L’évaluation de l’impact des polluants dans l’environnement est une des préoccupations majeures qui s’inscrit dans la Directive Européenne Cadre Eau 2000. Les réglementations préconisées ont notamment pour objectif de parvenir au bon état chimique et écologique des masses d’eau. Dans ce contexte, notre étude a consisté à développer une approche multibiomarqueur sur des juvéniles de poisson afin d’évaluer les effets biologiques de la pollution chimique en milieu littoral. Des paramètres moléculaires de détoxification (EROD, GST) et une enzyme antioxydante (CAT) ont été utilisés en tant que «système d’alarme » susceptibles de détecter une perturbation avant l’apparition de signes pathologiques irréversibles. En parallèle, différents biomarqueurs physiologiques (croissance somatique et récente, rapport ARN/ADN, indices morphométrique et lipidique) ont été analysés en considérant que ceux-ci pourraient révéler les dommages induit par les polluants sur l’état de santé des juvéniles. La sensibilité et la pertinence des biomarqueurs moléculaires et physiologiques ont été testés expérimentalement sur des juvéniles : i) de bar exposés à une pollution aigüe de pétrole, ii) de bar et de turbot soumis à des mélanges de contaminants en concentrations environnementales en conditions contrôlée et semi-contrôlée (« caging »). Nos résultats montrent la capacité de l’EROD, et à un degré moindre de la GST, à détecter une exposition courte (2 et 4 jours) des organismes au pétrole et à refléter ses effets délétères sur leur état de santé. Cette relation entre biomarqueurs moléculaires et physiologiques a par contre été plus difficilement établie dans un contexte de pollution multiple. Les indices de croissance et de condition utilisés se sont avérés plus sensibles aux différents niveaux de contamination analysés (métaux et HAPs). Leur utilisation a permis d’évaluer la condition affaiblie des organismes mis en cage en milieu portuaire pendant 38 jours. Cette expérience de « caging » s’est révélée concluante, notamment pour les juvéniles de bar, sur lesquels aucun stress physiologique de la mise en cage n’a été détecté dans la station de référence. Les effets délétères des contaminants chimiques sur l’état de santé des juvéniles de turbot ont également été observés en condition contrôlée après exposition de 21 jours aux mêmes sédiments portuaires et à un sédiment estuarien. En complément de ces expériences, une étude de terrain a été réalisée sur des juvéniles de flet prélevés dans des estuaires le long de la côte française et belge. Une diminution des indices morphométrique et lipidique des juvéniles de flet, issu des trois estuaires anthropisés, a été observée en relation avec des bioconcentrations en métaux plus élevées que l’estuaire de référence. Les résultats issus de ces différentes études montrent la potentialité des indices de croissance et de condition à révéler les effets biologiques des contaminants chimiques sur les juvéniles de poissons marins. Cependant, leur spécificité vis à vis des polluants étant plus faible que les paramètres de détoxification, leur utilisation peut être limitée. Ces travaux montrent ainsi le besoin d’utiliser des biomarqueurs à différents niveaux d’organisation biologique dans les programmes de biosurveillance. / Evaluation of pollutant effects in environment is one of the major issues of the European Water Framework Directive 2000. Regulations have particularly the objective to reach to a good chemical and ecological status of water bodies. In this context, the aim of our study was to develop a multibiomarker approach on juvenile marine fish in order to evaluate the biological effects of chemical pollution in coastal areas. Molecular detoxification parameters (EROD, GST) and an antioxidant enzyme (CAT) were used as early warning tools of toxicity allowing the prevention of irreversible damages. In parallel, different physiological biomarkers (somatic and recent growth, RNA:DNA ratio, morphometric and lipidic indices) were analysed as reflecting damages on juveniles health. Sensitivity and relevance of molecular and physiological biomarkers were tested experimentally on juvenile : i) sea bass exposed to acute petroleum pollution, ii) sea bass and turbot submitted to a mix of contaminants in environmental concentrations during controlled and semi-controlled (caging) conditions. Our results show the ability of EROD, and in lower degree the GST, to detect short exposure (2 and 4 days) of organisms to petroleum and to reflect their deleterious effects on fish health. This relationship between molecular and physiological biomarkers was more difficultly established under multiple pollutions. Growth and condition indices were found to be more sensitive to the different levels of chemical contamination analysed (metal, PAHs). Their analyses allowed us to evaluate the weakened condition of organisms caged in the harbour area during 38 days. This caging experiment was relevant especially for juvenile sea bass in which no physiological stress was detected in the reference station. Deleterious effects of chemical contaminant on turbot juvenile health were also observed in controlled condition after 21 days exposure to the same harbour sediments and to an estuarine sediment. In complement to these experiments, a field study was realized on juvenile flounders sampled in some estuaries along the French and Belgium coast. A decrease of morphometric and lipidic indices were found in juvenile flounders from the three anthropogenic estuaries showing the highest metal bioconcentrations compared to the reference estuary. Results from these different studies showed the potentiality of growth and condition indices to reflect biological effects of chemical contaminants on juvenile marine fish. However, their use could be limited by their lower specificity to pollutant than parameters involved in detoxification. These works show therefore the need to use biomarkers at different level of biological organization in biomonitoring programs.

