A presença de antibióticos no ecossistema representa um sério risco à saúde humana e animal em virtude do desenvolvimento crescente de resistência bacteriana. Uma vez que a maioria dos antibióticos é persistente à degradação biológica, os processos oxidativos avançados são apontados como uma das tecnologias mais efetivas para decompor esses compostos em águas residuárias. A bacitracina zíncica (Bc-Zn) é um potente antibiótico constituído por uma mistura complexa de peptídeos não-biodegradáveis, conjugados ao zinco. Apesar de ser um antibiótico amplamente consumido na medicina humana e animal, é preocupante a escassez de estudos que investigam sua degradação e destino ambiental. O presente trabalho analisou a degradação da Bc-Zn através dos processos de fotólise direta e UV/H2O2 em diferentes condições de radiação UVC e concentração inicial de H2O2. Os parâmetros cinéticos rendimento quântico da fotólise, constantes cinéticas de pseudo-primeira ordem e constante cinéticas de segunda ordem foram satisfatoriamente estimados pela modelagem do sistema fotoquímico experimental. Os resultados revelaram que a fotólise direta permitiu degradar todos os congêneres da mistura de Bc-Zn nas maiores doses de radiação UVC empregadas. No entanto, não houve remoção de TOC após 120 minutos de irradiação. A adição de H2O2 acelerou substancialmente a fotodegradação do antibiótico, apresentando constantes cinéticas de pseudo-primeira ordem uma ordem de grandeza superiores às obtidas por fotólise direta. Além disso, remoção considerável de até 71% do TOC foi alcançada. A análise estatística demonstrou que a radiação UV foi um fator bem mais significativo para a fotodegradação da Bc-Zn em relação à concentração inicial de H2O2, sendo as melhores condições do processo alcançadas para a maior taxa específica de emissão de fótons (1,11×10-5 Einstein L-1 s-1). Ensaios biológicos com soluções tratadas por fotólise direta e UV/H2O2 indicaram remoção completa da atividade antimicrobiana residual, ainda que os produtos da fotodegradação tenham se mostrado não-biodegradáveis. Análises de toxicidade indicaram que o metal zinco presente no antibiótico é responsável pela a toxicidade no micro-organismo-teste Vibrio fischeri. Estudos adicionais devem ser realizados para identificar os sub-produtos formados, bem como para investigar a degradação da Bc-Zn em efluentes industriais reais. / The presence of antibiotics in ecosystems represents a serious risk to human and animal health, caused by the increase in bacterial resistance. Since most antibiotics resist to biological degradation, advanced oxidation processes are pointed out as the most effective technologies for degrading these compounds in wastewater. Zinc bacitracin (Bc-Zn) is a potent antibiotic with a complex mixture of non-biodegradable peptides conjugated to zinc. Despite being a widely used antibiotic in human and animal medicine, the scarcity of studies dealing with its degradation and environmental fate is a matter of concern. In this work, Bc-Zn degradation by direct photolysis and the UV/H2O2 process was investigated for different UVC radiation conditions and initial H2O2 concentrations. Kinetic parameters, namely the photolysis quantum yield, pseudo-first order kinetic constants and second-order kinetic constants, were satisfactorily estimated from experimental data by modeling the photochemical system. The results showed that all the congeners of the Bc-Zn mixture were photolyzed at the highest UVC doses applied, while no TOC removal was observed after 120 minutes of irradiation. The addition of H2O2 substantially accelerated Bc-Zn photodegradation, with pseudo-first order kinetic constants of one order of magnitude higher than those observed under direct photolysis. In addition, a remarkable removal of up to 71% of TOC was achieved. Statistical analyses showed that UV radiation had a much more important effect on Bc-Zn photodegradation in comparison with initial H2O2 concentration, with the best process conditions achieved for the highest specific photon emission rate (1.11×10-5 Einstein L-1 s-1). Biological assays carried out with the solutions treated by direct photolysis and UV/H2O2 revealed no residual antimicrobial activity, though photodegradation products remained non-biodegradable. In addition, toxicity analyses indicated that the zinc metal present in the antibiotic is responsible for the toxic effect on the test microorganism Vibrio fischeri. Finally, further studies should be performed to identify the by-products formed and to investigate Bc-Zn degradation in real industrial wastewater.

A presença de antibióticos no ecossistema representa um sério risco à saúde humana e animal em virtude do desenvolvimento crescente de resistência bacteriana. Uma vez que a maioria dos antibióticos é persistente à degradação biológica, os processos oxidativos avançados são apontados como uma das tecnologias mais efetivas para decompor esses compostos em águas residuárias. A bacitracina zíncica (Bc-Zn) é um potente antibiótico constituído por uma mistura complexa de peptídeos não-biodegradáveis, conjugados ao zinco. Apesar de ser um antibiótico amplamente consumido na medicina humana e animal, é preocupante a escassez de estudos que investigam sua degradação e destino ambiental. O presente trabalho analisou a degradação da Bc-Zn através dos processos de fotólise direta e UV/H2O2 em diferentes condições de radiação UVC e concentração inicial de H2O2. Os parâmetros cinéticos rendimento quântico da fotólise, constantes cinéticas de pseudo-primeira ordem e constante cinéticas de segunda ordem foram satisfatoriamente estimados pela modelagem do sistema fotoquímico experimental. Os resultados revelaram que a fotólise direta permitiu degradar todos os congêneres da mistura de Bc-Zn nas maiores doses de radiação UVC empregadas. No entanto, não houve remoção de TOC após 120 minutos de irradiação. A adição de H2O2 acelerou substancialmente a fotodegradação do antibiótico, apresentando constantes cinéticas de pseudo-primeira ordem uma ordem de grandeza superiores às obtidas por fotólise direta. Além disso, remoção considerável de até 71% do TOC foi alcançada. A análise estatística demonstrou que a radiação UV foi um fator bem mais significativo para a fotodegradação da Bc-Zn em relação à concentração inicial de H2O2, sendo as melhores condições do processo alcançadas para a maior taxa específica de emissão de fótons (1,11×10-5 Einstein L-1 s-1). Ensaios biológicos com soluções tratadas por fotólise direta e UV/H2O2 indicaram remoção completa da atividade antimicrobiana residual, ainda que os produtos da fotodegradação tenham se mostrado não-biodegradáveis. Análises de toxicidade indicaram que o metal zinco presente no antibiótico é responsável pela a toxicidade no micro-organismo-teste Vibrio fischeri. Estudos adicionais devem ser realizados para identificar os sub-produtos formados, bem como para investigar a degradação da Bc-Zn em efluentes industriais reais. / The presence of antibiotics in ecosystems represents a serious risk to human and animal health, caused by the increase in bacterial resistance. Since most antibiotics resist to biological degradation, advanced oxidation processes are pointed out as the most effective technologies for degrading these compounds in wastewater. Zinc bacitracin (Bc-Zn) is a potent antibiotic with a complex mixture of non-biodegradable peptides conjugated to zinc. Despite being a widely used antibiotic in human and animal medicine, the scarcity of studies dealing with its degradation and environmental fate is a matter of concern. In this work, Bc-Zn degradation by direct photolysis and the UV/H2O2 process was investigated for different UVC radiation conditions and initial H2O2 concentrations. Kinetic parameters, namely the photolysis quantum yield, pseudo-first order kinetic constants and second-order kinetic constants, were satisfactorily estimated from experimental data by modeling the photochemical system. The results showed that all the congeners of the Bc-Zn mixture were photolyzed at the highest UVC doses applied, while no TOC removal was observed after 120 minutes of irradiation. The addition of H2O2 substantially accelerated Bc-Zn photodegradation, with pseudo-first order kinetic constants of one order of magnitude higher than those observed under direct photolysis. In addition, a remarkable removal of up to 71% of TOC was achieved. Statistical analyses showed that UV radiation had a much more important effect on Bc-Zn photodegradation in comparison with initial H2O2 concentration, with the best process conditions achieved for the highest specific photon emission rate (1.11×10-5 Einstein L-1 s-1). Biological assays carried out with the solutions treated by direct photolysis and UV/H2O2 revealed no residual antimicrobial activity, though photodegradation products remained non-biodegradable. In addition, toxicity analyses indicated that the zinc metal present in the antibiotic is responsible for the toxic effect on the test microorganism Vibrio fischeri. Finally, further studies should be performed to identify the by-products formed and to investigate Bc-Zn degradation in real industrial wastewater.

