Les substances perturbatrices du système endocrinien sont des substances qui, de par leur capacité à induire des changements hormonaux chez les organismes vivants, génèrent des préoccupations dans le domaine de la qualité des eaux et, par extension, dans le domaine du traitement des effluents aqueux. Particulièrement, ce projet de recherche s’est attardé sur l’élimination des perturbateurs endocriniens phénoliques nonylphénol (NP), bisphénol A (BPA) et triclosan (TCS) en solution aqueuse à l’aide de la laccase (E.C. 1.10.3.2) sécrétée par la souche fongique Coriolopsis polyzona. Cette oxydase est une métalloprotéine pouvant catalyser l’oxydation d’une vaste gamme de substances phénoliques. En premier lieu, l’impact du pH et de la température sur l’élimination de ces composés à l’aide de la laccase libre en utilisant un design factoriel. L’oxydation de ces composés produit des oligomères (dimère à pentamère) via le couplage des radicaux phénoxy produits par l’action de la laccase. Il s’avère que les substances produites suite à l’oxydation du NP et du BPA par la laccase ont perdu leurs similitudes structurales avec l’estrogène. Ainsi, l’élimination de l’activité estrogénique de ces substances est directement liée à la transformation des composés. Finalement, l’utilisation d’ABTS comme médiateur a permis d’augmenter le taux d’oxydation enzymatique de ces composés chimiques. Puis, de façon à augmenter la possibilité d’utilisation de la laccase dans des biotechnologies environnementales, cette enzyme a été immobilisée sur un support siliceux et via la réticulation d’agrégats. L’impact des conditions d’immobilisation sur l’activité enzymatique, la stabilité du catalyseur et les propriété biocatalytiques apparentes a été déterminé pour différentes stratégies d’immobilisation. Globalement, l’immobilisation génère un biocatalyseur stable vis-à-vis les dénaturations chimique, physique et biologique. Particulièrement, l’immobilisation sur un support solide produit un biocatalyseur facile à utiliser ayant une faible activité massique et des propriétés cinétiques moindres que celle de l’enzyme libre. La formation de CLEAs de laccase a permis d’obtenir une activité massique élevée et des propriétés cinétiques supérieures à celle de l’enzyme soluble. Ces biocatalyseurs solides ont étés utilisés pour éliminer en continu le NP, BPA et TCS dans différents types de bioréacteur. Le biocatalyseur sur silice a été utilisé pour éliminer ces substances dans un réacteur garni, tandis que les CLEAs ont été utilisés dans un réacteur à lit fluidisé et un réacteur à perfusion développé au cours de ce projet. Ces différentes configurations de bioréacteur ont permis d’éliminer efficacement ces différents perturbateurs endocriniens. Globalement, les différents résultats obtenus, à l’échelle de laboratoire, au cours de ce projet de recherche démontrent que la laccase et particulièrement les biocatalyseurs formés via les différentes stratégies d’immobilisation testées représentent des approches extrêmement prometteuses pour le développement de biotechnologies environnementales vouées à l’élimination des perturbateurs endocriniens phénoliques.

<p>Aim: To determine whether there was any significant difference in the antimicrobial activity of 4 herbal toothpastes against cultures of 3 primary plaque colonizers (Streptococcus mutans, Streptococcus sanguinis and a non-specific &alpha / -heamolytic streptococcus).</p>

Nowadays, organic pollutants occurring in surface waters have raised substantial concern in public. Triclosan (TCS) is one of the antimicrobial agents which are utilized in both domestic and industrial application. In this study nanofiltration (NF) of TCS in surface water was investigated. Laboratory scale cross-flow device is operated in total recycle mode and DK-NF and DL-NF membranes were used. Kesikk&ouml / pr&uuml / Reservoir (Ankara) water was used as raw water. Effect of natural organic matter (NOM) content of raw water on TCS removal is searched through addition of humic acid (HA) into the raw water as to represent for NOM. Steady state permeate fluxes are monitored throughout the experiments to explore the flux behavior of the membranes. During the experiments, performance of the membranes is assessed by monitoring TCS, as well as other water quality parameters, such as UVA254 and total organic carbon (TOC) in the feed and permeates waters. Results obtained put forward that TCS removal by NF membrane is not as same as reported in the literature. In the literature, membrane removal efficiency is reported as above 90%. However, this study proved that this would be true if and only if one does not considers the adsorption of TCS by the system itself, in the absence of membrane. It is now clear that, because of adsorption of the TCS onto the experimental set up (feed tank, pipings etc.) / the real TCS removal efficiency of the nanofiltration is around 60-70%.

