M. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences) -- Vaal University of Technology / The widespread use of phenols and phenolic derivatives in industrial applications has resulted in their discharge as part of industrial wastewater. These chemicals are toxic and need to be removed from the aqueous environment. Amongst the available pollutant removal technologies, adsorption has been widely used due to its simplicity, ease of operation, cost-effectiveness and ability to sequester pollutants at very low concentrations. Different adsorbents have been applied for removal of phenols and their derivatives. Use of agricultural waste as adsorbents seems to offer a much cheaper alternative in pollutant removal. This study examines the synthesis of a hydrophobic biomaterial composite by cross-linking of Fenton treated pine cone and applying the prepared adsorbent for 2-nitrophenol removal from aqueous solution. Pine cone biomass, in its raw and modified forms was tested for its ability to remove 2-nitrophenol from simulated industrial wastewater. The experimental procedure is divided into two main parts: (1) pine cone modification using Fenton’s reagent and 1.6-hexamethylene diisocyanate and (2) application of the prepared hydrophobic adsorbent for 2-nitrophenol removal from wastewater. Fenton’s reagent was used to remove pigments, extractives and other soluble organic compounds from the raw pine. FTIR spectroscopy showed an increase in magnitude of oxygenated surface groups which resulted in a decrease in pHpzc. The effect of Fenton treatment on further modification of the pine biomass via cross-linking using 1.6-hexamethylene diisocyanate was investigated. Optimum reaction variables for the cross-linking using dibutyltin dilaurate as catalyst under an inert nitrogen gas atmosphere in anhydrous hexane solvent were determined using FTIR spectroscopy. Success of the cross-linking procedure was confirmed by use of analytical techniques (XRD, TGA, SEM, EDX and BET surface area) and weight percent gain calculations. Pine and modified pine biomass were tested for their ability to sequester 2-nitrophenol via batch adsorption technique. The effect of pine modification on affinity for the biosorbate was investigated. The mechanism of the adsorption process was determined via use of kinetic, diffusion and equilibrium isotherm models. Two error functions (coefficient of determination and percent variable error) were employed to substantiate the model showing a good fit to the experimental adsorption data. The experimental adsorption kinetic data was fit to the pseudo-first-order and pseudo-second-order kinetic models. Due to the large size of the pollutant molecules diffusion process analysis was also conducted. The effect of pine modification on kinetic and diffusion parameters was determined. The experimental equilibrium adsorption data was fit to the Freundlich, Redlich-Peterson and Hill isotherm models. The initial shapes of the adsorption isotherms for 2-nitrophenol adsorption onto pine and modified pine biomass determined the type of equilibrium isotherm models to fit the experimental data to. Thermodynamic parameters were calculated to determine the spontaneity, feasibility and energy changes associated with the adsorption process. The degree of disorder at the solid/liquid interface after the adsorption was determined. The effect of temperature on the adsorption process was used to show whether the adsorption is physical or chemical. The effect of pine modification on equilibrium isotherm parameters was determined. The study is divided into seven chapters: Chapter 1: The chapter covers the introduction, problem statement, aim and objectives of the research. It gives an insight into the research project. Chapter 2: The literature review of pollutants in industrial wastewater and methods of their removal is dealt with in this chapter. Adsorption is introduced as an alternative technique for pollutant removal from aqueous systems. An in-depth review of various adsorbents (including pine cone), their merits and limitations are also discussed together with methods of modifying and use of modified adsorbents. Equilibrium, kinetic and thermodynamic models used to treat adsorption experimental data are presented. Chapter 3: The experimental procedures on the synthesis, characterization and application of the hydrophobic biosorbent in the removal of 2-nitrophenol from aqueous solution are presented. Kinetic and equilibrium experiments are described in detail. Chapter 4: It describes the first part of the results and discussions. The chapter focuses on optimization of reaction variables and characterization (using various analytical techniques) of the hydrophobic biomaterial composite. Chapter 5 The chapter discusses the second part of the results. It focuses on magnitude of surface charge, pHpzc and kinetic studies. Fitting of the adsorption experimental data to kinetic and diffusion models is presented together with the error functions. Chapter 6 The chapter discusses part three of the results on equilibrium studies. The adsorption experimental data is fitted to equilibrium isotherm equations and error determination is presented. Thermodynamic parameters are calculated and interpreted. Chapter 7: Conclusion and recommendations are presented. The optimum reaction variables for cross-linking of Raw and Fenton treated pine cone were determined using FTIR analysis and found to be: 0.2 g pine biomass, 3.5 cm3 1.6-hexamethylene diisocyanate cross-linker, 50 cm3 anhydrous hexane solvent, 1.5 cm3 dibutyltin dilaurate catalyst, temperature of 50 °C and a reaction time of 4 hours. The pine surface showed an increase in phenolic, lactonic and carboxylic acid groups due to the modification. The pHpzc showed a decrease due to modification of the pine cone biomass. The pHpzc values for the pine and modified pine cone biomass were found to be: Raw = 7.49, Raw-HMDI modified = 6.68, Fenton treated pine = 5.40 and Fenton-HMDI modified = 6.12. The optimum pH for the adsorption of 2-nitrophenol onto raw pine and modified pine cone biomass was determined to be 6. The optimum