Suspended titanium dioxide (TiO2) nanoparticles produce hydroxyl radicals (•OH) that synergistically aid in disinfection when irradiated with UV light. To exploit the benefits of TiO2 photocatalysis without having to remove them, TiO2 was deposited onto 3M Company’s nanostructured thin film (NSTF). •OH production by suspended and TiO2-NSTF was determined by para-chlorobenzoic acid (pCBA), a •OH probe compound. Both techniques of introducing TiO2 to the samples produced equivalent •OH without forming bromate, a regulated byproduct in drinking water at all UV and TiO2 levels. Formation of bromate by ozone in brackish water and seawater were used to compare the disinfection byproduct (DBP) formation between the disinfection methods. Additionally, monitoring bromate, typically performed by ion chromatography, is complicated by chloride and other anions present in brackish water or seawater. Thus, a spectrophotometric method to measure bromate in saline systems is introduced.

Ozonation is an integral process in ozone-biofiltration treatment systems and is beginning to be widely adopted worldwide for water reuse applications. Ozone is effective for pathogenic inactivation and organics oxidation: both increasing assimilable organic carbon for biofiltration and eliminating trace organic contaminants which may pose a threat to human health. However, ozone can also form disinfection byproducts such as bromate from the oxidation of naturally occurring anion bromide. Bromate is a known human carcinogen and is regulated by the EU, WHO, and USEPA to a maximum limit of 10µg/L. In waters high in bromide, especially above 100µg/L, bromate formation becomes a major concern. In the secondary wastewater effluent studied, bromide concentration may exceed 500µg/L. Several bromate suppression techniques have been devised in previous work, including free ammonia addition, monochloramination, and the chlorine-ammonia process. While free ammonia addition was not found to adequately reduce bromate formation below the required MCL, monochloramine addition and the chlorine-ammonia process were found to be effective. However, the impact of these chemical suppression techniques on organics oxidation and disinfection has not been fully studied. This study explored the impact of these bromate suppression techniques at a wide range of ozone doses on bromate formation, pathogenic inactivation, ozone-refractory organics oxidation through the surrogate 1,4-dioxane, and N-nitrosodimethylamine (NDMA) formation. Additionally, bromate suppression mechanisms of monochloramine were explored further through a variety of different water quality parameters, such as through hydroxyl radical exposure and ultraviolet absorption spectrum measurements, which were correlated and utilized to develop a hydroxyl radical exposure predictive model. / Master of Science / Ozone is a powerful oxidant used in water treatment in order to degrade contaminants of emerging concern into less harmful moieties and to inactivate pathogens. Upon application to process water, ozone quickly reacts with constituents in the water to form hydroxyl radicals: the most powerful oxidant in water treatment. These hydroxyl radicals, though with extremely short half-lives, are able to degrade ozone-recalcitrant organics, such as 1,4-dioxane through a process called advanced oxidation. Ozone itself also has the capability of inactivating a multitude of pathogenic organisms, including viruses Giardia and Cryptosporidium parvum when specific contacts times are met. However, ozone does have the potential to form disinfection byproducts such as Nnitrosodimethylamine (NDMA) and bromate. NDMA, though not currently regulated by the United States’ Environmental Protection Agency (USEPA), has a drinking water health advisory limit of 10ng/L in the State of California. Bromate, on the other hand, is a known human carcinogen regulated to 10µg/L by the USEPA. Formed within the ozone system from the naturally occurring ion bromide, bromate can be limited through various chemical treatments such as ammonia addition, pH adjustment, monochloramination, and the chlorine-ammonia process. To date, these methods of bromate suppression have not been comprehensively studied in terms of bromate suppression as well as disinfection and organics oxidation in water reuse systems. The purpose of this research was to minimize bromate formation while ensuring NDMA formation was minimized, and disinfection and organics oxidation were maximized. Through this study, system efficiencies were improved and water quality for future generations will be improved.

