Presented is a study of persistent organic pollutants in Australian sewage sludge, focusing on environmental monitoring and a sewage sludge land application human health risk contaminated with these compounds. The chemicals of concern were: • Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and

Apesar da pequena influência antrópica direta em seu território, a Antártida não pode ser considerada livre do alcance de poluentes. No presente estudo, avaliou-se a distribuição e transferência de poluentes orgânicos (PCBs, pesticidas organoclorados e PBDEs) em compartimentos abióticos (neve e água de degelo) e bióticos (liquens, musgos, invertebrados, peixes, ovos de aves e tecidos de aves e pinípedes, para os quais também foi aplicada análise isotópica de nitrogênio-15 e carbono-13) do ecossistema da Baía do Almirantado. Os compartimentos abióticos tiveram concentrações entre 1,4 e 156 pg L-1, apenas para grupos de organoclorados, com variação intra-sazonal importante e compatibilidade com níveis tróficos inferiores e amostras de vegetação, que por sua vez refletiram a importância de fontes secundárias de poluentes. Nos animais, grosso modo, os compostos prevalecentes (em ng g-1 peso úmido) foram PCBs, (6,82-1821), HCB (0,060-136) e DDTs, (0,410-524), níveis de duas a três ordens de grandeza superiores aos encontrados em vegetação. PBDEs ocorreram, de modo geral, em níveis uma ou duas ordens de grandeza abaixo dos organoclorados. A análise isotópica mostrou-se útil como ferramenta indicadora de nível trófico e origem de matéria orgânica consumida, correlacionando-se quantitativa e qualitativamente com os poluentes orgânicos pela indicação de fatores como stress nutricional e mudança de área de forrageio e/ou de dieta. Como alternativa, foi proposto um novo indicador de biomagnificação baseado no peso molecular dos PCBs, que apresentou resultados estatisticamente superiores ao ?15N na maioria dos casos. / Despite the small antropic direct influence on its territory, Antarctica cannot be considered out of pollutants\' reach. The present study evaluated the distribution and transfer of organic pollutants (PCBs, organochlorine pesticides and PBDEs) in both abiotic (snow and melting water) and biotic (lichens, mosses, invertebrates, fishes, bird eggs and bird and pinnipeds\' tissues, for which was also applied carbon-13 and nitrogen-15 stable isotopes analyses) compartments of the ecosystem from Admiralty Bay. Abiotic compartments showed concentrations between 1,4 and 156 pg L-1, only for organochlorine groups, with considerable intraseasonal variation and compatibility with lower trophic levels and vegetation samples, which in turn reflected the importance of secondary pollutants sources. In animal samples, grosso modo, the prevailing compounds were (in ng g-1 wet weight) PCBs (6,82-1821), HCB (0,060-136) and DDTs, (0,410-524), levels from two to three orders of magnitude superior to the ones found in vegetations. PBDEs occurred, in a general way, in levels from one to two orders of magnitude lower than the organochlorines. Stable isotope analyses proved useful as an indicator tool for trophic level and consumed organic matter, correlating itself in a qualitative and quantitative way with the organic pollutants by indication of factors as nutritional strees and variation in foraging areas and/or diet. As an alternative, a new biomagnifications indicator based on PCBs molecular weight was proposed, showing results statistically superior to the ?15N in the majority of the cases.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Persistent Organic Pollutants (POPs) are chemical substances that are widely distributed throughout the environment, accumulate in the fatty tissue of living organisms, are found at higher concentrations in the food chain and are toxic to both humans and wildlife. In the present work, POPs were determined in honey samples from different geographic regions, evaluating both the quality and safety of honey as food, and the environmental contamination of the studied regions. Organochlorine pesticides were analysed in 186 samples from the South region of Brazil, with concentrations between <LOQ and 92 ng g-1. Pesticides Endosulfan alpha and Endosulfan sulfate were the most frequent, with mean of 1.84 and 1.68 ng g-1, respectively. Samples from Santa Catarina State had higher Aldrin concentrations when compared to those from Rio Grande do Sul and Paraná States, while there was a reduction in