adsorbent dosage was determined as 1.5 g/dm3. The adsorption kinetics show a good fit with the pseudo-second-order model. This suggests that surface adsorption is the controlling step in the adsorption of 2-nitrophenol onto pine cone biomass. The analysis of diffusion processes showed that the initial rapid stage during the adsorption is due to external mass transfer processes. The adsorption experimental data also showed that pore diffusion was rate-limiting amongst the diffusion processes. Pine modification using Fenton’s reagent and 1.6-hexamethylene diisocyanate increased magnitude of kinetic and diffusion parameters. Experimental data for 2-nitrophenol adsorption onto pine and modified pine cone biomass showed better correlation with the Redlich-Peterson and Hill isotherm models and poor correlation with the Freundlich isotherm model. This suggests that the mechanism does not show complete multilayer coverage with cooperative phenomena between adsorbate molecules. Thermodynamic parameters showed that the adsorption is feasible, spontaneous, and exothermic and results in a decrease in degree of disorder at the solid/liquid interface. An increase in temperature resulted in a decrease in adsorption capacity showing that the adsorption is physical. Pine modification using Fenton’s reagent and 1.6-hexamethylene diisocyanate increased magnitude of kinetic, diffusion and isotherm parameters. The kinetic and equilibrium results show that the adsorption of 2-nitrophenol onto pine cone biomass follows the order: Fenton treated-HMDI > Fenton treated > Raw-HMDI > Raw. Hence, it can be concluded that Fenton treatment and HMDI cross-linking modification did increase the adsorptive capabilities of the pine cone biomass. / VUT Research Directorate

Les troubles reliés à la dépression, l’épuisement professionnel et l’anxiété sont de plus en plus répandus dans notre société moderne. La consommation croissante d’antidépresseurs dans les différents pays du monde est responsable de la récente détection de résidus à l’état de traces dans les rejets urbains municipaux. Ainsi, ces substances dites « émergentes » qui possèdent une activité pharmacologique destinée à la régulation de certains neurotransmetteurs dans le cerveau suscitent maintenant de nombreuses inquiétudes de la part de la communauté scientifique. L’objectif principal de ce projet de doctorat a été de mieux comprendre le devenir de plusieurs classes d’antidépresseurs présents dans diverses matrices environnementales (i.e. eaux de surfaces, eaux usées, boues de traitement, tissus biologiques) en développant de nouvelles méthodes analytiques fiables capables de les détecter, quantifier et confirmer par chromatographie liquide à haute performance couplée à la spectrométrie de masse en tandem (LC-QqQMS, LC-QqToFMS). Une première étude complétée à la station d’épuration de la ville de Montréal a permis de confirmer la présence de six antidépresseurs et quatre métabolites N-desmethyl dans les affluents (2 - 330 ng L-1). Pour ce traitement primaire (physico-chimique), de faibles taux d’enlèvement (≤ 15%) ont été obtenus. Des concentrations d’antidépresseurs atteignant près de 100 ng L-1 ont également été détectées dans le fleuve St-Laurent à 0.5 km du point de rejet de la station d’épuration. Une seconde étude menée à la même station a permis l’extraction sélective d’antidépresseurs dans trois tissus (i.e. foie, cerveau et filet) de truites mouchetées juvéniles exposées à différentes concentrations d’effluent dilué traité et non-traité à l’ozone. Un certain potentiel de bioaccumulation dans les tissus (0.08-10 ng g-1) a été observé pour les spécimens exposés à l’effluent non-traité (20% v/v) avec distribution majoritaire dans le foie et le cerveau. Une intéressante corrélation a été établie entre les concentrations de trois antidépresseurs dans le cerveau et l’activité d’un biomarqueur d’exposition (i.e. pompe N/K ATPase impliquée dans la régulation de la sérotonine) mesurée à partir de synaptosomes de truites exposées aux effluents. Une investigation de l’efficacité de plusieurs stations d’épuration canadiennes opérant différents types de traitements a permis de constater que les traitements secondaires (biologiques) étaient plus performants que ceux primaires (physico-chimiques) pour enlever les antidépresseurs (taux moyen d’enlèvement : 30%). Les teneurs les plus élevées dans les boues traitées (biosolides) ont été obtenues avec le citalopram (1033 ng g-1), la venlafaxine (833 ng g-1) et l’amitriptyline (78 ng g-1). Des coefficients de sorption expérimentaux (Kd) calculés pour chacun des antidépresseurs ont permis d’estimer une grande sorption des composés sertraline, desméthylsertraline, paroxetine et fluoxetine sur les solides (log Kd > 4). Finalement, un excellent taux d’enlèvement moyen de 88% a été obtenu après ozonation (5 mg L-1) d’un effluent primaire. Toutefois, la caractérisation de nouveaux sous-produits N-oxyde (venlafaxine, desmethylvenlafaxine) par spectrométrie de masse à haute résolution (LC-QqToFMS) dans l’effluent traité à l’ozone a mis en lumière la possibilité de formation de multiples composés polaires de toxicité inconnue. / Mood disorders such as depression, burn-out and anxiety have increased in our modern society. Increasing amounts of antidepressant prescriptions around the world are now suspected to be the main cause of the recent detection of traces of antidepressant residues within urban wastewaters. These so-called “emerging” substances that possess pharmacological activity towards neurotransmitter regulation in the brain have raised serious concerns from the scientific community. The initial goal of the study was to better understand the fate of various classes of antidepressants present in different environmental matrices (e.g. surface waters, wastewaters, treatment sludge, and biological tissues) by developing novel reliable analytical methods that can detect, quantify and confirm antidepressants using high performance liquid chromatography coupled to tandem-mass spectrometry (LC-QqQMS,LC- QqToFMS). A preliminary study completed at the Montreal sewage treatment plant (STP) confirmed