Ce travail a permis d'acquérir de nouvelles connaissances sur la micropollution issue de l'activité domestique. Un état des lieux a été réalisé sur la présence de certains micropolluants dans les eaux usées (dans les phases liquide et solide) de deux zones urbaines, résidentielle et mixte (habitats, hôpital, administrations), et dans deux stations d'épuration (STEP) biologiques. Les micropolluants étudiés ont été choisis selon leurs usages et en fonction de leurs propriétés physico-chimiques afin de mieux appréhender leur répartition entre les phases liquides et solides. Dans un premier temps, les méthodes d'extraction et d'analyse des micropolluants dans les matrices liquides (eau usée et eau traitée) et solides (matières en suspension et boue) ont été développées et validées. Les prélèvements d'eaux usées dans les égouts des deux zones urbaines ont mis en évidence différents usages de certains composés en fonction de la zone urbaine et de la saison (été ou hiver). Les mesures des concentrations en micropolluants en entrée et en sortie de STEP dans les eaux et les boues ont permis d'évaluer leurs rendements d'élimination et ont révélé une différence d'efficacité entre les deux STEP biologiques. Une étude statistique a montré qu'il existe des corrélations entre les concentrations en micropolluants et en macropolluants (DCO, ammonium, et turbidité) en entrée et en sortie de chacune des STEP étudiées. L'effet des micropolluants sur l'activité bactérienne a été examiné en conditions de laboratoire par des tests de toxicité sur Escherichia coli et par des expériences sur la biomasse de STEP en réacteur batch / This work allowed to acquire new knowledge on micropollution issued from household activities. The occurrence of some micropollutants in urban wastewater (liquid and solid phases) of two urban areas, residential and mixed (houses, hospital, administrations), and in two biological wastewater treatment plants (WWTPs) was assessed. The studied micropollutants were chosen according to use and as function of their physical and chemical properties in order to consider their partitioning between liquid and solid phases. Firstly, the methods for the extraction and the analysis of micropollutants in liquid and solid matrices (wastewater and treated water, suspended matter and sludge) were developed and validated. Wastewater sampling in the sewers of the two urban catchments showed some differences of the use of certain compounds according to the catchment and to the season (summer or winter). Measurements of micropollutant concentrations at the inlet and outlet of the plants, on water and sludge, allowed to assess their removal yields and revealed a difference of efficiency of the two biological WWTPs. A statistical treatment showed that there are some correlations between concentrations of micro and macropollutants (COD, ammonium and turbidity) at the inlet and at the outlet of each studied WWTPs. The effect of the target micropollutants on bacterial activity was evaluated under laboratory conditions, by toxicity tests on Escherichia coli, and by experiments on biological sludge in batch reactors

O Rio Paraíba do Sul é um dos mais importantes mananciais da região sudeste, mas devido ao aumento da população e ao crescimento industrial da região, o rio vem sofrendo grandes alterações de natureza antropológica muito em parte devido a elevada carga de descarte de esgoto doméstico e industrial. Assim, é de se esperar, que o rio receba grande concentração de contaminantes tanto em matéria orgânica como também outros contaminantes, como os microcontaminantes. Dentre esses compostos se incluem os fármacos, produtos de higiene pessoal, pesticidas e os Desreguladores Endócrinos (DEs), que é uma classe de substância que vem sendo muito investigada atualmente devido aos efeitos causados em organismos expostos e que chegam ao ambiente principalmente através do descarte de efluente doméstico e industrial. Os DEs são substâncias exógenas, que podem afetar negativamente o funcionamento do sistema endócrino levando a alterações no crescimento, desenvolvimento e reprodução. Essas substâncias vêm sendo detectadas em todo o mundo em pequenas concentrações (?g e ng), mas mesmo assim possuem capacidade de interagir com organismos expostos e causar algum tipo de efeito. Neste trabalho foram analisadas amostras de água superficial, a 0,60 m e 1,20 m de profundidade, na cidade de Aparecida no Estado de São Paulo, em um ponto próximo a captação de água para abastecimento público, sendo este mesmo ponto a aproximadamente 50 m a jusante do descarte de esgoto do Santuário Nacional e de bairros próximos. As amostras foram analisadas pelo método de HPLC-UV que foi desenvolvido para análise dos DEs Bisfenol-A (BFA), ?-estradiol (E2), 17?