Understanding of the fate of oil in the environment is of utmost importance; however, accurate, predictive models are still in very early stages. To aid in the development of these models, photodegradation of selected polycyclic aromatic hydrocarbons (PAHs) in an n-alkane hydrocarbon matrix was followed for individual PAHs and mixtures of PAHs similar to that found in the Deepwater Horizon spill. Tetracene in tetradecane photodegraded quickest of all observed PAHs, with a loss of 99% after only one hour of irradiation. Binary mixtures of PAHs showed different degradation amounts, including changes in PAH kinetics. These results suggest that the formation of dimers or aggregates as well as photosensitization reaction is important in the degradation of PAHs in oil. Kinetics of PAH photodegradation and PAH sensitized photodegradation will be presented. This information will provide a better understanding of the fate of oil in environmental systems.

Ce travail a eu pour objectif l’étude de la dégradation hétérogène d’hydrocarbures aromatiques polycycliques (HAP) et de polybromo diphényles éthers (PBDE) en présence d’oxydants atmosphériques. La réactivité du benzo[a]pyrène et du dibenzo[a,l]pyrène pour les HAP et du BDE 153 (hexabromé) et du BDE 209 (décabromé) pour les PBDE, a été étudiée lorsqu’ils sont adsorbés sur des particules minérales modèles (des particules de silice) et exposés à l’ozone, au dioxyde d’azote ou aux radicaux hydroxyles. L’extraction et l’analyse de ces composés ont été optimisées. Le suivi de l’évolution de la concentration en composé adsorbé en fonction de son temps d’exposition à l’oxydant a permis de déterminer les paramètres cinétiques de chaque composé, pour chaque oxydant. L’influence de la concentration particulaire et de la structure moléculaire sur la réactivité a ainsi été évaluée et débattue. L’identification des produits de réactions majoritaires a été effectuée pour les réactions des HAP avec le dioxyde d’azote et les radicaux hydroxyles et les réactions des PBDE avec les radicaux hydroxyles. Enfin, l’étude de la génotoxicité des extraits de particules pour différents temps d’exposition aux oxydants a été réalisée. Cette étude regroupe une approche cinétique, une approche mécanistique et une approche toxicologique. / This work deals with the heterogeneous degradation of polycyclic aromatic hydrocarbons (PAH) and polybromo diphenyls ethers (PBDE) with various atmospheric oxidants. The reactivity of Benzo[a]pyrene (BaP) and dibenzo[a,l]pyrene (DalP) for PAH and BDE 153 and BDE 209 for PBDE, had been studied when they are adsorbed on a model of mineral particles (silica particles) and exposed to ozone, nitrogen dioxide and hydroxyl radical. Extraction and analyse of compounds were optimised. For all studied reactions, kinetic parameters were obtained following the remaining concentration of compound for different exposure times. Influence of the particle loading and molecular structure on the reactivity had been evaluated and discussed. Identification of the main degradation products was made for the reaction of PAH with nitrogen dioxide and hydroxyl radical and for the reaction of PBDE with hydroxyl radical. Then, the genotoxicity of the particle extracts was made for different exposure times. This study talks about kinetics, mechanistic and genotoxicity.