the Endrin concentration in the samples collected in 2011, when compared with those collected in 2010. With regard to food security, 18% of the samples exceeded the maximum residue limits allowed by law for compounds Aldrin, p,p'-DDT, Endosulfan alpha, Endrin, and Heptachlor, which may pose a risk to consumer health. Indicator PCBs were analysed in 137 samples from Rio Grande do Sul, Santa Catarina, Paraná, and São Paulo States. PCBs 28 and 52 were the most frequent, with means of 1.18 and 0.74 ng g-1, respectively. Samples from São Paulo State exhibited the highest levels (ΣPCBs 7.52 ng g-1), followed by samples from Paraná (ΣPCBs 5.4 ng g-1), Santa Catarina (ΣPCBs 2.59 ng g-1), and Rio Grande do Sul (ΣPCBs 1.24 ng g-1), with significant difference for PCBs 28 and 52. There was no difference between the concentrations of samples collected in the years 2009, 2010, and 2011. DL-PCBs, PCDDs and PCDFs were analysed in 16 samples from four Brazilian States (RS, SC, PR and SP). DL-PCB concentrations ranged between 24.3 and 260 pg g-1, while PCDD/Fs, between <LOD and 5.4 pg g-1. TEQ values were between 0.002 and 0.343 pg WHO-TEQ g-1. No significant difference was found among the concentration levels of the samples from the four States. Brominated flame retardants (PBDEs, BTBPE and DBDPE) were analysed in 35 honey samples from Brazil, Spain, Portugal, Morocco, and Slovenia, with concentrations ranged between <LOD and 24.7 pg g-1. Brazilian honeys exhibited the highest mean concentration (5.19 pg g-1), followed by Moroccan (4.4 pg g-1), Portuguese (2.24 pg g-1), Spanish (1.77 pg g-1), and Slovenian (0.93 pg g-1) samples. PBDE 47 was the most frequent, being detected in 91% of samples, and followed by PBDE 99, in 63%. These compounds were the main contributors in the BFR total concentration in samples from Europe, while the novel flame retardants, BTBPE and DBDPE, had greater contribution in samples from Brazil and Morocco. With regard to food security, there is no limit established by law for PCBs, PCDDs, PCDFs, and BFRs in honey. Although the levels detected were quite low when compared to other foods of animal origin, the honey samples analysed showed significant contamination, demonstrating that the studied regions contain sources of environmental contamination to be investigated. / Os Poluentes Orgânicos Persistentes (POPs) são compostos químicos sintéticos que estão amplamente distribuídos no meio ambiente, acumulam-se nos tecidos lipídicos dos seres vivos, são encontrados em altas concentrações na cadeia alimentar e apresentam efeitos tóxicos aos seres humanos e animais. No presente trabalho, os POPs foram determinados em mel de abelhas de diferentes regiões geográficas, buscando avaliar a qualidade e segurança do mel como alimento, bem como a contaminação ambiental das regiões estudadas. Os praguicidas organoclorados foram analisados em 186 amostras da região Sul do Brasil, com concentrações que variaram entre <LQ e 92 ng g-1. Os praguicidas Endosulfan alfa e Endosulfan sulfato foram os mais frequentes, com média de 1,84 e 1,68 ng g-1, respectivamente. As amostras provenientes de Santa Catarina apresentaram concentrações maiores de Aldrin quando comparadas às provenientes do Rio Grande do Sul e Paraná, enquanto que observou-se uma redução na concentração de Endrin nas amostras coletadas no ano de 2011, quando comparadas com as coletadas em 2010. Com relação à segurança alimentar, 18% das amostras superaram o limite máximo de resíduos permitido pela legislação para os compostos Aldrin, p,p -DDT, Endosulfan alfa, Endrin e Heptacloro, o que pode representar risco à saúde do consumidor. Os PCBs indicadores foram analisados em 137 amostras provenientes dos estados do Rio Grande do Sul, Santa Catarina, Paraná e São Paulo. Os congêneres 28 e 52 foram os mais frequentes, com média de 1,18 e 0,74 ng g-1, respectivamente. As amostras provenientes do estado de São Paulo apresentaram os níveis mais elevados (ΣPCBs 7,52 ng g-1), seguidas das amostras do Paraná (ΣPCBs 5,4 ng g-1), Santa Catarina (ΣPCBs 2,59 ng g-1) e Rio Grande do Sul (ΣPCBs 1,24 ng g-1), com diferença significativa para os PCBs 28 e 52. Não houve diferença entre as concentrações das amostras coletadas nos anos de 2009, 2010 e 2011. DL-PCBs, PCDDs e PCDFs foram analisados em 16 amostras provenientes de quatro estados brasileiros (RS, SC, PR e SP). As concentrações de DL-PCBs variaram entre 24,3 e 260 pg g-1, enquanto que as de PCDD/Fs, entre <LD e 5,4 