A indústria têxtil gera grandes volumes de efluentes com elevada carga orgânica, forte coloração e toxicidade. Neste trabalho, estuda-se o tratamento de solução aquosa contendo o corante Solophenyl Yellow Arle 154% por meio dos processos O3-H2O2/UV e foto-Fenton, avaliando-se as repostas: remoção de cor em 5 minutos, remoção de cor em 60 minutos, taxa máxima de remoção de cor e remoção de COT em 60 minutos. Os experimentos foram realizados em semibatelada com circulação usando um reator fotoquímico com campo de radiação anular coaxial, constituído de corpo cilíndrico em aço com refletor interno de alumínio para 12 lâmpadas fixadas simetricamente na superfície refletora e um tubo reator em quartzo de 0,7 L, posicionados verticalmente no eixo do refletor. Para o processo O3-H2O2/UV foram utilizadas lâmpadas Phillips TUV (36 W, 254 nm). A corrente gasosa contendo O3 foi introduzida no reator por meio de um difusor. Para o processo foto-Fenton foram utilizadas lâmpadas Sylvania (12 W cada, 300 400 nm) e concentração de Fe(II) de 0,25 mmol/L. Em ambos os processos, solução de peróxido de hidrogênio foi adicionada durante os 30 minutos iniciais de tratamento. As amostras foram analisadas por medidas de carbono orgânico total (COT) e remoção de cor (absorbância medida em 405 nm em espectrofotômetro UV-visível). Em ambos os processos utilizou-se o planejamento experimental Doehlert, definindo os valores mínimo e máximo para cada variável adotada. No caso do processo O3- H2O2/UV (ETAPA I), foram estudados os efeitos da potência elétrica total das lâmpadas (144 432 W), concentração de H2O2 (5 30 mmol/L), concentração inicial de corante (20 100 mg/L), concentração de ozônio (10 40 mg/L) e pH (3 10). No processo foto-Fenton (ETAPA II), estudaram-se os efeitos da potência (160 480 W), concentração de H2O2 (5 30 mmol/L) e concentração inicial de corante (20 100 mg/L). Os resultados da ETAPA I indicaram que o aumento da concentração do corante, em meio ácido, aumenta a remoção de cor em 5 e 60 minutos, sugerindo a eficiência da ação via ozônio molecular sob o grupo cromóforo do corante. Os melhores resultados apresentaram remoção acima de 95% em 5 e 60 minutos de tratamento. Entretanto, para a remoção de COT em 60 minutos o processo não foi eficiente, apresentando resultado máximo de 35,6%. Na ETAPA II obtiveram-se resultados menos satisfatórios para remoção de cor se comparados aos da ETAPA I (56,1% em 5 minutos e 78% em 60 minutos de tratamento), mas melhores em relação à remoção de COT em 60 minutos atigindo 45,1% de remoção. As maiores taxas de remoção de cor foram observadas nos 5 primeiros minutos de tratamento para todos os experimentos. Experimentos complementares realizados em uma terceira etapa (ETAPA III) mostraram que a aplicação do processo O3 seguido do processo foto-Fenton permitiu resultados satisfatórios tanto para remoção de cor (97,2%), quanto para remoção de COT (69,5%). O estudo da ação do processo O3 em modo contínuo e a avaliação econômica preliminar do processo integrado O3 - foto-Fenton sugerem o potencial de aplicação do tratamento integrado a indústrias têxteis. / The textile industry generates large volumes of wastewater with high organic load, strong coloration and toxicity. In this work, the treatment of an aqueous solution containing the dye Solophenyl Yellow Arle 154% was studied by the O3-H2O2/UV and photo-Fenton processes, in order to evaluate the responses color removal after 5 minutes; color removal after 60 minutes; maximum rate of color removal; and TOC removal after 60 minutes. The experiments were carried out in the semi-batch mode with circulation using a photochemical reactor with annular coaxial radiation field, consisting of a cylindrical stainless steel support with an aluminum internal reflector with 12 lamps fixed symmetrically in the internal reflecting surface, and a quartz tube reactor of 0.7 L, positioned vertically along the axis of the reflector. For the O3- H2O2/UV process, Phillips TUV lamps (36 W, 254 nm) were used; the gas stream containing zone was introduced into the reactor through a diffuser. For the photo- Fenton process, Sylvania lamps (12 W each, 300 - 400 nm) and a concentration of Fe (II) of 0.25 mmol/L were used. In both cases, the hydrogen peroxide solution was added in the first 30 minutes of treatment. The samples were analyzed by the measurement of total organic carbon (TOC) and color removal (absorbance measured at 405 nm in a UV-visible spectrophotometer). In both cases the Doehlert experimental design was used, defining the minimum and maximum values of each variable adopted. In the case of O3-H2O2/UV process (PHASE I), the effects of the total electric power of the lamps (144 - 432 W), H2O2 concentration (5 - 30 mmol/L), initial dye concentration (20 - 100 mg/L), ozone concentration (10 - 40 mg/L), and pH (3 - 10) were studied. For the photo-Fenton process, the studied variables were: total electric power of the lamps (160 - 480 W), H2O2 concentration (5 - 30 mmol/L), and initial dye concentration (20 - 100 mg/L). The results of PHASE I indicated that the increase of dye concentration in acidic conditions increases color removal after 5 and 60 minutes, thus suggesting the efficiency of molecular ozone action upon the chromophore group of the dye. The best results showed color removal above 95% after 5 and 60 minutes of treatment. However, for the TOC removal the process was not efficient, with maximum removal after 60 minutes of only 35.6%. In PHASE II less satisfactory results for color removal were obtained in comparison with PHASE I (56.1% after 5 minutes and 78% after 60 minutes of treatment), but with higher TOC removal after 60 minutes, achieving over 45.1%. The highest color removal rates were observed within the first 5 minutes of treatment for all runs. Additional experiments carried out in PHASE III showed that the oxidation by O3 followed by the photo-Fenton process enabled to achieve suitable results for both color (97.2%) and TOC removals (69.5%). The study of the O3 process in the continuous mode and a preliminary economic evaluation suggests a high potential for the use of the integrated O3-photo-Fenton process in textile industries.

As técnicas de remediação para solos contaminados como os processos de oxidação avançados \"in situ\" visam essencialmente a mineralização dos contaminantes, reduzindo-os, em última instância, a CO2 e H2O. O objetivo deste estudo é apresentar os resultados de experimentos conduzidos para investigar como as características do solo, tais como a granulação, o teor e a natureza dos minerais argilosos, e o teor da matéria orgânica influem no desempenho da mineralização do contaminante linar alquilbenzeno no solo. Em várias partes da cidade de São Paulo há locais contaminados por esse e outros tipos de vazamentos e os responsáveis e as autoridades estão interessadas em possíveis soluções. Uma possível solução seria o tratamento in situ através dos processos de oxidação avançada. Porém, não há como decidir a priori sobre a melhor técnica, pois ela dependerá tanto do reagente empregado como do tipo de solo contaminado. Essa resposta poderá ser cientificamente fundamentada a partir de ensaios no laboratório desenhados para investigar os fatores que controlam a eficácia do processo. Os experimentos em laboratório foram conduzidos com dois tipos de solo da região metropolitana de São Paulo contaminados com linear alquilbenzeno, composto utilizado como óleo térmico em revestimentos de cabos subterrâneos de alta voltagem. Os desempenhos da mineralização com o Reagente de Fenton e Persulfato de Sódio foram avaliados na oxidação do composto linear alquilbenzeno com uma concentração inicial de 10 mg/grama de solo contaminado. Os resultados mostram uma redução considerável em massa de 82% a 85% do contaminante nos dois solos com a utilização de Persulfato de Sódio ativado termicamente e através de metal de transição \'Fe POT.2+\' disponível naturalmente no solo . O reagente de Fenton nas mesmas condições do experimento mostrou um desempenho mais limitado entre 10 % a 30% de redução em massa do contaminante. O conhecimento prévio das características do solo como o teor de argila , teor de carbono orgânico que influem fortemente os fenômenos de sorção e desorção e a composição mineralógica são variáveis importantes na definição dos reagentes e nas condições de reação de oxidação dos poluentes e contribuem na escolha mais acertada da tecnologia de remediação \'in situ\". / The remediation techniques used in contaminated soils such as \"in situ\" chemical oxidation aim essentially the mineralization of contaminants, reducing it to CO2 and H2O. The objective of this study is pointing out the results of experiments conducted to investigate how the soil characteristics such as granulometry, assay and nature of clay minerals as well as organic matter can influence in the mineralization performance of linear alkylbenzene in the soil. In some areas of São Paulo city there are contaminated sites by leakage of linear alkylbenzene and many other chemical leakages and site\'s responsible and local authorities are interested in possible technical solutions to clean it. One possible solution would be in situ treatment through advanced oxidation process; however there is no way how to decide about the best technique because it depends on contaminant substance, reagents used as well as the contaminated soil characteristics. The answer could be scientifically based on bench laboratory experiments properly designed to investigate the factors that control the process performance. The bench lab experiments were conducted with two soils sampled from metropolitan region of São Paulo and contaminated with linear alkyl benzene, used in high and medium voltage underground electrical cables. The mineralization performance was evaluated in soils contaminated with an initial concentration of 10 mg / gr of contaminated soil by oxidation of linear alkyl benzene with Fenton reagent and sodium persulfate. The final results pointed out a considerable mass reduction from 82% to 85% in both soils tested with sodium persulfate thermally activated and by naturally available transition metal \'Fe pot.2+\' in the soil. The Fenton reagent in the same experiment conditions pointed out a more limited mass reduction performance between 10% and 30%. The previous knowledge of soil characteristics such as clay assay , natural carbon content in the soil which influence the sorption / desorption phenomenon as well as the mineral composition of the soil are the key variables to define reagents and the oxidation reaction conditions which contribute to select a proper in situ chemical oxidation technology.

