Les rejets urbains modifient la qualité de la matière organique dissoute (MOD) dans les milieux récepteurs et sont une source majeure de micropolluants. Il a été montré que la MOD naturelle influençait la spéciation et le devenir des micropolluants, que ce soit dans le milieu récepteur ou dans les ouvrages de traitement. L’objectif ici est d’étudier l’impact de la présence et de la qualité de la MOD sur la répartition dissous/particulaire des micropolluants dans les systèmes aquatiques, de la station d’épuration au milieu récepteur. L’originalité de notre travail est de comparer l’influence d’une MOD fulvique naturelle et d’une MOD urbaine, et de travailler à des concentrations proches des concentrations du milieu aquatique. Dans un premier temps, nous avons caractérisé l’adsorption de différents types de MOD (acides fulviques (AF) et rejets de STEP) sur différents types de particules (calcite, goethite, montmorillonite, quartz et charbon actif). Dans un second temps, nous avons caractérisé l’adsorption de certains micropolluants (éléments traces métalliques (ETM) et As (V), Hydrocarbures Aromatiques Polycycliques (HAP) et 13 produits pharmaceutiques) sur les particules en absence de MOD ou en présence de MOD ((AF) et rejets de STEP). Concernant l’influence de la MOD sur l’adsorption des ETM par les particules, les résultats obtenus montrent une diversité importante de situations selon les ETM et les particules considérées. Pour la goethite, nous avons observé une diminution de l’adsorption en présence de MOD urbaine par rapport à ce qui est observé en l’absence de MOD. Pour le charbon actif, au contraire, il y a plus d’adsorption en présence d’AF pour tous les ETM sauf pour le Cu qui est plus adsorbé en présence de MOD urbaine. Les différentes particules ont globalement présenté une capacité d’adsorption importante des HAP mais cette capacité est très fortement modulée par la MOD et ce, de manière différente selon les particules. Pour la goethite et la montmorillonite, l’adsorption des HAP a diminué en présence de MOD. Elle est plus forte en présence de MOD d’origine urbaine qu’en présence des AF dans le cas de l’adsorption des HAP légers sur la goethite et de l’adsorption de tous les HAP sur la montmorillonite. L’adsorption des HAP plus lourds sur la goethite est par contre plus faible avec la MOD urbaine qu’en présence d’AF. Concernant l’adsorption des HAP par le CAP, nous avons observé une diminution en présence de MOD particulièrement dans le cas de la MOD urbaine. Les expérimentations menées avec le sulfaméthoxazole n’ont pas permis de mettre en évidence une influence de l’origine de la MOD sur l’adsorption de cette substance. Pour les autres produits pharmaceutiques, l’adsorption sur le CAP en présence de MOD urbaine est globalement beaucoup plus faible qu’en matrice minérale et aussi plus faible qu’en matrice acides fulviques. L’abattement de ces contaminants sera donc plus faible en présence de MOD urbaine. Cela peut être relié au fractionnement de la MOD urbaine lors de son adsorption sur le CAP. Les résultats obtenus démontrent qu’il est indispensable de tenir compte du rôle de la MOD urbaine dans les milieux récepteurs anthropisés (où elle peut être majoritaire en basses-eaux) pour mieux comprendre le devenir des micropolluants dans les systèmes aquatiques et en particulier leur répartition particulaire/dissous. En outre, dans un contexte d’épuration des eaux usées, l’abattement des micropolluants est dépendant de la nature de la MOD présente, par conséquent, les résultats d’abattement des micropolluants observés en potabilisation des eaux pourraient être sensiblement différents en épuration des eaux usées / Urban discharges alter the quality of dissolved organic matter (DMO) in receiving environments and are a major source of micropollutants. Natural MOD has been shown to influence the speciation and fate of micropollutants in both the receiving and treatment media. The objective here is to study the impact of the presence and quality of MOD on the dissolved/particulate distribution of micropollutants in aquatic systems, from the treatment plant to the receiving environment. The originality of our work is to compare the influence of a natural fulvic MOD and an urban MOD, and to work at concentrations close to concentrations in the aquatic environment. Initially, we characterized the adsorption of different types of MOD (fulvic acids (AF) and releases of STEP) on different types of particles (calcite, goethite, montmorillonite, quartz and activated carbon). In a second step, we characterized the adsorption of certain