O presente trabalho trata do desenvolvimento um novo material, diatomita modificada por ferro, como ativador dos oxidantes persulfato de sódio e peróxido de hidrogênio para degradar poluentes prioritários (fenantreno e antraceno), diesel e o poluente emergente ácido perfluoroctanóico (PFOA). Os objetivos deste estudo foram comparar esse novo método com métodos convencionais de ativação para esses oxidantes; e estudar, estatisticamente, a relação ótima entre a quantidade deste material e a concentração de oxidante para a degradação dos contaminantes. A diatomita bruta e as diatomitas modificadas (CAT-5 e CAT-20) foram caracterizadas por diferentes técnicas. Os principais resultados da caracterização mostraram que os materiais são amorfos e que a concentração de ferro foi 4%, 17% e 25% para diatomita bruta, CAT-5 e CAT-20, respectivamente. Os resultados mostraram que os materiais modificados apresentaram significativa atividade catalítica para ativar os oxidantes e degradar os poluentes, sendo a CAT-5 a mais reativa. Resultados satisfatórios foram obtidos utilizando 45 g L-1 de persulfato de sódio com 2,5 g de diatomita modificada (CAT-5), com degradação de 87% e 96% de fenantreno e antraceno, respectivamente, em 168 horas de tratamento. Para o tratamento de solo arenoso contaminado com diesel, os melhores resultados foram obtidos utilizando 41 g L-1 de persulfato de sódio e 1,56 g de CAT-5, obtendo decaimento de 91% de carbono total em 146 horas. A eficiência da decomposição de PFOA mostra que a reatividade dos sistemas seguiu a ordem: peróxido de hidrogênio em altas concentrações > peróxido de hidrogênio em paralelo com persulfato > persulfato alcalino, ambos ativados com CAT-5, atingindo 86%, 69% e 48%, respectivamente, após 6 horas de reação. / The present work deals with the development of a new materials, modified diatomite by iron, as an activator of the oxidants sodium persulfate and hydrogen peroxide to degrade priority pollutants (phenantherene and anthracene), diesel and emerging pollutant perfluorooctanoic acid (PFOA). The aims of this study were to compare this new method with traditional activation method for these oxidants; and to study, statistically, the optimal ratio between the quantity of the material and the concentration of oxidant to the degradation of contaminants. The raw and modified materials were characterized by different techniques. The main characterization results showed that materials are amorphous, and that the iron concentrations were 4,78%, 17,65% and 25% for the raw diatomite, CAT-5 and CAT-20, respectively. The results showed that the modified material showed significant catalytic activity to activate the oxidants and to degrade pollutants, with CAT-5 being the most reactive. Satisfactory results were obtained using 2,5 g of modified diatomite (CAT-%) with sodium persulfate at 45 g L-1, with degradation of 87% and 96% of phenanthrene and anthracene, respectively, in 168 hours of treatment. For the treatment of sandy soil contaminated with diesel, the best result was obtained using 41 g L-1 of sodium persulfate sodium and 1,56 g of CAT-5, resulting in a decrease of 91% of total carbon present in diesel. The PFOA decomposition efficiency for the systems shows that hydrogen peroxide at high concentrations > hydrogen peroxide-activated persulfate > alkaline-activated persulfate, both with CAT-5, achieving 83%, 69% and 48% , respectively, after 6 hours of reaction.