As técnicas de remediação para solos contaminados como os processos de oxidação avançados \"in situ\" visam essencialmente a mineralização dos contaminantes, reduzindo-os, em última instância, a CO2 e H2O. O objetivo deste estudo é apresentar os resultados de experimentos conduzidos para investigar como as características do solo, tais como a granulação, o teor e a natureza dos minerais argilosos, e o teor da matéria orgânica influem no desempenho da mineralização do contaminante linar alquilbenzeno no solo. Em várias partes da cidade de São Paulo há locais contaminados por esse e outros tipos de vazamentos e os responsáveis e as autoridades estão interessadas em possíveis soluções. Uma possível solução seria o tratamento in situ através dos processos de oxidação avançada. Porém, não há como decidir a priori sobre a melhor técnica, pois ela dependerá tanto do reagente empregado como do tipo de solo contaminado. Essa resposta poderá ser cientificamente fundamentada a partir de ensaios no laboratório desenhados para investigar os fatores que controlam a eficácia do processo. Os experimentos em laboratório foram conduzidos com dois tipos de solo da região metropolitana de São Paulo contaminados com linear alquilbenzeno, composto utilizado como óleo térmico em revestimentos de cabos subterrâneos de alta voltagem. Os desempenhos da mineralização com o Reagente de Fenton e Persulfato de Sódio foram avaliados na oxidação do composto linear alquilbenzeno com uma concentração inicial de 10 mg/grama de solo contaminado. Os resultados mostram uma redução considerável em massa de 82% a 85% do contaminante nos dois solos com a utilização de Persulfato de Sódio ativado termicamente e através de metal de transição \'Fe POT.2+\' disponível naturalmente no solo . O reagente de Fenton nas mesmas condições do experimento mostrou um desempenho mais limitado entre 10 % a 30% de redução em massa do contaminante. O conhecimento prévio das características do solo como o teor de argila , teor de carbono orgânico que influem fortemente os fenômenos de sorção e desorção e a composição mineralógica são variáveis importantes na definição dos reagentes e nas condições de reação de oxidação dos poluentes e contribuem na escolha mais acertada da tecnologia de remediação \'in situ\". / The remediation techniques used in contaminated soils such as \"in situ\" chemical oxidation aim essentially the mineralization of contaminants, reducing it to CO2 and H2O. The objective of this study is pointing out the results of experiments conducted to investigate how the soil characteristics such as granulometry, assay and nature of clay minerals as well as organic matter can influence in the mineralization performance of linear alkylbenzene in the soil. In some areas of São Paulo city there are contaminated sites by leakage of linear alkylbenzene and many other chemical leakages and site\'s responsible and local authorities are interested in possible technical solutions to clean it. One possible solution would be in situ treatment through advanced oxidation process; however there is no way how to decide about the best technique because it depends on contaminant substance, reagents used as well as the contaminated soil characteristics. The answer could be scientifically based on bench laboratory experiments properly designed to investigate the factors that control the process performance. The bench lab experiments were conducted with two soils sampled from metropolitan region of São Paulo and contaminated with linear alkyl benzene, used in high and medium voltage underground electrical cables. The mineralization performance was evaluated in soils contaminated with an initial concentration of 10 mg / gr of contaminated soil by oxidation of linear alkyl benzene with Fenton reagent and sodium persulfate. The final results pointed out a considerable mass reduction from 82% to 85% in both soils tested with sodium persulfate thermally activated and by naturally available transition metal \'Fe pot.2+\' in the soil. The Fenton reagent in the same experiment conditions pointed out a more limited mass reduction performance between 10% and 30%. The previous knowledge of soil characteristics such as clay assay , natural carbon content in the soil which influence the sorption / desorption phenomenon as well as the mineral composition of the soil are the key variables to define reagents and the oxidation reaction conditions which contribute to select a proper in situ chemical oxidation technology.

A indústria têxtil gera grandes volumes de efluentes com elevada carga orgânica, forte coloração e toxicidade. Neste trabalho, estuda-se o tratamento de solução aquosa contendo o corante Solophenyl Yellow Arle 154% por meio dos processos O3-H2O2/UV e foto-Fenton, avaliando-se as repostas: remoção de cor em 5 minutos, remoção de cor em 60 minutos, taxa máxima de remoção de cor e remoção de COT em 60 minutos. Os experimentos foram realizados em semibatelada com circulação usando um reator fotoquímico com campo de radiação anular coaxial, constituído de corpo cilíndrico em aço com refletor interno de alumínio para 12 lâmpadas fixadas simetricamente na superfície refletora e um tubo reator em quartzo de 0,7 L, posicionados verticalmente no eixo do refletor. Para o processo O3-H2O2/UV foram utilizadas lâmpadas Phillips TUV (36 W, 254 nm). A corrente gasosa contendo O3 foi introduzida no reator por meio de um difusor. Para o processo foto-Fenton foram utilizadas lâmpadas Sylvania (12 W cada, 300 400 nm) e concentração de Fe(II) de 0,25 mmol/L. Em ambos os processos, solução de peróxido de hidrogênio foi adicionada durante os 30 minutos iniciais de tratamento. As amostras foram analisadas por medidas de carbono orgânico total (COT) e remoção de cor (absorbância medida em 405 nm em espectrofotômetro UV-visível). Em ambos os processos utilizou-se o planejamento experimental Doehlert, definindo os valores mínimo e máximo para cada variável adotada. No caso do processo O3- H2O2/UV (ETAPA I), foram estudados os efeitos da potência elétrica total das lâmpadas (144 432 W), concentração de H2O2 (5 30 mmol/L), concentração inicial de corante (20 100 mg/L), concentração de ozônio (10 40 mg/L) e pH (3 10). No processo foto-Fenton (ETAPA II), estudaram-se os efeitos da potência (160 480 W), concentração de H2O2 (5 30 mmol/L) e concentração inicial de corante (20 100 mg/L). Os resultados da ETAPA I indicaram que o aumento da concentração do corante, em meio ácido, aumenta a remoção de cor em 5 e 60 minutos, sugerindo a eficiência da ação via ozônio molecular sob o grupo cromóforo do corante. Os melhores resultados apresentaram remoção acima de 95% em 5 e 60 minutos de tratamento. Entretanto, para a remoção de COT em 60 minutos o processo não foi eficiente, apresentando resultado máximo de 35,6%. Na ETAPA II obtiveram-se resultados menos satisfatórios para remoção de cor se comparados aos da ETAPA I (56,1% em 5 minutos e 78% em 60 minutos de tratamento), mas melhores em relação à remoção de COT em 60 minutos atigindo 45,1% de remoção. As maiores taxas de remoção de cor foram observadas nos 5 primeiros minutos de tratamento para todos os experimentos. Experimentos complementares realizados em uma terceira etapa (ETAPA III) mostraram que a aplicação do processo O3 seguido do processo foto-Fenton permitiu resultados satisfatórios tanto para remoção de cor (97,2%), quanto para remoção de COT (69,5%). O estudo da ação do processo O3 em modo contínuo e a avaliação econômica preliminar do processo integrado O3 - foto-Fenton sugerem o potencial de aplicação do tratamento integrado a indústrias têxteis. / The textile industry generates large volumes of wastewater with high organic load, strong coloration and toxicity. In this work, the treatment of an aqueous solution containing the dye Solophenyl Yellow Arle 154% was studied by the O3-H2O2/UV and photo-Fenton processes, in order to evaluate the responses color removal after 5 minutes; color removal after 60 minutes; maximum rate of color removal; and TOC removal after 60 minutes. The experiments were carried out in the semi-batch mode with circulation using a photochemical reactor with annular coaxial radiation field, consisting of a cylindrical stainless steel support with an aluminum internal reflector with 12 lamps fixed symmetrically in the internal reflecting surface, and a quartz tube reactor of 0.7 L, positioned vertically along the axis of the reflector. For the O3- H2O2/UV process, Phillips TUV lamps (36 W, 254 nm) were used; the gas stream containing zone was introduced into the reactor through a diffuser. For the photo- Fenton process, Sylvania lamps (12 W each, 300 - 400 nm) and a concentration of Fe (II) of 0.25 mmol/L were used. In both cases, the hydrogen peroxide solution was added in the first 30 minutes of treatment. The samples were analyzed by the measurement of total organic carbon (TOC) and color removal (absorbance measured at 405 nm in a UV-visible spectrophotometer). In both cases the Doehlert experimental design was used, defining the minimum and maximum values of each variable adopted. In the case of O3-H2O2/UV process (PHASE I), the effects of the total electric power of the lamps (144 - 432 W), H2O2 concentration (5 - 30 mmol/L), initial dye concentration (20 - 100 mg/L), ozone concentration (10 - 40 mg/L), and pH (3 - 10) were studied. For the photo-Fenton process, the studied variables were: total electric power of the lamps (160 - 480 W), H2O2 concentration (5 - 30 mmol/L), and initial dye concentration (20 - 100 mg/L). The results of PHASE I indicated that the increase of dye concentration in acidic conditions increases color removal after 5 and 60 minutes, thus suggesting the efficiency of molecular ozone action upon the chromophore group of the dye. The best results showed color removal above 95% after 5 and 60 minutes of treatment. However, for the TOC removal the process was not efficient, with maximum removal after 60 minutes of only 35.6%. In PHASE II less satisfactory results for color removal were obtained in comparison with PHASE I (56.1% after 5 minutes and 78% after 60 minutes of treatment), but with higher TOC removal after 60 minutes, achieving over 45.1%. The highest color removal rates were observed within the first 5 minutes of treatment for all runs. Additional experiments carried out in PHASE III showed that the oxidation by O3 followed by the photo-Fenton process enabled to achieve suitable results for both color (97.2%) and TOC removals (69.5%). The study of the O3 process in the continuous mode and a preliminary economic evaluation suggests a high potential for the use of the integrated O3-photo-Fenton process in textile industries.

Le secteur industriel du traitement de surface (TS), secteur d’excellence en Bourgogne Franche-Comté, est contraint de recourir à de nouvelles méthodes d’épuration des eaux du fait d’une règlementation européenne de plus en plus stricte. En effet, notamment dans le cadre de la Directive Cadre sur l’Eau, les industriels doivent sans cesse améliorer la qualité de leurs rejets et diminuer les impacts générés par ceux-ci. Ce travail de thèse s’inscrit dans cet objectif. Ainsi, trois grands types d’investigations ont été menés : le premier a permis de définir la composition qualitative et quantitative en substances dangereuses (SD) des rejets de TS et d’étudier leur variabilité temporelle ; le second a validé des modifications d’une station physico-chimique de traitement des eaux franc-comtoise pour diminuer le flux de SD ; le dernier a proposé des solutions innovantes par bioadsorption sur des matériaux de cyclodextrine et par procédé d’oxydation avancée (POA) soit par ozone/UV, soit par l’utilisation de catalyseurs Pd-Cu pour atteindre le même objectif.[...] / The industrial sector of surface treatment (ST), sector of excellence in Bourgogne Franche-Comté, is forced to resort to new methods for water treatment due to European regulations increasingly strict. Indeed, particularly in the context of the Water Framework Directive, industries must continually improve the quality of their discharge waters and reduce the impacts generated by them. This work is part of this. Thus, three types of investigations were conducted: the first has defined qualitative and quantitative composition of hazardous substances (HS) in ST discharge waters and study their temporal variability; the second has approved changes in a physicochemical wastewater decontamination station to decrease HS water flow; the last proposed innovative solutions by biosorption on cyclodextrin materials and advanced oxidation process (AOP) by ozone / UV, or by the use of Pd-Cu catalysts to achieve the same objective.[...]