micropollutants (metallic trace elements (ETMs) and As (V), Polycyclic Aromatic Hydrocarbons (PAHs) and 13 pharmaceutical products) on particles in the absence of MOD or in the presence of MOD (AF) and releases of STEPs. Concerning the influence of MOD on the adsorption of ETMs by particles, the results obtained show a significant diversity of situations depending on the ETMs and particles considered. For goethite, we observed a decrease in adsorption in the presence of urban MOD compared to what is observed in the absence of MOD. For activated carbon, on the other hand, there is more adsorption in the presence of AF for all VTE except for Cu, which is more adsorbed in the presence of urban MOD. The various particles have generally exhibited a high adsorption capacity of PAHs, but this capacity is strongly modulated by the MOD, and this varies according to the particles. For goethite and montmorillonite, adsorption of PAHs decreased in the presence of MOD. It is stronger in the presence of urban MOD than in the presence of AF in the case of adsorption of light PAHs on goethite and adsorption of all PAHs on montmorillonite. The adsorption of heavier PAHs on goethite is lower with urban MOD than in the presence of AF. Concerning the adsorption of PAHs by the CAP, we observed a decrease in the presence of MOD, particularly in the case of urban MOD. Experiments conducted with sulfamethoxyazole did not reveal any influence of the origin of MOD on adsorption of this substance. For other pharmaceutical products, adsorption on CAP in the presence of urban MOD is generally much lower than in the mineral matrix and also lower than in the fulvic acid matrix. The abatement of these contaminants will therefore be lower in the presence of urban MOD. This can be related to the fractionation of urban MOD when adsorbed on the CAP. The results obtained show that it is essential to take into account the role of urban MOD in anthropized receptor environments (where it can be the majority in low-water environments) in order to better understand the fate of micropollutants in aquatic systems and in particular their particle/dissolved distribution. In addition, in a wastewater treatment context, the abatement of micropollutants is dependent on the nature of the present MOD, therefore, the abatement results of micropollutants observed in water purification could be significantly different in wastewater treatment

Les micropolluants organiques (MPO) tels que les HAPs, PCBs et NP sont sous la surveillance étroite des différentes agences de santé et de l'environnement à cause de leurs effets toxiques, cancérigènes et perturbateurs endocriniens sur les organismes vivants. Dans l'environnement, ils se retrouvent dans le sol, les aquifères, les eaux usées, et en raison de leurs propriétés hydrophobes, ces MPO sont principalement associés aux compartiments matière organique dans les boues d'épuration et les sédiments de rivières. La digestion anaérobie, procédé de stabilisation des boues, présente un potentiel pour l'abattement de ces composés. Les deux principaux mécanismes qui régissent l'abattement dans ces conditions des MPO sont le cométabolisme et la biodisponibilité. Leur double influence est évaluée dans ce travail, avec un focus fort sur l'étude des interactions MPO-matrice, la détermination de la distribution des MPO dans les compartiments physiques de la matrice (libre, sorbé à la matière dissoute et colloïdale (DCM) et sorbé aux particules) et avec une caractérisation fonctionnelle, physique et chimique détaillée de la matrice. Pour cela, des réacteurs anaérobies continus et batch ont été mis en œuvre avec des boues de caractéristiques différentes. L'abattement des MPO varie considérablement en fonction des caractéristiques des boues s'expliquant soit par des variations du niveau de cométabolisme, soit par les différents niveaux de biodisponibilité ; ceci suggère qu'une caractérisation détaillée de la matrice boue pourrait aider à prévoir les niveaux d'abattement des MPO. Par ailleurs, les cinétiques en batch montrent que l'abattement des MPO est associé aux premières étapes de la digestion anaérobie, conjointement à leur transfert du compartiment des particules vers le compartiment aqueux. L'abattement des MPO s'observe simultanément dans les trois compartiments libre, sorbé à la DCM et sorbé aux particules. Il est aussi noté l'importance du compartiment DCM sur l'abattement des MPO de haut poids moléculaire. Les coefficients de partage KDOC et Kpart ont été calculés pour étudier les interactions MPO-matrice., Ces données couplées à celles de