A study was conducted to evaluate the sorption characteristics of six disinfection byproducts (DBPs) on four sorbents. To investigate sorption of volatile organic compounds (VOCs), specially designed experimental batch and continuous flow modules were developed. The investigated compounds included: chloroform, 1,2-dichloroethane (DCE), trichloroethylene (TCE), bromodichloromethane (BDCM), methyl tertiary butyl ether (MTBE), bromate and bromide ions. Sorbents used included light weight aggregate (LWA), an inorganic porous material with unique surface characteristics, Amberlite® XAD-16, a weakly basic anion exchange resin, Amberjet®, a strongly basic anion exchange resin, and granular activated carbon (GAC). Batch experiments were conducted on spiked Milli-Q® and lake water matrices. Results indicate considerable sorption of TCE (68.9%), slight sorption of bromate ions (19%) and no appreciable sorption for the other test compounds on LWA. The sorption of TCE increased to 75.3% in experiments utilizing smaller LWA particle size. LWA could be a viable medium for removal of TCE from contaminated surface or groundwater sites. Amberlite® was found unsuitable for use due to its physical characteristics, and its inability to efficiently remove any of the test compounds. Amberjet® showed an excellent ability to remove the inorganic anions (>99%), and BDCM (96.9%) from aqueous solutions but with considerable elevation of pH. Continuous flow experiments evaluated GAC and Amberjet® with spiked Milli-Q® and tap water matrices. The tested organic compounds were sorbed in the order of their hydrophobicity. Slight elevation of pH was observed during continuous flow experiments, making Amberjet® a viable option for removal of BDCM, bromate and bromide ions from water. The continuous flow experiments showed that GAC is an excellent medium for removal of the tested VOCs and bromate ion. Each of the test compounds showed different breakthrough and saturation points. The unique design of the continuous flow apparatus used in the study proved to be highly beneficial to assess removal of volatile organic compounds from aqueous solutions.

Prior to full-scale implementation of process modifications at the Brantford WTP, a pilot-scale treatability study was conducted to investigate intermediate ozonation/AOP and to determine the most suitable granular media (anthracite, GAC, and Filtralite®) for deep-bed biological filtration. The primary objectives of this research were to provide insight into the destruction of natural and synthetic organics and assess ozonated and halogenated DBP formation. Ozone alone was unable to achieve the 1-log removal target for geosmin or MCPA, unless disinfection-level dosages were applied. No improvement was observed when adding hydrogen peroxide. A major obstacle to the implementation of ozonation in bromide-laden source waters is the formation of bromate. There is a direct correlation between ozone dose and bromate formation and by applying ozone dosages at disinfection levels, bromate is likely to exceed regulatory limits. However, adding hydrogen peroxide reduced the amount of bromate formed, and in most cases levels fell below regulatory limits. A linear correlation was established between bromate inhibition and increasing H2O2/O3 ratio at constant ozone dose. Amongst the three filtration media investigated, only GAC achieved 1-log removal for geosmin and MCPA. The superiority of GAC over anthracite and Filtralite® was attributed to its adsorption affinity. Filtralite® and anthracite media were both ineffective for MCPA removal due to its non-biodegradable nature under conventional water treatment conditions. At a 1 mg/L-ozone dose, GAC and Filtralite® filters achieved a 1-log geosmin removal. In contrast, a 1.44 mg/L ozone dose was required to meet this target with anthracite. The tandem of ozone followed by biological filtration was very effective for the control of distribution system TTHM production regardless of filter media, with levels well below current and anticipated provincial regulatory limits. The combination of intermediate ozonation followed by deep-bed biological filtration is well suited for treating Grand River water. Scale-up considerations include pairing the proper filter media to the size of the ozone generator. The best two treatment scenarios were: Option 1: select GAC media and size the ozone generator to produce a 1 mg/L dose. Option 2: select anthracite media and size the ozone generator to deliver a 2 mg/L dose.

<p>In this research, ozone hydrodynamics and disinfection by-products formation in a novel hybrid ozonation-ceramic membrane filtration system was studied to minimize membrane fouling while also ensuring that the system meets regulatory criteria for disinfection by-products. The influence of important operating parameters including inlet ozone mass injection rate, initial bromide concentration, membrane molecular weight cut off (MWCO), membrane coating, hydroxyl radical scavenger (<em>t</em>-butanol), pH, and temperature on bromate concentration in the absence and presence of natural organic matter (NOM) was examined. Experiments were also conducted under various operating conditions to investigate the formation of total trihalomethanes (TTHMs) and halo-acetic acids (HAAs) in the water distribution system due to post chlorination. Moreover, variations in the TOC, UV₂₅₄, color and turbidity with respect to operating parameters were monitored.</p> <p>Bromate and TTHMs formation increased with increasing ozone mass injection rate, and initial bromide concentration. An increase in the bromate concentration was observed with decreasing membrane MWCO. Less bromate and TTHM was formed with the coated membrane and <em>t</em>-butanol significantly reduced bromate and TTHM formation. Bromate formation decreased significantly with decreasing pH. Increasing the temperature resulted in enhanced bromate formation. NOM exerted a favorable effect on bromate formation as the bromate concentration was observed to decrease as the NOM content was increased.</p> <p>Experimental results indicated that ozonation can greatly reduce color and turbidity of water and can be used to overcome membrane fouling. Ensuring a minimum ozone residual in the system enables the continuous treatment of water at a relatively high permeate flux (up to 85% of the clean water flux) and eliminates the need for membrane cleaning procedures.</p> <p>An empirical model was developed to predict bromate formation in the hybrid ozone- membrane system (R²=0.903). Theoretical models were developed to estimate the rate of bromate formation and to describe the ozone mass transfer in a hybrid system. In all cases, good correlation between the model predictions and the experimental data was achieved.</p> / Doctor of Philosophy (PhD)