The main goal of this thesis is to investigate the effects of consequences of global change on fluvial biofilms. To achieve this objective a multi-marker approach has been used at different experimental scales. Our results revealed that the consequences of eutrophication and riparian simplification caused changes in biofilm spatial organization, microbial structure and functioning. This thesis evidenced that pharmaceuticals and antibiotics detected in Llobregat River waters may cause responses at the base of river food web with still unknown consequences for freshwater ecosystems. Furthermore, we demonstrated that the bactericide Triclosan reduces the capacity of biofilm to remove phosphorus from water column. Our results also evidenced that drought episode may affect biofilms structure and function amplifying the toxicity of Triclosan for these communities. Finally, our study validates the use of biofilm phosphorus uptake capacity as a tool for the understanding of pollutions’ consequences for river self-depuration capacity / L’objectiu principal d’aquesta tesi és investigar els efectes del canvi global sobre els biofilms fluvials. Amb aquesta finalitat s’ha utilitzat un enfoc de multi-marcadors a diferents escales experimentals. Els nostres resultats demostren que l’eutrofització i la simplificació ripària causen canvis en l’organització espacial, l’estructura microbiana i el funcionament dels biofilms. Aquesta tesis evidencia que fàrmacs i antibiòtics que es varen detectar al Llobregat causen respostes a la base de la xarxa tròfica amb conseqüències ecològiques desconegudes. Es va demostrar que el bactericida Triclosan redueix la capacitat dels biofilms de captar fòsfor. Els nostres resultats també evidencien que un episodi de sequera afecta la estructura i funció dels biofilms amplificant la toxicitat del Triclosan per aquestes comunitats. Finalment, el nostre estudi valida l'ús de la capacitat de captació de fòsfor dels biofilms com eina per la comprensió dels efectes de la contaminació sobre la capacitat de auto-depuració dels rius

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.

Η ανθρώπινη δραστηριότητα (γεωργική, βιομηχανική, αστική κ.α.) καθώς και η διαχείριση των λυμάτων στις μονάδες επεξεργασίας υγρών αποβλήτων (ΜΕΥΑ) επηρεάζουν τα επιφανειακά και υπόγεια υδατικά συστήματα όπως ποτάμια, λίμνες, λιμνοθάλασσες, θάλασσες κ.α. αποτελούν σημαντικές πηγές ρύπανσης και επιφέρουν επιπτώσεις στα οικοσυστήματα αυτά. Η μεταφορά, η κατανομή και η απομάκρυνση των οργανικών μικρορύπων όπως είναι τα παρασιτοκτόνα, οι φαρμακευτικές ενώσεις, οι ενώσεις που περιέχονται στα προϊόντα προσωπικής φροντίδας, κ.α., καθώς και οι μεταβολίτες τους, αποτελεί τις τελευταίες δεκαετίες αντικείμενο συστηματικής έρευνας προκαλώντας το ενδιαφέρον τόσο της επιστημονικής κοινότητας όσο και της κοινωνίας γενικότερα. Ο ποταμός Αχελώος (η κατώτερη λεκάνη απορροής του), που βρίσκεται στην Δυτική Ελλάδα καθώς και η μονάδα επεξεργασίας υγρών αποβλήτων (ΜΕΥΑ) της πόλης του Αγρινίου της οποίας τα επεξεργασμένα λύματα απορρίπτονται σε αυτόν, αποτελεί την περιοχή μελέτης της παρούσας διατριβής. Πρόκειται για ένα υδατικό σύστημα υψηλής περιβαλλοντικής σημασίας αφού συνδέεται με τις λίμνες Τριχωνίδα και Λυσιμαχία καθώς και με τις λιμνοθάλασσες Μεσολογγίου και Αιτωλικού. Επιπροσθέτως, το δέλτα του ποταμού προστατεύεται από διεθνείς περιβαλλοντικές συνθήκες (Ramsar και Natura 2000). Η κατώτερη λεκάνη απορροής του Αχελώου περιλαμβάνει μεγάλες εκτάσεις καλλιεργούμενης γης (πεδιάδες Αγρινίου και Νεοχωρίου-Κατοχής). Σκοπός της παρούσας διατριβής είναι: (α) η μελέτη των επιπέδων των συγκεντρώσεων της μεταβολής (χρονικής και χωρικής) και των επιπτώσεων παρασιτοκτόνων, φαρμακευτικών ενώσεων που ανήκουν σε διαφορετικές χημικές ομάδες και οργανικών ενώσεων προϊόντων προσωπικής φροντίδας στον ποταμό Αχελώο, (β) η απομάκρυνσή τους από την μονάδα επεξεργασίας υγρών αποβλήτων της πόλης του Αγρινίου, (γ) η μελέτη των επιπέδων ρύπανσης από τα επεξεργασμένα λύματα που καταλήγουν στον Αχελώο, (δ) η φωτολυτική και φωτοκαταλυτική αποικοδόμηση (κινητική, μηχανισμοί αποικοδόμησης, σχηματισμός παραπροϊόντων) επιλεγμένων οργανικών ενώσεων από τις παραπάνω ομάδες (του παρασιτοκτόνου tebuconazole και της βακτηριοκτόνου triclosan) στην υδατική φάση (απεσταγμένο νερό και επεξεργασμένα λύματα) ως εναλλακτική τεχνολογία επεξεργασίας για την μείωση των επιπέδων ρύπανσης από τις μονάδες βιολογικού καθαρισμού. Αναπτύχθηκαν και εφαρμόστηκαν πολυ-υπολειμματικές μεθοδολογίες προσδιορισμού