O presente trabalho trata do desenvolvimento um novo material, diatomita modificada por ferro, como ativador dos oxidantes persulfato de sódio e peróxido de hidrogênio para degradar poluentes prioritários (fenantreno e antraceno), diesel e o poluente emergente ácido perfluoroctanóico (PFOA). Os objetivos deste estudo foram comparar esse novo método com métodos convencionais de ativação para esses oxidantes; e estudar, estatisticamente, a relação ótima entre a quantidade deste material e a concentração de oxidante para a degradação dos contaminantes. A diatomita bruta e as diatomitas modificadas (CAT-5 e CAT-20) foram caracterizadas por diferentes técnicas. Os principais resultados da caracterização mostraram que os materiais são amorfos e que a concentração de ferro foi 4%, 17% e 25% para diatomita bruta, CAT-5 e CAT-20, respectivamente. Os resultados mostraram que os materiais modificados apresentaram significativa atividade catalítica para ativar os oxidantes e degradar os poluentes, sendo a CAT-5 a mais reativa. Resultados satisfatórios foram obtidos utilizando 45 g L-1 de persulfato de sódio com 2,5 g de diatomita modificada (CAT-5), com degradação de 87% e 96% de fenantreno e antraceno, respectivamente, em 168 horas de tratamento. Para o tratamento de solo arenoso contaminado com diesel, os melhores resultados foram obtidos utilizando 41 g L-1 de persulfato de sódio e 1,56 g de CAT-5, obtendo decaimento de 91% de carbono total em 146 horas. A eficiência da decomposição de PFOA mostra que a reatividade dos sistemas seguiu a ordem: peróxido de hidrogênio em altas concentrações > peróxido de hidrogênio em paralelo com persulfato > persulfato alcalino, ambos ativados com CAT-5, atingindo 86%, 69% e 48%, respectivamente, após 6 horas de reação. / The present work deals with the development of a new materials, modified diatomite by iron, as an activator of the oxidants sodium persulfate and hydrogen peroxide to degrade priority pollutants (phenantherene and anthracene), diesel and emerging pollutant perfluorooctanoic acid (PFOA). The aims of this study were to compare this new method with traditional activation method for these oxidants; and to study, statistically, the optimal ratio between the quantity of the material and the concentration of oxidant to the degradation of contaminants. The raw and modified materials were characterized by different techniques. The main characterization results showed that materials are amorphous, and that the iron concentrations were 4,78%, 17,65% and 25% for the raw diatomite, CAT-5 and CAT-20, respectively. The results showed that the modified material showed significant catalytic activity to activate the oxidants and to degrade pollutants, with CAT-5 being the most reactive. Satisfactory results were obtained using 2,5 g of modified diatomite (CAT-%) with sodium persulfate at 45 g L-1, with degradation of 87% and 96% of phenanthrene and anthracene, respectively, in 168 hours of treatment. For the treatment of sandy soil contaminated with diesel, the best result was obtained using 41 g L-1 of sodium persulfate sodium and 1,56 g of CAT-5, resulting in a decrease of 91% of total carbon present in diesel. The PFOA decomposition efficiency for the systems shows that hydrogen peroxide at high concentrations > hydrogen peroxide-activated persulfate > alkaline-activated persulfate, both with CAT-5, achieving 83%, 69% and 48% , respectively, after 6 hours of reaction.