caractérisation fonctionnelle de la matrice par fluorescence 3D ont permis de construire un modèle explicatif et prédictif des interactions MPO-matrice à l'aide de la méthode de régression partielle des moindres carrés (PLS). Il a été constaté que le compartiment type acide humique a un rôle important dans les interactions MPO-matrice, principalement dans la phase aqueuse, et dans la phase particulaire, les protéines complexes régissent les interactions. Enfin, des modèles PLS explicatifs et prédictifs d'abattement total des MPO ont été construits. Il en ressort que l'abattement des MPO est favorisé par tous les paramètres du cométabolisme (abattement des divers compartiments matière) et par la concentration des MPO en phase aqueuse ce qui tenterait à confirmer que ce compartiment correspond au compartiment biodisponible. Le modèle prédictif basé sur les caractéristiques des boues initiales a identifié les concentrations initiales de MPO (libre, sorbé à la DCM et aux particules) comme les variables les plus importantes qui permettent de prédire l'abattement total des MPO. Cette étude contribue ainsi à mieux comprendre la répartition des MPO dans les matrices boue, et son implication dans le devenir des MPO, de prévoir cette répartition par une caractérisation fonctionnelle de la matrice et de proposer des stratégies pour optimiser l'abattement des MPO au cours de la digestion anaérobie. / Organic micropollutants (OPs) such as PAHs, NP and PCBs, are nowadays looked as environmental pollutants by environmental and health agencies because of their toxic, carcinogenic and endocrine disrupting effect on living organisms. Within the environment, they can deposit to soil, water bodies and sewage system and due to their hydrophobic properties, they are mainly associated with hydrophobic compartments such as organic matter in sewage sludge. Anaerobic digestion has been shown as a potential biological process for removing these compounds. The two main mechanisms that govern their anaerobic removals are the cometabolism and the bioavailability. In this work, cometabolism and bioavailability influences were evaluated focusing mainly on the study of the OP-organic matrix interactions, the determination of the OPs distribution among the physical compartments (free, sorbed to dissolved and colloidal matter (DCM) and sorbed to particles) combined with a detailed physical, chemical and functional matrix characterization. For this, continuous and batch anaerobic reactors were fed with different sludge samples. It was found that the OPs removals varied greatly as a function of sludge characteristics and that greater or lesser removal might be explained either by variations in cometabolism or by different levels of bioavailability, suggesting that a detailed characterization of the feed may help to predict the OPs removals. Additionally, batch kinetics demonstrated that OPs removals are coupled to the first step of the anaerobic digestion, jointly to the OPs transfer from the particules to the aqueous compartment. The OPs are simultaneously removed from the three physical compartments (free, DCM and particules). Moreover, it was highlighted the importance of the DCM fraction on the removal of the high molecular weight OPs. KDOC and Kpart partition coefficients were calculated to study the OP-organic matrix interactions coupled to a functional characterization by 3D fluorescence of the matrix in order to construct an explicative and predictive model of the OP-organic matrix interactions using partial least square regression (PLS). It was found that the humic acid-like compartment has a great role in the OP-organic matrix interactions mainly in the aqueous phase, and in the particulate phase, the complex proteins govern the interactions. Finally, explanatory and predictive PLS models of total OPs removals were constructed. It was concluded that OPs removals are favored by all cometabolic parameters (substrates removals) jointly to the aqueous OPs concentration which tends to confirm that this compartment corresponds to the bioavailable one. The predictive model based on the initial sludge characteristics, identified the initial OPs concentrations (free, DCM and particulate) as the most important variables that predict the total OPs removals. This study contributes to better understand the OPs distribution among the sludge compartments and its role in the fate and removal of the compounds, to predict this distribution through matter functional characterization and to propose strategies in order to optimize the OPs removals under anaerobic conditions.