-etinilestradiol (EE2) e Estrona (E1). O método foi validado e se mostrou adequado. Foram realizados estudos das variáveis precipitação pluviométrica, radiação ultravioleta (UV), pH, temperatura da água e número de visitantes presentes na cidade, em função da concentração dos DEs encontrados nas amostras. Os resultados mostraram a presença dos analitos de interesse em concentrações elevadas. O BFA foi efetivamente detectado em 16,7% das amostras em concentrações que variaram de 0,032 ± 0,009 a 0,088 ±0,06 ?g.L-1. O E2 foi efetivamente detectado em 39,2% das amostras com valores variando de 0,009 ± 0,002 a 0,40 ±0,08 ?g.L-1. O EE2 foi efetivamente detectado em 45,1% das amostras com valores variando de 0,07 ± 0,01 a 0,6 ±0,1 ?g.L-1 . O E1 foi efetivamente detectado em 90,2% das amostras com valores variando de 0,107 ± 0,08 a 0,91 ±0,07 ?g.L-1. A análise estatística dos resultados mostrou que somente parte das variáveis estudadas apresentou correlação. Foram estabelecidas correlações entre índice pluviométrico e BFA, temperatura e concentrações de E1 e EE2, pH e concentrações de BFA, E1 e EE2 e número de visitantes com EE2. As demais variáveis não apresentaram nenhuma correlação. / The Paraíba do Sul River is one of the most important water sources in the Brazilian Southeast, but due to increasing population and industrial growth in the region, the river has undergone great anthropological changes mostly due to high domestic sewage disposal and industrial charges. Thus, it is expected that the river receives large concentration of contaminants both in organic matter as well as other contaminants, such as microcontaminants. Among these compounds include pharmaceuticals, personal care products, pesticides and Endocrine Disruptors (EDs), which is a class of substances that has been widely currently investigated due to the effects in exposed organisms and reach the environment mainly through the disposal domestic and industrial effluent. The EDs are exogenous substances that can adversely affect the functioning of the endocrine system leading to changes in growth, development and reproduction. These substances have been detected worldwide in small concentrations (?g and ng), but yet have the capacity to interact with exposed organisms and cause some kind of effect. In the present study the river water samples were collected at surface, at 0.60 m and 1.20 m deep in the city of Aparecida in São Paulo, at a point close to abstraction of water for public supply, which is also located about 50 m downstream of the sewage disposal of the National Shrine and nearby neighborhoods. The samples were analyzed by HPLC-UV method developed for analysis of EDs Bisphenol A (BFA), ?-estradiol (E2), 17?-ethinylestradiol (EE2), and estrone (E1). The method was validated and proved adequate. Studies have been conducted considering as variables the rainfall, ultraviolet radiation (UV), pH, water temperature and number of visitors present in the city, depending on the concentration of EDs found in the samples. The results showed the presence of the analytes at high concentrations. The BFA was effectively detected in 16.7% of the samples at concentrations ranging from 0.032 ± 0.009 to 0.088 ± 0.06 ?g.L-1. E2 was effectively detected in 39.2% of the samples with values ranging from 0.009 ± 0.002 to 0.40 ± 0.08 ?g.L-1. The EE2 was effectively detected in 45.1% of the samples with values ranging from 0.07 ± 0.01 to 0.6 ± 0.1 ?g.L-1. The E1 was effectively detected in 90.2% of the samples with values ranging from 0.107 ± 0.08 to 0.91 ± 0.07 ?g.L-1. Statistical analysis of the results showed that only part of the variables correlated. Correlations have been established between rainfall and BFA, temperature and concentrations of E1 and EE2, pH and concentrations of BFA, E1 and EE2 and number of visitors with EE2. The other variables did not show any correlation.

O Rio Paraíba do Sul é um dos mais importantes mananciais da região sudeste, mas devido ao aumento da população e ao crescimento industrial da região, o rio vem sofrendo grandes alterações de natureza antropológica muito em parte devido a elevada carga de descarte de esgoto doméstico e industrial. Assim, é de se esperar, que o rio receba grande concentração de contaminantes tanto em matéria orgânica como também outros contaminantes, como os microcontaminantes. Dentre esses compostos se incluem os fármacos, produtos de higiene pessoal, pesticidas e os Desreguladores Endócrinos (DEs), que é uma classe de substância que vem sendo muito investigada atualmente devido aos efeitos causados em organismos expostos e que chegam ao ambiente principalmente através do descarte de efluente doméstico e industrial. Os DEs são substâncias exógenas, que podem afetar negativamente o funcionamento do sistema endócrino levando a alterações no crescimento, desenvolvimento e reprodução. Essas substâncias vêm sendo detectadas em todo o mundo em pequenas concentrações (?g e ng), mas mesmo assim possuem capacidade de interagir com organismos expostos e causar algum tipo de efeito. Neste trabalho foram analisadas amostras de água superficial, a 0,60 m e 1,20 m de profundidade, na cidade de Aparecida no Estado de São Paulo, em um ponto próximo a captação de água para abastecimento público, sendo este mesmo ponto a aproximadamente 50 m a jusante do descarte de esgoto do Santuário Nacional e de bairros próximos. As amostras foram analisadas pelo método de HPLC-UV que foi desenvolvido para análise dos DEs Bisfenol-A (BFA), ?-estradiol (E2), 17?