Human activities over the years, especially the unconventional exploitation of oil sands deposits, downstream on the Athabasca River (AR), might have affected the water quality and ecological integrity of the river basin, thereby presenting a threat to the environment and human health. There have been concerns that the oil sands process-affected waters stored in tailing ponds may be percolating to surface waters as well as underground waters, contaminating neighboring watersheds with a cocktail of chemicals including Polycyclic aromatic hydrocarbons (PAHs). PAHs are present both naturally and from human activities as pollutants in the environment. Forest fires, geologic activities, and oil seeps are examples of natural sources of PAHs in the environment. The major sources of PAHs in the Athabasca region are leaching of oil sands deposits and contamination from oil sands production. On occasions, forest fires contribute PAHs in the area. There has been no comparative data on the exposure of PAHs to fish along the AR and Slave River. I used an integrative monitoring of selected fishes as an indicator to achieve four objectives: i) describe the spatial and seasonal distribution of measurable concentrations of products of biotransformation of polycyclic aromatic hydrocarbons (PBPAH) in bile of fish; ii) determine the levels of parent PAHs in the muscle of fish, and extrapolate the data to estimate potential risk to human consumers, and to identify which species and geographic regions, if any, pose the greatest risk to humans; iii) use patterns of contamination to provide a scientific basis for elucidating the source of contamination; and iv) perform fish health investigation by collecting morphometric health measures and perform a systematic assessment of the occurrence of lesions in the fishes. I sampled whitefish (Coregonus clupeaformis), jackfish/northern pike (Esox luscius), walleye (Sander vitreus), goldeye (Hiodon alosoides) and burbot (Lota lota) from Fort McMurray, Fort McKay, and Fort Chipewyan in Alberta, and from Fort Smith and Fort Resolution on the Slave River in the Northwest Territories. The rationale for selecting fishes included: their abundance along the basin (some have short ranges, e.g., northern pike); their dietary/nutritional and cultural significance to communities in the area; their feeding strategy, such as benthic, supra-benthic, or pelagic, trophic status, and patterns of migration and habits of spawning. I addressed the first objective in Chapter 2, where the total PBPAHs were determined. Concentrations of products of biotransformation of 2 and 3-ringed, 4-ringed, and 5-ringed PAHs were measured using synchronous fluorescence spectroscopy. Spatial and seasonal differences were observed with greater concentrations of PBPAHs in samples of bile of fish collected from Fort McKay as well as greater concentrations of PBPAHs in bile of fish collected during summer compared to those collected in other seasons. Overall, PBPAHs were greater in fishes of lower trophic levels and fishes more closely associated with sediments. In particular, goldeye (Hiodon alosoides), consistently contained greater concentrations of all the PBPAHs studied. In Chapter 3, I achieved the second objective by measuring levels of parent PAHs in muscle of selected fishes and extrapolated the results to determine potential human health risks due to fish consumption. Dorsal muscle of fishes from upstream reaches of the AR close to oil sands extraction and upgrading activities, contained greater concentrations of individual PAHs than concentrations in muscle of fishes from further downstream in the Slave River. Risks posed by PAHs to humans were assessed using a B[a]P equivalents approach. According to the risk assessment results, the average lifetime risk of additional cancers for humans who consumed fish was less than 10-6. In Chapter 4, alkylated PAHs were also measured in fish muscle to achieve the third objective. The general presence of naphthalenes and phenanthrenes and the evaluation of molecular ratios (i.e., LMW/HMW alkyl-PAHs) allowed me to conclude that the major source of pollution is petrogenic, probably due to increases in oil sand activities around Fort McMurray and Fort McKay. I achieved the fourth objective in Chapter 5 by studying the health status and potential effects of industrial development on individuals of economically and culturally significant fishes. A resurgence in condition factor of all species after a low in 2011 was observed. Annual variation was also observed in condition factor and the incidence of anomalies or lesions. Morphometric data demonstrated relatively consistent health among fishes in both the Athabasca and Slave rivers. Analysis of condition factor and somatic indices did not demonstrate consistent differences along the river system. Overall, the health of fish as determined by the metrics employed in this study, does not appear to be adversely affected by the current level of development in the Alberta oil sands region. The data presented in this dissertation make invaluable contribution to the much needed monitoring program in the Athabasca and Slave Rivers. Overall, my findings provide baseline data on fish health, concentrations of parent and alkylated PAHs, and products of biotransformation of PAH in five species of large-bodied fishes consumed by humans in communities in the Lower Athabasca and Slave River basin. These results will be useful for establishing the status and trends and spatial distribution of PAHs during monitoring of the lower Athabasca basin and most importantly, as a valuable reference point before any potential permitted discharges of wastewaters from processing of oil sands to the AR.