<p>Predmet&nbsp; istraživanja&nbsp; ove&nbsp; doktorske&nbsp; disertacije&nbsp; je&nbsp; procena&nbsp; potencijalno&nbsp; biodostupne&nbsp; frakcije odabranih&nbsp; prioritetnih&nbsp; organskih&nbsp; polutanata&nbsp;&nbsp; (pentahlorbenzena,&nbsp; heksahlorbenzena,&nbsp; lindana, trifluralina, 4-oktilfenola i 4-nonilfenola) u sedimentu, ispitivanje biodegradacionog potencijala ovih&nbsp; jedinjenja&nbsp; u&nbsp; sedimentu&nbsp; u&nbsp; različitim&nbsp; uslovima,&nbsp; kao&nbsp; i&nbsp; procena&nbsp; potencijala&nbsp; stabilizacije<br />sedimenta&nbsp; dodatkom&nbsp; ugljeničnih&nbsp; sorpcionih&nbsp; agenasa.&nbsp; U&nbsp; cilju&nbsp; razvoja&nbsp; metoda&nbsp; za&nbsp; određivanje biodostupnosti odabranih organskih polutanata ispitivane su i&nbsp; optimizovane metode vi&scaron;estepene i jednostepene parcijalne ekstrakcije primenom sledećih hemijskih agenasa:&nbsp; Tenaks&nbsp; smole, XAD-4&nbsp; smole&nbsp; i&nbsp; rastvora&nbsp; ciklodekstrina&nbsp; (2-hidroksipropil-&beta;-ciklodekstrina,&nbsp; &beta;-ciklodekstrina&nbsp; i&nbsp; metil-&beta;-ciklodekstrina).&nbsp; Optimalni&nbsp; agens&nbsp; za&nbsp; procenu&nbsp; biodostupne&nbsp; frakcije&nbsp; odabranih&nbsp; organskih zagađujućih&nbsp; materija&nbsp; sa&nbsp; sedimenta&nbsp; XAD-4&nbsp; smola,&nbsp; a&nbsp; optimalno&nbsp; vreme&nbsp; ekstrakcije&nbsp; primenom jednostepenih&nbsp; ekstrakcija&nbsp; je&nbsp; oko&nbsp; 8&nbsp; h.&nbsp; Procena&nbsp; biodegradacionog&nbsp; potencijala&nbsp; odabranih prioritetnih&nbsp; organskih&nbsp; zagađujućih&nbsp; materija&nbsp; u&nbsp; sedimentu&nbsp; ispitana&nbsp; je&nbsp; u&nbsp; različitim&nbsp; aerobnim&nbsp; i anaerobnim uslovima uz optimizaciju uslova putem biostimulacije i bioaugmentacije. Pokazano je&nbsp; da&nbsp; svih&nbsp; &scaron;est&nbsp; odabranih&nbsp; jedinjenja&nbsp; poseduju&nbsp; značajan&nbsp; potencijal&nbsp; biodegradacije&nbsp; u&nbsp; anaerobnoj sredini&nbsp; pri&nbsp; čemu&nbsp; u&nbsp; slučaju&nbsp; lindana&nbsp; i&nbsp; trifluralina&nbsp; dolazi&nbsp; do&nbsp; potpunog&nbsp; uklanjanja&nbsp; biodostupne količine&nbsp; jedinjenja&nbsp; primenom&nbsp; sva&nbsp; četiri&nbsp; ispitana&nbsp; inokuluma.&nbsp; Aerobni&nbsp; potencijal&nbsp; u&nbsp; ispitanim uslovima&nbsp; pokazali&nbsp; su&nbsp; samo&nbsp; alkil&nbsp; fenoli,&nbsp; gde&nbsp; je&nbsp; takođe&nbsp; uklonjena&nbsp; skoro&nbsp; celokupna&nbsp; količinabiodostupne&nbsp; frakcije&nbsp; jedinjenja&nbsp; u&nbsp; sedimentu&nbsp; (78-85%).&nbsp; Potencijal&nbsp; remedijacije&nbsp; sedimenta dodatkom&nbsp; ugljeničnih&nbsp; materijala&nbsp; ispitan&nbsp; je&nbsp; sa&nbsp; aspekta&nbsp; odabira&nbsp; ugljeničnih&nbsp; sorpcionih&nbsp; agenasa (aktivni&nbsp; ugalj,&nbsp; biougalj&nbsp; i&nbsp; humus);&nbsp; određivanja&nbsp; optimalne&nbsp; količine&nbsp; materijala;&nbsp; isptivanja dugoročnih i kratkoročnih efekata dodatka ovih agenasa na biodostupnost organskih zagađujućih materija&nbsp; kako&nbsp; bi&nbsp; se&nbsp; ispitao&nbsp; efekat&nbsp; starenja &nbsp; i&nbsp; toksičnosti&nbsp; dobijenih&nbsp; sme&scaron;a.&nbsp; Rezultati&nbsp; stabilizacije zagađujućih&nbsp; supstanci&nbsp; u&nbsp; sedimentu&nbsp; pokazuju&nbsp; da:&nbsp; (1)&nbsp; povećanje&nbsp; doze&nbsp; sva&nbsp; tri&nbsp; sorpciona&nbsp; agensa dovodi&nbsp; do&nbsp; povećanja&nbsp; efikasnosti&nbsp; imobilizacije&nbsp; i&nbsp; smanjenja&nbsp; biodostupne&nbsp; frakcije&nbsp; odabranih organskih jedinjenja; (2) starenjem sme&scaron;a sedimenta i&nbsp; sorbenata u toku prvih 90 dana dolazi do daljeg smanjenja biodostupne frakcije svih jedinjenja, nakon čega se biodostupna koncentracija ispitivanih&nbsp; jedinjenja&nbsp; primenom&nbsp; aktivnog&nbsp; uglja&nbsp; ne&nbsp; menja,&nbsp; dok&nbsp; primenom&nbsp; biouglja&nbsp; i&nbsp; humusa&nbsp; dolazi&nbsp; do&nbsp; porasta&nbsp; biodostupne&nbsp; frakcije&nbsp; jedinjenja.&nbsp; Testovi&nbsp; fitotoksičnosti&nbsp; su&nbsp; pokazali&nbsp; da&nbsp; je&nbsp; <em>Zea mays&nbsp; </em>akumulirao&nbsp; značajno&nbsp; veće&nbsp; količine&nbsp; ispitivanih&nbsp; jedinjenja&nbsp; iz&nbsp; netretiranog&nbsp; sedimenta&nbsp; u poređenju sa&nbsp; <em>Cucurbita pepo</em>&nbsp; i&nbsp;<em> Lactuca sativa. </em>Toksičnost sme&scaron;a sedimenta sa aktivnim ugljom i humusom&nbsp; procenjena&nbsp; na&nbsp; osnovu&nbsp; inhibicije&nbsp; luminiscencije&nbsp; na&nbsp; <em>Vibrio&nbsp; fischeri</em>&nbsp; kao&nbsp; i&nbsp; ispitivanjem <em>Zea&nbsp; mays&nbsp; </em>germinacije&nbsp; i&nbsp; produkcije&nbsp; biomase&nbsp; je&nbsp; pokazala&nbsp; značajno&nbsp; smanjenje&nbsp; u&nbsp; odnosu&nbsp; na netretirani&nbsp; sediment.