No description available.

Le p-tert-octylphénol est un produit présent dans l’environnement et issu de la dégradation des alkylphénols éthoxylés. Ce composé a la capacité de se lier au récepteur œstrogénique et d’exercer ainsi un léger effet œstrogénique. Les objectifs de cette étude étaient de 1) développer une méthode d'identification de l'octylphénol dans le sang et les tissus à l'aide de la chromatographie en phase gazeuse jumelée à la spectrométrie de masse, 2) caractériser la toxicocinétique sanguine et tissulaire de l’octylphénol chez le rat Sprague-Dawley mâle et femelle et 3) développer un modèle toxicocinétique à base physiologique permettant de décrire la cinétique sanguine et tissulaire de l’octylphénol inchangé. Pour ce faire, des rats mâle et femelle Sprague-Dawley ont reçu des doses uniques d’octylphénol par les voies intraveineuse, orale et sous-cutanée. Deux autres groupes ont reçu des doses répétées d'octylphénol par voie orale pour une durée de 35 jours consécutifs pour les femelles ou 60 jours pour les mâles. Les concentrations sanguines et tissulaires d’octylphénol ont été mesurées à différents moments après administration à partir d’une méthode d’analyse développée dans nos laboratoires dans le cadre de ce projet. Les expériences impliquant des administrations uniques ont montré que les concentrations sanguines et tissulaires d'octylphénol étaient en général plus élevées chez les femelles que chez les mâles. Des expériences réalisées avec des microsomes hépatiques ont confirmé que ces différences étaient vraisemblablement reliées au métabolisme de l'octylphénol. Les expériences impliquant des administrations répétées ont montré qu'il n'y avait pas d'accumulation d'octylphénol dans l'organisme aux doses étudiées. Les résultats obtenus expérimentalement ont servi à développer et valider un modèle toxicocinétique à base physiologique. Ce modèle a permis de simuler adéquatement les concentrations sanguines et tissulaires d'octylphénol suite à des expositions intraveineuses, orales et sous-cutanées. En conclusion, cette étude a fourni des données essentielles sur la toxicocinétique de l'octylphénol. Ces données sont nécessaires pour établir la relation entre la dose externe et la dose interne et vont contribuer à une meilleure évaluation des risques liés à l'octylphénol. / p-tert-Octylphenol is a degradation product of alkylphenol ethoxylates that can be found in the environment. It has been reported to act as a weak estrogenic compound by binding to the estrogen receptor. This study was undertaken to 1) develop a sensitive method for the determination of octylphenol in blood and various tissues using gas chromatography coupled with detection by mass spectrometry, 2) characterize the blood and tissues toxicokinetics of octylphenol in male and female Sprague-Dawley rats and 3) develop a physiologically-based toxicokinetic model for octylphenol that can describe/predict unchanged blood and tissues octylphenol concentrations in rats. Male and female Sprague-Dawley rats were given a single dose of octylphenol either by oral gavage, intravenous injection or subcutaneous injection. In a repeated dosing experiment, rats were given octylphenol (oral) daily for 35 days (female) or 60 days (male). Blood and tissue samples were collected at various time following the onset of exposure and analyzed for octylphenol content using a method developed in our laboratory. These results showed that blood and tissues octylphenol concentrations were generally higher in female than male rats. Experiments done with rat liver microsomes confirmed that these differences were related to octylphenol metabolism. The results of the repeated exposure study indicate that there is no bioaccumulation of octylphenol at these exposure levels. A physiologically-based pharmacokinetic model for octylphenol was developed and validated using the data obtained in female and male rats. The model simulates adequately blood and tissues octylphenol concentrations following oral, intravenous or subcutaneous exposure. In conclusion, this study provided essential data on the toxicokinetics of octylphenol. These data are essential to predict the relationship between the internal and the external dose of octylphenol and will facilitate the risk assessment of octylphenol in humans.