A presente dissertação é um estudo da evolução ambiental do Reservatório de Salto Grande (RSG), Americana, SP, realizado a partir de análises granulométrica, geomagnética, geoquímica (especiação fósforo e carbono, elementos traço, compostos organoclorados e hidrocarbonetos aromáticos policíclicos) e biológica (tecamebas) de amostras de um testemunho sedimentar de 233 cm. Com base nos resultados obtidos, foi possível: 1) avaliar a toxicidade dos sedimentos, de acordo com os valores-guia de qualidade de sedimentos (VGQS) TEL e PEL, fator de enriquecimento (EF) e índice de geoacumulação (Igeo) e 2) identificar cinco fácies sedimentares, ao longo do testemunho. Fácies 1, situada na base do testemunho, é constituída por lama, com baixas concentrações de elementos traço, compostos organoclorados e HPAs, presença de material radicular e ausência de tecamebas. Essa sequência sedimentar pode ser atribuída às unidades de solos e sedimentos depositados na planície aluvial do Rio Atibaia e representa a fase Préreservatório. A partir de 177 cm de profundidade rumo ao topo, passam ocorrer mais quatro fácies, indicativas dos 65 anos de existência do RSG. A Fácies 2 (transição de solo e início do reservatório) caracteriza-se pela presença de lama, com tênue estratificação plana paralela e surgimento de tecamebas (Arcella gibbosa, A. megastoma, Difflugia corona, D. oblonga, D. gramen e Centropyxis discoide aculeata). Nessa fácies não foram detectados sedimentos contaminados, segundo VGQS. Contudo, foi constatado aumento expressivo de HPAs, provavelmente relacionado a queimadas ocorridas no entorno do reservatório. Fácies 3 (Reservatório) é marcada por sucessão de camadas de lama escura, intercaladas com lama clara, associadas às variações sazonais de produtividade do reservatório. Na porção final da Fácies 2 e toda a Fácies 3, ocorrem as maiores concentrações dos elementos traço (principalmente Cu, e Cr), parâmetros geomagnéticos, PCBs, DDT e HPAs, bem como o primeiro e maior declínio das populações de tecamebas. Nessa fácies 3 os VGQS indicam a presença de sedimentos fortemente contaminados. Fácies 4 continua a apresentar sucessão de camadas escuras e claras, contudo, as concentrações dos elementos traço, parâmetros geomagnéticos, PCBs, DDT e HPAs diminuem sensivelmente e os valores de densidade e diversidade das tecamebas aumentam. Valores de Cu diminuem mas, continuam expressivos, indicando sedimentos contaminados. As oscilações da concentração de Cu podem estar relacionadas ao uso de algicidas à base de CuSO4, que são utilizados no RSG para controlar a floração de cianobactérias e macrófitas. Fácies 5, correspondente ao período mais recente da história do RSG, caracteriza-se pela presença de lama preta, contaminada por Cu, pobre em tecamebas e baixas concentrações de DDT e HPAs. As curvas de evolução dos fluxos de fósforo inorgânico, Mn e Zn apresentaram forte similaridade com as curvas de crescimento demográfico da cidade de Americana e com as variações do regime de chuvas local. Estes resultados sugerem que as variações do aporte de nutrientes no reservatório encontram relação direta com as mudanças no escoamento de água pluvial na bacia de drenagem do Atibaia e com os influxos industriais e domésticos no RSG / This works presents an environmental evolution of the Reservatório de Salto Grande (RSG), Americana, accomplished through the grain-size, geochemical (phosphorous, carbon, trace elements, organochlorines and polycyclic aromatic hydrocarbons), and biological (thecamoebians) analyses from sample of a sediment core. Based on the results it was possible to: 1) evaluate the sediments according to the Sediment Quality Guideline Values for metals and associated (SQGV), enrichment factors, and geoaccumulation index and 2) identify five sedimentary facies through the core. Facies 1 located at the base of the core is composed of muddy sediments with low concentrations of trace elements, organochlorines and PAHs, presence of small trees roots and absence of thecamoebians. This sedimentary sequence could be attributed to soil units and sediments deposited in the alluvial basin of the Atibaia river and represents the pre-reservoir succession. From 177 cm through the top of the core more 4 facies are identified, all correlated with the time span of 65 years since the inundation of the RSG. Facies 2 (transition between soil portion and the reservoir inundation) is characterized by the presence of a homogeneous mud and a thin parallel planar stratification and by the appearance of thecamoebians (Arcella gibbosa, A. megastoma, Difflugia corona, D. oblonga, D. gramen, Centropyxis discoide aculeata). In this facies no contaminants were registered according to SQGV standards. But a high concentration of PAHs was detected possibly indicative of vegetation burning. Facies 3 (Reservoir) is marked by a succession of dark mud interleaved by whitish mud likely associated to seasonal variation of primary productivity in the reservoir. At the top portion of facies 2 and the whole extension of facies 3 were found the highest concentration of trace elements (Cu, and Cr), geomagnetic parameters, PCBs, DDT and PAHs, and the first and major decline of thecamoebians populations. In this facies SQGV are indicative of highly contaminated sediments. Facies 4 continuously shows the same succession of mud and the concentrations of trace elements, geomagnetic parameters, PCBs, DDT and PAHs show a sensitive decrease, and the values of richness and abundance of thecamoebians show an increase. Although the values of Cu diminish, they still remain expressive, indicative of sediment contamination. The oscillations of Cu concentrations may be related to the use of algaecides composed of CuSO4 in order to control populations of cyanobacteria and macrophytes. Facies 5 corresponds to the last centimeters of the core and to recent periods of the history of RSG, characterized by the presence of a black mud contaminated with Cu poor in species of thecamoebians and low concentrations of PCBs, DDT and PAHs. The curves of inorganic phosphorous, Mn and Zn showed a similar pattern to the curves of demographic growth and rain fall in the city of Americana. These results suggest that the variations of nutrients income are related to the change in water flow regimes in the Atibaia river watershed and to industrial and domestic input in the RSG