&nbsp; Akumulacija&nbsp; ispitivanih&nbsp; jedinjenja&nbsp; u&nbsp; biomasi&nbsp; <em>Zea&nbsp; mays&nbsp; </em>u&nbsp; netretiranom sedimentu je bila značajno veća u odnosu na sve sme&scaron;e sedimenta i aktivnog uglja i humusa. Sva tri&nbsp; sorbenta&nbsp; pokazala&nbsp; su&nbsp; veliki&nbsp; remedijacioni&nbsp; potencijal&nbsp; za&nbsp; sediment&nbsp; zagađen&nbsp; organskim zagađujućim supstancama, ali je aktivni ugalj pokazao najbolje performance.</p> / <p>The&nbsp; aim&nbsp; of&nbsp; the&nbsp; research&nbsp; in&nbsp; this&nbsp; PhD&nbsp; dissertation&nbsp; is&nbsp; the&nbsp; assessment&nbsp; of&nbsp; the&nbsp; potentially biodegradable&nbsp; fraction&nbsp; of&nbsp; selected&nbsp; organic&nbsp; pollutants&nbsp;&nbsp; (pentachlorbenzene,&nbsp; hexachlorobenzene, lindane,&nbsp; trifluraline,&nbsp; 4-octylphenol&nbsp; and&nbsp;&nbsp;&nbsp; 4-nonylphenol)&nbsp; in&nbsp; the&nbsp; sediment,&nbsp; estimation&nbsp; of&nbsp; the biodegradation potential of these compounds in sediment in different conditions, as well as the assessment&nbsp; of&nbsp; the&nbsp; stabilization&nbsp; potential&nbsp; sediment&nbsp; by&nbsp; the&nbsp; sediment&nbsp; amendment&nbsp; with&nbsp; of&nbsp; carbon rich sorption agents. In order to develop and optimise&nbsp; methods for the bioavailability assessment of&nbsp; the&nbsp; selected&nbsp; organic&nbsp; pollutants,&nbsp; methods&nbsp; of&nbsp; multistage&nbsp; and&nbsp; single-step&nbsp; non&nbsp; exhaustive extraction&nbsp; were&nbsp; studied&nbsp; using&nbsp; the&nbsp; following&nbsp; chemical&nbsp; agents:&nbsp; Tenax&nbsp; resin,&nbsp; XAD -4&nbsp; resin&nbsp; and&nbsp; a cyclodextrin&nbsp; solution&nbsp; (2-hydroxypropyl- &beta;-cyclodextrin,&nbsp; &beta;-cyclodextrin&nbsp; and&nbsp; methyl-&beta;-cyclodextrin).&nbsp; Results&nbsp; showed&nbsp; that&nbsp; optimal&nbsp; agent&nbsp; for&nbsp; estimating&nbsp; the&nbsp; bioavailable&nbsp; fraction&nbsp; of selected organic pollutants from the sediment is XAD-4 resins, and that the optimum extraction time using single-step extraction is about 8 h. The assessment of the biodegradation potential of selected&nbsp; priority&nbsp; organic&nbsp; pollutants&nbsp; in&nbsp; the&nbsp; sediment&nbsp; was&nbsp; examined&nbsp; in&nbsp;&nbsp; various&nbsp; aerobic&nbsp; and anaerobic&nbsp; conditions,&nbsp; with&nbsp; the&nbsp; optimization&nbsp; of&nbsp; conditions&nbsp; through&nbsp; biostimulation&nbsp; and bioaugmentation.&nbsp; It&nbsp; has&nbsp; been&nbsp; shown&nbsp; that&nbsp; all&nbsp; six&nbsp; selected&nbsp; compounds&nbsp; possess&nbsp; significant biodegradation&nbsp; potential&nbsp; in&nbsp; the&nbsp; anaerobic&nbsp; environment,&nbsp; where&nbsp; in&nbsp; the&nbsp; case&nbsp; of&nbsp; lindane&nbsp; and trifluraline there is complete removal of the bioavailable amount of the compound&nbsp;&nbsp; using all four inoculum tested. Aerobic potential under the applied conditions has been showen only for alkyl phenols,&nbsp; where&nbsp; almost&nbsp; all&nbsp; of&nbsp; the&nbsp; bioavailable&nbsp; fraction&nbsp; of&nbsp; the&nbsp; compound&nbsp; in&nbsp; the&nbsp; sediment&nbsp; was removed (78-85%). The potential of sediment remediation with the amendment of sediment withcarbon&nbsp; rich&nbsp; materials&nbsp; was&nbsp;&nbsp; examined&nbsp; from&nbsp; the&nbsp; aspect&nbsp; of&nbsp; selecting&nbsp; carbon&nbsp; sorption&nbsp; agents (activated carbon, biochar and humus); estimation the optimal material doses; the long -term and short-term effects of the addition&nbsp; of these agents on the bioavailability of organic pollutants&nbsp; in order to examine the effect of aging and the toxicity of the resulting mixtures. The