Le fipronil, insecticide largement utilisé, est un perturbateur thyroïdien chez le rat modulant le catabolisme hépatique des hormones thyroïdiennes. Ses effets chez le mouton, considéré comme un modèle plus pertinent que le rat pour étudier une régulation de la fonction thyroïdienne chez l'Homme, sont plus limités. Le but de cette thèse était de caractériser au niveau hépatique le mode d'action du fipronil sur la fonction thyroïdienne en s'intéressant 1) au rôle potentiel du principal métabolite du fipronil formé in vivo, le fipronil sulfone, et 2) aux différences interspécifiques de métabolisme du fipronil et/ou de sensibilité à la perturbation thyroïdienne qui peuvent préjuger de la pertinence des différents modèles animaux pour l'analyse du risque du fipronil pour la santé humaine. L'efficacité du fipronil sulfone à induire l'expression et/ou l'activité d'enzymes responsables du métabolisme hépatique des hormones thyroïdiennes ou du fipronil était la même que celle du fipronil autant in vivo chez le rat que in vitro sur hépatocytes. L'utilisation d'un modèle de souris déficientes pour des récepteurs nucléaires xénosenseurs suggérait fortement une implication des récepteurs nucléaires Constitutive Androstane Receptor et/ou Pregnane X Receptor dans la perturbation thyroïdienne induite par le fipronil / The widely used insecticide fipronil is a thyroid disruptor in rat acting on thyroid hormone hepatic metabolism. In sheep, a more relevant species for the human thyroid regulation, fipronil-induced thyroid-disruption is much more limited. The goal of this thesis was to characterize the mode of action of fipronil on thyroid function at the hepatic level focusing on 1) the potential role of fipronil sulfone, the main fipronil metabolite formed in vivo, and on 2) interspecific differences in terms of fipronil metabolism and/or sensitivity to thyroid disruption that can prejudge of the relevance of the different animal models for the risk assessment of fipronil for human health. Fipronil sulfone was as efficient as fipronil to induce the expression and/or activity of enzymes involved in thyroid hormone or fipronil hepatic metabolism both in vivo in rat and in vitro on hepatocytes. The use of knock-out mice for xenosensors nuclear receptors strongly suggested an implication of the nuclear receptor Constitutive Androstane Receptor and/or Pregnane X Receptor on fipronil-induced thyroid disruption

Le bisphénol A (BPA), ubiquitaire dans l'environnement, est reconnu comme étant un perturbateur endocrinien (PE). La forte réactivité du BPA avec le chlore entraine la formation de dérivés chlorés du BPA (ClxBPA), possédant une activité perturbatrice endocrinienne supérieure au BPA. En santé environnementale, l'évaluation du risque chez l'homme implique notamment la mise en place d'études de biomonitoring et de toxicocinétique nécessitant l'analyse des micropolluants environnementaux dans les milieux biologiques.Afin d'estimer l'exposition des populations au BPA et ClxBPA, une méthode d'analyse par LC-MS/MS du BPA et des ClxBPA non conjugués a été validée dans l'urine. Cette méthode a ensuite été modifiée afin d'améliorer la rapidité et la sensibilité du dosage, et a été appliquée à la mesure de l'exposition aux PE dans une cohorte de femmes enceintes.L'étude de la toxicocinétique du BPA montre la formation de dérivés conjugués, éliminés par voie urinaire. Classiquement, pour la mesure des dérivés conjugués, des méthodes indirectes utilisant la déconjugaison enzymatique sont proposées. Dans ce cadre, nous avons développé une méthode originale permettant de valider l'efficacité de la déconjugaison. Si la mesure indirecte des métabolites après déconjugaison semble plus aisée, il reste néanmoins plus rationnel de doser directement l'analyte recherché. C'est pourquoi, après synthèse des substances étalons, nous avons pu développer, pour la 1ère fois, une méthode de dosage des dérivés glucuronides et sulfates du BPA et du Cl2BPA dans l'urine.Ce travail propose, à travers notamment le développement de méthodes d'analyse, des outils fiables pour la mesure de l'exposition aux PE. / Bisphenol A (BPA), a well-known endocrine disruptor (ED), is ubiquitously found in the environment. The high reactivity of BPA with chlorine results in the formation of chlorinated derivatives of BPA (ClxBPA), having a higher endocrine disrupting