Os constantes vazamentos de combustíveis derivados do petróleo nos postos de abastecimento têm gerado grande preocupação em diversos países do mundo. Estes combustíveis apresentam em sua composição compostos orgânicos, entre eles os hidrocarbonetos poliaromáticos (HPAs) nocivos à saúde humana. Este trabalho visa ao estudo da eficiência de uma camada de impermeabilização, constituída por uma Geomembrana de Polietileno de Alta Densidade (PEAD) de 2,5 mm de espessura. Os estudos se basearam em análises físicas (Densidade), mecânicas (Tração e Permeabilidade) e térmicas (Calorimetria de Varredura Diferencial) da geomembrana exposta aos três combustíveis, além de analisar a estanqueidade por Difusão, na geomembrana intacta. Os resultados mostraram que: a densidade das geomembranas sofre pequenas variações, e que para um período de até 6 meses o parâmetro é mantido; as resistências mecânicas apresentam maior influência nas suas propriedades em relação ao óleo diesel e gasolina, e menor para o álcool; os testes de análise térmica mostram que as cadeias poliméricas mantiveram as ligações atômicas, baseado nas temperaturas de fusão e degradação; os testes de permeabilidade ao vapor d\'água mostram que a geomembrana exposta à gasolina apresenta tendência de aumento da permeabilidade em função do tempo; os resultados dos testes de impermeabilização a um grupo de compostos policíclicos aromáticos, mostram que a geomembrana apresenta desempenho menos satisfatório para os compostos antraceno e naftaleno. A geomembrana de polietileno de alta densidade de 2,5 mm é uma boa alternativa na prevenção da contaminação pelos compostos estudados, até um período aproximado de um ano, tendo em vista seu desempenho no período estudado. / The constant petrol fuel leaks in gas stations has been caused concern in many countries around the world. This fuel has toxic organic compounds in their composition, like Polyciclic Aromatic Hidrocarbons (PAHs) harmful to the human health. In this work the efficiency of the protection layer with a Hight Density Polyetilene Geomembrane (HDPE) 2.5 mm thickness was used. The study is based upon the physical (density), mecanical (Tensile and Permeability) and thermal tests (Differential Scanning Calorimetry) and was used for the three fuels, as well as the difusion test of intact geomembrane. The results show that the geomembrane density has changed a little bit, holding the standard values up to 6 months; the mecanical resistence decreases in diesel oil and gasoline, and increases in alcohol; the thermic analisys tests show that the polimeric chains maintain the same chemical bonds, based on the melting point and degradation temperature; the water vapor permeability test shows, as the time increases, the water vapor throught the geomembrane which was exposed to gasoline tends to increase; the results of impermeabilization test of a poliaromatic compound group shows that the geomembrane is less efective to antracene and naftalene compounds. The hight density polyethylene geomembrane of 2.5 mm thickness is a good alternative preventing contamination of water and soil, by the compounds under stusy, about up to one year, based on this time of study performance.

O presente estudo visou reconstruir o histórico de impactos antrópicos na bacia de drenagem do Lago das Garças durante o século XX por meio da deposição de contaminantes no compartimento sedimentar. O Lago das Garças está localizado em uma unidade de conservação, Parque Estadual das Fontes do Ipiranga (PEFI), inserida em área altamente povoada e urbanizada da cidade de São Paulo. Dois testemunhos de sedimento (LG05-03 e LG05-04, com 70 cm e 65 cm, respectivamente) foram amostrados mediante auxílio de mergulhadores no ponto mais profundo do reservatório, sendo, posteriormente, fatiados a cada 1 cm. Em LG05-03 foram quantificadas as distribuições verticais de carbono orgânico total (COT), nutrientes totais (NT e PT), hidrocarbonetos policíclicos aromáticos (HPA), hidrocarbonetos alifáticos (n-alcanos), bem como foi feita a classificação granulométrica. Em LG05-04 foi determinada a deposição de metais pesados (Co, Cr, Cu, Fe, Mn, Ni, Pb e Zn) e a geocronologia através do isótopo radioativo \'ANTPOT. 210 Pb\', usando o modelo CIC (Constant Initial Concentration). Os dados foram analisados por meio de análises estatísticas multivariadas (ACP: Análise de Componentes Principais). Com base nas tendências dos dados e na ACP, foi possível estabelecer três fases principais: Fase I: 64-43 cm (~1894-1975): caracterizada por baixas concentrações de nutrientes e contaminantes, sendo possível recuperar níveis préindustriais destes compostos, propostos como valores de referência regionais. Ainda, com base na razão C/N e em razões entre n-alcanos, notou-se, nesta fase o predomínio de aporte de matéria orgânica de origem alóctone; Fase II: 43-26 cm (~1975-1990): aumento abrupto das concentrações de metais pesados e HPA traçadores de veículos automotores, marcando o aumento da poluição atmosférica devido ao grande crescimento econômico do município e maior circulação de veículos na região. Ainda, foi observado aumento gradual das concentrações de NT e PT, atribuídos aos despejos de esgotos não tratados oriundos da Secretaria de Agricultura e Abastecimento e da Fundação Parque Zoológico; Fase III: 26-0 cm (~1990-2005): aumento mais acentuado das concentrações de nutrientes devido aos despejos de esgotos, acarretando em maior eutrofia do sistema, registrada pelo perfil do n-\'C IND.17\'. Pico das concentrações de HPA traçadores do uso de carvão mineral associado às atividades de uma siderúrgica vizinha (Siderúrgica J.L. Alipeti), bem como queda das concentrações destes traçadores coincidindo com mudanças no processo industrial da empresa. Ainda nesta fase notaram-se aumentos expressivos dos teores e fluxos dos HPA traçadores de veículos automotores, corroborando o cenário de aumento vertiginoso da frota de veículos na última década. Desse modo, este estudo contribuiu com o cenário nacional em termos de manejo de bacias hidrográficas urbanas, incluindo registros desde a época pré-revolução industrial no Brasil (~1894) até os dias atuais, demonstrando o potencial do uso de testemunhos lacustres no resgate de informações relativas à contaminação de ecossistemas aquáticos associadas às atividades antropogênicas. / Present study aimed to reconstruct the human impact history on the Garças Lake Drainage Basin during the 20th Century based on contaminants deposition on the lacustrine sediment. Garças Lake is located in a preservation area, the Parque Estadual das Fontes do Ipiranga (PEFI), located in a highly populated urban area within the city of São Paulo. Two sediment cores (LG05-03 and LG05-04, 70 cm and 65 cm long) were sampled by divers at the deepest site of the lake, which were sliced at 1 cm intervals. Information for LG05-03 included total organic carbon (TOC), total nutrients (TN and TP), polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (n-alkanes) and grain size vertical distributions. Deposition of heavy metals (Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and the geocronology by \'ANTPOT. 210 Pb\', using CIC model (Constant Initial Concentration), were determined in LG05-04. Data were analyzed by multivariate statistic analysis (PCA, principal components analysis). Based on data trends and PCA, it was possible to recognized three main phases: Phase I: 64-43 cm (~1894-1975) characterized by low nutrients and contaminants concentrations, allowing retrieving preindustrial levels of these compounds, which are proposed as regional reference values. Besides, C/N ratio and n-alkanes ratios demonstrated aloctonous organic matter predominance; Phase II: 43-26 cm (~1975-1990) characterized by the abrupt increase of heavy metals and vehicular PAHs concentration, indicating the atmospheric pollution increase, due to the great economic rise experienced by the city of São Paulo over that time and the higher vehicles circulation in the region. Yet, it was observed a gradual increase in nutrient concentration attributed to the untreated sewage inputs from the São Paulo State Department of Agriculture and Provisioning headquarters and the city Zoo; Phase III: 26-0 cm (~1990-2005) characterized by a marked increase in nutrient concentration related to the untreated sewage inputs, leading to the increase of eutrophication, as registered by the n-\'C IND.17\' distribution. A peak of coal PAHs concentration was also noticed, related to a neighbor steel mill (J.L. Aliperti), followed by a subsequent decrease of these compounds, coincident with industrial procedures changes. Besides, there was an expressive increase in vehicular PAHs concentrations, corroborating the scenery of a drastic raise of vehicles in the last decade. The present study contributed to the national scenario towards urban drainage basin management. It included records since preindustrial time (~1894) up to the present, highlighting the potential use of lacustrine sediment on the retrieval of historical environmental changes of aquatic ecosystems and associated anthropogenic impacts.

Thesis (MTech(Environmental Health)--Cape Peninsula University of Technology, 2011 / Coke ovens may occur in the aluminium, steel, graphite, electrical, and construction industries. In the work area coke-oven workers may be exposed to various chemical compounds. Polycyclic aromatic hydrocarbons (PAHs), as human carcinogen, are primary compounds in coke oven emissions (COEs) generated in the coking process. Coke oven workers are often exposed to PAHs and can lead to a variety of human diseases.The primary routes of potential human exposure to coke oven emissions are inhalation and dermal contact. Occupational exposure may occur during the production of coke from coal, or while using coke to extract metals from their ores to synthesize calcium carbide, or to manufacture graphite and electrodes. Workers at coking plants and coal tar production plants, as well as the residents surrounding these plants, have a high risk of possible exposure to coke oven emissions.It is known that coke production could be carcinogenic to humans (Group-1) by IARC. There has been sufficient epidemiological evidence suggesting an etiological link between carcinogenic polycyclic aromatic hydrocarbon (PAHs) exposure and lung cancer risk among coke-oven workers. Lung cancer among coke-oven workers has been classified as one of the eight prescribed occupational cancers in China, and its incidence rate was about 10 times that of the general population. Therefore, lung cancer of coke-oven workers is still a critical issue in the field of prevention and control of occupational cancers in China.This thesis explores the various exposure levels of workers to PAHs at a steel plant in China. The measurement will focus on the exposure difference of personal sampling among workers in selected job classifications given the job descriptions and the coking process. The Benxi Steel Industry in Liaoning province of China (BXSI) was selected as the research location. Liaoning province is in the North of China and the location of various heavy industries in China. The measurements will be done two separate coke ovens in Benxi Steel Industry. One new coke oven was built in the 90's last century (coke oven N) and the other older coke oven was built in the 1940's in last century (coke oven O). In this research, the total number of employees that were selected in the sample for both coke ovens are 64 samples included 54 coke oven exposure workers and 10 non-exposure administrative workers working at the plants.