Polycyclic aromatic hydrocarbons (PAHs) are a group of ubiquitous environmental contaminants with two or more aromatic rings and originating from different emission sources. They are extremely toxic, carcinogenic and mutagenic to human, animals and plants. Consequently, the need to expand economical and practical remediation technologies for PAH contaminated sites is evident. In this study, the effect of biotic and abiotic factors on degradation of PAH was studied. The degradation was studied on the key model PAH (phenanthrene, anthracene, fluoranthene and pyrene) in J. Arthur Bower’s top soil. The hypothesis for this study was that roadside soil would contain PAH degrading bacteria; pH would influence the microbial degradation of PAH, chemical oxidation of PAH would be as efficient as microbial breakdown of PAH and mobilising agents, would move PAH throughout soil, potentially making the PAH more available for biodegradation. The greatest degradations were found for the lowest molecular weight PAH, phenanthrene and anthracene; whilst lowest degradation was observed for higher molecular weight PAH, fluoranthene and pyrene. Twelve bacteria genera were isolated and identified by biochemical and molecular techniques from the roadside soil with the four PAHs as the sole carbon source. However, potentially new PAH biodegrader bacteria species and a novel were found in this study, which was not reported in the literature. The effect of pH between 5.0 and 8.0 at half pH intervals on biodegradation of the four PAHs and on bacterial populations in the soil over 32 days was monitored. The greatest population of bacteria and greatest biodegradation for the four PAHs was found at pH of 7.5. It is likely that the general increase in population was also linked with greater metabolic activities of bacteria at basic pHs which assists pollutant biodegradation. Although there is high pollutant mobility at low pHs, the biodegradation was limited due to reduced microbial activity. High pHs resulted in greater PAH biodegradation suggesting that pH manipulation by liming may be an effective way of stimulating biodegradation of PAH. The effect of potassium permanganate on oxidation of the four PAHs in the soil was examined. Studies in this thesis, indicated that potassium permanganate had a significant (p<0.05) effect on oxidation of the four PAHs at pH 7.5 over 35 days. However in comparison to biodegradation, chemical oxidation has significantly (p<0.05) less effect. Finally, the effect of Tween 20 only on translocation and biodegradation of the four PAHs at pH 7.5 over 35 days was examined. Studies indicated that Tween 20 had significantly (p<0.05) enhanced translocation of the four PAHs in the sterile soil. Moreover, the greatest biodegradation was found in the soil inoculated with only the roadside soil microorganisms but without Tween 20. This suggested that Tween 20 had a significant (p<0.05) inhibitory effect on the roadside soil microorganisms and therefore less microorganism were grown in the soil containing Tween 20. This indicated that Tween 20 was translocated PAH, but inhibited breakdown. This study indicated microbial biodegradation was the most effective technique for removing of the PAH from contaminated soil, which was cost effective and easier to perform in comparison to the other two techniques. Microbial biodegradation could be improved by adjusting pH through liming if soil was acid.

O objetivo deste trabalho foi avaliar a biodisponibilidade de HPAs na água do mar no sistema estuarino de Santos e no sistema lagunar de Cananéia-Iguape, para isso foi feita a exposição de membranas semipermeáveis (SPMD) e de bivalves (Crassostrea brasiliana) a fim de se obter um melhor panorama das concentrações desse poluente nessas duas regiões. De forma complementar foram analisadas também amostras de água, material particulado em suspensão (MPS) e sedimentos. A bioacumulação de HPAs no tecido de bivalves foi cerca de quatro vezes superior às suas concentrações iniciais para a região de Santos. Foram também estimadas as concentrações de HPA na água do mar através das concentrações encontradas nos SPMDs e nos bivalves transplantados. Essas concentrações foram comparáveis às concentrações encontradas nas amostras de água. Através da análise de componentes principais juntamente com índices diagnósticos foi possível estabelecer as possíveis fonte de HPAs para as matrizes analisadas, identificando assim a predominância de HPAs pirolíticos em bivalves e sedimentos, enquanto que na água, MPS e SPMDs há predominância de HPAs petrogênicos. A comparação entre compartimentos mostrou a importância da avaliação de múltiplas matrizes, em função da concentração de HPAs cada grupo de compostos e de seus diferentes padrões de