των παρασιτοκτόνων και φαρμακευτικών ενώσεων σε δείγματα από τον ποταμό Αχελώο και από την ΜΕΥΑ του Αγρινίου. Η μεθοδολογία περιελάμβανε την απομόνωση των ενώσεων με την τεχνική της υγρής-στερεάς εκχύλισης και τον προσδιορισμό τους με τεχνικές αέριας χρωματογραφίας. Επιλέχτηκαν 32 ενώσεις παρασιτοκτόνων και μεταβολιτών τους (alachlor, atrazine, atrazine desethyl, EPTC, s-metolachlor, simazine, trifluralin, azinphos methyl, chlorpyrifos, chlorpyrifos methyl, chlorfenviphos, diazinon, dichlorvos, dimethoate, fenthion, fenthion sulfoxide, malaoxon, methidathion, methyl parathion, cyproconazole, pyrimethanil, triadimefon, pirimiphos methyl, isoproturon, diuron, carbofuran, quinalphos, triazophos, phosalone, pyrazophos, penconazole, tebuconazole) σύμφωνα με προηγούμενες και σύγχρονες χρήσεις τους στην λεκάνη απορροής του ποταμού Αχελώου. Για την ανίχνευση και την ποσοτικό προσδιορισμό τους χρησιμοποιήθηκε η αέρια χρωματογραφία με ανιχνευτή θερμοϊονισμού φλόγας (GC-FTD) και με φασματομετρία μάζας (GC-MS). Επίσης, έγινε επιλογή 12 φαρμακευτικών ενώσεων και μεταβολιτών τους (salicylic acid, paracetamol, clofibric acid, ibuprofen, phenazone, gemfibrozile, triclosan, naproxen, diclofenac, carbamazepine, caffeine, fenofibrate) σύμφωνα με τα δεδομένα ανίχνευσης και επιπέδων συγκέντρωσης που έχουν καταγραφεί στην Ευρώπη και σε ελάχιστες μελέτες για τον Ελλαδικό χώρο. Για την ανίχνευση και την ποσοτικό προσδιορισμό τους χρησιμοποιήθηκε επίσης αέρια χρωματογραφία με φασματομετρία μάζας (GC-MS). Η χωρική και χρονική διακύμανση των συγκεντρώσεων των παρασιτοκτόνων παρακολουθήθηκε από τον Μάρτιο του 2005 έως τον Φεβρουάριο του 2008. Η χρονική περίοδος δειγματοληψίας περιλαμβάνει ένα έτος πριν την κατάργηση της καλλιέργειας του καπνού, η οποία έγινε σταδιακά από 1/1/2006 μετά την αναθεώρηση της Κοινής Αγροτικής Πολιτικής (ΚΑΠ) σχετικά με τις καλλιέργειες καπνού, και δύο έτη μετά με συνέπεια οι αλλαγές στις γεωργικές χρήσεις γης να εμφανίσουν σημαντικές επιδράσεις στις εισροές παρασιτοκτόνων στον ποταμό Αχελώο. Τις μεγαλύτερες συχνότητες ανίχνευσης εμφάνισαν από τα εντομοκτόνα τα diazinon (78.6%) και fenthion (52.6%), από τα ζιζανιοκτόνα τα DEA (69.3%) και alachlor (50%) και από τα μυκητοκτόνα τα pyrimethanil (67,3%) και tebuconazole (44,7%). Η στατιστική ανάλυση των συγκεντρώσεων των ανιχνευθέντων παρασιτοκτόνων ανέδειξε σημαντικά μεγαλύτερες συγκεντρώσεις την περίοδο εφαρμογής τους, δηλαδή την άνοιξη και τις αρχές του καλοκαιριού, καθώς και μια αυξητική τάση κατά μήκος του ποταμού προς τα σημεία δειγματοληψίας που βρίσκονται στο δέλτα του ποταμού. Διαπιστώθηκε επίσης μείωση των μέσων τιμών των συγκεντρώσεων των παρασιτοκτόνων τα έτη 2006 και 2007 σε σχέση με το 2005 αποδεικνύοντας ότι η κατάργηση της καλλιέργειας του καπνού και η αλλαγή καλλιεργειών είχε σημαντική επίδραση στα επίπεδα ρύπανσης του ποταμού. Το συμπέρασμα αυτό επιβεβαιώθηκε και από την εκτίμηση του κινδύνου που υπολογίστηκε ξεχωριστά για κάθε έτος δειγματοληψίας με την προσδιοριστική μέθοδο του πηλίκου κινδύνου (Risk Quotient). Έτσι, το 2005 έξι παρασιτοκτόνα εμφάνισαν υψηλή επικινδυνότητα, ενώ το 2007 μόλις ένα. Η παρουσία και η απομάκρυνση των παρασιτοκτόνων από τη μονάδα επεξεργασίας υγρών αποβλήτων του Αγρινίου μελετήθηκε για χρονική περίοδο δεκατεσσάρων μηνών (Απρίλιος 2007-Μάιος 2008). Τα ζιζανιοκτόνα isoproturon, atrazine και ο μεταβολίτης DEA, alachlor, τα μυκητοκτόνα tebuconazole και cyproconazole και τα εντομοκτόνα diazinon, methidathion, chlorfenviphos και chlorpyriphos εντοπίστηκαν πιο συχνά στα δείγματα εισροής και εκροής. Οι εποχιακές διακυμάνσεις που παρατηρήθηκαν για τα περισσότερα παρασιτοκτόνα δείχνουν ότι στο παντοροϊκό σύστημα της μονάδας επεξεργασίας υγρών αποβλήτων καταλήγουν τα υπολείμματα των παρασιτοκτόνων από τις γεωργικές εφαρμογές στην περιαστική περιοχή καθώς και από την καταπολέμηση των παρασίτων στην πόλη, με υψηλότερες συγκεντρώσεις κατά τη διάρκεια της περιόδου κύριας εφαρμογής τους από τα μέσα Μαρτίου έως τα τέλη Ιουνίου. Εξαίρεση στην παραπάνω τάση παρατηρήθηκε στα μυκητοκτόνα της κατηγορίας των υποκατεστημένων αζολών, εκτός του triadimefon, όπου ανιχνεύσεις καταγράφηκαν για μεγαλύτερα χρονικά διαστήματα κατά τη διάρκεια του έτους, λόγω της χρήσεις τους ως συντηρητικά-βιοκτόνα σε επιφάνειες και επιχρίσματα. Μελετήθηκε επιπρόσθετα το ποσοστό της απομάκρυνσης των παρασιτοκτόνων κατά τα στάδια της δευτεροβάθμιας και τριτοβάθμιας επεξεργασίας των υγρών αποβλήτων. Η % απομάκρυνση συνολικά για όλα τα στάδια της επεξεργασίας, για τα ζιζανιοκτόνα