-etinilestradiol (EE2) e Estrona (E1). O método foi validado e se mostrou adequado. Foram realizados estudos das variáveis precipitação pluviométrica, radiação ultravioleta (UV), pH, temperatura da água e número de visitantes presentes na cidade, em função da concentração dos DEs encontrados nas amostras. Os resultados mostraram a presença dos analitos de interesse em concentrações elevadas. O BFA foi efetivamente detectado em 16,7% das amostras em concentrações que variaram de 0,032 ± 0,009 a 0,088 ±0,06 ?g.L-1. O E2 foi efetivamente detectado em 39,2% das amostras com valores variando de 0,009 ± 0,002 a 0,40 ±0,08 ?g.L-1. O EE2 foi efetivamente detectado em 45,1% das amostras com valores variando de 0,07 ± 0,01 a 0,6 ±0,1 ?g.L-1 . O E1 foi efetivamente detectado em 90,2% das amostras com valores variando de 0,107 ± 0,08 a 0,91 ±0,07 ?g.L-1. A análise estatística dos resultados mostrou que somente parte das variáveis estudadas apresentou correlação. Foram estabelecidas correlações entre índice pluviométrico e BFA, temperatura e concentrações de E1 e EE2, pH e concentrações de BFA, E1 e EE2 e número de visitantes com EE2. As demais variáveis não apresentaram nenhuma correlação. / The Paraíba do Sul River is one of the most important water sources in the Brazilian Southeast, but due to increasing population and industrial growth in the region, the river has undergone great anthropological changes mostly due to high domestic sewage disposal and industrial charges. Thus, it is expected that the river receives large concentration of contaminants both in organic matter as well as other contaminants, such as microcontaminants. Among these compounds include pharmaceuticals, personal care products, pesticides and Endocrine Disruptors (EDs), which is a class of substances that has been widely currently investigated due to the effects in exposed organisms and reach the environment mainly through the disposal domestic and industrial effluent. The EDs are exogenous substances that can adversely affect the functioning of the endocrine system leading to changes in growth, development and reproduction. These substances have been detected worldwide in small concentrations (?g and ng), but yet have the capacity to interact with exposed organisms and cause some kind of effect. In the present study the river water samples were collected at surface, at 0.60 m and 1.20 m deep in the city of Aparecida in São Paulo, at a point close to abstraction of water for public supply, which is also located about 50 m downstream of the sewage disposal of the National Shrine and nearby neighborhoods. The samples were analyzed by HPLC-UV method developed for analysis of EDs Bisphenol A (BFA), ?-estradiol (E2), 17?-ethinylestradiol (EE2), and estrone (E1). The method was validated and proved adequate. Studies have been conducted considering as variables the rainfall, ultraviolet radiation (UV), pH, water temperature and number of visitors present in the city, depending on the concentration of EDs found in the samples. The results showed the presence of the analytes at high concentrations. The BFA was effectively detected in 16.7% of the samples at concentrations ranging from 0.032 ± 0.009 to 0.088 ± 0.06 ?g.L-1. E2 was effectively detected in 39.2% of the samples with values ranging from 0.009 ± 0.002 to 0.40 ± 0.08 ?g.L-1. The EE2 was effectively detected in 45.1% of the samples with values ranging from 0.07 ± 0.01 to 0.6 ± 0.1 ?g.L-1. The E1 was effectively detected in 90.2% of the samples with values ranging from 0.107 ± 0.08 to 0.91 ± 0.07 ?g.L-1. Statistical analysis of the results showed that only part of the variables correlated. Correlations have been established between rainfall and BFA, temperature and concentrations of E1 and EE2, pH and concentrations of BFA, E1 and EE2 and number of visitors with EE2. The other variables did not show any correlation.

La limitation des ressources énergétiques fossiles et les lourds impacts environnementaux pouvant résulter de leur exploitation, entraînent un regain d’intérêt pour la digestion anaérobie. Face aux enjeux énergétiques et sanitaires, la conduite d’un méthaniseur implique l’optimisation de la production de méthane, mais aussi d’assurer la qualité sanitaire du digestat du point de vue des micropolluants. C’est dans ce cadre que s’inscrit ce projet de thèse réalisé en partenariat avec la ferme expérimentale de la Bouzule. L’optimisation de la co-digestion de substrats a montré que l’ajout d’herbe ensilée durant 36 semaines, améliorait le rendement du procédé de 20%. Le suivi des micropolluants (métaux lourds et HAPs) contenus dans les herbes provenant des bordures de route a montré que la qualité du digestat ne serait pas affectée si elles sont incorporées au digesteur. L’étude en réacteur batch de l’impact des antibiotiques sur la production de méthane a montré que : à 8 mg/L et 16 mg/L de tétracycline on observe une baisse de 23% et 28% respectivement, à 14 mg/L de spiramycine on observe une baisse de 40%, et à 20 mg/L de tylosine on observe une baisse de 30%. En réacteur continu, les faibles concentrations de tétracycline (0,2 mg/L et 2 mg/L) amélioraient d’environ 5% de la production de méthane au bout de 7 jours. A 200 mg/L et 2000 mg/L de tétracycline, on atteint des baisses de 30% et 40%, et le système ne récupère pas au bout de 7 jours. Quant à la spiramycine, à 1,4 mg/L, 14 mg/L et 140 mg/L, les baisses ont été de 14%, 24% et 39% respectivement, et