the presence of six antidepressants and four N-desmethyl metabolites in raw sewage (2 – 330 ng L-1). For this primary treatment (physico-chemical), low removal rates (≤ 15%) were obtained. Concentrations of antidepressant close to 100 ng L-1 were also detected directly in the St. Lawrence River at 0.5 km of the effluent outfall. A second study conducted at the same STP allowed the selective extraction of antidepressants in three biological tissues (e.g. liver, brain, and filet) dissected from juvenile brook trouts previously exposed to diluted untreated and treated effluents with ozone. Bioaccumulation of antidepressants was readily observed in fish tissues (0.08-10 ng g-1) for the specimens exposed to untreated effluent (20% v/v), with major distribution in liver and brain. During experiments, a significant correlation was established between the concentrations of three antidepressant detected in brain tissues and the activity of a selected biomarker of exposition (e.g. an N/K ATPase pump involved in the serotonin regulation) measured within dissected synaptosomes from trout exposed to effluents. Investigation of estimated treatment removal efficiencies from various Canadian STPs operating different disinfection modes showed that secondary treatments (biological) were more efficient than primary (physico- chemical) to remove antidepressants (mean removal rates : 30%). The highest amounts detected in treated sludge (biosolids) were obtained respectively with citalopram (1033 ng g-1), venlafaxine (833 ng g-1), and amitriptyline (78 ng g-1). Experimental calculated sorption coefficients (Kd) of each antidepressant predicted fairly good sorption capacities for sertraline, desmethylsertraline, paroxetine, and fluoxetine to solid matters (log Kd > 4). Finally, an excellent mean removal rate of 88% was obtained after ozonation (5 mg L-1) of a primary effluent. However, the characterization of new N-oxide side-products (venlafaxine, desmethylvenlafaxine) in ozonized effluent by high-resolution mass spectrometry (LC-QqToFMS) highlighted the possibility of formation of multiple polar compounds with unknown toxicity.

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology / Water pollution caused by organic and inorganic contaminants represents an important ecological and health hazard. Simultaneous treatment of organic and inorganic contaminants had gradually gained great scientific interest. Advanced oxidation processes such as photocatalysis, using TiO2 as a photocatalyst, have been shown to be very robust in the removal of biorecalcitrant pollutants. These methods offer the advantage of removing the pollutants, in contrast to conventional techniques. At present, the main technical challenge that hinder its commercialization remained on the post-recovery of the photocatalyst particles after water treatment. Supporting of the photocatalyst on the adsorbent surface is important as it assists during the filtration step, reducing losses of the materials and yielding better results in degrading pollutants. To overcome this challenge, in this study composite photocatalysts of TiO2/zeolite and TiO2/silica were prepared and investigated to explore the possible application in the simultaneous removal of organic and inorganic compounds from contaminated water. The main objective of this study was to investigate the heterogeneous photocatalytic degradation of organic compounds in the presence of metal ions using composite photocatalysts. The Brunauer–Emmett–Teller (BET), Scanning Electron Microscopy and Energy Dispersive X-ray (SEM-EDX), Raman spectroscopy (RS) and zeta potential (ZP) analyses were used to characterize the prepared composite photocatalysts. The successive composite photocatalysts were used in a semi-batch reactor under an irradiation intensity of 5.5 mW/m2 (protected by a quartz sleeve) at 25 ± 3°C for the photocatalytic degradation of synthetic textile (methyl orange) and agricultural (atrazine) wastewater in the presence of ions. The effect of operating parameters such as TiO2 composition on supporting material, particle size, composite photocatalyst loading, initial pollutant concentration and pH were optimized. The effects of inorganic salts and humic acid on dye and pesticides degradation were also studied, respectively. The performance of the photocatalyst reactor was evaluated on the basis of color removal, metal ion reduction, total organic carbon (TOC) reduction, intermediates product analysis and modeling of kinetics and isotherms. Different kinetic and isotherm models were introduced and applied in this work. Important aspects such as error functions with the optimal magnitude were used for the selection of the best suitable model. / European Union. City of Mikkeli, Finland. Water Research Commission (RSA)

O complexo hidrelétrico da Serra de Cubatão foi considerado a grande obra de engenharia da primeira metade do século XX no Brasil. Este complexo polêmico foi possível graças à opção do poder público de legitimar o predomínio das forças produtivas e do capital na incorporação das planícies aluviais do rio Pinheiros à malha urbana da cidade, permitindo a execução de um projeto de infraestrutura que transformou o leito natural e sinuoso do rio Pinheiros em um canal de derivação das águas do rio Tietê, que passam pela bacia de São Paulo e são desviadas para a geração de energia, lançando esta água Serra do Mar abaixo. A sinergia obtida com as múltiplas funções incorporadas ao projeto da São Paulo Tramway, Light and Power Company acelerou o processo de construção da cidade sobre os novos terrenos metamorfoseados. Este ganho de tempo, proporcionado pelo capital internacional investido, contrapõe-se à ausência, no espaço urbano, de infraestruturas e equipamentos públicos essenciais para o equilíbrio socioambiental da metrópole paulistana. A dissertação aborda a transformação da natureza do lugar e a transformação das prioridades na infraestrutura urbana já instalada. Apresenta, em seu desenvolvimento, um diálogo entre o Projeto da Serra executado pela Companhia Light e o plano apresentado pelo Município de São Paulo, através da Comissão