Constructed wetlands (CW) and soil aquifer treatment (SAT) represent natural wastewater treatment systems (NWTSs). The high costs of conventional wastewater treatment techniques encourage more studies to investigate lower cost treatment methods which make these appropriate for developing and also in developed countries. The main objective of this research was to investigate the removals of nutrients and organic micropollutants (OMPs) through SAT, CW and the CW-SAT hybrid system. CWs are an efficient technology to purify and remove different nutrients as well as OMPs from wastewater. They removed most of the dissolved organic matter (DOC), total nitrogen (TN), ammonium and phosphate. Furthermore, CWs aeration could be used as one of the alternatives to reduce CWs footprint by around 10%. The vegetation in CWs plays an essential role in the treatment especially for nitrogen and phosphate removals, it is responsible for the removal of 15%, 55%, 38%, and 22% for TN, dissolved organic nitrogen (DON), nitrate and phosphate, respectively. CWs achieved a very high removal for some OMPs; they attenuated acetaminophen, caffeine, fluoxetine and trimethoprim (>90%) under different redox conditions. Moreover, it was found that increasing temperature (up to 36 C) could enhance the removals of atenolol, caffeine, DEET and trimethoprim by 17%, 14%, 28% and 45%, respectively. On the other hand, some OMPs, were found to be removed by vegetation such as: acetaminophen, caffeine, fluoxetine, sulfamethoxazole, and trimethoprim. Moreover, atenolol, caffeine, fluoxetine and trimethoprim, showed high removal (>80%) through SAT system. It was also found that, temperature increasing and using primary instead of secondary effluent could enhance the removal of some OMPs. The CWs performance study showed that these systems are adapted to the prevailing extreme arid conditions and the average percent removals are about, 88%, 96%, 98%, 98% and 92%, for COD, BOD and TSS, ammonium and phosphate, respectively. Additionally, the natural hybrid system (CW-SAT) can provide an effective treatment technology of reclaimed water for replenishing aquifers and subsequent reuse. This hybrid system embodied the performance advantages of both processes and exhibits a high potential for removal of OMPs, nutrients, metals as well as pathogens, bacteria and viruses.

The current global water crisis in addition to continues contamination of natural water bodies with harmful organic micropollutants (OMPs) have driven the development of new water treatment technologies that allow the efficient removal of such compounds. Among a long list of OMPs, antibiotics are considered as top priority pollutants to be treated due to their great resistance to biological treatments and their potential to develop bacterial resistance. Different approaches, such as membrane-based and advance oxidation processes have been proposed to alleviate or minimize antibiotics discharge into aquatic environments. However most of these processes are costly and generate either matrices with high concentration of OMPs or intermediate products with potentially greater toxicity or persistence. Therefore, this thesis proposes the study of an anaerobic membrane bioreactor (AnMBR) for the treatment of synthetic municipal wastewater containing sulfamethoxazole (SMX), a world widely used antibiotic. Besides the general evaluation of AnMBR performance in the COD removal and biogas production, this research mainly focuses on the SMX removal and its degradation pathway. Thus 5 SMX quantification was performed through solid phase extraction-liquid chromatography/mass spectrometry and the identification of its transformation products (TPs) was assessed by gas chromatography/mass spectrometry technique. The results achieved showed that, working under optimal conditions (35°C, pH 7 and ORP around -380 to -420 mV) and after a biomass adaptation period (maintaining 0.85 VSS/TSS ratio), the AnMBR process provided over 95% COD removal and 95-98% SMX removal, while allowing stable biogas composition and methane production (≈130 mL CH4/g CODremoved). Kinetic analysis through a batch test showed that after 24 h of biological reaction, AnMBR process achieved around 94% SMX removal, indicating a first order kinetic reaction with K= 0.119, which highlights the high degradation capacity of the anaerobic bacteria. Along the AnMBR process, 7 TPs were identified and possible degradation pathways were proposed. At low influent SMX concentrations (<10ppb), the only TPs detected was (1) Benzene sulfonamide N-Butyl. However, as the influent SMX concentration increased, it was possible to identify (2) Sulfanilamide, (3) Sulfisomidine and (4) 4-Aminothiophenol. Further degradation of compounds 2, 3 and 4 were detected after 9 hours of biological reaction in a batch test, producing three new intermediate products: (5) Aniline, (6) 4-Pyrimidinamine, 2,6-dimethyl and (7) Acetamide, N-(4-mercaptophenyl). Most of the detected TPs present a less complex structure than SMX, which can be associates with a lower toxicity.

