Previous research indicates that pharmaceutically active compounds (PhACs) and endocrine-disrupting compounds (EDCs) are poorly removed during conventional drinking water treatment processes including coagulation; however, removal efficiency increases in the presence of natural organic matter (NOM). Therefore, this project investigates the link between various NOM types with EDC/PhAC removal. Bench-scale coagulation tests were conducted on three different source waters spiked with environmentally relevant levels (nominally 1000 ng/L) of EDCs/PhACs. Two different coagulants were used: polyaluminum chloride (PACl) and aluminum sulphate (alum). NOM was characterized using size exclusion liquid chromatography-organic carbon detection (LC-OCD). Results for Lake Ontario, Otonabee and Grand River water indicate that certain EDCs/PhACs are significantly removed during coagulation while others increase in concentration. Concurrently, particular NOM fractions (biopolymers and humic substances) are also being removed. Solvents used for EDC/PhAC spiking (acetone and acetonitrile) did not affect coagulation, but contributed to low molecular weight neutral and hydrophobic NOM fractions.

Phosphorus (P) is one of the essential nutrients for living organisms; however, excess P in aquatic systems often causes environmental and ecological problems including eutrophication. Removal of P from domestic wastewater, industrial wastewater, and agricultural organic-waste systems is required to minimize loading of P to receiving water bodies. A variety of sorbents or filter materials have previously been evaluated for P removal, including natural materials, industrial byproducts, and synthetic products. Among these materials industrial byproducts were reported as most effective. However, only a few of these studies were based on field experiments. Pharmaceutically active compounds (PhACs) and acesulfame-K (an artificial sweetener) are emerging contaminants observed in wastewater. The removal of PhACs in conventional wastewater treatment systems has been studied; however, few studies on alternative treatment systems are available. Studies related to the removal of acesulfame-K are even more limited. This thesis was focused on evaluation of basic oxygen furnace slag (BOFS), a byproduct from the steel manufacturing industry, as a potential reactive media for P removal from surface water and wastewater. The removal of PhACs and acesulfame-K in wastewater treatment systems containing BOFS as a treatment component was also evaluated. The effectiveness of BOFS for removing P from lake water was evaluated in a three year pilot-scale hypolimnetic withdrawal P treatment system at Lake Wilcox, Richmond Hill, Ontario. Phosphate concentrations of the hypolimnion water ranged from 0.3 to 0.5 mg L-1. About 83-100% P was removed during the experiment. The reactive mixtures were changed each year to improve the performance of the treatment system. Elevated pH (9-12) at the effluent of the treatment system was adjusted by sparging CO2(g) to near neutral pH. Elevated Al was removed through this pH adjustment. Elevated concentrations of V were removed in a column containing 5 wt% zero valent iron (ZVI) mixed with sand (0.5 m3) at the end of the BOFS based column. Removal of P in the BOFS based media is attributed to adsorption and co-precipitation at the outer layer of BOFS. Geochemical modeling results showed supersaturation with respect to hydroxyapatite, ß-tricalciumphosphate, aragonite, and calcite. Solid phase analyzes of the BOFS based reactive media collected after completion of the year 2 experiment (spent media) through combination of scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and X-ray absorption near edge structure spectroscopy (XANES) support the presence of calcium phosphate minerals on the outer layer of the spent media. A multistep wastewater treatment experiment was carried out in an indoor facility at the Center for Alternative Wastewater Treatment, Fleming College, Lindsay, Ontario, Canada. This experiment evaluated the removal of P, ammonia, cBOD5, COD, E. coli, total coliform, and trace metals in a series of treatment cells including a mixing cell, a vertical subsurface flow aerobic cell, a vertical subsurface flow P treatment cell containing BOFS, and a horizontal subsurface flow anaerobic cell. About 97-99% removal of P, NH3, cBOD5, E. coli, and total coliform; and ~72% removal of COD were achieved in the treatment system. The mixing cell and the aerated cell reduced the concentrations of P, ammonia, cBOD5, E. coli, and total coliform significantly and the P treatment cell provided additional treatment. However, the primary objective of the P treatment cell was to reduce P concentrations to the acceptable range according to the water quality guidelines. The P treatment cell had successfully fulfilled this objective. Elevated concentration of Al and V were also observed in the P treatment cell effluent. The concentration of Al decreased to below the guideline value of 0.075 mg L-1 after introducing a pH adjustment unit between the P treatment cell and the anaerobic cell. The concentration of V was decreased in the anaerobic cell effluent. However, the effluent concentration of V was much higher than the guideline value. Geochemical speciation modeling results showed supersaturation with respect to hydroxyapatite, ß-tricalciumphosphate, aragonite and calcite along the flow path. Accumulation of P on the outer layer of the spent BOFS media was identified by energy dispersive X-ray spectroscopy (EDX). Although X-ray photoelectron spectroscopy (XPS) can provide information to a depth of 5-7 nm from the outer layer of the spent media, both Ca and P were positively identified in some of the samples. Accumulation of P at the edge of the grains