Dans le cadre de l'application de la directive cadre sur l'eau, la liste des substances « prioritaires » a été révisée et une nouvelle liste dite « de vigilance » a été récemment proposée pour des substances dont les connaissances sur l'exposition et la dangerosité sont à documenter. Or, les stations de traitement des eaux usées (STEU) domestiques actuelles, majoritairement des procédés secondaires biologiques, n'ont pas été conçues pour éliminer les micropolluants. Si elles en éliminent une grande partie, de nombreux micropolluants organiques (pesticides, composés pharmaceutiques, hormones, etc.) sont encore présents dans les eaux traitées. Certains procédés de traitement complémentaires (ou tertiaires) intensifs ou extensifs ont récemment été étudiés de façon à déterminer leur capacité à éliminer des micropolluants considérés comme réfractaires au traitement biologique (peu biodégradable ou faiblement sorbables sur les MES) et/ou présents en fortes concentrations dans les eaux usées brutes. Ainsi, l'oxydation par l'ozone ou par le peroxyde d'hydrogène, et l'adsorption sur charbon actif présentent des rendements supérieurs à 70% pour la majorité des pesticides et des pharmaceutiques étudiés. Concernant les procédés extensifs, de récentes études suggèrent que le rayonnement solaire pénétrant dans une colonne d'eau (ex. zone de rejet végétalisée, ZRV de type bassin) permettrait d'éliminer partiellement certains micropolluants par photodégradation (diclofénac, kétoprofène, etc.). L'objectif général de ce travail de doctorat était d'améliorer la compréhension des processus d'élimination des micropolluants organiques quantifiés en sortie de traitement secondaire par deux procédés de traitement complémentaire prometteurs : la photodégradation dans une ZRV de type bassin et l'oxydation à l'ozone mis en oeuvre par une tour d'ozonation sur une STEU réelle. Nous avons développé une méthodologie commune qui a été appliquée à l'étude de ces deux processus pour une sélection de 63 micropolluants réfractaires au traitement secondaire. La première étape a consisté à réaliser un état de l'art sur les études cinétiques disponibles dans la littérature. Deux bases de données ont ainsi été créées pour documenter les constantes cinétiques et rendements d'élimination pour 12 micropolluants. Ce travail a permis d'avoir une vision critique sur ces données issues de la littérature, notamment en ce qui concerne le réalisme des expérimentations vis-à-vis du traitement complémentaire d'eaux usées traitées. Lors de la deuxième étape, des études à l'échelle pilote ont été menées afin d'améliorer les connaissances sur les mécanismes d'élimination par oxydation par voie directe (photons ou O3) ou bien par voie indirecte (OH●). Ainsi, la voie de dégradation majeure (directe ou indirecte) a été déterminée pour les micropolluants étudiés. L'influence de certains paramètres physico-chimiques de l'effluent (nitrates, nitrites, MES, MOD) a également été abordée. Deux modèles numériques permettant de simuler l'élimination des micropolluants par photodégradation ou oxydation à l'ozone, respectivement, ont été développés et calés à partir des résultats obtenus. Dans la troisième étape, nous avons évalué les performances d'élimination des micropolluants à l'échelle des procédés de traitement complémentaire. Les constantes cinétiques mesurées expérimentalement ont permis de classer en 3 groupe (rapide, intermédiaire et lent) 47 micropolluants selon leur cinétique de dégradation par oxydation à l'ozone et, d'autre part, 42 micropolluants selon leur cinétique de photodégradation. Enfin des prévisions effectuées avec les deux modèles ont été comparées avec les mesures sur site. Ces résultats ont confirmé leur utilisation possible comme outil d'aide à la prédiction du comportement des micropolluants en traitement complémentaire / In the context of the implementation of the Water Framework Directive, the list of "priority" substances has been revised and a new list called "vigilance" was recently proposed for substances whose knowledge on exposure and dangerousness need to be document. However, current domestic wastewater treatment plants(WWTP), mostly secondary biological processes, were not designed to eliminate micropollutants. If WWTP eliminate the most part, many organic micropollutants (pesticides, pharmaceuticals, hormones, etc.) are still present in the treated water. Some tertiary treatment processes (or complementary) intensive or extensive recently been studied to determine their ability to remove micropollutants considered refractory to biological treatment (low biodegradable or low sorption on total suspended solids (TSS)) and / or present strong concentrations in raw water. Thus, oxidation by ozone or hydrogen peroxide, and the activated carbon adsorption have removal efficiencies higher than 70% for the majority of pesticides and pharmaceuticals. On extensive processes, recent studies suggest that solar radiation penetrating the water column (eg. soil-based constructed wetlands with basin) would partially eliminate some micropollutant with significant photodegradability (diclofenac, ketoprofen, etc.). The general objective of this PhD was to improve the understanding of the removal process of organic micropollutants quantified at the output of secondary treatment by two promising complementary treatment