No / Extracting waterborne contaminants to ozone-loaded Volasil¿245 (a siloxane solvent in which ozone is ten times more soluble than water) has been studied as a means of enhancing reaction kinetics and thus, providing more rapid wastewater decontamination. Investigation was carried out with respect to 2-chlorophenol and dichloromethane. Using a pilot scale continuous flow liquid¿liquid/ozone water treatment system, 2-chlorophenol was extracted to the ozone-loaded solvent phase and considerable extents of destruction were achieved. However, the approach was demonstrated to yield slightly less destruction than direct gas contact for the same utilization of ozone and enhanced reaction kinetics were not shown to occur. This was suggested to be due to increased interfacial mass transfer resistance and/or the promotion of less destructive reaction pathways. Modification of the existing pilot system, by conversion from co- to counter-current solvent-loading, enabled greater dissolved ozone concentrations to be achieved within the solvent. Increasing the counter-current exchange column height to not, vert, similar2.5 m was suggested for achieving a near optimum level of performance. The liquid¿liquid/ozone approach was demonstrated to be an effective means of indirectly exposing wastewater contaminants to concentrated ozone. As such the technology may be applicable as an alternative to direct gas contact in instances where the avoidance of contaminant sparging is desired (i.e. where contaminants are highly volatile, pungent and/or toxic) or foaming occurs

In this master thesis project, the removal of micro-pollutants (MPs) from water and wastewater were investigated by ozonation and the peroxone process O3/H2O2. Themain aim of the study was to compare the degradation efficiency of the two processes for a selection of organic biocides and active pharmaceutical ingredients (APIs) in wastewater and synthetic water. Synthetic water and wastewater effluent were spiked with fifteen compounds including twelve biocides and three APIs and samples were taken at different time points to determine degradation kinetics in treatment by the two processes, respectively. Most of the biocides tested in this study showed moderately reactivity, or were non-reactive, with O3 (e.g., Carbendazim, 1H-Benzotriazole, 1, 2-Benzisothiazol-3(2H)-one, 2, 4-Dinitrophenol, 4-nitrophenol) and some of the biocides and APIs were readily reactive with ozone (O3) and were removed from the water by direct O3 oxidationduring both processes. Trimethoprim was found to be an ozone reactive micropollutants and showed highest reactivity with O3. In the abatement mechanism, these micro-pollutants are removed based on the ozone-based processes and with hydroxyl radical •OH in peroxone process. Comparing the two processes, the peroxone process showed highest percentage removal of compounds (90-100%) within moderate time periods (30 s - 2 min) in synthetic water and (30 s to 10 min) in wastewater. The results revealed that the peroxone process showed highest removal efficiency and with higher reproducibility. Further, generally

La thèse a porté principalement sur la mise en œuvre de procédés d'oxydation avancée permettant l'élimination de trois anti-inflammatoires non stéroïdiens, le kétoprofène, le naproxène et le piroxicam dans l'eau. Ces trois composés sont parmi les médicaments les plus utilisés, dont la présence dans les eaux naturelles présente potentiellement un risque toxicologique. En raison de la faible efficacité d'élimination des produits pharmaceutiques par les stations traditionnels de traitement des eaux usées, les scientifiques se sont mis à la recherche de technologies de traitements efficaces et respectueuses de l'environnement. Les procédés d'oxydation avancée, comme l'ozonation-biofiltration, l'électro-Fenton et l'oxydation anodique peuvent permettre d'atteindre la destruction presque complète des polluants étudiés et de ce fait ils ont suscité un intérêt grandissant au cours des deux dernières décennies. Tout d'abord, ce travail s'intéresse à l'élimination de certains produits pharmaceutiques dans des solutions synthétiques préparées dans l'eau de robinet à l'aide des procédés électro-Fenton et oxydation anodique dans une cellule électrochimique équipée d'une anode de platine ou de diamant dopé au bore et d'une cathode de feutre de carbone. Cette étude a été menée à l'échelle du laboratoire. Les vitesses d'élimination des molécules pharmaceutiques ainsi que le degré de minéralisation des solutions étudiées ont été déterminées sous différentes conditions opératoires. Pendant ce temps, les sous-produits de l'oxidation générés au cours de la minéralisation ont également été identifiés, ce qui nous a permis de proposer les voies d'oxydation possible pour chaque composé pharmaceutique en présence du radical hydroxyl •OH. Enfin, l'évolution de la toxicité au cours des traitements a été suivie en utilisant la méthode Microtox, basée sur l'inhibition de la fluorescence des bactéries Vibrio fischeri. Dans la deuxième partie de ce travail de thèse, les trois