This dissertation presents experimental and instrumentation developments that take full advantage of the multidimensional nature of line narrowing spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2 K) temperatures. The inconvenience of sample freezing procedures is eliminated with the aid of cryogenic fiber optic probes. Rapid collection of multidimensional data formats such as wavelength time matrices, excitation emission matrices, time-resolved excitation emission matrices and time resolved excitation emission cubes is made possible with the combination of a pulsed tunable dye laser, a spectrograph and an intensifier-charged coupled device. These data formats provide unique opportunities for processing vibrational luminescence data with second order multivariate calibration algorithms. The use of cryogenic fiber optic probes is extended to commercial instrumentation. An attractive feature of spectrofluorimeters with excitation and emission monochromators is the possibility to record synchronous spectra. The advantages of this approach, which include narrowing of spectral bandwidth and simplification of emission spectra, were demonstrated with the direct analysis of highly toxic dibenzopyrene isomers. The same is true for the collection of steady-state fluorescence excitation-emission matrices. These approaches provide a general solution to unpredictable spectral interference, a ubiquitous problem for the analysis of organic pollutants in environmental samples of unknown composition. Since commercial spectrofluorimeters are readily available in most academic institutions, industrial settings and research institutes, the developments presented here should facilitate the widespread application of line-narrowing spectroscopic techniques to the direct determination, no chromatographic separation, of highly toxic compounds in complex environmental matrixes of unknown composition.

Este projeto nasceu inserido num contexto de crescentes pesquisas em direção à construção de um cabedal de conhecimento acerca das ciências ambientais que tratam e estudam a dinâmica dos reservatórios de carbono e suas contribuições para o Efeito Estufa. Extrapolações de novos mapas digitalizados de solos sugerem que os espodossolos hidromórficos da Amazônia podem estar com uma contagem de carbono subestimada em até 12,3 Pg de C e trabalhos anteriores mostram que o carbono imobilizado neste perfil pode sofrer mineralização devido ao corte na rede de drenagem ou rebaixamento do nível freático, podendo assim contribuir em grande parte para o aumento de emissão dos Gases do Efeito Estufa. Nesta circunstância, coube a este trabalho, caracterizar espectroscopicamente, a matéria orgânica estocada em profundidade em 9 perfis de solo da região de São Gabriel da Cachoeira - AM, na floresta amazônica. Foram analisadas 127 amostras em quantidade de carbono e por fluorescência induzida por laser (FIL). A partir destas análises preliminares, foi possível selecionar 12 amostras de 2 perfis para análise mais detalhada através da extração das substâncias húmicas. Foram realizadas análises para obtenção da textura destes perfis, análise dos ácidos húmicos como relação C/N, espectroscopia de infravermelho com transformada de Fourier (FTIR), RMN de 13C no estado sólido, fluorescências bidimensional e tridimensional com aplicação do método estatístico análise dos fatores paralelos (PARAFAC) e também análise dos ácidos fúlvicos como carbono orgânico total (TOC), espectroscopia na região do ultra-violeta e visível e fluorescência 3D associada ao PARAFAC. Em geral, as amostras se dividiram em 3 grupos diferentes, onde a matéria orgânica em superfície se mostrou lábil e recente, a matéria orgânica nos horizontes B húmicos se mostraram com características recalcitrantes e a matéria orgânica contida nos horizontes onde existia água livre (lençol freático), se mostraram com características diferentes, indicando não serem tão jovens quanto as em superfície, porém mais jovens do que a armazenada no Bh, devido a uma possível migração por movimentos laterais do lençol freático. A correlação entre os resultados mostrou que a textura do solo é importante para o acúmulo da matéria orgânica e conseqüentemente sua humificação. Os resultados de fluorescência