au bout de 7 jours, une baisse résiduelle est toujours observable. Par ailleurs, les digestats issus des tests avec les antibiotiques sont en accord avec la réglementation / The limitation of fossil energy resources and heavy environmental impacts arising from their operation, there is a renewed interest for anaerobic digestion. According to the energy, and health issues, the monitoring of an anaerobic digester involves the maximization of the methane production, but also to ensure a good quality of digestate from the perspective of micropollutants. It is within this framework that this project of thesis is realized in partnership with the experimental farm of “La Bouzule”. The optimization of the co-digestion of substrates, showed that the use of 36 weeks grass silage improved the process yield by 20%. The monitoring of heavy metals and PAHs content in the grasses from roadsides showed that these grasses – if used as co-substrate in the digester – will not affect the digestate quality. The study of the impact of antibiotics on methane production in batch reactor showed that: 8 mg/L and 16 mg/L of tetracycline led to 23% and 48% decrease respectively, 14 mg/L of spiramycin led to 40% decrease, and 20 mg/L tylosin to 30% decrease. The monitoring of the continuous reactor showed that low levels of tetracycline (0.2 mg/L and 2 mg/L) led to an improvement of about 5% of the methane production. At 200 mg/L and 2000 mg/L of tetracycline, reductions of 30% and 40% are achieved, and the system did not recover after 7 days. The addition of spiramycin to the continuous reactor at 1.4 mg/L, 14 mg/L and 140 mg/L resulted in decreases of 14%, 24% and 39% respectively. For the latter, after one week, a residual drop is still observable. Furthermore, the digestate resulting from the monitoring of the continuous reactor during the tests with antibiotics is in accordance with current regulations

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2015-10-23T12:13:09Z No. of bitstreams: 2 Dissertação - Eli José Miranda Ribeiro Júnior - 2015.pdf: 709119 bytes, checksum: baa5cef4451e6bd53886e3cc249f19df (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-10-23T12:15:43Z (GMT) No. of bitstreams: 2 Dissertação - Eli José Miranda Ribeiro Júnior - 2015.pdf: 709119 bytes, checksum: baa5cef4451e6bd53886e3cc249f19df (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-10-23T12:15:43Z (GMT). No. of bitstreams: 2 Dissertação - Eli José Miranda Ribeiro Júnior - 2015.pdf: 709119 bytes, checksum: baa5cef4451e6bd53886e3cc249f19df (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2015-01-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Laccase is a poliphenoloxidase enzyme that catalyzes the oxidation of phenolic compounds in the corresponding quinones. The current obtained in this redox process can be used for quantitative analysis. In this work, a carbon paste biosensor modified gluteraldehyde functionalized silica and an enzymatic extract of the “Pycnoporus sanguineus” fungi as a lacase source is proposed for phenol determination. The effect of carbon paste and electrolyte composition, pH from 3,0 to 8,0, start potential from 0,55 to 0,25mV, scan rate from 5 to 25 mV s-1 and potential pulse amplitude from 10 to 60mV on the differential pulse voltammetric response was investigated. A linear correlation of R² = 0,9946 was obtained for the phenol content (catechol) in the concentration range from 50 to 500nMol L-1, with a detection limit of 30nMol L-1. This biosensor was used for the determination of different kinds of phenolic compounds, presenting a better response for catechol. / A lacase é uma enzima poliphenoloxidase que catalisa a oxidação de compostos fenólicos nas correspondentes quinonas. A corrente obtida neste processo redox pode ser usada para a análise quantitativa da concentração dos fenóis na água. Neste trabalho, é proposto o uso de um biossensor modificado para a determinação de fenol. O biossensor de pasta de carbono com sílica funcionalizada foi modificado com glutaraldeído e um extrato enzimático de fungos “Pycnoporus sanguineus” como uma fonte de lacase. O efeito da pasta de carbono e da composição de electrólito, permite trabalhar com pH compreendido entre 3,0 - 8,0, e um potencial inicial entre 0,55 - 0,25mV. A velocidade de varrimento foi de 5 a 25mV s-1 e amplitude de pulso de 10 a 60mV, estudando-se na resposta voltamétrica de pulso diferencial .Uma correlação linear de R2 = 0,9946 foi obtida para o teor de fenol (catecol) na gama de concentrações de 50 a 500nMol L-1, com um limite de detecção de 30nMol L-1. Este biossensor foi utilizado para a determinação de diferentes tipos de compostos fenólicos, apresentando uma melhor resposta para o catecol.