activity than BPA. In the field of environmental health sciences, human risk assessment implies, in particular, to perform biomonitoring and toxicokinetic studies requiring the analysis of environmental micropollutants in biological matrices. To estimate population exposure to BPA and ClxBPA, a LC-MS/MS method to assay BPA and ClxBPA was validated in urine. This method was then modified to improve the speed and sensitivity of the assay, and was applied to the measurement of ED exposure in a cohort of pregnant women.Toxicokinetic studies of BPA report the formation of conjugates, excreted in urine. Conventionally, for the measurement of conjugated derivatives, indirect methods using enzymatic deconjugation are proposed. In this context, we have developed an original method for validating the deconjugation efficiency.If the indirect measurement of metabolites after deconjugation appears easier, it is more rationale to assay directly the metabolite. Therefore, after synthesis of analytical standards, we were able to develop, for the first time, a method for assaying glucuronides and sulfates BPA and Cl2BPA derivatives in urine.This work offers, especially through the development of analytical methods, reliable tools for assessing human exposure to ED.

O tratamento de águas residuárias industriais, submetido constantemente a cargas de choque, é pouco estudado no Brasil, sendo limitado o grau de conhecimento que se tem no mundo sobre os mecanismos de remoção de disruptores endócrinos nos sistemas de tratamento físico-químicos e biológicos. O presente trabalho traz um estudo de caso, envolvendo uma indústria com uma composição de produtos muito diversificada, com despejos líquidos de unidades isoladas de qualidades diversas e que tem como uma das principais matérias-primas, nonil fenóis, conhecidos disruptores endócrinos. Os mecanismos de remoção de carga orgânica e a avaliação da toxicidade da água residuária ao processo biológico de tratamento foram estudados em escala de laboratório, enquanto que a sua tratabilidade por coagulação, floculação, flotação com ar dissolvido seguido de sistema de lodos ativados, em escala piloto. Avaliou-se, também, a aplicabilidade do tratamento biológico com carvão ativado em pó. A grande variação qualitativa e quantitativa da água residuária bruta requer uma unidade de equalização com tempo de detenção de pelo menos 30 horas. O maior responsável por esta variação de qualidade é o processo da unidade química, cujo efluente é proveniente de lavagens de tanques e reatores. Apesar da reduzida eficiência de remoção de DQO obtida com a coagulação, floculação e flotação com ar dissolvido (20 a 30%), constatou-se que este tratamento é essencial para a redução da toxicidade ao processo biológico. A dosagem de coagulante e o pH ótimos variam conforme a característica do despejo e devem ser determinadas diariamente. No sistema biológico, observou-se uma remoção significativa da DQO do efluente bruto gerado na indústria, não apenas por biodegradação, mas também por volatilização e adsorção. Os testes de bancada evidenciaram remoções de DQO por arraste com ar de 47 a 77 % e por adsorção no lodo biológico, de 42%. Apesar dos constantes choques de carga orgânica e de poluentes tóxicos, conseguiu-se atingir o estado estacionário com variações máximas da concentração de sólidos em suspensão voláteis no tanque de aeração entre 20 e 30%. Neste período, a idade do lodo situou-se em torno de 25 a 30 dias e o tempo de detenção hidráulico foi de 3,8 dias. A eficiência média de remoção de DQO neste período foi de 86%. Os testes com a unidade piloto demonstraram que a utilização de carvão ativado em pó (CAP) produz resultados satisfatórios, comprovando a redução de poluentes tóxicos da água residuária e refletindo em uma significativa melhora na biodegradabilidade do efluente, com aumento da concentração de sólidos em suspensão voláteis no tanque de aeração (de 1380 mg/L para 3820 mg/L) e redução da amplitude de variação da DQO do efluente tratado que passou de 600 a 3200 mgO2/L para o sistema sem CAP para 300 a 600 mgO2/L para o sistema com CAP. Notou-se, também, com a adição de CAP, melhoria na sedimentação do lodo. Pode-se concluir também que o sistema de tratamento atendeu a legislação atual do Estado de São Paulo, com uma remoção média de 80% da DBO5. / Wastewater treatment systems continuously receiving