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[ES] Los procesos de oxidación avanzada, caracterizados por su capacidad de generar especies con gran poder oxidante, son una de las soluciones para la eliminación de compuestos orgánicos no biodegradables en aguas residuales. Entre los procesos referidos se encuentra la llamada fotocatálisis heterogénea, donde destaca el uso de dióxido de titanio (TiO2) para la generación de, entre otras especies radicalarias, radicales hidroxilo, una de las especies más oxidantes conocidas. No obstante, una de los grandes desventajas que presenta el TiO2 es el aprovechamiento de únicamente un 9 % del espectro solar. Frente a esta problemática, en los últimos años se ha presentado el trióxido de tungsteno (VI) (WO3) como una prometedora alternativa al TiO2, gracias a la presencia de una banda prohibida estrecha, así como por la capacidad para absorber radiación en el rango del espectro visible. A pesar de estas atractivas características, el WO3 presenta una capacidad fotocatalítica limitada debido a la rápida recombinación del par electrón-hueco tras haber sido fotoexcitado. Ante esta situación, este trabajo de fin de máster se ha centrado en evitar dicha recombinación del par electrón-hueco, proponiendo dos soluciones que ayudarán eventualmente a aumentar la capacidad fotocatalítica del WO3. En primer lugar, se ha propuesto la utilización de H2O2 por su capacidad para secuestrar el electrón fotoexcitado del WO3. En segundo lugar, se ha llevado a cabo la formación de una heterounión con el WO3 y el óxido de hierro (Fe3O4) con el objetivo de hacer migrar los electrones excitados desde la banda de conducción del WO3 a la banda de conducción del Fe3O4. Con estos antecedentes, en este trabajo presentamos la síntesis de dos fotocatalizadores basados en WO3. Primero, se ha soportado WO3 sobre partículas de óxido de silicio (SiO2), lo que ha dado lugar a fotocatalizadores de tipo SiO2@WO3. Segundo, se han decorado los fotocatalizadores SiO2@WO3 previamente sintetizados con nanopartículas, [EN] Advanced oxidation processes, which are characterized by their ability to generate species with great oxidizing power, are one of the solutions for the elimination of non-biodegradable organic compounds in wastewater. One of the referred processes is heterogeneous photocatalysis, where the use of titanium dioxide (TiO2) stands out in the generation of, among other radical species, hydroxyl radicals, one of the most oxidizing species known. However, one of the biggest disadvantages of TiO2 is that it can only take advantadge of the 9 % of the solar spectrum. In order to overcome this problem, tungsten trioxide (VI) (WO3) has been proposed as a promising alternative to TiO2 in recent years, due to its narrow band-gap and its ability to absorb radiation in the visible spectrum range. Despite these attractive features, WO3 exhibits a limited photocatalytic ability due to the fast recombination of the electron-hole pair after being photoexcited. In this context, this master's thesis has focused on avoiding the mentioned recombination of the electronhole pair, proposing two solutions that will eventually help to increase WO3's photocatalytic activity. First of all, the use of H2O2 has been proposed due to its capacity to capture the photoexcited electron from WO3. Secondly, the formation of a heterojunction between WO3 and iron oxide (Fe3O4) has also been proposed, which will make the excited electrons migrate from the conduction band of WO3 to the conduction band of Fe3O4. In this regard, herein we present the synthesis of two photocatalysts based on WO3. First, WO3 has been supported on silicon oxide (SiO2) particles, leading to SiO2@WO3 type photocatalysts. Second, the previously synthesized SiO2@WO3 photocatalysts have been decorated with Fe3O4 nanoparticles, leading to SiO2@WO3@Fe3O4 photocatalysts. Subsequently, the synthesized photocatalysts have been characterized with several techniques. Finally, the photocatalytic activity of SiO2@WO3 and SiO2@WO3@Fe3O4 pho

