biomarcadores de petróleo e ainda o total de hidrocarbonetos de petróleo (THP). Os resultados identificaram como principal aporte de matéria orgânica para as águas superficiais dos rios Barigüi e Iguaçu, os fluxos materiais originados em região a montante do acidente, refletindo a contribuição antropogênica crônica da cidade de Curitiba. Em 2007 e 2008, as concentrações de THP e HPA nas águas superficiais e sedimentos dos rios Barigüi e Iguaçu refletem uma expressiva melhoria nas condições desses rios em relação a 2000. Na área interna da refinaria (Ponto Zero), observou-se uma nítida diminuição (atenuação) natural das concentrações de THP no solo em todas as profundidades dos perfis amostrados ao longo do tempo nos Banhados 1 e 4 e, em particular, uma diminuição importante das concentrações entre 2004 e 2007. Para a identificação das fontes de hidrocarbonetos foram utilizadas razões diagnósticas e quimiometria. As razões diagnósticas calculadas a partir de concentrações de HPA sugeriram que, na maioria dos sedimentos dos Rios Barigüi e Iguaçu coletados nas campanhas de 2000 e 2001, a fonte petrogênica é a principal. Somente na estação a montante do acidente no Rio Barigüi, a fonte pirolítica predominou nestas duas campanhas. As razões diagnósticas que apresentaram maior eficiência na identificação de fontes de hidrocarbonetos nos sedimentos dos rios Barigüi e Iguaçu foram: ΣC1-Fenantrenos/Fenantreno; e (ΣHPA parentais de 3-6 anéis)/(Σ5 séries de HPA alquilados). A identificação de fontes através de razões diagnósticas calculadas a partir de áreas e alturas de picos cromatográficos demonstrou sua aplicabilidade verificando a relação entre os compostos encontrados em amostras de solo da área interna da refinaria com a amostra de petróleo derramado no acidente, após quase uma década da ocorrência do vazamento. A identificação de fontes através método de quimiométrico baseado na análise de componentes principais (ACP) de seções pré-processadas e combinadas dos Cromatogramas de Íons Selecionados (CIS) mostrou que as amostras mais contaminadas estão na área interna da refinaria. Essas amostras apresentam um padrão de distribuição petrogênica e diferentes graus de intemperismo. As amostras da área externa à refinaria (Guajuvira, General Lúcio e Balsa Nova) são menos ou não contaminadas e/ou contém uma mistura de contribuições diagenéticas, pirolíticas e petrogênicas onde predominam diferentes proporções. Os locais mais distantes da atividade industrial (Balsa Nova) contem, como esperado, os níveis mais baixos de contaminação por HPA. Os resultados de biomarcadores demonstraram que não há evidências para concluir que as amostras da área externa à refinaria e o óleo Cusiana vazado tenham a mesma origem. Os resultados ao longo dos rios Barigüi e Iguaçu e do Ponto Zero demonstraram que as ações de emergência para a contenção do óleo foram adequadas para os rios, e que a contaminação decorrente do derrame ficou predominantemente contida no Ponto Zero e diminuiu significativamente após uma década. / Hydrocarbons present in the environment consist of complex mixtures of compounds derived from multiple sources. The main contribution lies on fossil fuel inputs due to the rate and spatial scale by which petroleum has been used as an energy source and chemical feedstock. The aim of this study was to assess the concentration levels and identify sources of hydrocarbons in the Upper Iguaçu Watershed and, in particular, in the area of influence of the President Getulio Vargas Refinery (REPAR). In addition to the factors of chronic pollution, the study area was the scenario of an acute accidental oil spill in July 2000. Numerous indicators in different environmental compartments (surface water, sediment, soil and groundwater) were assessed in the post spill phase and during the environmental monitoring programs over the course of several campaigns for more than a decade. Assessment efforts were concentrated on the following indicators: n-alkanes, alkanes isoprenoids, polycyclic aromatic hydrocarbons (PAH), petroleum biomarkers and total petroleum hydrocarbons (TPH). The results identified as the main contribution of organic matter to surface waters of the Barigüi and Iguaçu Rivers the materials flows originated in the region upstream of the accident, reflecting chronic anthropogenic contribution of the city of Curitiba. In 2007 and 2008, the TPH and PAH concentrations in surface waters and sediments of the Barigüi and Iguaçu Rivers revealed a significant improvement in the conditions of these rivers when compared with 2000. Inside the refinery area (Point Zero), it was observed a clear natural decrease (attenuation) of the concentrations of TPH in the soil at all depths sampled over time in Marshes 1 and 4 and, in particular, an important decrease of concentrations between 2004 and 2007. Diagnostic ratios and chemometrics were used to identity hydrocarbon sources. The diagnostic ratios calculated from the concentrations of PAH suggested that, in the majority of sediments from the Barigüi and Iguaçu Rivers collected in 2000 and 2001 campaigns, the main source is petrogenic. Only in the station upstream the accident in the Barigüi River, the pyrolytic source predominated in these two campaigns. The diagnostic ratios that presented higher efficiency in identifying sources of hydrocarbons in sediments of the Barigüi and Iguaçu Rivers were: ΣC1- Phenantrenes/Phenanthrene; and (Σ3-6 rings parental PAH)/(Σ5 alkylated PAH series). The source identification through diagnostic ratios calculated from heights and areas of chromatographic peaks demonstrated its applicability establishing a relationship between the compounds found in soil samples of the internal area of the refinery and the sample of the oil spilled in the accident, after nearly a decade of occurrence of the spillage. The source identification through chemometric method based on principal components analysis (PCA) of preprocessed and combined sections of Selected Ion Chromatograms (SIC) showed that the most contaminated samples are inside the refinery area. These samples present a petrogenic pattern and different weathering degrees. Samples from outside the refinery area (Guajuvira, General Lúcio e Balsa Nova) are either less or not contaminated, and/or contain mixtures of diagenetic, pyrogenic and petrogenic inputs where different proportions predominate. The locations farthest away from industrial activity (Balsa Nova) contain, as expected, the lowest levels of PAH contamination. The biomarkers results do not show any evidences to conclude positive matches between the samples from outside the refinery area and the spilled Cusiana oil. The results along Barigüi and Iguaçu rivers and Point Zero demonstrated that emergency actions to contain the oil were appropriate for the rivers, and that the contamination resulting from the spill was mostly contained in the Point Zero and decreased significantly after one decade