corroboraram a interpretação dos dados de RMN, FTIR e textura, apontando que o Perfil 4 (mais próximo ao rio) por ter C2 maior nos horizontes intermediários, contém maior quantidade de exsudatos microbianos frescos. Para o Perfil 5, que é uma mancha de Espodossolo dentro de um Latossolo e encontra-se mais longe do rio, os fluoróforos mais representativos são oriundos de anéis aromáticos mais antigos e conseqüentemente mais humificados, devido às maiores intensidades de C1 e C3. Vale ressaltar que esta interpretação se alinha com os resultados de datação do 14C desta região. Foi notório que a humificação ocorre a partir do começo do horizonte Bh e que seu acúmulo pode ocorrer tanto nos horizontes intermediários (Bh) quanto mais os profundos (úmidos). Dessa forma, pode-se concluir que uma drenagem excessiva das bordas dos rios nesta região que acumula carbono em profundidade, poderá expor a MO guardada e estocada a longo tempo, contribuindo para o aumento da temperatura global e por conseguinte catalisando um desequilíbrio no clima da sua maior reguladora no mundo: a Floresta Amazônica. / This project was born inserted in a context of increasing research towards building knowledge about environmental science that treat and study the dynamics of carbon reservoirs and their contribution to the greenhouse. Extrapolation of new digital soil maps suggests that Amazonian hydromorphic Spodosols may be with a carbon accounting underestimated by up to 12.3 Pg of C and previous work show that the carbon fixed in this profile may suffer mineralization due to the cut in the drainage network or lowering of the water level and can contribute largely to the increased emission of greenhouse gas. In this circumstance, it was instructed to this work, the spectroscopic characterization, of the stored organic matter in depth at 9 soil profiles of São Gabriel da Cachoeira - AM, in the Amazon rainforest. 127 samples were analyzed for amount of carbon and laser-induced fluorescence (LIF). From these preliminary analyzes, it was possible to select 12 samples of 2 profiles for humic substances extraction and further detailed analysis. Analyzes were conducted to obtain the texture of these profiles, analysis of humic acids as C/N ratio, Fourier Transform Infrared Spectroscopy (FTIR), solid state 13C NMR, two and three dimensional fluorescence with applying of the Parallel factors analysis (PARAFAC) statistical method and also fulvic acid analysis as Total Organic Carbon (TOC), ultra-violet and visible region spectroscopy and 3D fluorescence associated with PARAFAC. In general, the samples were divided into 3 different groups, wherein the surface organic matter evinced labile and recent. The B humic horizons organic matter proved recalcitrant characteristics and organic matter contained in horizons which had free water (groundwater), showed different characteristic, indicating they are not so young as the surface, but younger than stored in Bh, because of possible migration by lateral movements of the water table. The correlation between the results showed that soil texture is important for the accumulation of organic matter and therefore its humification. The fluorescence results confirmed the interpretation of the NMR, FTIR and texture datas, indicating that the profile 4 (closest to the river), presenting major C2 in intermediate horizons, contains larger amount of fresh microbial exudates. To profile 5, which is a Spodosol spot within a Ferrasol and is thither from the river, the most representative fluorophores came from older aromatic rings and therefore is more humified, due to higher intensities C1 and C3. It is noteworthy that this interpretation is in accord with the results of 14C dating of samples from this region. It was clear that the humification occurs from the beginning of the Bh horizon and their accumulation can occur both in the intermediate horizons (Bh) and in deeper (wet). Thus, it can be concluded that excessive drainage of the edges of rivers in this region that collects carbon in depth, may expose the OM stored for long time, contributing to increase the overall temperature and therefore catalyzing an imbalance in the climate of the biggest regulatory of it in the world: the Amazon rainforest.