of the spent media was clearly identified on the element map of polished cross-sections and corresponding FTIR spectra. The phosphate and carbonate functional groups were identified by the distribution of different vibrational frequencies through FTIR spectroscopy. The presence of calcite and hydroxyapatite were inferred based on the wave numbers assigned for these minerals in the literature. Finally, X-ray absorption near edge structure spectroscopy (XANES) on the outer layer samples from the spent BOFS media and corresponding linear combination fitting analysis indicated the presence of ß-tricalciumphosphate, hydroxyapatite, and calcium phosphate dibasic. Based on the observations from the indoor wastewater treatment experiment, a multistep demonstration-scale outdoor wastewater treatment experiment was conducted to investigate the applicability of the integration of the P treatment technology and engineered wetland technology at a relatively large scale prior to a full-scale field installation. The anaerobic treatment cell was not included in this outdoor system because this unit did not efficiently remove ammonia and metals (e.g. V) from the Cell 4 effluent in the indoor system. A 10 cm layer of zero valent iron was placed at the bottom part of the down flowing P treatment cell to address the elevated V in the P treatment cell effluent observed in the indoor system and also to treat PhACs in the effluent. More than 99% removal of P, E. coli, and total coliform; >82, >98, and >76% removal of ammonia, cBOD5, and COD were achieved in this treatment system. The effluent pH (10.88±1.47) was neutralized and the concentration of V remained < 0.006 mg L-1. The Al concentration was adjusted to <0.075 mg L-1 with the neutralization of pH. Geochemical speciation modeling results showed the supersaturation of hydroxyapatite, ß-tricalciumphosphate, octatricalciumphosphate, aragonite, and calcite. The FTIR and XANES spectra showed the presence of calcium phosphate minerals on the outer layer of the spent media. Removal of the PhACs, including caffeine, ibuprofen, carbamazepine, naproxen, and sulfamethoxazole, and acesulfame-K was monitored in the demonstration-scale outdoor wastewater treatment system, which consisted of five different treatment cells including a horizontal subsurface flow constructed wetland, a vertical subsurface flow aerated cell, a vertical subsurface flow BOFS cell, and a pH neutralization unit. Significant removal of caffeine (>75%) and ibuprofen (50-75%), and moderate removal of sulfamethoxazole and naproxen (25-50%) were observed. The removal of carbamazepine was less effective with <25% removal observed. Acesulfame-K was also persistent along the flow path with <25% removal. This study demonstrated that removal of P from lake water and wastewater in excess of 95% could be achieved using BOFS as a reactive media. Integration of this media into an engineered wetland system enhances its performance in removing nutrients and other wastewater contaminants.

Endocrine disruption and high occurrences of intersex have been observed in wild fish associated with wastewater treatment plant (WWTP) effluents in the urbanized reaches of the Grand River watershed located in southern Ontario, Canada. WWTP effluent is a complex matrix with diverse aquatic environmental contaminants and stressors. This study aimed to: (1) characterize the spatio-temporal distribution and fate of antiandrogenic personal care products (triclosan, chlorophene, and dichlorophene), along with selected pharmaceuticals (carbamazepine, ibuprofen, naproxen, and venlafaxine) and the herbicide, atrazine in the Grand River watershed and (2) model the behaviour of these contaminants in the aquatic environment. Water sampling of 29 sites which covered six municipal WWTPs and ~100 km of river length was completed during summer low flows (July 2012). Monthly samples were also collected immediately upstream and downstream of a major WWTP (Kitchener) from August to November 2012. Many of the target pharmaceuticals and triclosan were detected in WWTP effluents in the Grand River watershed, especially those that did not nitrify (minimal treatment with high ammonia). Chlorophene was either undetected or was only found at trace levels in the effluents. Under low flow conditions, triclosan and several other pharmaceuticals exhibited a spatial pattern where concentrations increased directly downstream of the WWTPs, then decreased with distance downstream (dilution and/or degradation). Chlorophene, in contrast, was not found downstream of most of the WWTP outfalls but was first detected at a site 5 km upstream of a WWTP and then continued with relatively constant concentrations for approximately 29 km downstream. It was also only found during the summer sampling period. Atrazine was consistently found in all sampling locations which reflected the agricultural non-point source nature of this compound. The WASP 7.5 model (US Environmental Protection Agency) was adapted and calibrated to a reach of the Grand River associated with the Kitchener WWTP. The simulation of the fate and transport of the target compounds revealed that flow-driven transport processes (advection and dispersion) greatly influence their behaviour in the aquatic environment. However, fate mechanisms such as biodegradation and photolysis also potentially play an important role in the attenuation of most compounds. The exception was carbamazepine where it was shown to act as a conservative tracer compound for wastewater specific contaminants in the water phase. The fate model developed can be applied in the future to predict the fate of a wide variety of contaminants of emerging concern across the watershed to help define the exposure of these biologically active chemicals to sensitive ecosystems.