La présence de micropolluants organiques dans l’environnement et notamment le milieu aquatique, est devenue une préoccupation grandissante au cours des années. En effet, les micropolluants sont éliminés de façon variable par les différents systèmes de traitement des eaux. Ainsi, les stations d’épuration constituent une voie majeure de dissémination de ces composés dans l’environnement. Ces substances chimiques doivent être suivis et traités car elles peuvent avoir des effets indésirables sur les organismes une fois rejetées dans l’environnement. La biodégradation étant un des mécanismes de transformation dominant pour les micropolluants, les procédés biologiques, et notamment les procédés hybrides (biomasse libre et fixée), semblent pertinents pour les éliminer efficacement. Dans ce travail, nous nous sommes focalisés sur la biodégradation de la carbamazépine (CBZ), du diclofénac (DCF) et du diuron (DIU) par des microorganismes sélectionnés en utilisant un bioréacteur hybride. La méthodologie proposée a reposé sur la mise en place de tests de biodégradation en batch afin de sélectionner des microorganismes pertinents pour la dégradation des molécules cibles, avant de travailler avec un bioréacteur hybride. Les souches sélectionnées ont permis de dégrader complètement le DCF en moins de 24 heures et ont montré des résultats encourageants en 72 heures pour les autres composés. L’efficacité des souches a ensuite été évaluée sur des bioréacteurs hybrides prototypes sous différentes conditions. Bien que l’élimination du DCF ait été importante en conditions stériles, la cinétique observée était plus faible. La CBZ et le DIU ont quant à eux été faiblement éliminés. / The occurrence of organic micropollutants in the environment and notably in the aquatic bodies has become a growing concern over the years. Indeed, micropollutants are variably eliminated with different wastewater treatment systems. Thus, wastewater treatment plants represent the main transfer pathways for micropollutants to enter the environment. Among these chemical substances present in the environment at very low concentrations, pharmaceutical compounds and pesticides are of a great concern because of their potential adverse effects to ecosystems. Since biodegradation is one of the predominant transformation pathway for micropollutants, biological processes and notably hybrid processes (combining free and supported biomasses), seem relevant to remove them efficiently. In this work, our interest focuses on the biodegradation of carbamazepine, diclofenac, and diuron by selected microorganisms using a hybrid bioreactor. The methodology developed in this work consisted in the implementation of batch degradation experiments in order to select efficient microorganisms able to break down target molecules, before evaluating their efficiency using a hybrid bioreactor. The selected strains allowed degrading completely diclofenac by a co-metabolism process in less than 24 hours, and showed encouraging results in 72 hours for the other compounds. Then, the efficiency of selected strains has been evaluated using hybrid bioreactors prototypes under different conditions. Even though the removal of diclofenac was very high under sterile conditions, the observed kinetic was lower. Carbamazepine and diuron showed low removal.

No description available.

<p>Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.</p><p>The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment. </p><p>In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.</p><p>I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters. </p><p>Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.</p> / Dissertation

Submitted by Eunice Novais (enovais@uepg.br) on 2018-06-25T18:19:59Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Angélica de Sousa Hrysyk.pdf: 2633413 bytes, checksum: 814955f505551d7d05e203f53483d1c3 (MD5) / Made available in DSpace on 2018-06-25T18:19:59Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Angélica de Sousa Hrysyk.pdf: 2633413 bytes, checksum: 814955f505551d7d05e203f53483d1c3 (MD5) Previous issue date: 2018-04-06 / Por muito tempo os estudos sobre os tratamentos de resíduos estavam voltados a determinados grupos de poluentes considerados resistentes e tóxicos. Nos últimos anos espécies consideradas micropoluentes, com concentrações da ordem de μg L-1, têm recebido atenção, pois muitos destas possuem atividade farmacológica e devido ao seu grande uso e da baixa eficiência de remoção apresentada pelos sistemas de tratamento de esgoto podem contaminar águas superficiais e subterrâneas. Dessa forma, diversas pesquisas têm sido desenvolvidas na busca de novas formas de tratamento, com capacidade para a remoção de antibióticos, analgésicos, antiinflamatórios, entre outros. Os