Due to the growing problem of water scarcity, as well as the need to preserve the environment, studies have been conducted aiming at the reuse of agroindustrial waste so that biofuels can be produced to promote the reuse of wastewater in crop irrigation as well as used in the removal of emerging micropollutants in wastewater. The bioadsorption arouses great interest in the research of new materials that can be used as adsorbents, because it presents a promising, efficient, economically viable and ecologically sustainable proposal when compared to other decontamination methods. In this context, the present study was based on the production of a biochar from the orange bagasse at 550oC to compose a tertiary treatment in the tetracycline retention as well as the use of the effluent in the irrigation of the radish culture. Samples of in natura orange pomace, biochar and activated commercial charcoal were characterized. The samples were characterized by thermogravimetry, surface area and porosity measurements, scanning electron microscopy and X-ray diffraction. Irrigation with the filtered effluent with activated charcoal and biocarbon did not influence representatively the agronomic variables of the culture, the physical- chemical properties of water and effluents were met by the aforementioned resolution and / or work on the subject. He observed the risk of salinization and sodification of the soil by the practice. The Langmuir model was the one that best adapted to the biochar, configuring adsorption of physical nature, beneficial to the desorption process. The kinetic model that fitted the most was the pseudo-second order and the estimated equilibrium time for the biochar was eight minutes. The spectrophotometric method was safe, economical and feasible in all the analyzes used. The biocarbon had a capacity of 100% tetracycline adsorption in domestic wastewater and the efficiency of the filtration with biochar was on average 25% higher than with the commercial coal. In view of the above, the possibility of converting a waste from the low-value agro-industry and without appropriate destination to a value-added product, orange marc bagasse, to be used as a tertiary treatment for reuse of effluent in irrigation and as adsorbent for the removal of tetracycline in domestic wastewater. / Devido ao crescente problema de escassez de água, bem como pela necessidade da preservação do meio ambiente, estudos têm sido conduzidos visando o reaproveitamento de resíduos da agroindústria para que possam ser produzidos biocarvões para a promoção do reuso de águas residuárias na irrigação de culturas, bem como utilizados na remoção de micropoluentes emergentes em águas residuárias. A bioadsorção desperta elevado interesse em relação à pesquisa de novos materiais que possam ser utilizados como adsorventes, por apresentar uma proposta promissora, eficiente, economicamente viável e ecologicamente sustentável quando comparado aos demais métodos de descontaminação. Neste contexto, o estudo do presente trabalho se baseou na produção de um biocarvão a partir do bagaço da laranja a 550oC para compor um tratamento terciário na retenção da tetraciclina bem como a utilização do efluente na irrigação da cultura do rabanete. Foram caracterizadas amostras do bagaço de laranja in natura, o biocarvão e o carvão comercial ativado. As amostras foram caracterizadas por termogravimetria, medidas de área superficial e porosidade, microscopia eletrônica de varredura e difração de raios X. A irrigação com o efluente filtrado com o biocarvão e carvão comercial ativado não influenciaram representativamente nas variáveis agronômicas da cultura, nas análises físico-químicas da água e efluentes foram atendidos pela referida Resolução e/ou trabalhos sobre a temática. Observou o risco de salinização e sodificação do solo pela prática. O modelo de Langmuir foi o que melhor se adaptou ao biocarvão, configurando adsorção de natureza física, benéficas para a processo de dessorção. O modelo cinético que mais se ajustou foi o de pseudo-segunda ordem e o tempo de equilíbrio estimado para o biocarvão foi de oito minutos. O método espectofotométrico apresentou-se seguro, econômico e viável em todas as análises utilizadas. O biocarvão teve capacidade de adsorção da tetraciclina de 100% em águas residuárias domésticas e a eficiência da filtração com biocarvão foi em média 25% maior do que com o carvão comercial. Diante do exposto conclui-se a possibilidade de conversão de um resíduo da agroindústria de baixo valor e sem destinação apropriada, a um produto de valor agregado, o biocarvão do bagaço da laranja, a ser utilizado como tratamento terciário para o reuso de efluentes na irrigação de culturas e como adsorvente para remoção da tetraciclina em águas residuárias domésticas. / São Cristóvão, SE

