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.

La présence de micropolluants dans tous les milieux aquatiques est aujourd'hui une préoccupation importante. La réduction des émissions de micropolluants organiques vers le milieu aquatique par les stations d'épuration (STEP) domestiques est donc un enjeu important. Ce travail porte sur l'amélioration du traitement de ces substances par les traitements secondaires et tertiaires des STEP. En premier lieu, l'objectif a été de mieux comprendre les processus d'élimination des micropolluants organiques lors de leur passage au sein d'un procédé de type boues activées aération prolongée (BA-AP). Notre travail a consisté à proposer un outil permettant de prévoir a priori le comportement de substances organiques en BA-AP par rapport à certaines de leurs propriétés physico-chimiques (i.e. constante de Henry, log Dow, structure moléculaire). La démarche adoptée a consisté à sélectionner des données de rendements d'élimination fiables et robustes, puis à les associer aux caractéristiques physico-chimiques des substances. La méthode développée est simple ; elle nécessite de connaitre uniquement des paramètres physico-chimiques facilement accessibles et la structure moléculaire des substances. Elle constitue donc une alternative crédible aux méthodes faisant intervenir la modélisation. Cette méthode permet une prédiction a priori du niveau de traitement d'une substance (rendement supérieur ou inférieur à 70%) par les traitements secondaires existants. Dans un second temps, l'objectif a été de proposer une étape de traitement tertiaire, spécifique à l'élimination de micropolluants organiques réfractaires aux traitements secondaires. Le procédé proposé est une filtration sur support fin spécifique capable de retenir par des processus d'adsorption les substances ciblés (i.e. phytosanitaires et substances pharmaceutiques dont l'élimination est insuffisante en traitement secondaire conventionnel). Une étude bibliographique a permis tout d'abord de dresser un état des lieux sur les adsorbants utilisés et leur capacité d'adsorption. Suite à cette étude, la zéolite et l'argile expansée ont été retenus ; les potentialités d'adsorption de ces deux matériaux ont été étudiées à l'échelle laboratoire (tests en réacteur fermé) et à l'échelle pilote (suivi des performances de réacteurs à garnissage drainé à écoulement horizontal). Les tests d'adsorption en réacteur fermé montrent que les matériaux choisis (argile expansée et zéolite) possèdent une potentialité pour adsorber les substances étudiées (14 substances soient 10 pharmaceutiques et 4 pesticides). Le suivi des réacteurs ouvert confortent les résultats obtenus en réacteur fermé et démontrent que les matériaux étudiés possèdent un potentiel pour l'adsorption des substances ciblées, et ce y compris dans des conditions de filtration lente, proches des conditions réelles. Les résultats obtenus démontrent le potentiel de matériaux minéraux microporeux à éliminer des micropolluants organiques de la phase dissoute et ainsi à se substituer au charbon actif, matériau onéreux et peu adapté aux petites collectivités. / The aim of the present work was to propose solutions to reduce organic micropollutants emissions by wastewater treatment plants (WWTP). First, the objective was to improve the comprehension of micropollutants behaviour in nitrifying activated sludge process. The use of a reliable removal efficiency dataset allowed setting up a removal efficiency prediction method only from the micropollutants physico-chemical characteristics (i.e. log Kow, Henry constant and molecular structure). This method represents a first progress through a better micropollutants removal by the existing secondary WWTP. Second, the aim was to set up a tertiary stage process to enhance the removal of micropollutants refractory to conventional WWTP. This tertiary stage process is a filtration of the secondary effluent by adsorbent materials that could represent a credible alternative to expensive materials such as activated carbons. Experimental approaches at different scales (lab and pilot) demonstrated that some alternative materials such as expanded clay and zeolite have the potential to adsorb refractory substances (e.g. pesticids and pharmaceuticals) and thus to decrease the concentration of organic micropollutants in effluent.

