This study examined temporal variation of pharmaceutical concentrations in two streams with differing land uses: 1) a suburban stream with combined sewer overflow point sources; and, 2) a rural stream influenced by septic systems and agricultural runoff. Sites were sampled monthly for pharmaceutical concentrations and stream physiochemical parameters. Pharmaceuticals were frequently detected in both the urban and agricultural stream with the highest concentrations measured during winter. Across sites, water column dissolved oxygen concentrations positively correlated with several pharmaceuticals suggesting microbial activity is important in pharmaceutical persistence. Potential for degradation of pharmaceuticals as a carbon or nitrogen source by stream sediment microbial communities was also estimated using pharmaceutical-amended basal salt media incubated under different temperature and ultraviolet (UV) light treatments. Under 4°C incubation, caffeine and acetaminophen were the most recalcitrant compounds whereas cotinine was the most labile. Under UV-B exposure, cotinine and sulfamethoxazole were the most recalcitrant compounds whereas ibuprofen was the most labile. / Temporal variation of pharmaceuticals in an urban and agriculturally influenced stream -- Degradation potential of six pharmaceuticals by sediment microbial communities. / Department of Biology

A cafeína está presente no cotidiano humano desde o tradicional café até como constituinte de medicamentos, estimulantes, chás, chocolate entre outros produtos alimentícios. Essa substância é considerada um contaminante orgânico emergente provindo de águas residuárias não tratadas. Sua presença nos corpos hídricos vem sendo documentada em baixas concentrações, desde ηg.L-1 até µg.L-1 e os efeitos dessas concentrações nos organismos aquáticos ainda não foram efetivamente investigados. Com o objetivo de avaliar os efeitos tóxicos da cafeína em concentrações comumentemente encontradas em corpos hídricos, foram realizados testes de ecotoxicidade aguda e crônica com os organismos-teste Chironomus sancticaroli e Daphnia magna e intergeracional com C. sancticaroli, com enfoque em respostas biológicas de mortalidade, imobilidade, crescimento, desenvolvimento e reprodução. Como resultado, a cafeína não apresentou toxicidade aguda no teste de curta duração realizado para D. magna e C. sancticaroli. Foi observado efeito de toxicidade crônica da cafeína, havendo interferência no desenvolvimento das larvas de Chironomus principalmente na concentração de 200 µg.L-1 e no crescimento e reprodução de D. magna, na qual foi observada indução na produção de neonatos e desaceleração para o desenvolvimento do organismo (retardo no processo de ecdise). No teste intergeracional, foram observadas mudanças nos padrões de desenvolvimento larval. Os resultados demonstram que a cafeína, em concentrações ambientalmente detectadas, pode causar pequenas alterações no ciclo de vida dos organismos, como por exemplo, alterações no tamanho das asas das fêmeas e no comprimento do corpo das larvas de C. sancticaroli. Recomendam-se o uso de técnicas biomoleculares para avaliar as respostas metabólicas dos organismos quando exposto à cafeína em baixas concentrações. / Caffeine is present in human daily life either as traditional coffee or constituent of medicines, stimulants, teas, chocolate, among other products. This substance is an emerging organic contaminant from untreated wastewater. Its presence in aquatic systems has been documented at low concentrations, from ηg.L-1 to µg.L-1 and the effects of these concentrations on aquatic organisms have not yet been effectively investigated. In order to evaluate the toxic effects of caffeine, at concentrations usually found in aquatic systems, acute and chronic ecotoxicological tests were performed with Chironomus sancticaroli and Daphnia magna and, an intergenerational with C. sancticaroli, focusing on biological responses of mortality, immobility, growth, development and reproduction. As a result, caffeine did not present acute toxicity in the shor-term test performed for D. magna and C. sancticaroli. Chronic toxicity of caffeine was observed, with interference in the Chironomus larvae development, mainly in the concentration of 200 µg.L-1, and in the growth and reproduction of D. magna, in which it was observed presence of induction in the production of neonates and deceleration to the development of the organism (delay in the process of ecdysis). In intergeneration test, changes in the larval developmental patterns were observed. In intergenerational testing, changes in larval developmental patterns were observed. The results demonstrate that caffeine, in concentrations detected environmentally, can cause small influences in the organism\'s life cycle of the, for example, changes in the size of the wings of the females and in the length of the body of the larvae of C. sancticaroli. The use of biomolecular techniques to evaluate the metabolic responses of organisms when exposed to caffeine at low concentrations is recommended.