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / No Brasil, estudos de avaliaÃÃo de micropoluentes emergentes em matrizes ambientais como esgotos sanitÃrios e hospitalares, e corpos de Ãgua, ainda sÃo bastante incipientes, assim como a remoÃÃo desses compostos em EstaÃÃes de Tratamento de Esgotos (ETEs) de baixo custo como lagoas de estabilizaÃÃo, assim como em sistemas de lodos ativados e sistemas anaerÃbio-aerÃbio compactos. O presente trabalho teve como objetivo geral investigar a presenÃa de micropoluentes em matrizes ambientais como esgotos sanitÃrios e hospitalares, e Ãgua superficial, avaliar a remoÃÃo destes compostos em ETEs de baixo custo e aplicar o processo de oxidaÃÃo avanÃada (POA) UV/H2O2 como opÃÃo de pÃs-tratamento. Os principais micropoluentes emergentes estudados foram: 2,4,6-triclorofenol, pentaclorofenol, cafeÃna (CAF), dipirona (DIP), diclofenaco de sÃdio (DCF), bis (2-etil-hexil) ftalato (DEHP), estrona (E1), 17β-estradiol (E2), β-estradiol 17-acetato (EA2), 17α-etinilestradiol (EE2) e colesterol (COL). As amostras foram coletadas em ETEs localizadas em Fortaleza e em sua regiÃo metropolitana. Os corpos receptores investigados foram o Rio Maranguapinho e o Riacho Paupina. Para a prÃ-concentraÃÃo dos micropoluentes utilizou-se extraÃÃo em fase sÃlida (SPE) com cartuchos C-18 e extraÃÃo lÃquido-lÃquido (ELL). A SPE foi a tÃcnica mais eficiente na concentraÃÃo da maioria dos micropoluentes emergentes, e a ELL se mostrou a melhor tÃcnica para compostos organoclorados. Foram realizados estudos de otimizaÃÃo das condiÃÃes de detecÃÃo dos compostos pelo uso de tÃcnicas de cromatografia gasosa acoplada à espectrometria de massas (GC/MS). Foram identificados compostos farmacÃuticos e desreguladores endÃcrinos em todas as amostras de esgotos com as seguintes faixas de concentraÃÃes efluentes: CAF (3,0-15,8 μg/L), DIP (0,3 μg/L), DCF (1,9 μg/L), DEHP (0,01-8,5μg/L), E1 (0,04-1,7 μg/L), E2 (0,03-4,0 μg/L), EA2 (0,14-9,3 μg/L), EE2 (1,0 μg/L) e COL (0,01-6,2 μg/L). Nos dois corpos receptores estudados (Rio Maranguapinho e Riacho Paupina) foram identificados desreguladores endÃcrinos. Os tratamentos realizados pelas ETEs nÃo foram suficientes para remoÃÃo total de todos os micropoluentes estudados, no entanto, a eficiÃncia para a maioria dos compostos foi acima de 50%. Em se tratando da avaliaÃÃo em sistemas de lagoas de estabilizaÃÃo, o estudo revelou boas eficiÃncias de remoÃÃo em sistemas constituÃdos de lagoa anaerÃbia seguida de facultativa e de maturaÃÃo, sendo os menores valores de remoÃÃo alcanÃados quando uma Ãnica lagoa facultativa primÃria estava presente. A avaliaÃÃo do uso do POA por meio do planejamento fatorial multivariado revelou que as melhores condiÃÃes para remoÃÃo de micropoluentes emergentes foram pH Ãcido (pH 3), concentraÃÃo de perÃxido de hidrogÃnio acima de 400 mg/L e tempos de detenÃÃo hidrÃulica no reator acima de 50min. / In Brazil, studies evaluating emerging micropollutants in environmental matrices such as sewage and hospital wastewater, as well as surface waters, are still quite incipient as well as the removal of these compounds in low cost Wastewater Treatment Plants (WWTPs) such as stabilization ponds, as well as in activated sludge systems or anaerobic/aerobic compact systems. This work aimed to investigate the presence of micropollutants in environmental matrices such as sewage and hospital wastewaters, and in surface waters. Additionally, this study evaluated the removal of these compounds in low-cost WWTPs and studied the advanced oxidation process (AOP) â UV/H2O2 â as a post-treatment option. The main emerging micropollutants studied were: 2,4,6-trichlorophenol, pentachlorophenol, caffeine (CAF), dipyrone (DIP), sodium diclofenac (DCF), bis (2-ethylhexyl) phthalate (DEHP), estrone (E1), 17β-estradiol (E2), estradiol acetate (EA2), 17α-ethinyl estradiol (EE2) and cholesterol (CHO). The samples were collected from WWTPs located in Fortaleza and its metropolitan region. The receiving surface waters investigated were: Maranguapinho River and Paupina Creek. For the pre-concentration studies of micropollutants, solid phase extraction (SPE) with C-18 cartridges was used, as well as the liquid-liquid extraction (LLE) method. The SPE technique was the most efficient method in concentrating the majority of emerging micropollutants, and the LLE proved to be the best technique for organochlorine compounds. Optimization studies were performed to detect the ideal conditions to determine the compounds by using gas chromatography (GC) and gas chromatography-mass spectrometry (GC/MS) techniques. In all wastewater samples pharmaceuticals and endocrine disrupting compounds were identified, and the range of effluent concentrations were: CAF (3.0-15.8 μg/L), DIP (0.3 μg/L), DCF (1.9 μg/L), DEHP (0.01-8.5μg/L), E1 (0.04-1.7 μg/L), E2 (0.03-4.0 μg/L), EA2 (0.14-9.3 μg/L), EE2 (1.0 μg/L) and CHO (0.01-6.2 μg/L). Endocrine disrupting compounds were identified in the Maranguapinho River and Paupina Creek. The wastewater treatment in the WWTPs was not enough for the complete removal of all micropollutants studied; however, the efficiency level for most of compounds was above 50%. Regarding the evaluation in stabilization ponds systems, the study revealed good removal of micropollutants in systems composed of anaerobic pond followed by facultative and maturation ponds, in which the lowest efficiency levels were verified when a single facultative pond was present. The evaluation of the AOP as a post-treatment option by multivariate factorial design showed that the optimal conditions for the removal of emerging micropollutants were acidic pH (pH 3), hydrogen peroxide concentration above 400 mg/L and hydraulic retention times in the reactor above 50 minutes.

