The presence of pollutants known as emerging contaminants in water and wastewater is a topic of growing interest. Emerging contaminants, which include endocrine disrupting chemicals (EDCs) and pharmaceutical and personal care products (PPCPs), are compounds that remain relatively unknown, although their adverse effects have been proven. Emerging contaminants are not satisfactorily removed by traditional treatment methods; therefore, there is a need for innovative techniques. Advanced oxidation processes (AOPs) have been recognized as successful removal methods for these problematic pollutants. However, technical success is not the only factor that must be considered. Process engineering, environmental, and economic and social parameters were considered. A holistic analysis was completed using a ranking system to determine the performance of several AOPs (ozonation, UV, photocatalysis, the Fenton reaction, and integrated processes). Ultimately, H2O2/O3 presented the highest average ranking (3.45), with the other processes showing similar performance, with the exception of TiO2 photocatalysis (2.11).

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In 2012, mandatory effluent quality standards were established in Canada as part of the Wastewater Systems Effluent Regulations (WSER) with compliance deadlines starting in 2020. Maintaining the treatment process efficacy to meet these new stringent discharge regulations is extremely challenging at treatment facilities that treat wastewater from multiple industries due to the high variation in the composition of the incoming feed to the process. In this work, application of two new analytical tools, PeCOD® and Liquid Chromatography-Organic Carbon Detection (LC-OCD), for measurement and characterization of industrial wastewater organic pollution respectively, has been investigated. Organic pollution is commonly measured as Chemical Oxygen Demand via the dichromate method (CODCr) which requires 2-3 hours to complete. Thus this method is not suitable for applications that require rapid and frequent pollution monitoring. The Photoelectrochemical Oxygen Demand (peCOD) is an alternative parameter of organic pollution that can be measured in approximately 15 minutes via a method that utilizes the high oxidation potential of UV-irradiated TiO2 nano-particulates. Herein peCOD suitability to replace CODCr for analysis of industrial wastewater was investigated. The results indicated that for both untreated (i.e. incoming) and treated (i.e. effluent) industrial wastewater samples, peCOD results are lower than CODCr results. However, for the effluent samples, the two methods’ results are strongly correlated. Containing hard to oxidize materials (i.e. macromolecules) and high concentrations of chloride and nitrogenous compounds were identified as potential causes of difference between the results of the two methods. When there is variation in the composition of the incoming wastewater to a treatment process, information about the wastewater composition is required for process optimization. Thus optimization cannot be based solely on bulk measurements of organic pollution (e.g. COD). In this study, a novel combination of LC-OCD analysis with Design-Of-Experiments (DOE) methods was used to optimize the Fenton Advanced Oxidation (AO) treatment conditions in terms of chemical reagent concentrations, to develop statistical models of the process, and to identify potential mechanisms of COD removal. / Thesis / Master of Applied Science (MASc) / Many industrial facilities do not treat their wastewater on-site and instead ship it to specialized treatment facilities. Ensuring that the treated effluent meets the stringent discharge regulations is a challenging task for such facilities as the composition of the incoming feed to the treatment process changes with each shipment. In this work, application of two new analytical tools, PeCOD® and Liquid Chromatography-Organic Carbon Detection (LC-OCD), for measurement and characterization of industrial wastewater organic pollution respectively, has been investigated. The conventional method of measuring organic pollution, Chemical Oxygen Demand (COD), requires 2-3 hours to complete. Herein the suitability of an alternative parameter, Photoelectrochemical Oxygen Demand (peCOD), that can be measured in approximately 15 minutes for replacing COD analysis in industrial wastewater plants was investigated. Implementation of effective treatment processes that are operated at their optimum conditions is required to meet the stringent discharge regulations. Advanced Oxidation (AO) is an effective method of industrial wastewater treatment. Herein, optimum AO treatment conditions were studied via application of the LC-OCD analysis for organic pollution characterization.

No / In the search for an efficient and economical method to treat a leachate generated from a controlled municipal solid waste landfill site (Jebel Chakir) in the region of greater Tunis in Tunisia, ozone alone and ozone combined with hydrogen peroxide were studied. The leachate was characterised by high COD, low biodegradability and intense dark colour. A purpose-built reactor, to avoid foaming, was used for the study. It was found that ozone efficacy was almost doubled when combined with hydrogen peroxide at 2 g/L but higher H2O2 concentrations gave lower performances. Enhancement in the leachate biodegradability from about 0.1 to about 0.7 was achieved by the O3/H2O2 system. Insignificant changes in pH that may due to buffering effect of bicarbonate was found. A small decrease in sulphate concentrations were also observed. In contrast, chloride concentration declined at the beginning of the experiment then increased to reach its initial value. Estimates of the operating costs were made for comparison purposes and it was found that the O3/H2O2 system at 2 g/L H2O2 gave the lowest cost of about 3.1 TND (2.3 USD)/kg COD removed.