O presente trabalho estuda a remoção dos fármacos amoxicilina (AMX), diclofenaco sódico (DCF) e paracetamol (PAR) em solução aquosa pelos processos de adsorção em batelada e coluna de leito fixo utilizando o carvão ativado granulado (CAG) como adsorvente. Os experimentos foram realizados para cada fármaco de forma independente. Na adsorção em batelada foram avaliadas as influências do pH (2 – 10), concentração de adsorvente (5 – 20 g L-1) e tempo de contato (5 – 350 min). Foi realizada a investigação da cinética de adsorção e também do equilíbrio de adsorção através de isotermas nas temperaturas de 25, 35 e 45 ºC. A adsorção em leito fixo foi estudada através de planejamentos experimentais, onde foram avaliados os efeitos da concentração inicial do poluente (C0: 20 – 100 mg L-1), massa do leito (W: 0,5 – 1,5 g) e vazão (Q: 3 – 5 mL min-1) sobre o tempo de saturação (tsat) e a quantidade adsorvida (qsat). Os modelos de Thomas, Bohart-Adams e Yan, além de um modelo desenvolvido no software EMSO foram utilizados para análise das curvas de ruptura. O CAG utilizado apresentou área BET de 463 m² g-1 e maior volume de microporos, de 0,20 cm³ g-1. Os experimentos em batelada mostraram que o pH não teve influência significativa sobre a remoção dos três fármacos. O equilíbrio de adsorção da AMX e do DCF foi atingido após 150 min e do PAR após 180 min. O modelo de PSO foi o que melhor representou a cinética de adsorção dos três fármacos. A isoterma de Langmuir descreveu o equilíbrio da AMX a 25 e 35 ºC, e o modelo de Sips a 45 ºC. Já a adsorção do DCF foi representada pela isoterma de Freundlich e o PAR pela de Redlich-Peterson. O estudo termodinâmico indicou que a adsorção dos três fármacos foi espontânea e favorável, além de aumentar com o aumento da temperatura. Na adsorção em leito fixo, foi observado menores valores de tsat com o aumento de C0 e de Q e diminuição de W. Foi verificado que qsat aumentou com o aumento de C0 e diminuição da Q para o planejamento do PAR, onde essa variável foi significativa. Já o aumento de W aumentou qsat no planejamento do PAR e diminuiu nos casos da AMX e DCF. A AMX foi o poluente que apresentou os menores tempos de saturação, seguido do DCF e do PAR, na adsorção em leito fixo. Foi constatado que o modelo de Yan foi o que melhor reproduziu o comportamento das curvas de ruptura para os três fármacos, na comparação com os outros modelos analíticos e com o modelo numérico proposto no software EMSO. De forma geral, foi verificado que os processos de adsorção tanto em batelada quanto em leito fixo apresentam potencial de aplicação como alternativa de tratamento avançado de água e efluentes que contenham fármacos. / The present work studies the removal of amoxicillin (AMX), sodium diclofenac (DCF), and paracetamol (PAR) from water by adsorption onto granular activated carbon in batch process and fixed bed column. Batch adsorption experiments were performed to evaluate the influence of pH (2 – 10), adsorbent concentration (5 – 20 g L-1) and contact time (5 – 350 min). Pseudo-first order, pseudo-second order and intraparticle diffusion models were evaluated in the kinetics investigation. Equilibrium adsorption was investigated using Langmuir, Freundlich, Sips and Redlich-Peterson equations. Fixed bed adsorption was studied through experimental design to evaluate initial contaminant concentration (C0, 20 – 100 mg L-1), amount of adsorbent (W, 0.5 – 1.5 g) and feed flow rate (Q, 3 – 5 mL min-1) effects. The analytical models of Thomas, Bohart-Adams and Yan were selected to investigate the breakthrough curves behavior. In addition, a numerical model was developed and solved using EMSO software. The granular activated carbon (GAC) used had BET surface area of 463 m² g-1 and volume of 0.20 cm³ g-1 of micropores. The pH had no significant