Les bassins de retenue des eaux pluviales constituent des éléments importants de gestion des rejets urbains de temps de pluie (RUTP). De nombreuses études montrent que, lorsqu’ils sont bien conçus, ils permettent de lutter contre les inondations et de décanter efficacement la pollution métallique et les hydrocarbures fortement fixés aux matières en suspension (MES). Le travail se propose d’étudier les performances de ce type de système afin d’en mesurer et d’en modéliser leur efficacité en termes d’abattement de micropolluants à une échelle évènementielle. Pour cela, il a été développé un suivi expérimental d’un bassin en service sec et étanche de grande taille localisé à l’exutoire d’un bassin versant drainé par un réseau d’assainissement séparatif pluvial faisant partie de l’Observatoire de Terrain en Hydrologie Urbaine (OTHU). Ainsi un total de 100 micropolluants (MP) a–t-il été suivi : 22 éléments traces métalliques (ETM), 16 hydrocarbures aromatiques polycycliques (HAP), 2 alkylphénols (AP), 5 alkylphénols éthoxylates (APEO), Bisphénol A, 9 polybromodiphényléthers (PBDE) et 45 pesticides. Dans les eaux, ils ont été analysés en phase dissoute et particulaire en entrée et en sortie. 67 % des MP recherchés ont été détectés au moins une fois en entrée ou en sortie. Les concentrations moyennes évènementielles à l’exutoire du bassin versant alimentant l’ouvrage sont comparables aux données de la littérature quand elles existent et montrent une grande variabilité. L’efficacité massique évènementielle (EME) de piégeage des MP a été évaluée selon différentes méthodes, prenant en compte les incertitudes totales. L’efficacité est avérée pour la majorité des ETM et HAP, sur un nombre limité de campagnes pour les PBDE et les APEO, très limité pour le 4-Tert-Octylphénol et le 4-Nonyphénol (1 sur 5). Les performances de l’ouvrage ont été mises en avant pour 7 pesticides (sur 15 détectés) mais des efficacités négatives témoignent d’un relargage possible des polluants. L’étude des sédiments accumulés dans le bassin depuis 6 ans montre qu’ils sont assez chargés tant en métaux, HAPs qu’en 4-Nonylphénol, BDE209 et Diuron. Enfin, nous avons expérimenté 3 niveaux de modèles afin d’identifier des pistes pertinentes pour la suite des travaux dans ce domaine. / Detention basins are at stake in urban stormwater discharges (USWD) management strategies. If well designed, they are not only used to mitigate stormwater flood impacts but also to trap metals and hydrocarbon compounds strongly bounded to total suspended solids (TSS). An experimental monitoring, in the framework the Field Observatory on Urban Hydrology (OTHU), was developed on a large dry detention basin located at the outlet of a catchment drained by a separate stormwater system. This basin presents a rather classical and current configuration.A sum of 100 substances was studied: 22 metals (ETM), 16 polycyclic aromatic hydrocarbons (PAH), 2 alkylphenols (AP), 5 ethoxylate alkylphenols (APEO), Bisphénol A, 9 polybromodiphenylethers (PBDE) and 45 pesticides. They were analyzed in both dissolved and particulate phases in water at the inlet and outlet of the device. 67% of MP studied was detected at least once at the inlet or outlet. Event mean concentrations were in the same range as literature data when available and showed an important variability.Event mass efficiency (EME) in trapping MP was assessed by different methods taking account for global uncertainties. Acceptable efficiency was found for most of ETM and PAH and in a lesser extent for PBDE and APEO on a limited number of campaign. The detention basin had only a positive impact on alkylphenols (4-Tert-Octylphenol and 4-Nonylphenol) for one campaign out 5. Negative values for 7 pesticides (among 15 detected) indicated possible pollutant release. Accumulated sediments study showed high MP concentrations in particular for metals, PAH, 4-Nonylphenol, BDE209 and Diuron. Lastly, different levels of models were tested to try to identify relevant ones for further work.