anti-inflammatoires non stéroïdiens ont été ajoutés dans une eau déminéralisée ou dans une eau de surface. Ces eaux ont été traitées à l'aide de différentes doses d'ozone; puis le traitement à l'ozone à été combiné à un traitement biologique par biofiltration. Un biofilm biologique déposé à la surface d'un filtre de charbon actif a été utilisé pour déterminer la biodégradabilité des sous-produits d'oxydation formés dans les eaux de surface ozonée. L'identification des intermédiaires formés lors des processus de traitement et des contrôles de toxicité bactérienne ont été menées pour évaluer la voie de dégradation des produits pharmaceutiques et des effets biologiques potentiels, respectivement / The thesis mainly focused on the implementation of advanced oxidation processes for the elimination of three non-steroidal anti-inflammatory drugs-ketoprofen, naproxen and piroxicam in waters. The three compounds are among the most used medicines, whose presence in waters poses a potential ecotoxicological risk. Due to the low pharmaceuticals removal efficiency of traditional wastwater treatement plants, worldwide concerns and calls are raised for efficient and eco-friendly technologies. Advanced oxidation processes, such as ozonation-biofiltration, electro-Fenton and anodic oxidation processes, which attracted a growing interest over the last two decades, could achieve almost complete destruction of the pollutants studied. Firstly, removal of selected pharmaceuticals from tap water was investigated by electrochemical advanced oxidation processes “electro-Fenton” and “anodic oxidation” with Pt or boron-doped diamond anode and carbon felt cathode at lab-scale. Removal rates and minieralization current efficencies under different operatioanl conditions were analysed. Meanwhile, intermediates produced during the mineralization were also identified, which helps to propose plausible oxidation pathway of each compound in presence of •OH. Finally, the evolution of the global toxicity of treated solutions was monitored using Microtox method, based on the fluorescence inhibition of Vibrio fischeri bacteria. In the second part, the three nonsteroidal anti-inflammatory molecules added in organics-free or surface water were treated under varying ozone treatment regimes with the quite well established technology ozone/biofiltration. A bench-scale biological film was employed to determine the biodegradability of chemical intermediates formed in ozonized surface water. Identification of intermediates formed during the processes and bacterial toxicity monitoring were conducted to assess the pharmaceuticals degradation pathway and potential biological effects, respectively

Le travail de la thèse se focalise sur le traitement de l'air chargé en composés organiques volatils (COV) par un procédé d'ozonation avancée sur les zéolithes. Le procédé est basé sur la combinaison de deux techniques, utilisées de manière séquentielle : l'adsorption des COV sur un lit de zéolithes puis la régénération du lit saturé par ozonation. Avant d'étudier leur performance sur l'adsorption puis l'ozonation, les zéolithes ont été caractérisées par l'adsorption à l’azote, par spectroscopie Infra Rouge et par microscopie électronique. La concentration des sites acides de Lewis et de Brønsted ont également été quantifiées. Les interactions binaires entre le toluène et les zéolithes, puis entre l'ozone et les zéolithes sont étudiées. Les équilibres d'adsorption et les courbes de percées sur les différentes zéolithes sont déterminés expérimentalement, puis modélisés. La réactivité de l'ozone sur les zéolithes a été clarifiée, mettant en évidence la décomposition de l'ozone et la création d’espèces oxygénées oxydantes, adsorbées à la surface. L'influence de la concentration en sites acides de Lewis sur la décomposition de l’ozone a été discutée. Enfin, la régénération des adsorbants chargés en COV par l'ozone gazeux a été réalisée. L'influence des propriétés des zéolithes et des conditions opératoires ont été étudiées. / The PhD work focuses on the treatment of Organic Volatile Compound polluted air by an advanced ozonation process on hydrophobic zeolites. The process is based on two steps: gaseous pollutants are firstly adsorbed on zeolite bed; the second step is the regeneration of zeolites charged of COV by gaseous ozone. Firstly, zeolites are characterized by Nitrogen adsorption, analysis of Lewis and Brønsted acid sites, Infrared spectroscopy and Scanning Electron Microscopy. The adsorption equilibrium and breakthrough curve of toluene on different kind of zeolites are determined experimentally and modelled. The study of the reactivity of ozone on fresh zeolites shows that ozone is mainly decomposed on its surface and stable surface oxygenated species are produced. The latter can react with organic pollutant. The influence of Lewis acid site and operating conditions are discussed. Finally, the oxidation by ozone of toluene adsorbed on zeolites is realised. The comparison of zeolite structure and operating conditions (Air humidity, inlet ozone concentration) are carried out.