Im Rahmen der vorliegenden Arbeit wurden zwei verschiedene Klassen oxidischer Nanomaterialien nasschemisch synthetisiert und strukturell-morphologisch charakterisiert. Zum einen betrifft dies TiO2-, TiO2/SiO2-, Ag/TiO2- und Pd/TiO2-Sole, welche die photokatalytisch aktive Modifikation Anatas in nanokristalliner Form enthalten und über einen solvothermalen Sol-Gel-Prozess hergestellt werden konnten. Im Hinblick auf eine potentielle Anwendung in der Desinfektionstechnologie und für den Abbau organischer Umweltschadstoffe wurde die photokatalytische Aktivität von Pulvern und Beschichtungen auf Textil durch E. coli-Abtötung bzw. Modellfarbstoffabbau untersucht. Im Weiteren wurde die antimikrobielle Aktivität pyroelektrischer LiNbO3- und LiTaO3-Pulvermaterialien unter zyklischer thermischer Anregung nachgewiesen. Diese als Pyroelektrokatalyse bezeichnete Nutzung des pyroelektrischen Effektes in einem katalytischen bzw. elektrochemischen Prozess ist dabei von grundlegender Neuheit. Aufsetzend auf den physiko-chemischen Grundlagen dieses Phänomens wurde eine Hypothese des Mechanismus entwickelt und in Analogie zur Photokatalyse diskutiert. / This thesis deals with two classes of oxidic nanomaterials that were synthesized by chemical solution routes and characterized with respect to structure and morphology. Sols of TiO2, TiO2/SiO2, Ag/TiO2 and Pd/TiO2 containing the photocatalytically active modification anatase in nanocrystalline form were prepared via a solvothermal sol-gel process. With regard to potential application in disinfection and environmental remediation technology the photocatalytic activity of powders and coatings on textile was investigated by means of E. coli decomposition and organic dye degradation. Further the antimicrobial activity of pyroelectric LiNbO3 and LiTaO3 powder materials under cyclical thermal excitation was demonstrated. In this context the application of the pyroelectric effect in a catalytic or electrochemical process – termed as pyroelectrocatalysis – is of fundamental novelty. Based on the physico-chemical principles of the phenomenon a hypothesis of the mechanism was developed and discussed in analogy with photocatalysis.

<p>Cilj&nbsp; istraživanja&nbsp; u&nbsp; okviru&nbsp; ove&nbsp; doktorske&nbsp; disertacije&nbsp; je&nbsp; utvrđivanje&nbsp; efekata&nbsp; različitih<br />oksidacionih procesa na bazi ozona, vodonik-peroksida i UV zračenja na sadržaj i reaktivnost prirodnih&nbsp; organskih&nbsp; materija&nbsp; (POM)&nbsp; u&nbsp; različitim&nbsp; vodenim&nbsp; matriksima.&nbsp; Ispitivanja&nbsp; su sprovedena&nbsp; na&nbsp; a)&nbsp; podzemnoj&nbsp; vodi&nbsp; sa&nbsp; teritorije&nbsp; Kikinde&nbsp; i&nbsp; Temerina&nbsp; (prirodni&nbsp; matriks)&nbsp; i&nbsp; b) sintetičkom&nbsp; vodenom&nbsp; matriksu&nbsp; (rastvoru&nbsp; komercijalno&nbsp; dostupne&nbsp; huminske&nbsp; kiseline),&nbsp; koji&nbsp; se među sobom razlikuju po sastavu i strukturi prisutne POM i sadržaju bromida. Za oksidacioni proces&nbsp; (ozonizacija,&nbsp; UV&nbsp; fotoliza,&nbsp; oksidacija&nbsp; sa&nbsp; H₂O₂,&nbsp; kombinovani&nbsp; O ₃/UV&nbsp; proces&nbsp; i kombinovani&nbsp; H ₂O₂<br />/UV&nbsp; proces)&nbsp; pojedinačno&nbsp; ispitan&nbsp; je&nbsp; uticaj&nbsp; različitih&nbsp; doza&nbsp; oksidanata&nbsp; i reakcionih&nbsp; uslova.Posebna&nbsp; pažnja&nbsp; posvećena&nbsp; je&nbsp; ispitivanju&nbsp; uticaja&nbsp; navedenih&nbsp; tretmana&nbsp; na<br />formiranje&nbsp; neorganskog&nbsp; bromata,&nbsp; kao&nbsp; i&nbsp; uticaja&nbsp; na&nbsp; sadržaj&nbsp; prekursora&nbsp;&nbsp; dezinfekcionih nusproizvoda nakon hlorisanja (THM, HAA, HAN, HK i CP).<br />Analiza&nbsp; hemijskih&nbsp; parametara&nbsp; sintetičkog&nbsp; matriksa&nbsp; (5,44&plusmn;0,30&nbsp; mg&nbsp; C/l; 0,255&plusmn;0,015 cm^-1 ;&nbsp; 4,68&plusmn;0,41&nbsp; lm^-1 mg ^-1)&nbsp; pokazuje&nbsp; da&nbsp; u&nbsp; njemu&nbsp; preovladavaju&nbsp; huminnske materije&nbsp; visoke&nbsp; hidrofobnosti.&nbsp; Visok&nbsp; sadržaj&nbsp; POM&nbsp; pretežno&nbsp; hidrofobnog&nbsp; karaktera&nbsp; je zabeležen i u vodi iz Kikinde (5,170,72 mg C/l; 0,2010,001 cm <span id="cke_bm_192S" style="display: none;">&nbsp;</span><span id="cke_bm_190S" style="display: none;">&nbsp;</span>^-1<span id="cke_bm_192E" style="display: none;">&nbsp;</span><span id="cke_bm_190E" style="display: none;">&nbsp;</span> ; 3,88&plusmn;0,70 lm<span id="cke_bm_193S" style="display: none;">&nbsp;</span>^-1<span id="cke_bm_193E" style="display: none;">&nbsp;</span> mg^-1 ), dok je&nbsp; sadrža<span id="cke_bm_194E" style="display: none;">&nbsp;</span>j&nbsp; POM&nbsp; u&nbsp; sirovoj&nbsp; vodi&nbsp; iz&nbsp; Temerina&nbsp; (2,060,38&nbsp; mg&nbsp; C/l;&nbsp; 0,0500,001&nbsp; cm<span id="cke_bm_203S" style="display: none;">&nbsp;</span><span id="cke_bm_201S" style="display: none;">&nbsp;</span>^-1<span id="cke_bm_203E" style="display: none;">&nbsp;</span><span id="cke_bm_201E" style="display: none;">&nbsp;</span>&nbsp; ; 2,43&plusmn;0,21 lm <span id="cke_bm_204S" style="display: none;">&nbsp;</span>^-1<span id="cke_bm_204E" style="display: none;">&nbsp;</span> mg ^-1<span id="cke_bm_205E" style="display: none;">&nbsp;</span><span id="cke_bm_202E" style="display: none;">&nbsp;</span><span id="cke_bm_191E" style="display: none;">&nbsp;</span><br />) značajno niži i preovladavaju POM hidrofilnog karaktera. Veći stepen hidrofobnosti sintetičkog matriksa u poređenju sa&nbsp; prirodnim matriksima, rezultovao&nbsp; je&nbsp; i&nbsp; većom&nbsp; reaktivnosti&nbsp; organske&nbsp; materije&nbsp; sa&nbsp; hlorom,&nbsp; &scaron;to&nbsp; se&nbsp; može&nbsp; zaključiti&nbsp; na<br />osnovu visokih vrednosti PFDBP nakon hlorisanja. Vrednost PFTHM u sintetičkom matriksu iznosi&nbsp; 544&plusmn;85,9&nbsp; &micro;g/l,&nbsp; dok&nbsp; je&nbsp; PFTHM&nbsp; u&nbsp; kikindskoj&nbsp; i&nbsp; temerinskoj&nbsp; sirovoj&nbsp; vodi&nbsp; znatno&nbsp; niži (279&plusmn;32,3&nbsp; i&nbsp; 180&plusmn;44,0&nbsp; &micro;g/l,&nbsp; respektivno).&nbsp; Vrednost&nbsp; PFHAA&nbsp; u&nbsp; sintetičkom&nbsp; matriksu&nbsp; iznosi 484&plusmn;77,5 &micro;g/l, dok je PFHAA u kikindskoj 244&plusmn;11,1 &micro;g/l i u temerinskoj vodi 165&plusmn;32,5 &micro;g/l. Sadržaj&nbsp; HK&nbsp; (8,05&plusmn;3,63&nbsp; &micro;g/l&nbsp; sintetički&nbsp; matriks;&nbsp; 14,91,38&nbsp; &micro;g/l&nbsp; Kikinda;&nbsp; 7,400,25&nbsp; &micro;g/l Temerin)&nbsp; je&nbsp; znatno&nbsp; niži&nbsp; u&nbsp; poređenju&nbsp; sa&nbsp; prekursorima&nbsp; THM&nbsp; i&nbsp; HAA,&nbsp; dok&nbsp; prekursori&nbsp; HAN&nbsp; i hlorpikrina&nbsp; nisu&nbsp; detektovani&nbsp; u&nbsp; sirovoj&nbsp; vodi.&nbsp; Nusproizvodi&nbsp; koji&nbsp; se&nbsp; dominantno&nbsp; formiraju&nbsp; u svim&nbsp; ispitivanim&nbsp; vodenim&nbsp; matriksima&nbsp; su&nbsp; hlorovani&nbsp; THM&nbsp; i&nbsp; HAA,&nbsp; dok&nbsp; se&nbsp; bromovani&nbsp; DBPformiraju u znatno nižim koncentracijama. Zastupljenost bromovanih DBP u temerinskoj vodi<br />je&nbsp; znatno&nbsp; veći&nbsp; u&nbsp; poređenju&nbsp; sa&nbsp; vodom&nbsp; iz&nbsp; Kikinde,&nbsp; kao&nbsp; rezultat&nbsp; prisustva&nbsp; veće&nbsp; koncentracije bromida u sirovoj vodi (0,05&plusmn;0,01 mg Br -/l Temerin; 0,03&plusmn;0,01 mg Br<br />-/l Kikinda). Ispitivanjem&nbsp; uticaja&nbsp; oksidacionih&nbsp; procesa&nbsp; (UV&nbsp; fotolize,&nbsp; ozonizacije,&nbsp; oksidacije vodonik-peroksidom)&nbsp; na&nbsp; sadržaj&nbsp; i&nbsp; reaktivnost&nbsp; POM&nbsp; u&nbsp; ispitivanim&nbsp; vodenim&nbsp; matriksima utvrđeno&nbsp; je&nbsp; da&nbsp; tretman&nbsp; vode&nbsp; UV&nbsp; zračenjem&nbsp; i&nbsp; vodonik-peroksidom,&nbsp; kada&nbsp; se&nbsp; primenjuju&nbsp; kao samostalan&nbsp; tretman,&nbsp; ne&nbsp; pokazuju&nbsp; značajnu&nbsp; efikasnost&nbsp; u&nbsp; smanjenju&nbsp; sadržaja&nbsp; POM.Tretman vode&nbsp; ozonom&nbsp; se&nbsp; pokazao&nbsp; kao&nbsp; veoma&nbsp; efikasan&nbsp; u&nbsp; uklanjanju&nbsp; POM&nbsp; i&nbsp; u&nbsp; smanjenju&nbsp; sadržaja prekursora&nbsp; DBP&nbsp; kod&nbsp; svih&nbsp; ispitivanih&nbsp; vodenih&nbsp; matriksa,&nbsp; kao&nbsp; rezultat&nbsp; smanjenja&nbsp; reaktivnosti POM&nbsp; ka&nbsp; formiranju&nbsp; ovih&nbsp; DBP.