Este projeto nasceu inserido num contexto de crescentes pesquisas em direção à construção de um cabedal de conhecimento acerca das ciências ambientais que tratam e estudam a dinâmica dos reservatórios de carbono e suas contribuições para o Efeito Estufa. Extrapolações de novos mapas digitalizados de solos sugerem que os espodossolos hidromórficos da Amazônia podem estar com uma contagem de carbono subestimada em até 12,3 Pg de C e trabalhos anteriores mostram que o carbono imobilizado neste perfil pode sofrer mineralização devido ao corte na rede de drenagem ou rebaixamento do nível freático, podendo assim contribuir em grande parte para o aumento de emissão dos Gases do Efeito Estufa. Nesta circunstância, coube a este trabalho, caracterizar espectroscopicamente, a matéria orgânica estocada em profundidade em 9 perfis de solo da região de São Gabriel da Cachoeira - AM, na floresta amazônica. Foram analisadas 127 amostras em quantidade de carbono e por fluorescência induzida por laser (FIL). A partir destas análises preliminares, foi possível selecionar 12 amostras de 2 perfis para análise mais detalhada através da extração das substâncias húmicas. Foram realizadas análises para obtenção da textura destes perfis, análise dos ácidos húmicos como relação C/N, espectroscopia de infravermelho com transformada de Fourier (FTIR), RMN de 13C no estado sólido, fluorescências bidimensional e tridimensional com aplicação do método estatístico análise dos fatores paralelos (PARAFAC) e também análise dos ácidos fúlvicos como carbono orgânico total (TOC), espectroscopia na região do ultra-violeta e visível e fluorescência 3D associada ao PARAFAC. Em geral, as amostras se dividiram em 3 grupos diferentes, onde a matéria orgânica em superfície se mostrou lábil e recente, a matéria orgânica nos horizontes B húmicos se mostraram com características recalcitrantes e a matéria orgânica contida nos horizontes onde existia água livre (lençol freático), se mostraram com características diferentes, indicando não serem tão jovens quanto as em superfície, porém mais jovens do que a armazenada no Bh, devido a uma possível migração por movimentos laterais do lençol freático. A correlação entre os resultados mostrou que a textura do solo é importante para o acúmulo da matéria orgânica e conseqüentemente sua humificação. Os resultados de fluorescência corroboraram a interpretação dos dados de RMN, FTIR e textura, apontando que o Perfil 4 (mais próximo ao rio) por ter C2 maior nos horizontes intermediários, contém maior quantidade de exsudatos microbianos frescos. Para o Perfil 5, que é uma mancha de Espodossolo dentro de um Latossolo e encontra-se mais longe do rio, os fluoróforos mais representativos são oriundos de anéis aromáticos mais antigos e conseqüentemente mais humificados, devido às maiores intensidades de C1 e C3. Vale ressaltar que esta interpretação se alinha com os resultados de datação do 14C desta região. Foi notório que a humificação ocorre a partir do começo do horizonte Bh e que seu acúmulo pode ocorrer tanto nos horizontes intermediários (Bh) quanto mais os profundos (úmidos). Dessa forma, pode-se concluir que uma drenagem excessiva das bordas dos rios nesta região que acumula carbono em profundidade, poderá expor a MO guardada e estocada a longo tempo, contribuindo para o aumento da temperatura global e por conseguinte catalisando um desequilíbrio no clima da sua maior reguladora no mundo: a Floresta Amazônica. / This project was born inserted in a context of increasing research towards building knowledge about environmental science that treat and study the dynamics of carbon reservoirs and their contribution to the greenhouse. Extrapolation of new digital soil maps suggests that Amazonian hydromorphic Spodosols may be with a carbon accounting underestimated by up to 12.3 Pg of C and previous work show that the carbon fixed in this profile may suffer mineralization due to the cut in the drainage network or lowering of the water level and can contribute largely to the increased emission of greenhouse gas. In this circumstance, it was instructed to this work, the spectroscopic characterization, of the stored organic matter in depth at 9 soil profiles of São Gabriel da Cachoeira - AM, in the Amazon rainforest. 127 samples were analyzed for amount of carbon and laser-induced fluorescence (LIF). From these preliminary analyzes, it was possible to select 12 samples of 2 profiles for humic substances extraction and further detailed analysis. Analyzes were conducted to obtain the texture of these profiles, analysis of humic acids as C/N ratio, Fourier Transform Infrared Spectroscopy (FTIR), solid state 13C NMR, two and three dimensional fluorescence with applying of the Parallel factors analysis (PARAFAC) statistical method and also fulvic acid analysis as Total Organic Carbon (TOC), ultra-violet and visible region spectroscopy and 3D fluorescence associated with PARAFAC. In general, the samples were divided into 3 different groups, wherein the surface organic matter evinced labile and recent. The B humic horizons organic matter proved recalcitrant characteristics and organic matter contained in horizons which had free water (groundwater), showed different characteristic, indicating they are not so young as the surface, but younger than stored in Bh, because of possible migration by lateral movements of the water table. The correlation between the results showed that soil texture is important for the accumulation of organic matter and therefore its humification. The fluorescence results confirmed the interpretation of the NMR, FTIR and texture datas, indicating that the profile 4 (closest to the river), presenting major C2 in intermediate horizons, contains larger amount of fresh microbial exudates. To profile 5, which is a Spodosol spot within a Ferrasol and is thither from the river, the most representative fluorophores came from older aromatic rings and therefore is more humified, due to higher intensities C1 and C3. It is noteworthy that this interpretation is in accord with the results of 14C dating of samples from this region. It was clear that the humification occurs from the beginning of the Bh horizon and their accumulation can occur both in the intermediate horizons (Bh) and in deeper (wet). Thus, it can be concluded that excessive drainage of the edges of rivers in this region that collects carbon in depth, may expose the OM stored for long time, contributing to increase the overall temperature and therefore catalyzing an imbalance in the climate of the biggest regulatory of it in the world: the Amazon rainforest.