pg g-1. Os valores de TEQ ficaram entre 0,002 e 0,343 pg WHO-TEQ g-1. Nenhuma diferença significativa foi encontrada entre as concentrações das amostras provenientes dos quatro estados. Retardantes de chama bromados (PBDEs, BTBPE e DBDPE) foram analisados em 35 amostras provenientes do Brasil, Espanha, Portugal, Marrocos e Eslovênia, com concentrações que variaram entre <LD e 24,7 pg g-1. As amostras provenientes do Brasil apresentaram a maior concentração média (5,19 pg g-1), seguidas das provenientes do Marrocos (4,4 pg g-1), Portugal (2,24 pg g-1), Espanha (1,77 pg g-1) e Eslovênia (0,93 pg g-1). O PBDE 47 foi o mais frequente, tendo sido detectado em 91% das amostras analisadas, seguido do PBDE 99, em 63%. Estes compostos foram os que mais contribuíram na concentração total de BFRs nas amostras provenientes da Europa, enquanto que os novos retardantes de chama, BTBPE e DBDPE, tiveram maior contribuição nas amostras do Brasil e Marrocos. Com relação à segurança alimentar, não há limite máximo estabelecido para PCBs, PCDDs, PCDFs e BFRs em mel de abelhas. Embora os níveis detectados destes compostos tenham sido baixos quando comparados a outros alimentos de origem animal, as amostras de mel de abelhas analisadas apresentaram contaminações importantes, demonstrando que as regiões estudadas contêm fontes de contaminação ambiental a serem investigadas.

Os albatrozes e petréis (Procellariiformes) são aves oceânicas e migratórias de grande interesse conservacionista. Neste trabalho foram estudadas duas classes de poluentes bastante conhecidos por afetarem negativamente as aves marinhas: os poluentes orgânicos persistentes e os plásticos. Bifenilos policlorados (PCBs) e pesticidas organoclorados foram detectados no tecido adiposo, fígado e músculo de oito espécies de Procellariiformes. Apesar da grande variabilidade intraespecífica nas concentrações, os perfis de PCBs e pesticidas organoclorados foram semelhantes entre os indíviduos, com predôminância de PCBs penta, hexa e heptaclorados e do p´p-DDE. A condição corporal se mostrou um fator importante na variação e redistribuição dos organoclorados nos tecidos das aves. As análises de isótopos estáveis de carbono e nitrogênio no fígado e músculo das aves mostraram que a dieta não foi suficiente para explicar as concentrações de organoclorados nas espécies estudadas e reforçaram a influência de fatores como idade, distribuição e especifidade da dieta na contaminação por estes compostos em aves marinhas. PCBs e pesticidas organoclorados foram detectados em pellets e fragmentos plásticos encontrados no trato digestório das aves estudadas, com perfis semelhantes aos encontrados nos tecidos dos Procellariiformes. A ocorrência de poluentes orgânicos em plásticos evidencia a capacidade destes de adsorver e transportar estes compostos e reforça o potencial dos plásticos como uma fonte adicional de contaminação para os animais que os ingerem, como as aves marinhas. / Albatrosses and petrels (Procellariiformes) are migratory oceanic birds of considerable conservational interest. The aim of the present study was to evaluate two classes of pollutants that negatively affect seabirds: persistent organic pollutants and plastics. Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were detected in the adipose tissue, liver and muscle of eight species of Procellariiformes. Although organochlorine concentrations exhibited a high degree of intra-species variability, the profiles of PCBs and OCPs were similar among the individuals, with predominance of penta, hexa and heptachlorobiphenyls and p´p-DDE. Body condition was an important factor in the variation and redistribution of organochlorine compounds in the tissues of the birds. Stable isotope analysis of carbon and nitrogen in the liver and muscle revealed that diet alone was insufficient to explain the organochlorine concentrations in the species studied, suggesting the influence of factors such as age, distribution and diet specificity regarding organochlorine contamination in seabirds. PCBs and OCPs were detected in plastic fragments and pellets found in the digestive tract of Procellariiformes, with profiles very similar to those found in the tissues of the birds. The occurrence of organic pollutants in plastics demonstrates their ability to adsorb and transport these compounds and underscores the potential of plastics as an additional source of contamination in organisms that ingest these products, such as seabirds.