[ES] Los procesos de oxidación avanzada, caracterizados por su capacidad de generar especies con gran poder oxidante, son una de las soluciones para la eliminación de compuestos orgánicos no biodegradables en aguas residuales. Entre los procesos referidos se encuentra la llamada fotocatálisis heterogénea, donde destaca el uso de dióxido de titanio (TiO2) para la generación de, entre otras especies radicalarias, radicales hidroxilo, una de las especies más oxidantes conocidas. No obstante, una de los grandes desventajas que presenta el TiO2 es el aprovechamiento de únicamente un 9 % del espectro solar. Frente a esta problemática, en los últimos años se ha presentado el trióxido de tungsteno (VI) (WO3) como una prometedora alternativa al TiO2, gracias a la presencia de una banda prohibida estrecha, así como por la capacidad para absorber radiación en el rango del espectro visible. A pesar de estas atractivas características, el WO3 presenta una capacidad fotocatalítica limitada debido a la rápida recombinación del par electrón-hueco tras haber sido fotoexcitado. Ante esta situación, este trabajo de fin de máster se ha centrado en evitar dicha recombinación del par electrón-hueco, proponiendo dos soluciones que ayudarán eventualmente a aumentar la capacidad fotocatalítica del WO3. En primer lugar, se ha propuesto la utilización de H2O2 por su capacidad para secuestrar el electrón fotoexcitado del WO3. En segundo lugar, se ha llevado a cabo la formación de una heterounión con el WO3 y el óxido de hierro (Fe3O4) con el objetivo de hacer migrar los electrones excitados desde la banda de conducción del WO3 a la banda de conducción del Fe3O4. Con estos antecedentes, en este trabajo presentamos la síntesis de dos fotocatalizadores basados en WO3. Primero, se ha soportado WO3 sobre partículas de óxido de silicio (SiO2), lo que ha dado lugar a fotocatalizadores de tipo SiO2@WO3. Segundo, se han decorado los fotocatalizadores SiO2@WO3 previamente sintetizados con nanopartículas, [EN] Advanced oxidation processes, which are characterized by their ability to generate species with great oxidizing power, are one of the solutions for the elimination of non-biodegradable organic compounds in wastewater. One of the referred processes is heterogeneous photocatalysis, where the use of titanium dioxide (TiO2) stands out in the generation of, among other radical species, hydroxyl radicals, one of the most oxidizing species known. However, one of the biggest disadvantages of TiO2 is that it can only take advantadge of the 9 % of the solar spectrum. In order to overcome this problem, tungsten trioxide (VI) (WO3) has been proposed as a promising alternative to TiO2 in recent years, due to its narrow band-gap and its ability to absorb radiation in the visible spectrum range. Despite these attractive features, WO3 exhibits a limited photocatalytic ability due to the fast recombination of the electron-hole pair after being photoexcited. In this context, this master's thesis has focused on avoiding the mentioned recombination of the electronhole pair, proposing two solutions that will eventually help to increase WO3's photocatalytic activity. First of all, the use of H2O2 has been proposed due to its capacity to capture the photoexcited electron from WO3. Secondly, the formation of a heterojunction between WO3 and iron oxide (Fe3O4) has also been proposed, which will make the excited electrons migrate from the conduction band of WO3 to the conduction band of Fe3O4. In this regard, herein we present the synthesis of two photocatalysts based on WO3. First, WO3 has been supported on silicon oxide (SiO2) particles, leading to SiO2@WO3 type photocatalysts. Second, the previously synthesized SiO2@WO3 photocatalysts have been decorated with Fe3O4 nanoparticles, leading to SiO2@WO3@Fe3O4 photocatalysts. Subsequently, the synthesized photocatalysts have been characterized with several techniques. Finally, the photocatalytic activity of SiO2@WO3 and SiO2@WO3@Fe3O4 pho

[ES] En la presente tesis doctoral se ha estudiado la degradación de diferentes mezclas de contaminantes mediante el proceso de oxidación avanzada foto-Fenton solar, buscando alternativas que lo hagan más eficiente a un pH próximo a la neutralidad. Este proceso oxidativo se ha llevado a cabo a pH 5 mediante la adición de sustancias tipo húmicas (STH) extraídas de diferentes residuos orgánicos. Las STH se han extraído del residuo de la producción del aceite de oliva, del residuo del café y de lodos de depuradora deshidratados del reactor anaerobio de EDAR. Estas STH se han caracterizado por diferentes técnicas analíticas y se han adicionado al proceso foto-Fenton para comprobar su eficacia y eficiencia en el mismo. En el caso del uso de las STH provenientes del residuo de la oliva se han obtenido diferentes tiempos de fermentación y diferentes