A bench-scale study of the degradation of four selected pharmaceuticals and personal care products (PPCPs) was carried out using UV and UV/H₂O₂ treatment employing low pressure (LP) and medium pressure (MP) lamps. The target substances included the pharmaceutical compounds ibuprofen, naproxen, and gemfibrozil, along with the bactericide triclosan. There were four main objectives of the study, as follows: to evaluate the removal of the target compounds using UV irradiation alone and UV/H₂O₂, to determine the reaction kinetics for direct and indirect photolysis of each selected compound, to determine the influence of major water quality parameters on the efficacy of treatment, and to compare the applied UV and UV/H₂O₂ doses to those that have been found to be effective for disinfection and removal of taste and odour compounds, respectively. For initial ultra-pure water experiments the target compounds were spiked at concentrations of approximately 250 µg/L (~1 µM). In latter ultra-pure water experiments and in the partially-treated water experiments, the selected PPCPs were spiked at a lower range (c~500-1000 ng/L), which is more representative of reported environmental concentrations. In an ultra-pure water matrix, a high LP fluence of 1000 mJ/cm² caused only triclosan to substantially degrade. Furthermore, with LP-UV/H₂O₂ only triclosan and naproxen had average percent removals above 60% at a typical disinfection fluence of 40 mJ/cm² with 100 mg/L H₂O₂. Complete degradation of all four compounds in ultra-pure water was achieved with very high fluences (compared to those used for UV disinfection) with MP-UV alone (at or above 1000 mJ/cm²) or with relatively high fluences for MP-UV/H₂O₂ (200-300 mJ/cm²) with 10 mg/L H₂O₂. Overall, when compared at similar applied fluences, the MP lamp was much more effective than the LP lamp. Furthermore, the addition of H₂O₂ typically increased removal rates, in some cases substantially, through formation and subsequent reaction of the PPCP with the •OH radical. When target substances were treated all together in an ultra-pure water solution, removals were lower than when they were treated independently at the same individual concentrations (~250 µg/L) this may simply have been the result of a higher total contaminant concentration in solution, which lessened the availability of the •OH radical and incident UV irradiation for degradation of all compounds. On the other hand, removals were improved when the combined target compounds were present at a lower individual concentration range (~750 ng/L), which suggests that removals may be concentration driven, with reduced matrix effects seen at lower overall contaminant concentrations. Furthermore, during the partially-treated water experiments, variability in treatment performance was observed with differing water quality; however, it was not evident which specific quality parameters influenced treatment effectiveness. On the other hand, substantial and sometimes complete, degradation of the target compounds was still seen in the partially-treated water with high MP-UV/H₂O₂ doses (e.g. 300 mJ/cm² + 10 mg/L H₂O₂ and 500 + 10 mg/L H₂O₂). For the kinetic experiments, compounds were spiked individually in ultra-pure water (c~250 µg/L = ~1µM). The photolysis of the target compounds during treatment was assumed to be a pseudo-first-order reaction. Kinetic parameters were determined for both direct and indirect photolysis for both lamps. The calculated rate constants confirmed the importance of •OH radicals for degradation of these compounds, especially for ibuprofen and gemfibrozil. For ibuprofen and gemfibrozil, direct photolysis rate constants could not be determined for LP-UV because very little degradation was seen at the fluences tested. LP-UV direct phototlysis rate constants for naproxen and triclosan were 0.0002 and 0.0033 cm²/mJ, respectively. Overall rate constants describing degradation of the four compounds due to LP-UV/H₂O₂ ranged from 0.0049 to 0.0124 cm²/mJ. All four compounds had fluence-based reaction rate constants for MP-UV indirect photolysis of approximately 0.01 cm²/mJ, while MP-UV direct photolysis rate constants ranged between 0.0007-0.007 cm²/mJ, with ibuprofen having the lowest and triclosan the highest. The overall trends were similar to those seen by other researchers for the removal of taste and odour compounds. For example, fluences required for substantial removal were much higher than typical disinfection doses, the MP lamp was more effective than the LP lamp (when compared solely on a fluence-basis), and the addition of H₂O₂ improved removals. On the whole, UV/H₂O₂ appears to be a very promising technology for the removal of these selected PPCPs during drinking water treatment, and is likely to be equally effective for other, similar contaminants.