results of the stabilization of pollutants in the sediment show that: (1)&nbsp; increasing the dose of all three&nbsp;&nbsp; sorption agents&nbsp; leads&nbsp; to&nbsp; an&nbsp; increase&nbsp; in&nbsp; the&nbsp; immobilization&nbsp; efficiency&nbsp; and&nbsp; reduction&nbsp; of&nbsp; the&nbsp; bioavailable fraction of the selected&nbsp; organic compounds; (2) aging of the amended sediment during the first 90 days results in a further reduction of the biodegradable fraction of all compounds, after which the&nbsp; biodegradable&nbsp; concentration&nbsp; of&nbsp; the&nbsp; selected&nbsp; compounds&nbsp; remain&nbsp; the&nbsp; same&nbsp; in&nbsp; the&nbsp; case&nbsp; of activated carbon amendment, while the bioavailable fraction of&nbsp; the compound increases with the use&nbsp; of&nbsp; biohar&nbsp; and&nbsp; humus.&nbsp; Phytotoxicity&nbsp; tests&nbsp; showed&nbsp; that&nbsp; <em>Zea&nbsp; mays&nbsp;</em> accumulated&nbsp; significantly higher amount of selected organic pollutants from unamended sediment, comparing to&nbsp; <em>Cucurbita pepo&nbsp;</em> and <em>Lactuca sativa</em>. Toxicity of activated carbon and humus amended sediment assessed by <em>Vibrio&nbsp; fischeri&nbsp;</em> luminescence&nbsp; inhibition&nbsp; test&nbsp; and&nbsp; by&nbsp; measuring&nbsp; <em>Zea&nbsp; mays&nbsp; </em>germination&nbsp; and biomass yield was significantly reduced in the amended sediment samples. Accumulation of the selected&nbsp; organic&nbsp; pollutants&nbsp; in&nbsp; the&nbsp; <em>Zea&nbsp; mays</em>&nbsp; biomass&nbsp; in&nbsp; the&nbsp; unamended&nbsp; sediment&nbsp; were&nbsp; a significantly&nbsp; higher&nbsp; than&nbsp; in&nbsp; the&nbsp; humus&nbsp; and&nbsp; activated&nbsp; carbon&nbsp; amended&nbsp; sediment.&nbsp; Both&nbsp; sorbents show&nbsp; potential&nbsp; to&nbsp; be&nbsp; used&nbsp; as&nbsp; remediation&nbsp; agents&nbsp; for&nbsp; organically&nbsp; contaminated&nbsp; sediment,&nbsp; but activated carbon exhibited the better performance.</p>

O trabalho foi desenvolvido com o objetivo de caracterizar e estudar formas de tratamento de águas residuárias de indústrias de refino de óleo lubrificante e de recuperação de solventes. A fase preliminar teve por objetivo avaliar a biodegradabilidade do despejo combinado dessas duas indústrias. A segunda foi realizada em instalação piloto composta, basicamente, de uma unidade de arraste com ar/tanque de equalização, tanques de correção de pH e de aeração com tempos de detenção distintos, seguidos de tanques de sedimentação. Foram executados testes para avaliar a remoção de material solúvel em n-hexano do despejo da indústria de refino de óleo lubrificante e do efluente final. A unidade de arraste com ar difuso operando com subpressão de 15 mmhg a saída dos gases, vazão específica de ar de 20 ml/l min. E tempo de detenção de 5 dias foi eficiente na remoção de acetona, piridina, benzeno, tolueno, hexano, metil etil cetona e provavelmente solventes clorados. Não apresentou remoção significativa de álcoois, que foram eficientemente degradados no sistema biológico subsequente. Obteve-se remoções superiores a 90%, em termos de dbo e dqo, no processo biológico com tempos de detenção de 20 e 30 dias, e em torno de 80% para os demais. Os sistemas biológicos responderam bem as cargas transientes de solventes, exceto para o tolueno e o álcool isopropílico. / Traditionally, raw materials from solvent recovery and from reclaimed lubricating oil industries are considered hazardous solid waste. Consequently, the best control technology is incineration. This work was developed in order to characterize and to study ways of treating wastewaters from lubricating oil refinery and solvent recovery industries. The experimental part was divided in two phases. The preliminar step aimed to evaluate the biodegradability of combined wastewater from both industries. The second phase was basically