Philosophiae Doctor - PhD / Emerging micropollutants such as bisphenol-A and 2-nitrophenol present a great threat in drinking water due to their adverse effects. Most conventional technologies in water and wastewater treatment are not designed to eliminate these xenobiotics; instead pollutants are merely transferred from one phase to another. Advanced oxidation technologies (AOTs) however, have been identified as suitable routes for the degradation of these potential damaging substances based on free radical mechanisms and use of less expensive chemicals. Moreover, due to the structural complexity of wastewater and the existence of pollutants as mixtures, no single advanced oxidation technology can convincingly remove all forms of contaminants and then most often than not, a combination of treatment processes is required for an effective purification process. Besides, the problem of adequate degradation of emerging contaminants in the environment, when AOT(s) are used individually, they present inherent problems. For instance, powder TiO₂ photocatalysts obstruct light penetration, thus prevent effective interaction of UV light with the target pollutants, and particulates present problems of post-filtration and recovery of catalyst particles after treatment. Additionally, TiO₂ has a high band gap energy, high electron-hole recombination rate, and is prone to aggregation of the suspended particles. Similarly, the dielectric barrier discharge (DBD) system produces ultra violet light and hydrogen peroxide within the plasma zone which is not fully maximised for the mineralization of persistent organic pollutants. Rapid oxidation and aggregation of nano zero valent iron particles in photo-Fentons process reduce the particles mobility and affect its performance. In the same vein, the jet loop reactor (JLR) system is characterised by low impingement yield, which is responsible for low mineralization rate. In light of this background, this research investigated the degradation of bisphenol-A and 2- nitrophenol in aqueous solution using the following combined advanced oxidation methods: DBD/supported TiO₂ or Ag doped TiO₂ photocatalysts, DBD/photo-Fenton induced process and JLR/UV/H₂O₂. The target was to assess the performance of each single system and then identify the best combined AOTs capable of significantly mineralizing the target compounds. Firstly, two materials were developed namely supported TiO₂ and stabilized nano zero valent Fe. The TiO₂ photocatalyst supported on a stainless steel mesh was synthesised using sol-gel solution of 8 % PAN/DMF/TiCl₄. The influence of calcination temperature and holding time on the formation of nanocrystals was investigated. Afterwards, various amounts of metallic silver were deposited on the (optimum) supported TiO₂ photocatalyst using thermal evaporation. The catalysts were characterized by several analytical methods; HRSEM, HRTEM, EDS, SAED, FTIR, TGA-DSC, UV-vis/diffuse reflectance spectroscopy, XRD, BET, and XPS. The photocatalytic activity of the prepared catalysts was determined using methylene blue as a model pollutant under ultra-violet light irradiation. Secondly, the TiO2 photocatalyst and 2.4 % Ag doped TiO₂ nanocomposites obtained as optimums (in section 1) were combined with the DBD to decompose BPA or 2-NP in aqueous solution. Moreover, the photo-Fenton process was applied for degradation of the model pollutants, and different dosages of stabilized nZVI (in the range of 0.02 -1.00 g) were added to the DBD system to induce the photo-Fenton process and improve BPA or 2-NP degradation efficiency. Finally, a jet loop reactor (JLR) presenting advanced mixing by the “impinging effect” was explored to decompose BPA or 2-NP in aqueous solution as a function of inlet applied pressure, solution pH, and initial concentration of BPA or 2-NP. Subsequently, different concentrations of hydrogen peroxide (H₂O₂) were added to the JLR to enhance the mineralization process. Furthermore, a combination of JLR with in-line UV light and H₂O₂ were further utilised to decompose BPA or 2-NP in aqueous solution. The residual concentration of the model compounds and intermediates were analysed using high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LCMS). The concentration of the ozone, hydrogen peroxide and hydroxyl radicals generated by the DBD in the presence or absence of a catalyst was monitored using Ultraviolet-visible