shock loads and the behavior of contaminants under unsteady state conditions are not very well documented in our country, with limited degree of knowledge in the world on the removal of specific pollutants like endocrine disrupting chemicals (EDC) in physical chemical and biological wastewater treatment systems. The present work brings a case study regarding an industry which wastewaters were generated from plants with multiproducts and campaign production with variable composition, and with nonylphenols as one of their raw materials which is known as an endocrine disrupting chemical. The organic load and toxicity removal mechanisms of the wastewater to the biological treatment were studied in bench scale whilst their treatability was evaluated through coagulation, flocculation, dissolved air flotation followed by activated sludge, in pilot scale. The feasibility of the addition of powdered activated carbon to the biological system was also studied. The large qualitative and quantitative variability of the wastewater requires an equalization time of at least 30 hours. The main responsible for this variability in quality is the chemical unit process which wastewaters are originated from reactors and tanks cleanings. Although the low efficiency in COD removal obtained with coagulation, flocculation and dissolved air flotation (20 to 30%), it was found that this process is essential to the toxicity reduction for the biological process. Optimum pH and coagulant dose vary with the wastewater characteristics, and must be determined on a daily basis. On the biological system, it was observed important raw wastewater COD elimination not only through biodegradation, but also through volatilization and adsorption. Bench tests revealed COD elimination of 47 to 77% by air stripping and 42% by adsorption onto the biological sludge. Despite of constant organic and toxic shock loads, it had been possible to reach the steady state during which the maximum variation on the volatile suspended solids concentration was 20 to 30%. During this period, sludge age was around 25 to 30 days, and the hydraulic detention time was 3,8 days. Average efficiency on COD removal in this period was 86%. Tests results with PAC dosage on the pilot plant showed satisfactory, proving the reduction of toxic compounds from the wastewater and resulting in biodegradability improvement. The increase of volatile suspended solids in the aeration tank was from 1380 mg/L to 3820 mg/L, and reduction in the range of variation of remaining treated water COD from 600 to 3200 mgO2/L (system without CAP) down to 300 to 600 mgO2/L (system with CAP). The improvement on the sludge sedimentation with PAC addition was also remarkable. One can also conclude the treatment system attained the current legislation of the State of São Paulo, with 80% BOD5 removal.

No description available.

Le p-tert-octylphénol est un produit présent dans l’environnement et issu de la dégradation des alkylphénols éthoxylés. Ce composé a la capacité de se lier au récepteur œstrogénique et d’exercer ainsi un léger effet œstrogénique. Les objectifs de cette étude étaient de 1) développer une méthode d'identification de l'octylphénol dans le sang et les tissus à l'aide de la chromatographie en phase gazeuse jumelée à la spectrométrie de masse, 2) caractériser la toxicocinétique sanguine et tissulaire de l’octylphénol chez le rat Sprague-Dawley mâle et femelle et 3) développer un modèle toxicocinétique à base physiologique permettant de décrire la cinétique sanguine et tissulaire de l’octylphénol inchangé. Pour ce faire, des rats mâle et femelle Sprague-Dawley ont reçu des doses uniques d’octylphénol par les voies intraveineuse, orale et sous-cutanée. Deux autres groupes ont reçu des doses répétées d'octylphénol par voie orale pour une durée de 35 jours consécutifs pour les femelles ou 60 jours pour les mâles. Les concentrations sanguines et tissulaires d’octylphénol ont été mesurées à différents moments après administration à partir d’une méthode d’analyse développée dans nos laboratoires dans le cadre de ce projet. Les expériences impliquant des administrations uniques ont montré que les concentrations sanguines et tissulaires d'octylphénol étaient en général plus élevées chez les femelles que chez les mâles. Des expériences réalisées avec des microsomes hépatiques ont confirmé que ces