de Melhoramentos do Rio Tietê, para o combate às enchentes, diluição de efluentes e navegação no trecho do rio que fazia frente à cidade. Os dois projetos, delineados na década de 20, são partes distintas de uma mesma iniciativa da sociedade, que tinha como os principais propósitos o progresso, o avanço sobre as planícies aluviais paulistanas, a valorização da terra, o saneamento e a integração da metrópole. / The hydropower complex of Serra de Cubatão was considered the greatest engineering work of the first half of the 20th Century in Brazil. This controversial complex was made viable because the government has chosen to legitimize the predominance of the forces of production and capital in the incorporation of the floodplains of the Pinheiros River into the urban network of the city allowing the implementation of an infrastructure project that turned the river\'s natural and sinuous bed into a bypass channel of the waters from the Tietê River, which flow through the basin of São Paulo and are diverted for power generation , being discharged down the Serra do Mar. The synergy resulting from the multiple functions that were incorporated to the Project implemented by São Paulo Tramway, Light and Power Company accelerated the process of construction of the city on new metamorphosed land plots. This time saving initiative, which was enabled by the international capital invested, is opposed to the lack of essential public infrastructure and equipment in the urban space, which are essential for the socio-environmental balance of the metropolis of São Paulo. This dissertation addresses the transformation in the nature of the place and the changes in the priorities related to the infrastructure already installed. It introduces throughout its development a dialog between the Projeto da Serra performed by Companhia Light and the plan created by the City of São Paulo, through the Comissão de Melhoramentos do Rio Tietê (Comission for Improving the Tietê river), which established initiatives to fight floods, approached the dilution of effluents and navigation in the part of the river that stretched along the city. Both projects, outlined during the 20\'s, are different parts of the same initiative performed by society, whose main objectives were progress, the occupation of the floodplains of São Paulo, increasing land value, sanitation and the integration of the metropolis.

O complexo hidrelétrico da Serra de Cubatão foi considerado a grande obra de engenharia da primeira metade do século XX no Brasil. Este complexo polêmico foi possível graças à opção do poder público de legitimar o predomínio das forças produtivas e do capital na incorporação das planícies aluviais do rio Pinheiros à malha urbana da cidade, permitindo a execução de um projeto de infraestrutura que transformou o leito natural e sinuoso do rio Pinheiros em um canal de derivação das águas do rio Tietê, que passam pela bacia de São Paulo e são desviadas para a geração de energia, lançando esta água Serra do Mar abaixo. A sinergia obtida com as múltiplas funções incorporadas ao projeto da São Paulo Tramway, Light and Power Company acelerou o processo de construção da cidade sobre os novos terrenos metamorfoseados. Este ganho de tempo, proporcionado pelo capital internacional investido, contrapõe-se à ausência, no espaço urbano, de infraestruturas e equipamentos públicos essenciais para o equilíbrio socioambiental da metrópole paulistana. A dissertação aborda a transformação da natureza do lugar e a transformação das prioridades na infraestrutura urbana já instalada. Apresenta, em seu desenvolvimento, um diálogo entre o Projeto da Serra executado pela Companhia Light e o plano apresentado pelo Município de São Paulo, através da Comissão de Melhoramentos do Rio Tietê, para o combate às enchentes, diluição de efluentes e navegação no trecho do rio que fazia frente à cidade. Os dois projetos, delineados na década de 20, são partes distintas de uma mesma iniciativa da sociedade, que tinha como os principais propósitos o progresso, o avanço sobre as planícies aluviais paulistanas, a valorização da terra, o saneamento e a integração da metrópole. / The hydropower complex of Serra de Cubatão was considered the greatest engineering work of the first half of the 20th Century in Brazil. This controversial complex was made viable because the government has chosen to legitimize the predominance of the forces of production and capital in the incorporation of the floodplains of the Pinheiros River into the urban network of the city allowing the implementation of an infrastructure project that turned the river\'s natural and sinuous bed into a bypass channel of the waters from the Tietê River, which flow through the basin of São Paulo and are diverted for power generation , being discharged down the Serra do Mar. The synergy resulting from the multiple functions that were incorporated to the Project implemented by São Paulo Tramway, Light and Power Company accelerated the process of construction of the city on new metamorphosed land plots. This time saving initiative, which was enabled by the international capital invested, is opposed to the lack of essential public infrastructure and equipment in the urban space, which are essential for the socio-environmental balance of the metropolis of São Paulo. This dissertation addresses the transformation in the nature of the place and the changes in the priorities related to the infrastructure already installed. It introduces throughout its development a dialog between the Projeto da Serra performed by Companhia Light and the plan created by the City of São Paulo, through the Comissão de Melhoramentos do Rio Tietê (Comission for Improving the Tietê river), which established initiatives to fight floods, approached the dilution of effluents and navigation in the part of the river that stretched along the city. Both projects, outlined during the 20\'s, are different parts of the same initiative performed by society, whose main objectives were progress, the occupation of the floodplains of São Paulo, increasing land value, sanitation and the integration of the metropolis.

