Actuellement, les systèmes d’épuration des eaux n’ont pas été conçus pour éliminer les substances médicamenteuses notamment les hormones (estrogènes). Ces molécules sont ainsi déversées dans le milieu naturel et contaminent les rivières. Le 17 α-éthinylestradiol a été choisie comme molécule modèle pour illustrer la présence d’un perturbateur endocrinien dans une eau résiduaire. Cette molécule présente un réel risque pour la faune et la flore (Féminisation des poissons mâles, diminution de la reproduction…). L’objectif de ce travail est d’évaluer l’efficacité de la photocatalyse et de l’ozonation pour éliminer l’Ethinylestradiol dans les eaux. Le procédé d’oxydation utilisant l’ozone a été appliqué dans un premier temps sur des solutions concentrées d’éthinylestradiol (EE2 = 10 mg/L) préparées dans une eau ultrapure tamponnée afin de mieux comprendre les mécanismes d’élimination de ce composé et d’évaluer l’efficacité en terme de taux de conversion de EE2 et de la minéralisation du substrat. Les expériences réalisées ont permis de montrer que l’ozone est un oxydant très efficace pour oxyder l’éthinylestradiol. L’oxydation se fait essentiellement par réaction directe de l’ozone sur la molécule d’EE2 alors que sa minéralisation nécessite la conversion de l’ozone en radicaux hydroxyles qui vont ensuite réagir sur la structure saturée de la molécule organique. L’étude de l’ozonation de solutions EE2 à différentes concentrations a permis d’établir une relation entre la concentration initiale en polluant dans l’eau et la dose d’ozone à introduire pour éliminer ce composé à un pH proche de la neutralité. Cette relation a été utilisée pour estimer la dose d’ozone à appliquer pour une eau contaminée par EE2 à une concentration proche de celle rencontrée dans les eaux résiduaires et comparée à celle obtenue sur une eau provenant de la station d’épuration du Bourget du Lac. L’efficacité du procédé photocatalytique a été évaluée en travaillant sur les vitesses de disparition et de minéralisation de EE2 en présence de TiO2 «Degussa P25» et TiO2 PC500. Les cinétiques d’adsorption et de dégradation photocatalytiques ont été évaluées dans une gamme de concentration allant de 1 à 10 mg/L en travaillant à différentes masses de photocatalyseur. Les constantes d’adsorption et de vitesse, modélisés avec les modèles de Langmuir et Langmuir-Hinshelwood respectivement révèlent, (1) des propriétés d’adsorption et de photocatalyse plus importante pour le photocatalyseur TiO2 «Degussa P25», (2) des constantes d’adsorption différentes en présence ou en absence d’irradiation et aucune proportionnalité entre quantité de EE2 adsorbée et concentration en photocatalyseur. Cette absence de corrélation est expliquée en considérant la taille des particules. La formation d’agrégats de plus en plus important est observée en augmentant la masse de TiO2. La minéralisation de EE2 est totale après moins d’une heure d’irradiation en travaillant avec une puissance lumineuse de 5,5 mW/cm2 et 10 mg/L de EE2 indiquant l’efficacité de ce procédé. / Currently, systems for water treatment have not been designed to eliminate drug substances such as hormones (estrogen). These molecules are thus discharged into the environment and contaminate rivers. The 17 α-ethinylestradiol has been chosen as model molecule to illustrate the presence of an endocrine disrupter in water waste. This molecule presents a real risk to wildlife (feminization of male fish, reduced reproduction ...). The objective of this work is to evaluate the effectiveness of photocatalysis and ozonation to remove Ethinylestradiol waters. The oxidation process using ozone was applied initially in concentrated solutions of ethinylestradiol (EE2 = 10 mg / L) prepared in ultrapure water buffered to better understand the mechanisms of elimination of this compound and evaluate the effectiveness in terms of conversion rate of EE2 and mineralization of the substrate. Experiments have shown that ozone is a very effective oxidant for oxidation of ethinylestradiol. Oxidation occurs mainly by direct reaction of ozone on the molecule while EE2 mineralization involves the conversion of ozone into hydroxyl radicals which will then react on the structure of the saturated organic molecule. The study of ozonation of EE2 solutions at different concentrations has established a relationship between the initial concentration of pollutant in the water and the dose of ozone introduced to eliminate this compound at a pH near neutrality. This relationship was used to estimate the dose of ozone applied to water contaminated with EE2 at a concentration close to that found in