Abstract Water in the coastal areas of Ostrobothnia typically contains high levels of humus, iron and manganese. Organic matter and iron contained in groundwater form compounds that make water treatment more difficult. The treatment process of such water usually resembles that used in a traditional chemical water treatment plant. This kind of chemical treatment process is, however, an expensive alternative in view of the resources of a small or a medium-sized treatment plant. The aim of this research was to find out whether ozonation and oxidation with hydrogen peroxide can be used for the treatment of water containing high amounts of organic matter. Ozone is rather widely used in surface water plants for the final treatment of water. The most common applications include the disinfection and oxidation of substances that cause unpleasant taste and odour in water. This research deals with the use of ozone for the treatment of groundwater containing iron and manganese. Since ozone is a powerful oxidizer, it is able to oxidize iron and manganese contained in water into an insoluble form. Also a noticeable amount of organic matter is precipitated in the same process. However, in some of the researched cases the precipitate was so fine that it was impossible to separate it with traditional methods. A combination of ozonation and microfiltration proved to be a successful form of treatment when dealing with this type of water. Ozonation increased the AOC of water in all of the researched cases. The content of bromide is reasonably low in Finnish groundwater. The median measured in coastal Northern Ostrobothnia was 0.025 mgl-1. With the used ozone dosage, the bromate formed in the process stayed below the limit value of 10 μgl-1. Therefore it can be stated that the formation of bromate does not hinder ozone treatment from becoming a more common form of water treatment in Finland. However, the formation of bromate must be taken into consideration, especially if ozonation is made in hig pH. Hydrogen peroxide can be used as an alternative chemical in the oxidation and precipitation processes of iron in groundwater. The chemical is used for the oxidation of iron before filtration. If the formed precipitate is fine, microfiltration or flocking chemical can be used to remove the precipitate. / Tiivistelmä Pohjanmaan rannikkoseudun pohjavesille on tyypillistä korkeat rauta- ja mangaanipitoisuudet yhdistettynä suureen humuspitoisuuteen. Orgaaninen aine muodostaa pohjaveden raudan kanssa yhdisteitä, jotka vaikeuttavat vedenkäsittelyn toimintaa. Kyseisten vesien käsittely lähestyy yleensä perinteistä kemiallista pintavesilaitosta. Kuitenkin pienten ja keskisuurten vesilaitosten resursseihin nähden täydellinen kemiallinen käsittely on kallis vaihtoehto. Tämän tutkimuksen tarkoituksena oli selvittää otsonoinnin ja vetyperoksidihapetuksen käyttökelpoisuutta näiden runsaasti orgaanista ainetta sisältävien vesien käsittelyssä. Otsonoinnin yleisimmät sovellutukset ovat hajua ja makua aiheuttavien aineiden hapettaminen ja desinfiointi. Tässä tutkimuksessa selvitettiin otsonin käyttöä rauta- ja mangaanipitoisten pohjavesien käsittelyssä. Otsoni saa voimakkaana hapettimena vedessä olevan raudan ja mangaanin hapettumaan ei liukoiseen muotoon. Samalla kerasaostui huomattava määrä orgaanista ainetta. Kuitenkin muodostuva sakka on joissain tapauksissa niin hienojakoista, että sen erottaminen perinteisin menetelmin on mahdotonta. Näiden ns. ongelmavesien käsittelyssä saatiin hyviä tuloksia otsonoinnin ja mikrosuodatuksen yhdistelmällä. Otsonointi nosti huomattavasti kaikkien tutkittujen vesien AOC-pitoisuutta. Bromidipitoisuudet suomen pohjavesissä olivat kohtuullisia. Pohjanmaan rannikkoseudun pohjavesien bromidipitoisuuksien mediaani oli 0,025 mgl-1. Kaikilla vesillä käytännön otsoniannostuksilla syntyvät bromaattimäärät alittivat 10 μgl-1 raja-arvon. Bromaattiongelma ei ole este otsonikäsittelyn yleistymiselle Suomessa. Se on kuitenkin tiedostettava, varsinkin, jos otsonointi tehdään korkeassa pH:ssa. Vetyperoksidi on vaihtoehtoinen kemikaali pohjaveden raudan hapettamiseen ja saostamiseen. Vetyperoksidia voidaan käyttää raudan saostamiseen ennen suodatusta. Mikäli muodostuva sakka on hienojakoista, voidaan sakanerotus tehdä mikrosuodatuksella tai käyttää hyväksi flokkauskemikaaleja.