A bench-scale study of the degradation of four selected pharmaceuticals and personal care products (PPCPs) was carried out using UV and UV/H₂O₂ treatment employing low pressure (LP) and medium pressure (MP) lamps. The target substances included the pharmaceutical compounds ibuprofen, naproxen, and gemfibrozil, along with the bactericide triclosan. There were four main objectives of the study, as follows: to evaluate the removal of the target compounds using UV irradiation alone and UV/H₂O₂, to determine the reaction kinetics for direct and indirect photolysis of each selected compound, to determine the influence of major water quality parameters on the efficacy of treatment, and to compare the applied UV and UV/H₂O₂ doses to those that have been found to be effective for disinfection and removal of taste and odour compounds, respectively. For initial ultra-pure water experiments the target compounds were spiked at concentrations of approximately 250 µg/L (~1 µM). In latter ultra-pure water experiments and in the partially-treated water experiments, the selected PPCPs were spiked at a lower range (c~500-1000 ng/L), which is more representative of reported environmental concentrations. In an ultra-pure water matrix, a high LP fluence of 1000 mJ/cm² caused only triclosan to substantially degrade. Furthermore, with LP-UV/H₂O₂ only triclosan and naproxen had average percent removals above 60% at a typical disinfection fluence of 40 mJ/cm² with 100 mg/L H₂O₂. Complete degradation of all four compounds in ultra-pure water was achieved with very high fluences (compared to those used for UV disinfection) with MP-UV alone (at or above 1000 mJ/cm²) or with relatively high fluences for MP-UV/H₂O₂ (200-300 mJ/cm²) with 10 mg/L H₂O₂. Overall, when compared at similar applied fluences, the MP lamp was much more effective than the LP lamp. Furthermore, the addition of H₂O₂ typically increased removal rates, in some cases substantially, through formation and subsequent reaction of the PPCP with the •OH radical. When target substances were treated all together in an ultra-pure water solution, removals were lower than when they were treated independently at the same individual concentrations (~250 µg/L) this may simply have been the result of a higher total contaminant concentration in solution, which lessened the availability of the •OH radical and incident UV irradiation for degradation of all compounds. On the other hand, removals were improved when the combined target compounds were present at a lower individual concentration range (~750 ng/L), which suggests that removals may be concentration driven, with reduced matrix effects seen at lower overall contaminant concentrations. Furthermore, during the partially-treated water experiments, variability in treatment performance was observed with differing water quality; however, it was not evident which specific quality parameters influenced treatment effectiveness. On the other hand, substantial and sometimes complete, degradation of the target compounds was still seen in the partially-treated water with high MP-UV/H₂O₂ doses (e.g. 300 mJ/cm² + 10 mg/L H₂O₂ and 500 + 10 mg/L H₂O₂). For the kinetic experiments, compounds were spiked individually in ultra-pure water (c~250 µg/L = ~1µM). The photolysis of the target compounds during treatment was assumed to be a pseudo-first-order reaction. Kinetic parameters were determined for both direct and indirect photolysis for both lamps. The calculated rate constants confirmed the importance of •OH radicals for degradation of these compounds, especially for ibuprofen and gemfibrozil. For ibuprofen and gemfibrozil, direct photolysis rate constants could not be determined for LP-UV because very little degradation was seen at the fluences tested. LP-UV direct phototlysis rate constants for naproxen and triclosan were 0.0002 and 0.0033 cm²/mJ, respectively. Overall rate constants describing degradation of the four compounds due to LP-UV/H₂O₂ ranged from 0.0049 to 0.0124 cm²/mJ. All four compounds had fluence-based reaction rate constants for MP-UV indirect photolysis of approximately 0.01 cm²/mJ, while MP-UV direct photolysis rate constants ranged between 0.0007-0.007 cm²/mJ, with ibuprofen having the lowest and triclosan the highest. The overall trends were similar to those seen by other researchers for the removal of taste and odour compounds. For example, fluences required for substantial removal were much higher than typical disinfection doses, the MP lamp was more effective than the LP lamp (when compared solely on a fluence-basis), and the addition of H₂O₂ improved removals. On the whole, UV/H₂O₂ appears to be a very promising technology for the removal of these selected PPCPs during drinking water treatment, and is likely to be equally effective for other, similar contaminants.