différences étaient vraisemblablement reliées au métabolisme de l'octylphénol. Les expériences impliquant des administrations répétées ont montré qu'il n'y avait pas d'accumulation d'octylphénol dans l'organisme aux doses étudiées. Les résultats obtenus expérimentalement ont servi à développer et valider un modèle toxicocinétique à base physiologique. Ce modèle a permis de simuler adéquatement les concentrations sanguines et tissulaires d'octylphénol suite à des expositions intraveineuses, orales et sous-cutanées. En conclusion, cette étude a fourni des données essentielles sur la toxicocinétique de l'octylphénol. Ces données sont nécessaires pour établir la relation entre la dose externe et la dose interne et vont contribuer à une meilleure évaluation des risques liés à l'octylphénol. / p-tert-Octylphenol is a degradation product of alkylphenol ethoxylates that can be found in the environment. It has been reported to act as a weak estrogenic compound by binding to the estrogen receptor. This study was undertaken to 1) develop a sensitive method for the determination of octylphenol in blood and various tissues using gas chromatography coupled with detection by mass spectrometry, 2) characterize the blood and tissues toxicokinetics of octylphenol in male and female Sprague-Dawley rats and 3) develop a physiologically-based toxicokinetic model for octylphenol that can describe/predict unchanged blood and tissues octylphenol concentrations in rats. Male and female Sprague-Dawley rats were given a single dose of octylphenol either by oral gavage, intravenous injection or subcutaneous injection. In a repeated dosing experiment, rats were given octylphenol (oral) daily for 35 days (female) or 60 days (male). Blood and tissue samples were collected at various time following the onset of exposure and analyzed for octylphenol content using a method developed in our laboratory. These results showed that blood and tissues octylphenol concentrations were generally higher in female than male rats. Experiments done with rat liver microsomes confirmed that these differences were related to octylphenol metabolism. The results of the repeated exposure study indicate that there is no bioaccumulation of octylphenol at these exposure levels. A physiologically-based pharmacokinetic model for octylphenol was developed and validated using the data obtained in female and male rats. The model simulates adequately blood and tissues octylphenol concentrations following oral, intravenous or subcutaneous exposure. In conclusion, this study provided essential data on the toxicokinetics of octylphenol. These data are essential to predict the relationship between the internal and the external dose of octylphenol and will facilitate the risk assessment of octylphenol in humans.

O tratamento de águas residuárias industriais, submetido constantemente a cargas de choque, é pouco estudado no Brasil, sendo limitado o grau de conhecimento que se tem no mundo sobre os mecanismos de remoção de disruptores endócrinos nos sistemas de tratamento físico-químicos e biológicos. O presente trabalho traz um estudo de caso, envolvendo uma indústria com uma composição de produtos muito diversificada, com despejos líquidos de unidades isoladas de qualidades diversas e que tem como uma das principais matérias-primas, nonil fenóis, conhecidos disruptores endócrinos. Os mecanismos de remoção de carga orgânica e a avaliação da toxicidade da água residuária ao processo biológico de tratamento foram estudados em escala de laboratório, enquanto que a sua tratabilidade por coagulação, floculação, flotação com ar dissolvido seguido de sistema de lodos ativados, em escala piloto. Avaliou-se, também, a aplicabilidade do tratamento biológico com carvão ativado em pó. A grande variação qualitativa e quantitativa da água residuária bruta requer uma unidade de equalização com tempo de detenção de pelo menos 30 horas. O maior responsável por esta variação de qualidade é o processo da unidade química, cujo efluente é proveniente de lavagens de tanques e reatores. Apesar da reduzida eficiência de remoção de DQO obtida com a coagulação, floculação e flotação com ar dissolvido (20 a 30%), constatou-se que este tratamento é essencial para a redução da toxicidade ao processo biológico. A dosagem de coagulante e o pH ótimos variam conforme a característica do despejo e devem ser