Treatment of textile wastewaters containing dye materials using the conventional methods based on biological treatment is not possible. In order to overcome this problem, ozonation based on the oxidation of organic pollutants with ozone gas dissolved in aqueous phase have been studied widely. Catalytic ozonation and advanced oxidation processes (AOP) are also used in order to increase the efficiency of sole ozonation In this work, catalytic ozonation processes in the presence of Copper Sulfide (CuS) powder and a synthesized catalyst by the impregnation of iron on alumina (Fe/Al2O3) were studied separately in the treatment of dye solutions, namely Remazol Brilliant Blue-R (RBBR) and Reactive Black-5 (RB-5). Besides catalytic ozonation runs, ozonation parameters and ozonation mechanism were also studied and a model was developed for the semi-batch ozonation. Both catalysts increased the oxidation of side products measured by the decrease in the amount of total organic carbon (TOC) in the treated dye solutions. Dye removal rates were also enhanced in the treatment of RB-5 dye solutions while no significant effect was observed on dye removal rates of RBBR solutions. TOC removals above 90% were observed in the catalytic ozonation using CuS for both of the dye solutions at pH =10 having initial dye concentration of 100 mg/L. The most significant effect of the catalyst addition was observed at pH = 3 where the TOC removals of non-catalytic ozonation were the lowest. CuS addition increased percent TOC removal at the end of the reaction period of 80 min by 123% in the treatment of 100 mg/L RBBR solution, and by 65% in the treatment of 100 mg/L RB-5 solution at pH = 3. On the other hand, addition of Fe/Al2O3 catalyst increased TOC removal of 100 mg/L RB-5 solution by 52 % at pH = 3. In addition, volumetric mass transfer coefficients (kLa) of ozone in the absence and in the presence of a chemical reaction between dye and ozone were estimated from modeling. A correlation for the enhancement factor of ozone absorbed into dye solutions in terms of initial dye concentration was obtained and reported.

Le principal objectif de la thèse est l'optimisation d'un procédé d'oxydation avancée par la mise en œuvre des outils de l'automatique moderne.Le procédé considéré concerne l'ozonation catalytique utilisé pour traiter les eaux résiduaires industrielles. L'optimisation de ce procédé consiste à contrôler l'abattement des polluants tout en minimisant le coût de fonctionnement du procédé. La mesure en ligne de la concentration en polluant est fournie par l'absorbance, grandeur corrélée à la DCO. Le procédé est alors considéré comme un système à une entrée, la puissance du générateur d'ozone, et deux sorties, l'ozone dans les évents et l'absorbance.L'identification du procédé a mené à l'estimation d'un modèle linéaire pour construire les lois de commande et d'un modèle non-linéaire, de type modèle de Wiener, pour tester les correcteurs en simulation avant les essais expérimentaux.Les trois commandes testées, la commande par modèle interne, la commande optimale et la commande H∞, permettent de rejeter des perturbations sur la concentration en polluant dans les effluents à traiter. Des analyses de stabilité du système bouclé, vis-à-vis de retards sur la commande, ont été menées.Les résultats expérimentaux obtenus ont permis de conclure sur les gains significatifs apportés par ces développements.La méthodologie développée pour cette application peut être étendue à d'autres procédés afin de faciliter le développement industriel des procédés d'oxydation avancée. / The main goal of the PhD thesis focuses on the optimization of an advanced oxidation process by implementing the modern control tools.The considered process is a lab-scale pilot of industrial wastewater treatment by catalytic ozonation. The optimization of this process is achieved by controlling the pollutant abatement while minimizing the high operating costs. The online measurement of the pollutant concentration is provided by the absorbance which is correlated with COD. Therefore, the process is considered as a system with one input, the ozone generator power, and two outputs, the ozone gas concentration at the top of the reactor and the absorbance.A linear model of the process was identified. It allowed calculating the control laws. And a nonlinear model, with a so-called Wiener model structure, was also identified to test the controllers in simulation before the experiments.The three control methods applied, the internal model control, the optimal control and the H∞ control, allow rejecting disturbance on the pollutant concentration of the effluent to be treated.The stability of closed-loop system with delayed control input was analyzed.The experimental results show the significant benefits provided by this closed-loop system.The methodology developed for this application can be extended to other processes to facilitate the industrial development of advanced oxidation processes.