A bench-scale study of the degradation of four selected pharmaceuticals and personal care products (PPCPs) was carried out using UV and UV/H₂O₂ treatment employing low pressure (LP) and medium pressure (MP) lamps. The target substances included the pharmaceutical compounds ibuprofen, naproxen, and gemfibrozil, along with the bactericide triclosan. There were four main objectives of the study, as follows: to evaluate the removal of the target compounds using UV irradiation alone and UV/H₂O₂, to determine the reaction kinetics for direct and indirect photolysis of each selected compound, to determine the influence of major water quality parameters on the efficacy of treatment, and to compare the applied UV and UV/H₂O₂ doses to those that have been found to be effective for disinfection and removal of taste and odour compounds, respectively. For initial ultra-pure water experiments the target compounds were spiked at concentrations of approximately 250 µg/L (~1 µM). In latter ultra-pure water experiments and in the partially-treated water experiments, the selected PPCPs were spiked at a lower range (c~500-1000 ng/L), which is more representative of reported environmental concentrations. In an ultra-pure water matrix, a high LP fluence of 1000 mJ/cm² caused only triclosan to substantially degrade. Furthermore, with LP-UV/H₂O₂ only triclosan and naproxen had average percent removals above 60% at a typical disinfection fluence of 40 mJ/cm² with 100 mg/L H₂O₂. Complete degradation of all four compounds in ultra-pure water was achieved with very high fluences (compared to those used for UV disinfection) with MP-UV alone (at or above 1000 mJ/cm²) or with relatively high fluences for MP-UV/H₂O₂ (200-300 mJ/cm²) with 10 mg/L H₂O₂. Overall, when compared at similar applied fluences, the MP lamp was much more effective than the LP lamp. Furthermore, the addition of H₂O₂ typically increased removal rates, in some cases substantially, through formation and subsequent reaction of the PPCP with the •OH radical. When target substances were treated all together in an ultra-pure water solution, removals were lower than when they were treated independently at the same individual concentrations (~250 µg/L) this may simply have been the result of a higher total contaminant concentration in solution, which lessened the availability of the •OH radical and incident UV irradiation for degradation of all compounds. On the other hand, removals were improved when the combined target compounds were present at a lower individual concentration range (~750 ng/L), which suggests that removals may be concentration driven, with reduced matrix effects seen at lower overall contaminant concentrations. Furthermore, during the partially-treated water experiments, variability in treatment performance was observed with differing water quality; however, it was not evident which specific quality parameters influenced treatment effectiveness. On the other hand, substantial and sometimes complete, degradation of the target compounds was still seen in the partially-treated water with high MP-UV/H₂O₂ doses (e.g. 300 mJ/cm² + 10 mg/L H₂O₂ and 500 + 10 mg/L H₂O₂). For the kinetic experiments, compounds were spiked individually in ultra-pure water (c~250 µg/L = ~1µM). The photolysis of the target compounds during treatment was assumed to be a pseudo-first-order reaction. Kinetic parameters were determined for both direct and indirect photolysis for both lamps. The calculated rate constants confirmed the importance of •OH radicals for degradation of these compounds, especially for ibuprofen and gemfibrozil. For ibuprofen and gemfibrozil, direct photolysis rate constants could not be determined for LP-UV because very little degradation was seen at the fluences tested. LP-UV direct phototlysis rate constants for naproxen and triclosan were 0.0002 and 0.0033 cm²/mJ, respectively. Overall rate constants describing degradation of the four compounds due to LP-UV/H₂O₂ ranged from 0.0049 to 0.0124 cm²/mJ. All four compounds had fluence-based reaction rate constants for MP-UV indirect photolysis of approximately 0.01 cm²/mJ, while MP-UV direct photolysis rate constants ranged between 0.0007-0.007 cm²/mJ, with ibuprofen having the lowest and triclosan the highest. The overall trends were similar to those seen by other researchers for the removal of taste and odour compounds. For example, fluences required for substantial removal were much higher than typical disinfection doses, the MP lamp was more effective than the LP lamp (when compared solely on a fluence-basis), and the addition of H₂O₂ improved removals. On the whole, UV/H₂O₂ appears to be a very promising technology for the removal of these selected PPCPs during drinking water treatment, and is likely to be equally effective for other, similar contaminants.