processes: photodegradation in a basin of soil based constructed wetlands and oxidation by ozone implemented by an ozonation tower on real WWTP. We have developed a common methodology that has been applied to the study of these processes for a selection of 63 micropollutants refractory to secondary treatment. The first step was to achieve a state of the art on kinetic studies in the literature. Two databases were created to document the kinetic constants and removal efficiencies for 12 micropollutants. This work allowed to have a critical view on the data from the literature, especially regarding the realism of the experiments for complementary treatment of treated wastewater. In the second step, studies on pilot scale have been carried out to improve knowledge about the oxidative removal mechanisms by direct (O3 or photons) or indirect pathway (OH●). Thus, the major contribution of degradation (direct or indirect) was determined for all micropollutants studied and the influence of specific physicochemical parameters of the effluent (nitrates, nitrites, TSS, DOM, etc.) was discussed. Two numerical models for simulating the removal of micropollutants by photodegradation or ozone oxidation have been developed and calibrated from the results. In the third step, we evaluated the removal performance of the micropolluants in the complementary treatment processes. The experimentally measured kinetic constants were used to classify in 3 groups (fast, medium and low) 47 micropollutants according to their kinetics of degradation by oxidation with ozone and, secondly, 42 micropolluants according to their photodegradation kinetics. Finally, predictions made with both models and were compared with measurements in real scale. These results confirmed their possible use as a tool to help to predict the behavior of complementary micropolluants treatment

La croissance démographique mondiale induit une pression accrue sur les ressources en eau potable. Une des solutions pour répondre à cette problématique environnementale est de réutiliser les eaux en sortie de station d’épuration (STEP). Cependant, la présence de microorganismes pathogènes et de micropolluants bio-récalcitrants et potentiellement toxiques ne permet pas une réutilisation directe des effluents urbains. Les procédés membranaires peuvent alors être envisagés afin d’éliminer efficacement ces polluants à l’état de trace. Cependant, la mise en œuvre des procédés membranaires implique la production de retentâts concentrés en micropolluants dont le traitement n’est, à ce jour, pas envisagé. Cette thèse propose alors d’étudier l’ozonation pour le traitement de retentâts de nanofiltration (NF) dans le cadre de la réutilisation des eaux usées, l’ozone étant un puissant oxydant et précurseur de radicaux hydroxyles. Pour cela, quatre micropolluants pharmaceutiques ont été sélectionnés comme molécules cibles. Par la suite, l’étude de la NF a mis en évidence qu’elle peut constituer une alternative viable au standard industriel qu’est l’osmose inverse en assurant des rétentions élevées pour des coûts opératoires moindres. L’ozonation s’avère efficace comme prétraitement des concentrâts en éliminant totalement les polluants les plus réactifs à l’ozone moléculaire. Toutefois, ce procédé reste limité quant à l’abattement des polluants réfractaire à l’ozone du fait de l’inhibition de la voie radicalaire par la forte teneur en matière organique des retentâts. Finalement, bien que cette association de procédés soit prometteuse, un traitement supplémentaire en aval de l’ozonation serait nécessaire afin de permettre la réutilisation des retentâts traités et aboutir à l’avènement d’une filière épuratoire à zéro rejet liquide / Global population growth induces increased threat on drinking water resources. One way to address this environmental issue is to reuse water from wastewater treatment plant (WWTP). However, the presence of pathogenic microorganisms and potentially toxic organic micropollutants does not allow a direct reuse of urban effluents. Membrane processes such RO or NF can be considered to effectively eliminate these pollutants. However, the integration of membrane processes involves the production of concentrated retentates which require to be disposed. To date, no treatment is set up to manage safely this pollution. This thesis project focuses on the application of ozonation for the treatment of NF retentates in the framework of the wastewater reuse. Ozonation is a powerful oxidation process able to react and degrade a wide range of organic pollutants. Four pharmaceutical micropollutants frequently detected in wastewater, were selected as target molecules. This study highlighted that NF can represent a viable alternative to the commonly used reverse osmosis process ensuring high retention at much lower operating costs. Ozonation appear to be effective to degrade the most reactive pollutants toward molecular ozone. However, this method is limited for the reduction of refractory ozone pollutants due to the inhibition of the radical chain by the high content of organic matter in the retentates. Finally, the ozonation processe appear to be a promising NF retentate treatment and further processing downstream of ozonation should allow reuse of treated retentates and lead to the emergence of a zero liquid discharge treatment scheme.