<p>In this thesis some multivariate spectroscopic methods for the analysis of solutions are proposed. Spectroscopy and multivariate data analysis form a powerful combination for obtaining both quantitative and qualitative information and it is shown how spectroscopic techniques in combination with chemometric data evaluation can be used to obtain rapid, simple and efficient analytical methods. These spectroscopic methods consisting of spectroscopic analysis, a high level of automation and chemometric data evaluation can lead to analytical methods with a high analytical capacity, and for these methods, the term high-capacity analysis (HCA) is suggested. It is further shown how chemometric evaluation of the multivariate data in chromatographic analyses decreases the need for baseline separation. </p><p>The thesis is based on six papers and the chemometric tools used are experimental design, principal component analysis (PCA), soft independent modelling of class analogy (SIMCA), partial least squares regression (PLS) and parallel factor analysis (PARAFAC). The analytical techniques utilised are scanning ultraviolet-visible (UV-Vis) spectroscopy, diode array detection (DAD) used in non-column chromatographic diode array UV spectroscopy, high-performance liquid chromatography with diode array detection (HPLC-DAD) and fluorescence spectroscopy. The methods proposed are exemplified in the analysis of pharmaceutical solutions and serum proteins.</p><p>In Paper I a method is proposed for the determination of the content and identity of the active compound in pharmaceutical solutions by means of UV-Vis spectroscopy, orthogonal signal correction and multivariate calibration with PLS and SIMCA classification. Paper II proposes a new method for the rapid determination of pharmaceutical solutions by the use of non-column chromatographic diode array UV spectroscopy, i.e. a conventional HPLC-DAD system without any chromatographic column connected. In Paper III an investigation is made of the ability of a control sample, of known content and identity to diagnose and correct errors in multivariate predictions something that together with use of multivariate residuals can make it possible to use the same calibration model over time. In Paper IV a method is proposed for simultaneous determination of serum proteins with fluorescence spectroscopy and multivariate calibration. Paper V proposes a method for the determination of chromatographic peak purity by means of PCA of HPLC-DAD data. In Paper VI PARAFAC is applied for the decomposition of DAD data of some partially separated peaks into the pure chromatographic, spectral and concentration profiles. </p>

In this thesis some multivariate spectroscopic methods for the analysis of solutions are proposed. Spectroscopy and multivariate data analysis form a powerful combination for obtaining both quantitative and qualitative information and it is shown how spectroscopic techniques in combination with chemometric data evaluation can be used to obtain rapid, simple and efficient analytical methods. These spectroscopic methods consisting of spectroscopic analysis, a high level of automation and chemometric data evaluation can lead to analytical methods with a high analytical capacity, and for these methods, the term high-capacity analysis (HCA) is suggested. It is further shown how chemometric evaluation of the multivariate data in chromatographic analyses decreases the need for baseline separation. The thesis is based on six papers and the chemometric tools used are experimental design, principal component analysis (PCA), soft independent modelling of class analogy (SIMCA), partial least squares regression (PLS) and parallel factor analysis (PARAFAC). The analytical techniques utilised are scanning ultraviolet-visible (UV-Vis) spectroscopy, diode array detection (DAD) used in non-column chromatographic diode array UV spectroscopy, high-performance liquid chromatography with diode array detection (HPLC-DAD) and fluorescence spectroscopy. The methods proposed are exemplified in the analysis of pharmaceutical solutions and serum proteins. In Paper I a method is proposed for the determination of the content and identity of the active compound in pharmaceutical solutions by means of UV-Vis spectroscopy, orthogonal signal correction and multivariate calibration with PLS and SIMCA classification. Paper II proposes a new method for the rapid determination of pharmaceutical solutions by the use of non-column chromatographic diode array UV spectroscopy, i.e. a conventional HPLC-DAD system without any chromatographic column connected. In Paper III an investigation is made of the ability of a control sample, of known content and identity to diagnose and correct errors in multivariate predictions something that together with use of multivariate residuals can make it possible to use the same calibration model over time. In Paper IV a method is proposed for simultaneous determination of serum proteins with fluorescence spectroscopy and multivariate calibration. Paper V proposes a method for the determination of chromatographic peak purity by means of PCA of HPLC-DAD data. In Paper VI PARAFAC is applied for the decomposition of DAD data of some partially separated peaks into the pure chromatographic, spectral and concentration profiles.