carried out in a pilot plant composed by an air stripping unit/equalization tank, pH correction tanks and bioreactors with different retention times, followed by sedimentation tanks. Other than these assays, tests were performed to evaluate the removal of soluble material in n-hexane of the wastewater of the lubricating oil refinery industry and of the supernatant of the sedimentation tank after the bioreactor of 20 days retention.The buble aeration unit operating with a 15 mmHg suppresion to the gas exit, with a specific air flow of 20 mL/L.min. and with a retention time of 5 days was efficient to remove acetone, pyridine, benzene, toluene, hexane, methyl ethyl ketone and probably chlorinated solvents. There was no significative removal of alcohols, that were efficiently degraded in the subsequent biological system. BOD and COD removal efficiencies were better than 90% in the biological process with retention times of 20 and 30 days, and about 80% for the rest. The responses of biological systems to the transient inputs of solvents were well, except for toluene and isopropilic alcohol. Several physico-chemical processes for soluble material in n-hexane removal were studied. The only one to present effluent concentration under the legal limit was the addition of the sodium xylene-sulphonate base demulsifier to the supernatant of the sedimentation tank the bioreactor of 20 days retention.

Η ανάγκη αντιμετώπισης του προβλήματος της ρύπανσης των επιφανειακών και υπόγειων υδάτων έχει οδηγήσει στην ανάπτυξη νέων και αποτελεσματικών μεθόδων για την απομάκρυνση έμμονων και μη βιοαποικοδομήσιμων ενώσεων από το νερό και τα υγρά απόβλητα. Η παρούσα διατριβή πραγματεύτηκε τη συστηματική μελέτη της διάσπασης ρύπων προτεραιότητας και αναδυόμενων ρύπων που ανήκουν σε διαφορετικές χημικές κατηγορίες (DEET, metribuzin, 2-ισοπρόπυλο-3-μεθόξυ πυραζίνη, η πενταχλωροφαινόλη, βενζοϊκό οξύ, Cr(VI) και φαινολικές ενώσεις) με τη μέθοδο της ετερογενούς φωτοκατάλυσης και τη χρήση εμπορικά διαθέσιμων δραστικών μορφών TiO2 και τροποποιημένων σωματιδίων ΤiΟ2 με αμέταλλα που παρουσιάζουν φωτοκαταλυτική δραστικότητα στο ορατό φάσμα της ακτινοβολίας. Για το σύνολο των ενώσεων που μελετήθηκαν, η έρευνα επικεντρώθηκε: i) στη μελέτη της κινητικής της αποδόμησης και της ολικής ανοργανοποίησης τους με τη μέθοδο της ετερογενούς φωτοκατάλυσης, ii) στη μελέτη της επίδρασης λειτουργικών παραμέτρων στην απόδοση της φωτοκαταλυτικής απομάκρυνσης των ρύπων και στην εύρεση των βέλτιστων συνθηκών με την εφαρμογή των δύο ευρέως χρησιμοποιούμενων χημειομετρικών μεθόδων, της μεθοδολογίας επιφάνειας απόκρισης (RSM) και των τεχνητών νευρωνικών δικτύων (ANNs), iii) στην ανίχνευση και ταυτοποίηση ενδιάμεσων προϊόντων διάσπασης των οργανικών ρύπων με φασματομετρικές τεχνικές όπως υγρή χρωματογραφία-φασματομετρία μαζών υψηλής διακριτικής ικανότητας και ακρίβειας μάζας με αναλυτή τροχιακής παγίδας (Orbitrap) και αέρια χρωματογραφία–φασματομετρία μάζας με την τεχνική ιοντισμού με πρόσκρουση ηλεκτρονίων (Εlectron Impact, EI) και φασματοσκοπία ηλεκτρονικού παραμαγνητικού συντονισμού, iv) στη συνεισφορά των δραστικών ειδών οξυγόνου, οπών και ηλεκτρονίων στη φωτοκαταλυτική αποικοδόμηση των ρύπων, v) στη μελέτη του ρόλου των φυσικών συστατικών (χουμικά και φουλβικά οξέα) διαφόρων υδατικών συστημάτων καθώς και στην εκτίμηση της επίδρασης του υδατικού μέσου στην κινητική της διεργασίας, vi) στην εκτίμηση της τοξικότητας πριν και κατά τη διάρκεια της φωτοκαταλυτικής επεξεργασίας. Με την εφαρμογή της ετερογενούς φωτοκατάλυσης επετεύχθη πλήρης απομάκρυνση όλων των ρύπων-μοντέλων που μελετήθηκαν και υψηλός βαθμός ανοργανοποίησης των διαλυμάτων τους. H φωτοκαταλυτική διάσπαση λαμβάνει χώρα σε ποσοστό μεγαλύτερο του 90% σε χρόνους που κυμαίνονται από 20-180 λεπτά ανάλογα με το μελετώμενο ρύπο. Ένας μεγάλος αριθμός κύριων προϊόντων διάσπασης και τουλάχιστον ένα ισομερές για τα περισσότερα από