Large and ever-increasing numbers of chemicals, including large quantities of a broad spectrum of organic compounds are used in modern society. More than 30 000 of the more than 100 000 chemical substances registered in the EU are estimated to be daily used, of which many will be discharged into the waste-streams handled by municipal sewage treatment plants (STPs). The main objective of the work underlying this thesis was to improve understanding of the relationships between the characteristics of sewage contaminants and their sewage treatment efficiency. Further objectives were to examine the relationships between socio-economic uses of chemicals and sludge quality, and the effects of regulatory actions on sludge quality. The quality of the sewage sludge and the levels and distribution patterns of the sludge contaminants, both within and between the STPs, seem to remain quite constant over time. The overall findings indicate that the levels of contaminants in sewage sludge seem to be largely independent of the location, size and treatment techniques applied at the STPs, and generally, of the types of human activity connected to them. The total and relative concentrations of the sludge contaminants were found to be fairly constant on a dry weight basis, with some exceptions, indicating that the pollutants originate from broad usage and diffuse dispersion rather than (industrial) point sources. The proportion of cyclic methylsiloxanes recovered in sludge seems to strongly depend on their vapour pressure, which decreases with the number of siloxane units. The higher water solubility and biodegradability of organophosphorus flame retardants and plasticizers than polybrominated diphenyl ethers (PBDEs) were also reflected in lower percentages (relative to their national use) found in sludge. Significant time-trends in levels of a-third of the sludge contaminants included in the annual national measurement program were detected over a period of seven years. The levels of compounds displaying significant time-trends generally decreased following declines in the quantities used nationally. However, a quarter of these compounds showed increasing trends, of which the linear methylsiloxanes followed the same trend as used quantities. The decaBDE was also found to be increasing in sludge, probably as a result of the phase-out of pentaBDE and octaBDE. The results indicate that the STP removal efficiency of anthropogenic substances, in Sweden, is generally good and that STPs, at least those in cold climates, do not efficiently remove certain polar contaminants. A non-targeted screening (by use of environmetrics and GCxGC-TOFMS) was performed and found to fulfil the objective to assess the STP removal efficiency, with emphasis to systematically analyse which compound classes that are not efficiently removed using the current STP technology. Many polar aromatic compounds were identified to be poorly removed. The acquired data on levels, profiles and variations in sludge contaminants (sludge quality) extend both the available information and understanding of the degree and nature of sludge contamination, which should help attempts to track changes in its contaminants and revisions, if necessary, of guideline values. This thesis also contributes to improve the knowledge base for the development of future STP technologies, and that archived sewage sludge can be used in retrospective analysis of new and emerging pollutants.

The efficiency of wastewater treatment systems is commonly measured by the reductions of parameters such as biological oxygen demand (BOD), chemical oxygen demand (COD) and total suspended solids (TSS) and/or reductions in levels of selected macro compounds (e.g. long-chained hydrocarbons and inorganic compounds). Less attention has generally been paid to micropollutants with high potential toxic effects, such as polycyclic aromatic compounds (PACs), including unsubstituted and alkylated polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes, polychlorinated biphenyls (PCBs), human pharmaceuticals and by-products formed during the treatment process. These organic micropollutants occur in wastewaters at trace and ultra-trace levels, therefore their detection requires advanced, costly analyses and large sample volumes. Furthermore, concentrations of micropollutants can fluctuate widely both diurnally and between days. Thus, in order to understand the fate of micropollutants in wastewaters there is a need to develop sampling techniques that allow representative samples to be readily collected. In the work underlying this thesis two types of diffusive passive samplers, semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs), were used to monitor non-polar and polar organic micropollutants in wastewaters subjected to various treatment processes. The pollutants sequestered in these samplers represent micropollutants in the dissolved phase that are available for aquatic organisms. Further, since they collect pollutants in an integrative manner, i.e. they sample continuously during the selected exposure time (usually approx. one to ca. three weeks), the results provide time-weighted average (TWA) concentrations. In addition, the effects of various environmental factors on the uptake of analyzed micropollutants in POCISs and SPMDs were investigated using laboratory calibration and in situ calibration with performance reference compounds (PRCs). The results confirm that SPMDs are good sampling tools for investigating the efficacy of wastewater treatment processes for removing non-polar PACs and PCBs, and the effects of varying the process settings. In addition, analyses of process streams in municipal sewage treatment plants demonstrated that conventional sewage treatment processes are not optimized for removing dissolved four-ringed PAHs, some of the five-ringed PAHs, and tri- to hexa-chlorinated biphenyls. The removal of bioavailable PACs was enhanced by adding sorbents with high sorption capacities to the sludge used in the activated sludge treatment step, and a biologically activated carbon system was designed that robustly removed bioavailable PACs, with removal efficiencies of 96.9-99.7 percent across the tested ranges of five varied process parameters. In situ SPMD calibration data acquired show that uptake of PACs, described by SPMD sampling rates (Rs), were four to eight times higher than published laboratory calibrated Rs values, mainly due to strong (bio)fouling and turbulence effects. In addition, the laboratory calibration study demonstrated that temperature affects the POCIS uptake of pharmaceuticals. The uptake of four pharmaceuticals was higher, by 10-56 percent, at 18 °C compared to 5 °C. For two of the pharmaceuticals our data indicate that the uptake was lower by 18-25 percent at 18 °C. Our results also indicate that uptake of the studied pharmaceuticals was in the linear phase throughout the 35 day exposure period at both temperatures. Finally, calibration studies enabled aqueous concentrations of micropollutants to be more accurately estimated from amounts collected in the passive samplers.