κυμάνθηκε από 65% έως 77%, για τα alachlor και trifluralin αντίστοιχα, ενώ για το DEA έφτασε το 82%, για τα εντομοκτόνα κυμάνθηκε μεταξύ 62% και 98% για τα chlorfenviphos και dichlorvos, αντίστοιχα ενώ από όλα τα μυκητοκτόνα, το triadimefon εμφάνισε την μεγαλύτερη μέση απομάκρυνση (93%) και το pyrimethanil την μικρότερη (46%). Γενικά, η πρωτοβάθμια επεξεργασία στην ΜΕΥΑ δεν συμβάλει σημαντικά στην απομάκρυνση των παρασιτοκτόνων από τα υγρά λύματα, ενώ η τριτοβάθμια είναι αποτελεσματική για ένα μικρό αριθμό παρασιτοκτόνων. Αναδείχτηκε ότι μια σημαντική πηγή εισόδου παρασιτοκτόνων στον ποταμό Αχελώο αποτελούν και οι εκροές από την ΜΕΥΑ του Αγρινίου, αφού μόνο μερικές από αυτές τις ενώσεις απομακρύνονται σε υψηλά ποσοστά κατά τη διάρκεια της επεξεργασίας των αποβλήτων. Με στόχο την διερεύνηση της ρύπανσης του ποταμού Αχελώου από τις 12 επιλεχθέντες φαρμακευτικές ουσίες, έγιναν μηνιαίες δειγματοληψίες για χρονικό διάστημα ενός έτους ή 14 μηνών. Σύμφωνα με τα αποτελέσματα που προέκυψαν, το salicylic acid, η paracetamol, το carbamazepine και η caffeine ανιχνεύθηκαν στο 100 % των δειγμάτων, ενώ η υψηλότερη συγκέντρωση που ανιχνεύθηκε ήταν 350,13 ng/L για την paracetamol. Σύμφωνα με την στατιστική επεξεργασία των αποτελεσμάτων δεν παρατηρήθηκαν εποχιακές διαφορές στις μέσες τιμές των συγκεντρώσεων των φαρμακευτικών ενώσεων. Αντίθετα, για την χωρική κατανομή τους παρατηρήθηκε στατιστικά σημαντική διαφορά (Ρ<0,050) για το σημείο δειγματοληψίας, που βρίσκεται μετά την έξοδο της ΜΕΥΑ της πόλης του Αγρινίου για το σύνολο των ενώσεων που μελετήθηκαν. Τέλος, πραγματοποιήθηκε η εκτίμηση του κινδύνου για δύο σενάρια: της γενικής (RQm) και της ακραίας υπόθεσης (RQex) όπου η διάμεση και η μέγιστη συγκέντρωση που προσδιορίστηκαν, χρησιμοποιήθηκαν για τον υπολογισμό του πηλίκου κινδύνου. Τα αποτελέσματα ανέδειξαν και για τα δύο σενάρια ότι μόνο το triclosan εμφανίζει υψηλή επικινδυνότητα ενώ οι υπόλοιπες ενώσεις εμφανίζουν χαμηλή ή μέτρια επικινδυνότητα. Τα επίπεδα συγκέντρωσης της ομάδας των φαρμακευτικών ουσιών καθώς και η απομάκρυνσή τους από τη ΜΕΥΑ του Αγρινίου εξετάστηκαν κατά τη διάρκεια μιας δεκατετράμηνης δειγματοληψίας. Οι περισσότερες από αυτές (salicylic acid, clofibric acid, paracetamol, caffeine, gemfibrozil, triclosan, diclofenac και carbamazepine) ανιχνεύτηκαν σε ποσοστό 100% των αναλυθέντων δειγμάτων. Οι υψηλές συχνότητες ανίχνευσης οφείλονται είτε στην συχνή τους κατανάλωση (π.χ. salicylic acid, clofibric acid, paracetamol, caffeine και gemfibrozil), είτε στα μικρά ποσοστά απομάκρυνσής τους κατά τη διάρκεια της επεξεργασίας στη ΜΕΥΑ (π.χ. carbamazepine), είτε και στους δύο παραπάνω λόγους (π.χ. triclosan και diclofenac). Οι μέσες τιμές απομάκρυνσης των φαρμακευτικών ενώσεων από τη ΜΕΥΑ υπολογίστηκαν μεταξύ 46,3% και 96,8%, με τις υψηλότερες τιμές να καταγράφονται για το naproxen (96,8%) και την caffeine (96%) ενώ οι χαμηλότερες για το carbamazepine (46,3%) και το triclosan (63,2%). Κατά τη διάρκεια των χειμερινών μηνών παρατηρήθηκαν μικρότερες μέσες τιμές απομάκρυνσης λόγω των χαμηλότερων θερμοκρασιών αλλά και λόγω των βροχοπτώσεων που προκαλούν αραίωση από τη μια και μικρότερους υδραυλικούς χρόνους παραμονής των λυμάτων στη ΜΕΥΑ από την άλλη. Μελετήθηκε η φωτολυτική και φωτοκαταλυτική αποικοδόμηση (κινητική, μηχανισμοί αποικοδόμησης, σχηματισμός παραπροϊόντων) επιλεγμένων οργανικών ενώσεων από τις παραπάνω ομάδες (του παρασιτοκτόνου tebuconazole και της βακτηριοκτόνου triclosan) στην υδατική φάση (απεσταγμένο νερό και επεξεργασμένα λύματα) ως εναλλακτική τεχνολογία επεξεργασίας για την μείωση των επιπέδων ρύπανσης από τις μονάδες βιολογικού καθαρισμού. Το tebuconazole επιλέχθηκε λόγω της μεγάλης εφαρμογής του τα τελευταία χρόνια σε γεωργικές και αστικές χρήσεις, της μικρής του απομάκρυνσης κατά την επεξεργασία των υγρών αποβλήτων στη ΜΕΥΑ και της μεγάλης ανθεκτικότητάς του στο περιβάλλον. Το triclosan παρόλο που δεν ανιχνεύτηκε σε μεγάλες συγκεντρώσεις, επιλέχθηκε επειδή είναι η μόνη από τις φαρμακευτικές ενώσεις που μελετήθηκαν που εμφανίζει υψηλή επικινδυνότητα για το περιβάλλον ,καθώς επίσης και λόγω της χημικής του δομής, που είναι παρόμοια και μπορεί να είναι πρόδρομη με ιδιαίτερα τοξικές ενώσεις όπως τα πολυχλωριωμένα φουράνια και οι διοξίνες. Επιδεικνύει ανθεκτικότητα στην αποικοδόμησή του ενώ αποδεδειγμένα προκαλεί ενδοκρινική διαταραχή σε έμβια όντα. Ως πρώτος στόχος της μελέτης της φωτοκαταλυτικής αποικοδόμησης ήταν η διερεύνηση των βασικών πειραματικών παραμέτρων που επιδρούν στο ρυθμό και την απόδοση της