Les stations d’épuration constituent une voie majeure de dissémination des micropolluants minéraux et organiques dans l’environnement. De nombreux composés émergents ne sont pas totalement éliminés des eaux usées et sont transférés aux boues par sorption du fait de leurs propriétés physico-chimiques. Parmi ces composés, les résidus de médicaments doivent être suivis car ils peuvent avoir des effets indésirables sur les organismes une fois rejetés dans l’environnement. L’épandage des boues stabilisées sur les sols étant le procédé de valorisation le plus employé en France, le choix du traitement des boues en amont, permettant de réduire au maximum la dissémination des micropolluants constitue une question scientifique et technique fondamentale. Dans ce travail, le devenir de micropolluants métalliques (cadmium et cuivre) et de plusieurs médicaments (carbamazépine, ciprofloxacine, sulfaméthoxazole, acide salicylique, ibuprofène, paracétamol, diclofénac, kétoprofène, éconazole, aténolol et propranolol) a été étudié pour différents lots de boues urbaines (avec ou sans traitement par ozonation) et aussi de manière originale sur des boues provenant exclusivement du traitement d’effluents hospitaliers (station de SIPIBEL), au cours de leur traitement (épaississement puis stabilisation par compostage, chaulage ou digestion anaérobie). La méthodologie proposée a reposé sur la mise en relation : d’une part des coefficients de répartition de ces micropolluants entre les fractions soluble et particulaire (Kdsorption) dans la boue après chaque traitement de stabilisation ainsi que de leur potentiel de désorption (Kdésorption) avec d’autre part les propriétés des micropolluants et les caractéristiques des boues (composition biochimique et groupements fonctionnels). Cette mise en relation a abouti, grâce à une analyse statistique de type PLS à la proposition de modèles permettant de prédire les valeurs de Kdsorption et Kdésorption. Il a ainsi pu être démontré que le pH des boues ainsi que les groupements fonctionnels de type phosphorique dans la phase soluble et de type amine/hydroxyle dans la fraction particulaire des boues avaient une influence majeure sur le comportement de sorption des micropolluants organiques, de même que la masse molaire et la solubilité de ces derniers. D’autre part, ce travail a permis de montrer que l’ozonation des boues en amont des traitements de stabilisation s’est avérée efficace car elle a permis d’éliminer huit composés pharmaceutiques sur les onze étudiés. Pour tous les lots de boues, le sulfaméthoxazole a été biodégradé au cours de la digestion anaérobie. Les tests de désorption en batch effectués sur les boues après chaulage et digestion ont montré que les micropolluants dans les boues chaulées ont tendance à être plus facilement relargués qu’après digestion anaérobie. Enfin, l’étude de la disponibilité des micropolluants lors de l’épandage des différents lots de boues urbaines et hospitalières stabilisées sur des colonnes de sol à l’échelle du laboratoire a montré que l’ibuprofène, l’acide salicylique, le diclofénac et le paracétamol étaient les seuls composés détectés dans les phases lixiviées des sols amendés, ce qui traduit une faible mobilité des autres composés dans le sol. / Wastewater treatment plants represent the main transfer pathways for micropollutants to enter the environment. Emerging contaminants are not totally eliminated and are transferred to the sludge by sorption process due to their physico-chemical properties. Among them, pharmaceutical compounds are of a great concern because of their potential adverse effects to ecosystems. As sludge landspreading is the main process of valorization employed in France, the choice of the kind of sludge stabilization treatment able to reduce the amount of micropollutants is crucial. In this work, the fate of trace metallic elements (cadmium and copper) and pharmaceutical compounds (carbamazepine, ciprofloxacin, sulfamethoxazole, salicylic acid, ibuprofen, paracetamol, diclofenac, ketoprofen, econazole, atenolol and propranolol) has been investigated in sludge from different origins: urban (with and without ozone oxidation treatment) and hospital, during their treatment (thickening and stabilization by composting, liming or anaerobic digestion). The methodology developed in this work consisted in connecting the partition coefficients of micropollutants (between the soluble and particulate fractions of sludge, Kdsorption) and their desorption potential (Kdesorption) with micropollutants physico-chemical properties and sludge characteristics (biochemical composition and functional groups). Statistical analysis leads to the determination of models able to predict Kdsorption and Kdesorption. Molecular weight and solubility of pharmaceutical compounds, sludge’s pH, phosphoric functional groups in the soluble phase and amine/hydroxyl groups in the particulate fraction of sludge had the main impact on the sorption behavior. Moreover the oxidation of sludge with ozone before stabilization was efficient to eliminate eight from eleven organic compounds. For all sludge samples, sulfamethoxazole was biodegraded during anaerobic digestion. Batch desorption tests showed that micropollutants were more easily desorbed in limed sludge compared to digested sludge. Finally, the study of micropollutants availability during stabilized urban and hospital sludge landspreading on laboratory soil columns revealed that ibuprofen, salicylic acid, diclofenac and paracetamol were the only compounds present in leachates. This means that the other pharmaceutical compounds exhibited a lower mobility in soil.