Os constantes vazamentos de combustíveis derivados do petróleo nos postos de abastecimento têm gerado grande preocupação em diversos países do mundo. Estes combustíveis apresentam em sua composição compostos orgânicos, entre eles os hidrocarbonetos poliaromáticos (HPAs) nocivos à saúde humana. Este trabalho visa ao estudo da eficiência de uma camada de impermeabilização, constituída por uma Geomembrana de Polietileno de Alta Densidade (PEAD) de 2,5 mm de espessura. Os estudos se basearam em análises físicas (Densidade), mecânicas (Tração e Permeabilidade) e térmicas (Calorimetria de Varredura Diferencial) da geomembrana exposta aos três combustíveis, além de analisar a estanqueidade por Difusão, na geomembrana intacta. Os resultados mostraram que: a densidade das geomembranas sofre pequenas variações, e que para um período de até 6 meses o parâmetro é mantido; as resistências mecânicas apresentam maior influência nas suas propriedades em relação ao óleo diesel e gasolina, e menor para o álcool; os testes de análise térmica mostram que as cadeias poliméricas mantiveram as ligações atômicas, baseado nas temperaturas de fusão e degradação; os testes de permeabilidade ao vapor d\'água mostram que a geomembrana exposta à gasolina apresenta tendência de aumento da permeabilidade em função do tempo; os resultados dos testes de impermeabilização a um grupo de compostos policíclicos aromáticos, mostram que a geomembrana apresenta desempenho menos satisfatório para os compostos antraceno e naftaleno. A geomembrana de polietileno de alta densidade de 2,5 mm é uma boa alternativa na prevenção da contaminação pelos compostos estudados, até um período aproximado de um ano, tendo em vista seu desempenho no período estudado. / The constant petrol fuel leaks in gas stations has been caused concern in many countries around the world. This fuel has toxic organic compounds in their composition, like Polyciclic Aromatic Hidrocarbons (PAHs) harmful to the human health. In this work the efficiency of the protection layer with a Hight Density Polyetilene Geomembrane (HDPE) 2.5 mm thickness was used. The study is based upon the physical (density), mecanical (Tensile and Permeability) and thermal tests (Differential Scanning Calorimetry) and was used for the three fuels, as well as the difusion test of intact geomembrane. The results show that the geomembrane density has changed a little bit, holding the standard values up to 6 months; the mecanical resistence decreases in diesel oil and gasoline, and increases in alcohol; the thermic analisys tests show that the polimeric chains maintain the same chemical bonds, based on the melting point and degradation temperature; the water vapor permeability test shows, as the time increases, the water vapor throught the geomembrane which was exposed to gasoline tends to increase; the results of impermeabilization test of a poliaromatic compound group shows that the geomembrane is less efective to antracene and naftalene compounds. The hight density polyethylene geomembrane of 2.5 mm thickness is a good alternative preventing contamination of water and soil, by the compounds under stusy, about up to one year, based on this time of study performance.

L'essor que connaît aujourd'hui la gestion intégrée des eaux pluviales s'accompagne d'un recours croissant à des techniques favorisant l'infiltration de l'eau “à la source”, disséminées sur des bassins versants urbains. Néanmoins, de telles pratiques suscitent des interrogations sur la capacité du sol à jouer le rôle de “filtre” vis-à-vis des polluants présents dans le ruissellement. Ces travaux de thèse s'intéressent à la contamination du sol par les métaux et les hydrocarbures aromatiques polycycliques (HAP) dans ces dispositifs, avec trois objectifs : (i) évaluer les niveaux et l'étendue spatiale de la contamination, (ii) mieux comprendre les mécanismes qui gouvernent le devenir de ces contaminants dans le sol des ouvrages, et (iii) proposer des recommandations sur la conception et la maintenance de ces installations, afin de leur assurer un fonctionnement épuratoire durable.La première partie du travail consiste en une série d'investigations expérimentales sur dix sites d'étude aux caractéristiques contrastées, en service depuis plus de dix ans. Cette phase donne lieu à des cartographies de la contamination superficielle en éléments traces métalliques, puis à des profils verticaux de métaux et HAP, accompagnés de différentes variables explicatives. La distribution spatiale des métaux en surface, qui est toujours structurée autour de la zone d'arrivée de l'eau, porte la signature du fonctionnement hydraulique réel des dispositifs, et révèle le caractère non-uniforme de l'infiltration lors des événements pluvieux courants, qui représentent la plus grande partie du flux polluant à l'échelle annuelle. Dans la zone la plus contaminée des ouvrages, métaux et HAP présentent un enrichissement significatif sur 10 à 40 centimètres de profondeur. La rétention des contaminants résulte de la combinaison de processus physico-chimiques (adsorption) et mécaniques (sédimentation et filtration) ; leur importance relative peut être quantifiée grâce au déficit de zirconium dans le sédiment urbain par rapport au bruit de fond géochimique local. La variabilité inter-sites des niveaux de contamination s'explique à la fois par les capacités de rétention du sol et par les flux de polluants issus du bassin versant d'apport. Bien que les teneurs de surface excèdent, sur certains sites, les seuils internationaux de remédiation du sol pour des espaces “multifonctionnels”, la zone concernée représente — latéralement et verticalement — une région assez limitée dans les ouvrages.La seconde partie de la thèse consiste en