φωτοκαταλυτικής οξείδωσης (συγκέντρωση του καταλύτη, αρχική συγκέντρωση του ρύπου, ένταση της ακτινοβολίας) και η εύρεση των βέλτιστων συνθηκών για τη μέγιστη φωτοκαταλυτική δραστικότητα με τη χρήση Κεντρικού Σύνθετου Πειραματικού Σχεδιασμού (Central Composite Design, CCD) και μεθοδολογία απόκρισης επιφανείας. Εν συνεχεία μελετήθηκε η κινητική της αποικοδόμησής τους σε διάφορες πειραματικές συνθήκες, η εκτίμηση του βαθμού ανοργανοποίησης των ρύπων και τέλος η μελέτη του μηχανισμού της αποικοδόμησής τους. Τα πειράματα της φωτόλυσης και της φωτοκατάλυσης πραγματοποιήθηκαν σε φωτο-αντιδραστήρα με χρήση οργανολογίας (SUNTEST XLS+, ATLAS) που προσομοιώνει την ηλιακή ακτινοβολία. Ο ποσοτικός προσδιορισμός των tebuconazole και triclosan για τη μελέτη της κινητικής της αντίδρασης διάσπασης σε υδατικά διαλύματα πραγματοποιήθηκε με υγρή χρωματογραφία υψηλής απόδοσης (HPLC). Στα δείγματα που λαμβάνονταν σε τακτά χρονικά διαστήματα εκτός από τη συγκέντρωση του ρύπου, προσδιορίζονταν και ο ολικός οργανικός άνθρακας (TOC) καθώς και οι συγκεντρώσεις των ανόργανων ιόντων που προκύπτουν από την διάσπαση της μητρικής ένωσης με τη χρήση ιοντικού χρωματογράφου. Επίσης, για την διερεύνηση του μηχανισμού των αντιδράσεων της φωτοκαταλυτικής διάσπασης των επιλεχθέντων ρύπων έγινε κινητική μελέτη με τη χρήση παρεμποδιστών ενώ παράλληλα προσδιορίστηκαν τα ενδιάμεσα προϊόντα της διάσπασής τους με ταυτοποίηση τους σε αέριο χρωματογράφο με φασματοσκοπία μάζας (GC-MS). Από τα αποτελέσματα των πειραμάτων του Κεντρικού Σύνθετου Πειραματικού Σχεδιασμού (CCD), οι βέλτιστες συνθήκες για την αποδόμηση του tebuconazole βρέθηκαν να είναι Cteb=1ppm, CTiO2=550ppm, I=650W/m2 ενώ για το triclosan Ctric=1ppm, CTiO2=550ppm, I=700W/m2. Στις βέλτιστες συνθήκες πραγματοποιήθηκαν τα πειράματα κινητικής μελέτης με ή χωρίς παρεμποδιστές, μελέτης των ενδιάμεσων προϊόντων της φωτοκαταλυτικής τους διάσπασης καθώς και της ανοργανοποίησής τους. Η διάσπαση των ρύπων ακολούθησε κινητική ψευδό-πρώτης τάξης. Τα αποτελέσματα από τα πειράματα κινητικής με χρήση παρεμποδιστών κατέδειξαν ότι η φωτοκαταλυτική αποικοδόμηση του tebuconazole λαμβάνει χώρα κυρίως μέσω των ελευθέρων ριζών υδροξυλίου και με μικρότερη συμμετοχή και των θετικών οπών. Αντίστοιχα, για το triclosan η φωτοκαταλυτική αποικοδόμηση λαμβάνει χώρα κυρίως μέσω ελευθέρων ριζών υδροξυλίου. Σχεδόν πλήρης ανοργανοποίηση επιτυγχάνεται μετά το τέλος της φωτοκαταλυτικής διεργασίας για το triclosan, ενώ για το tebuconazole, το άζωτο προσδιορίστηκε στο 80% της θεωρητικά αναμενόμενης ποσότητάς του που απελευθερώνεται στο διάλυμα με τη μορφή ΝΟ3- και ΝΟ2-, γεγονός που υποδηλώνει ότι είτε τα τελικά οργανικά προϊόντα διάσπασης του tebuconazole (αζολικοί δακτύλιοι) απαιτούν μεγάλους χρόνους ακτινοβόλησης για την αποικοδόμησή τους είτε ότι σχηματίζεται ελεύθερο Ν2 μετά τη διάνοιξη του αζολικού δακτυλίου. Τέλος, μετά την ανίχνευση και ποσοτικοποίηση των ενδιαμέσων προϊόντων των αντιδράσεων της φωτοκαταλυτικής διάσπασης των δύο ρύπων προτάθηκαν οι μηχανισμοί αποικοδόμησής τους σε υδατικά συστήματα. Σύμφωνα με τα αποτελέσματα της φωτοκαταλυτικής οξείδωσης των δύο ρύπων-μοντέλων που μελετήθηκαν στην παρούσα διατριβή η εφαρμογή της φωτοκατάλυσης σε ευρύτερη κλίμακα και σε πραγματικά υδατικά απόβλητα και συστήματα επεξεργασίας φυσικών νερών είναι μια γρήγορη και πολύ αποδοτική τεχνολογία επεξεργασίας οργανικών μίκρο-ρύπων. Απαιτείται όμως έλεγχος και βελτιστοποίηση των διαφόρων παραμέτρων που επιδρούν στην απόδοση της διεργασίας και η χρήση ηλιακής ακτινοβολίας, ώστε η εφαρμογής της να είναι πιο εφικτή τόσο από οικονομική όσο και περιβαλλοντική άποψη. Επιπλέον, η δυνατότητα συνδυασμού της μεθόδου αυτής με άλλες μεθόδους επεξεργασίας, βιολογικές ή/και φυσικοχημικές, θα μπορούσε να αποτελέσει μια πιο ολοκληρωμένη και οικονομική λύση σε προβλήματα περιβαλλοντικής ρύπανσης, σύμφωνα με τα σύγχρονα κριτήρια και τις απαιτήσεις. / Human activities (agricultural, industrial, urban, etc.) and wastewater disposal in sewage treatment plants affect surface and ground water bodies such as rivers, lakes, lagoons, sea waters etc., consisting major pollution sources leading to significant negative impacts on ecosystems. The transportation, distribution and elimination of organic micropollutants, such as pesticides, pharmaceutical and personal care products compounds, etc., and their metabolites has been the subject of systematic research in recent decades, arousing a great interest for both the scientific community and modern societies. The lower part of Acheloos