Η μελέτη ενός πειράματος μικρής πιλοτικής κλίμακας, με δύο παράλληλα συστήματα ρηχών λεκανών (ύψους 0.35m), η μία λεκάνη με φύτευση του είδους Typha Latifolia και η άλλη χωρίς φύτευση, διεξάχθηκε για τον σχεδιασμό ελεύθερης επιφανειακής ροής (FWS) τεχνητού υγροτόπου. Οι δύο λεκάνες τροφοδοτήθηκαν με πραγματικά αστικά λύματα όπου οι χρόνοι παραμονής κυμάνθηκαν από 27,6 έως 38,0 ημέρες. Η μεταβολή του όγκου κάθε λεκάνης παρακολουθήθηκε για 2 συνεχή έτη και ταυτόχρονα υπολογίστηκαν οι ρυθμοί βροχόπτωσης και εξάτμισης. Η διαφορά του όγκου μεταξύ των δύο λεκανών οφειλόταν στην πρόσληψη νερού από τα φυτά, η οποία συγκρίθηκε με τις προβλέψεις της εξατμισοδιαπνοής παρόμοιων φυτών με την χρήση του υπολογιστικού προγράμματος REF-ET. Η συγκομιδή των φυτών πραγματοποιήθηκε τρείς φορές στην διάρκεια του 1ου έτους του πειράματος, ώστε να εκτιμηθεί ο ρυθμός πρόσληψης αζώτου από τα φυτά. Η σημαντικότερη διαφορά των δύο συστημάτων ήταν η αφαίρεση νερού μέσω της εξατμισοδιαπνοής των φυτών. Η πιλοτική μονάδα λειτούργησε έτσι ώστε να επιτευχθεί και απομάκρυνση της οργανικής ύλης (BOD5) και του ολικού αζώτου (TN) από τα λύματα. Ο σχεδιασμός της διευκόλυνε την ανάπτυξη ενός μαθηματικού μοντέλου, ακολουθώντας το πλαίσιο του μοντέλου της ενεργής ιλύος (ASM). Αρχικά το μαθηματικό μοντέλο αναπτύχθηκε για τις δύο λεκάνες με τις μικροβιακές διεργασίες που επικράτησαν στο εσωτερικό τους, ώστε να περιγραφεί πλήρως η συμπεριφορά τους. Η προσομοίωση και η εκτίμηση των παραμέτρων του μοντέλου επιτεύχθηκε με την χρήση του υπολογιστικού περιβάλλοντος του AQUASIM. Οι κύριες διεργασίες που ελήφθησαν υπόψη για την μοντελοποίηση ήταν η αμμωνιοποίηση, η αερόβια ετεροτροφική ανάπτυξη, η νιτροποίηση και η ανάπτυξη φυκών. Μια ισχυρή εποχική εξάρτηση παρατηρήθηκε για την συμπεριφορά κάθε λεκάνης όταν το μοντέλο εφαρμόστηκε για το 1ο έτος του πειράματος. Αυτό το μοντέλο επαληθεύτηκε ικανοποιητικά με τα πειραματικά δεδομένα του 2ου έτους. Η παρατηρούμενη μέση ετήσια απόδοση απομάκρυνσης του BOD5 και του TN ήταν 60% και 69%, αντίστοιχα για την λεκάνη χωρίς φυτά και 83% και 75%, αντίστοιχα για την λεκάνη με φυτά. Το μοντέλο προέβλεψε μέση ετήσια απόδοση απομάκρυνσης 82% για το BOD5 και 65% για το TN στην λεκάνη με φυτά, ικανοποιώντας τα κριτήρια για τον σχεδιασμό πλήρους κλίμακας τεχνητού υγροτόπου . Η ικανότητα του μοντέλου να προβλέπει όχι μόνο την απομάκρυνση της οργανικής ύλης αλλά και του ολικού αζώτου, θεωρήθηκε επαρκής όταν δοκιμάστηκε με έναν ελεύθερης επιφανειακής ροής τεχνητό υγρότοπο με 400 ισοδύναμο πληθυσμό, με μοναδική τροποποίηση τον συνυπολογισμό του περιορισμού του οξυγόνου στον ρυθμό της διεργασίας της νιτροποίησης. Επομένως, το δυναμικό μοντέλο διαμορφώθηκε με την ενσωμάτωση της πρόβλεψης του ρυθμού της εξατμισοδιαπνοής των φυτών και χρησιμοποιήθηκε για τον σχεδιασμό περίπτωσης μελέτης τεχνητού υγροτόπου πλήρους κλίμακας. Τα στοιχεία που απαιτούνται για αυτό τον σχεδιασμό περιλάμβαναν την παροχή εισόδου και κλιματολογικά στοιχεία (θερμοκρασίας και βροχόπτωσης) για την περιοχή του σχεδιασμού, καθώς και οι απαιτήσεις της ποιότητας εκροής. Η περίπτωση μελέτης για 4000 ισοδύναμο πληθυσμό όπου η ποιότητα εκροής ήταν σε μέσες ετήσιες τιμές BOD5=25mg/L και TN=15mg/L, χρειάστηκε μία συνολική επιφάνεια υγροτόπου 11 εκταρίων. Εάν χρησιμοποιηθούν δύο λεκάνες σε σειρά, η 1η με φυτά και η 2η χωρίς, τότε η συνολική επιφάνεια μειώνεται κατά περίπου 27%, ελέγχοντας μόνο την αρχική μέγιστη φύτευση της πρώτης λεκάνης του υγροτόπου. / The study at pilot-scale of two parallel systems with shallow basins (height h=0.35m), one planted with Typha Latiofolia and the other without vegetation, was conducted for the modeling of free water surface (FWS) constructed wetland systems. The basins were fed with real sewage at retention times ranging from 27.6 to 38.0 days. The variation of the volume in each basin was monitored for two consecutive years and simultaneously, rainfall and evaporation rates were calculated. The difference of the volume between the basins was due to the water absorption