acumulação. Não foram observadas diferenças significativas entre as concentrações médias de HPAs nas duas regiões de estudo. O Complexo de Cananéia - Iguape antes considerada como área controle, apresentou concentrações de HPAs elevadas, indicando influencia antrópica para a região. / The aim of this work was to evaluate PAH\'s bioavailability in the sea water in Santos Estuarine System and Cananéia - Iguape Lagoon System. SemiPermeable Membrane Devices (SPMD) and bivalves (Crassostrea brasiliana) were deployed in both areas to obtain an overview of all these pollutants concentration, further than the potential of bioaccumulation of contaminants. Aiming comparative purposes, samples of water, suspended particulate matter (SMP) and sediments were also analyzed. PAHs bioaccumulation in bivalves tissues after deployment represented fourfold the initial concentration for Santos region. The estimated concentration of 16 priority PAHs in the water SPMD- and bivalve-based were within the concentration of PAH analyzed in the water samples, demonstrating the effectiveness of those tools to assessment of PAH in water. Through the Principal Components Analysis (PCA), and the diagnostic ratios it was possible to establish the potential sources of PAHs for analyzed compartments, identifying the pyrolytic PAH influence for bivalves and sediments under, while for water, MPS and SPMDs the mainly PAHs source were from petrogenic PAHs. Comparison between compartments showed the importance of multiple tools analyzes due to the concentration of PAH of each compound group and the different pattern of accumulation. It was not observed significant difference between the mean concentrations of PAHs in both studied regions. Cananéia - Iguape Complex was first considered as control area reported PAHs concentration higher PAH concentrations, suggesting anthropic influence in this area.

As concentrações de HPAs foram analisadas em invertebrados (Laternula elliptica, Nacella concinna, Yoldia eightsi, Glyptonotus antarcticus, Serolis polita, Euphausia superba, Bovalia gigantea, Sterechinus neumayeri, Odontaster validus e Ophionotus victoriae), peixes (Notothenia rossii), e aves (Pygoscelis Adélia, P. papua, P. antarcticus, Macronectes giganteus, Catharacta sp. e Larus dominicanus) da Baía do Almirantado. As análises de HPAs foram realizadas através de GC/MS. A ocorrência de HPAs nas amostras indicou a biodisponibilidade destes compostos para os organismos da região. As concentrações de HPAs totais para os invertebrados (3,09-174,4 ng g -1 pu) foram maiores que em peixes (0,97-58,9 ng g -1 pu) e menores que em aves (60,1-6861,0 ng g-1 pu), porém apresentaram similaridade entre si. As aves voadoras adultas apresentaram maiores concentrações que os pinguins. Compostos leves e alquilados predominaram em quase todas as amostras, principalmente os alquilnaftalenos. A principal fonte de HPAs para os organismos foi o DFA utilizado na EACF. Espécies predadoras/necrófagas apresentaram HPAs individuais diferentes das espécies suspensívoras/depositívoras. Não ocorreu relação entre o aumento da concentração de HPAs e o aumento do nível trófico dos grupos, e a absorção de HPAs pelas espécies sofreu a influência de fatores como metabolismo, fisiologia, hábito alimentar e teor de lipídio das espécies analisadas. / The concentrations of PAHs had been analyzed in invertebrates (Laternula elliptica, Nacella concinna, Yoldia eightsi, Glyptonotus antarcticus, Serolis polita, Euphausia superba, Bovalia gigantea, Sterechinus neumayeri, Odontaster validus and Ophionotus victoriae), fish (Notothenia rossii) and birds (Pygoscelis adélia, P. papua, P. antarcticus, Macronectes giganteus, Catharacta sp. and Larus dominicanus) Admiralty Bay. The analyses of HPAs had been carried through GC/MS. The occurrence of PAHs in the samples indicated the bioavailability of these compounds for the organisms of the region. The concentration of total PAHs for the invertebrates (3,09 to 174,4 ng g-1 pu) were higher than fish (0,97 to 58,9 ng g-1 pu) and lower than in birds (60,1- 6861,0 ng g-1 pu) however, they had presented similarity between themselves. The adult flying birds had presented higher concentrations than penguins. Light and alkylated compounds had predominated in almost all samples, mainly the alkylnaphthalenes. The main source of PAHs for the organism was the DFA used in the EACF. Predators/necrophagous species had presented different individual PAHs from the feeder/deposit species. There was no relation between the increase of concentrations of PAHs and the increase of the trophic level of the groups, and the absorption of PAHs for the species had the influence of factors such as metabolism, physiology, alimentary habits and lipid content of the analyzed species.

