In this master thesis project, the removal of micro-pollutants (MPs) from water and wastewater were investigated by ozonation and the peroxone process O3/H2O2. Themain aim of the study was to compare the degradation efficiency of the two processes for a selection of organic biocides and active pharmaceutical ingredients (APIs) in wastewater and synthetic water. Synthetic water and wastewater effluent were spiked with fifteen compounds including twelve biocides and three APIs and samples were taken at different time points to determine degradation kinetics in treatment by the two processes, respectively. Most of the biocides tested in this study showed moderately reactivity, or were non-reactive, with O3 (e.g., Carbendazim, 1H-Benzotriazole, 1, 2-Benzisothiazol-3(2H)-one, 2, 4-Dinitrophenol, 4-nitrophenol) and some of the biocides and APIs were readily reactive with ozone (O3) and were removed from the water by direct O3 oxidationduring both processes. Trimethoprim was found to be an ozone reactive micropollutants and showed highest reactivity with O3. In the abatement mechanism, these micro-pollutants are removed based on the ozone-based processes and with hydroxyl radical •OH in peroxone process. Comparing the two processes, the peroxone process showed highest percentage removal of compounds (90-100%) within moderate time periods (30 s - 2 min) in synthetic water and (30 s to 10 min) in wastewater. The results revealed that the peroxone process showed highest removal efficiency and with higher reproducibility. Further, generally

Submitted by Jaqueline Silva (jtas29@gmail.com) on 2016-08-31T16:48:26Z No. of bitstreams: 2 Dissertação - Manoel Barbosa Soares - 2016.pdf: 4279565 bytes, checksum: 89bf14a593b4bb1bf61e9c7e0becb0c2 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Jaqueline Silva (jtas29@gmail.com) on 2016-08-31T16:49:50Z (GMT) No. of bitstreams: 2 Dissertação - Manoel Barbosa Soares - 2016.pdf: 4279565 bytes, checksum: 89bf14a593b4bb1bf61e9c7e0becb0c2 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-08-31T16:49:51Z (GMT). No. of bitstreams: 2 Dissertação - Manoel Barbosa Soares - 2016.pdf: 4279565 bytes, checksum: 89bf14a593b4bb1bf61e9c7e0becb0c2 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-03-04 / The toxicology of endocrine disruptors (ED), known as micro-pollutants, disposed in the environment through urine or excrements may cause physiological changes in aquatic living things. Therefore, it was aimed to evaluate the 17β – estradiol (E2) and progesterone and measure the quality of the wastewaters from the effluent of some Sewage Treatment Plants (STP’s) as of potable water in the Water Treatment Plant (WTP), located in Goiânia – GO, through the physical and chemical parameters, such as: Potential Hydrogen (PH), Temperature (T), Electric Conductivity (EC), Turbidity, Total Dissolved Solids (TDS), Salinity, Dissolved Oxygen (DO), Total Organic Nitrogen, Chemical Oxygen Demand (COD) and Biochemical Oxygen Demand (BOD). The quantization of endocrine disruptors was obtained through direct and competitive ELISA’s method, and all physical-chemical parameters were determined based on the APHA's Manual (2012). The effluent samples were collected at three distinct points: affluent (raw sewage), confluence of the effluent to the river (CER) and downstream of the release in STP’s Hélio Seixo de Brito (HSB), Samambaia (S) and Parque Atheneu (PA), while the samples of potable water were collected at two different points: in the capture of João Leite’s stream and after the water treatment in the WTP Jaime Câmara (JC). Through the physical-chemical parameters evaluated in the STP’s , the Turbidity , both DO and BOD, do not agree with the standards of CONAMA 357/05 and 430/11, which means that a lot of organic and inorganic matter are being dumped into the Meia Ponte River without treatment. In relation to the JC’s WTP, the same physical-chemical parameters are in accordance with the Decree No. 2,914 / 11 from the Ministry of Health, which deals with drinking water quality. The measured values for the E2 in the STP’s ranged in the rainy season around 53, 7 to 178, 24 ng/L and 45, 8 to 275, 0 ng/L in the dry season. In contrast with the progesterone