αυτά, ταυτοποιήθηκε κατά τη φωτοκαταλυτική διάσπαση της PCP, του DEET, του ΜΕΤ και της ΙPMP με τη χρήση προηγμένων τεχνικών φασματομετρίας μάζας. Με βάση τα προϊόντα που ταυτοποιήθηκαν, προτάθηκαν οι μηχανισμοί της φωτοκαταλυτικής διάσπασης των μελετώμενων ρύπων που περιλαμβάνουν κυρίως αντιδράσεις υδροξυλίωσης, οξείδωσης και απαλκυλίωσης. Η οξείδωση μέσω ριζών υδροξυλίου (HO•)βρέθηκε να αποτελεί το κύριο οξειδωτικό είδος σε όλα τα μελετώμενα συστήματα. Η δοκιμή τοξικότητας που πραγματοποιήθηκε, πριν και κατά τη διάρκεια της φωτοκαταλυτικής επεξεργασίας των οργανικών ρύπων έδειξε ότι η μέθοδος της ετερογενούς φωτοκατάλυσης οδηγεί σε πλήρη αποτοξικοποίηση των διαλυμάτων. Σύμφωνα με τα αποτελέσματα της φωτοκαταλυτικής οξείδωσης των οργανικών ρύπων-μοντέλων και της φωτοκαταλυτικής αναγωγής του Cr(VI) που μελετήθηκαν στην παρούσα διατριβή, η μέθοδος της ετερογενούς φωτοκατάλυσης μπορεί να αποτελέσει μια αποδοτική εναλλακτική πρόταση αντιρρύπανσης έναντι των κλασσικών μεθόδων. Η ουσιαστική λύση σε προβλήματα ρύπανσης αποφεύγοντας τη μεταφορά των ρύπων από τη μία φάση στην άλλη, η δυνατότητα χρήσης και αξιοποίησης ήπιων μορφών ενέργειας όπως η ηλιακή ακτινοβολία και η σύζευξη της μεθόδου με άλλες βιολογικές ή/και φυσικοχημικές μεθόδους επεξεργασίας αποδεικνύουν τις μεγάλες προοπτικές που παρουσιάζει. / In order to avoid deterioration of water resources, considerable efforts have been devoted to develop suitable purification methods that can easily remove recalcitrant (persistent) and non-biodegradable contaminants from water and wastewater. In the present thesis the photocatalytic removal of selected priority pollutants and emerging contaminants belonging in different chemical categories has been investigated in detail. DEET, metribuzin, 2 isopropyl-3-methoxy pyrazine, pentachlorophenol (PCP), benzoic acid (BA), Cr(VI) and phenolic compounds were selected as target compounds. The commercial form of TiO2 (Degussa P25) and NF-codoped TiO2, a material with improved photo efficiency and visible light response were used as photocatalysts. The main objectives of this thesis were: i) to evaluate the kinetics of selected pollutants disappearance and mineralization, ii) to investigate the effect of significant parameters on the total process efficiency as well as to optimize the photocatalytic procedure by means of chemometric optimization tools such as central composite design, response surface methodology and artificial neural networks, iii) to identify the transformation products formed during the photocatalytic treatment by using powerful analytical techniques such as high resolution accurate mass LC-MS, GC–MS and EPR spectroscopy, iv) to assess the role of the reactive species in the reaction mechanism using different scavengers, v) to assess the macroscopic effects of DOM (HA, FA) and water matrix on the photocatalytic degradation and vi) to evaluate the toxicity along the photocatalytic process. By the application of heterogeneous photocatalysis almost compete removal of the selected model contaminants and high percentages of mineralization were achieved. Photocatalytic removal (> 90%) was succeeded after 20-180 min of irradiation time, depending on the studied pollutant. Numerous different structures of transformation products (TPs), with at least one isomer for the majority of them, were identified with high resolution accurate mass liquid chromatography (HR-LC–MS) and gas chromatography mass spectrometry (GC–MS). Based on by-product identification using HR-LC-MS and GC–MS techniques possible degradation pathways were proposed. The pathways mainly include hydroxylation, oxidation and dealkylation reactions. Hydroxyl radicals (HO•) were determined to be the predominant reactive species during photocatalysis in all the studied systems. Toxicity assessment revealed the efficiency of the photocatalytic treatment to achieve almost complete detoxification of the solution. According to the results obtained for the photocatlytic oxidation of the studied organic pollutants-models and photocatalytic reduction of Cr(VI), heterogeneous photocatalyis was shown to be a great potential as a sustainable treatment technology. Ιts inherent destructive nature, not involving mass transfer, the potential use of solar radiation as well as the combination of heterogeneous photocatalysis with biological and/or physicochemical methods make this method particularly attractive for environmental decontamination and detoxification.