O crescente mercado dos produtos naturais, fomentado pelo interesse dos consumidores por alimentos que auxiliem a promoção da saúde, tem pressionado a indústria alimentícia na oferta por novos alimentos. Dentre estes alimentos, encontram-se os óleos vegetais extraídos a frio, reconhecidos por preservarem compostos bioativos característicos e, alguns deles, serem fontes de ácidos graxos (AG) essenciais. A categoria dos óleos e gorduras apresenta, dentre outros alimentos, uma importante fonte de exposição aos hidrocarbonetos policíclicos aromáticos (HPAs), um grupo de contaminantes químicos orgânicos, alguns com ação carcinogênica. Este trabalho teve como objetivo avaliar os óleos vegetais extraídos a frio quanto aos parâmetros de identidade, de qualidade e à ocorrência de HPAs. Foram avaliadas 40 amostras, dez de cada tipo (coco, cártamo, prímula e linhaça), de diferentes marcas, adquiridas no comércio da cidade de São Paulo. Foram realizados os ensaios de perfil de AG, índice de acidez, índice de peróxido, p-anisidina, valor total de oxidação (totox) e HPAs (benzo(a)antraceno, criseno, benzo(b)fluoranteno e benzo(a)pireno). Quanto aos AG, catorze óleos (35 por cento ) não apresentaram perfis de ácidos graxos característicos que os declarados em seus rótulos, incluindo um de coco, quatro de cártamo e nove de prímula. Os valores para acidez estavam inadequados em relação a legislação para três óleos de linhaça (7,5 por cento ). Para o peróxido, quatro óleos (10 por cento ) estavam acima do limite da legislação, sendo dois de linhaça e dois de prímula. Os valores de p-anisidina variaram de &lt;LQ a 12,98, sendo o menor valor encontrado nas amostras de coco e o maior em uma de prímula, que apresentava um odor alterado. No ensaio de totox, 37,5% das amostras apresentaram valores acima da recomendação da literatura, especialmente os óleos de cártamo e prímula. Já para os HPAs, pelo menos um dos hidrocarbonetos analisados foi detectado em 97,5% das amostras avaliadas; três amostras de prímula (7,5%) apresentaram níveis acima do permitido pela Comunidade Européia para BaP e, para a soma dos 4 HPAs, oito óleos (20%) estavam em desacordo: dois de cártamo, quatro de prímula e dois de linhaça. Este trabalho expõe os problemas relacionados aos parâmetros de identidade, qualidade e contaminação dos óleos vegetais comercializados como extraídos a frio e reforçam a importância de um contínuo monitoramento destes produtos. / The natural product market growth, stimulated by the interest of consumers in foods that support health promotion, has encouraged the food industry to supply new kinds of foods. Among these are the cold-pressed vegetable oils, recognized by preserving characteristic bioactive compounds and, some of them, are sources of essential fatty acids (FA). The category of oils and fats owns, within others foods, an important source of exposure to polycyclic aromatic hydrocarbons (PAHs), a group of organic chemical contaminants, some of them with carcinogenic activity. This study aimed at evaluating cold-pressed vegetable oils in relation to the PAHs occurrence, as well as the quality and identity parameters. Forty samples being ten of each type (coconut oil, safflower oil, evening primrose oil and flaxseed oil) of distinct brands, which were acquired in different markets from São Paulo, were evaluated. Fatty acids profile, acid value, peroxide value, p-anisidine value, total oxidation value (totox) and PAHs (benzo(a)anthracene, chrysene, benzo(b)fluoranthene and benzo(a)pyrene) were analyzed. As for FA, fourteen oils (35 per cent ) showed different fatty acids profiles according to the ones on their labels, including one of coconut oil, four of safflower oils and nine of evening primrose oils. The acid values were unsuitable towards the legislation to three flaxseed oils (7.5 per cent ). As for peroxide values, four of the oils (10 per cent ) were above the legislation limit, including two of flaxseed oils and two of evening primrose ones. The p-anisidine values ranged from &lt;LOQ to 12.98, being the smallest value found in the coconut oils samples and the biggest ones in an evening primrose oil, which featured an altered odor. In the totox analysis, 37,5% of the samples presented values above the normal pattern according to literature, mailly the safflower and theevening primrose oils. Regarding the PAHs, at least one of the analyzed hydrocarbons was detected in 97,5% of the samples; three of the primrose samples (7,5%) had levels above those allowed by the European Community for BaP. According to the sum of 4 PAHs, eight oils (20%) were in disagreement: two of safflower oils, four of evening primrose oils and two of flaxseed oils. This study exposes problems related to identity and quality parameters, contamination of vegetable oils marketed as cold-pressed. It also aims at reinforcing the importance of a continuous monitoring os these products.