effect on the adsorption removal of the three drugs. Adsorption equilibrium of AMX and DCF was reached after 150 min and 180 min for PAR. Pseudo second order model best represented kinetic adsorption of the three compounds. At best conditions in batch process, adsorbent concentration was 12.5 g L-1 for AMX and DCF and 10 g L-1 for PAR. Langmuir isotherm best described AMX adsorption equilibrium at 25 and 35 ºC, and Sips model at 45 ºC. DCF and PAR adsorption followed the Freundlich isotherm and Redlich-Peterson model, respectively. Thermodynamic study indicated that the three drugs adsorption were spontaneous and favorable processes. In addition, adsorption increased at higher temperatures. In fixed bed adsorption experiments, saturation time (tsat) decreased with the increase of initial concentration and flow rate for both drugs. W had positive effect on tsat. The amount adsorbed (qsat) was enhanced at higher C0 and lower Q. qsat was higher at higher Q for AMX and DCF and lower Q for PAR adsorption. Yan model best reproduced breakthrough curves behavior for all drugs among the analytical models and the numerical model developed on EMSO software. Thus, adsorption processes in batch mode and fixed bed column showed to be effective for the removal of drugs of different therapeutic classes from water.

A degradação de antibiótico tetraciclina (TeC) foi avaliada por vários processos a saber, eletroquímico, eletroquímico foto-assistido, Fenton e foto-Fenton. Uma vez que este tipo de antibiótico é excretado principalmente pelo sistema urinário, o meio selecionado foi uma mistura de sais predominantes na composição de urina, a qual apresenta alta concentração de diferentes íons, especialmente íons cloretos. As degradações eletroquímica e eletroquímica foto-assistida foram realizadas em uma célula de fluxo do tipo filtro-prensa, usando um ânodo dimensionalmente estável comercial com composição nominal Ti/Ru0,3Ti0,7O2. O decaimento da concentração do TeC foi determinado por cromatografia líquida de alta eficiência (CLAE) e a remoção da carga orgânica por análise de carbono orgânico total (COT). Os processos de degradação eletroquímica e eletroquímica foto-assistido utilizaram densidades de correntes de 20 a 40 mA cm-2 e concentração inicial de TeC de 200 mg L-1. Aplicando 30 mA cm-2, após duas horas a remoção de TeC foi de 91% e 98%, utilizando processo eletroquímico sem e com foto- assistência, respectivamente. A remoção de COT foi incompleta com um máximo de 17%. A fim de comparar o efeito da mistura salina sobre a degradação de TeC, as eletrólises também foram realizadas em NaCl 0,1 mol L-1, onde foi obtida degradação rápida e completa (100%) em ambos os processos, a remoção de COT também foi melhorada (~29%). A degradação de TeC obedeceu uma cinética de pseudo-primeira ordem. A degradação também foi avaliada utilizando os processos Fenton e foto-Fenton na mesma mistura salina variando a concentração inicial de H2O2 (50-150 mg L-1) e de Fe2+ (2,5-15 mg L-1). A concentração inicial de Fe2+ e H2O2 tem uma influência maior sobre a degradação durante ambos os processos. Durante o processo Fenton, sob condições otimizadas, a TeC foi degradada >96%, sendo 57% a redução de COT correspondente, enquanto em meio de NaCl ocorreu a remoção de 99% e redução de COT de 41%. Um ligeiro decaimento foi observado utilizando o processo foto-Fenton devido à influência de íons presentes no meio. Os intermediários de degradação também foram identificados por CLAE acoplado a espectrometria de massa durante os processos Fenton e foto-Fenton, sendo então proposta uma sequência reacional de degradação da TeC . / The degradation of antibiotics tetracycline (TeC) was evaluated by various processes such as electrochemical, photo-assisted electrochemical, Fenton and photo-Fenton. Since