Un aspect clé permettant de surmonter les défis énergétiques et environnementaux est d'améliorer l'efficacité des nouveaux procédés. La plupart des produits chimiques majeurs se faisant par des procédés catalytiques, une meilleure compréhension des cinétiques de réaction est nécessaire. Dans le domaine du traitement des eaux usées, l'ozonation catalytique est en un exemple typique. Dans cette thèse, des microréacteurs catalytiques sont utilisés en tant qu’outils analytiques innovants afin de déterminer la cinétique de l'ozonation catalytique. Ceux-ci ont pu être élaborés à l'aide de procédés plasma en déposant et en activant un catalyseur à base d’oxyde de fer et de cobalt. L’efficacité de ces catalyseurs a été mesurée en utilisant de l'acide pyruvique en tant que polluant modèle. Pour Fe2O3, les mesures HPLC ont montré l'inactivité de celui-ci par rapport à Co3O4 (20%). Cet effet a été doublé après post-traitement par un plasma d'Ar, démontrant ainsi le rôle du plasma. Une simulation numérique portant sur les réactions à la surface du catalyseur a été réalisée en utilisant le logiciel Comsol Multiphysics. Le modèle utilisé s’est partiellement approché des données expérimentales en raison du manque de données concernant les constantes de réactions des espèces intermédiaires. Ces constantes cinétiques pourront être déterminées grâce à l'utilisation de la technique de spectroscopie Raman Anti-Stokes Cohérente (technique CARS) en tant qu’outil d'analyse en temps réel. En perspectives, l’utilisation de cette dernière conduira à l’élaboration d’un outil efficace qui pourrait prédire la pertinence et les futures stratégies d'amélioration sur des réactions chimiques catalysées. / A key aspect in overcoming the energy and environmental challenges is to improve the efficiency of existing and new processes. Nowadays, almost all major chemicals are produced by catalytic processes. However, a better understanding of the reaction pathways and kinetics is needed. In the field of wastewater treatment, catalytic ozonation is a typical example of this problem. In this study, catalytic microreactors were used as innovative analytical tools for the determination of kinetics of catalytic ozonation and were elaborated by using low pressure plasma processes for the deposition and activation of iron and oxide-based catalysts on polymer-based materials. Catalytic ozonation with pyruvic acid as a refractory probe compound was performed with both catalysts. HPLC measurements showed the inactivity of the iron oxide layer compared to the cobalt oxide one which led to 20 % of degradation. The effect was doubled when the latter was post-treated by an argon plasma, demonstrating the role and importance of the plasma post-treatment step. A numerical study dealing with the reactions taking place on the surface of the catalyst was carried out using the Comsol Multiphysics software and showed that the model partially fitted the experimental data due to the lack of information. However, access to the reactions rate constants of the intermediate species generated during the catalytic ozonation step could be achieved through the use of the Coherent Anti-Stokes Raman Spectroscopy technique and would lead to an efficient tool to predict the relevance and the direction of future improvement strategies regarding catalyzed chemical reactions.

Due to the widespread application of pesticides and herbicides in agricultural industries, these substances have been highlighted as emerging contamination of natural ground and surface water resources. Conventional water treatment processes are only effective in removing emerging contaminants in water. The mechanism of degradation of organic impurities present in water using ozone is known to either directly involve the ozone molecule or to occur by the indirect effect of free hydroxyl radicals (•OH). The latter are produced in the radical chain reaction of ozone decomposition. A series of experiments were carried out to investigate the effects of particle sizes of nano-ZnO catalysts on removal of atrazine (ATZ). Nano-ZnO catalysts increase the rate of ozone decomposition and atrazine removal by production of hydroxyl radicals as oxidative intermediates. However, different particle sizes have a minimal effect on the rate of ozone decomposition and atrazine removal. It is believed that molecular ozone is adsorbed on the surface of nano-ZnO followed by the oxidation of the ozone molecule. This leads to the production of OH radicals. Therefore, it is reasonable to assume that reaction is carried out in the bulk of the solution and the rate is independent of catalyst’s surface area. This is probably the reason for similar reaction rates of different particle sizes of nano-Zno catalysts. Additionally three different metal oxides (ZnO, Mn2O3 and Fe2O3) loaded on ƴ-alumina and ƴ-alumina (metal oxide-free) were used in catalytic ozonation of aquatic atrazine samples. The findings substantiate the strong influence of molecular ozone on degradation of ATZ and the partial involvement of hydroxyl radicals in the mechanism. Based on adsorption studies, atrazine has a low affinity towards adsorption on the surface of the catalysts. It is logical to assume that ozone reacts with the hydroxyl groups of the catalyst to form a highly reactive metal-ozone complex. This layer could react with a molecule of atrazine through an electron-transfer mechanism. The residual concentration of ATZ and total organic carbon (TOC) were determined by High Performance Liquid Chromatography (HPLC) and Total Organic Carbon (TOC) analyses.