Este trabalho descreve a otimização e validação de um método analítico para a análise de hidrocarbonetos policíclicos aromáticos (PAHs) em água usando uma interface SPME/LC/DAD. Parâmetros como tipos de fibra, tempo de extração, temperatura e força iônica foram estudados no modo \"off line\" e a influência destes na eficiência de extração foi avaliada. Os melhores resultados foram obtidos com a fibra Carbowax/templeted resin. Uma interface \"lab made\" foi utilizada para a etapa de validação e as curvas de calibração mostraram boa linearidade (r>0,99) para a maioria dos compostos analisados, tanto na linearidade da amostra como na linearidade do padrão. Os dados de precisão obtidos na concentração de trabalho variaram de 1 a 3%, aproximadamente, e os valores de recuperação se mantiveram na faixa de 4 a 27%. Os PAHs foram determinados na faixa de 0,025 micro g até 0,5 micro g. Pode-se considerar os valores obtidos nos itens de precisão e linearidade satisfatórios para a análise dos PAHs, considerando-se os critérios internacionais estabelecidos para esta classe de compostos, mas o método não atende as especificações relacionadas a recuperação e faixa de concentração. / This work describes the optimization and validation of an analytical method to determine Polycyclic Aromatic Hydrocarbons (PAHs) in water using a SPME/LC/DAD interface. Parameters as fibers kind, sampling time, temperature and ionic strength were studied and their influence on the extraction efficiency were evaluated. The best results were obtained with the Carbowax/templeted resin fiber. A \"lab made\" interface was used to validate the method and the calibration curves showed good linearity (r > 0,99) to almost all the compounds analyzed, considering both the sample linearity and the standard linearity. The data obtained for precision showed a variation from 1 to 3 % and the recovery values were bellow 27%. The PAHs analysis was performed for concentrations from 0,025 micro g/fiber to 0,5 micro g/fiber. The method does not show good recoveries values but the data obtained for precision and linearity can be considered satisfactory according to international criteria established for theses compounds.