Afin de gérer au mieux le pilotage des unités d'ozonation lors de la potabilisation des eaux, un modèle prédictif a été développé. L'objectif du modèle était de pouvoir prédire, sur une installation industrielle, les concentrations en ozone, en bromates et en différents micropolluants. Le modèle chimique proposé est mécanistique et peut être subdivisé en plusieurs parties : auto-décomposition de l'ozone, influence de l'alcalinité, formation de bromates, influence de la MON (Matière Organique Naturelle). Le modèle d'influence de la MON comporte 12 paramètres ajustables, le modèle pour la formation des bromates comporte un paramètre ajustable, les valeurs des autres paramètres sont fixées d'après la littérature. Le modèle hydraulique est de type systémique et comprend des réacteurs idéaux (parfaitement agités et piston). L'identifiabilité du jeu de paramètres a été conduite par une analyse de sensibilité (eFAST). La procédure d'optimisation par méthode de Nelder-Mead a été testée. Le modèle proposé permet de rendre bien compte des variations de temps de contact avec l'ozone, de pH, de température, de concentration de MON, de doses d'ozone sur la décomposition de l'ozone et la génération de radicaux. Les essais sur la formation de bromates ont montré que le modèle donne de bons résultats pour des concentrations inférieures à 20 μg.L-1, ce qui est particulièrement intéressant dans le cas d'une application industrielle. Enfin, une étude sur une unité industrielle a montré que des modèles calibrés en laboratoire (chimie, hydraulique) peuvent être appliqués directement sur site. Le modèle de formation des bromates est néanmoins instable dans le temps et doit être périodiquement réajusté.

High-valent iron-oxo intermediates play central roles as active oxidants in enzymatic and synthetic catalytic oxidations. Many transition metal catalysts are designed for biomimetic studies of the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes. In this work, a new photochemical method to generate high-valent iron-oxo porphyrin models was discovered. As controlled by the electronic nature of porphyrin ligands, iron(IV)-oxo porphyrin radical cations (Compound I model) and iron(IV)-oxo porphyrin derivatives (Compound II model) were produced. These observations indicate that the photochemical reactions involve a heterolytic cleavage of O-Br in precursors to give a putative iron(V)-oxo intermediate, which might relax to Compound I through electron transfer from porphyrin to the iron or undergo rapid comproportionation reaction with residual iron(III) to afford the Compound II derivative. Furthermore, visible light photolysis of bis-porphyrins-dimanganese(III)-μ-oxo complexes, [MnIII(Por)]2O, was studied in three porphyrin systems. Direct conversion of manganese(III)-μ-oxo dimers to manganese(IV)-oxo porphyrins [MnIV(Por)(O)] and manganese(III) products was observed in benzene solution upon light irradiation. The spectral signature of [MnIV(Por)(O)] was further confirmed by production of the same species in the reported reaction of the [MnIII(Por)Cl] with PhI(OAc)2. Continuous irradiation of bis-porphyrins-dimanganese(III)-μ-oxo complexes in the presence of pyridine or triphenylphospine gave rise to the formation of [MnII(Por)(Py)] or [MnII(Por)(PPh3)], which are stable to be detected. A photo-disproportionation mechanism similar to that for bis-porphyrins-diiron(III)-μ-oxo complex was proposed to explain above photochemical behaviors of bis-porphyrins-dimanganese(III)-μ-oxo complexes. With iodobenzene diacetate [PhI(OAc)2] as the oxygen source, manganese(III) porphyrin complexes exhibit remarkable catalytic activity towards the selective oxidation of alkenes and activated hydrocarbons. Conspicuous is the fact that the readily soluble PhI(OAc)2 in the presence of a small amount of water is more efficient oxygen source than the commonly used PhIO under same conditions. High selectivity for epoxides and excellent catalytic efficiency with up to 10,000 Turnovers (TONs) were achieved in alkene epoxidations. A manganese(IV)-oxo porphyrin was observed in the oxidation of the manganese(III) porphyrin and PhI(OAc)2. However, catalytic competition and Hammett studies suggested that the more reactive manganese(V)-oxo intermediate was favored as the premier active oxidant, even it is too short-lived to be detected in the catalytic reaction.