this type of antibiotic is excreted mainly by urinary system, the selected medium was a mixture of salts prevailing in composition of urine, which has high concentration of different ions, especially chloride ions. The electrochemical and photo-assisted electrochemical degradations were performed in a filter press type flow cell using a dimensionally stable anode with nominal composition of Ti/Ru0.3Ti0.7O2. The decrease in TeC concentration was analyzed by high performance liquid chromatography and total organic carbon analysis. The electrochemical and photo-assisted electrochemical degradation was performed at current densities of 20 to 40 mA cm-2 and initial TeC concentration of 200 mg L-1. At a current density of 30 mA cm-2,91% and 98% TeC was removed after 2 hours, during electrochemical and photo-assisted electrochemical processes respectively. The TOC removal was incomplete with maximum of 17%. In order to compare the TeC degradation in saline medium, electrolysis was also carried out in 0.1 mol L-1 NaCl, where fast and complete (100%) degradation was observed in both processes and TOC removal was also improved (~29 %). The degradation of TeC followed pseudo-first order kinetics. Fenton and Photo-Fenton process was also evaluated for the degradation of TeC in similar saline medium varying the initial concentration of H2O2 (50_150 mg L-1) and Fe2+ (2.5-15 mg L-1). The initial concentration of Fe2+ and H2O2 has a high influence upon TeC degradation during both processes. During Fenton process under optimized conditions, >96% of TeC was degraded and 57% TOC was removed. However in NaCl medium, 99% degradation 41% TOC was obtained. The degradation was slightly decreased during photo-Fenton process due to the influence of ions in the medium. The degradation Intermediates were also identified by HPLC coupled with mass spectrometer and proposed a reaction sequence for the degradation of TeC.

Guan, Lijie. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 139-161). / Abstracts in English and Chinese. / Acknowledgements --- p.i / Table of contents --- p.vii / List of Figures --- p.X / List of Tables --- p.xiii / Abbreviations --- p.xiv / Chapter 1. --- INTRODUCTION --- p.1 / Chapter 1.1 --- Source and Fate of Pharmaceuticals in the Environment --- p.1 / Chapter 1.2 --- Occurrence of Pharmaceuticals --- p.2 / Chapter 1.2.1 --- Wastewater --- p.2 / Chapter 1.2.2 --- Sewage sludge and soil --- p.5 / Chapter 1.2.3 --- "Surface water, ground water and seawater" --- p.6 / Chapter 1.2.4 --- Drinking water --- p.9 / Chapter 1.3 --- Effects on the Environment --- p.11 / Chapter 1.3.1 --- Antibiotic resistance --- p.11 / Chapter 1.3.2 --- Ecotoxicity on the aquatic organisms --- p.14 / Chapter 1.4 --- Removal in the Environment --- p.19 / Chapter 1.4.1 --- Adsorption --- p.20 / Chapter 1.4.2 --- Photodegradation and hydrolysis --- p.22 / Chapter 1.4.3 --- Biodegradation --- p.23 / Chapter 1.5 --- Analytical Method of Pharmaceuticals in Environmental Samples --- p.25 / Chapter 1.5.1 --- Solid-phase extraction --- p.25 / Chapter 1.5.2 --- Liquid chromatography mass spectrometry --- p.30 / Chapter 1.6 --- Objectives and Outline of Thesis --- p.33 / Chapter 2 --- OCCURRENCE AND FATE OF SELECTED PHARMCEUTICALS IN STPS --- p.35 / Chapter 2.1 --- Introduction --- p.35 / Chapter 2.2 --- Materials and Methods --- p.36 / Chapter 2.2.1 --- Choice of pharmaceuticals for study --- p.36 / Chapter 2.2.2 --- Description of sewage treatment plants (STPs) --- p.41 / Chapter 2.2.3 --- Experimental approach --- p.49 / Chapter 2.3 --- Results and Discussion --- p.55 / Chapter 2.3.1 --- Occurrence of azithromycin --- p.55 / Chapter 2.3.2 --- Fate of azithromycin --- p.59 / Chapter 2.3.3 --- Occurrence of erythromycin --- p.63 / Chapter 2.3.4 --- Fate of erythromycin --- p.67 / Chapter 