une approche de modélisation, dont la finalité est de décrire l'évolution à long terme de la contamination du sol, et d'évaluer l'incidence de différentes pratiques de conception ou de gestion. Une analyse de sensibilité est d'abord mise en œuvre afin d'identifier les “éléments-clés” dans la description du système, et d'orienter le choix du modèle. Les résultats montrent qu'une mauvaise estimation de la dispersivité ou de l'isotherme d'adsorption du sol est susceptible de biaiser significativement la prévision des profils de contamination. Dans la suite du travail, on propose une méthode visant à décrire l'infiltration non-uniforme et la filtration des polluants particulaires. Le modèle ainsi construit est validé via une comparaison entre mesures et simulations sur l'un des sites d'étude faisant l'objet d'une nouvelle caractérisation approfondie. Enfin, une analyse de scénarios illustre les bénéfices d'un amendement de l'horizon superficiel par un matériau adsorbant, ainsi que d'une répartition homogène des flux d'eau en surface, en matière de durée de vie des installations et de fréquence d'intervention. / Sustainable Urban Drainage Systems (SUDS) are increasingly used for stormwater management. However, the generalization of runoff infiltration in urban watersheds raises some concerns regarding the soil's ability to retain ubiquitous micropollutants. The present work addresses soil contamination by trace metals and polycyclic aromatic hydrocarbons (PAHs) in such infiltration devices, with the aims of: (i) appraising the levels and spatial extent of soil contamination, (ii) better understanding the mechanisms which govern the fate of contaminants in these systems, and (iii) identifying design and maintenance guidelines which may enhance long-term pollutant control through SUDS.The first part of the study consists in a series of experimental investigations in ten contrasting study sites, which have been in operation for more than ten years. The two-stage methodology successively leads to cartographies of metal contamination in the surface soil, and vertical profiles of metal and PAH concentrations, along with different explanatory variables. The spatial distribution of trace metals in the upper horizon displays a systematic structure with respect to the inflow area, and bears the time-integrated signature of the infiltration fluxes and flow pathways at the surface. In the most contaminated zone of the facilities, a significant enrichment of metals and PAHs is detectable until 10 to 40 cm depth. Contaminant retention results from the combination of different physicochemical and mechanical processes (resp. sorption and sedimentation/filtration), the contribution of which can be assessed via the zirconium deficit in urban sediment in comparison to the soil's geochemical background. The inter-site variability of contamination levels is attributable to (i) differences in the soil's retention capacities, and (ii) differences in pollutant loads from the watershed. Although surface contents may exceed intervention thresholds for “multi-functional” spaces in several study sites, the area which would require soil remediation is laterally and vertically limited.These experimental assessments are complemented by a modelling approach, to describe the long-term evolution of soil contamination, and to evaluate the effect of various SUDS designs and maintenance operations. A sensitivity analysis is first carried out so as to identify the “key elements” in the system description: the results show that a wrong estimation of the soil's dispersivity or sorption isotherm is likely to induce significant biases in the predicted contamination profiles. A method is then proposed to describe non-uniform water infiltration fluxes, and the filtration of particle-bound contaminants. The model is validated via a comparison between measured and predicted metal profiles in one of the study sites, where a comprehensive soil characterization is undertaken. Finally, a “scenario analysis” illustrates the benefits of (i) using soil enrichment products with enhanced sorption capacities, and (ii) facilitating water spreading at the surface, in terms of “lifespan” of the devices and maintenance requirements.

L’objectif principal de ce travail était de réaliser une étude écotoxicologique du complexe lac Ichkeul-lagune de Bizerte. Un recensement des pesticides agricoles les plus utilisés dans le bassin versant agricole a été effectué afin de déterminer les pesticides les plus problématiques. Le recensement effectué auprès des agriculteurs, des revendeurs de produits phytosanitaires et le commissariat régional de développement agricole de Bizerte a permis d’identifier les molécules les plus utilisées au niveau des zones agricoles du bassin versant du complexe lac Ichkeul – lagune de Bizerte: l’iodosulfurone, le mésosulfurone, le 2,4D, le glyphosate et le fénoxaprop comme matières actives des herbicides ; le tébuconazole et l’époxiconazole comme fongicide et la deltaméthrine matières active des insecticides. Ensuite, les concentrations en pesticides, HAP et PCB ont été déterminées. Les résultats ont montré une contamination au niveau de certains sites du complexe. Les stations situées dans la lagune de Bizerte ont des teneurs en HAP dépassant les limites tolérées. Les concentrations en pesticides dépassent les normes au niveau de quelques sites du lac Ichkeul. Enfin, l’impact de ces polluants sur les communautés microbiennes et la densité de nématodes a été déterminé. La CCA combinant les résultats des analyses chimiques et les données T-RFLP des communautés bactériennes met en évidence que les communautés bactériennes du lac sont influencées parles pesticides alors que celles de la lagune sont