tamaños de fracciones. El estudio sobre STH preparadas sobre residuos con diferentes tiempos de fermentación, demuestra que los mejores resultados de degradación se obtienen con las muestras fermentada un mes, pero en cualquier caso no son significativas las diferencias, por lo que no sería necesario someter al residuo a ningún tiempo de fermentación previo a la extracción de las STH. En los ensayos con diferentes fracciones de STH, se determina que no es necesario el proceso de separación por membranas ya que las degradaciones obtenidas son muy similares, independientemente del uso de una u otra. Se ha probado su eficiencia en diferentes matrices de agua y se ha comprobado su capacidad para complejar el hierro manteniéndolo en disolución, obteniendo buenos resultados en todos los casos. Se han realizado ensayos de toxicidad sobre diferentes organismos para comprobar la detoxificación de las muestras tratadas. Los ensayos de toxicidad determinan que el compuesto clorfenvinfos es el más tóxico y que las muestras en presencia de las STH son más tóxicas antes de aplicar ningún tratamiento, debido a la capacidad surfactante de las, [CA] En la present tesi doctoral s'ha estudiat la degradació de diferents mescles de contaminants mitjançant el procés d'oxidació avançada foto-Fenton solar, buscant alternatives que ho facen més eficient a un pH pròxim a la neutralitat. Aquest procés oxidatiu s'ha dut a terme a pH 5 mitjançant l'addició de substàncies tipus húmiques (STH) extragudes de diferents tipus de residus orgànics. Les STH s'han extret del residu de la producció de l'oli d'oliva, del residu del café i de lodes de depuradora deshidratats del reactor anaerobi d'EDAR. S¿han caracteritzat per diferents tècniques analítiques i s'han addicionat al procés foto-Fenton per a comprovar la seua eficàcia i eficiència en el mateix. En el cas de les STH provinents del residu de l'oliva s'han obtingut diferents temps de fermentació i diferents tamanys de fraccions. En l'ús de diferents temps de fermentació millors resultats de degradació s'observen en el cas de la mostra fermentada un mes, però, en qualsevol cas no son significatives les diferències, per el que no és necesari sotmetre al residu a cap temps de fermentació abans de l'extracció. Respecte al assatjos en els diferents tamanys de fraccions es determina que no es necessari la separació per membranes, ja que, les degradacions obtenides son molt similars independentment de l'ús d'una fracció o altra. S'ha comprovat l'efectivitat en diferents matrius d'aigua i la capacitat de les mateixes per a complexar el ferro mantenint-lo en disolució, en bons resultats en tots els casos estudiats. Complementàriament s'han realitzat assajos de toxicitat sobre diferents organismes per tal de comprovar la detoxificació de les mostres tractades. Els assatjos de toxicitat determinen que el compost clorfenvinfos és el més tòxic i que les mostres en presència de les STH són més tòxiques, a causa de la capacitat surfactant d'aquestes. El tractament d'una mescla de parabens en STH de diferent procedència milloren els resultats de degradació de contaminants quan es porta, [EN] In the present doctoral thesis, degradation of different pollutant mixtures using the advanced oxidation process called photo-Fenton has been studied, gaining further insight in how this process would take place at circumneutral pHs. Photo-Fenton was carried out at pH 5 by adding humic like substances (HLS) isolated from different organic residues. HLS have been isolated from olive mill wastes, coffee wastes and from wastewater treatment plant sludges. These HLS have been characterized by different analytical techniques and were added to photo-Fenton process to determine their efficacy and efficiency. In the use of HLS isolated from olive mill wastes, different fermentation times and different sizes were obtained. For the HLS from different fermentation times slightly better degradation results were obtained with one month fermentation time, however differences were insignificant to take it into account, and the conclusion of no need of residue fermentation was achieved. In the use of different sizes, the pollutant degradation kinetics were practically the same, concluding that the best option is to use a mixture of them all. Iron complexing ability were studied using different water matrixes with good results in all cases. Toxicity bioassays were carried out using different organisms