in the same place where the values ranged from 69, 34 to 97, 54 ng / L in the rainy season from 60, 2 to 603, 8 ng / L in the dry season. While in the Meia Ponte River these values to the E2 ranged between 2,04 to 31,62 ng / L in the rainy season from 6,02 to 72,44 ng / L in the dry season and in relation to progesterone 4,35 to 52,48 ng / L in the rainy season 6,6 to 218,25 ng / L in the dry season. At João Leite’s stream, where is made the abstraction of the water for treatment, both in the rainy and drought seasons, E2 values were found 2,13 and 4,89 ng / L and progesterone 5,37 and 6,76 ng / L, however, the treated water that leaves the ETA, it was found in it values of E2 1,81 ng / L and 2,51 ng / L and progesterone 4,78 ng / L and 4,67 ng / L during the rainy and dry seasons, respectively. This search concludes that the biological method ELISA was efficient for the quantification of the studied hormones, and the values found for both the E2 and progesterone to the STP’s and ETA was xvii greater than 1.0 ng / L, and according to the literature these values are able to cause physiological damage in aquatic species. / A toxicologia dos desreguladores endócrinos (DE), conhecidos como micropoluentes, eliminados no meio ambiente através da urina ou fezes, causam alterações fisiológicas em seres vivos aquáticos. Assim, objetivou-se neste estudo avaliar os hormônios 17β-estradiol (E2) e progesterona, e medir a qualidade das águas residuais dos efluentes de algumas Estações de Tratamento de Esgotos (ETEs) e de água potável da Estação de Tratamento de água (ETA) localizados em Goiânia-GO, por meios dos parâmetros físico-químicos como: Potencial Hidrogeniônico (pH), Temperatura (T), Condutividade Elétrica (CE), Turbidez, Sólidos Totais Dissolvidos (TDS), Salinidade, Oxigênio Dissolvidos (OD), Nitrogênio Orgânico Total, Demanda Química de Oxigênio (DQO) e Demanda Bioquímica de Oxigênio (DBO). A quantificação dos desreguladores endócrinos foi realizada através do método de ELISA direto e competitivo e, todos os parâmetros físico químicos foram determinados com base no Manual da APHA (2012). As amostras dos efluentes foram coletadas em três pontos distintos: afluentes (esgoto bruto), confluência do efluente com o rio (CER) e jusante do lançamento nas ETEs Hélio Seixo de Britto (HSB), Samambaia (S) e Parque Ateneu (PA), enquanto que as amostras para avaliar a potabilidade da água em dois pontos diferentes: na captação do Ribeirão João Leite e após o tratamento da água na ETA Jaime Câmara (JC). Dos parâmetros físico químicos avaliados, nas ETEs, a Turbidez, o OD e a DBO, estão em desacordo com as normas do CONAMA 357/05 e 430/11, o que significa que estão sendo despejados no rio Meia Ponte grande quantidade de matéria orgânica e inorgânica sem tratamento. Em relação à ETA JC os parâmetros físico-químicos estão em conformidade com a portaria nº 2.914/11, do Ministério da Saúde, que trata da potabilidade da água. Os valores obtidos para o E2 nas ETEs variaram no período chuvoso entre 53,7 a 178,24 ng/L e no período de estiagem entre 45,8 a 275,0 ng/L. Em contrapartida, em relação a progesterona no mesmo local, esses valores variaram entre 69,34 a 97,54 ng/L no período chuvoso e 60,2 a 603,8 ng/L no período de estiagem. No rio Meia Ponte esses valores para o E2 estiveram entre 2,04 a 31,62 ng/L no período chuvoso e 6,02 a 72,44 ng/L no período de estiagem, e com relação à progesterona, os valores variaram de 4,35 a 52,48 ng/L no período chuvoso e 6,6 a 218,25 ng/L no período de estiagem. No ribeirão João Leite onde é feito a captação de água para tratamento, tanto no período de chuva como estiagem, foram encontrados valores de E2 de 2,13 a 4,89 ng/L, e progesterona de 5,37 e 6,76 ng/L. Na água tratada, que sai da ETA, verificaram-se valores de 1,81 ng/L e 2,51 ng/L, e da progesterona de 4,78 ng/L e 4,67 ng/L nos períodos de chuva e estiagem, respectivamente. Dessa pesquisa se conclui que o método biológico ELISA, foi eficiente para quantificação dos hormônios estudados, e os valores encontrados tanto para o E2 como para a progesterona nas ETEs e ETA foi maior que 1,0 ng/L e segunxv do a literatura esses valores são capazes de provocar danos fisiológicos em espécies aquáticas.