Dans ce travail de thèse, nous avons analysé les résidus des plusieurs contaminants anthropiques dans des prédateurs de la chaîne alimentaire aquatique et des proies de la chaîne terrestre. En effet, la loutre, le grand cormoran et le silure sont prédateurs piscivores au sommet de la chaîne alimentaire, les pesticides organochlorés, les PCBs et les éléments traces métalliques (plomb, cadmium, cuivre et mercure) ont été détectés dans tous les foies de ces prédateurs prélevés dans les bassins de la Loire en France. Les PCBs sont les organochlorés les plus répandus dans les trois espèces, suivi des DDTs. Les valeurs maximales de PCBs ont atteint 1,61, 1,96 et 0,28 mg/kg de poids frais pour les cormorans, les loutres et les silures, respectivement. La concentration du mercure a dépassé la limite toxique pour plus de 40 % des cormorans analysés. L‘effet « cocktail » de ces contaminants sur les trois espèces n‘est pas étudié dans cette thèse. Cependant, Les concentrations des organochlorés et des éléments traces dans ces prédateurs sont généralement modestes ou faibles. Ainsi, Il nous semble que ces contaminants ne constituent pas une menace pour la conservation de ces espèces à court ou moyen terme. Par ailleurs, dans le réseau trophique terrestre, nous avons trouvé que trois rodenticides anticoagulants la chlorophacinone, la bromadiolone et le brodifacoum s‘accumulent dans les limaces de la manière rapide et stable au cours de temps, par contre aucune mortalité n‘a été observée chez les limaces. Le brodifacoum a été détecté dans plus de 90 % des limaces prélevées sur le terrain, et nous avons constaté que ces limaces représentaient un risque élevé d'empoisonnement secondaire pour trois de leurs prédateurs, le hérisson européen, la musaraigne commune et l'étourneau sansonnet. On pourrait donc confirmer que les invertébrés constituent une source non négligeable de rodenticides pour leurs prédateurs.L‘objectif de cette thèse est de montrer l‘influence du régime alimentaire sur la contamination des proies, des prédateurs et d‘évaluer les risques toxicologiques pour ces espèces / In this work, we analyzed the residues of several anthropogenic contaminants in predators of the aquatic food chain and prey of the terrestrial chain. The otter, the great cormorant and the catfish are piscivorous predators at the top of the food chain. Organochlorine pesticides, PCBs and trace elements (lead, cadmium, copper and mercury) were detected in all these predators collected from the basins of the Loire in France. Residue level of PCBs in these predators was the highest followed by DDTs and maximal PCB values reached 1.61, 1.96, and 0.28 mg/kg wet weight for cormorants, otters, and catfish, respectively. The concentration of mercury exceeded the toxic thresholds for more than 40% of the cormorants analyzed. The possible combined effect of these contaminants on the three species has not been studied in this thesis. However, the concentrations of organochlorines and trace elements are generally modest or low. Thus, it seems that these contaminants do not constitute a major threat to the conservation of these species for the short or medium term. Furthermore, in the terrestrial food chain, we found that three anticoagulant rodenticides chlorophacinone, bromadiolone and brodifacoum accumulate in slugs in a stable way over the time, whereas no mortality was observed in slugs. Brodifacoum was detected in more than 90% of the slugs collected in the field, and we found that these slugs represented a high risk of secondary poisoning for three of their predators, European hedgehog, common shrew and European starling. Therefore, it could be confirmed that invertebrates constitute a non-negligible source of rodenticides for their predators.The objective of this thesis is to show the influence of the diet on the contamination of prey, predators and to evaluate the toxicological risks for these species

The gut microbiota plays a major part in maintaining the health of a human host. Countless of crucial functions in the body, including immune responses, cell signaling and energy metabolism to name a few, are conducted by the gut microbiota and its metabolites. Accordingly, it is of interest to gain knowledge on what can alter the gut microbiota, as these alterations by extension can give rise to adverse health effects. In this study, the impact of polychlorinated biphenyl (PCB)- and organochlorine pesticide (OCP) exposure on tricarboxylic acid (TCA) cycle metabolites, short-chain fatty acids (SCFAs) and bile acids, as well as other polar and semi-polar metabolites, which are all related to the gut microbiota, were investigated. An in vitro fermentation of faecal samples exposed to a PCB/OCP mixture was performed, and liquid chromatography-time of flight mass spectrometry (LC-qToF-MS) targeted and non-targeted approaches were applied to the extracts. The results obtained suggested that PCBs and OCPs most likely have an effect on the levels of several features of the gut metabolome with either increased or decreased levels upon exposure. Bile acids and TCA metabolites appear to follow a trend of decreasing levels, while no apparent effects could be seen for the SCFAs. Furthermore, distinct concentrations of the PCB/OCP mixture appear to induce different changes in gut microbiota functioning, which highlights the importance of performing dose-response studies when exploring biological effects of these compounds. The identification of different metabolite profiles during fermentation also allows for the possibility of further investigation of potential biomarkers to assess PCB/OCP exposure.