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.

This research involved an investigation of the application and reaction mechanisms of UV/H₂O₂ for the simultaneous removal of regulated halogenated disinfection byproducts (DBPs) and odorous aldehydic algal byproducts in the presence of geosmin and 2-methylisoborneol, which are earthy-musty odorants that commonly occur in drinking water. UV/H₂O₂ is an expensive advanced oxidation process that is used to successfully control geosmin and 2-methylisoborneol. The aqueous oxidation of odorous aldehydes and halogenated DPBs were compared to that of the earthy-musty odorants and the changes to the sensory properties of the drinking water were examined. Geosmin, 2-methylisoborneol, heptadienal, decadienal, and nonadienal, hexanal, and the two most prevalent classes of DBPs, trihalomethanes (THMs) and haloacetic acids (HAAs) were oxidized by UV photolysis alone and the UV/H₂O₂ process with 6 mg/L H₂O₂ and realistic ng/l to μg/L concentrations of the test compounds. The di-, and tri-brominated THMs and HAAs were substantially (80-99%) removed by direct UV photolysis mechanism at the same UV/H₂O₂ dose required for removing 95% of geosmin and 65% of 2-methylisoborneol with faster reaction rates for the more bromine substituted compounds. The C-Br bond cleavage is the first step of brominated HAAs degradation by UV photolysis, and followed by either of two second steps: reaction with oxygen producing peroxyl radical or interaction with water molecule causing O-H insertion/H-Br elimination. Trichloromethane and mono-, di-, and tri-chlorinated HAAs were not substantially removed under the same conditions used for the brominated compounds. The principal removal mechanism was by the reaction with hydroxyl radical for the UV/H₂O₂ process. The second order reaction rate constants were on the order of 10⁶ - 10⁸ M⁻¹ s⁻¹ with faster reaction rates for the less chlorine substituted compounds. Based on the reaction rates, hydrogen and halogen ion balance, and isotope effect, both hydrogen abstraction and electron transfer reaction were involved in the first steps of the chlorinated HAA degradation. Three odorous aldehydes - heptadienal, decadienal, and nonadienal - were removed faster than geosmin or 2-methylisoborneol, and direct UV photolysis was the principal reaction mechanism for the removal of these unsaturated aldehydes. Hexanal was poorly removed. In sensory tests, new odors such as sweet or chalky odors were produced while the concentration and initial odor intensity of these fishy/grassy-smelling aldehydes were reduced with increasing exposure time to UV/H₂O₂. Carbonyl compounds were detected as products of the UV photolysis of nonadienal. These carbonyls were not removed by further UV irradiation, which was thought to be partially related with production of new odors. The results indicate that the UV/H₂O₂ is effective to control both odorous compounds and brominated DBPs. This process can be seasonally applied to control both contaminants especially, in the warm summer when both odorants and DBPs have their higher concentrations. Removal of brominated DBPs can be a significant addition to water utilities that have difficulty in meeting regulatory levels for these highly toxic compounds. The result on the removal of odorous aldehydes indicate that new types of odors were produced from the oxidation of odorous aldehydes suggesting sensory test coupled with chemical analysis should be considered in designing oxidation process to control recalcitrant odorants. / Ph. D.