determinadas diariamente. No sistema biológico, observou-se uma remoção significativa da DQO do efluente bruto gerado na indústria, não apenas por biodegradação, mas também por volatilização e adsorção. Os testes de bancada evidenciaram remoções de DQO por arraste com ar de 47 a 77 % e por adsorção no lodo biológico, de 42%. Apesar dos constantes choques de carga orgânica e de poluentes tóxicos, conseguiu-se atingir o estado estacionário com variações máximas da concentração de sólidos em suspensão voláteis no tanque de aeração entre 20 e 30%. Neste período, a idade do lodo situou-se em torno de 25 a 30 dias e o tempo de detenção hidráulico foi de 3,8 dias. A eficiência média de remoção de DQO neste período foi de 86%. Os testes com a unidade piloto demonstraram que a utilização de carvão ativado em pó (CAP) produz resultados satisfatórios, comprovando a redução de poluentes tóxicos da água residuária e refletindo em uma significativa melhora na biodegradabilidade do efluente, com aumento da concentração de sólidos em suspensão voláteis no tanque de aeração (de 1380 mg/L para 3820 mg/L) e redução da amplitude de variação da DQO do efluente tratado que passou de 600 a 3200 mgO2/L para o sistema sem CAP para 300 a 600 mgO2/L para o sistema com CAP. Notou-se, também, com a adição de CAP, melhoria na sedimentação do lodo. Pode-se concluir também que o sistema de tratamento atendeu a legislação atual do Estado de São Paulo, com uma remoção média de 80% da DBO5. / Wastewater treatment systems continuously receiving shock loads and the behavior of contaminants under unsteady state conditions are not very well documented in our country, with limited degree of knowledge in the world on the removal of specific pollutants like endocrine disrupting chemicals (EDC) in physical chemical and biological wastewater treatment systems. The present work brings a case study regarding an industry which wastewaters were generated from plants with multiproducts and campaign production with variable composition, and with nonylphenols as one of their raw materials which is known as an endocrine disrupting chemical. The organic load and toxicity removal mechanisms of the wastewater to the biological treatment were studied in bench scale whilst their treatability was evaluated through coagulation, flocculation, dissolved air flotation followed by activated sludge, in pilot scale. The feasibility of the addition of powdered activated carbon to the biological system was also studied. The large qualitative and quantitative variability of the wastewater requires an equalization time of at least 30 hours. The main responsible for this variability in quality is the chemical unit process which wastewaters are originated from reactors and tanks cleanings. Although the low efficiency in COD removal obtained with coagulation, flocculation and dissolved air flotation (20 to 30%), it was found that this process is essential to the toxicity reduction for the biological process. Optimum pH and coagulant dose vary with the wastewater characteristics, and must be determined on a daily basis. On the biological system, it was observed important raw wastewater COD elimination not only through biodegradation, but also through volatilization and adsorption. Bench tests revealed COD elimination of 47 to 77% by air stripping and 42% by adsorption onto the biological sludge. Despite of constant organic and toxic shock loads, it had been possible to reach the steady state during which the maximum variation on the volatile suspended solids concentration was 20 to 30%. During this period, sludge age was around 25 to 30 days, and the hydraulic detention time was 3,8 days. Average efficiency on COD removal in this period was 86%. Tests results with PAC dosage on the pilot plant showed satisfactory, proving the reduction of toxic compounds from the wastewater and resulting in biodegradability improvement. The increase of volatile suspended solids in the aeration tank was from 1380 mg/L to 3820 mg/L, and reduction in the range of variation of remaining treated water COD from 600 to 3200 mgO2/L (system without CAP) down to 300 to 600 mgO2/L (system with CAP). The improvement on the sludge sedimentation with PAC addition was also remarkable. One can also conclude the treatment system attained the current legislation of the State of São Paulo, with 80% BOD5 removal.