influencées par les HAP. La répartition des T-RFs montre la présence de T-RFs spécifiques dans les sites contaminés : le T-RF 114 bp caractérise le site le plus contaminé en pesticide, les microorganismes associés à ce T-RF correspondent probablement à des microorganismes résistants aux pesticides et capables de les dégrader. La composition des communautés bactériennes a été déterminée par pyroséquençage 454 sur les sites les plus représentatifs : le moins contaminé du complexe, le plus contaminé en HAP, le plus contaminé en pesticides et un site présentant une contamination multiple HAP-Pesticides. L’impact de la présence des pesticides sur la densité des nématodes libres marins a été étudié. L'analyse taxinomique des données de pyroséquençage regroupe les séquences dans 44 embranchements différents. En général, Proteobacteria étaient l’embranchement le plus dominant avec une prédominance de Gammaproteobacteria, Alphaproteobacteria et deltaproteobacteria dans les sédiments. Les communautés bactériennes des quatre sites ont 211 OTU commun. Le lac Ichkeul a été caractérisé par 219 OTU spécifique et la lagune de Bizerte 235 OTU. Le Site 2, le plus contaminé en pesticides présente l’abondance la plus élevée en nématodes libres marins. / The main objective of this work was to conduct an ecotoxicological study of the complex Ichkeul Lake-Bizerta lagoon. A survey of the most used agricultural pesticides in the watershed of the complex was conducted to determine the most problematic compounds. The survey of pesticides use with farmers, dealers of pesticides and the Regional Commissioner for Agricultural Development Bizerte has helped to identify the most used pesticides in agricultural areas of the watershed of the complex Ichkeul Lake-Bizerta lagoon: iodosulfuron, the mesosulfurone, 2,4D, glyphosate and fenoxaprop as herbicides active materials, tebuconazol epoxiconazol as fungicide active materials and deltamethrin as insecticides. Then, the concentrations of pesticides, PAHs and PCBs were determined in the sediment of the complex. The results showed a contamination of some complex sites. Stations located in the lagoon of Bizerte have a level of PAH in excess of permissible limits. Pesticide concentrations exceed the standards at some sites from the Ichkeul Lake. Finally, the impact of these pollutants on microbial communities and nematode density was determined. CCA combines the results of chemical analyzes and T-RFLP data of bacterial communities shows that the bacterial communities of the lake are influenced by pesticides while those of the lagoon are influenced by PAHs. The distribution of T-RFs showed the presence of specific T-RFs in contaminated sites: the T-RF 114 bp characterizes the most contaminated site in pesticides, microorganisms associated with the T-RF are probably microorganisms resistant to pesticides and capable of degrading this pollutant. The composition of bacterial communities was determined by 454 pyrosequencing of the most representative sites: the least contaminated of the complex, the most contaminated by PAH, the most contaminated by pesticides and a site with multiple PAH-pesticides contamination. The impact of the presence of pesticides on the density of free living marine nematodes was studied. The taxonomic analysis of the pyrosequencing data grouped the sequences into 44 different phyla. In general, Proteobacteria were the most dominant phyla with predominance of Gammaproteobacteria, Alphaproteobacteria and Deltaproteobacteria within the sediments. Besides Proteobacteria, there are a number of sequences affiliated to the following major phyla detected in all four sites: Chloroflexi, Bacteroidetes, Nitrospirae, Planctomycetes, Actinobacteria, Gemmatimonadetes, Firmicutes, Cyanobacteria, Spirochaetes, Acidobacteria. The bacterial communities of the four sites shared 211 common OTUs. The Lake Ichkeul was characterized by 219 specific OTUs and the Bizerta lagoon by 235 OTUs. Site 2, the most contaminated by pesticides has the highest abundance of free living marine nematodes.

Made available in DSpace on 2014-12-17T15:41:49Z (GMT). No. of bitstreams: 1 DayanneCM_DISSERT.pdf: 2858760 bytes, checksum: 79d38db851fa949cbc454e621806fe1c (MD5) Previous issue date: 2009-12-18 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / PAHs (Polycyclic Aromatic Hydrocarbons) are a group of organic substances which receive considerable attention because of the carcinogenic and mutagenic properties of some of them. It is therefore important to determine the PAHs in different environmental matrices. Several studies have shown the use of gas chromatography coupled to mass spectrometry as a technique for quantification of PAHs by presenting excellent detection limits. This study aimed to develop an analytical methodology for the determination of 16 PAHs listed by the USEPA, test two methods for extraction of PAHs in water from a 23 factorial design, quantify them through the analytical technique coupled to gas chromatography mass spectrometry (GC/MS) using the method developed, and finally apply the results in chemometrics. The sample was synthesized and subjected to tests of the 23 factorial design, which has the factors: the type of extraction technique (ultrasound and digester), the ratio solvent / sample (1:1 and 1:3) and the type of solvent (dichloromethane / hexane and acetone / dichloromethane). The responses of eight combinations of the factorial design were obtained from the quantification by external calibration in GC/MS. The quantification method was developed from an optimized adaptation of the USEPA Method 8270. We used the full scan mode as a way of acquiring the mass spectra of 16 PAHs. The time in which the samples were subjected