During ferrochrome (FeCr) production, three types of generic chromium (Cr) containing wastes are generated, i.e. slag, bag filter dust (BFD) and venturi sludge. The loss of these Cr units contributes significantly to the loss in revenue for FeCr producers. In this study, the liberation of Cr units was investigated utilising two case study waste materials, i.e. BFD from a semi-closed submerged arc furnace (SAF) operating on acid slag and the ultrafine fraction of slag (UFS) originating from a smelter operating with both open and closed SAFs on acid slag. A detailed material characterisation was conducted for both case study materials, which included particle size distribution, chemical composition, chemical surface composition and crystalline content. Cr liberation was achieved utilising two methods, i.e. aqueous ozonation and the advanced oxidation method. Various advanced oxidation processes could be applied. However, the advanced oxidation processes considered in this study was the use of gaseous ozone (O3) in combination with hydrogen peroxide (H2O2). Controlling parameters such as the influence of pH, ozonation contact time, waste material solid loading, gaseous O3 concentration and temperature on Cr liberation were investigated for the aqueous ozonation process. The influence of pH, volume H2O2 added and the method of H2O2 addition were considered for the advanced oxidation process. Results indicated that with aqueous ozonation, limited Cr liberation could be achieved. The maximum Cr liberation achieved was only 4.2% for BFD by varying the process controlling parameters. The Cr liberation for UFS was significantly lower than that of the BFD. The difference in the results for the two waste materials was attributed to the difference in characteristics of the materials. The Cr content in BFD was mostly related to chromite and/or altered chromite particles, while the Cr content of the UFS was mostly related to FeCr particles. It is possible that the Cr(III) present in the chromite and/or partially altered chromite might be more susceptible to oxidation to Cr(VI) than the metallic Cr(0) present in the FeCr. During ozonation, aqueous O3 spontaneously decomposes to form hydroxyl (OH•) radicals, which are very strong oxidants in water. The above-mentioned Cr liberation observed was related to the formation of the OH• radicals during the spontaneous decomposition of aqueous O3. This was indicated especially by enhanced Cr liberation at higher pH values, which was attributed to the acceleration of the spontaneous decomposition to OH• radicals at higher pH levels. The advanced oxidation method gave significantly higher Cr liberation results for both case study materials considered, achieving Cr liberations of more than 21%. The advance oxidation processes improve normal oxidation methods. In this study, the H2O2 used in combination with O3 enhanced the formation of the OH• radicals that are responsible for the oxidation of Cr. The Cr liberation levels achieved are possibly not high enough to be feasible for industrial purposes. However, a further investigation of the advanced oxidation process could optimise the process to yield even higher Cr liberation. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

During ferrochrome (FeCr) production, three types of generic chromium (Cr) containing wastes are generated, i.e. slag, bag filter dust (BFD) and venturi sludge. The loss of these Cr units contributes significantly to the loss in revenue for FeCr producers. In this study, the liberation of Cr units was investigated utilising two case study waste materials, i.e. BFD from a semi-closed submerged arc furnace (SAF) operating on acid slag and the ultrafine fraction of slag (UFS) originating from a smelter operating with both open and closed SAFs on acid slag. A detailed material characterisation was conducted for both case study materials, which included particle size distribution, chemical composition, chemical surface composition and crystalline content. Cr liberation was achieved utilising two methods, i.e. aqueous ozonation and the advanced oxidation method. Various advanced oxidation processes could be applied. However, the advanced oxidation processes considered in this study was the use of gaseous ozone (O3) in combination with hydrogen peroxide (H2O2). Controlling parameters such as the influence of pH, ozonation contact time, waste material solid loading, gaseous O3 concentration and temperature on Cr liberation were investigated for the aqueous ozonation process. The influence of pH, volume H2O2 added and the method of H2O2 addition were considered for the advanced oxidation process. Results indicated that with