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

Préserver les ressources en eau est l’une des problématiques environnementales majeures du 21è siècle. Pour faire face à cette nécessité, il est essentiel de mettre en place une surveillance réglementée de la qualité des eaux et des rejets se déversant dans le milieu aquatique et de développer de nouveaux outils d’échantillonnage. L’échantillonnage ponctuel est la technique la plus facile à mettre en œuvre. Toutefois, elle n’est pas toujours représentative d’un milieu hétérogène parfois soumis à des variabilités spatiales et temporelles importantes. L’échantillonnage passif, notamment avec l’outil POCIS (Polar Organic Chemical Integrative Sampler), est une approche complémentaire aux techniques traditionnelles, qui permet de concentrer des molécules organiques semi-polaires directement sur site. La pertinence du résultat obtenu (la concentration moyennée sur la durée d’exposition), couplée à la simplicité de sa mise en œuvre en font a priori un outil de choix pour suivre des hydrosystèmes complexes.Dans ce contexte, des familles des composés diversifiées ont été sélectionnées : pesticides, composés pharmaceutiques, hormones stéroïdiennes et composés perfluorés. Au sein de chaque famille, plusieurs composés traceurs, présents dans l’environnement, comportant des propriétés physico-chimiques variées et aux statuts règlementaires différents (Directive Cadre sur l’Eau notamment), ont été choisis.Des essais d’optimisation de design du POCIS (quantité et nature de phase réceptrice, nature de la membrane) ont été conduits, menant à la validation de la configuration classique dans le cas général. L’influence de différents paramètres environnementaux pertinents : débit, température, matrice, présence de biofilm et dispositif de déploiement a été évaluée lors de calibrations de l’outil réalisées dans des systèmes de complexité croissante : au laboratoire, sur pilote et sur site.Les différents déploiements sur site (effluent de STEP et rivière) ont permis de valider l’utilisation de cet outil de prélèvement passif dans le cadre d’un suivi environnemental. Le potentiel du POCIS a été pleinement confirmé, tant en termes de logistique que de résultats (justesse par rapport aux concentrations mesurées par des techniques classiques, intégration d’événements ponctuels, limite de quantification…). / The protection of water resources is one of the major environmental stakes of 21st century. Regulation concerning water quality and effluents is therefore definitely needed, as well as new approaches regarding water sampling. Spot sampling is the easiest strategy. However, it may not be representative of a heterogeneous matrix, with sometimes important spatial and temporal variability. Passive sampling, including POCIS (Polar Organic Chemical Integrative Sampler) is a complementary approach, which enables an on-site pre-concentration of semi-polar organic compounds. The relevance of the result (time-weighted average concentrations) and the ease to implement POCIS make it an appropriate tool to monitor complex hydrosystems.Within this work, various compound classes were selected: pesticides, pharmaceuticals, steroid hormones and perfluorinated compounds. Among each family, several tracer molecules, widely encountered in the environment, with different physic-chemical properties and regulatory status (particularly in the Water Framework Directive), were chosen.POCIS design optimization (amount and nature of sorbent, nature of membrane) was carried out, leading to the validation of the standard configuration for general purposes. The impact of different relevant environmental parameters (flow-rate, temperature, matrix, biofouling and deployment device), was assessed during calibrations of POCIS conducted in systems of increasing complexity: in the laboratory, at pilot-scale and on-site.All on-site deployments (WWTP effluent and river) enabled to validate the use of this passive sampling tool in the framework of an environmental monitoring. The potential of this tool was fully confirmed, both logistically and in terms of results (trueness compared to concentrations measured with traditional techniques, integration of punctual events, quantification limit…).

Occurrence of organic micropollutants (OMPs) in aquatic environment is a worldwide concern. A long list of anthropogenic substances, including pharmaceuticals, hormones, etc., are frequently detected in natural water sources. Wastewater treatment plants are one main source of OMPs pollution, but also a key step to control OMPs dissemination into the environment. This dissertation focuses on the evaluation of Membrane Aerated Biofilm Reactor (MABR) as a sustainable process to treat wastewater polluted by OMPs. Furthermore, application of high intensity pulsed light is proposed as an innovative tertiary treatment to produce reclaimed water of high quality. In Chapter 1, a literature review was performed to investigate the occurrence and toxicity of 12 selected organic micropollutants (OMPs) in surface and ground water and the limitations of current available biological processes. Among these technologies, systems with enriched nitrifying activity were able to enhance the removal of specific OMPs through cometabolic activities. Thus, I proposed the use of a MABR with enriched nitrifying biomass to treat OMP polluted water. In Chapter 2, I studied the influence of biofilm thickness on the removal of 13 OMPs via MABR. Results demonstrated OMP removal was dependent on biofilm thickness and bacterial cell density. MABR demonstrated important efficiencies in the removal of ammonium, COD, acetaminophen and triclosan at early stages of biofilm thickness. However, the removal of nonpolar, hydrophobic 4 OMPs and anionic, acidic OMPs required thicker biofilms, achieving maximum removal at biofilm with 1.02 mm thickness and 2.2 × 106 cell mL-1. In Chapter 3, the contribution of sorption and biodegradation in the removal of OMPs via MABR was evaluated. At three stages of biofilm thickness studied, biodegradation dominated the removal for most OMPs. Heterotrophs played an important role in OMP biodegradation at all biofilm thickness, while autotrophic nitrifiers enhanced their contribution at thickness beyond 0.58 mm. Increased removal of pollutants like estrone and ethinyl estradiol were linked to the MABR enrichment with nitrifying bacteria. Sorption was essential for the removal of lipophilic and recalcitrant pollutants like triclosan. Finally, to provide high quality treated water for reuse, Chapter 4 explores the use of high-intensity pulsed light (HIPL) as post-treatment. The number of pulses and optical energy dose have a significant impact on the OMPs removal. HIPL demonstrated fast kinetics and efficient photodegradation – with significant OMPs removal within milliseconds. The findings from my Ph.D. dissertation indicate that MABR combined with high-intensity pulse light may be an effective treatment train for the efficient removal OMPs present in municipal wastewaters. This combined treatment process could potentially pave the way to produce high quality reclaimed water for various reuse purposes.