O Pinguim-de-Magalhães, Spheniscus magellanicus, é o mais abundante dos pinguins que vivem em regiões temperadas da América do Sul, sendo um bom indicador de poluição ambiental. Poluentes orgânicos persistentes (POPs) foram detectados em fígado de Pinguins-de-Magalhães encontrados debilitados ou mortos nas praias do Brasil (Rio de Janeiro, São Paulo, Santa Catarina e Rio Grande do Sul) entre 2008 - 2012 e, do Uruguai e do Chile, em 2011. Os bifenilos policlorados (PCBs) predominaram em relação aos pesticidas organoclorados (DDTs &#8764; HCB &#8764; Drins) e aos éteres difenilos polibromados (PBDEs). O contaminante emergente fipronil não foi detectado apesar de seu uso na América do Sul. Entre os PCBs predominaram os congeneres penta, hexa e heptaclorados. Concentrações de POPs foram similares entre as áreas de migração e reprodução exceto para os PCBs que foram relativamente maiores na área de reprodução. Avaliação temporal (2008 - 2012) de POPs apresentou constância para os pesticidas organoclorados e tendência ao declínio para os PCBs. A glândula uropigiana de Pinguim-de-Magalhães mostrou-se um tecido alternativo adequado para análise de POPs em aves debilitadas. No geral, as regiões de reprodução e migração dos pinguins na América do Sul apresentam baixas concentrações de POPs com tendência constante ou indícios de declínio. / The Magellanic Penguin , Spheniscus magellanicus, is the most abundant penguin that live in temperate regions of South America and a good indicator of environmental pollution in that region. Persistent organic pollutants (POPs) were detected in the liver of Magellanic penguins found debilitated or dead on the beaches of Brazil (Rio de Janeiro, Sao Paulo, Santa Catarina and Rio Grande do Sul) between 2008 - 2012, and in Uruguay and Chile in 2011. Polychlorinated biphenyls (PCBs) were more prevalent than organochlorine pesticides (DDTs &#8764; HCB &#8764; Drins) and polybrominated diphenyl ethers (PBDEs). Fipronil, an emerging contaminant, was not detected despite its use in South America. Among PCBs, the congeners penta, hexa and heptaclorados were predominant. Concentrations of POPs are similar between the migration and reproduction areas except for PCBs that are relatively higher in the breeding area. At this time point (2008 - 2012) POPs showed constancy for organochlorine pesticides and PCBs tendency to decline. The Magellanic penguin uropygian gland has proved to be a suitable alternative for POPs tissue analysis in debilitated birds. Overall, southern South America has low concentrations of POPs with constant trend or decline evidence.