A bench-scale study of the degradation of four selected pharmaceuticals and personal care products (PPCPs) was carried out using UV and UV/H₂O₂ treatment employing low pressure (LP) and medium pressure (MP) lamps. The target substances included the pharmaceutical compounds ibuprofen, naproxen, and gemfibrozil, along with the bactericide triclosan. There were four main objectives of the study, as follows: to evaluate the removal of the target compounds using UV irradiation alone and UV/H₂O₂, to determine the reaction kinetics for direct and indirect photolysis of each selected compound, to determine the influence of major water quality parameters on the efficacy of treatment, and to compare the applied UV and UV/H₂O₂ doses to those that have been found to be effective for disinfection and removal of taste and odour compounds, respectively. For initial ultra-pure water experiments the target compounds were spiked at concentrations of approximately 250 µg/L (~1 µM). In latter ultra-pure water experiments and in the partially-treated water experiments, the selected PPCPs were spiked at a lower range (c~500-1000 ng/L), which is more representative of reported environmental concentrations. In an ultra-pure water matrix, a high LP fluence of 1000 mJ/cm² caused only triclosan to substantially degrade. Furthermore, with LP-UV/H₂O₂ only triclosan and naproxen had average percent removals above 60% at a typical disinfection fluence of 40 mJ/cm² with 100 mg/L H₂O₂. Complete degradation of all four compounds in ultra-pure water was achieved with very high fluences (compared to those used for UV disinfection) with MP-UV alone (at or above 1000 mJ/cm²) or with relatively high fluences for MP-UV/H₂O₂ (200-300 mJ/cm²) with 10 mg/L H₂O₂. Overall, when compared at similar applied fluences, the MP lamp was much more effective than the LP lamp. Furthermore, the addition of H₂O₂ typically increased removal rates, in some cases substantially, through formation and subsequent reaction of the PPCP with the •OH radical. When target substances were treated all together in an ultra-pure water solution, removals were lower than when they were treated independently at the same individual concentrations (~250 µg/L) this may simply have been the result of a higher total contaminant concentration in solution, which lessened the availability of the •OH radical and incident UV irradiation for degradation of all compounds. On the other hand, removals were improved when the combined target compounds were present at a lower individual concentration range (~750 ng/L), which suggests that removals may be concentration driven, with reduced matrix effects seen at lower overall contaminant concentrations. Furthermore, during the partially-treated water experiments, variability in treatment performance was observed with differing water quality; however, it was not evident which specific quality parameters influenced treatment effectiveness. On the other hand, substantial and sometimes complete, degradation of the target compounds was still seen in the partially-treated water with high MP-UV/H₂O₂ doses (e.g. 300 mJ/cm² + 10 mg/L H₂O₂ and 500 + 10 mg/L H₂O₂). For the kinetic experiments, compounds were spiked individually in ultra-pure water (c~250 µg/L = ~1µM). The photolysis of the target compounds during treatment was assumed to be a pseudo-first-order reaction. Kinetic parameters were determined for both direct and indirect photolysis for both lamps. The calculated rate constants confirmed the importance of •OH radicals for degradation of these compounds, especially for ibuprofen and gemfibrozil. For ibuprofen and gemfibrozil, direct photolysis rate constants could not be determined for LP-UV because very little degradation was seen at the fluences tested. LP-UV direct phototlysis rate constants for naproxen and triclosan were 0.0002 and 0.0033 cm²/mJ, respectively. Overall rate constants describing degradation of the four compounds due to LP-UV/H₂O₂ ranged from 0.0049 to 0.0124 cm²/mJ. All four compounds had fluence-based reaction rate constants for MP-UV indirect photolysis of approximately 0.01 cm²/mJ, while MP-UV direct photolysis rate constants ranged between 0.0007-0.007 cm²/mJ, with ibuprofen having the lowest and triclosan the highest. The overall trends were similar to those seen by other researchers for the removal of taste and odour compounds. For example, fluences required for substantial removal were much higher than typical disinfection doses, the MP lamp was more effective than the LP lamp (when compared solely on a fluence-basis), and the addition of H₂O₂ improved removals. On the whole, UV/H₂O₂ appears to be a very promising technology for the removal of these selected PPCPs during drinking water treatment, and is likely to be equally effective for other, similar contaminants.