La disponibilité et la persistance à l'échelle locale des métaux lourds pourraient être critiques notamment pour l'usage futur des zones agricoles ou urbaines, au droit desquelles de nombreux sites industriels se sont installés dans le passé. La gestion de ces situations environnementales complexes nécessitent le développement de nouvelles méthodes d'analyse peu invasives (capteurs environnementaux), comme celles utilisant des biosenseurs bactériens, afin d'identifier et d'évaluer directement l'effet biologique et la disponibilité chimique des métaux. Ainsi dans ce travail de thèse, nous avons cherché à identifier, à l'aide d'outils mathématiques de l'algèbre multi-linéaire, les réponses de senseurs bactériens fluorescents dans des conditions environnementales variées, qu'il s'agisse d'un stress engendré par la présence à forte dose d'un métal ou d'une carence nutritive engendrée par son absence. Cette identification est fondée sur l'analyse quantitative à l'échelle d'une population bactérienne de signaux multidimensionnels. Elle repose en particulier sur (i) l'acquisition de données spectrales (fluorescence) multivariées sur des suspensions de biosenseurs multicolores interagissant avec des métaux et sur (ii) le développement d'algorithme de décomposition tensoriels. Les méthodes proposées, développées et utilisées dans ce travail s'efforcent d'identifier " sans \textsl{a priori} " (\textsl{a minima}), la réponse fonctionnelle de biosenseurs sous différentes conditions environnementales, par des méthodes de décomposition de tenseurs sous \hyphenation{con-train-tes} des signaux spectraux observables. Elles tirent parti de la variabilité des réponses systémiques et permettent de déterminer les " sources " élémentaires identifiant le système et leur comportement en fonction des paramètres extérieurs. Elles sont inspirées des méthodes CP et PARALIND . L'avantage de ce type d'approche, par rapport aux approches classiques, est l'identification unique des réponses des biosenseurs sous de faibles contraintes. Le travail a consisté à développer des algorithmes efficaces de séparations de sources pour les signaux fluorescents émis par des senseurs bactériens, garantissant la séparabilité des sources fluorescentes et l'unicité de la décomposition. Le point original de la thèse est la prise en compte des contraintes liées à la physique des phénomènes analysés telles que (i) la parcimonie des coefficients de mélange ou la positivité des signaux "source", afin de réduire au maximum l'usage d'a priori ou (ii) la détermination non empirique de l'ordre de la décomposition (nombre de sources). Cette posture a permis aussi d'améliorer l'identification en optimisant les mesures physiques par l'utilisation de spectres synchrones ou en apportant une diversité suffisante aux plans d'expériences. L'usage des spectres synchrones s'est avéré déterminant à la fois pour améliorer la séparation des sources de fluorescence, mais aussi pour augmenter le rapport signal sur bruit des biosenseurs les plus faibles. Cette méthode d'analyse spectrale originale permet d'élargir fortement la gamme chromatique des biosenseurs fluorescents multicolores utilisables simultanément. Enfin, une nouvelle méthode d'estimation de la concentration de polluants métalliques présents dans un échantillon à partir de la réponse spectrale d'un mélange de biosenseurs non-spécifiques a été développée.

No description available.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23179号 / 工博第4823号 / 新制||工||1754(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 田中 宏明, 教授 清水 芳久, 講師 中田 典秀 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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 / TESIS / Compendio