Novel integrated ozone contactor design and optimization tools which consist of an instrument that measures ozone decay kinetics, a program that performs predictive simulation, and an experimental method to examine mixing characteristics within the ozone contactor, were developed in this study. A multi-channel stopped-flow reactor (MC-SFR) is an instrument that performs automatic, real-time, and continuous analysis of ozone decay kinetics in natural waters. Ozone Contactor Model (OCM) is the software to simulate the performance of full-scale ozone bubble-diffuser contactors in support of current and future regulations regarding pathogen and bromate control in drinking water. The MC-SFR and OCM developed in this study were further applied to simulate Cryptosporidium parvum oocyst log inactivation and bromate formation in Linnwood Water Plant Ozone Facility (LWPOF) at Milwaukee Water Works, Milwaukee, WI and model predictions were verified with experimental results. Three dimensional laser induced fluorescence(3DLIF) allowed real time characterization of mixing conditions in a physical model ozone contactors by capturing fluorescence image emitted from a laser dye (i.e. Rhodamine 6G) using a high speed CCD camera. 3DLIF system was applied to analyze the hydrodynamics of two representative types of ozone contactor: direct discharge side-stream venturi injector (SVI) and multi-chambered fine bubble diffuser (FBD). Experimental results verified the presence of circulative swirling related for low dispersion for SVI reactor and the existence of non-ideal flow including short circuiting and internal recirculation in FBD reactor. Finally, integrated tools were applied to the design of a new ozone contactor under planning stage to assess current design and to recommend the improvement.

118 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-11T17:50:31Z No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-05-14T17:22:34Z (GMT) No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) / Made available in DSpace on 2013-05-14T17:22:34Z (GMT). No. of bitstreams: 1 Dissertação de Mestrado - PDF[1].pdf: 2378495 bytes, checksum: 988193a81cd9a137da1f1458daa95968 (MD5) Previous issue date: 2011 / CAPES / Devido aos inúmeros incentivos governamentais que impulsionam a produção do Biodiesel no mundo, tal combustível está sendo produzido largamente, e um fator preocupante frente a esse crescimento é o destino do glicerol excedente, já que seu uso é condicionado ao seu grau de pureza, que deve estar usualmente acima de 95%. No caso do glicerol bruto, resultante do processo de transesterificação do biodiesel, são necessários processos complexos e onerosos para que essa matéria-prima alcance as exigências em grau de pureza necessária para seu emprego. Além disso, os mercados tradicionais que o consomem (indústria de cosméticos, resinas, indústria farmacêutica, têxtil e alimentícia) têm uma capacidade limitada de absorção de quantidades maiores desse sub-produto. Sendo assim, esse trabalho tem como objetivo promover modificações estruturais na molécula do glicerol (comercial, alcalino e bruto), utilizando como agentes oxidantes os sais de bismuto (Zn(BiO3)2 e NaBiO3), NaClO e KBrO3/NaHSO3. As reações foram realizadas em ácido acético , ácido lático, acetona, água, com variação de tempo, temperatura, concentração dos reagentes e catalisadores. Essa metodologia sintética tem como finalidade gerar produtos com maior valor agregado tornando o glicerol um sub-produto mais reaproveitado e competitivo no mercado. Os melhores resultados na conversão do glicerol para os produtos mono, di e triacetilados foram alcançados utilizando 1mol% do catalisador NaBiO3 em diferentes concentrações de ácido acético glacial. Na ausência do catalisador a reação também ocorre, porém com tempo elevado. Em nenhum dos experimentos ocorreu à oxidação do glicerol. O modelo experimental realizado mostrou que é necessário excesso de ácido a fim de promover o equilíbrio na direção da conversão do glicerol e seletividade para os produtos mais valiosos comercialmente, o di e triacetilados. / Salvador