&nbsp; Smanjenje&nbsp; sadržaja&nbsp; POM&nbsp; u&nbsp; vodi&nbsp; tokom&nbsp; tretmana&nbsp; raste&nbsp; sa povećanjem&nbsp; primenjene&nbsp; doze&nbsp; ozona,&nbsp; pri&nbsp; čemu&nbsp; se&nbsp; najbolji&nbsp; rezultati&nbsp; postižu&nbsp; pri&nbsp; najvećoj primenjenoj&nbsp; dozi&nbsp; od&nbsp; 3,0&nbsp; mg&nbsp; O 3/mg&nbsp; DOC&nbsp; (do&nbsp; 32%&nbsp; DOC,&nbsp; 92%&nbsp; UV254 sintetički&nbsp; matriks;&nbsp; do 17%&nbsp; DOC,&nbsp; 76%&nbsp; UV 254&nbsp; Kikinda;&nbsp; do&nbsp; 15%&nbsp; DOC&nbsp; i&nbsp; 66%&nbsp; UV254&nbsp;&nbsp;&nbsp; Temerin).&nbsp; U&nbsp; sintetičkom matriksu&nbsp; najveće&nbsp; smanjenje&nbsp; PFTHM&nbsp; (za&nbsp; 76%)&nbsp; i&nbsp; PFHAA&nbsp; (za&nbsp; 80%)&nbsp; u&nbsp; odnosu&nbsp; na&nbsp; sadržaj&nbsp; u sirovoj vodi se postiže pri dozi od 1,0&nbsp; mg O₃/mg DOC. Najveće smanjenje PFTHM (za 38%)<br />i PFHAA (za 42%) u vodi iz Kikinde postiže se pri dozi od 3,0 mg O ₃/mg DOC. U vodi iz Temerina najveće smanjenje PFTHM (za&nbsp; 27%) je pri dozi od 3,0 mg O ₃ /mg DOC, dok se za smnjenje&nbsp; PFHAA&nbsp; (za&nbsp; 54%)&nbsp; najbolje&nbsp; pokazala&nbsp; doza&nbsp; od&nbsp; 1,0&nbsp; mg&nbsp; O<br />3 /mg&nbsp; DOC.&nbsp; Sadržaj prekursora&nbsp; HK&nbsp; i&nbsp; HAN&nbsp; (temerinska&nbsp; voda)&nbsp; je&nbsp; veoma&nbsp; nizak&nbsp; nakon&nbsp; tretmana.&nbsp; Tretman&nbsp; vode ozonom&nbsp; vodi&nbsp; ka&nbsp; formiranju&nbsp; DBP&nbsp; sa&nbsp; vi&scaron;e&nbsp;&nbsp; supstituisanih&nbsp; atoma&nbsp; broma,&nbsp; dok&nbsp; u&nbsp; vodama&nbsp; sa srednjim sadržajem bromida (50 &micro;g Br -/l) dovodi do formiranja bromata. Kombinacijom&nbsp; ozonizacije&nbsp; sa&nbsp; UV&nbsp; zračenjem&nbsp; se&nbsp; značajno&nbsp; može&nbsp; pospe&scaron;iti&nbsp; efiksnost uklanjanja&nbsp; POM&nbsp; postignuta&nbsp; primenom&nbsp; samostalne&nbsp; ozonizacije.&nbsp; Najveće&nbsp; smanjenje&nbsp; sadržaja POM u&nbsp; sintetičkom matriksu (za 85% DOC, 98% UV254 i 87% SUVA), u vodi iz Kikinde (za<br />23% DOC, 83% UV 254, 77% SUVA), i vodi iz Temerina (za 15% DOC, 80% UV<br />254 i 75% SUVA), u odnosu na vrednosti u netretiranoj vodi postignuto je pri najvećoj primenjenoj dozi od&nbsp; 3,0&nbsp; mg&nbsp; O₃ /mg&nbsp; DOC&nbsp; i&nbsp; 6000&nbsp; mJ/cm 2 .&nbsp; Efikasnost&nbsp; procesa&nbsp; raste&nbsp; u&nbsp; vodama&nbsp; u&nbsp; kojima preovladavaju&nbsp; POM&nbsp; veće&nbsp; hidrofobnosti.&nbsp; MeĎutim,&nbsp; iako&nbsp; se&nbsp; O₃ /UV&nbsp; procesom&nbsp; postiže&nbsp; visok stepen&nbsp; smanjenja&nbsp; PFTHM&nbsp; u&nbsp; sintetičkom&nbsp; matriksu&nbsp; se&nbsp; najbolje&nbsp; pokazao&nbsp; tretman&nbsp; ozonom (1,0 mg&nbsp; O3/mg&nbsp; DOC),&nbsp; dok&nbsp; se&nbsp; najveće&nbsp; smanjenje&nbsp; PFHAA&nbsp; (82%)&nbsp; postiže&nbsp; pri&nbsp; dozi&nbsp; ozona&nbsp; od 1,0 mg O_3/mg DOC i UV zračenja od 6000 mJ/cm ^{2 .} U vodi iz Kikinde se PFTHM smanjuje za 50% pri dozi od 3,0 mg O ₃/mg DOC i 6000 mJ/cm 2 , dok se u slučaju uklanjanja prekursora<br />HAA&nbsp; ozonizacija&nbsp; pokazala&nbsp; kao&nbsp; superiorniji&nbsp; proces.&nbsp; U&nbsp; vodi&nbsp; iz&nbsp; Temerina&nbsp; se&nbsp; u&nbsp; pogledu uklanjanja&nbsp; prekursora&nbsp; THM&nbsp; i&nbsp; HAA&nbsp; ozonizacija&nbsp; pokazala&nbsp; kao&nbsp; optimalan&nbsp; proces.&nbsp; Visok alkalitet&nbsp; prirodnih&nbsp; voda&nbsp; inhibira&nbsp; radikalski&nbsp; mehanizam&nbsp; u&nbsp; toku&nbsp; AOP&nbsp; i&nbsp; favorizuje&nbsp; oksidaciju POM molekulskim ozonom.&nbsp; Prekursori HK se formiraju u&nbsp; veoma niskim koncentracijama i njihov sadržaj ne varira značajno tokom tretmana. U prirodnim matriksima tokom AOP pri dozi&nbsp; ozona&nbsp; od&nbsp; 3,0 mg&nbsp; O₃ /mg&nbsp; DOC&nbsp; dolazi&nbsp; do&nbsp; formiranja&nbsp; HAN,&nbsp; međutim,&nbsp; nije&nbsp; uočen&nbsp; jasan trend&nbsp; sa&nbsp; povećanjem&nbsp; doze&nbsp; UV&nbsp; zračenja.&nbsp; Tretman&nbsp; doprinosi&nbsp; formiranju&nbsp; bromovanih&nbsp; vrsta THM,&nbsp; dok&nbsp; se&nbsp; tokom&nbsp; AOP&nbsp; pri&nbsp; najvećoj&nbsp; dozi&nbsp; ozona&nbsp; od&nbsp; 3,0 mg&nbsp; O₃ /mg&nbsp; DOC&nbsp; formiraju bromovani HAN.<br />Najveće&nbsp; smanjenje&nbsp; sadržaja&nbsp; POM&nbsp; primenom&nbsp; kombinacije&nbsp; oksidacije&nbsp; sa&nbsp; H ₂O₂<br />i&nbsp; UV zračenja u sintetičkom matriksu (za do 17% DOC, 70% UV 254 ), u vodi iz Kikinde (za do 22% DOC, 53% UV₂₅₄), i vodi iz Temerina (za do 7% DOC, 68% UV<br />₂₅₄), u odnosu na vrednosti u sirovoj vodi, se postižu pri dozi H ₂O₂ i UV zračenja od 3,0 mg H₂O₂/mg DOC i 6000 mJ/cm ² .<br />Najveće&nbsp; smanjenje&nbsp; PFTHM&nbsp; od&nbsp; 54%&nbsp; u&nbsp; sintetičkom&nbsp; matriksu&nbsp; se&nbsp; postiže&nbsp; pri&nbsp; dozi&nbsp; od 0 mg H₂O₂/mg DOC i 6000 mJ/cm ² ,&nbsp; dok se smanjenje PFHAA (za 35%)&nbsp; postiže primenom doze vodonik-peroksida i UV zračenja od 1,0 mg H ₂O₂ /mg&nbsp; DOC i 3000 mJ/cm ² . U vodi izKikinde&nbsp; H₂O₂ /UV&nbsp; proces&nbsp; ne&nbsp; utiče&nbsp; značajno&nbsp; na&nbsp; sadržaj&nbsp; prekursora&nbsp; THM,&nbsp; dok&nbsp; se&nbsp; najveće smanjenje&nbsp; PFHAA&nbsp; (za&nbsp; 35%)&nbsp; postiže&nbsp; pri&nbsp; dozi&nbsp; od&nbsp; 3,0&nbsp; mg&nbsp; H_{<span id="cke_bm_235S" style="display: none;">&nbsp;</span>2<span id="cke_bm_235E" style="display: none;">&nbsp;</span>}O₂/mg&nbsp; DOC&nbsp; i&nbsp; 600&nbsp; mJ/cm ² .H<span id="cke_bm_184S" style="display: none;">&nbsp;</span>₂<span id="cke_bm_184E" style="display: none;">&nbsp;</span>O₂<span id="cke_bm_185E" style="display: none;">&nbsp;</span>/UV&nbsp; proces&nbsp; dovodi&nbsp; do&nbsp; smanjenja&nbsp; PFTHM&nbsp; u&nbsp; Temerinskoj&nbsp; vodi&nbsp; za&nbsp; 74%&nbsp; pri&nbsp; dozi&nbsp; od 3,0 mg H₂O₂/mg DOC i 600 mJ/c<span id="cke_bm_236E" style="display: none;">&nbsp;</span>m ² ,&nbsp; dok primenjeni tretman ne pokazuje značajan uticaj na<br />PFHAA.&nbsp; Prekursori HK su detektovani u sintetičkom matriksu i temerinskoj vodi u niskim koncentracijama.&nbsp; U&nbsp; temerinskoj&nbsp; vodi&nbsp; nakon&nbsp; AOP&nbsp; pri&nbsp; dozi&nbsp; vodonik-peroksida&nbsp; od 3,0 mg H₂O₂ /mg DOC dolazi&nbsp; do formiranja HAN i hlorpikrina. Primenjeni tretman vodi ka formiranju bromovanih DBP. Svi rezultati dobijeni u toku istraživanja ukazuju na neophodnost optimizacije procesa u&nbsp; tretmanu&nbsp; ispitivanih&nbsp; vodenih&nbsp; matriksa&nbsp; i&nbsp; određivanja&nbsp; optimalnog&nbsp; procesa uzimajući&nbsp; u&nbsp; obzir<br />karakteristika&nbsp; sirove&nbsp; vode&nbsp; i&nbsp; efikasnost&nbsp; koja&nbsp; se&nbsp; želi&nbsp; postići.Kombinacijom&nbsp; dva&nbsp; i&nbsp; vi&scaron;e konvencionalnih&nbsp; tretmana&nbsp; i&nbsp; optimizacijom&nbsp; reakcionih&nbsp; uslova&nbsp; može&nbsp; se&nbsp; postići&nbsp; visoka efikasnost uklanjanja POM, kao i ciljano uklanjanje prekursorskog materijala odabranih DBP, međutim&nbsp; tretman&nbsp; vode&nbsp; ozonom&nbsp; pri&nbsp; dozi&nbsp; od&nbsp; 1,0 mg&nbsp; O₃<br />/mg&nbsp; DOC&nbsp; se&nbsp; pokazao&nbsp; kao&nbsp; optimalan proces.