Neste trabalho buscaram-se formas de aumentar a eficiência do processo de ozonização sobre a degradação/mineralização de corantes empregados pela indústria têxtil, especificamente do azocorante Preto Remazol B, avaliando o emprego do processo de ozonização catalítica tanto homogênea quanto heterogênea. O ozônio mostrou uma grande eficiência para promover a degradação dos três tipos de corantes estudados (azo, antraquinona e ftalocianina); permitindo que soluções destes corantes com concentração de 100 mg L-1 sofressem uma total descoloração (destruição do grupo cromóforo) em menos de 2 minutos de ozonização. Em meio ácido, o ozônio tende a reagir via o mecanismo direto e devido a isto a redução no teor de carbono orgânico total (COT) dos poluentes costuma ser menos eficiente. Em 30 minutos de tratamento o processo O3/pH3 permitiu somente 30% de mineralização do azocorante estudado. Por outro lado, o O3 pode ter sua decomposição catalisada por vários materiais, levando à formação de espécies radicalares, principalmente o radical hidroxila (HO.). Devido ao caráter não seletivo dos radicais hidroxila, o mecanismo de ozonização indireto costuma ser mais eficiente na oxidação de compostos orgânicos. Um exemplo clássico deste mecanismo é o processo O3/pH11, que mineralizou 56% do COT do azocorante após 30 minutos de ozonização. Uma estratégia para promover uma melhora na mineralização do corante Preto Remazol B pelo processo de ozonização em meio ácido foi a adição de peróxido de hidrogênio ao meio reacional. O tratamento O3/pH3/H2O2 permitiu um aumento de 51% na mineralização do azocorante após 30 minutos de ozonização. O aumento da eficiência do ozônio também foi avaliado empregando-se o processo de ozonização na presença de metais (Mn2+e Fe3+). Em 30 minutos de tratamento, o processo O3/pH3/Mn2+ mineralizou 67, 78 e 57% do COT dos corantes Preto Remazol B, Azul Brilhante RN e Turquesa Remazol G, respectivamente. No mesmo tempo de tratamento O3/pH3/Fe3+ permitiu uma remoção de COT de 57, 64 e 41% para Preto Remazol B, Azul Brilhante RN e Turquesa Remazol G, respectivamente. A presença dos metais estudados na forma sólida (MnO2) ou em suportes (SiO2/MnO2 e SiO2/Fe2O3), além de permitir uma remoção de até 79% do COT do azocorante em 30 minutos de tratamento, também mostra uma alternativa para viabilizar o emprego dos agentes catalisadores da decomposição do ozônio, uma vez que na forma suportada os mesmos podem ser utilizados de forma contínua, minimizando etapas de recuperação ou perdas destes materiais. / The main goal of this study was to find means to increase the efficiency of ozonation process over the degradation/mineralization of dyes used in the textile industry, mainly the azodye Remazol Black B, evaluating the use of either homogeneous or heterogeneous catalytic ozonation methods. Ozone showed great efficiency to promote the degradation of the three types of studied dyes (azo, anthraquinone and phtalocyanine) enabling the discoloration (destruction of chromophore group) of solutions with 100 mgdye L-1 in less than 2 minutes. In acidic medium, ozone tends to react via the direct mechanism. In this way, the reduction of total organic carbon (TOC) of the polluents uses to be less efficient. In 30 minutes of treatment, the process O3/pH3 allowed only 30% of mineralization of the studied azodye. On the other hand, O3 can be decomposed by several materials, leading to the formation of radical species, mainly the hydroxyl radical (HO.). Due to the nonselective character of hydroxyl radicals, the indirect mechanism of ozonation usually is more efficient in the oxidation of organic compounds. A classic example of this mechanism is the process O3/pH11 that mineralized 56% of TOC of the azodye after 30 minutes of ozonation. Another strategy to promote an improvement in the mineralization of the azodye Remazol Black B using the ozonation process in acid medium was the addition of hydrogen peroxide to the reactional medium. The treatment O3/pH3/H2O2 enabled an increase of 51% in the mineralization of the azodye after 30 minutes. The increase in the efficiency of ozone was also evaluated using the ozonation process in the presence of metallic ions (Mn2+ and Fe3+). In 30 minutes of treatment, the process O3/pH3/Mn2+ mineralized 67, 78 and 57% of the TOC of the dyes Remazol Black B, Blue Brilliant RN and Remazol Turquoise G133, respectively. In the same time of treatment, the process O3/pH3/Fe3+ mineralized 57, 64 and 41% of the TOC of he dyes Remazol Black B, Blue Brilliant RN and Remazol Turquoise G133, respectively. The presence of the studied metals in the solid form (MnO2) or on supports (SiO2/MnO2 e SiO2/Fe2O3), enabled the removal of up to 79% of the TOC of the azo in 30 minutes of ozonation. Moreover, these methods showed an alternative to permit the use of catalytic agents to decompose ozone, as in the supported form, they can be used in a continuous form, minimizing steps of recuperation or loss of these materials.