L’objectif de ce travail a été d’étudier la présence, le devenir et le traitement de biocides dans les rejets d’un établissement hospitalier. Pour cela, 3 substances biocides, représentatives d’une activité de soins (i.e. didécylmethylammonium (DDAC), digluconate de chlorhexidine (CHD) et bis(aminopropryl)laurylamine (BAPLA)) ont été ciblées et 5 campagnes de prélèvements réalisées sur l’ensemble du réseau de collecte des eaux usées du CHU de Poitiers ont été menées. Dans ces conditions, une émission continue de biocides sur 24 h, avec des quantités rejetées en journée plus importantes du fait de la plus forte activité de soins et de nettoyage durant cette période a été montrée. Des concentrations de l’ordre de quelques mg/L pour le DDAC et de quelques dizaines de µg/L pour le CHD et le BAPLA ont été observées. En termes de flux massiques, la comparaison des quantités retrouvées dans les rejets aux quantités utilisées par le CHU a permis de préciser la nature des sources d’émission ainsi que les usages et/ou les pratiques les plus propices à ces rejets.Parallèlement, une étude laboratoire de la stabilité et du devenir des biocides dans les eaux résiduaires a été menée. Une première estimation des quantités adsorbées sur les matières en suspension a été obtenue. De même, les produits de dégradation susceptibles d’être générés lors du rejet de biocides en présence d’un résiduel de chlore ont été identifiés et l’évolution de l’écotoxicité vis-à-vis de Vibrio fisheri a été évaluée.Enfin, la possibilité d’un traitement à la source utilisant l’ozone pour limiter les rejets de biocides a été envisagée et une étude pilote sur le terrain a été menée. / The objectives of this study was to study the presence, the fate and the treatment of some biocides in the wastewaters from a hospital. 3 biocidal substances specific to healthcare activities (i.e. didecylmethylammonium chloride (DDAC), chlorhexidine digluconate (CHD) and bis(aminopropryl)laurylamine (BAPLA)) were selected and 5 sampling campaigns were conducted throughout the entire Poitiers University Hospital sewage system. Under these conditions, a continuous biocide discharges over 24 h was shown, with higher quantities discharged during the day. This was pointing out the greater healthcare and facility cleaning activities taking place during this period. Concentrations of a few mg/L for DDAC and a few dozens of µg/L for CHD and BAPLA were detected. In terms of mass flows, the comparison of the quantities found in the discharges with the quantities used by the university hospital made it possible to specify the nature of the sources of emission as well as the uses and / or the practices most favorable to these discharges.In parallel, a laboratory study of the stability and fate of biocides in wastewater was conducted. A first estimate of the amounts adsorbed on suspended solids was obtained. Similarly, the degradation products likely to be generated during the release of biocides in the presence of a chlorine residual have been identified and the evolution of the ecotoxicity towards Vibrio fisheri has been evaluated.Finally, the proposal of an ozone based treatment at source was carried out to limit biocide discharges and a pilot study was conducted on the hospital wastewaters.