Processos Oxidativos Avançados (POA’s) têm apresentado reconhecida importância, pois mostram eficiente degradação desses micropoluentes que, em alguns casos, permitem a sua completa mineralização, ou seja, sua conversão em dióxido de carbono, água e íons inorgânicos. Em função de seu elevado uso pela população e potenciais problemas atribuídos a sua presença no ambiente existe a necessidade de investigação sobre metodologias de remediação para os fármacos amoxicilina (AMX), fluoxetina (FLU) e sinvastatina (SIN). Por isso, neste trabalho, foi estudada a potencialidade da fotocatálise heterogênea empregando dióxido de titânio imobilizado em acetato de celulose (TiO2/AC) assistido sob radiação ultravioleta (UV) em relação à remediação de matrizes aquosas contendo os fármacos AMX, FLU e SIN. O fotocatalisador sintetizado foi caracterizado por termogravimetria (TG) e análise térmica diferencial (DTA), Microanálise Quantitativa com mapeamento químico por Espectroscopia de Energia Dispersiva de Raios X (EDS), Difratometria de Raios X (DRX) e Espectroscopia no Infravermelho (FTIR). Os ensaios de degradação dos fármacos foram conduzidos em reator fotoquímico e as frações provenientes foram analisadas por cromatografia líquida de alta eficiência no comprimento de onda de máxima absorção para cada fármaco. Obtiveram-se degradações de 99,1% (SIN em 30 minutos), 85% (FLU em 180 minutos) e 99,0% (AMX em 240 minutos). Ensaios de fotólise foram realizados comprovando a baixa fotossensibilidade dos fármacos, sendo assim, atribui-se a degradação como resultante da interação entre o fotocatalisador TiO2/AC e a radiação ultravioleta. Análises de Cromatografia Gasosa acoplado ao detector de massas (CG/EM) permitiram quantificar e identificar os produtos de degradação, com resultados de Carbono Orgânico Total (COT) foi possível determinar a taxa de mineralização de 70, 43 e 15%, para AMX, FLU e SIN, respectivamente. Ensaios ecotoxicológicos realizados com a planta aquática Lemna aequinoctials Welw mostraram-se eficientes para se compreender como os fármacos e seus produtos de degradação podem afetar os organismos aquáticos. / For a long time the studies on the treatment of residues were directed at certain groups of pollutants considered resistant and toxic. In recent years, species considered micropollutants, with concentrations of the order of μg L-1, have received attention, since many of them have pharmacological activity and due to their great use and the low removal efficiency presented by sewage treatment systems can contaminate surface waters and underground. In this way, several researches have been developed in search of new forms of treatment, with capacity for the removal of antibiotics, analgesics, anti-inflammatories, among others. The Advanced Oxidative Processes (POAs) have been recognized as important because they show an efficient degradation of these micropollutants, which in some cases allow their complete mineralization, that is, their conversion into carbon dioxide, water and inorganic ions. Due to its high use by the population and potential problems attributed to its presence in the environment there is a need for research on remediation methodologies for the drugs amoxicillin (AMX), fluoxetine (FLU) and simvastatin (SIN). Therefore, the potential of heterogeneous photocatalysis using titanium dioxide immobilized in cellulose acetate (TiO2/AC) assisted under ultraviolet (UV) radiation in relation to the remediation of aqueous matrices containing the AMX, FLU and SIN drugs was studied. The photocatalyst was characterized by thermogravimetry (TG) and differential thermal analysis (DTA), Quantitative Microanalysis with chemical mapping by X-ray Dispersive Energy Spectroscopy (EDS), X-ray Diffraction (XRD) and Infrared Spectroscopy (FTIR). The drug degradation assays were conducted in a photochemical reactor and the fractions obtained were analyzed by high performance liquid chromatography at the maximum absorption wavelength for each drug. Degradations of 99.1% (SIN in 30 minutes), 85% (FLU in 180 minutes) and 99.0% (AMX in 240 minutes) were obtained. Photolysis assays were performed proving the low photosensitivity of the drugs, thus, degradation is attributed as a result of the interaction between the TiO2 / AC photocatalyst and ultraviolet radiation. Analysis of Gas Chromatography coupled to the mass detector (GC / MS) allowed to quantify and identify the degradation products, with results of Total Organic Carbon (TOC), it was possible to determine the mineralization rate of 70, 43 and 15% for AMX, FLU and SIN, respectively. Ecotoxicological assays performed with the aquatic plant Lemna aequinoctials Welw have been shown to be effective in understanding how drugs and their degradation products can affect aquatic organisms.

