The ubiquity of pharmaceuticals and personal care products in water systems is well known. With the increasing implementation of water reuse schemes in the US, concern about potential health effects of these compounds in humans has risen. While potential synergistic effects of chronic low doses exposure to a cocktail of these compounds is still being studied, it is prudent to monitor and attenuate these trace organic compounds (TOrCs) from our water sources. This research initially focused on identifying suitable `indicator' TOrCs based on theoretical physico-chemical parameters and actual experimental data. It was concluded that an indicator list will be specific to the goal targeted with dependence on treatment process, occurrence and analytical ease. Quantification of these TOrCs are part per trillion levels in water requires accurate, precise and robust analytical techniques. The next part of this research was spent on developing three different analytical methods with LC-MS/MS for the sensitive detection of TOrCs in several different water matrices including raw sewage and final drinking water. The treatment efficacy of granular activated carbon for attenuation of TOrCs is studied in detail with emphasis on developing correlations between TOrC removal and bulk organic parameters of water like UV absorbance and fluorescence by using rapid small-scale column testing. The results indicate a correlation between removal of TOrCs and bulk organic parameters that is independent of water quality. The effectiveness of commercially available activated carbon based point-of-use (POU) devices for removal of a set of TOrCs from water was evaluated. The data indicated that POUs are a viable option for treatment of TOrCs but specific removal depends on type of device, water quality and amount of water treated. Finally, further research was targeted at identifying transformation products as a result of oxidation of polyfluorinated precursor materials in reclaimed waters. The results illustrated that toxic perfluorocarboxylic acids can be formed on oxidation of fluorotelomer unsaturated carboxylic acids that are known to be present in water.

Stringent water quality regulations and general aesthetic issues have urged drinking water industry to apply advanced water treatment technologies that can meet multiple treatment objectives. Removal of significant amount of natural organic matter (NOM), including colour causing organics, to meet stringent disinfection by product (DBP) regulations from source water with low alkalinity and low turbidity is very challenging with conventional water treatment processes. Membrane filtration processes are effective in removing significant amount of NOM thus minimizing the formation of carcinogenic DBPs. However, fouling of membrane is a major problem affecting system performance. Improved pretreatment of feed water helps reduce or eliminate membrane fouling. This study characterized source water, examined fouling in nanofiltration (NF) membranes and explored various pretreatment options to reduce NF fouling. Resin fractionation was performed to characterize NOM and to identify the major fractions responsible for DBP formation in natural source water of the Tatamagouche water treatment plant (WTP) in Nova Scotia. The source water primarily comprised of hydrophilic neutrals (HIN) and hydrophobic acid (HOA) compounds, with the latter being a major contributor to the DBP formation. Fouling behaviour of the NF membranes was examined at bench- and full-scale levels to understand the impact of source water quality on membrane fouling in the Tatamagouche and Collins Park WTPs. Bench- and full-scale results revealed higher fouling in the Collins Park WTP which together supported ongoing membrane cleaning practices in the plant. Surface enhanced Raman spectroscopy (SERS), demonstrated here as a novel technique, suggested that carbohydrates and proteins are the main foulants in the source water. Bench-scale experiments conducted to evaluate the performance of ozone (O3), ultraviolet (UV), hydrogen peroxide plus ozone (H2O2/O3), H2O2 plus UV (H2O2/UV) and O3 plus UV (O3/UV) for reducing NOM and DBP precursors suggested that the O3/UV AOP offers the optimum reduction of NOM. Integrating AOP pretreatments with NF membrane resulted in an improved permeate flux but not permeate quality of the NF membrane.

No description available.