spectroscopy and Photoluminescence spectroscopy. The results revealed that the optimal thermal conditions to obtain well supported uniformly grown, highly active crystalline TiO₂ catalysts with high specific surface area was 350 ºC at a 3 h holding time in N2 atmosphere with a flow rate of 20 mL/min. Pyrolysis temperature and holding time played an important role on the crystalline nature and photocatalytic activity of the catalyst. Moreover, 2.4 % Ag doped TiO₂ nanocomposites exhibited higher photocatalytic activity for methylene blue degradation than the undoped supported TiO₂ nanocrystals. The results indicated that combining DBD with 2.4 % Ag doped TiO₂ nanocomposites achieved 89 % and 81 % removal efficiency for BPA or 2-NP compared to 67.22 % or 56.8 % obtain when using the DBD system alone. The 2.4 % Ag doped TiO₂ nanocomposites demonstrated excellent activity and offered photochemical stability after four repeated applications.In the case of the photo-Fenton induced process, nano zero valent iron particles (nZVI) stabilized with polyethylene glycol were synthesised using a modified borohydride reduction method. The HRSEM, BET, XRD, and XPS analysis confirmed the formation of filamentous, high surface area iron nanoparticles in the zero valent state. Unlike combined DBD/Ag doped TiO2 nanocomposites, 100 % or complete removal of BPA or 2-NP in aqueous solution was achieved with DBD/nZVI system within 30 minutes compared to 67.9 % (BPA) or 56.8 % (2-NP) with DBD alone after 80 minutes. The removal efficiency was attributable to the production of an increased concentration of OH radicals as well as existence of a synergetic effect in the combined DBD/nZVI system. Five new transformation products namely: 4-nitrophenol (C₆H₅NO₃), 4-nitrosophenolate (C₆H₄NO₂), 4-(prop-1-en-2-yl) cyclohexa-3,5-diene-1,2-dione, (C₉H₈O₂), 4-(2- hydroxylpropan-2-yl)cyclohexane-3,5-diene-1,2-dione (C₉H₁₀O₃), and 1,2-dimethyl-4-(2- nitropropan-2-yl)benzene (C₉H₁₀NO₄) were identified during the degradation of BPA. While, three aromatic intermediate compounds such as 2-nitro-1,3,5-benzenetriolate (C₆H₂NO₅), 2- nitro-1,4-benzoquinone (C₆H₃NO₄), and 2,5-dihydroxyl-1,4-benzoquinone (C₆H₄O₄) respectively were identified during the degradation of 2-NP for the first time in the DBD with JT14 or JT17 using LC-MS. These intermediate compounds have never been reported in the literature, thereby expanding the number of BPA or 2-NP intermediates in the data base in the DBD/JT14 or DBD/nZVI system. BPA degradation proceeded via ozonation, hydroxylation, dimerization, and decarboxylation and nitration step, while 2-NP proceeded via hydroxylation, nitration and denitration respectively. Furthermore, maximum removal efficiency of BPA or 2-NP in aqueous solution using JLR alone under the optimum solution pH (3), inlet pressure (4 bar), flow rate (0.0007 m3/s) was 14.0 % and 13.2 % respectively after 80 minutes. A removal efficiency of 34.9 % was recorded for BPA while 33.2 % was achieved for 2-NP using combined JLR/UV under the same conditions as JLR alone. For the combined JLR/H₂O₂ under optimum conditions of inlet pressure (4 bar), solution pH (3) and peroxide dosage (0.34 g/L), a 51.3 % and 50.1 % removal efficiency was achieved for BPA and 2-NP respectively under same conditions relative to JLR alone. Combination of JLR/UV/H₂O₂ achieved 77.7 % (BPA) or 76.6 % (2- NP) removal efficiency under the same conditions. The combined JLR/UV/H₂O₂ process was found to be most effective combination under the optimized operating parameters due to existence of a synergetic index value of 6.42 or 6.84. This implies that JLR should be coupled with UV and H₂O₂ to achieve greater mineralization efficiency instead of using the system individually. The obtained experimental data of these combined treatment processes fitted the pseudo-first order kinetic models. The combination of the JLR/UV/H₂O₂ was found to be energy efficient and could effectively degrade BPA or 2-NP in aqueous solution to a greater extent than the JLR, JLR/UV or JLR/H₂O₂ system. However, the total organic carbon (TOC) reduction value by all combined DBD and JLR system recorded was not completely achieved due to the formation of recalcitrant intermediate compounds under the applied conditions. In conclusion, this study is reporting for the first time a combination of supported 2.4 % Ag doped TiO₂ nanocomposites with dielectric barrier discharge system for BPA/2-NP degradation in aqueous solution; a combination jet loop reactor based on impingement with in-line UV lamp and H2O2 for successfully decomposing BPA or 2-NP in aqueous