Dans le cadre des objectifs définis par la Directive Cadre sur l’Eau, ce travail de thèse porte sur la quantification du transfert de micropolluants organiques à la confluence entre la Fensch et la Moselle. Une nouvelle méthodologie a été développée pour déterminer les niveaux d’anthropisation dans les matrices environnementales. Basée sur la quantification exhaustive des marqueurs moléculaires, cette approche permet de comparer les apports naturels et anthropiques et de différencier les apports anthropiques selon leurs origines (combustion, pétrogénétique, eaux usées). Elle est parfaitement appropriée à l’étude de la matière organique des différentes matrices environnementales fournissant des informations beaucoup plus complètes que le dosage de quelques molécules cibles. Appliquée aux sédiments du système Fensch-Moselle, cette approche a permis d’analyser l’évolution des contributions organiques le long de la Fensch ainsi que leur transfert à la confluence avec la Moselle, tout en déterminant les sources principales de contamination. Ce travail souligne l’importance de l’hydrodynamisme sur la sédimentation et la biodégradation des micropolluants organiques. L’étude de ce système a également été l’occasion de développer deux outils utiles pour répondre à des questionnements environnementaux majeurs. Le premier, basé sur la déconvolution de l’unresolved complex mixture, permet de quantifier la masse de produits pétroliers accumulés dans des sédiments. Le second se base sur l’étude de la répartition des micropolluants organiques en phase aqueuse (dissous, colloïdale, particulaire) lors de la mobilisation de sédiments contaminés, permettant d’évaluer leur biodisponibilité / According to the objectives of the Water Framework Directive, this study deals with the quantification of the transfer of organic micropollutants at the confluence between Fensch and Moselle Rivers. A new methodology has been developed in order to quantify the anthropogenic pressure in environmental matrices. Based on the exhaustive quantification of molecular markers, this approach allows the comparison between natural and anthropogenic inputs and the differentiation between anthropogenic sources (pyrogenic, petrogenic, sewage waters). It is fully appropriate in order to study organic matter in different environmental matrices providing much more information than the quantification of few target compounds. In sediments of the system Fensch-Moselle, this approach has been applied in order to study the evolution of the anthropogenic pressure due to organic micropollutants along the Fensch River, their transfer at the confluence with the Moselle River and the major sources of contamination. This work highlights the relationship between hydrodynamism and settling and biodegradation of organic micropollutants. Together with the mutimolecular approach, two methodologies have been developed in order to answer to major environmental questionings. The first one, based on the deconvolution of unresolved complex mixture, allows quantifying the amount of petroleum by-products stored in sediments. The second one is based on the analysis of organic micropollutants in aqueous phases (dissolved, colloidal, particulate) during mobilization of contaminated sediments, which allows the evaluation of their bioavailability

En Lorraine, environ 7000 ha d’étangs sont exploités pour la production piscicole. Le présent travail a été consacré à la compréhension des mécanismes de transfert des micropolluants dans les étangs en mettant l'accent sur trois questions : (1) évaluer l'ampleur de la contamination métallique des étangs (n=45) ; (2) évaluer l'influence des étangs (n=3) sur les concentrations, le risque de toxicité et les flux de pesticides; (3) évaluer l'importance relative des voies de transfert des PCB vers le poisson. (1) Les enrichissements calculés soulignent des contaminations généralement faibles à modérés à l’exception des étangs localisés dans la Vôge et de deux étangs localisés dans la Woëvre. Cet enrichissement est plus prononcé pour le Cd et semble être lié à la richesse du sédiment en matière organique et carbonates (perte au feu). (2) Dans les cours d’eau de tête de bassin versant sur lesquels s’inscrivent ces trois étangs de barrage, les concentrations les plus élevées étaient généralement réduites de plus de 90% entre l'amont et l'aval de l'étang. Le risque de toxicité, évalué par la méthode de l'unité toxique, était atténué en aval des étangs. Lorsqu’on considère les flux de pesticides, les résultats obtenus suggèrent que, selon les substances considérées, les charges en pesticides sont réduites de 10 à 100% entre l'amont et l'aval de l'étang. (3) Les résultats montrent que le sédiment contaminé n’a pas d’impact sur la biodisponibilité orale des trois congénères de PCB chez la carpe commune. L’effet géosorbant du sédiment, qui explique son rôle de réservoir environnemental de PCB, paraît insuffisant dans les conditions du tractus digestif de la carpe commune, pour éviter un transfert vers le poisson / In the Lorraine Region, about 7,000 ha of ponds are exploited for fish production. The present work was dedicated to the understanding of micropollutants transfer mechanisms in freshwater fishponds focusing on three issues: (1) evaluate the extent of fishpond (n=45) exposure to trace metals (2) evaluate the influence of fishponds (n=3) on concentrations, potential toxicity and mass flows of pesticides; (3) evaluate the relative importance of transfer pathways of PCBs to fish. (1) The enrichments measured were generally low to moderate with the exception of the sites located in the Vôge and two sites located in the Woëvre. Enrichment was particularly high for Cd and seemed related to the loss of ignition. No relationship between enrichment and land use could however be observed. (2) High pesticide concentrations were generally reduced by more than 90% between upstream and downstream location. The risk of toxicity, evaluated under the toxic unit approach was attenuated downstream of the ponds. When considering the flow of pesticides, the results suggest that, depending on the substances in question, 10 to 100% of the loads of pesticides are retained in fishponds. (3) The oral transfer of polychlorinated biphenyls (PCBs 138, 153, and 180) from a contaminated sediment to a benthic fish (carp) was studied by the in vivo relative bioavailability method. The results show that the contaminated sediment has no effect on the oral bioavailability of the three PCB congeners in common carp. The geosorbing effect of sediment, which explains its role as an environmental reservoir of PCBs, seems insufficient under the conditions of the digestive tract of the common carp, to prevent transfer to fish