2.3.5 --- Occurrence of roxithromycin --- p.70 / Chapter 2.3.6 --- Fate of roxithromycin --- p.74 / Chapter 2.3.7 --- Occurrence of atenolol --- p.75 / Chapter 2.3.8 --- Fate of atenolol --- p.79 / Chapter 2.3.9 --- Occurrence of simvastatin --- p.81 / Chapter 2.3.10 --- Fate of simvastatin --- p.84 / Chapter 2.3.11 --- Fate of pharmaceuticals during different treatment process --- p.85 / Chapter 2.3.12 --- Contribution of industrial (manufacturing) plants to STPs --- p.87 / Chapter 2.3.13 --- Seasonal variation --- p.87 / Chapter 2.4 --- Summary --- p.90 / Chapter 3 --- EFFECTS OF PHARMACEUTICALS ON ACTIVATED SLUDGE BACTERIA --- p.91 / Chapter 3.1 --- Introduction --- p.91 / Chapter 3.2 --- Materials and Methods --- p.92 / Chapter 3.2.1 --- Growth inhibition test --- p.92 / Chapter 3.2.2 --- Nitrification inhibition test --- p.94 / Chapter 3.3 --- Results and Discussion --- p.96 / Chapter 3.3.1 --- Growth inhibition of activated sludge bacteria --- p.96 / Chapter 3.3.2 --- Inhibition of nitrifying bacteria --- p.102 / Chapter 4 --- BIODEGRADATION PATHWAYS OF FOUR PHARMACEUTICALS --- p.106 / Chapter 4.1 --- Introduction --- p.106 / Chapter 4.2 --- Materials and Methods --- p.107 / Chapter 4.2.1 --- Test procedures --- p.107 / Chapter 4.2.2 --- Detection method --- p.108 / Chapter 4.3 --- Results and Discussion --- p.109 / Chapter 4.3.1 --- Degradation of atenolol --- p.109 / Chapter 4.3.2 --- Degradation of azithromycin --- p.117 / Chapter 4.3.3 --- Degradation of erythromycin --- p.129 / Chapter 4.3.4 --- Degradation of roxithromycin --- p.133 / Chapter 4.4 --- Summary --- p.134 / Chapter 5 --- GENERAL CONCLUSIONS --- p.136 / References --- p.139

O presente trabalho estuda a degradação fotocatalítica da nicotina em solução aquosa, um alcaloide altamente tóxico que tem sido detectado em efluentes, águas subterrâneas e água mineral. Os experimentos foram realizados em um reator batelada sob irradiação ultravioleta, tendo sido avaliadas três principais variáveis: concentração inicial do contaminante, concentração de catalisador e pH inicial da solução. Foram realizados dois planejamentos de experimentos para os catalisadores comerciais ZnO e TiO2, com o objetivo de encontrar a melhor condição para promover a degradação da nicotina em água. Outros catalisadores, preparados a partir de resíduos industriais e laboratoriais, foram testados nas condições otimizadas. O método analítico empregado para quantificar a nicotina nas amostras foi a cromatografia líquida de alta eficiência, o que permitiu registrar a formação de intermediários e subprodutos de reação. Os resultados experimentais demostraram que a degradação da nicotina por fotocatálise heterogênea é um processo bastante eficiente. Em ambos os planejamentos, o pH foi a variável que exerceu o maior efeito sobre a degradação, sendo este fortemente positivo. Já a concentração inicial de nicotina exerceu efeito negativo sobre a resposta e a concentração de catalisador em suspensão exibiu um ponto ótimo, que correspondeu a 0,91 g.L-1 para o ZnO, e 1,20 g.L-1 para o TiO2. Ensaios foram realizados nas condições otimizadas encontradas, onde cerca de 98% da molécula foi degradada utilizando ZnO em suspensão e 88% empregando TiO2, em uma hora de reação. A degradação fotocatalítica da nicotina demonstrou seguir uma cinética de pseudoprimeira ordem dentro do tempo de reação de 60 minutos, para os dois catalisadores comerciais. Entre os catalisadores não convencionais que foram testados, aquele que demonstrou o maior percentual de degradação foi obtido a partir de resíduo de uma indústria petroquímica, cerca de 43%. / The present work studies the photocatalytic degradation of nicotine in aqueous solution. This alkaloid is highly toxic and it has been detected in wastewater, groundwater and mineral water. The