aqueous ozonation, limited Cr liberation could be achieved. The maximum Cr liberation achieved was only 4.2% for BFD by varying the process controlling parameters. The Cr liberation for UFS was significantly lower than that of the BFD. The difference in the results for the two waste materials was attributed to the difference in characteristics of the materials. The Cr content in BFD was mostly related to chromite and/or altered chromite particles, while the Cr content of the UFS was mostly related to FeCr particles. It is possible that the Cr(III) present in the chromite and/or partially altered chromite might be more susceptible to oxidation to Cr(VI) than the metallic Cr(0) present in the FeCr. During ozonation, aqueous O3 spontaneously decomposes to form hydroxyl (OH•) radicals, which are very strong oxidants in water. The above-mentioned Cr liberation observed was related to the formation of the OH• radicals during the spontaneous decomposition of aqueous O3. This was indicated especially by enhanced Cr liberation at higher pH values, which was attributed to the acceleration of the spontaneous decomposition to OH• radicals at higher pH levels. The advanced oxidation method gave significantly higher Cr liberation results for both case study materials considered, achieving Cr liberations of more than 21%. The advance oxidation processes improve normal oxidation methods. In this study, the H2O2 used in combination with O3 enhanced the formation of the OH• radicals that are responsible for the oxidation of Cr. The Cr liberation levels achieved are possibly not high enough to be feasible for industrial purposes. However, a further investigation of the advanced oxidation process could optimise the process to yield even higher Cr liberation. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Orientador: Maria Valnice Boldrin Zanoni / Coorientador: Juliano Carvalho Cardoso / Banca: Paulo Clairmont Feitosa de Lima Gomes / Banca: Marcelo Ornaghi Orlandi / Banca: Romeu Cardozo Rocha Filho / Banca: Germano Tremiliosi Filho / Resumo: O esforço de tratar efluentes e águas superficiais contaminados por corantes tem sido intenso e uma das alternativas de interesse é a fotoeletrocatálise (FEC), baseada no uso de processos capazes de gerar radicais •OH, com grande potencial oxidante. O presente trabalho investiga a preparação, caracterização e aplicação de nanotubos de TiO2 (TiO2NTs) dopados com boro e modificados com Sb2S3 como ânodos no tratamento fotoeletrocatalítico de corantes de cabelo do tipo temporário. Tais modificações podem contornar limitações de filmes de óxido de titânio convencionais. Os eletrodos de nanotubos de TiO2 foram preparados por meio de anodização eletroquímica de placas de titânio metálico em eletrólitos contendo íon fluoreto. A deposição de nanopartículas de Sb2S3 foi realizada por meio da técnica de deposição por banho químico e a dopagem com boro por meio da adição de um precursor no eletrólito de anodização. Tais eletrodos foram caracterizados e aplicados na degradação fotoeletrocatalítica dos corantes Básico Vermelho 51 (BV51), Básico Azul 99 (BA99) e Ácido Amarelo 1 (AA1), escolhidos como modelos de corantes de cabelo para tal tratamento. Ambos os eletrodos mostraram eficiência de degradação significativamente superior à obtida para eletrodos não modificados, além de fotoativação na região do visível. Para contornar a limitação da FEC, que é a baixa eficiência em soluções altamente coloridas, foi investigada a combinação da FEC com ozonização no intuito de melhorar a eficiência ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Intense effort has been devoted to the treatment of effluents and surface water contaminated by dyes, and one of the alternatives of interest is the photoelectrocatalysis (PEC), based on the use of processes capable of generating • OH radicals, with great o xidizing potential. The present work investigates the preparation, characterization and application of TiO 2 nanotubes (TiO 2 NTs), doped with boron and modified with Sb 2 S 3, as anodes in the photoelectrocatalytic treatment of hair dyes of the temporary type. Such modifications could circumvent limitations of conventional TiO 2 oxide films. The TiO 2 nanotubes electrodes were prepared by electrochemical anodization of metallic titanium plates in fluoride - containing electrolytes. The deposition of nanoparticles of Sb 2 S 3 was carried out by chemical bath deposition technique and the doping with boron was done by the addition of a boron precursor in the anodizing electrolyte. These electrodes were characterized and applied in the photoelectrocatalytic degradation of B asic Red 51 ( BV51 ), Basic Blue 99 ( BA99 ) and