River basin, located in Western Greece, and the wastewater treatment plant (WWTP) of Agrinio city, the effluents of which discharge into the river, are selected to be studied in the present thesis in order to monitor the occurrence, patterns and effects of organic micropollutants such as pesticides and pharmaceutical compounds in the sewage-impacted river as well as the removal of such pollutants using conventional (WWTP) and alternative advanced oxidation (photocatalysis) technologies. Acheloos River is one of the most important water resources in Greece with a great environmental significance since it is connected with the lakes Trichonida, Lysimachia and the Messolonghi and Etoliko lagoons. In addition, river's delta is protected by international environmental conventions (Ramsar and Natura 2000). The lower basin Acheloos includes large areas of cultivated land (Agrinio and Neochori-Katochi plains). The aims of the present study were the study of: (a) the occurrence and patterns (temporal and spatial distribution), of selected pesticides, pharmaceutical compounds and personal care products, belonging to different chemical groups in Acheloos River as well as the assessment of the environmental risk associated with their levels in river waters; (b) the occurrence and the removal rates along the secondary and tertiary treatments in the wastewater plant of Agrinio city; (c) the pollution levels from wastewater discharges into Acheloos River; (d) the photolytic and photocatalytic degradation (kinetic studies, degradation mechanisms, by-products formation, mineralization) of selected model compounds (pesticide tebuconazole and antimicrobial triclosan) within the detected micro-pollutants in different water substrates (distilled water and treated wastewater) as an alternative treatment technology for the reduction of pollution levels of the sewage treatment plants. For the achievement of the above aims and objectives two multi-residue methods have been developed and applied for the determination of pesticide and pharmaceutical compounds in water samples sampled from the river and the influent and effluents of WWTP. The analytical method included the isolation of compounds from the water matrices using solid phase extraction and the qualitative and quantitative determination by gas chromatography techniques using selective detectors (FTD) and mass spectrometry. Thirty-two pesticides including metabolites were selected (i.e. alachlor, atrazine, atrazine desethyl, EPTC, s-metolachlor, simazine, trifluralin, azinphos methyl, chlorpyrifos, chlorpyrifos methyl, chlorfenviphos, diazinon, dichlorvos, dimethoate, fenthion, fenthion sulfoxide, malaoxon, methidathion, methyl parathion, cyproconazole, pyrimethanil, triadimefon, pirimiphos methyl, isoproturon, diuron, carbofuran, quinalphos, triazophos, phosalone, pyrazophos, penconazole, tebuconazole) according to previous and current agricultural and urban uses in the basin river. In addition, twelve pharmaceutical compounds and metabolites (i.e. salicylic acid, paracetamol, clofibric acid, ibuprofen, phenazone, gemfibrozil, triclosan, naproxen, diclofenac, carbamazepine, caffeine, fenofibrate) were chosen according to the occurrence and data reported in the open literature for other water bodies in Europe and few studies in Greece. Gas chromatography mass spectrometry (GC-MS) was also used for the detection and the quantification of pharmaceutical compounds. Spatial and temporal variations in pesticide concentrations were monitored during the period March 2005 - February 2008. Sampling period began one year before the restrictions imposed in tobacco cultivation (from 1/1/2006), the main agricultural activity in the area, within the framework of Common Agricultural Policy, and lasted two years after the restriction in order to reveal probable changes in pesticide uses and inputs to the river flow. The most frequently detected pesticides within the monitoring period were diazinon (78.6%) and fenthion (52.6%), from the group of insecticides, DEA (69.3%) and alachlor (50%) from the group of herbicides and pyrimethanil (67.3%) and tebuconazole (44.7%) from the group of fungicides. Statistical analysis of the detected pesticide concentrations showed significantly higher concentrations during the spring and early summer coinciding frequently with the application periods, and an increasing trend along the river flow with the sampling sites located in the river's delta presenting the higher