O trabalho foi desenvolvido com o objetivo de caracterizar e estudar formas de tratamento de águas residuárias de indústrias de refino de óleo lubrificante e de recuperação de solventes. A fase preliminar teve por objetivo avaliar a biodegradabilidade do despejo combinado dessas duas indústrias. A segunda foi realizada em instalação piloto composta, basicamente, de uma unidade de arraste com ar/tanque de equalização, tanques de correção de pH e de aeração com tempos de detenção distintos, seguidos de tanques de sedimentação. Foram executados testes para avaliar a remoção de material solúvel em n-hexano do despejo da indústria de refino de óleo lubrificante e do efluente final. A unidade de arraste com ar difuso operando com subpressão de 15 mmhg a saída dos gases, vazão específica de ar de 20 ml/l min. E tempo de detenção de 5 dias foi eficiente na remoção de acetona, piridina, benzeno, tolueno, hexano, metil etil cetona e provavelmente solventes clorados. Não apresentou remoção significativa de álcoois, que foram eficientemente degradados no sistema biológico subsequente. Obteve-se remoções superiores a 90%, em termos de dbo e dqo, no processo biológico com tempos de detenção de 20 e 30 dias, e em torno de 80% para os demais. Os sistemas biológicos responderam bem as cargas transientes de solventes, exceto para o tolueno e o álcool isopropílico. / Traditionally, raw materials from solvent recovery and from reclaimed lubricating oil industries are considered hazardous solid waste. Consequently, the best control technology is incineration. This work was developed in order to characterize and to study ways of treating wastewaters from lubricating oil refinery and solvent recovery industries. The experimental part was divided in two phases. The preliminar step aimed to evaluate the biodegradability of combined wastewater from both industries. The second phase was basically carried out in a pilot plant composed by an air stripping unit/equalization tank, pH correction tanks and bioreactors with different retention times, followed by sedimentation tanks. Other than these assays, tests were performed to evaluate the removal of soluble material in n-hexane of the wastewater of the lubricating oil refinery industry and of the supernatant of the sedimentation tank after the bioreactor of 20 days retention.The buble aeration unit operating with a 15 mmHg suppresion to the gas exit, with a specific air flow of 20 mL/L.min. and with a retention time of 5 days was efficient to remove acetone, pyridine, benzene, toluene, hexane, methyl ethyl ketone and probably chlorinated solvents. There was no significative removal of alcohols, that were efficiently degraded in the subsequent biological system. BOD and COD removal efficiencies were better than 90% in the biological process with retention times of 20 and 30 days, and about 80% for the rest. The responses of biological systems to the transient inputs of solvents were well, except for toluene and isopropilic alcohol. Several physico-chemical processes for soluble material in n-hexane removal were studied. The only one to present effluent concentration under the legal limit was the addition of the sodium xylene-sulphonate base demulsifier to the supernatant of the sedimentation tank the bioreactor of 20 days retention.