solution; as well as a combination of dielectric barrier discharge system and stabilised nano zero valent iron particles, which induced a photo-Fenton process for highly effective removal of BPA or 2-NP in aqueous solution. This study conclusively supports the hypothesis that combined advanced oxidation technologies offer a sustainable and highly efficient means of achieving partial or complete removal of BPA or 2-NP in aqueous solutions. Considering all the combinations of AOTs investigated in this study, the novel DBD/photo-Fenton-induced process under optimised operating parameters was found to be the most efficient in the elimination of BPA or 2-NP in aqueous solutions. The combination of DBD with photo- Fenton like process offers a promising advanced waste water purification technology in the immediate future. Based on these findings, it is recommended that DBD should be redesigned to prevent loss of ozone and JLR system reconfigured to increase impingement and cavitational yield in order to have an effective combination treatment strategy for waste water purification especially in large scale waste water management. / National Research Foundation (NRF) and Water Research Commission, South Africa

This thesis deals with advanced oxidation processes (AOPs) and it’s use for removal of micropollutants from wastewater. The first chapter explains the need AOPs, water quality, pollution and substances that are present in the water. Further, the first chapter outlines approach of the current legislation to micropollutants. The second chapter explains the theory and principle of operation of AOPs. This chapter is divided into two sections. The first section describes AOPs, which were tested at selected WWTP. In the second section, there are described some other AOPs. The third chapter is a literature retrieval of AOPs dealing with the removal of micropollutants. This chapter is focused on the removal of hormones by AOPs using ozone-based AOPs. The fourth chapter describes the actual testing of selected AOPs. The chapter describes selected WWTP, pilot-scale AOP unit and test results. In the last chapter there is designed and described full-scale AOP tertiary unit for removing of micropollutants. The last chapter also contains economic analysis of the proposed tertiary unit.

This diploma thesis is engaged in problems of micropollutants removal by water treatment process. The first part aims to define single micropollutants, possibilities of their removal in laboratory and micropollutants removal on water treatment plant. In the second part, there is data evaluation of water analyses on factual water treatment plant. Also there is description and evaluation of experiment, which aims to pesticide removal from river by using filtration across granulated active carbon.

Les micropolluants d'origine pharmaceutique tels que les antibiotiques, les hormones, les anti-inflammatoires ou les médicaments anticancéreux sont généralement réfractaires aux procédés classiques de traitement des eaux et leur rejet dans l'environnement même à l'état de traces (< µg/L) pose de réels problèmes environnementaux et de santé publique. Le traitement de ces effluents par voie enzymatique semble être une alternative intéressante et ce d'autant plus si le biocatalyseur est immobilisé directement à la surface d'une membrane afin d'améliorer sa stabilité et permettre sa réutilisation. Le travail à réaliser dans le cadre de cette thèse vise la conception et l'optimisation de bioréacteurs destinés à la dégradation de micropolluants ciblés. Réalisé dans le cadre d'un contrat Européen (ENDETECH), ce travail est une collaboration avec d'autres équipes de recherche européennes en charge de sélectionner les biocatalyseurs et de mettre au point les méthodes analytiques de détection et de caractérisation des produits de la réaction. / Pharmaceutical micropollutants such as antibiotics, hormones, anti-inflammatory or anti-cancer drugs are usually reluctant to conventional wastewater treatment processes and their disposal in the environment, even at low concentrations (< µg/L) may have an impact on human health. The enzymatic treatment of these effluents seems a promising alternative if the biocatalyst is immobilized on a membrane to enhance its stability and to enable its reuse. This thesis work aims at designing and optimizing bioreactors for micropollutants degradation. It is a collaboration (ENDETECH project) with other European research teams in charge of selecting the biocatalysts and developing analytical methods for the detection and characterization of transformation products.