Estudos ambientais têm demonstrado que substâncias geradas por processos antropogênicos podem causar efeitos prejudiciais interferindo no equilíbrio natural do ecossistema. Manguezais exercem funções essenciais nos ciclos biológicos e constituem Área de Proteção Permanente no Brasil. Infelizmente, eles estão sendo degradados acima do seu limite de suporte, levando a uma redução das áreas remanescentes no mundo. Este trabalho apresenta os resultados de mutagenicidade e genotoxicidade observados em quatro amostragens (PI, V, O e PII) entre 2009 e 2010, relacionados com metais e hidrocarbonetos policíclicos aromáticos (HPA) em sedimento de mangue para a caracterização dos valores de referência. Os testes de genotoxicidade foram feitos a partir de hemócitos do caranguejo Goniopsis cruentata, coletados em um ecossistema potencialmente não poluído do Brasil, localizado no sul do Rio de Janeiro (Parati/RJ), chamado de "Saco do Mamanguá". Coleta, armazenamento e manipulação dos sedimentos e material biológico de cinco pontos de amostragem (M1- M5) foram processados de acordo com normas norte-americanas reconhecidas. A identificação das substâncias químicas foi realizada com extratos de sedimentos e utilizada no bioensaio Salmonella/microssoma (Kado). A avaliação de potenciais danos genotóxicos estabelecidos foi realizada através do Teste de Micronúcleo, que apresentou valores significativos na amostra V. Resultados negativos foram observados para as cepas de Salmonella typhimurium TA97, TA98, TA100 e TA102, tanto na ausência quanto na presença de fração de metabolização exógena de mamíferos (S9 mix 4%) em todas as análises. A quantificação por cromatografia gasosa com detecção por espectrometria de massas dos 16 HPA prioritários em termos de conservação ambiental apresentou valores baixos nas duas primeiras amostragens (PI e V) e nulos nas coletas seguintes (O e PII), nos mesmos pontos. De acordo com os valores utilizados nos Estados Unidos e Canadá como referência, os detectados por nós não são considerados como toxicantes ambientais positivos, com exceção do Benzo(a)pireno, que em M1V apresentou valores um pouco acima do limite a partir do qual já podem ser observados pequenos efeitos na biota. A análise dos metais (Cd, Cr, Cu, Fe, Mn, Ni, Pb e Zn) por Espectrometria de Absorção Atômica inicialmente realizada com a água intersticial foi melhor interpretada a partir da matriz sedimento. Este estudo contribuirá com a implementação de indicadores para valores de referência em mangue. / Environmental studies have shown that substances generated by anthropogenic processes can cause adverse effects by interfering with the ecosystem natural balance. Mangroves perform essential functions in biological cycles and are Permanent Protection Area in Brazil. Unfortunately, they are being degraded above its support limit, leading to a reduction of the remaining areas in the world. This paper presents the results of mutagenicity and genotoxicity observed in four samples (PI, V, O, and PII) between years 2009 and 2010 linked to metals and polycyclic aromatic hydrocarbons (PAHs) in mangrove sediment in order to characterize reference values. The genotoxicity tests were made from the hemocytes Goniopsis cruentata collected in a potential unpolluted ecosystem of Brazil, located in the southern Rio de Janeiro (Parati/RJ), called "Saco do Mamanguá. Collection, storage, manipulation of sediment and biological material from five sampling sites (M1-M5) were processed according to U.S. standards recognized. The identification of the chemicals was performed with extracts of sediments and bioassay used in the Salmonella / microsome (Kado). The assessment of potential genotoxic damage were done down through the Micronucleus Test, and showed significant values in the sample V. Negative results were observed for the Salmonella typhimurium strains TA97, TA98, TA100 and TA102, both in the absence or presence of exogenous fraction of mammalian metabolism (S9 mix 4%) for all analysis. Quantification by Gas chromatography-mass spectrometry of the 16 priority PAHs in terms of environmental conservation, presented low values in the first two samples (V and PI) and null value in the following collections (and the IIP), in the same points. According to United States and Canada references, we detected chemicals not regarded as a positive environmental toxicants, with the exception of benzo(a)pyrene, which showed values in M1V just above the threshold at which already small effects can be observed in the biota. The analysis of metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) by Atomic Absorption Spectrometry initially performed with the pore water was best interpreted from the sediment matrix. This study will contribute to the implementation of indicators to benchmarks in the swamp.