Orientador: Ruben Bresaola Junior / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo / Made available in DSpace on 2018-08-11T06:31:37Z (GMT). No. of bitstreams: 1 Fernandes_Roberto_M.pdf: 1490135 bytes, checksum: 28ec6cd0c6b627114af37a1ee1c25693 (MD5) Previous issue date: 2007 / Resumo: O 17'alfa'-Etinilestradiol é um princípio-ativo sintético presente na formulação dos contraceptivos utilizados por parcela expressiva da população feminina. Por ser um composto persistente, o 17'alfa'-Etinilestradiol não absorvido pelo organismo da mulher, fração que pode chegar a 80%, é eliminado pela usuária, principalmente pela urina. Na rede de esgotos, mesmo sobre a existência de tratamento, este não é removido completamente, alcançando, posteriormente, mananciais que podem ser utilizados para abastecimento público. Nesse sentido, o presente trabalho teve por objetivo estudar as eficiências de remoção do 17'alfa'-Etinilestradiol de águas para abastecimento, quando empregadas as tecnologias: pré-oxidação com Hipoclorito de Sódio ou Dióxido de Cloro, adsorção em carvão ativado em pó (CAP) e tratamento físico-químico composto de coagulação, floculação, sedimentação e filtração rápida. A metodologia empregada para as determinações do estrogênio foi a cromatografia líquida de alta eficiência (CLAE), aplicada após processo de extração em fase sólida (EFS) do analito presente na água. O cromatógrafo HPLC utilizado, possuía coluna cromatográfica modelo C18, de fase reversa e detector de arranjo de diodos com UV. O trabalho mostrou que o Hipoclorito de Sódio foi mais efetivo que o Dióxido de Cloro, na oxidação do 17'alfa'- Etinilestradiol. Sua maior ação foi observada sob dosagens de 5 e 10 mg/L e tempos de oxidação entre 3 e 5 horas. Esta combinação de parâmetros experimentais impactou na redução da concentração do estrogênio na água, em níveis superiores a 97,5%. Este nível de remoção também foi observado, quando aplicado carvão ativado em pó, sob dosagens a partir de 50 mg/L e tempo de contato de 60 minutos. O tratamento físico-químico apresentou melhores resultados quando aumentada a dosagem de carvão para 5 mg/L. Os resultados alcançados constituem-se de fundamental importância na formação de base para futuras soluções dedicadas ao problema, dada a escassez de estudos de remoção de fármacos contaminantes da água / Abstract: The 17'alfa'-Etinilestradiol is a synthetic active pharmaceutical ingredient presents in the formulation of contraceptives used by a large amount of the female population. As a bioaccumulative molecule, the 17'alfa'-Etinilestradiol is not completely absorbed by woman organism; up to 80% can be eliminated by user, mainly by urine. Even after sewage treatment, the residual of 17'alfa'-Etinilestradiol it is not totally removed reaching, later, water sources that can be used for public supplying. In this direction, the present work has for objective the study of 17'alfa'-Etinilestradiol removal efficiency in waters supplies, using different technologies such as: pre-oxidizing with Sodium Hypochlorite or Chlorine Dioxide, adsorption in powder activated carbon (CAP) and physic-chemical treatment composed by coagulation, flocculation, sedimentation and fast filtration. The methodology used for the estrogen determination was the High Performance Liquid Chromatography (HPLC), applied after solid phase extraction process (SFE) of the hormone present in water. The HPLC equipment used was composed by a model C18 chromatographic column with reverse phase, and diodes arrangement detector, with UV. The work showed that the Sodium Hypochlorite was more effective than the Chlorine Dioxide, to the 17'alfa'-Etinilestradiol oxidizing. Its higher action was observed when applying 5 and 10 mg/L of oxidants in a time of reaction between 3 and 5 hours. This interaction between concentration of oxidant and time of reaction provided estrogen concentration reduction in water, in levels upper to 97.5%. This same removal level also was observed when applied powder activated carbon, mainly when 50 mg/L in a contact time of 60 minutes was performed. The physic-chemical treatment presented better results when 5 mg/L of activated carbon was applied. The present results consist of fundamental importance in the base formation for future solutions dedicated to the problem, due to lack of studies present now a days in pharmaceutical products removal from water / Mestrado / Saneamento e Ambiente / Mestre em Engenharia Civil