Les PCB (polychlorobiphényles), PBDE (éthers de biphényles polybromés) et OCP (pesticides organochlorés) sont des composés d’origine anthropique classés comme POP (polluants organiques persistants) dont l’usage a progressivement été restreint ou interdit. Ces composés, de par leur caractère ubiquiste, persistant et bioaccumulable, sont néanmoins toujours présents dans l’environnement, d’où l’importance de continuer à étudier leur présence, leur dynamique et leur impact. Du fait de la restriction de leurs usages, d’autres composés sont maintenant utilisés pour les remplacer, tels que les retardateurs de flamme alternatifs (RFA). Ces composés bromés et chlorés ont des propriétés physico-chimiques comparables à celles des POP précités et peuvent potentiellement constituer un danger chimique pour l’environnement. Par ailleurs, les RFA sont attendus à des niveaux de concentration plus faibles que les PCB et les PBDE que ce soit dans les compartiments biotiques et abiotiques. Ainsi, l’un des enjeux de ce travail de thèse était de développer une méthode multi-résidus, associant chromatographie en phase gazeuse et spectrométrie de masse à temps de vol, permettant d’analyser simultanément 17 RFA à des niveaux inférieurs au ng.g-1. Les niveaux et profils de contamination en POP et RFA ont ensuite été renseignés dans les compartiments biotiques et abiotiques de différents systèmes aquatiques contrastés. Le caractère bioamplifiable de ces composés a été étudié grâce à la détermination de facteurs d’amplification trophique (TMF) dans l’estuaire de la Gironde et dans le bassin du Rhône, à l’aide d’outils statistiques innovants. Dans l’estuaire de la Gironde il a été mis en évidence que certains RFA étaient autant voire plus bioamplifiables que certains POP historiques. Par ailleurs, dans le bassin du Rhône, l’utilisation des TMF comme outil prédictif, pour le BDE-47 ou la ΣPBDE-DCE par exemple, a été discutée et parait envisageable dans un cadre réglementaire. / PCBs (polychlorinated biphenyls), PBDEs (polybrominated biphenyl ethers) and OCPs (organochlorine pesticides) are anthropogenic compounds classified as POPs (Persistent Organic Pollutants), their use was restricted or prohibited. These compounds are ubiquitous, persistent and bioaccumulative and they are still present in the environment; this is the reason why it is important to continue the study of the fate and impact in the environment. Due to their usage restriction, other compounds are now used to replace them, such as alternative flame retardants (RFAs). These brominated and chlorinated compounds have physicochemical properties comparable to those of POPs and can thus be potentially hazardous to the environment. In addition, RFAs are expected to occur at lower concentrations than PCBs and PBDEs, whether in the biotic and abiotic compartments. Thus, one of the challenges of the present work was to develop a multiresidue method, based on gas chromatography coupled with a time-of-flight mass spectrometer, allowing for the simultaneous analysis of 17 RFAs at levels below ng.g-1. The levels and patterns of POP and RFA contamination were reported in the biotic and abiotic compartments of selected hydrosystems. The biomagnification potential of these compounds was also studied by determining trophic magnification factors (TMF) in the Gironde estuary and in the Rhône basin. In the Gironde estuary, it was shown that some RFA biomagnify as much or more than some historical POPs. Furthermore, in the Rhône basin, the use of TMF for predictive purpose, for BDE-47 or ΣPBDEs-WFD for example, was discussed and found possible.