The development of functionalized membranes with tunable pores and catalytic properties provides us an opportunity to manipulate the membrane pore structure, selectivity and reactivity. By introducing the functional groups into membrane pores, dissolved metal ions and reactive particles can be effectively immobilized within the polymer matrix for toxic chloro-organic and heavy metal remediation in water. A polyelectrolyte functionalized membrane platform with tunable pore size and ion exchange capacity has been developed for iron/iron oxide nano-catalyst synthesis and chlorinated organic compound (trichloroethylene, TCE and polychlorinated biphenyls, PCBs) degradation. Highly robust polyvinylidene fluoride (PVDF) microfiltration membranes are used as the support with cross-linked polyacrylic acid (PAA) filled in the pores. By varying the environmental pH, PAA hydrogels have either swelling or collapsing behavior, resulting in different effective membrane pore sizes for different separation purposes. Cation exchange groups (i.e. carboxyl groups) in PAA chains prevent the aggregation and leaching of nanoparticles (NPs) during in-situ synthesis and reaction. Depending on the catalyst loading and residence time, TCE and PCBs can be completely degraded by reduction of zero-valent iron and bimetallic iron/palladium NPs, or iron oxide catalyzed free radical oxidation at near-neutral pH. Biphenyl from PCB dechlorination can be further oxidized by hydroxyl radicals (OH•) generated from hydrogen peroxide (H2O2) decomposition. Hydroxybiphenyls and benzoic acid are identified as oxidation products. Line scan and elemental mapping in transmission electron microscopy (TEM) and X-ray photo electron spectroscopy (XPS) characterizations are conducted to understand the effect of iron surface transformation on NP reactivity, and to optimize the membrane functionalization. The same platform can also be used to remove toxic metal selenium in the scrubber water of coal-fired power plants. By reducing the salt concentration in water or increasing the residence time and temperature, the concentration of selenium oxyanions in functionalized membrane permeate can be reduced to less than 10 µg/L. Selenium is captured in membranes by both iron reduction to metallic selenium and iron oxide adsorption. The full-scale flat sheet functionalized membrane and spiral wound modules have also been developed. Iron NPs with alterable loadings are successfully synthesized inside the membrane module for real water applications.

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.

Visible light-driven photocatalysis has shown considerable potential in the area of clean and renewable energy, as well as in wastewater treatment. This thesis describes the synthesis, characterization and applicability of a visible-light active photocatalyst, bismuth oxybromide (BiOBr). The photocatalytic activity of BiOBr was investigated through its preparation via hydrothermal and solvothermal synthesis routes under various conditions. Hydrothermal catalyst was prepared using non template based method while for solvothermal synthesis CTAB was used as a template. Parameters of temperature and time of thermal treatment were optimized for each synthesis method and overall tests for catalyst dosage and recyclability were performed. An overall optimal route leading to high photocatalytic performance was also proposed based on the obtained results. Studies were also conducted to examine the applicability of optimally synthesized BiOBr in drinking water applications by studying catalyst-mediated disinfection of E. coli and degradation of phenol. Favourable results were obtained, confirming the prospective application of BiOBr as a viable photocatalyst for disinfection. Furthermore, the potential of enhancing BiOBr to further improve its performance is described through synthesis of a novel PdCl2/BiOBr based photocatalyst. Overall, the performance of BiOBr under various conditions in this study establishes its potential as a holistic photocatalyst and merits further development.