Acid Yellow 1 ( AA1 ) dyes, chosen as models of hair dyes for treatment. Both electrodes promoted degradation efficiency significantly higher than that obtained for unmodified electrodes, in addition to the photoactivation in the visible region. To circumvent PEC limitation, which is the low efficiency in highly colored solutions, the combination of PEC technique with ozonation was investigated in order to improve the treatment efficiency of the AA1 dye in higher concentration and in the treatment of effluents resulting from h air dyeing. The combined method was the most efficient among those tested and the simple application of a voltage (O3 + FEC) greatly increases the decolorization rate (2×), decreases the time required for mineralization and the consumption of 'electric ene rgy per order' compared to an... / Doutor

Espécies de microalgas como Chlorella sorokiniana têm sido investigadas para as mais variadas aplicações como biocombustíveis, nutrição e a recuperação de nutrientes. Entretanto, a separação de microalgas do meio líquido permanece um desafio tanto técnico quanto econômico. O objetivo deste trabalho é propor e investigar a utilização de pré-ozonização e flotação por ar dissolvido para a separação sólido-líquido de Chlorella sorokiniana cultivada em meio padrão M8a em fotobiorreator flat panel, utilizando polímero catiônico à base de poliacrilamida como coagulante. Primeiramente, foi avaliado o sistema de tratamento com flotação por ar dissolvido, que foi otimizada em escala de laboratório visando eficiência de remoção de algas e flexibilização do sistema. Utilizando dosagens de polímero catiônico de 10 mg L-1 obteve-se remoções de cor aparente, turbidez e densidade óptica próximas de 95 % em pH 7. Posteriormente, a etapa de mistura lenta foi retirada do sistema, a razão de recirculação foi diminuída de 10 para 4 % e após essas alterações, obteve-se remoção de microalgas acima de 90 % para dosagem de polímero de 10 mg L-1. Para analisar o efeito da pré-ozonização a dosagem de polímero catiônico foi reduzida para 7 mg L-1, e observou-se que com FAD esta dosagem removeu 81,12 % de turbidez, e após pré-ozonização por 5 minutos seguida de FAD a eficiência de remoção de turbidez chegou a 91,78 % e remoção de cor aparente aumentou 6,25 %. A utilização da pré-ozonização permitiu utilização de velocidades de flotação da ordem de 24 cm min-1 sem prejuízo da eficiência de remoção de cor, turbidez e densidade óptica. Observou-se que a pré-ozonização demonstra efeitos positivos no sistema de tratamento, mas constatou-se uma dosagem ótima de ozônio, e que a partir desta dosagem a eficiência do tratamento pode ser prejudicada. Foi constatado que uma possível explicação para esse fato seja a liberação de matéria orgânica algal após pré-ozonização, em dosagens acima do valor ótimo de dosagem de ozônio. / Microalgal species as Chlorella sorokiniana have been investigated for a variety of applications such as biofuels, nutrition and nutrient recovery. However, the solid-liquid separation microalgae of the liquid medium remains a challenge both technical as economical. This work aims to propose and investigate the use of preozonation and dissolved air flotation for solid liquid separation of Chlorella sorokiniana cultivated in standard M8a medium in a flat panel photobioreator, using cationic polyacrylamide based polymer as coagulant. Initially, treatment system including dissolved air flotation was evaluated, which was optimezed at laboratory scale targeting removal efficiency of microalgae and system flexibility. Using cationic polymer dosage of 10 mg L-1, were obtained apparent color, turbidity and optical density removals nearly to 95% in pH 7. Further, the step of slow mixing was removed from the system, the recycle ratio was decreased from 10 to 4% and after these changes, was obtained microalgae removal over 90% at polymer dosage of 10 mg L-1. To analyse the effect of preozonation, cationic polymer dosage was decreased to 7 mg L-1, and was observed 81.12 % turbidity removal with this polymer dosage at FAD, and after 5 minutes preozonation followed by FAD, turbidity removal efficiency reached 91.8 % and apparent color removal increased 6.25 %. The utilization of preozonation allowed use of flotation velocities in the order of 24 cm min-1 without damaging variables removal efficiency. It was observed tha preozonation shows positive effects in treatment system, but was found an optimum ozone dosage from which the treatment efficiency is hampered. It was observed that a possible explanation to this fact is the release of algogenic organic matter after preozonation in dosages over the optimum value of ozone dosage.