The Chlorine-Ammonia Process was developed recently as a preoxidation process to minimize the formation of bromate during ozonation of the waters containing a significant bromide concentration. Chlorine is added first, followed by ammonia 5-10 minutes later, with the goal of sequestering bromide in monobromamine before the subsequent ozonation step. The goal of this research was to improve the Chlorine-Ammonia Process by introducing a very short prechlorination step (i.e., 30 seconds before addition of ammonia) to minimize overall disinfection by-product formation. Also, in this strategy, formation of a powerful halogenating agent, HOBr, is minimized and bromochloramine (NHBrCl) is used predominantly instead of monobromamine to sequester bromide during ozonation. To support this improved approach to bromide sequestration, this study examined the formation and decay of bromochloramine as a function of operating conditions, such as pH and Cl2/N ratio, and refined a chemical kinetic model to predict haloamine concentrations over time. Two natural organic matter (NOM) sources were used in this study (Lake Austin, Texas and Claremore Lake, Oklahoma) to study the effect of NOM on monochloramine and total chlorine decay after 30 seconds of prechlorination. The rate of the reaction between haloamines and fast and slow sites on the NOM was estimated. A kinetics model was developed to model total chlorine decay after a short prechlorination time. The model is based on the Unified Haloamine Kinetic Model developed by Pope (2006). Pope`s model failed to model the initial monochloramine concentration after 30 seconds prechlorination time as well as the monochloramine and total chlorine decay over time. The modified model shows an excellent prediction of monochloramine and total chlorine decay after 30 seconds prechlorination time at pH range of 6.5-8.0 and over a carbonate buffer concentration range of 2-10 mM. The model includes a new bromochloramine decay scheme via the reaction with monochloramine and with itself. In addition, new rate constants for the reaction of HOCl with bromide ion and reaction of HOBr with monochloramine were added. The hypobromous acid formation rate was found to be an acid-catalyzed reaction, which confirms the finding of Kumar et al. (1987). A new value of the acid catalysis effect of hydrogen ion was estimated. New terms were introduced to the hyprobromous acid formation rate including the acid catalysis effect of bicarbonate, carbonic acid, and ammonium ion. In addition, the reaction of HOBr with monochloramine to form bromochloramine was found to be an acid-catalyzed reaction, and a new value of the rate constant was estimated. / text

<p>Syftet med examensarbetet var att undersöka effekterna av ozonering och filtrering på råvattnet från sjön Mälaren. Studien är utförd i en pilotanläggning på Lovö vattenverk, Stockholm Vatten AB, under våren 2004.</p><p>En negativ effekt med den konventionella reningen är den stora konsumtionen av kemiska koagulanter. Kemikalieanvändningen leder till många transporter och processen producerar också ett slam som för närvarande transporteras till Mälaren. År 2001 byggdes en pilotanläggning på Lovö vattenverk för utveckling av nya processer, en av processerna är ozonering följt av olika filter.</p><p>Ozonering har använts i Europa i många år som desinfektion i slutet av dricksvattenreningsprocessen. Intresset för ozonering har ökat markant sista åren och idag används ozonet också i andra steg i processen. Förutom desinfektion har ozonet andra fördelar, som oxidation av järn och magnesium, mikroflockning, reduktion av lukt och smak samt är bra på att reducera färgen på vattnet. Mikroflockningen leder till att kemikalieanvändningen kan minska och i vissa fall tas bort helt.</p><p>Den här studien startade med en litteraturundersökning följd av försök med ozonering och filtrering i pilotanläggningen. De första undersökningarna sammanfattades med att ozonering följt av filtrering inte gav tillräckligt bra resultat och processen behöver ett komplement för att producera ett högklassigt vatten.</p><p>Undersökningen fortsatte med laboratorieanalyser för att undersöka effekterna av olika kemiska koagulanter. Resultatet visade att järnsulfat tillsammans med kalcium var ett bra alternativ och en lägre kemikaliedos kunde användas.</p><p>Efter implementering av kalcium och järnsulfat till pilotanläggningen testades olika ozondoser och olika järnsulfatdoser. Det bästa resultatet erhölls då man använde sig av en ozondos på 6 mg O3/l och en järnsulfatdos på 50-60 μmol/l. Denna mängd av järnsulfat är ca 60 % lägre än den dos som används vid den konventionella reningen på Lovö vattenverk.</p><p>Olika filter används i pilotanläggningen och för att förbättra resultatet provades även ett Filtralite-filter som biofilter istället för GAC-filtret. Jämförelsen mellan Filtralite-filter och GAC-filter visade på stora skillnader i parametervärden i början av studietiden. När bakteriepopulationen ökade i Filtralite-filtret blev skillnaderna mindre och i slutet av undersökningstiden var parametervärdena likartade. Det slutliga resultatet indikerar att Filtralite-filter kan vara ett bra alternativ som biofilter.