</p> / <p>The aim of the research&nbsp; of&nbsp; this&nbsp; PhD thesis&nbsp; was&nbsp; to determine the effects of various oxidation processes based on ozone, hydrogen peroxide and UV irradiation on the content and reactivity of natural organic matter&nbsp; (NOM)&nbsp; in different water matrices. The&nbsp; tests were carried out&nbsp; on&nbsp; a)&nbsp; groundwater&nbsp; from&nbsp; the&nbsp; territory&nbsp; of&nbsp; Kikinda&nbsp; and&nbsp; Temerin&nbsp; (natural&nbsp; matrix)&nbsp; and&nbsp; b) synthetic aqueous matrix (solution of commercially available humic&nbsp; acid), which differ in the composition&nbsp; and&nbsp; structure&nbsp; of&nbsp; NOM&nbsp; present&nbsp; and&nbsp; the&nbsp; content&nbsp; of&nbsp; bromide.&nbsp; For&nbsp; the&nbsp; oxidation process&nbsp; (ozonation,&nbsp; UV&nbsp; photolysis,&nbsp; oxidation&nbsp; with&nbsp; H 2O2 ,&nbsp; combined&nbsp; O 3 /UV&nbsp; process&nbsp; and combined&nbsp; H 2O2 /UV&nbsp; process),&nbsp; the&nbsp; influence&nbsp; of&nbsp; different&nbsp; doses&nbsp; of&nbsp; oxidants&nbsp; and&nbsp; reaction conditions&nbsp; was&nbsp; examined&nbsp; individually.&nbsp; Particular&nbsp; attention&nbsp; was&nbsp; paid&nbsp; to&nbsp; the&nbsp; influence&nbsp; of&nbsp; the above treatment on the formation of inorganic bromate, as well as the effect on the content of precursors of disinfectant by-products after chlorination (THM, HAA, HAN, HK and CP).Analysis&nbsp; of&nbsp; the&nbsp; chemical&nbsp; parameters&nbsp; of&nbsp; the&nbsp; synthetic&nbsp; matrix&nbsp; (5.44&plusmn;0.30&nbsp; mg&nbsp; C/L; 0.255&plusmn;0.015 cm -1 ;&nbsp; 4.68&plusmn;0.41&nbsp; lm -1 mg -1 )&nbsp; shows&nbsp; that&nbsp; the&nbsp; high-hydrophobic&nbsp; humic&nbsp; compounds predominate in this water. Also, high NOM content of predominantly hydrophobic character was recorded in Kikinda water (5.170.72 mg C/L; 0.2010.001 cm -1 ;&nbsp; 3.88&plusmn;0.70 lm -1 mg -1 ), while&nbsp; NOM&nbsp; content&nbsp; in&nbsp; raw&nbsp; water&nbsp; from&nbsp; Temerin&nbsp; (2.060.38&nbsp; mg&nbsp; C/L;&nbsp; 0.0500.001&nbsp; cm -1 ; 2.43&plusmn;0.21 lm -1 mg -1 ) significantly lower and predominate NOM of hydrophilic character. A higher degree of hydrophobicity of the synthetic matrix in comparison with&nbsp; natural matrices, resulted in higher reactivity of organic matter with chlorine, which can be concluded on&nbsp; the&nbsp; basis&nbsp; of&nbsp; high&nbsp; PFDBP&nbsp; values&nbsp; after&nbsp; chlorination.&nbsp; The&nbsp; PFTHM&nbsp; value&nbsp; in&nbsp; the&nbsp; synthetic matrix&nbsp; was&nbsp; 544&plusmn;85.9 &micro;g/L, while the PFTHM in the raw waters from Kikinda and Temerin was&nbsp; significantly&nbsp; lower&nbsp; (279&plusmn;32.3&nbsp; and&nbsp; 180&plusmn;44.0&nbsp; &micro;g/L,&nbsp; respectively).&nbsp; The&nbsp; PFHAA&nbsp; value&nbsp; in the&nbsp; synthetic&nbsp; matrix&nbsp; was&nbsp; 484&plusmn;77.5&nbsp; &micro;g/L,&nbsp; while&nbsp; PFHAA&nbsp; in&nbsp; the&nbsp; Kikinda&nbsp; water&nbsp; was 223 244&plusmn;11.1 &micro;g/L&nbsp; and in&nbsp; the&nbsp; Temerin&nbsp; water&nbsp; was&nbsp; 165&plusmn;32.5 &micro;g/L.&nbsp; The content of&nbsp; precursors of HK&nbsp; (8.05&plusmn;3.63&nbsp; &micro;g/L&nbsp; synthetic&nbsp; matrix;&nbsp; 14.91.38&nbsp; &micro;g/L&nbsp; Kikinda;&nbsp; 7.400.25&nbsp; &micro;g/L&nbsp; Temerin) was&nbsp; significantly&nbsp; lower&nbsp; compared&nbsp; to&nbsp; precursors&nbsp; of&nbsp; THMs&nbsp; and&nbsp; HAAs,&nbsp; while&nbsp; precursors&nbsp; of HANs&nbsp; and&nbsp; chloropicrin&nbsp; were&nbsp; not&nbsp; detected&nbsp; in&nbsp; raw&nbsp; water.&nbsp; The&nbsp; by- products&nbsp; that&nbsp; were predominantly&nbsp; formed&nbsp; in&nbsp; all&nbsp; the&nbsp; tested&nbsp; water&nbsp; matrices&nbsp; were&nbsp; chlorinated&nbsp; THMs&nbsp; and&nbsp; HAAs, while the brominated DBPs&nbsp; were&nbsp; formed at substantially lower concentrations. The presence of&nbsp; brominated DBPs&nbsp; in&nbsp; Temerine&nbsp; water&nbsp; were&nbsp; significantly higher compared to Kikinda water as&nbsp; a&nbsp; result&nbsp; of&nbsp; the&nbsp; presence&nbsp; of&nbsp; higher&nbsp; bromide&nbsp; content&nbsp; in&nbsp; raw&nbsp; water&nbsp; (0.05&plusmn;0.01&nbsp; mg&nbsp; Br -/L Temerin; 0.03&plusmn;0.01 mg Br -/L Kikinda). By&nbsp; examining&nbsp; the&nbsp; influence&nbsp; of&nbsp; oxidation&nbsp; processes&nbsp; (UV&nbsp; photolysis,&nbsp; ozonation,hydrogen&nbsp; peroxide&nbsp; oxidation)&nbsp; on&nbsp; the&nbsp; content&nbsp; and&nbsp; reactivity&nbsp; of&nbsp; NOM&nbsp; in&nbsp; the&nbsp; tested&nbsp; water matrix, it was&nbsp; found that the UV&nbsp; irradiation and&nbsp; treatment by&nbsp; hydrogen peroxide, when used as an independent treatment, did&nbsp; not show significant efficacy in reducing the&nbsp; NOM content. Water treatment by ozone&nbsp; proved to be very effective in eliminating&nbsp; NOM and reducing the content of DBP precursors in all tested water&nbsp; matrices, as a result of the reduction of&nbsp; NOM reactivity &nbsp; to&nbsp; the&nbsp; formation&nbsp; of&nbsp; these&nbsp; DBPs.&nbsp; Reduction&nbsp; of&nbsp; NOM&nbsp; content&nbsp; in&nbsp; water&nbsp; during treatment increased&nbsp; with increasing the applied dose of ozone, with the best results achieved at the highest dosage of&nbsp; 3.0 mg O 3/mg DOC&nbsp; (up to 32% DOC, 92% UV 254&nbsp; synthetic matrix, up&nbsp; to&nbsp; 17%&nbsp; DOC,&nbsp; 76%&nbsp; UV 254 Kikinda,&nbsp; up&nbsp; to&nbsp; 15%&nbsp; DOC&nbsp; and&nbsp; 66%&nbsp; UV254 Temerin).&nbsp; In&nbsp; the synthetic&nbsp; matrix the highest reduction&nbsp; in&nbsp; PFTHM (76%) and PFHAA (by 80%)&nbsp; compared to raw water content&nbsp; was&nbsp; achieved at a dosage&nbsp; of 1.0 mg O 3/mg DOC. The highest reduction in PFTHM&nbsp; (38%)&nbsp; and&nbsp; PFHAA&nbsp; (42%)&nbsp; in&nbsp; Kikinda&nbsp; water&nbsp; was&nbsp; achieved&nbsp; at&nbsp; a&nbsp; dose&nbsp; of 3.0 mg O3 /mg DOC. In Temerin water, the highest reduction in PFTHM (27%) was at a dose of&nbsp; 3.0 mg O 3/mg DOC, while the dose of 1.0&nbsp; mg O3 /mg&nbsp; DOC&nbsp; was best shown for removing PFHAA (by 54%). The content of the precursors of HKs and HANs (Temerin water) was very low&nbsp; after&nbsp; treatment.&nbsp; Water&nbsp; treatment&nbsp; by&nbsp; ozone&nbsp; led&nbsp; to&nbsp; the&nbsp; formation&nbsp; of&nbsp; DBPs&nbsp; with&nbsp; more substituted bromine atoms, while in waters with a mean bromide content (50 &mu;g Br -/L) led&nbsp; to bromate formation.Combination of ozonation with UV irradiation can greatly accelerate the effectiveness of&nbsp; NOM&nbsp; removal&nbsp; achieved&nbsp; by&nbsp; the&nbsp; use&nbsp; of&nbsp; ozonation&nbsp; alone.&nbsp; The&nbsp; highest&nbsp; reduction&nbsp; in&nbsp; NOM content in the synthetic matrix (by 85% DOC, 98% UV 254 and 87% SUVA), in Kikinda water (by 23%&nbsp; DOC, 83% UV 254 , 77% SUVA) and water from Temerin (by 15% DOC, 80% UV 254 and 75% SUVA), compared to the values in&nbsp; raw&nbsp; water, was achieved at the highest&nbsp; dose of 3.0&nbsp; mg&nbsp; O 3 /mg&nbsp; DOC&nbsp; and&nbsp; 6000&nbsp; mJ/cm 2 .