Wood is a material with an enormous number of applications. For decades, the development of wastewater treatment technologies tailored for the wood sector has focused on those industries that have water as an integral part of the industrial production, such as paper and pulp. However, there is a large and potentially growing sector that has been neglected, which is formed by industries in which water is not part of their production line, as for example, the wood floor and furniture industries (named wood-based dry industries). These industries still produces relatively low volumes of highly polluted wastewaters, with COD up to 30,000 mg/L, due to cleaning/washing procedure (named cleaning wastewaters). These cleaning wastewaters are often sent to the municipal wastewater treatment plant after dilution with potable water. Once there, recalcitrant pollutants are diluted and discharged into recipient water bodies or trapped in the municipal wastewater sludge. Another type of contaminated water these “dry industries” often generate in high volumes, and which is usually discharged with no previous treatment, is storm-water containing contaminants that have leached from large wood storage areas. The overall aim of this thesis was to increase the level of knowledge and competence and to present on-site wastewater treatment options for wood-based dry industries using the wood floor industry as a case-study, with a focus on combined treatment methods and solutions applicable to both the cleaning wastewater and storm-water. Among the treatment technologies investigated, electrocoagulation was studied both as a standalone treatment and combined with sorption using activated carbon. The combined treatment achieved a COD reduction of approximately 70%. Some advanced oxidation processes (AOP) were also studied: a COD reduction of approximately 70% was achieved by photo-Fenton, but the most successful AOP was ozone combined with UV light, were a COD reduction around 90% was achieved, with additional improvement in the biodegradability of the treated effluent. Ozone also proved to be effective in degrading organic compounds (approximately 70% COD reduction) and enhanced the biodegradability of the storm-water runoff from wood storage areas. The results have shown that the application of ozone can be considered an option for treatment of cleaning wastewaters and possibly for storm-water biodegradation enhancement. / Trä är ett material med ett stort antal möjliga användningsområden. Inom träindustrin har utvecklingen av vattenbehandlingsmetoder varit inriktat på de branscher som har vatten som en del av produktionen, såsom papper- och massaindustrin. Men det finns en stor och potentiellt växande sektor inom träindustrin som har försummats, den utgörs av industrier som inte har vatten som en del av produktionen, t.ex. trägolv och trämöbel industrier. Trots detta så producerar dessa industrier fortfarande relativt kraftigt förorenade avloppsvatten med t.ex. COD-värden upp till 30000 mg/l men i relativt låga volymer. Dessa avloppsvatten uppkommer vid rengöring av maskiner och städning av lokaler, varefter de oftast efter utspädning med dricksvatten skickas till det kommunala reningsverket. Väl där späds det förorenade vattnet vidare ut med annat inkommande vatten men passerar dock till stor del obehandlat och släpps ut i mottagande vattendrag eller så fastnar föroreningarna i avloppsslamet. Dagvatten är en annan typ av förorenat vatten från dessa "torra industrier" som ofta genereras i stora volymer och innehåller föroreningar som lakats från de trämaterial som förvaras i de stora upplag som ofta förekommer vid denna typ av industrier. Det övergripande syftet med avhandlingen var att öka kunskapen och kompetensen för att kunna miljömässigt riktigt och ekonomiskt billigt behandla industriavloppsvatten lokalt på plats inom trävaruindustrin, genom att använda en trä-golvsindustri som fallstudie. Fokus lades på kombinerade behandlingsmetoder och lösningar som skulle kunna vara lämpliga både för industriavloppsvatten och dagvatten. Ett antal behandlingstekniker har undersökts; elektrokoagulering studerades både som en fristående behandling och i kombination med aktivt kol. Den kombinerade behandlingen gav en COD-reduktion på ungefär 70 %. Flera avancerade oxidationsprocesser (AOP) studerades också, och en COD-reduktion på cirka 70% uppnåddes med en kombination av UV-ljus och Fenton behandling. Den mest framgångsrika behandlingen var ozon i kombination med UV-ljus där en COD-reduktion runt 90 % uppnåddes varvid en avsevärd förbättring av den biologisk nedbrytbarhet på det behandlade avloppsvattenet erhölls. Ozon visade sig också vara effektivt för nedbrytning av organiska föreningar (ca 70% COD reduktion) och förbättrade den biologiska nedbrytbarheten av föroreningarna i dagvattnet från den studerade industrin. Resultaten har visat att ozon kan anses vara ett lämpligt alternativ för att behandla industriavloppsvatten inom trävarusektorn och möjligen för att öka den biologiska nedbrytbarheten av dagvattnet från dessa industrier / Integrated Approach for Handling of Industrial Wastewater and Stormwater / Triple Helix Collaboration on Industrial Water Conservation in Småland and the Islands