Resumo: A pesquisa vem testar duas tecnologias conhecidas, mas no Brasil nunca utilizada em conjunto. O processo de oxidação com utilização de radiação solar seguida pelo processo de filtração lenta pode ser muito promissor no tratamento de água para pequenas comunidades ou comunidades rurais. A praticidade em conjunto com uma nova tecnologia vem mostrar a eficiência de uma energia que não é aproveitada ou até pouco aproveitada no mundo todo. A incidência de raios Ultra Violeta presente na radiação solar quebrou as moléculas de ácido húmico e de fármacos facilitando sua remoção pela camada biológica dos filtros lento. As moléculas restantes poderão ser retiradas por adsorção pelo carvão ativado granular presente em uma coluna. Tanto o ácido húmico quanto os fármacos são moléculas difíceis de serem retiradas da água em um processo convencional de tratamento de água, estes são micro poluentes que tem causado preocupação entre os estudiosos. Devido a esta dificuldade pensou-se em desenvolver um método que é mais eficaz e tornar-se a água mais potável e financeiramente mais acessível pela classe baixa. No tratamento da água obteve-se uma remoção de ácido húmico em torno de 55% e de fármacos na média de 60%, variando de acordo com os compostos utilizados que foram diclofenaco, dipirona, ibuprofeno e naproxeno / Abstract: The study is to test two known technologies, but never used in Brazil together. The oxidation process using solar radiation followed by slow filtration process can be very promising in the treatment of water for small communities or rural communities. The practice together with a new technology comes along to show the efficiency of energy that is wasted or even little advantage worldwide. The breaking of the molecule by the impact of UV rays present in sunlight broke the molecules of humic acid and drugs facilitating its removal by biological layer of slow filters. The remaining molecules may be removed by adsorption by granular activated carbon present in a column. Both the humic acid molecules as drugs are difficult to be removed from the water in a conventional process water treatment, these are micro pollutants that has caused concern among scholars. This difficulty incentived the developing of the method that is more efficient and become more potable water and more financially accessible for the lower class. In water treatment obtained a removal of humic acid and about 55% of drugs on average 60%, varying according to the compounds used were diclofenac, dipyrone, ibuprofen and naproxen / Orientador: Milton Dall'Aglio Sobrinho / Coorientador: Edson Pereira Tangerino / Banca: Alessandro Minillo / Banca: Mauricio Luiz Sens / Mestre

Made available in DSpace on 2014-06-11T19:29:13Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-09-24Bitstream added on 2014-06-13T20:38:39Z : No. of bitstreams: 1 rossi_ch_me_ilha.pdf: 922500 bytes, checksum: dbbaa1ad90ec1303c0d86e1ff3956c7a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A pesquisa vem testar duas tecnologias conhecidas, mas no Brasil nunca utilizada em conjunto. O processo de oxidação com utilização de radiação solar seguida pelo processo de filtração lenta pode ser muito promissor no tratamento de água para pequenas comunidades ou comunidades rurais. A praticidade em conjunto com uma nova tecnologia vem mostrar a eficiência de uma energia que não é aproveitada ou até pouco aproveitada no mundo todo. A incidência de raios Ultra Violeta presente na radiação solar quebrou as moléculas de ácido húmico e de fármacos facilitando sua remoção pela camada biológica dos filtros lento. As moléculas restantes poderão ser retiradas por adsorção pelo carvão ativado granular presente em uma coluna. Tanto o ácido húmico quanto os fármacos são moléculas difíceis de serem retiradas da água em um processo convencional de tratamento de