to ultrasound was fixed at 10 min and held an investigation to establish the conditions of power and time in the digester. We had the best response in the investigation of the digester power of 100 watts and the time of six minutes. The factorial design of liquid-liquid extraction showed that the most representative factors were: the use of the digester as extraction technique, the ratio solvent / sample 1:1 and the use of a 1:1 mixture of dichloromethane / hexane as a solvent more suitable. These results showed that the 1:1 mixture of dichloromethane / hexane is an excellent mixture to recover the extraction of PAHs an aqueous sample using the microwave digester. The optimization of the method of separation, identification and quantification of PAHs in the GC/MS was valid for 16 PAHs present in each chromatogram of the samples / Os HPAs (Hidrocarbonetos Polic?clicos Arom?ticos) pertencem a um grupo de subst?ncias org?nicas que recebem uma aten??o consider?vel devido ?s propriedades carcinog?nicas e mutag?nicas de alguns deles. Por isso, ? importante a determina??o dos HPAs em diversas matrizes ambientais. In?meros trabalhos apresentam o uso da t?cnica de cromatografia gasosa acoplada ? espectrometria de massas como t?cnica de quantifica??o dos HPAs por apresentar ?timos limites de detec??o. Este trabalho teve como objetivo desenvolver uma metodologia anal?tica para a determina??o dos 16 HPAs indicados pela USEPA, testar duas metodologias de extra??o de HPAs em ?gua, a partir de um Planejamento Fatorial 23, quantific?-las atrav?s da t?cnica anal?tica Cromatografia Gasosa acoplada ? Espectrometria de Massas (CG/EM) utilizando o m?todo desenvolvido e, por fim aplicar a Quimiometria nos resultados. A amostra utilizada foi sintetizada e submetida aos ensaios do planejamento fatorial 23, que teve como fatores: o tipo de t?cnica de extra??o (ultra-som e digestor), a propor??o solvente/amostra (1:1 e 1:3) e o tipo de solvente utilizado (Diclorometano/Hexano e Acetona/Diclorometano). As respostas das oito combina??es do planejamento fatorial foram obtidas da quantifica??o por calibra??o externa no CG/EM. O m?todo de quantifica??o desenvolvido foi otimizado a partir de uma adapta??o da metodologia 8270 da USEPA. Utilizou-se o Full Scan como modo de aquisi??o dos espectros de massas dos 16 HPAs. O tempo em que as amostras foram submetidas no ultra-som foi fixado em 10 min e realizou-se uma investiga??o para se estabelecer as condi??es de pot?ncia e tempo no digestor. Tivemos como melhor resposta na investiga??o do digestor a pot?ncia de 100 Watts e o tempo de 6 minutos. O planejamento fatorial da extra??o l?quido-l?quido mostrou que os fatores mais representativos foram: a utiliza??o do digestor como t?cnica de extra??o, a propor??o solvente/amostra 1:1 e o uso da mistura 1:1 de Diclorometano/Hexano como solvente mais adequado. Esses resultados mostraram que a mistura 1:1 de Diclorometano/Hexano ? uma excelente mistura extratora para recuperar os HPAs de uma amostra aquosa, utilizando o digestor por microondas. A otimiza??o do m?todo de separa??o, identifica??o e quantifica??o dos HPAs no CG/EM foi v?lida por apresentar os 16 HPAs em cada cromatograma das amostras

Made available in DSpace on 2014-12-17T15:41:49Z (GMT). No. of bitstreams: 1 JulianaPSDP_DISSERT.pdf: 1777680 bytes, checksum: 11814e53360b103c7198cf617f2a583c (MD5) Previous issue date: 2010-07-06 / The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive / O presente trabalho ? dirigido ao tratamento de ?gua produzida de petr?leo usando uma tecnologia eletroqu?mica. A ?gua produzida ? um dos principais res?duos gerados durante o processo de explora??o e produ??o na ind?stria petrol?fera, onde corresponde a 98 % de todos os efluentes gerados. V?rias metodologias est?o sendo estudadas visando o tratamento desse efluente, dentre elas est?o os processos biol?gicos, os processos de oxida??o avan?ados (POAs), tratamentos eletroqu?micos como eletrooxida??o, eletrocoagula??o, eletroflota??o e eletroredu??o. Esse trabalho mostra a aplica??o da tecnologia de eletrooxida??o no tratamento da ?gua produzida, pois se trata de uma t?cnica com alta compatibilidade ambiental, onde atrav?s da a??o do pr?prio el?tron, as subst?ncias t?xicas e nocivas ao meio ambiente podem ser removidas ou transformadas atrav?s de rea??es de ?xido-redu??o em subst?ncias menos t?xicas. Para isso, foi utilizado efluente sint?tico contendo uma mistura de H2SO4 0,5M e de 16 hidrocarbonetos polic?clicos arom?ticos (HPAs), que s?o: naftaleno, acenaftileno, acenafteno, fluoreno, fenantreno, antraceno, fluoranteno, pireno, benzo(a)antraceno, criseno, benzo(b)fluoranteno, benzo(k)fluoranteno, benzo(a)pireno, indeno(1,2,3-cd)pireno, dibenzo(a,h)antraceno, benzo(g,h,i)perileno. Utilizou-se o processo de oxida??o eletroqu?mica com um reator eletroqu?mico em batelada contendo um par de eletrodos paralelos, acoplados a uma fonte de corrente cont?nua e usando um agitador magn?tico para favorecer o transporte de massa na solu??o sint?tica. Como material an?dico utilizou-se um eletrodo de ?nodo dimensionalmente est?vel (DSA), constitu?do de Ti/Pt, enquanto o material cat?dico foi o Ti. Para detec??o e quantifica??o dos HPAs utilizou ? t?cnica de cromatografia gasosa acoplada a espectrometria de massa (CG - EM), onde o efluente foi analisado antes e ap?s o tratamento eletroqu?mico. Os resultados se mostraram eficazes, obtendo-se remo??es significativas dos HPAs superiores a 80%. Como indicador da viabilidade econ?mica do tratamento eletroqu?mico foram analisados os consumos energ?ticos do processo para cada hora do tratamento eletroqu?mico com base no valor kWh cobrado pela ANEEL. Os custos dos tratamentos desta pesquisa foram bastantes atrativos