Ce travail de thèse propose d’examiner l’intérêt de la volatolomique pour révéler dans le foie, le plasma et le tissu adipeux des composés organiques volatils (COVs) marqueurs d’exposition des animaux d’élevage aux micropolluants. Des développements méthodologiques ont d’abord été réalisés pour lever deux principaux verrous à l’application de la volatolomique. Un premier volet de ce travail méthodologique a ainsi permis de proposer des conditions d’extraction par microextraction en phase solide à la fois efficace, fidèle et reproductible pour l’analyse du volatolome de matrices biologiques complexes. Une comparaison de trois méthodes chimiométriques non-supervisées- l’Analyse en Composantes Principales (ACP), l’Analyse en Composantes Indépendantes (ACI) et l’Analyse en Composantes Communes (ACC) – a montré ensuite l’intérêt de l’ACC pour révéler des différences volatolomiques et identifier des marqueurs candidats pour chaque type d’exposition.En s’appuyant sur ces développements, un second volet de ce travail a permis d’évaluer l’intérêt de la volatolomique pour tracer l’exposition des animaux d’élevage à différents types de micropolluants. Cette recherche a confirmé la pertinence de l’analyse volatolomique du foie et a montré que le plasma pouvait permettre également un diagnostic ouvrant la voie à des contrôles in vivo de l’exposition animale. Les résultats montrent également une complémentarité informative entre les deux matrices biologiques. En revanche, le potentiel informatif de l’analyse du volatolome de tissus adipeux s’est révélé beaucoup plus limité, l’étude ne permettant pas d’identifier le moindre marqueur d’exposition. Ainsi, si la robustesse de ces marqueurs est validée par des travaux ultérieurs, ces résultats ouvrent la voie à un diagnostic de l’exposition animale aux micropolluants à l’abattoir ou sur le lieu d’élevage. / The present study proposes to examine the relevance of liver, plasma and adipose tissue volatolomics to detect volatile organic compound (VOC) markers of animal exposure to micropollutants. Methodological developments were first carried to solve two main limits to the application of volatolomics. A first part of this methodological development enabled the determination of the efficient, accurate and reproducible solid phase microextraction conditions for the analysis of the volatolome in complex biological matrices. Then, a comparison of three unsupervised chemometric methods - Principal Components Analysis (PCA), Independent Components Analysis (ICA) and Common Components Analysis (CCA) - highlighted the potential of CCA for the determination of volatolomic differences in VOC profiles and for the identification of candidate VOC markers for each contamination.Based on these methodological developments, the second part of this work studied the potential of liver, plasma and adipose tissue volatolomics to back-trace animal exposure to different types of micropolluants. These results confirmed the relevance of the volatolomic analysis of the liver and showed that the plasma could also of interest, opening the way to in vivo controls of animal exposure to micropollutants. Moreover, the results demonstrated the complementarity of the biological matrices. The informative potential of the volatolome analysis of adipose tissue is much more limited, as the study did not lead to the identification of any marker of exposure. If the robustness of these candidate markers is validated by further studies, these results pave the way for the diagnosis of animal exposure to micropollutants in slaughterhouse and during animal breeding.

Organic pollutants such as carbon and nitrogen are effectively removed through nature-based solutions, particularly treatment wetlands, research is increasingly focusing on the behavior of and effects to the environment caused by micropollutants. The release of these anthropogenic chemicals into the environment creates a complex mixture of chemicals that can cause quantifiable adverse biological effects. While resent studies indicate the ability of treatment wetlands to remove micropollutants, major questions regarding the removal efficacy of biological effects, the most efficient design aspects (aerated vs. non-aerated; planted vs. non-planted; single-stage vs. two-stage), the resiliency of a treatment wetland, and the potential for optimization are still unsolved. This dissertation investigated these topics by combining cutting-edge methods from engineering, analytical chemistry, and environmental toxicology. The existing knowledge gaps were addressed and the understanding of treatment technologies as well as the potential of treatment technologies to reduce micropollutants and biological effects was improved. In this research, seven treatment wetlands and a municipal wastewater treatment plant were examined over the course of an entire year, to identify the most effective design of the treatment plants in terms of biological effect removal. Intensified wetlands showed higher annual removal efficacy (41 - >99%) than the non-aerated (conventional) horizontal flow wetland (24 – 78%) for investigated micropollutants and biological effects. Removal efficacy for carbamazepine, which is considered to be resistant to aerobic biodegradation, was observed to be higher in the non-aerated horizontal flow treatment wetland than in the intensified wetlands (24 %, 0 – 3 %, respectively). Benzotriazole, diclofenac, activation of aryl hydrocarbon receptor, activation of peroxisome proliferator-activated receptor gamma, and oxidative stress response were removed to a greater extend through the intensified treatment wetlands than by the municipal wastewater treatment plant. Also, for the first time, the effluent qualities of the treatment wetlands were compared with recently proposed effect-based trigger (EBT) values for surface water. The effluent bioanalytical equivalent concentrations (BEQs) for all intensified treatment wetlands and the municipal wastewater treatment plant were close to or even below the surface water EBTs, except for estrogenicity. This indicates the great benefit of using nature-based solutions for water treatment because the treated effluent would not impose a negative ecological effect on a receiving water. Aeration and therefore an elevated oxidation reduction potential was identified as a key environmental condition for increased removal of micropollutants and biological effects. In particular, the two-stage system (aerated vertical flow constructed wetland followed by an unsaturated vertical flow sand filter) achieved the highest removal efficacies for conventional parameters (66 to >99%), micropollutants (94 – 99%, except carbamazepine: 3%) and biological effects (91 – 99%). But also, the less cost-intensive one-stage treatment wetlands (aerated horizontal flow and aerated vertical flow) achieved high quality effluents for the observed parameters. With different aeration strategies, aerobic and anaerobic zones were created in an aerated horizontal flow treatment wetland. The sharp increase of the oxidation reduction potential resulted in a higher mass removal for the moderately biodegradable micropollutants benzotriazole (> 91 %; test system with 50% aeration), and diclofenac (81 %; test system with 50% aeration). But the removal efficacy of biological effects decreased with the enlargement of the non-aerated zone in the treatment wetland. Nevertheless, the combination of aerated and non-aerated zones can reduce moderate micropollutants. The advantage of high removal efficacy for micropollutants and biological effects through aeration comes with the susceptibility to technical disturbances such as a power failure or an air pump failure. A simulated aeration interruption of six days resulted in a poorer water quality (comparable to that of a conventional non-aerated horizontal flow treatment wetland). After switching the aeration back on, the investigated system recovered within a few days for most of the conventional wastewater parameters (8 – 22 d) and micropollutants (3 – 22 d). Results showed that removal of biological effects are negatively affected for a longer period of time (>22 d) than what was indicated by classical parameters or micropollutants alone. These results mark the importance of the use of bioassays for future water quality assessment. With respect to the removal of biological effects, three treatment wetland designs can be recommended: the two-stage system (aerated vertical flow treatment wetland followed by an unsaturated vertical flow sand filter); and the less cost-intensive one stage systems: aerated horizontal flow treatment wetland and aerated vertical flow treatment wetland. The aerated horizontal flow treatment wetland is also resistant to an aeration interruption of a couple of days and recovers, even if it takes longer (indicated by the in vitro bioassays) than indicated through conventional wastewater parameters and micropollutants. The complementary approach of this dissertation contributes to the further understanding of treatment wetlands. Furthermore, the research work provides new insights into removal efficacy of biological effects under various treatment wetland design aspects. This dissertation is intended to help generate and better understand a new generation of treatment technologies.