água, estes são micro poluentes que tem causado preocupação entre os estudiosos. Devido a esta dificuldade pensou-se em desenvolver um método que é mais eficaz e tornar-se a água mais potável e financeiramente mais acessível pela classe baixa. No tratamento da água obteve-se uma remoção de ácido húmico em torno de 55% e de fármacos na média de 60%, variando de acordo com os compostos utilizados que foram diclofenaco, dipirona, ibuprofeno e naproxeno / The study is to test two known technologies, but never used in Brazil together. The oxidation process using solar radiation followed by slow filtration process can be very promising in the treatment of water for small communities or rural communities. The practice together with a new technology comes along to show the efficiency of energy that is wasted or even little advantage worldwide. The breaking of the molecule by the impact of UV rays present in sunlight broke the molecules of humic acid and drugs facilitating its removal by biological layer of slow filters. The remaining molecules may be removed by adsorption by granular activated carbon present in a column. Both the humic acid molecules as drugs are difficult to be removed from the water in a conventional process water treatment, these are micro pollutants that has caused concern among scholars. This difficulty incentived the developing of the method that is more efficient and become more potable water and more financially accessible for the lower class. In water treatment obtained a removal of humic acid and about 55% of drugs on average 60%, varying according to the compounds used were diclofenac, dipyrone, ibuprofen and naproxen

The development of the chemical and pharmaceutical industry and the massive use of synthetic substances in various industries has become indispensable for our society. Unfortunately, this progress has brought a whole new kind of pollution. It is a group of substances which imagine for living organisms’ greater risk than 'normal' organic pollution. Because they have extraneous origin compared with naturally occurring compounds, they are called "Xenobiotics." It is a group comprising a large number of different substances, with dissimilar physical, chemical and biological properties such as pharmaceuticals, pesticides, detergents, paints, varnishes, plastic packaging, food additives, cosmetic products, drugs, and many others. Although these substances began to enter the water cycle as early as 30 years of the 20th century, their concentration often moves to the limit of the detection limit, so their presence in the water began to be examined in more detail in the 1980s, following the development of analytical technologies chemical composition of water. The main danger of these substances is that doesn’t primarily effect on water quality, but directly affect on the organisms by confusing of the endocrine system or by directly damaging RNA or DNA, causing mutagenic changes, cancer-causing proliferation, birth defects, metabolic disorders, gender changes, the degeneration of reproductive capacity of entire populations or the disappearance of self-preservation instinct. The source of xenobiotics in the water cycle is predominantly wastewater, which generated through the wastewater treatment, which not designed to eliminate this type of pollution. he dissertation thesis deals with the issue of xenobiotics in wastewater and is divided into the theoretical and experimental part. The theoretical part summarizes the xenobiotics current state of knowledge in wastewater from their history, origin, classification, possibilities of elimination to impacts on the environ