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Os hidrocarbonetos policÃclicos aromÃticos (HPAs) sÃo considerados poluentes orgÃnicos persistentes e apresentam propriedades mutagÃnica, carcinogÃnica e teratogÃnica, contudo existe uma grande carÃncia em dados da distribuiÃÃo de HPAs em centros urbanos e costeiros brasileiros. Assim o presente trabalho tem o intuito de gerar dados da situaÃÃo de HPAs nos ecossistemas costeiros da cidade de Fortaleza. Os principais objetivos foram: validaÃÃo da metodologia para a extraÃÃo e anÃlise de HPAs em Ãgua e sedimento; distribuiÃÃo atmosfÃrica de HPAs no perÃodo chuvoso; avaliaÃÃo da poluiÃÃo promovida por HPAs nos rios de Fortaleza e estimativa do tipo de fonte emissora de HPAs. O programa de temperatura elaborado para a separaÃÃo e resoluÃÃo dos picos foi eficiente para separar os HPAs em estudo, exceto acenafteno e acenaftileno. Para a determinaÃÃo de HPAs em sedimento estuarino observou-se mais vantagens utilizando a tÃcnica de ultra-som, hexano/acetona como solvente de extraÃÃo, e clean-up com hexano/acetato de etila. A recuperaÃÃo proveniente das matrizes aquosas ambientais fortificadas com HPAs variou de 63,7 a 93,1% para precipitaÃÃo lÃquida atmosfÃrica, de 38,3 a 95,1% para Ãgua superficial de rio e de 70,2 a 89,4% para Ãgua marinha. A distribuiÃÃo espacial de HPAs mostrou que a pluma de maior concentraÃÃo à mais intensa na zona com grande fluxo automobilÃstico e topografia favorÃvel para a concentraÃÃo de poluentes emitidos. A razÃo molecular de alguns HPAs na atmosfera, embora preliminar, mostrou emissÃo proveniente da exaustÃo de gasolina, diesel, madeira e carvÃo. Os somatÃrios da concentraÃÃo de HPAs em sedimento(&#8721;HPAs) variaram de 3,04 a 2234.76 Âg.kg-1 (rio CocÃ) e de 3,34 a 1.859,21 Âg.kg-1 (rio CearÃ). Na maioria dos testemunhos de sedimentos coletados, os nÃveis do &#8721;HPAs diminuem em direÃÃo ao fundo dos testemunhos, confirmando que a poluiÃÃo à maior nos dias atuais. Os dados mostram que a cidade de Fortaleza apresenta nÃveis de HPAs nos sedimentos dos seus principais rios, prÃximos aos de cidades com grau de desenvolvimento industrial superior e que o produto da queima de combustÃveis fÃsseis e outras fontes de energia sÃo responsÃveis pela poluiÃÃo dos dois principais rios da cidade. / Polycyclic aromatic hydrocarbons (PAHs) are considered persistent organic pollutants possessing mutagenic, carcinogenic and teratogenic properties, but there is lack of data about PAHs distribution in Brazilian urban centers. The present work was performed to generate data about PAHs in coastal ecosystems of Fortaleza city. The main objectives were: validation of methodologies for extraction and analysis of PAHs in water and sediment; atmospheric distribution of PAHs in rainy period; evaluation of the pollution caused by PAHs in the rivers of Fortaleza city and estimation of PAHs sources. The temperature program elaborated for PAHs separation and resolution was efficient, except acenaphthene and acenaphthylene. The ultrasound technique was more advantages for the extraction of PAHs from sediments using hexane/acetone as extraction solvent and hexane/ethyl acetate for the clean-up. The recovery from environmental aqueous matrices fortified with PAHs varied from 63.7 to 93.1% for atmospheric liquid precipitation, from 38.3 to 95.1% for superficial river water, and from 70.2 to 89.4% for marine water. PAHs spatial distribution showed that the highest concentration plume is intense in the zone with larger automobile flow and favorable topography for the concentration of emited pollutant. The molecular ratio of some PAHs in atmosphere (preliminary), showed emission from gasoline, diesel, wood and coal exhaustion. The total concentration of PAHs in sediment (&#8721;PAHs) ranged from 3.04 to 2234.76 Âg.kg-1 (Cocà river) and from 3.34 to 1859.21 Âg.kg-1 (Cearà river). To the sediments cores &#8721;PAHs decrease towards the sediment deep layer, confirming that the pollution now days is larger. The data show that the sediments of the principal rivers of Fortaleza city have PAHs levels similar to other cities with a superior industrial development. The data also show that the burning product of fossil fuels and other sources of energy are responsible by the pollution of both rivers.