There are about 700,000 on-site sewage facilities (OSSFs) in Sweden, almost a quarter of which amount only to septic tanks for sludge collection and removal, with no form of post-treatment. All these OSSFs contribute about 10 % of the total anthropogenic phosphorus (P) load from Swedish coasts to the Baltic Sea. They also leak a considerable, but hard to quantify, amount of micropollutants (MPs). This is a large, diverse group of organic trace contaminants, including e.g., pharmaceuticals and detergents. The interests concerning OSSFs in Sweden have over time shifted from merely disposal issues, to health (removal of pathogens) and then further on to nutrient leakage.   In recent years there has been a growing interest in a more comprehensive sustainability perspective. In that spirit, during this thesis project, environmental (n=5) and socio-economic (n=5) criteria were assessed for three conceptualized, full-scale OSSFs. The evaluation was based on the efficiency of domestic wastewater treatment from a single household. These systems comprised conventional post-treatment, as well as extra capabilities for treating P and MPs. The evaluation was done with a multi-criteria analysis (MCA), the goal of which was to provide a proof-of-concept analysis of these treatment technologies in order to serve as decision-support at a national policy level.   The first of the decision options was a sandbed filter with Polonite® and Granular Activated Carbon (GAC) filters, for the adsorption of P and MPs, respectively. The second option was a reference package treatment system (PTSs), with flocculation chemicals for the precipitation of P, but nothing for the removal of MPs. The third solution was another PTSs, but with Polonite and GAC filters. The stakeholders chosen in this study were the Swedish Agency for Marine and Water Management (SwAM), a municipal regulator and a property owner. A total of 100 weight points were assigned to the 10 sustainability criteria. The minimum and maximum of these created a range for each criterion, which was multiplied with the grades 1-5 and added together.   The most sustainable alternative in this study was found to be the sandbed filter with 102-694 points (mid-range of 398), followed by the PTSs reference with 79-560 points (mid-range of 319.5) and the PTSs with filters with 82-500 points (mid-range of 291). The property owner put the highest weight on the economy, while SwAM put the highest weight on the environmental criteria, and the regulator on the social criteria. The sensitivity analysis indicated possible impact by changing the ranking position between the PTSs. This was deemed likeliest for the weight change of life-cycle costs and the grade change of the ease of compliance (legislative) criterion, but the highest ranking of the sandbed filter seemed hard to budge. / Det finns ungefär 700,000 enskilda avlopp i Sverige, varav ca en fjärdedel endast består av trekammarbrunnar, eller liknande system, utan någon form av post-rening. Alla dessa enskilda avlopp belastar ungefär 10 % av den totala antropogena fosforn (P) från svenska kuster till Östersjön. Det sker också ett läckage av en betydande, men svår-kvantifierbar, mängd mikroföroreningar (MF). Detta är en stor, divers grupp av organiska spårföroreningar som t. ex inkluderar läkemedelsrester och tvättmedel. De övergripande intressena angående enskilda avlopp i Sverige har över tid skiftat från frågor gällande dess bortskaffande, till hälsa (avskiljning av smittämnen) och vidare till näringsläckage.   Under de senaste åren har det blivit ett växande intresse för ett mer omfattande hållbarhetsperspektiv. Under det här examensarbetet bedömdes miljö-kriterier (n=5) och socio-ekonomiska kriterier (n=5) för tre teoretiska, fullskaliga enskilda avlopp. Utvärderingen baserades på avloppsreningens effektivitet från ett enskilt hushåll. Dessa avloppssystem innefattade konventionell post-rening, såväl som ytterligare förmåga att behandla P och MF. Metoden som användes för utvärderingen var en multi-kriterie analys (MKA), vars mål var att förse en konceptuell analys av de här tre avloppssystemen med syfte att tjäna som beslutsstöd på en nationell policy-nivå.   Det första beslutsalternativet var en markbädd med Polonite® och granulärt aktivt kol (GAK) filter, för adsorption av P och MF. Det andra alternativet var ett referens minireningsverk (MRV) med fällningskemikalier för utfällning av P, men ingenting specifikt för avskiljning av MF från avloppsvattnet. Den tredje avloppslösningen var även den ett MRV, men med Polonite och GAK filter, som markbädden. Intressenterna som valdes i den här studien var Havs- och vattenmyndigheten (HaV), ett kommunalt miljökontor och en fastighetsbrukare. De 10 hållbarhetskriterierna fick var och en 100 viktpoäng tilldelade. De lägsta och högsta viktpoängen från de tre intressenterna skapade ett intervall för varje kriterie, vilket multiplicerades med betygen 1-5 och summerades.   Det mest hållbara alternativet i den här studien befanns vara markbädden med 102-694 poäng (mittvärde 398), följt av referens MRV med 79-560 poäng (mittvärde 319.5) och MRV med filter med 82-500 poäng (mittvärde 291). Fastighetsbrukaren tilldelade högst viktpoäng till ekonomin, medan HaV gjorde detsamma till miljökriterierna och miljökontoret till de sociala kriterierna. Känslighetsanalysen indikerade möjlig påverkan av de analyserade ändringarna genom att förändra den ovanstående rankingen mellan de båda MRV. Detta bedömdes vara troligast för viktändringen av livs-cykel kostnader och betygsändringen av kriteriet som avser lättheten att efterleva nutida och framtida (lagliga) krav, men den högsta rankingen av markbädden verkade svår att ändra på.

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.