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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.

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.

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.

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Philosophiae Doctor - PhD / Persistent organic pollutants (POPs) are very tenacious wastewater contaminants with negative impact on the ecosystem. The two major sources of POPs are wastewater from textile industries and pharmaceutical industries. They are known for their recalcitrance and circumvention of nearly all the known wastewater treatment procedures. However, the wastewater treatment methods which applied advanced oxidation processes (AOPs) are documented for their successful remediation of POPs. AOPs are a group of water treatment technologies which is centered on the generation of OH radicals for the purpose of oxidizing recalcitrant organic contaminants content of wastewater to their inert end products. Circumvention of the reported demerits of AOPs such as low degradation efficiency, generation of toxic intermediates, massive sludge production, high energy expenditure and operational cost can be done through the application of the combined AOPs in the wastewater treatment procedure. The resultant mineralisation of the POPs content of wastewater is due to the synergistic effect of the OH radicals produced in the combined AOPs. Hydrodynamic cavitation is the application of the pressure variation in a liquid flowing through the venturi or orifice plates. This results in generation, growth, implosion and subsequent production of OH radicals in the liquid matrix. The generated OH radical in the jet loop hydrodynamic cavitation was applied as a form of advanced oxidation process in combination with hydrogen peroxide, iron (II) oxides or the synthesized green nano zero valent iron (gnZVI) for the treatment of simulated textile and pharmaceutical wastewater.

[pt] A presente dissertação investiga a capacidade de remoção de amônia de efluentes através de processos de oxidação química. Testes preliminares foram feitos com peróxido de hidrogênio (H2O2), peróxido de hidrogênio foto ativado (UV + H2O2), reagente Fenton (Fe2+ + H2O2) e Ácido de Caro (H2SO5). Os resultados dos mesmos indicaram apenas a possibilidade do Ácido de Caro oxidar a amônia. Em seguida avaliou-se o desempenho do Ácido de Caro no processo, utilizando soluções sintéticas de cloreto de amônia. Foi estudada a influência dos parâmetros pH, tempo, e razão estequiométrica (oxidante:amônia). O tratamento de soluções com Ácido de Caro, mostrou-se viável, visto que houve uma redução significativa da concentração inicial de amônia de 100 mg/L até valores inferiores a 5 mg/L (limite permitido pela legislação). Estes resultados foram obtidos a pH=1,3 razão estequiométrica oxidante:amônia = 8:1, em tempo de reação de 12 horas, a temperatura ambiente. / [en] This dissertation investigates the removal capacity of ammonia from effluents by chemical oxidation. Preliminary tests were done with hydrogen peroxide (H2O2), photo activated hydrogen peroxide (UV + H2O2), Fenton reagent (Fe2+ + H2O2) and Caro s Acid (H2SO5). The results indicated that only the use of Caro s acid is possible for ammonia oxidization. Afterwards, the Caro s acid process was evaluated, utilizing synthetic solutions of the ammonia chloride. The influence of parameters: pH, time, and stoichiometric ratio (oxidizing agent:ammonia) were studied. The treatment of the solutions with Caro s Acid was found to be viable, showing that there was a significant reduction of initial concentration of ammonia of 100mg/L down to 5mg/L (the limit permitted by legislation). These results were obtained for the following parameter: pH=1,3, stoichiometric ratio (oxidizing agent:ammonia) = 8:1, at reaction time of 12 hours and at ambient temperature.

Orientador: Raquel Fernandes Pupo Nogueira / Banca: Maria Valnice Boldrin / Banca: Eduardo Bessa Azevedo / Banca: Pedro Sergio Fadini / Banca: Renato Sanches Freire / Resumo: A contaminação de compartimentos aquáticos com resíduos de fármacos é frequentemente relatada na literatura. Fármacos residuais de várias classes terapêuticas são detectados em concentrações que variam de ng L-1 a µg L-1 . Embora estes resíduos sejam encontrados em baixas concentrações, alguns estudos relatam a ocorrência de efeitos adversos a organismos aquáticos. Portanto, faz-se necessário o estudo de processos que promovam a degradação destes contaminantes emergentes. Nesse contexto, foi avaliada neste trabalho a eficiência do processo foto-Fenton na degradação dos fármacos diazepam, propranolol e lincomicina e também a eficiência de reações baseadas em ferro metálico para a degradação de diazepam. O monitoramento da concentração dos fármacos foi feito por meio da técnica de Cromatografia Líquida de Alta Eficiência com detector de arranjo de diodos (CLAE-UV) e a remoção da matéria orgânica foi avaliada por análises de Carbono Orgânico Total (COT). O processo foto-Fenton foi eficiente na degradação dos fármacos, pois promoveu total oxidação em aproximadamente 8 minutos de tratamento e mais de 80% de remoção de COT após 60 minutos, sob lâmpada de luz negra. Sob radiação solar, a oxidação dos três fármacos estudados ocorreu em aproximadamente 5 minutos de tratamento, além de um percentual de mais de 90% de remoção de COT alcançado em 60 minutos. Tanto sob radiação solar quanto sob lâmpada de luz negra, a espécie de ferro que promoveu maior degradação foi FeOx (0,20 mmol L-1 ), e das concentrações de H2O2 avaliadas (1,0, 5,0, 10,0 mmol L-1 ), as concentrações 5,0 e 10,0 mmol L-1 promoveram os melhores índices de degradação. A avaliação da interferência da matriz efluente de estação de tratamento de esgoto (ETE), onde normalmente os fármacos residuais são encontrados, demonstrou que ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Contamination of the aquatic environment with pharmaceutical residues is frequently reported in the literature. Pharmaceutical residues of several therapeutical classes are detected in concentrations that vary from ng L-1 to µg L-1 . Although these residues were found in low concentrations, some studies reported the occurrence of adverse effects to aquatic organisms. Therefore, the study of processes that promote the degradation of these emerging pollutants becomes necessary. In this context, the efficiency of the photo-Fenton process in the degradation of the pharmaceuticals diazepam, propranolol and lincomycin and also the efficiency of reactions based on metallic iron for the degradation of diazepam was evaluated in this work. The monitoring of the pharmaceuticals concentration was carried out using High Performance Liquid Chromatography with diode array detector (HPLC-UV) and the removal of the organic matter concentration was evaluated by Total Organic Carbon (TOC) analysis. The photo-Fenton process was efficient for the degradation of the pharmaceuticals since it promoted total oxidation after approximately 8 minutes treatment and more than 80% of TOC removal after 60 minutes under black light radiation. Under solar radiation, the oxidation of the three pharmaceuticals studied occurred after approximately 5 minutes and more than 90% of TOC removal was achieved in 60 minutes. FeOx (0,20 mmol L-1 ) promoted higher degradation not only under solar but also under blacklight radiation. Among the H2O2 concentrations evaluated (1,0, 5,0, 10,0 mmol L-1 ), the concentrations of 5,0 and 10,0 mmol L-1 promoted higher degradation. The evaluation of the interference of the matrix effluent of sewage treatment plant (STP), where the pharmaceutical residues are normally found, demonstrated that the oxidation of the pharmaceuticals was not hindered in the presence of this matrix. However, ... (Complete abstract click electronic access below) / Doutor