Water recycling by membrane treatment is widely accepted as a leading alternative water source. This separation process creates a concentrated stream (called concentrates), containing most of the pollutants in 10%-20% of the flow; and a treated water stream. As nitrogen is a major concern, environmental regulations have become more stringent, requiring additional treatment to meet effluent standards. Other concerns include organic contaminants and potential production of halogenated organics if disinfection of the reject was applied. One option to address the problem of dissolved organic nitrogen and carbon is advanced oxidation. This oxidation could lead to degradation of refractory organic materials, which are poorly removed in conventional treatment. This project aims to evaluate treatment extent and cost of alternatives for organic (particularly nitrogen) removal in reject water addressing the following research gaps: (i) identifying the key organic pollutants present in the concentrated stream, (ii) the effectiveness and optimisation of coagulation, ion exchange and advanced oxidation; (iii) apparent cost of the different treatment methods. The untreated reverse osmosis concentrates were collected from two treatment plants:- Luggage Point, and Bundamba, both near Brisbane, Queensland, Australia. The first contains more colourful of organics than the second plant. Stirred cell fractionation with ultrafiltration membranes was used to characterise the removed key pollutants, as it offers better accuracy and reproducibility compared to centrifugation fractionation. Fluorescence spectral was used to monitor and identify specific organic compounds. The largest fraction was smaller sized <1kDa. This is probably small humic substances and fulvic acids, as indicated by Excitation Emission Matrix (EEM) analysis. A smaller portion of soluble microbial products (SMPs) also contributes to the concentrates. Bundamba contains large non coloured organics including organic nitrogen with elevated ammonia-N. In contrast, Luggage Point has higher colour, inorganic carbon and conductivity with less ammonia-N. Advanced Oxidation Process (AOP) was the most effective treatment method (high removal of organics, e.g. 55% COD of initial), followed by magnetised ion exchange (MIEX) and coagulations. For UV/H2O2 AOP, the optimal operating condition 400mg.L-1 H2O2 and 3.1kWh.m-3 energy input resulted in organics removals up to 55% with complete decolourisation. The effective reduction was found in all size ranges, preferably in >1kDa. Low inorganic carbon and salinity in Bundamba may allow better overall oxidation rates. MIEX also performed better in Bundamba with organic removals up to 43% and 80% decolourisation at the optimum resin dose of 15mL.L-1. Removal was preferential in size range of >3kDa, with more proportional percentage for decolourisation. Similarly, ferric coagulation removed a wider size range of organics. Further, ferric achieved better organic removal in Luggage Point with up to 49%. At the same molar dose (1.5mM), ferric is superior to alum, especially in Bundamba where there were less hydrophobic compounds according to EEM. Alum is poor for treatment of high organics with less coloured water. MIEX with an operational cost (chemicals and power only) of $0.14-$0.20.m-3 treated water seemed to be the most effective treatment overall. The resin achieved better results with a slightly higher cost than coagulation, and had a lower environmental impact due to reduced sludge production. AOP offers better treatment, but at a higher cost ($0.47.m-3 treated). Combined alternatives may benefit the removal effectiveness. Furthermore, more specific identification of contaminants should be investigated separately to choose appropriate treatment for priority chemicals. Another issue is further investigation of costing, including capital, and full environmental impact of treatment.

Water recycling by membrane treatment is widely accepted as a leading alternative water source. This separation process creates a concentrated stream (called concentrates), containing most of the pollutants in 10%-20% of the flow; and a treated water stream. As nitrogen is a major concern, environmental regulations have become more stringent, requiring additional treatment to meet effluent standards. Other concerns include organic contaminants and potential production of halogenated organics if disinfection of the reject was applied. One option to address the problem of dissolved organic nitrogen and carbon is advanced oxidation. This oxidation could lead to degradation of refractory organic materials, which are poorly removed in conventional treatment. This project aims to evaluate treatment extent and cost of alternatives for organic (particularly nitrogen) removal in reject water addressing the following research gaps: (i) identifying the key organic pollutants present in the concentrated stream, (ii) the effectiveness and optimisation of coagulation, ion exchange and advanced oxidation; (iii) apparent cost of the different treatment methods. The untreated reverse osmosis concentrates were collected from two treatment plants:- Luggage Point, and Bundamba, both near Brisbane, Queensland, Australia. The first contains more colourful of organics than the second plant. Stirred cell fractionation with ultrafiltration membranes was used to characterise the removed key pollutants, as it offers better accuracy and reproducibility compared to centrifugation fractionation. Fluorescence spectral was used to monitor and identify specific organic compounds. The largest fraction was smaller sized <1kDa. This is probably small humic substances and fulvic acids, as indicated by Excitation Emission Matrix (EEM) analysis. A smaller portion of soluble microbial products (SMPs) also contributes to the concentrates. Bundamba contains large non coloured organics including organic nitrogen with elevated ammonia-N. In contrast, Luggage Point has higher colour, inorganic carbon and conductivity with less ammonia-N. Advanced Oxidation Process (AOP) was the most effective treatment method (high removal of organics, e.g. 55% COD of initial), followed by magnetised ion exchange (MIEX) and coagulations. For UV/H2O2 AOP, the optimal operating condition 400mg.L-1 H2O2 and 3.1kWh.m-3 energy input resulted in organics removals up to 55% with complete decolourisation. The effective reduction was found in all size ranges, preferably in >1kDa. Low inorganic carbon and salinity in Bundamba may allow better overall oxidation rates. MIEX also performed better in Bundamba with organic removals up to 43% and 80% decolourisation at the optimum resin dose of 15mL.L-1. Removal was preferential in size range of >3kDa, with more proportional percentage for decolourisation. Similarly, ferric coagulation removed a wider size range of organics. Further, ferric achieved better organic removal in Luggage Point with up to 49%. At the same molar dose (1.5mM), ferric is superior to alum, especially in Bundamba where there were less hydrophobic compounds according to EEM. Alum is poor for treatment of high organics with less coloured water. MIEX with an operational cost (chemicals and power only) of $0.14-$0.20.m-3 treated water seemed to be the most effective treatment overall. The resin achieved better results with a slightly higher cost than coagulation, and had a lower environmental impact due to reduced sludge production. AOP offers better treatment, but at a higher cost ($0.47.m-3 treated). Combined alternatives may benefit the removal effectiveness. Furthermore, more specific identification of contaminants should be investigated separately to choose appropriate treatment for priority chemicals. Another issue is further investigation of costing, including capital, and full environmental impact of treatment.