Os recursos hídricos urbanos são de grande importância para os municípios que têm desenvolvimento econômico crescente e aumento demográfico, sendo que a manutenção da qualidade da água dos mananciais de abastecimento para a população é imprescindível para a saúde e para diminuir o custo econômico. A bacia do Alto Jacaré-Guaçu, em cuja área está inserido o município de São Carlos/SP, tem como principais sub bacias a do Rio do Monjolinho e a do Ribeirão do Feijão, sendo este a principal fonte de abastecimento de água para a cidade. O trabalho foi proposto para avaliar a qualidade da água dos recursos hídricos da bacia do Alto Jacaré-Guaçu, através da análise das características limnológicas, das substâncias tóxicas e da comunidade de macroinvertebrados que permitem a indicação da qualidade da água. Foram efetuadas duas campanhas de amostragem em 1999: a) no período chuvoso (em março) e b) no período de estiagem (em agosto). Em março foram realizadas amostragens em 8 pontos e, em agosto, foram acrescidos mais 6 pontos, totalizando 14. Paralelamente, com o intuito de visualizar espacialmente os resultados e desta forma identificar as áreas com maior ou menor grau de impacto, foi elaborado um mapa com as sub-bacias correspondentes às áreas cuja água drena para cada um dos pontos de coleta. Os resultados obtidos demonstram que a qualidade da água no período da estiagem se torna mais critica devido à diminuição do fluxo da água. Com relação à poluição orgânica, a sub bacia do Monjolinho pode ser classificada em 3 grupos: a) trecho sem influência urbana, portanto não poluída ou ligeiramente poluída; b) trecho com influência da área urbana da cidade de São Carlos, sendo assim, fortemente poluída e c) trecho final do Rio Monjolinho, com uma poluição moderada ou em processo de recuperação. Quanto à presença de substâncias tóxicas analisadas as concentrações dos metais, em geral, apresentaram-se dentro dos limites da Resolução CONAMA 20/86, exceto o cobre, ferro, manganês e zinco. Já para os organoclorados, a maior parte da área da bacia não atende a Resolução Brasileira, detectando-se concentrações acima dos limites permitidos. Quanto à identificação dos diferentes impactos no uso da terra e da água na bacia do Alto Jacaré-Guaçu, pode-se citar, entre as atividades antrópicas que vem acelerando o processo de degradação ambiental, principalmente a qualidade da água :1- Falta de tratamento do esgoto doméstico, principalmente na área urbana; 2- Desmatamento contínuo levando a substituição da vegetação natural por monoculturas e pastagens; 3- Uso irregular do solo, causando erosão e assoreamento nos corpos de água; 4- Expansão sem controle da área urbana próximo às margens e principalmente nas nascentes dos corpos de água e 5-Falta de controle na comercialização e uso de defensivos agrícolas. / The water resources in urban areas are important for the municipalities in stage of economical development and demographic increase. The maintenance of quality of the water sources is indispensable for the human health and to reduce the economic costs. The Alto Jacaré-Guaçu basin, situated in São Carlos municipality, has as a principal sub-basins the Monjolinho River and Ribeirão do Feijão basins. Both are the main souce of water supply for the city. This study was proposed to analyze the water quality of the Alto Jacaré-Guaçu basin, according to the limnological conditions, toxic substances and utilization of macroinvertebrates as indicative of the water quality. Sampling was carried out in two periods: a) in the rainy season (March 1999) and b) in the dry season (August 1999). In March 8 stations were sampled, while in August 6 more stations were sampled, totalizing 14 stations. In Parallel, a map was elaborated with the sub-basins corresponding to the drainage area for each station in order to show spatially the results and to identify the areas with bigger or minor degree of impact. The results demonstrated that the water quality in the dry period became critical due to decreasing of the water flow. Concerning to the organic pollution, the sub-basin of Monjolinho can be classified under 3 groups: a) section without urban influence, with no or few pollution; b) section with no or few pollution; b) section with influence of the urban area of São Carlos city, being strongly contaminated and c) final section the Monjolinho River, with a moderate pollution or in process of recovery. In relation to the presence of toxic substances analyzed, the concentrations of metals generally appeared inside the limits of the Resolution CONAMA 20/86, except for copper, iron, manganese and zinc. For the organochlorine pesticides, the concentrations oberseved do not attend to the Brazilian Resolution, because the values were higler than the acceptable limits. Concerning to the identification of different impacts of the land and water uses in the Alto Jacaré-Guaçu basin, it is possible to identify the human activities that accelerate the process of environmental degration, specially for the water quality: 1- The lack of teatment of the domestic residues, specially in the urban area; 2- Continous deforestation and changing of natural vegetation to monocultures and pastures; 3-Irregular uses of the soil causing erosion and collapsing the water bodies; 4- Expansion without control of the urban area next to the margins and specially in the headwaters, and 5- Lack of control in the selling and uses of agricultural pesticides.