This thesis describes the development and application of solid phase microextraction (SPME) as a sample preparation technique for in vivo determination of pharmaceutical residues in fish tissue and wastewater. The occurrence, distribution and fate of pharmaceuticals in the environment are a subject of concern across the globe due to the impact they may have on human life and aquatic organisms. To address this challenge from an analytical perspective, a simplified and reliable analytical methodology is required to investigate and determine the concentration (bioconcentration factors) of trace pharmaceutical residue in fish tissue and environmental water samples (exposure). An improved SPME method, coupled with liquid chromatography with tandem mass spectrometry has been developed and applied to both controlled laboratory and field-caged fish exposed to wastewater effluent for quantitative determination of pharmaceutical residue in fish specific tissue. A new SPME configuration based on C18 thin film (blade) was developed and optimized to improve SPME sensitivity for in vivo determinations of trace pharmaceuticals in live fish. The C18 thin film extraction phase successfully quantified bioconcentrated fluoxetine, venlafaxine, sertraline, paroxetine, and carbamazapine in the dorsal-epaxial muscle of living fish at concentrations ranging from 1.7 to 259 ng/g. The reproducibility of the method in spiked fish muscle was 9-18% RSD with limits of detection and quantification ranging from 0.08 - 0.21 ng/g and 0.09 - 0.64 ng/g (respectively) for the analytes examined. Fish were sampled by in vivo SPME for 30 min to detect pharmaceutical uptake and bioconcentration, with experimental extracts analyzed using liquid chromatography coupled with tandem mass spectrometry. In addition, a simplified analytical methodology based on SPME was developed and optimized for determination and bioconcentration factor of different classes of pharmaceuticals residues in fish bile. The reproducibility of the method in spiked fish Rainbow Trout bile was 3-7% RSD with limits of detection (LOD) ranging from 0.3 – 1.4 ng/mL for the analytes examined. The field application of SPME sampling was further demonstrated in Fathead Minnow (Pimephales promelas), a small-bodied fish caged upstream and downstream of a local wastewater treatment plant where fluoxetine, atorvastatin, and sertraline were detected in fish bile at the downstream location. Also, a simple automated analytical method using high throughput robotic system was developed for the simultaneous extraction of pharmaceutical compounds detected in surface waters. The proposed method successfully determined concentrations of carbamazepine, fluoxetine, sertraline, and paroxetine in treated effluent at concentrations ranging from 240 - 3820 ng/L with a method detection limit of 2-13 ng/L, and a relative standard deviation of less than 16%. Application of the method was demonstrated using wastewater from pilot-scale municipal treatment plants and environmental water samples from wastewater-dominated reaches of the Grand River (Waterloo, ON). Finally, 4 and 8-d laboratory exposures were carried out with Rainbow Trout exposed to wastewater effluent collected from pilot scale at Burlington, ON. Additionally, wild fish, White Sucker (Catostomus commersonii) were collected and sampled from Waterloo and Kitchener downstreams containing local municipal effluent. Bioconcentration factors of the selected compounds were determined in both fish muscle and bile samples. The results show that anti-depressant drugs such fluoxetine, sertraline and paroxetine were uptake in the fish muscle and fish bile for both laboratory and field exposure. In summary, exposure of fish to micro-pollutants such as pharmaceuticals may be monitored through the analysis of bile, particularly at low concentration exposure of pharmaceuticals, where the sensitivity of analytical method may be challenged. SPME is a promising simple analytical tool which can potentially be used for monitoring of pharmaceuticals in fish tissue and wastewater.

Purpose of the Study To study how Apoteket AB can retain its customers after the government decision to implement de-regulation in Swedish pharmaceutical market. Apoteket AB was the only state-owned pharmacy for more than 38 years but now they are in competition with other pharmacy operators including supermarkets and gas stations. The main purpose of this study is to find out those vital factors which are important to customers in selecting pharmacy operators for buying prescription and non-prescription products. Approach The study begins by reviewing the Swedish pharmaceutical market and parliament decision of de-regulation about Apoteket AB monopoly. The literature then reviews the PESTEL framework, Porter model, customer relationship management and 7 P’s of marketing mix. We use Umeå university library for gathering material for our literature review. After that the authors reviewed different pharmacy operators and potential entrants in the Swedish pharmacy market. For this case study the authors have gathered the data through customer survey and semi-structured interview. The data was collected in Umeå (Sweden) with the help of questionnaire. We have collected the data with the help of convenience sampling technique at different locations in Umeå. Interview was conducted with Apoteket AB brand manager to understand their point of view about our research question. SPSS was used for analyzing the quantitative data, mainly descriptive statistic and Mann-Whitney U test were used for this purpose. Finally all the information’s were carefully analyzed by comparing with theories before drawing the final conclusion. Findings Four important aspects of customer’s retention were found; which are more community pharmacies, extended opening hours, low prices of over the counter products and added value to individual customers. Our respondents also show great confidence over the Apoteket AB personnel (Pharmacists). On the other hand we have also found that people appreciate the removal of Apoteket AB monopoly. Furthermore, we have found that after the implementation of de-regulation in Swedish pharmacy market over the counter (OTC) products have shown a 20% growth. The reason behind this growth may be the easy excess to such products and extended opening hours of supermarkets. The authors have also observed that people are willing to buy prescription products from other operators.