</p> / <p>This Master thesis was made to investigate the effects of ozonation and filtration on raw water from Lake Mälaren. The study was performed in lab-scale as well as in a pilot plant at Lovö waterworks, Stockholm Water Company during spring 2004.</p><p>The conventional treatment at Lovö waterworks comes with a few disadvantages, such as large consumption of chemical coagulants. The chemical consumption leads to many transports and the treatment also produces a sludge which is, in present, returned to Lake Mälaren. In 2001 a pilot plant were built at Lovö waterworks for research on new treatment processes, and ozonation followed by filtration is one of them.</p><p>Ozonation has been used in Europe for several years as disinfection at the end of the drinking water treatment process. The interests of ozonation has increased significantly in recent years and today the ozonation is used in other steps in the drinking water treatment process. Except for the disinfection, ozone has other benefits such as oxidation of iron and manganese, microflocculation, reduction of taste and odour and it is also effective to reduce the water colour. The microflocculation leads to the fact that less or no coagulants need to be used in the process.</p><p>This study started with a literature overview followed by experiments on ozonation and filtration in the pilot plant. After the first experiments the conclusions were that the ozonation and filtration did not reach the same results as Lovö waterworks. To continue, jar tests were made to see the effects of different coagulants. The result indicated that ferric sulphate together with calcium addition (pH-adjustment) was a good alternative. Thereby a lower coagulant dose could be used.</p><p>When ferric sulphate and calcium were implemented into the pilot plant, different ozone doses and ferric sulphate doses were tested. The best results occurred when an ozone dose of 6 mg O3/l and a ferric sulphate dose of 50-60 μmol/l were used. This amount of ferric sulphate is approximately 60 % lower than that for the conventional treatment at Lovö waterworks. To produce ozone electrons are needed and energy consumption increases with approximately 66 % compared to the conventional treatment. The decrease in chemical dose and increase in energy demand gives a decrease of the total cost with 10 % compared to the conventional treatment. The results indicate that the treatment with ozonation, calcium addition and ferric sulphate as a coagulant is an alternative to the conventional treatment.</p><p>Different filters were used in the pilot plant and to improve the results a Filtralite-filter was tested instead of the GAC-filter as a bio filter. When comparing Filtralite-filter with the GAC-filter there were large differences between the filters at the beginning of the study. When the bacteria population in the Filtralite-filter had started to increase the differences became less. In the end of the experimental period the filters had similar conditions and Filtralite-filter may be a good alternative as a biofilter.</p>

Ultrafine bubbles, often referred to as nanobubbles, have been used in various applications from environmental remediation to medicine. Even though the technology to generate ultrafine bubbles has been around for many years, the full potential of its applications has not been completely studied. This project seeks to study the use of ultrafine bubble technology for water treatment in combination with ozone gas. A factorial design experiment was chosen to test the effects of ultrafine bubbles on the concentration of an indicator organism, E. coli, in water as well as their effects on ozone gas being injected into water. Ozone gas or nitrogen gas was injected into water contaminated with E. coli as either ultrafine bubbles or fine bubbles as treatments for up to 60 minutes. Ultrafine bubbles were found to not have any significant effect on the concentration of E. coli in water. However, ultrafine bubbles did provide benefits when used in conjunction with ozone gas that regular, fine bubbles did not provide. The benefits included allowing the concentration of dissolved ozone in the water to decrease at a slower rate as well as allowing more ozone to dissolve into water at a higher rate than conventional methods of bubbling in ozone. While in this particular set of experiments the concentration of dissolved ozone in water didn't surpass 2 mg/L, which didn't allow for rapid disinfection and treatment of water, it is believed that with a more powerful ozone generator better results can be achieved. This project demonstrates the benefits and potential of injecting ozone gas as ultrafine bubbles into water as a way to effectively and efficiently disinfect and treat water.