Contexte : Les parabènes sont des substances antibactériennes et antifongiques utilisées comme conservateurs dans de nombreux produits d’usage courant (cosmétiques, soins personnels, pharmaceutiques et alimentaires). Des études in vitro et in vivo ont signalé les effets de perturbation endocrinienne des parabènes, soulevant des inquiétudes quant à leurs risques potentiels pour la santé humaine. Objectif : Évaluer l’association entre les concentrations urinaires de parabènes et les concentrations sériques d’hormones de la reproduction (estradiol, progestérone, hormone folliculostimulante et hormone lutéinisante) chez les jeunes filles de la population générale canadienne. Méthodes: Les données de l'Enquête canadienne sur les mesures de la santé (2014 – 2015) concernant les filles âgées entre 6 et 17 ans ont été utilisées pour cette étude. L’association entre les concentrations urinaires de parabènes et des hormones a été analysée par régression linéaire multivariée, en ajustant pour les covariables suivantes : âge, indice de masse corporelle, ethnicité, revenu, et saison lors de la collecte des échantillons urinaires et sanguins. Résultats : Les 382 participantes incluses dans cette étude étaient majoritairement blanches (76%), avaient un indice de masse corporelle normal (73%) et des niveaux détectables d’au moins un parabène (92 %). Des concentrations de parabènes plus élevées étaient associées à des concentrations d'hormones de la reproduction significativement inférieures pour l’estradiol, et les hormones folliculostimulante et lutéinisante; il n’y avait pas d’association pour la progestérone. Un doublement des concentrations des parabènes urinaires était associé à des concentrations inférieures d'estradiol de 5,8% (IC à 95% -9,3; -2,1), d’hormone folliculostimulante inférieure de 4,2% (IC à 95% -7,9; -0,3) et d’hormone lutéinisante inférieure de 10,8% (IC à 95% -17,4; -3,7). Discussion : Cette étude montre que l'exposition aux parabènes était associée à des concentrations circulantes plus faibles d'hormones de la reproduction chez des jeunes filles de la population générale. Le devis transversal ne permet pas de réaliser d’inférences causales. Néanmoins, ces résultats concordent avec les études animales et suggèrent que l’exposition aux parabènes pendant le développement puisse altérer le fonctionnement du système reproducteur. Des études longitudinales permettraient de confirmer, ou non, ces résultats. / Background: Parabens are chemical substances used as preservatives for their antibacterial and antifungal properties in many everyday products (personal care, cosmetics, pharmaceutical and food). Several in vitro and in vivo studies have shown their endocrine disrupting potential, raising some concerns for potential adverse human health effects. Objective: To assess the cross-sectional association between urinary concentration of parabens and serum reproductive hormones (estradiol, progesterone, follicle stimulating hormone and luteinizing hormone) in girls in the general Canadian population. Methods: Data from the Canadian Health Measures Survey (2014 – 2015) on girls aged 6-17 were used for this study. Associations between hormones and parabens were analyzed with multivariable linear regressions, adjusting for potential confounders (i.e., age, body mass index, ethnicity, household income, and sampling season). Results: The girls and teens included in the study (n=382) were mostly white (76%), had a normal body mass index (73%), and detectable levels of at least one paraben (92%). We observed significantly lower concentrations of reproductive hormones with higher paraben concentrations; there was no association with progesterone concentrations. A doubling in urinary parabens was associated with lower estradiol by 5.8% (95% CI -9.3, -2.1), lower FSH by 4.2% (95% CI -7.9, -0.3), and lower LH by 10.8% (95% CI -17.4, -3.7). Discussion: This study shows that exposure to parabens is associated with lower circulating levels of reproductive hormones in young girls in the general population. The cross-sectional design does not allow to make causal inferences. However, these results are consistent with animal studies and suggest that exposure to parabens during development may affect the functioning of the reproductive system. Future studies should employ a longitudinal design verify these results.