wastewater and compared to that obtained water from the treatment plant Bourget du Lac. In the second part of our work, we studied the advanced oxidation process "Photocatalysis". The adsorption and photodegradation of EE2 were performed on the surface of TiO2 Degussa P25 "and under UV radiation (λ = 365 nm). The results were modeled using the model of Langmuir and Langmuir Hinshelwood respectively. These models allowed us to determine for different masses of TiO2 quantities of EE2 adsorbed on the surface of TiO2 and the constants of adsorption in the dark under UV light, and the rate constants. These values were compared to those obtained under the same conditions but on a different type of catalyst TiO2 PC500. The measurement of particle size of TiO2 shows the formation of agglomerates increasingly important function of the mass of catalyst TiO2 PC500 and it allowed us to explain the values of the constants of adsorption and kinetic results

Desreguladores endócrinos são compostos que podem alterar o sistema endócrino dos indivíduos, bem como sua fertilidade e por em risco a saúde dos mesmos. Muitas questões relacionadas a esses compostos ainda não foram elucidadas, apesar de serem muito estudados recentemente. Diversas pesquisas têm sido feitas investigando-se o emprego de processos oxidativos avançados na degradação dos desreguladores endócrinos em águas naturais e residuárias. O presente trabalho teve como objetivo estudar a remoção do hormônio 17\'beta\'-estradiol em soluções aquosas por oxidação química. A pesquisa foi dividida em duas etapas, sendo que a primeira etapa consistiu na investigação do uso de brometo de prata/dióxido de titânio (\'AG\'BR\'/\'TI\'O IND.2\') como catalisador no processo de fotocatálise com luz visível. Para isso, foram avaliadas a influência da concentração de \'AG\'BR\'/\'TI\'O IND.2\' (0,020; 0,025; 0,050; 0,070 e 0,100 g/L) e a intensidade de luz visível incidente (6,6 x \'10 POT.5\' e 1,3 x \'10 POT.6\' Ix) na eficiência de degradação do 17\'beta\'-estradiol. Na segunda etapa avaliou-se o emprego de ozônio na degradação de 17\'beta\'-estradiol em soluções aquosas, variando-se as dosagens de ozônio (1,7; 3,3, 5,0 e 7,5 mg \'0 IND.3\'/L) aplicadas e o pH (3; 5; 7; 9 e 11) das amostras. Na primeira etapa, os resultados demonstram que E2 foi bastante sensível aos processos oxidativos empregados. A fotocatálise foi eficiente para oxidar 17\'beta\'-estradiol, demandando tempo de exposição pequeno, em torno de 4 minutos para obtenção de remoção da ordem de 98%, quando aplicada concentração de \'AG\'BR\'/\'TI\'O IND.2\' de 0,100 g/L e a intensidade de luz visível incidente de 1,3 x \'10 POT.6\' Ix. Na segunda etapa, observou-se que o aumento do pH promoveu maior rapidez na degradação do E2 e o aumento da massa de ozônio aplicada promoveu maior eficiência de degradação do 17\'beta\'-estradiol. / Endocrine disrupting chemicals are compounds that can alter the endocrine system of individuals and their fertility and threaten their health. Many issues related to these compounds have not been elucidated, although much studied recently. Many researchers have investigated the use of advanced oxidative processes in the degradation of endocrine disrupting compounds in water and wastewater. This work is a study of the removal of 17\'beta\'-estradiol in aqueous solutions by chemical oxidation. This work was divided into two stages. In the first one, the use of bromide of silver/titanium dioxide (\'AG\'BR\'/\'TI\'O IND.2\') was investigated as catalyst in the photocatalysis activity under visible light irradiation. It was evaluated the influence of the concentration of \'AG\'BR\'/\'TI\'O IND.2\' (0.020; 0.025; 0.050; 0.070 and 0.100 g/L) and the incident light intensity (6.6 x \'10 POT.5\' and 1.3 x \'10 POT.6\' Ix) in the efficiency of degradation of 17\'beta\'-estradiol. In the second step, it was evaluated the use of ozone in the degradation of 17\'beta\'-estradiol in aqueous solutions, ranging up the masses of applied ozone (1.7; 3.3; 5.0 and 7.5 mg \'0 IND.3\'/L) and the pH (3, 5, 7, 9 and 11) of the samples. In the first stage, the results show that E2 was very sensitive to oxidative processes applyed. The photocatalysis was efficient to oxidize the 17\'beta\'-estradiol, requiring short exposure time, around 4 minutes, to obtain the removal of 98% (0.100 g/L of \'AG\'BR\'/\'TI\'O IND.2\' and incident visible light intensity of 1.3 x \'10 POT.6\'. In the second step, it was observed that the raise in pH promoted faster degradation of E2 and the increase of the mass of applied ozone promoted high efficiency of degradation of 17\'beta\'-estradiol.