In komplexen Grundwasserleitern lassen sich grundlegende Informationen zur Abgrenzung von Quelleinzugsgebieten, zur Ableitung von Grundwasserfließrichtungen oder zur Bewertung der Vulnerabilität nicht allein über konventionelle hydrogeologische Methoden (beispielsweise Grundwassergleichenpläne, Quellschüttungsmessungen, Pumpversuche) gewinnen, so dass vielfach ergänzend hydrochemische Methoden eingesetzt werden. Zu den gängigen hydrochemischen Methoden gehören Auswertungen der Hauptionenverhältnisse, stabiler und radioaktiver Isotope, von Umwelttracern und Metallen der Seltenen Erden einschließlich des Yttriums sowie der aktive Einsatz künstlicher Markierungsstoffe. Die Anwendung gängiger hydrochemischer Methoden ist durch natürliche oder anthropogene Hintergrundkonzentrationen, die die Ausbildung eines ausreichenden Kontrasts behindern können, limitiert. Da diese Methoden meist nur an der Quelle als integrales Signal des gesamten Einzugsgebiets ansetzen, kann die Abgrenzung des Einzugsgebiets nur indirekt durch die Abschätzung von Volumina und darauf aufbauender Abschätzung der Flächengröße vorgenommen werden. Zur konkreten Lokalisierung der Einzugsgebietsgrenzen und der Ableitung von Grundwasserfließrichtungen sind also zusätzliche Informationen notwendig. Durch die menschliche Produktion organischer Verbindungen steht ein riesiges Spektrum potentieller Indikatoren zur Verfügung, das die Anzahl der bei etablierten Methoden eingesetzten Stoffe um ein Vielfaches übertrifft. Aufgrund ihrer rein anthropogenen Herkunft haben organische Spurenstoffe keine natürlichen Hintergrundkonzentrationen und sind daher bereits auf einem sehr geringen Konzentrationsniveau nutzbar. Im Gebiet der „Waldecker Scholle“ konnten sowohl die räumliche Verteilung organischer Spurenstoffe als auch deren saisonale Konzentrationsschwankungen in einem komplexen Grundwassersystem mit moderat verkarsteten Grundwasserleitern untersucht werden. Die auftretenden Stoffmuster reflektieren die hydrogeologischen Verhältnisse und können zur Lokalisierung von Quelleinzugsgebietsgrenzen genutzt werden. Weitere Hinweise liefern die organischen Spurenstoffe zur Identifikation von punktuellen Eintragsquellen und zur Ausbreitung der aus Punktquellen freigesetzten Stoffe im Grundwasserleiter sowie zum Attenuationspotential dieser Stoffe. Weiterhin kann die hydraulische Wirksamkeit von geringleitenden Zwischenschichten und Störungszonen mittels Identifikation einer Fließkomponente mit einer Verweilzeit von mehr als 20 Jahren abgeschätzt werden. Auch Annahmen hinsichtlich der Vulnerabilität lassen sich validieren. Der Vergleich mit dem hydrogeologisch gut untersuchten Einzugsgebiet der Gallusquelle, zeigt, dass Stoffgruppen wie Triazine und Triazole eine weite Verbreitung haben, andere Stoffe jedoch an bestimmte Gegebenheiten im Gebiet gebunden sind (beispielsweise Altablagerungen, Kanalsystem). Außerdem bestätigt sich in beiden Gebieten, dass das Auftreten von Stoffen sowohl von den Stoffeigenschaften als auch von den hydrogeologischen Eigenschaften abhängig ist. Das bedeutet, dass die Art der in einer Karstquelle auftretenden Stoffe selbst ohne aufwändige zeitlich hochaufgelöste Beprobung bereits Rückschlüsse auf Systemeigenschaften zulässt. Die vorliegende Arbeit zeigt somit, dass organische Spurenstoffe bereits auf der Untersuchungsebene des konzeptionellen Modells wertvolle Indikatoren zur Charakterisierung komplexer Grundwassersysteme sein können. Die große Menge an zur Verfügung stehenden Stoffen bietet die Möglichkeit, bestimmte Stoffe auszuwählen, die die jeweiligen Systemcharakteristika widerspiegeln. Mit organischen Spurenstoffen können sowohl Grundwasserkomponenten unterschiedlicher Verweilzeiten von wenigen Tagen bis zu mehreren Jahrzehnten identifiziert werden als auch räumliche Zusammenhänge von wenigen Metern bis über Einzugsgebietsgrenzen hinaus untersucht werden. Die Einbeziehung organischer Spurenstoffe in die Erkundungsstrategien komplexer Grundwassersysteme hat daher ein vielversprechendes zukunftsweisendes Potential.