by the plants and was compared with the predictions of evapotranspiration rates of similar plants using the REF-ET calculation software. The harvesting of the plants was performed three times during the first year, in order to estimate the nitrogen uptake by the plants. The main difference in the two systems was the water removal through plant evapotranspiration. The pilot unit was operated so as to achieve the removal of both organic matter (BOD5) and total nitrogen (TN) from the sewage. Its design enabled the development of a mathematical model, following the framework of the activated sludge model (ASM). The simulation and the parameter estimation were achieved using the AQUASIM framework. The mathematical model describes the microbial processes, which dominated within the basins describing satisfactorily their behavior. The key processes accounted for in the modeling were ammonification, aerobic heterotrophic growth, nitrification and algal growth. A strong seasonal dependence was observed for each basin. The model was satisfactorily validated with the data of the second year. An observed average annual removal efficiency of BOD5 and TN were 60% and 69%, respectively for the basin without plants and 83% and 75%, respectively for the basin with plants. The model predicted average annual removal efficiency 82% for BOD5 and 65% for TN in the basin with plants, satisfying the design criteria of a full-scale constructed wetland. The ability of the model to predict not only the removal of organic matter but also total nitrogen removal, was considered sufficient as tested with a real free water surface constructed wetland of 400 population equivalent, with the sole modification being the inclusion of oxygen limitation in the nitrification rate. The dynamic model was amended with the direct incorporation of the plant evapotranspiration rate and it was used to design a full-scale constructed wetland. The required elements for this design included the inflow rate and climatic data (temperature and rainfall) for the design region, as well as the effluent quality requirements. In the case study of 4000 population equivalent, the effluent quality requirement was: average annual values for BOD5=25mg/L and for TN=15mg/L. The model was used to determine a total wetland surface requirement of 11ha. If two sequential basins are used, the first with plants and the second without, then the total wetland surface could be reduced by approximately 27%, controlling only the maximum initial vegetation in the first wetland basin.

From the Proceedings of the 1978 Meetings of the Arizona Section - American Water Resources Assn. and the Hydrology Section - Arizona Academy of Science - April 14-15, 1978, Flagstaff, Arizona / As a part of the ongoing Phoenix Urban Study, Federal legislation mandates that land treatment of wastewater be seriously considered as a treatment option. Land treatment is a particularly viable alternative in the Phoenix area because in this arid desert climate, all water is a scarce and valuable resource and land treatment offers a positive opportunity for the conservation of this resource. In addition, land treatment systems are generally less expensive and have lower energy requirements than other conventional treatment processes while resulting in comparable treatment. The analysis of wastewater treatment systems for populated urban areas necessitates the preliminary investigation and comparison of a large number of alternatives to allow for a realistic engineering and economic evaluation. The site specific nature of land application adds additional variables that must be considered. A preliminary systems approach indicated that to minimize the effect of a human judgement factor between sites and yet maximize the depth of the initial analysis, computer techniques should be utilized for analysis and data storage. A summary of this analysis with appropriate cost, power usage, land requirements and other pertinent factors will be presented.