Ozonation is currently considered as one of the most effective microbial disinfection technologies due to its powerful disinfection capacity and reduction in levels of chlorinated disinfection by-products (DBP). However, ozonation of waters containing bromide can produce bromate ion above regulated levels, leading to tradeoffs between microbial and chemical risks. In efforts to meet increasingly stringent drinking water regulations and to be cost-effective, water suppliers are required to optimize ozone dosage. Therefore, there is a need to develop a robust and flexible tool to accurately describe ozone disinfection processes and contribute to their design and operation. Computational fluid dynamics (CFD) has come into use recently for evaluating disinfection systems. However, the focus of its application has been largely on modelling the hydraulic behaviour of contactors, which is only one component of system design. The significance of this dissertation is that a fully comprehensive three dimensional (3D) multiphase CFD model has been developed to address all the major components of ozone disinfection processes: contactor hydraulics, ozone mass transfer, ozone decay, and microbial inactivation. The model was validated using full-scale experimental data, including tracer test results and ozone profiles from full-scale ozone contactors in two Canadian drinking water treatment plants (WTPs): the DesBaillets WTP in Montréal, Quebec and the Mannheim WTP in Kitchener, Ontario. Good agreement was observed between the numerical simulation and experimental data. The CFD model was applied to investigate ozone contactor performance at the DesBaillets WTP. The CFD-predicted flow fields showed that recirculation zones and short circuiting existed in the DesBaillets contactors. The simulation results suggested that additional baffles could be installed to increase the residence time and improve disinfection efficiency. The CFD model was also used to simulate ozone contactor performance at the Mannheim Water Treatment Plant before and after installing new liquid oxygen (LOX) ozone generators and removing some diffusers from the system. The modelling results indicated that such changes led to an increase in effective residence time, and therefore an adjustment to operational parameters was required after system modification. Another significant contribution is that, for the first time, the Eulerian and Lagrangian (or particle tracking) approaches, two commonly utilized methods for predicting microbial inactivation efficiency have been compared for the study of ozone disinfection processes. The modelling results of two hypothetical ozone reactors and a full scale contactor suggested that the effective CT values predicted by the Lagriangian approach were slightly lower than those obtained from the Eulerian approach but their differences were within 10%. Therefore, both approaches can be used to predict ozone disinfection efficiency. For the full scale contactor investigated, the tracer residence time distribution predicted by the Euerlian approach provided a better fit to the experimental results, which indicated that the Eulerian approach might be more suitable for the simulation of chemical tracer performance. The results of this part of work provided important insight in understanding the complex performance of multiphase ozonation systems and played an important role in further improving CFD modelling approaches for full-scale ozone disinfection systems. The third significant contribution of this work is that a CFD model was applied to illustrate the importance of ozone residual monitoring locations and suggest an improved strategy for ozone residual monitoring. For the DesBaillets ozone contactors, the CFD modelling results showed that ozone residuals in the cross section of the outlets of some contactor chambers differed by an order of magnitude. The “optimal” area of monitoring locations however varied at different operational conditions. Therefore, it was suggested that multiple ozone residual sampling points should be installed based on CFD analysis and experimental studies, to provide more accurate indicators to system operators. The CFD model was also used to study the factors affecting the residence time distribution (RTD). The results suggested that the selection of the tracer injection locations as well as tracer sampling locations might affect the RTD prediction or measurement. The CFD-predicted T10 values at different outlet locations varied by more than 10% variation. It is therefore recommended that CFD modelling be used to determine tracer test strategy before conducting a full-scale tracer test, and multiple sampling points should be employed during tracer tests, if possible. In addition, a research based on full-scale investigation has also been done to compare the three different CT prediction approaches: CT10, integrated disinfection design framework (IDDF), and CFD, to determine the most appropriate method for design and operation of ozone systems. The CFD approach yielded more accurate predictions of inactivation efficacy than the other two approaches. The current results also suggested that the differences in the three approaches in CT predictions became smaller at higher contactor T10/T ratios conditions as the contactors performed more closely to ideal plug flow reactors. This study has demonstrated that the computational fluid dynamics (CFD) approach is an efficient tool for improving ozone disinfection performance of existing water treatment plants and designing new ozonation systems. The model developed in this study can be used for ozone contactor design, evaluation, and troubleshooting. It can also be used as a virtual experimental tool to optimize ozone contactor behaviour under varying water quality and operational conditions.