The efficiency of wastewater treatment systems is commonly measured by the reductions of parameters such as biological oxygen demand (BOD), chemical oxygen demand (COD) and total suspended solids (TSS) and/or reductions in levels of selected macro compounds (e.g. long-chained hydrocarbons and inorganic compounds). Less attention has generally been paid to micropollutants with high potential toxic effects, such as polycyclic aromatic compounds (PACs), including unsubstituted and alkylated polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes, polychlorinated biphenyls (PCBs), human pharmaceuticals and by-products formed during the treatment process. These organic micropollutants occur in wastewaters at trace and ultra-trace levels, therefore their detection requires advanced, costly analyses and large sample volumes. Furthermore, concentrations of micropollutants can fluctuate widely both diurnally and between days. Thus, in order to understand the fate of micropollutants in wastewaters there is a need to develop sampling techniques that allow representative samples to be readily collected. In the work underlying this thesis two types of diffusive passive samplers, semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs), were used to monitor non-polar and polar organic micropollutants in wastewaters subjected to various treatment processes. The pollutants sequestered in these samplers represent micropollutants in the dissolved phase that are available for aquatic organisms. Further, since they collect pollutants in an integrative manner, i.e. they sample continuously during the selected exposure time (usually approx. one to ca. three weeks), the results provide time-weighted average (TWA) concentrations. In addition, the effects of various environmental factors on the uptake of analyzed micropollutants in POCISs and SPMDs were investigated using laboratory calibration and in situ calibration with performance reference compounds (PRCs). The results confirm that SPMDs are good sampling tools for investigating the efficacy of wastewater treatment processes for removing non-polar PACs and PCBs, and the effects of varying the process settings. In addition, analyses of process streams in municipal sewage treatment plants demonstrated that conventional sewage treatment processes are not optimized for removing dissolved four-ringed PAHs, some of the five-ringed PAHs, and tri- to hexa-chlorinated biphenyls. The removal of bioavailable PACs was enhanced by adding sorbents with high sorption capacities to the sludge used in the activated sludge treatment step, and a biologically activated carbon system was designed that robustly removed bioavailable PACs, with removal efficiencies of 96.9-99.7 percent across the tested ranges of five varied process parameters. In situ SPMD calibration data acquired show that uptake of PACs, described by SPMD sampling rates (Rs), were four to eight times higher than published laboratory calibrated Rs values, mainly due to strong (bio)fouling and turbulence effects. In addition, the laboratory calibration study demonstrated that temperature affects the POCIS uptake of pharmaceuticals. The uptake of four pharmaceuticals was higher, by 10-56 percent, at 18 °C compared to 5 °C. For two of the pharmaceuticals our data indicate that the uptake was lower by 18-25 percent at 18 °C. Our results also indicate that uptake of the studied pharmaceuticals was in the linear phase throughout the 35 day exposure period at both temperatures. Finally, calibration studies enabled aqueous concentrations of micropollutants to be more accurately estimated from amounts collected in the passive samplers.

L'explosion démographique a conduit à une augmentation intensive des contaminants environnementaux issus de différentes émissions anthropiques, par exemple, les hydrocarbures de pétrole, les pesticides, les biphényles polychlorés (BPC) ainsi que d’autres déchets ménagers tels que les détergents utilisés comme nettoyants ménagers. Du fait de leur persistance et du point de vue toxicologique, les résidus de ces contaminants organiques, qui peuvent être détectés dans les différentes matrices environnementales (eau, sédiments, air et biotes), parfois à très faible concentration (micropolluants), ont conquis l'attention du public. Cette étude vise à déterminer les niveaux de concentration de contaminants sélectionnés dans les sédiments de surface et à identifier la source de ces produits chimiques dans le ruisseau Cortiou. Les résultats ont montré une forte contamination par les hydrocarbures dans la zone étudiée. De plus, ces résultats ont probablement reflété le fait que les processus de biodégradation se sont produits parallèlement à une répartition chronique des charges d’épuration non traitées. Ces polluants organiques ont également confirmé un effet néfaste sur le biote marin et plus particulièrement sur les communautés benthiques pour certaines stations / Demographic explosion has led to increase intensively environmental contaminants issued from different anthropogenic release e.g. petroleum hydrocarbons, pesticides, polychlorinated biphenyls (PCBs) and also other domestic waste such as detergents as household cleaner. Due to their persistence and the toxicological point of view, the remnants of these organic contaminants, which can be detected in the different environmental matrices (water, sediment, air and biota), sometimes with very low concentration (micropollutants), has gained the public attention. This study aims to determine the concentration levels of selected contaminants in surficial sediments and identifying the source of these chemicals in Cortiou Creek. The results showed high contamination by hydrocarbons in the studied area. Additionally, these results probably reflected that biodegradation processes occurred concomitantly with a chronic apportionment of untreated sewage loading. These organic pollutants also confirmed an adverse effect for marine biota and more particularly for benthic communities for some stations