Les processus d'oxydation avancés à base du radical sulfate (SO4•- -) ont prouvé leur efficacité pour l'élimination de nombreux contaminants. Dans ce travail de thèse, nous avons étudié les processus d'oxydation et de dégradation par le radical sulfate activé à partir du persulfate (PS) pour les molécules suivantes : le diatrizoate, molécule utilisée comme produit de contraste radiologique iodé (DTZ), le salbutamol (SAL) et la terbutaline (TBL), agonistes des récepteurs ß2-adrénergiques. En outre, la réactivité de SO4•- avec la matière organique naturelle (NOM) a également été déterminée. Plus précisément, pour déterminer la réactivité de SO4•- avec NOM, une technique de photolyse laser couplée à la spectroscopie (LFP) a été appliquée pour étudier l'évolution de SO4 • ainsi que la formation d'espèces transitoires à partir de la matière organique. Des constantes de vitesses comprises entre 1530 et 3500 s-1 mgC-1 L ont été obtenues par analyse numérique des équations différentielles et des valeurs moyennes de coefficient d'absorption molaires comprises entre 400 et 800 M-1 cm-1 ont été déterminées pour les espèces transitoires générées de la matière organique.Dans le processus de décomposition de DTZ par PS activé par UV, les principales voies d'oxydation sont la dé-iodination-hydroxylation, la dé-carboxylation-hydroxylation et le clivage de la chaîne latérale. Les résultats ont également indiqué que la vitesse de dégradation du DTZ augmentait avec l'augmentation de la concentration en PS. La présence de NOM a inhibé la dégradation de DTZ, tandis que le bicarbonate l'a amélioré. Pour les ions chlorure un effet négatif a été observé pour des concentrations supérieures à 500 mM.Pour la dégradation du SAL et du TBL, il a été montré que les radicaux phénoxy jouaient un rôle majeur en début de réaction. Par ailleurs, le chlorure n'a pas eu d'effet tangible sur l'efficacité d'oxydation de la SAL et du TBL, tandis que les ions bromures, bicarbonates et le NOM présentaient des effets inhibiteurs / Sulfate radical (SO4•-) based advanced oxidation processes (AOPs) has been proved to be effective for the removal of many contaminants. In this thesis, we investigated the oxidation processes of iodinated X-ray contrast media diatrizoate (DTZ), ß2-adrenoceptor agonists salbutamol (SAL) and terbutaline (TBL) by reaction with SO4•- generated from the activation of persulfate (PS); in addition, the reactivity of SO4•- with natural organic matter (NOM) was also estimated.Specifically, to determine the reactivity of SO4•- with NOM, laser flash photolysis (LFP) technique was applied to monitor the SO4•- decay and the formation of the transients from organic matters. Reaction rate constants comprised between 1530 and 3500 s-1 mgC-1 L were obtained by numerical analysis of differential equations and the weighted average of the extinction coefficient of the generated organic matters radicals between 400 and 800 M-1 cm-1.In the decomposition process of DTZ by UV-activated PS, major oxidation pathways include deiodination-hydroxylation, decarboxylation- hydroxylation and side chain cleavage. Results also indicated that DTZ degradation rate increased with increasing PS concentration. The presence of NOM inhibited DTZ removal rate, while, bicarbonate enhanced it, and chloride ions induced a negative effect above 500 mM. For the degradation of SAL and TBL, phenoxyl radicals were proven to play a very important role from the initial step. Chloride exhibited no effect on the oxidation efficiencies of SAL and TBL, while bromide, bicarbonate and NOM all showed inhibitory effects