Les troubles reliés à la dépression, l’épuisement professionnel et l’anxiété sont de plus en plus répandus dans notre société moderne. La consommation croissante d’antidépresseurs dans les différents pays du monde est responsable de la récente détection de résidus à l’état de traces dans les rejets urbains municipaux. Ainsi, ces substances dites « émergentes » qui possèdent une activité pharmacologique destinée à la régulation de certains neurotransmetteurs dans le cerveau suscitent maintenant de nombreuses inquiétudes de la part de la communauté scientifique. L’objectif principal de ce projet de doctorat a été de mieux comprendre le devenir de plusieurs classes d’antidépresseurs présents dans diverses matrices environnementales (i.e. eaux de surfaces, eaux usées, boues de traitement, tissus biologiques) en développant de nouvelles méthodes analytiques fiables capables de les détecter, quantifier et confirmer par chromatographie liquide à haute performance couplée à la spectrométrie de masse en tandem (LC-QqQMS, LC-QqToFMS). Une première étude complétée à la station d’épuration de la ville de Montréal a permis de confirmer la présence de six antidépresseurs et quatre métabolites N-desmethyl dans les affluents (2 - 330 ng L-1). Pour ce traitement primaire (physico-chimique), de faibles taux d’enlèvement (≤ 15%) ont été obtenus. Des concentrations d’antidépresseurs atteignant près de 100 ng L-1 ont également été détectées dans le fleuve St-Laurent à 0.5 km du point de rejet de la station d’épuration. Une seconde étude menée à la même station a permis l’extraction sélective d’antidépresseurs dans trois tissus (i.e. foie, cerveau et filet) de truites mouchetées juvéniles exposées à différentes concentrations d’effluent dilué traité et non-traité à l’ozone. Un certain potentiel de bioaccumulation dans les tissus (0.08-10 ng g-1) a été observé pour les spécimens exposés à l’effluent non-traité (20% v/v) avec distribution majoritaire dans le foie et le cerveau. Une intéressante corrélation a été établie entre les concentrations de trois antidépresseurs dans le cerveau et l’activité d’un biomarqueur d’exposition (i.e. pompe N/K ATPase impliquée dans la régulation de la sérotonine) mesurée à partir de synaptosomes de truites exposées aux effluents. Une investigation de l’efficacité de plusieurs stations d’épuration canadiennes opérant différents types de traitements a permis de constater que les traitements secondaires (biologiques) étaient plus performants que ceux primaires (physico-chimiques) pour enlever les antidépresseurs (taux moyen d’enlèvement : 30%). Les teneurs les plus élevées dans les boues traitées (biosolides) ont été obtenues avec le citalopram (1033 ng g-1), la venlafaxine (833 ng g-1) et l’amitriptyline (78 ng g-1). Des coefficients de sorption expérimentaux (Kd) calculés pour chacun des antidépresseurs ont permis d’estimer une grande sorption des composés sertraline, desméthylsertraline, paroxetine et fluoxetine sur les solides (log Kd > 4). Finalement, un excellent taux d’enlèvement moyen de 88% a été obtenu après ozonation (5 mg L-1) d’un effluent primaire. Toutefois, la caractérisation de nouveaux sous-produits N-oxyde (venlafaxine, desmethylvenlafaxine) par spectrométrie de masse à haute résolution (LC-QqToFMS) dans l’effluent traité à l’ozone a mis en lumière la possibilité de formation de multiples composés polaires de toxicité inconnue. / Mood disorders such as depression, burn-out and anxiety have increased in our modern society. Increasing amounts of antidepressant prescriptions around the world are now suspected to be the main cause of the recent detection of traces of antidepressant residues within urban wastewaters. These so-called “emerging” substances that possess pharmacological activity towards neurotransmitter regulation in the brain have raised serious concerns from the scientific community. The initial goal of the study was to better understand the fate of various classes of antidepressants present in different environmental matrices (e.g. surface waters, wastewaters, treatment sludge, and biological tissues) by developing novel reliable analytical methods that can detect, quantify and confirm antidepressants using high performance liquid chromatography coupled to tandem-mass spectrometry (LC-QqQMS,LC- QqToFMS). A preliminary study completed at the Montreal sewage treatment plant (STP) confirmed the presence of six antidepressants and four N-desmethyl metabolites in raw sewage (2 – 330 ng L-1). For this primary treatment (physico-chemical), low removal rates (≤ 15%) were obtained. Concentrations of antidepressant close to 100 ng L-1 were also detected directly in the St. Lawrence River at 0.5 km of the effluent outfall. A second study conducted at the same STP allowed the selective extraction of antidepressants in three biological tissues (e.g. liver, brain, and filet) dissected from juvenile brook trouts previously exposed to diluted untreated and treated effluents with ozone. Bioaccumulation of antidepressants was readily observed in fish tissues (0.08-10 ng g-1) for the specimens exposed to untreated effluent (20% v/v), with major distribution in liver and brain. During experiments, a significant correlation was established between the concentrations of three antidepressant detected in brain tissues and the activity of a selected biomarker of exposition (e.g. an N/K ATPase pump involved in the serotonin regulation) measured within dissected synaptosomes from trout exposed to effluents. Investigation of estimated treatment removal efficiencies from various Canadian STPs operating different disinfection modes showed that secondary treatments (biological) were more efficient than primary (physico- chemical) to remove antidepressants (mean removal rates : 30%). The highest amounts detected in treated sludge (biosolids) were obtained respectively with citalopram (1033 ng g-1), venlafaxine (833 ng g-1), and amitriptyline (78 ng g-1). Experimental calculated sorption coefficients (Kd) of each antidepressant predicted fairly good sorption capacities for sertraline, desmethylsertraline, paroxetine, and fluoxetine to solid matters (log Kd > 4). Finally, an excellent mean removal rate of 88% was obtained after ozonation (5 mg L-1) of a primary effluent. However, the characterization of new N-oxide side-products (venlafaxine, desmethylvenlafaxine) in ozonized effluent by high-resolution mass spectrometry (LC-QqToFMS) highlighted the possibility of formation of multiple polar compounds with unknown toxicity.