experiments were performed in a batch reactor under ultraviolet radiation. Three main variables of process were evaluated: initial concentration of pollutant, catalyst concentration and initial pH of the solution. Two experimental designs were performed for commercial catalysts ZnO and TiO2. The purpose was to find the best condition to promote the nicotine degradation in water. Other catalysts prepared from industrial and laboratory waste were tested under the optimized conditions. Analytical method used to quantify nicotine and its degradation products in all samples was high performance liquid chromatography. Experimental results showed that nicotine degradation by heterogeneous photocatalysis is a very efficient process. In both designs, initial pH was the most significant variable which has a strong positive effect. Initial nicotine concentration showed a negative effect, and catalyst concentration exhibited an optimal value for both commercial catalysts: 0,91 g.L-1 using ZnO, and 1,20 g.L-1 with TiO2. At the best conditions, about 98% of the molecule was degraded using ZnO and 88% with TiO2. Photocatalytic nicotine degradation followed a pseudo first order kinetic until 60 minutes of reaction for both commercial catalysts. Among the non-conventional catalysts tested, the one prepared from a petrochemical industry residue exhibited the highest photocatalytic degradation, about 43%.

The feasibility of using solid phase micro-extraction (SPME) as an in vivo sampling tool for analysis of trace environmental contaminants in fish exposed to municipal wastewater effluents (MWWEs) was validated using controlled laboratory and field experiments. SPME was compared with traditional extraction techniques， including solid phase extraction (SPE) in water and solid-liquid extraction (SLE) in fish tissues to assess relative efficiencies. All three techniques were used to quantify the presence of eight compounds of interest in fish exposed to MWWEs in the laboratory, as well as in wild and field caged fish upstream and downstream of three wastewater treatment plants in the Grand River watershed. Atrazine, carbamazepine, naproxen, diclofenac, gemfibrozil, bisphenol A, fluoxetine and ibuprofen were selected as target compounds due to their diverse chemical characteristics and frequent detection in surface waters and sediments around the world. The distribution coefficients between various sample matrices (water, fish) and extraction phases (SPME fibers) were compared, as were extraction profiles and bioconcentration factors of target analytes in muscle of fish exposed to MWWEs under laboratory conditions, during field caging studies, or collected (wild) from the Grand River. Poly(dimethylsiloxane) (PDMS) medical grade tubing was utilized as the SPME extraction phase, which when kinetically calibrated, were effective at extracting and quantifying the target analytes from both water and fish tissue relative to traditional techniques. Caged and in wild fish exposed to MWWEs from all three municipal treatment plants bio-accumulated detectable levels of several of the target chemicals. All target analytes (except for fluoxetine) were identified in the MWWEs and exposed fish by SPME at low concentrations (ng/L). The presence and concentration of the targeted analytes in both water and wild fish living in the Grand River watershed varied with season and proximity to the wastewater outfalls. Results demonstrate that properly applied SPME can detect and quantify selected contaminants in fish tissues, surface water, and wastewater effluents. In vivo SPME allows for non-lethal sampling of fish, which creates the opportunity for monitoring contaminant exposure in receiving environments influenced by MWWEs or non-point-source runoff while minimizing the impact on the organisms.