Desreguladores endócrinos são compostos que podem alterar o sistema endócrino dos indivíduos, bem como sua fertilidade e por em risco a saúde dos mesmos. Muitas questões relacionadas a esses compostos ainda não foram elucidadas, apesar de serem muito estudados recentemente. Diversas pesquisas têm sido feitas investigando-se o emprego de processos oxidativos avançados na degradação dos desreguladores endócrinos em águas naturais e residuárias. O presente trabalho teve como objetivo estudar a remoção do hormônio 17\'beta\'-estradiol em soluções aquosas por oxidação química. A pesquisa foi dividida em duas etapas, sendo que a primeira etapa consistiu na investigação do uso de brometo de prata/dióxido de titânio (\'AG\'BR\'/\'TI\'O IND.2\') como catalisador no processo de fotocatálise com luz visível. Para isso, foram avaliadas a influência da concentração de \'AG\'BR\'/\'TI\'O IND.2\' (0,020; 0,025; 0,050; 0,070 e 0,100 g/L) e a intensidade de luz visível incidente (6,6 x \'10 POT.5\' e 1,3 x \'10 POT.6\' Ix) na eficiência de degradação do 17\'beta\'-estradiol. Na segunda etapa avaliou-se o emprego de ozônio na degradação de 17\'beta\'-estradiol em soluções aquosas, variando-se as dosagens de ozônio (1,7; 3,3, 5,0 e 7,5 mg \'0 IND.3\'/L) aplicadas e o pH (3; 5; 7; 9 e 11) das amostras. Na primeira etapa, os resultados demonstram que E2 foi bastante sensível aos processos oxidativos empregados. A fotocatálise foi eficiente para oxidar 17\'beta\'-estradiol, demandando tempo de exposição pequeno, em torno de 4 minutos para obtenção de remoção da ordem de 98%, quando aplicada concentração de \'AG\'BR\'/\'TI\'O IND.2\' de 0,100 g/L e a intensidade de luz visível incidente de 1,3 x \'10 POT.6\' Ix. Na segunda etapa, observou-se que o aumento do pH promoveu maior rapidez na degradação do E2 e o aumento da massa de ozônio aplicada promoveu maior eficiência de degradação do 17\'beta\'-estradiol. / Endocrine disrupting chemicals are compounds that can alter the endocrine system of individuals and their fertility and threaten their health. Many issues related to these compounds have not been elucidated, although much studied recently. Many researchers have investigated the use of advanced oxidative processes in the degradation of endocrine disrupting compounds in water and wastewater. This work is a study of the removal of 17\'beta\'-estradiol in aqueous solutions by chemical oxidation. This work was divided into two stages. In the first one, the use of bromide of silver/titanium dioxide (\'AG\'BR\'/\'TI\'O IND.2\') was investigated as catalyst in the photocatalysis activity under visible light irradiation. It was evaluated the influence of the concentration of \'AG\'BR\'/\'TI\'O IND.2\' (0.020; 0.025; 0.050; 0.070 and 0.100 g/L) and the incident light intensity (6.6 x \'10 POT.5\' and 1.3 x \'10 POT.6\' Ix) in the efficiency of degradation of 17\'beta\'-estradiol. In the second step, it was evaluated the use of ozone in the degradation of 17\'beta\'-estradiol in aqueous solutions, ranging up the masses of applied ozone (1.7; 3.3; 5.0 and 7.5 mg \'0 IND.3\'/L) and the pH (3, 5, 7, 9 and 11) of the samples. In the first stage, the results show that E2 was very sensitive to oxidative processes applyed. The photocatalysis was efficient to oxidize the 17\'beta\'-estradiol, requiring short exposure time, around 4 minutes, to obtain the removal of 98% (0.100 g/L of \'AG\'BR\'/\'TI\'O IND.2\' and incident visible light intensity of 1.3 x \'10 POT.6\'. In the second step, it was observed that the raise in pH promoted faster degradation of E2 and the increase of the mass of applied ozone promoted high efficiency of degradation of 17\'beta\'-estradiol.