Water recycling has become a global trend because of water scarcity and increased demand of water supply. Therefore, attentions to the improvement of reclaimed water quality have been paid. In the past decade various environmental hormones and PPCPs (pharmaceuticals and personal care products) have been detected in different aquatic environments. Even though their concentrations are in the range of ng/L to £gg/L, these emerging contaminants might cause harm to human health and the environment. Nanoscale contaminants are another type of emerging contaminants cannot be neglected because many nanomaterials have been used in household goods of our daily lives. Thus, how to effectively separate and/or recover those nanomaterials from aqueous solution to reduce their potential hazards is an important issue The first objective of this study was to assess the efficiency of nano-Fe3O4/S2O82- oxidation against selected environmental hormones (i.e., di(2-ethylhexyl)phthalate (DEHP) and perfluorooctane sulphonates (PFOS)) and pharmaceuticals (i.e., erythromycin (ERY) and sulfamethoxazole (SMX)) in aqueous solution. The optimal operating conditions obtained from the above-indicated oxidation process were then transferred to a simultaneous electrocoagulation and electrofiltration (EC/EF) treatment module into which a tubular TiO2/Al2O3 composite membrane was incorporated. The purpose of this practice was to evaluate whether the EC/EF process could further enhance the removal of target contaminants. In this work nanoscale magnetite (nano-Fe3O4) used for activation of S2O82- oxidation was prepared by chemical coprecipitation. Then, X-ray powder diffractometry was used to confirm the crystal structure of the prepared particles as magnetite. The employment of 3 wt% soluble starch was found to be sufficient to stabilize nano-Fe3O4 for later uses. Further, slurries of nano-Fe3O4 and S2O82- (sodium persulfate) were prepared with three dosage ratios, namely 1:2.5, 1:5 and 1:10. Nano-Fe3O4/S2O82- slurries thus prepared were used for evaluating their efficiencies in removing target contaminants (i.e., DEHP, PFOS, ERY, and SMX) of two concentration levels. In this study the high concentration level referred to 38 mg/L for DEHP and 10 mg/L each for the rest of target contaminants, whereas 10 £gg/L as the low concentration level for each of target contaminants. Batch experiments of nano-Fe3O4/S2O82- oxidation against target contaminants were first carried out in glass beakers. In the case of high concentration level with a nano-Fe3O4-to-S2O82- dosage ratio of 1:10, the respective removal efficiencies for all target contaminants were greater than 98%. Using the same dosage ratio for the case of low concentration level, however, the respective removal efficiencies for all target contaminants decreased to 78-91% except for ERY. When all target contaminants of low concentration level co-existed in the reaction vessel, the residual concentrations of environmental hormones were found to be greater than that of pharmaceuticals. Under the circumstances, the removal efficiency of DEHP dropped to 70% or so. The reaction pathways of nano-Fe3O4/S2O82- oxidation against each of target contaminants with a high concentration level were also investigated. The degradation intermediates detected for all target contaminants were all in line with the literature. Besides, the degradation intermediates were all close to their respective end products except those originated from DEHP. In other words, nano-Fe3O4/S2O82- per se had a phenomenal oxidation rate against each target contaminant. The performance of EC/EF-assisted nano-Fe3O4/S2O82- oxidation against target contaminants of low concentration level was also evaluated in this study. In each test every contaminated aqueous solution was physically preconditioned within the EC/EF treatment module for 20 min prior to the application of an electric field to enact electrocoagulation and electrofiltration. The optimal operating conditions obtained were given as follows: aluminum anode, electric field strength of 60 V/cm, transmembrane pressure of 98 kPa, and crossflow velocity of 3.33 cm/s. Under such conditions, the removal efficiencies for DEHP, PFOS, ERY, and SMX were determined to be 95%, 99%, 100%, and 99%, respectively. In the case of mixed environmental hormones and pharmaceuticals, the respective removal efficiencies slightly decreased to 85-99%. It is evident that the coupling of the EC/EF process with nano-Fe3O4/S2O82- oxidation yielded a substantial removal increase for selected target contaminants. Additionally, in all tests of EC/EF-assisted nano-Fe3O4/S2O82- oxidation against target contaminants, no residual nano-Fe3O4 was found in permeate. After a simple adjustment of pH, permeate thus treated would be ready for reuse in cooling towers.