Nas mais diversas atividades industriais hoje existentes está presente a problemática dos resíduos gerados e seu gerenciamento. Os efluentes líquidos são uma grande fonte de poluição dos recursos hídricos, sendo necessário o controle das condições de seu descarte. Para efluentes contendo poluentes orgânicos uma das alternativas de tratamento que vem sendo muito utilizada é o uso de Processos Oxidativos Avançados - POA’s. Esses processos se baseiam na geração de radicais livres, principalmente o radical hidroxila (HO.), que possui alto poder oxidante e pode promover a degradação de vários compostos poluentes eficientemente. Esses processos têm obtido grande atenção devido ao aumento da complexidade e dificuldade no tratamento de águas residuárias, o que tem sido motivo para a busca de novas metodologias visando a remediação desses rejeitos. Diante disso, o presente trabalho tem por objetivo estudar os processos (POA’s), para a degradação da matéria orgânica em efluente oriundo da descontaminação de madeira tratada com Arseniato de Cobre Cromatado – CCA. Este efluente é gerado através de extração ácida em ciclos de madeira tratada com CCA que foram utilizados como postes tanto de eletricidade como de telefonia. O efluente gerado na extração ácida foi caracterizado através dos parâmetros de pH, Condutividade, Demanda Química de Oxigênio, Carbono Orgânico Dissolvido, Sólidos totais e metais. Após caracterização, o efluente foi submetido aos processos oxidativos avançados de Fotólise, Fotocatálise heterogênea, Eletrólise e Fotoeletrooxidação, a fim de degradar a matéria orgânica. Depois de realizados os processos, o efluente foi caracterizado novamente com os mesmos parâmetros. Pode-se concluir que todos os processos utilizados alcançaram resultados positivos, degradaram a matéria orgânica, mas o processo que obteve melhor rendimento de degradação foi o de Eletrólise que degradou 68% da matéria orgânica presente no efluente. / In the most diverse industrial activities exist today is present the problem of waste generated and its management. Liquid effluents are a major source of pollution of water resources, requiring the control of the disposal conditions. For wastewater containing organic pollutants the use of Advanced Oxidation Processes - POA's has been widely used. These processes are based on the generation of free radicals, especially the hydroxyl radical (HO.), which has high oxidizing power and can promote the degradation of several polluting compounds efficiently. These processes have achieved great attention due to the increasing complexity and difficulty in the treatment of residual waters, which has been the reason for the search of new methods for remediation of these wastes. Therefore, this paper aims to study these processes (POA's) for the degradation of organic matter in the effluent coming from the decontamination of wood treated with CCA - chromated copper arsenate. This effluent is generated by cycles of acid extraction of wood treated with CCA which were used as both telephone and electricity poles. The effluent generated by the acid extraction was characterized by the parameters pH, conductivity, chemical oxygen demand, dissolved organic carbon and metals. After characterization, the effluent was subjected to advanced oxidation processes photolysis, heterogeneous photocatalysis, Electrolysis and photoelectrooxidation (which are the three processes together) in order to degrade organic matter. After the effluent treatment, the solution was again characterized by the same parameters. It can be concluded that all the processes used have achieved positive results, degradeding organic matter, but the process that showed the best performance degradation was the electrolysis with 68% less organic matter.