&nbsp; The&nbsp; efficiency&nbsp; of&nbsp; the&nbsp; process&nbsp; was&nbsp; growing&nbsp; in&nbsp; the waters where NOM predominates of hydrophobicity. Although the O 3 /UV process achieved a high&nbsp; degree&nbsp; of&nbsp; reduction&nbsp; in&nbsp; PFTHM&nbsp; in&nbsp; the&nbsp; synthetic&nbsp; matrix&nbsp; the&nbsp; ozonation (1.0 mg O3 /mg DOC)&nbsp; was&nbsp; proved&nbsp; as&nbsp; more&nbsp; efficient,&nbsp; while&nbsp; the&nbsp; highest&nbsp; reduction&nbsp; in&nbsp; PFHAA (82%)&nbsp; was&nbsp; achieved&nbsp; at&nbsp; a&nbsp; ozone&nbsp; dose&nbsp; of&nbsp; 1.0&nbsp; mg&nbsp; O 3/mg&nbsp; DOC&nbsp; and&nbsp; UV&nbsp; irradiation&nbsp; of 6000 mJ/cm 2 . In the water from Temerin,&nbsp; in case to removal of precursors of THM and HAA, ozonation&nbsp; was proved&nbsp; to be an optimal process. High alkalinity of natural waters&nbsp; inhibits the radical &nbsp; mechanism&nbsp; during&nbsp; AOP&nbsp; and&nbsp; favors&nbsp; NOM&nbsp; oxidation&nbsp; with&nbsp; molecular&nbsp; ozone.&nbsp; HKs precursors were formed at very low concentrations and their content did not vary significantly during&nbsp; the&nbsp; treatment.&nbsp; In&nbsp; natural&nbsp; matrices&nbsp; during&nbsp; the&nbsp; AOP&nbsp; at&nbsp; a&nbsp; ozone&nbsp;&nbsp; dose&nbsp; of 3.0 mg O3 /mgDOC, HANs&nbsp; were&nbsp; formed, however, there&nbsp; was&nbsp; no clear trend with increasing UV irradiation. The treatment contributed to the formation of brominated THM species, while during&nbsp; the&nbsp; AOPs,&nbsp; brominated&nbsp; HANs&nbsp; were&nbsp; formed&nbsp; at&nbsp; the&nbsp; maximum&nbsp; dose&nbsp; of&nbsp; ozone&nbsp; of 3.0 mg O3/mg DOC. 224 The largest decrease in&nbsp; NOM content by the combination of oxidation with H2O2 and UV irradiation in the synthetic matrix (for up to 17% DOC, 70% UV 254 ), in Kikinda water (up to 22% DOC, 53% UV 254), and water from Temerin&nbsp; (7% DOC, 68% UV 254 ), compared&nbsp; to the values&nbsp; in&nbsp; raw&nbsp; water,&nbsp; were&nbsp; obtained&nbsp; at&nbsp; a&nbsp; dose&nbsp; of&nbsp; H 2O2 and&nbsp; UV&nbsp; irradiation&nbsp; of 3.0 mg O3 /mg DOC&nbsp; and 6000 mJ/cm 2 . The highest PFTHM reduction of 54% in the&nbsp; synthetic matrix was achieved at a dosage of 1.0 mg H2O2/mg DOC and 6000 mJ/cm 2 , while a decrease in&nbsp; PFHAA&nbsp; (35%)&nbsp; was&nbsp; achieved&nbsp; using&nbsp; a&nbsp; dose&nbsp; of&nbsp; hydrogen&nbsp; peroxide&nbsp; and&nbsp; UV&nbsp; irradiation&nbsp; of 1.0 mg H2O2/mg DOC and 3000 mJ/cm 2 . In the water from Kikinda, the H2O2 /UV process did not significantly affect on the THM precursors content, while the highest reduction in PFHAA (35%)&nbsp; was&nbsp; achieved&nbsp; at&nbsp; a&nbsp; dose&nbsp; of&nbsp; 3.0&nbsp; mg&nbsp; H2O2/mg&nbsp; DOC&nbsp; and&nbsp; 600&nbsp; mJ/cm 2 .&nbsp; The&nbsp; H 2O2 /UV process&nbsp; led&nbsp; to&nbsp; a&nbsp; decrease&nbsp; in&nbsp; PFTHM&nbsp; in&nbsp; the&nbsp; Temerin&nbsp; water&nbsp; by&nbsp; 74%&nbsp; at&nbsp; a&nbsp; dose&nbsp; of 3.0 mg&nbsp; 2O2 /mg&nbsp; DOC&nbsp; and&nbsp; 600&nbsp; mJ/cm 2 ,&nbsp; whereas&nbsp; the&nbsp; treatment&nbsp; applied&nbsp; had&nbsp; no&nbsp; significant effect on PFHAA. HKs precursors were detected in synthetic matrix and the Temerin water at low&nbsp; concentrations.&nbsp; In&nbsp; the&nbsp; water&nbsp; after&nbsp; the&nbsp; AOP&nbsp; at&nbsp; a&nbsp; dose&nbsp; of&nbsp; 3.0&nbsp; mg&nbsp; H 2O2 /mg&nbsp; DOC&nbsp; of hydrogen&nbsp; peroxide,&nbsp; HANs&nbsp; and&nbsp; chloropicrin&nbsp; were&nbsp; formed.&nbsp; The&nbsp; applied&nbsp; treatment&nbsp; led&nbsp; to&nbsp; the formation of brominated DBPs.<br />All the results obtained during the research indicate the necessity of optimization&nbsp; the process&nbsp; in&nbsp; the&nbsp; treatment&nbsp; of&nbsp; the&nbsp; examined&nbsp; water&nbsp; matrices&nbsp; and&nbsp; determination&nbsp; of&nbsp; the&nbsp; optimal process taking into account the characteristics of&nbsp; raw water and the efficiency to be achieved. By combining two or more conventional treatments and optimizing the reaction conditions, high&nbsp; NOM removal efficiency can be achieved, as well as removal of the&nbsp; targeted&nbsp; precursor material&nbsp; of&nbsp; the&nbsp; selected&nbsp; DBPs,&nbsp; but&nbsp; the&nbsp; treatment&nbsp; of&nbsp; ozone&nbsp; water&nbsp; at&nbsp; a&nbsp; dose&nbsp; of 1.0 mg O3 /mg DOC was proved to be an optimal process.</p>

Tesis por compendio / [ES] Los procesos (foto-)Fenton fueron empleados para degradar fluoroquinolonas (FQ) (una clase de antibióticos sintéticos considerados CEC) como contaminantes modelo en diferentes condiciones: pH (3 - 8), concentración de contaminante (3 - 300 μM), número de FQ presentes (1, 3 y 5), y matrices de agua (agua ultrapura, salina y de WWTP simulada). Los experimentos se realizaron a escala banco y planta piloto, empleando luz solar (simulada y real) e irradiaciones con luz ultravioleta. Las velocidades de degradación de los contaminantes obtenidas con procesos tipo-Fenton se compararon con las análogas de fotólisis, fotocatálisis heterogénea y H2O2/UV. En igualdad de condiciones, solo a través del proceso foto-Fenton se logró una mineralización significativa de las FQs. En aquellos casos en los que el carbono orgánico total no mostró una disminución considerable, la razón se atribuye a la liberación de subproductos de oxidación. EEM-PARAFAC ha demostrado ser una técnica económica, veloz y que no requiere del uso de reactivos, para seguir simultáneamente la eliminación de la degradación de hasta 5 FQs fluorescentes presentes en una misma muestra, en presencia de interferencias sin calibrar, y obtener información sobre las posibles estructuras moleculares de los intermediarios de reacción. Los resultados indicaron que la fotólisis por sí sola no es capaz de producir cambios importantes en la estructura de las FQs, mientras que con (foto-)Fenton sí que se observó una notable disminución de los scores de los componentes PARAFAC asociados con los compuestos del tipo FQ. Los ensayos de zona de inhibición empleando E. coli mostraron que la actividad antibiótica disminuyó en paralelo con la desintegración de todos los componentes PARAFAC relacionados con las FQs y subproductos similares a estas. El otro aspecto importante de la tesis fue el uso de procesos Fenton basados en ZVI. Algunos CEC, como los compuestos nitroaromáticos, exhiben tasas de degradación lentas incluso cuando son degradadas por una AOP. El desarrollo de trenes de tratamiento ZVI para la degradación de contaminantes ha despertado un gran interés en los últimos años. Este enfoque consiste en un primer pretratamiento solo con ZVI (es decir, reducción, deshalogenación), seguido del proceso Fenton aprovechando los iones de hierro liberados en el primer paso. Con el fin de analizar las posibles ventajas e inconvenientes de esta estrategia en las aplicaciones de tratamiento de aguas residuales, se ha estudiado este enfoque empleando micropartículas de ZVI (mZVI) comerciales utilizando ácido p-nitrobenzoico (PNBA) como contaminante modelo. Se analizó el efecto de la cantidad inicial de mZVI, H2O2, pH, conductividad, aniones y oxígeno disuelto. Utilizando agua natural en condiciones aeróbicas, pH inicial 3,0, y adicionando 1,4 g/L de mZVI, se consiguió en 2 h una reducción del 83% de PNBA 6 μM en ácido p-aminobenzoico (PABA). Se investigó también la conveniencia de separar las mZVI después de la fase reductora (antes de la etapa Fenton) así como la reutilización de las mZVI. El paso de Fenton contra el PABA, más reactivo que PNBA, requirió 50 mg/L de H2O2 para lograr una eliminación de más del 96% en 15 min a pH 7,5 (pH final del pretratamiento reductivo). Las mZVI reutilizadas fueron efectivas por lo menos por un ciclo