The presence of human pharmaceuticals in the aquatic environment is now becoming a well-established fact. The identified problems associated with their presence include the fact that these compounds are biologically active, some of them are toxic in nature, and a number of compounds have potential to foster and maintain drug resistant microorganisms. They are discharged into the aquatic environment from a variety of sources, but mainly by the excretion of incompletely metabolized pharmaceuticals by individuals into the wastewater. This situation makes finding a source-control strategy difficult. However, healthcare facility (hospitals and long-term-care homes) effluents are suspected to have relatively higher concentrations of these compounds, as such facilities use pharmaceuticals in large amounts for diagnostic, cure and research purposes. It is expected that controlling discharges from these facilities may provide a cost-effective solution to reduce the pharmaceutical loads entering the aquatic environment.

The feasibility of using solid phase micro-extraction (SPME) as an in vivo sampling tool for analysis of trace environmental contaminants in fish exposed to municipal wastewater effluents (MWWEs) was validated using controlled laboratory and field experiments. SPME was compared with traditional extraction techniques， including solid phase extraction (SPE) in water and solid-liquid extraction (SLE) in fish tissues to assess relative efficiencies. All three techniques were used to quantify the presence of eight compounds of interest in fish exposed to MWWEs in the laboratory, as well as in wild and field caged fish upstream and downstream of three wastewater treatment plants in the Grand River watershed. Atrazine, carbamazepine, naproxen, diclofenac, gemfibrozil, bisphenol A, fluoxetine and ibuprofen were selected as target compounds due to their diverse chemical characteristics and frequent detection in surface waters and sediments around the world. The distribution coefficients between various sample matrices (water, fish) and extraction phases (SPME fibers) were compared, as were extraction profiles and bioconcentration factors of target analytes in muscle of fish exposed to MWWEs under laboratory conditions, during field caging studies, or collected (wild) from the Grand River. Poly(dimethylsiloxane) (PDMS) medical grade tubing was utilized as the SPME extraction phase, which when kinetically calibrated, were effective at extracting and quantifying the target analytes from both water and fish tissue relative to traditional techniques. Caged and in wild fish exposed to MWWEs from all three municipal treatment plants bio-accumulated detectable levels of several of the target chemicals. All target analytes (except for fluoxetine) were identified in the MWWEs and exposed fish by SPME at low concentrations (ng/L). The presence and concentration of the targeted analytes in both water and wild fish living in the Grand River watershed varied with season and proximity to the wastewater outfalls. Results demonstrate that properly applied SPME can detect and quantify selected contaminants in fish tissues, surface water, and wastewater effluents. In vivo SPME allows for non-lethal sampling of fish, which creates the opportunity for monitoring contaminant exposure in receiving environments influenced by MWWEs or non-point-source runoff while minimizing the impact on the organisms.

The presence of human pharmaceuticals in the aquatic environment is now becoming a well-established fact. The identified problems associated with their presence include the fact that these compounds are biologically active, some of them are toxic in nature, and a number of compounds have potential to foster and maintain drug resistant microorganisms. They are discharged into the aquatic environment from a variety of sources, but mainly by the excretion of incompletely metabolized pharmaceuticals by individuals into the wastewater. This situation makes finding a source-control strategy difficult. However, healthcare facility (hospitals and long-term-care homes) effluents are suspected to have relatively higher concentrations of these compounds, as such facilities use pharmaceuticals in large amounts for diagnostic, cure and research purposes. It is expected that controlling discharges from these facilities may provide a cost-effective solution to reduce the pharmaceutical loads entering the aquatic environment.