Nas mais diversas atividades industriais hoje existentes está presente a problemática dos resíduos gerados e seu gerenciamento. Os efluentes líquidos são uma grande fonte de poluição dos recursos hídricos, sendo necessário o controle das condições de seu descarte. Para efluentes contendo poluentes orgânicos uma das alternativas de tratamento que vem sendo muito utilizada é o uso de Processos Oxidativos Avançados - POA’s. Esses processos se baseiam na geração de radicais livres, principalmente o radical hidroxila (HO.), que possui alto poder oxidante e pode promover a degradação de vários compostos poluentes eficientemente. Esses processos têm obtido grande atenção devido ao aumento da complexidade e dificuldade no tratamento de águas residuárias, o que tem sido motivo para a busca de novas metodologias visando a remediação desses rejeitos. Diante disso, o presente trabalho tem por objetivo estudar os processos (POA’s), para a degradação da matéria orgânica em efluente oriundo da descontaminação de madeira tratada com Arseniato de Cobre Cromatado – CCA. Este efluente é gerado através de extração ácida em ciclos de madeira tratada com CCA que foram utilizados como postes tanto de eletricidade como de telefonia. O efluente gerado na extração ácida foi caracterizado através dos parâmetros de pH, Condutividade, Demanda Química de Oxigênio, Carbono Orgânico Dissolvido, Sólidos totais e metais. Após caracterização, o efluente foi submetido aos processos oxidativos avançados de Fotólise, Fotocatálise heterogênea, Eletrólise e Fotoeletrooxidação, a fim de degradar a matéria orgânica. Depois de realizados os processos, o efluente foi caracterizado novamente com os mesmos parâmetros. Pode-se concluir que todos os processos utilizados alcançaram resultados positivos, degradaram a matéria orgânica, mas o processo que obteve melhor rendimento de degradação foi o de Eletrólise que degradou 68% da matéria orgânica presente no efluente. / In the most diverse industrial activities exist today is present the problem of waste generated and its management. Liquid effluents are a major source of pollution of water resources, requiring the control of the disposal conditions. For wastewater containing organic pollutants the use of Advanced Oxidation Processes - POA's has been widely used. These processes are based on the generation of free radicals, especially the hydroxyl radical (HO.), which has high oxidizing power and can promote the degradation of several polluting compounds efficiently. These processes have achieved great attention due to the increasing complexity and difficulty in the treatment of residual waters, which has been the reason for the search of new methods for remediation of these wastes. Therefore, this paper aims to study these processes (POA's) for the degradation of organic matter in the effluent coming from the decontamination of wood treated with CCA - chromated copper arsenate. This effluent is generated by cycles of acid extraction of wood treated with CCA which were used as both telephone and electricity poles. The effluent generated by the acid extraction was characterized by the parameters pH, conductivity, chemical oxygen demand, dissolved organic carbon and metals. After characterization, the effluent was subjected to advanced oxidation processes photolysis, heterogeneous photocatalysis, Electrolysis and photoelectrooxidation (which are the three processes together) in order to degrade organic matter. After the effluent treatment, the solution was again characterized by the same parameters. It can be concluded that all the processes used have achieved positive results, degradeding organic matter, but the process that showed the best performance degradation was the electrolysis with 68% less organic matter.