concentration levels. It was also found that mean concentrations of pesticides in years 2006 and 2007 were lower compared with the year 2005 proving that the restrictions of tobacco cultivation and changes in land uses had a significant effect on Acheloos River pesticide pollution levels. This is further confirmed by conducting the risk assessment for each year of the sampling period using the risk quotient method. Six pesticides showed high risk, in 2005 while just one in 2007. The occurrence and the removal of pesticides from the wastewater treatment plant of Agrinio were studied for a period of fourteen months (April 2007-May 2008). The herbicides isoproturon, atrazine and its metabolite DEA, alachlor, the insecticides diazinon, methidathion, chlorfenviphos and chlorpyriphos and the fungicides tebuconazole, cyproconazole were the most frequently detected in influent and effluent samples. Seasonal variations for the majority of pesticides showed that pesticide inputs in wastewater treatment plant from agricultural cultivations in the suburban area and pesticides control in the city, presented higher concentrations during the main period of applications from mid-March to late June. Fungicides belonging to the chemical group of substituted azoles were the exception to the above trend, except triadimefon, and were detected for longer periods during the year because of their uses as preservatives-biocides to surfaces and coatings of buildings. Additionally, the removal rates of pesticides during secondary and tertiary treatment of the WWTP were studied. Mean removal rates (%) after primary and secondary treatment ranged between 31% for pyrimethanil to 97% for dichlorvos. Mean cumulative removals (%) for the whole treatment ranged between 46% pyrimethanil to 93% for triadimefon. Generally, primary treatment in WWTP did not remove significantly pesticides from wastewater, while tertiary treatment was effective for a small number of pesticides. Based on the results of the pesticide occurrence and removal rates, the WWTP of Agrinio city should be considered as a significant point source of pesticides in Acheloos River. The occurrence and the removal of pharmaceuticals along wastewater treatment plant of Agrinio were also studied for the same sampling period (April 2007-May 2008). Most of the analyzed compounds (salicylic acid, clofibric acid, paracetamol, caffeine, gemfibrozil, triclosan, diclofenac and carbamazepine) were detected in 100% of the samples. The observed high detection frequencies were associated either to their frequent consumption (e.g. salicylic acid, clofibric acid, paracetamol, caffeine and gemfibrozil), or low elimination during treatment (e.g. carbamazepine), or both of the above reasons (e.g. triclosan and diclofenac). The highest mean removals after tertiary treatment were measured for naproxen (96.8%), caffeine (96%) and ibuprofen (92.3%), (except phenazone removals were not determined due to the low frequency of detection), while the lowest for carbamazepine (46.3%) and triclosan (63.2%). Between secondary and tertiary treatment mean removal efficiencies ranged from 18.3% for carbamazepine to 67.4% for naproxen. Lower mean removal rates were determined during winter probably due to low temperatures and high rainfall, causing dilution and lower hydraulic residence times in WWTP. Regarding the occurrence of pharmaceutical compounds along the river flow salicylic acid, paracetamol, carbamazepine and caffeine were detected in 100% of samples analyzed, while the highest detected concentration was 350,13 ng/L, recorded for paracetamol. Statistical analysis did not revealed seasonal differences in mean concentrations of pharmaceutical compounds. In contrary, spatial distribution showed statistically significant difference (P <0.050) for the sampling station located afterwards the discharge of WWTP for all studied compounds. Finally, risk assessment was estimated using the risk quotient method for different scenarios: the general (RQm) and extreme (RQex), where median and maximum concentrations were used respectively. The obtained results using both scenarios revealed that only triclosan exhibited high risk while the rest of the compounds presented low or moderate risk. Photolytic and photocatalytic degradation (kinetic studies, degradation mechanisms, by-products formation, mineralization) of the pesticide tebuconazole and the antibacterial compound triclosan were studied in different aqueous matrices (distilled