Ozonation is currently considered as one of the most effective microbial disinfection technologies due to its powerful disinfection capacity and reduction in levels of chlorinated disinfection by-products (DBP). However, ozonation of waters containing bromide can produce bromate ion above regulated levels, leading to tradeoffs between microbial and chemical risks. In efforts to meet increasingly stringent drinking water regulations and to be cost-effective, water suppliers are required to optimize ozone dosage. Therefore, there is a need to develop a robust and flexible tool to accurately describe ozone disinfection processes and contribute to their design and operation. Computational fluid dynamics (CFD) has come into use recently for evaluating disinfection systems. However, the focus of its application has been largely on modelling the hydraulic behaviour of contactors, which is only one component of system design. The significance of this dissertation is that a fully comprehensive three dimensional (3D) multiphase CFD model has been developed to address all the major components of ozone disinfection processes: contactor hydraulics, ozone mass transfer, ozone decay, and microbial inactivation. The model was validated using full-scale experimental data, including tracer test results and ozone profiles from full-scale ozone contactors in two Canadian drinking water treatment plants (WTPs): the DesBaillets WTP in Montréal, Quebec and the Mannheim WTP in Kitchener, Ontario. Good agreement was observed between the numerical simulation and experimental data. The CFD model was applied to investigate ozone contactor performance at the DesBaillets WTP. The CFD-predicted flow fields showed that recirculation zones and short circuiting existed in the DesBaillets contactors. The simulation results suggested that additional baffles could be installed to increase the residence time and improve disinfection efficiency. The CFD model was also used to simulate ozone contactor performance at the Mannheim Water Treatment Plant before and after installing new liquid oxygen (LOX) ozone generators and removing some diffusers from the system. The modelling results indicated that such changes led to an increase in effective residence time, and therefore an adjustment to operational parameters was required after system modification. Another significant contribution is that, for the first time, the Eulerian and Lagrangian (or particle tracking) approaches, two commonly utilized methods for predicting microbial inactivation efficiency have been compared for the study of ozone disinfection processes. The modelling results of two hypothetical ozone reactors and a full scale contactor suggested that the effective CT values predicted by the Lagriangian approach were slightly lower than those obtained from the Eulerian approach but their differences were within 10%. Therefore, both approaches can be used to predict ozone disinfection efficiency. For the full scale contactor investigated, the tracer residence time distribution predicted by the Euerlian approach provided a better fit to the experimental results, which indicated that the Eulerian approach might be more suitable for the simulation of chemical tracer performance. The results of this part of work provided important insight in understanding the complex performance of multiphase ozonation systems and played an important role in further improving CFD modelling approaches for full-scale ozone disinfection systems. The third significant contribution of this work is that a CFD model was applied to illustrate the importance of ozone residual monitoring locations and suggest an improved strategy for ozone residual monitoring. For the DesBaillets ozone contactors, the CFD modelling results showed that ozone residuals in the cross section of the outlets of some contactor chambers differed by an order of magnitude. The “optimal” area of monitoring locations however varied at different operational conditions. Therefore, it was suggested that multiple ozone residual sampling points should be installed based on CFD analysis and experimental studies, to provide more accurate indicators to system operators. The CFD model was also used to study the factors affecting the residence time distribution (RTD). The results suggested that the selection of the tracer injection locations as well as tracer sampling locations might affect the RTD prediction or measurement. The CFD-predicted T10 values at different outlet locations varied by more than 10% variation. It is therefore recommended that CFD modelling be used to determine tracer test strategy before conducting a full-scale tracer test, and multiple sampling points should be employed during tracer tests, if possible. In addition, a research based on full-scale investigation has also been done to compare the three different CT prediction approaches: CT10, integrated disinfection design framework (IDDF), and CFD, to determine the most appropriate method for design and operation of ozone systems. The CFD approach yielded more accurate predictions of inactivation efficacy than the other two approaches. The current results also suggested that the differences in the three approaches in CT predictions became smaller at higher contactor T10/T ratios conditions as the contactors performed more closely to ideal plug flow reactors. This study has demonstrated that the computational fluid dynamics (CFD) approach is an efficient tool for improving ozone disinfection performance of existing water treatment plants and designing new ozonation systems. The model developed in this study can be used for ozone contactor design, evaluation, and troubleshooting. It can also be used as a virtual experimental tool to optimize ozone contactor behaviour under varying water quality and operational conditions.