completo (reducción/oxidación). Este enfoque puede ser interesante para tratar aguas residuales que contienen contaminantes inicialmente resistentes al radical hidroxilo (HO), pero fácilmente reducibles, pudiendo disminuir su carga tóxica y aumentar su reactividad para un paso de oxidación posterior. / [CA] Fenton i foto-Fenton van ser emprats per a degradar fluoroquinolones (FQ) (una classe d'antibiòtics sintètics considerats CEC) com a contaminants model en diferents condicions: pH (3 - 8), concentració de contaminant (3 - 300 μM), nombre de FQ presents (1, 3 i 5), i matriu d'aigua (aigua ultrapura, salada i de WWTP simulada). Els experiments es van realitzar a escala de laboratori i planta pilot, emprant llum solar (simulada i real) i irradiacions amb llum ultraviolada. Les velocitats de degradació de contaminants obtingudes amb processos tipus-Fenton es van comparar amb fotòlisi, fotocatàlisi heterogènia i H2O2/UV. En igualtat de condicions, només a través del procés foto-Fenton es va aconseguir una mineralització significativa de FQ. En aquells casos en els quals el carboni orgànic total no va mostrar una disminució considerable, la raó s'atribueix a l'alliberament de subproductes d'oxidació. EEM-PARAFAC ha demostrat ser una tècnica econòmica, que no requereix de l'ús de reactius, i ràpida, per a seguir simultàniament l'eliminació de la degradació de fins a 5 FQ fluorescents presents en una mateixa mostra, en presència d'interferències sense calibrar, i obtindre informació sobre les possibles estructures moleculars dels intermediaris de reacció. Els resultats van indicar que la fotòlisi per si sola no és capaç de produir canvis importants en l'estructura de les FQ, mentre que amb (foto-)Fenton, sí que es va observar una notable disminució dels scores dels components PARAFAC associats amb el nucli de FQ. Els assajos de zona d'inhibició que empren E. coli van mostrar que l'activitat antibiòtica va disminuir en paral·lel amb la desintegració de tots els components PARAFAC relacionats amb FQ i subproductes similars a FQ. L'altre aspecte important de la tesi va ser l'ús de processos Fenton basats en ZVI. Alguns CEC, com els compostos nitroaromàtics, exhibeixen taxes de degradació lentes fins i tot quan són degradats per un AOP. El desenvolupament de trens de tractament basats en ZVI per a la degradació de contaminants ha despertat un gran interés en els últims anys. Aquesta aproximaciót consisteix en un primer pretractament amb ZVI (és a dir, reducció, deshalogenación), seguit del procés Fenton aprofitant els ions de ferro alliberats en el primer pas. Amb la finalitat d'analitzar els possibles avantatges i inconvenients d'aquesta estratègia en les aplicacions de tractament d'aigües residuals, s'han emprat micropartícules de ZVI (mZVI) comercials. Utilitzant àcid p-nitrobenzoic (PNBA) com a contaminant model, es va analitzar l'efecte de la quantitat inicial de mZVI, H2O2, pH, conductivitat, anions i oxigen dissolt. Utilitzant aigua natural en condicions aeròbiques, pH inicial 3,0, i addicionant 1,4 g/L de mZVI, es va aconseguir en 2 h una reducció del 83% de PNBA 6 μM a àcid p-aminobenzoic (PABA). Es va investigar també la conveniència d'eliminar les mZVI després de la fase reductora (abans de l'etapa Fenton) així com la reutilització de les mZVI. El pas de Fenton front el PABA, més reactiu que PNBA, va requerir 50 mg/L de H2O2 per a aconseguir una eliminació de més del 96% en 15 min a pH 7,5 (pH final del pretractament reductiu). Les mZVI reutilitzades van ser efectives almenys amb un cicle complet (reducció/oxidació). Aquest enfocament pot ser interessant per a tractar aigües residuals que contenen contaminants inicialment resistents al HO, però que es redueixen fàcilment, podent disminuir la seua càrrega tòxica i augmentar la seua reactivitat per a un pas d'oxidació posterior. / [EN] Dark Fenton and photo-Fenton were employed to degrade Fluoroquinolones (FQs) (a class of synthetic antibiotics considered CEC) as model pollutants under different conditions: pH (3 - 8), pollutant concentration (3 - 300 μM), number of present FQs (1, 3 and 5), and water matrix (ultra-pure, salty and simulated wastewater). Experiments were performed at bench and pilot plant scales, employing sunlight (simulated and real) and ultraviolet light irradiations. Obtained pollutant abatement rates with Fenton-related processes were compared with photolysis, heterogeneous photocatalysis and H2O2/UV. At equal conditions, only through photo-Fenton process significant FQs mineralization were achieved. In those cases where total organic carbon had not exhibit a considerable decrease, the reason was attributed to the release of oxidation by-products. Since FQs are fluorescent, we decided to employ fluorescence excitation-emission matrices (EEM) in combination with the chemometric tool, Parallel Factor Analysis (PARAFAC), to track their degradations. Although EEM-PARAFAC related studies are usually focused towards the characterization and monitoring of dissolved organic matter (DOM) in natural waters and wastewater effluents (work also included in this PhD Thesis following the DOM along the different stages of a drinking water plant), it is barely the first time that it is used for the purposes we have here proposed. The objective is demonstrating that EEM-PARAFAC could be a feasible complementary methodology for the study of fluorescent CECs degradations, avoiding the use of expensive and sophisticated techniques (e.g mass spectrometry), not always available. The other important aspect of the PhD Thesis was the use of ZVI-based Fenton processes. Some CECs such as nitroaromatic compounds, exhibit slow degradation rates even with AOPs. The development of new and more efficient ZVI treatment trains for pollutant degradation has been attracting great interest in the last few years. This approach consists of a first pre-treatment only with ZVI (i.e. reduction, dehalogenation), followed by a Fenton oxidation taking advantage of the released iron ions from the first step. In order to analyse the strategy's plausible advantages and potential drawbacks within wastewater treatment applications, reductive/oxidative treatment train based on commercial ZVI microparticles (mZVI) has been studied. The effect of the initial amount of mZVI, H2O2, pH, conductivity, anions, dissolved oxygen were analysed using p-nitrobenzoic acid (PNBA) as model pollutant. 83% reduction of PNBA 6 μM into p-aminobenzoic acid (PABA) was achieved in natural water at initial pH 3.0 and 1.4 g/L of mZVI under aerobic conditions in 2 h. An evaluation of the convenience of removing mZVI after the reductive phase (before the Fenton oxidation one) was investigated together with mZVI reusability. The Fenton step against the more reactive PABA required 50 mg/L of H2O2 to achieve more than 96% removal in 15 min at pH 7.5 (final pH from the pre-reductive step). At least one complete reuse cycle (reduction/oxidation) was obtained with the separated mZVI. This approach might be interesting to treat wastewater containing pollutants initially resistant to hydroxyl radical (HO), but easily reduced, being able to decrease its toxic load as well as increasing its reactivity for a subsequent oxidation step. / Sciscenko, IM. (2021). Emerging Photochemical Processes Involving Iron for Wastewater Treatment [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/177357 / Compendio