water and treated wastewater) Tebuconazole was chosen due to its wide application in recent years in agricultural and urban uses, low removal efficiency during treatment in WWTP and high persistence in aquatic environment. Although triclosan was not extensively detected, it was selected due to the high risk determined, and because of its chemical structure, which is similar to highly toxic compounds such as polychlorinated furans and dioxins and may be a precursor for the formation of them. Triclosan exhibited also resistance to degradation and causes endocrine disruption in living organisms. Photolysis of tebuconazole was a very low process, thus the environmental significance for the degradation of tebuconazole is considered negligible. On the contrary, significant photolysis rates were determined for triclosan with half lives of about 7 days using mean solar irradiance intensity for Greece. Primary goal of the photocatalytic study was to explore experimental parameters of photocatalytic degradation that affect the rate and efficiency of oxidation reaction (catalyst concentration, initial pollutant concentration, radiation intensity) and to find the optimum conditions for maximum photocatalytic activity, using Central Composite Design (CCD) and response surface methodology. The kinetics of the photocatalytic degradation and the degree of mineralization were studied in different experimental conditions. Photolytic and photocatalytic experiments were performed using SUNTEST XLS+ instrument, from ATLAS, simulating solar radiation. Quantification of tebuconazole and triclosan for the kinetic studies in aquatic solutions was carried out by high performance liquid chromatography (HPLC). Samples taken periodically during photocatalytic process were filtered and analyzed for determining the concentration of the pollutant, the concentration of total organic carbon (TOC) using a TOC instrument, as well as the concentration of inorganic ions resulting from the decomposition of the parent compound using ion chromatography. The determined optimum experimental conditions using CCD and RSm methodologies were Cteb=1 ppm, CTiO2=550 ppm, I=650 W/m2 for tebuconazole and Ctric=1 ppm, CTiO2=550 ppm, I=700 W/m2 for triclosan. Degradation kinetics of both pollutants followed pseudo-first order model. In order to investigate the major reactive species taking part of the photocatalytic degradation mechanism of the selected pollutants, kinetic studies using scavengers were conducted, while by-products were identified by means of gas chromatography-mass spectrometry (GC-MS). Kinetic experiments using scavengers showed that the photocatalytic degradation of tebuconazole occurred primarily via hydroxyl radical and to a lesser extent by positive holes. Triclosan photocatalytic degradation took place mainly through hydroxyl radicals. Almost complete mineralization was achieved for triclosan, while for tebuconazole, more than 80% of the theoretically expected amount of nitrogen was determined as NO3- and NO2-, suggesting either that the final organic decomposition products of tebuconazole require longer irradiation times for degradation or that free N2 was formed during degradation of azole rings. Finally, the mechanisms of the photocatalytic degradation of both compounds were proposed based on the detection and semi-quantification of by-products performed by gas chromatography-mass spectrometry. According to the results obtained for the photocatalytic oxidation of the two model-pollutants, photocatalysis could be a very fast and efficient treatment technology for the removal of organic micro-pollutants from real wastewaters and natural waters. However, before implementation it is necessary to control and optimize various parameters that affect the efficiency of process such as the catalyst loading, the intensity of solar radiation etc., in order to be more feasible both economically and environmentally. Moreover, the possibility of combining this method with other conventional biological and/or physicochemical methods of treatment, could result in a more integrated and cost-effective solution for environmental pollution problems in accordance with modern standards and requirements.

<p>Aim: To determine whether there was any significant difference in the antimicrobial activity of 4 herbal toothpastes against cultures of 3 primary plaque colonizers (Streptococcus mutans, Streptococcus sanguinis and a non-specific &alpha / -heamolytic streptococcus).</p>