Ce travail s’intéresse à évaluer l’efficacité de procédés d’oxydation avancée pour l’élimination de pesticides dans l’eau, plus particulièrement l’acide 2,4-dichlorophénoxyacétique (2,4-D), un herbicide largement répandu, qui a été récemment classé comme cancérogène possible pour l’homme. Ces procédés utilisent différents types de rayonnement – UV/visible, ultrasons, rayons gamma –, seuls ou en combinaison avec des oxydants et/ou catalyseurs (ozone, peroxyde d’hydrogène, réactif de Fenton). L'influence du pH, de la dose d'oxydant, du type et de la concentration du catalyseur, du spectre d'irradiation lumineuse, de la dose de rayons gamma et de la fréquence ultrasonore est également analysée, de façon à déterminer par plans d’expériences les plages de fonctionnement optimales pour la conversion et la minéralisation du polluant. Parmi les procédés individuels, seules l’ozonation et l’oxydation Fenton homogène d’une part, la photolyse et l’irradiation gamma d’autre part permettent d’éliminer plus de 25% du carbone organique total en 1 heure. La sonolyse (à haute fréquence) apparaît comme le traitement moins performant, avec une dégradation du 2,4-D inférieure à 15% sur la même durée. Par ailleurs, des effets synergiques marqués sont mis en évidence en associant les différents types de rayonnement avec H2O2 ou le réactif de Fenton. Dans le dernier cas, le polluant est décomposé en moins de 10 minutes, tandis que le rendement de minéralisation est plus que doublé par rapport aux procédés séparés. Il en est de même pour le procédé couplé UV/O3 par rapport à l’ozonation et la photolyse seules. Ramenés à leur consommation énergétique, les traitements les plus efficaces sont, respectivement en termes de conversion et de minéralisation, l’oxydation radio-Fenton et l’oxydation photo-Fenton utilisant une lampe UV à basse pression de mercure. Par ailleurs, contrairement à la photolyse, ce dernier procédé est également activé par une lampe à arc Xenon, dont le spectre d’émission est proche de celui de la lumière du soleil. Sur la base de ces résultats, un photo-réacteur solaire à recirculation est mis en oeuvre pour traiter par oxydation photo-Fenton homogène des solutions de 2,4-D, préparées dans l’eau du robinet ou une eau résiduaire en entrée de station d’épuration. Dans les deux cas, la conversion du pesticide dépasse 95% en 1 heure et sa minéralisation 75% en 5 heures. Par ailleurs, l’eau ainsi traitée respecte tous les paramètres de qualité établis par la norme cubaine de rejet des eaux usées, en incluant une étape successive de neutralisation avec Ca(OH)2 et de filtration. Enfin, plusieurs parmi les meilleurs procédés sont évalués pour éliminer deux autres pesticides organochlorés, particulièrement toxiques et persistants dans l’environnement : le chlordécone et le bêta-hexachlorocyclohexane. Des résultats encourageants sont obtenus, avec une dégradation pratiquement totale des polluants en cinq heures, ce qui démontre l’intérêt des méthodes étudiées pour cette problématique. / This work investigates the efficacy of advanced oxidation processes for the remediation of pesticidesin water, more particularly 2,4-dichlorophenoxyacetic acid (2,4-D), a widely used herbicide that hasrecently been classified as a possible carcinogen to humans. These methods use different types ofradiation - UV / visible, ultrasound, gamma rays - alone or in combination with oxidants and / orcatalysts (ozone, hydrogen peroxide, Fenton’s reagent). The influence of pH, oxidant dose, catalysttype and concentration, light irradiation spectrum, gamma radiation dose and ultrasound frequencyis also analyzed, in order to determine by experimental design the optimal operating ranges for theconversion and mineralization of the pollutant. Of individual processes, only ozonation andhomogeneous Fenton oxidation on the one hand, photolysis and gamma irradiation on the otherhand, achieve the abatement of more than 25% of total organic carbon in one hour. (High frequency)sonolysis appears as the less efficient treatment, resulting in less than 15% of 2,4-D being degradedover the same duration.In addition, marked synergistic effects are demonstrated by combining the different types of radiationwith H2O2 or Fenton’s reagent. In the latter case, the pollutant is decomposed in less than 10 minutes,while the mineralization yield more than doubles compared to the separate processes. It is the samefor UV/O3 coupled process with respect to ozonation and photolysis alone. When accounting for theirenergy consumption, the most effective treatments are, respectively in terms of conversion andmineralization, radio-Fenton oxidation and photo-Fenton oxidation using a low-pressure mercuryvaporUV lamp. Moreover, unlike photolysis, the latter method is also activated by a Xenon arc lamp,whose emission spectrum is close to that of sunlight. Bases