Cette thèse se propose de contribuer aux connaissances relatives à l’impact des facteurs spatiaux (occupation du sol) et temporels (saisons, étiages, pluies) sur la qualité des eaux de ressource à l’échelle du bassin versant. Ainsi les zones et conditions à risque pourront être identifiées à l’aide de l’exploitation et de l’interprétation de bases de données historiques et expérimentales de qualité d’eau à l’échelle du bassin versant de la Vilaine en Bretagne. Cette étude se focalise principalement sur les micropolluants, avec notamment les pesticides et les produits pharmaceutiques vétérinaires pour le contexte agricole, mais également les produits pharmaceutiques humains compte tenu de l’intérêt grandissant qui leur est porté dans le domaine de l’évaluation des risques sanitaires et environnementaux. De plus, cette thèse se propose également de contribuer à l’amélioration et à l’adaptation des traitements des produits pharmaceutiques humains en usine de production d’eau potable compte tenu de l’évolution de la règlementation et de la protection du consommateur. / This thesis aims at contributing to knowledge about the impact of spatial (land use) and temporal (seasonal, low water levels, rainfall) factors on the resource quality at river basin scale. Thus at risk conditions and areas risk could be identified with the exploitation and interpretation of historical and experimental databases on water quality of the Vilaine’s river basin in Brittany. This study focuses mainly on micropollutants, including pesticides and veterinary pharmaceutical products for the agricultural context, but also on human pharmaceutical products considering the growing interest which is carried in the field of health and environmental risk assessment. In addition, this thesis also proposes to contribute to the improvement and adaptation of human pharmaceuticals treatment in drinking water treatment plant according to regulation evolution and to consumer protection.

Les carbones activés, de par leur nanotexture développée, sont performants pour l’élimination de micropolluants organiques à l’état de traces. Ils trouvent une place prépondérante au sein des usines de traitement pour la dépollution de l’eau. Néanmoins, l’adsorption de ces composés, conduit à la saturation du matériau selon un processus d’adsorption irréversible. Un procédé électrochimique capable d’opérer à la régénération in situ des adsorbants carbonés chargés en polluants est proposé. L’applicabilité du procédé a été évaluée sur une grande diversité de micropolluants rencontrés dans les effluents traités. Ces molécules s’adsorbent préférentiellement au niveau des ultramicropores via des interactions dispersives de type π-π. La régénération électrochimique de l’adsorbant s’effectue grâce à l’application d’une polarisation, qui génère une interface chargée et induit un champ électrostatique entre les deux électrodes. La décomposition de l’électrolyte, confiné dans les pores, engendre des effets de pH localisés, responsables de la dissociation de la molécule adsorbée. La désorption sous polarisation fait intervenir des répulsions électrostatiques entre la surface chargée du matériau carboné et le polluant dissocié. Ce procédé de régénération, applicable à de nombreux micropolluants, montre des efficacités différentes selon de la nature du polluant adsorbé. La désorption est favorisée pour des polluants de petite taille, facilement ionisables et solubles ; des efficacités de régénération élevées (jusqu’à 80 %) à partir du quatrième cycle sont reportées. Une partie des polluants est piégée irréversiblement soit parce qu’ils sont bloqués dans les ultramicropores, soit parce qu’ils s’adsorbent au niveau de sites énergétiques ou via des interactions plus spécifiques. L’obstruction cumulative de la porosité par un adsorbat volumineux par exemple, engendre une diminution des efficacités de régénération avec la répétition des cycles. / Due to their developed porosity, the activated carbons are efficient for the removal of organic micropollutants at trace concentration. They find an important place in wastewater treatment for water decontamination. Nevertheless, the adsorption of these compounds leads to the adsorbent saturation and therefore makes the process irreversible. We have developed an electrochemical process which is able to operate to the in situ adsorbent regeneration. The process applicability was assessed on a wide range of micropollutants, found in the treated effluents. These molecules are adsorbed in the ultramicropores through π-π interactions. The electrochemical regeneration of the loaded adsorbent is performed by applying a polarization, which generates an electrically charged carbon surface and induced an electrostatic field between the two electrodes. The electrochemical decomposition of the electrolyte inside the porosity, leads to local pH effects which are responsible of the dissociation of the adsorbed molecule. The desorption under polarization implies electrostatic repulsions between the polarized carbon surface and the dissociated pollutant. This regeneration process can be broadened to numerous micropollutants and shows an efficiency which depends on the adsorbat nature. We have shown that the desorption of small pollutants which are easily ionisable and soluble is promoted. High desorption levels until 80 % after four desorption cycle are indeed reported. A part of the adsorbed molecules is trapped irreversibly either because they are blocked in the ultramicropores or due to the micropollutant adsorption at high energy sites and/or through specific strong interactions. For example, the porosity obstruction caused by a voluminous molecule leads to the decrease of the regeneration efficiency along the cycles repetition.