on these results, a solar photoreactoroperating in closed loop is used to treat 2,4-D solutions, prepared with tap water or inlet stream ofwastewater treatment plant, by homogeneous photo-Fenton oxidation. In both cases, the conversionof the pesticide exceeds 95% in 1 hour and its mineralization 75% in 5 hours. Moreover, the treatedwater complies with all the quality parameters established by the Cuban norm for wastewaterdischarge, when including a subsequent step of neutralization with Ca(OH)2 and filtration.Finally, several of the best processes are evaluated to eliminate two other organochlorine pesticides,particularly toxic and persistent in the environment: chlordecone and beta-hexachlorocyclohexane.Encouraging results are obtained, with an almost complete degradation of the pollutants in fivehours, which demonstrates the value of the investigated methods for this issue. / En este trabajo se estudió la factibilidad de diferentes procesos avanzados de oxidación para laeliminación de plaguicidas en aguas, específicamente el ácido 2,4-diclorofenoxiacético (2,4-D), unode los herbicidas más utilizados a nivel mundial y que recientemente ha sido clasificado comocancerígeno para el hombre. Estos procesos utilizan diferentes tipos de irradiación – UV/Visible,ultrasonido, radiación gamma – solos o en combinación con oxidantes y/o catalizadores (ozono,peróxido de hidrógeno, reactivo de Fenton). Con el objetivo de determinar las condiciones óptimaspara la degradación y mineralización del contaminante, se analizó la influencia del pH, la dosis deoxidante, el tipo y la concentración del catalizador, el espectro de irradiación luminosa, la dosis deirradiación gamma y la frecuencia y potencia ultrasónicas. Entre los procesos individuales,solamente la oxidación Fenton homogénea, la ozonización, la fotólisis y la radiación gamma lograroneliminar más de un 25% del carbono orgánico total en una hora. La sonólisis (a alta frecuencia)resultó el proceso menos eficiente, con una degradación del 2,4-D inferior al 15% en el mismotiempo.Al asociar los diferentes tipos de irradiación con el H2O2 o el reactivo de Fenton, se observaronefectos sinérgicos importantes. Para este último, el contaminante se degradó totalmente en menosde 10 minutos, mientras que la mineralización fue superior al doble de la obtenida para los procesospor separado. Lo mismo ocurrió para el proceso combinado UV/O3, respecto a los procesos defotólisis y ozonización solos. Teniendo en cuenta el consumo energético asociado a la degradacióny mineralización respectivamente, los tratamientos más eficientes fueron el radio-Fenton y el foto-Fenton utilizando una lámpara de baja presión de mercurio. Por otra parte, al contrario de la fotólisis,este último proceso se activó con una lámpara de arco de Xenon, la cual posee un espectro deemisión cercano a la luz solar. Teniendo en cuenta estos resultados, se realizó un grupo deexperimentos a escala de banco utilizando un foto-reactor solar, donde se trataron por oxidaciónfoto-Fenton homogénea disoluciones de 2,4-D preparadas con agua técnica y agua residualobtenida a la entrada de una planta de tratamiento de aguas. En los dos casos, la degradación delpesticida supera el 95% en 1 hora y su mineralización en 75% en 5 horas. Además, al incluir unaetapa de neutralización con Ca(OH)2, el agua residual tratada logra cumplir las normas de calidadestablecidas por la norma cubana de vertimiento de aguas residuales.Finalmente, algunos de los procesos con mejores resultados se evaluaron para la eliminación otrosdos pesticidas organoclorados de mayor toxicidad y persistencia en el medio ambiente: laclordecona y el beta hexaclorociclohexano. Al aplicar las técnicas de tratamiento a estoscompuestos se lograron buenos resultados, cercanos a la degradación total de ambos plaguicidasen cinco horas, lo que demuestra el interés de los métodos estudiados en esta tesis.

In this study, the Persistent Organic Pollutants (POPs) specifically / 17 Organochlorine Pesticides (OCPs) and 19 Polycyclic Aromatic Hydrocarbons (PAHs) were evaluated in the sediment samples of Balikesir (Ikizcetepeler) Dam Lake. Sixteen sampling points were chosen for determination of concentrations of OCPs and PAHs After ultrasonic bath extraction of the sediment samples GC-MS was used as analytical tool. Extraction efficiencies changes from 63.8 to 87.4% depending on the type of the POPs. Average OCP concentration was found in the range of 3.33-379 &micro / g/kg a, average PAH concentration was found in the range of 3.28-32.9 &micro / g/kg. Pollution maps regarding OCP and PAH distributions were drawn and the correlation between these two pollutant types was investigated. The quality control (QC) and quality assurance tests were applied by the analysis of standard reference materials (SRMs), surrogate standards and analysis replicates.