to know which level of detoxification has achieved. Concluding that these HLS were able to act as iron complexing agents, and that chlorfenvinphos is the most toxic compound, and that water samples containing HLS seems to be more toxic at the end of the treatment time due to their surfactant capacity. A mixture of parabens was treated using different origin HLS at mild photo-Fenton process. HLS isolated from coffee were the most efficient when and extra amount of hydrogen peroxide were added (stoichiometric doble amount). The conclusion reached from toxicology bioassays and endocrine disruption is that the treatment time t30w 30 minutes is not enough to eliminated toxicity, even w

[ES] Los procesos de oxidación avanzada, caracterizados por su capacidad de generar especies con gran poder oxidante, son una de las soluciones para la eliminación de compuestos orgánicos no biodegradables en aguas residuales. Entre los procesos referidos se encuentra la llamada fotocatálisis heterogénea, donde destaca el uso de dióxido de titanio (TiO2) para la generación de, entre otras especies radicalarias, radicales hidroxilo, una de las especies más oxidantes conocidas. No obstante, una de los grandes desventajas que presenta el TiO2 es el aprovechamiento de únicamente un 9 % del espectro solar. Frente a esta problemática, en los últimos años se ha presentado el trióxido de tungsteno (VI) (WO3) como una prometedora alternativa al TiO2, gracias a la presencia de una banda prohibida estrecha, así como por la capacidad para absorber radiación en el rango del espectro visible. A pesar de estas atractivas características, el WO3 presenta una capacidad fotocatalítica limitada debido a la rápida recombinación del par electrón-hueco tras haber sido fotoexcitado. Ante esta situación, este trabajo de fin de máster se ha centrado en evitar dicha recombinación del par electrón-hueco, proponiendo dos soluciones que ayudarán eventualmente a aumentar la capacidad fotocatalítica del WO3. En primer lugar, se ha propuesto la utilización de H2O2 por su capacidad para secuestrar el electrón fotoexcitado del WO3. En segundo lugar, se ha llevado a cabo la formación de una heterounión con el WO3 y el óxido de hierro (Fe3O4) con el objetivo de hacer migrar los electrones excitados desde la banda de conducción del WO3 a la banda de conducción del Fe3O4. Con estos antecedentes, en este trabajo presentamos la síntesis de dos fotocatalizadores basados en WO3. Primero, se ha soportado WO3 sobre partículas de óxido de silicio (SiO2), lo que ha dado lugar a fotocatalizadores de tipo SiO2@WO3. Segundo, se han decorado los fotocatalizadores SiO2@WO3 previamente sintetizados con nanopartículas, [EN] Advanced oxidation processes, which are characterized by their ability to generate species with great oxidizing power, are one of the solutions for the elimination of non-biodegradable organic compounds in wastewater. One of the referred processes is heterogeneous photocatalysis, where the use of titanium dioxide (TiO2) stands out in the generation of, among other radical species, hydroxyl radicals, one of the most oxidizing species known. However, one of the biggest disadvantages of TiO2 is that it can only take advantadge of the 9 % of the solar spectrum. In order to overcome this problem, tungsten trioxide (VI) (WO3) has been proposed as a promising alternative to TiO2 in recent years, due to its narrow band-gap and its ability to absorb radiation in the visible spectrum range. Despite these attractive features, WO3 exhibits a limited photocatalytic ability due to the fast recombination of the electron-hole pair after being photoexcited. In this context, this master's thesis has focused on avoiding the mentioned recombination of the electronhole pair, proposing two solutions that will eventually help to increase WO3's photocatalytic activity. First of all, the use of H2O2 has been proposed due to its capacity to capture the photoexcited electron from WO3. Secondly, the formation of a heterojunction between WO3 and iron oxide (Fe3O4) has also been proposed, which will make the excited electrons migrate from the conduction band of WO3 to the conduction band of Fe3O4. In this regard, herein we present the synthesis of two photocatalysts based on WO3. First, WO3 has been supported on silicon oxide (SiO2) particles, leading to SiO2@WO3 type photocatalysts. Second, the previously synthesized SiO2@WO3 photocatalysts have been decorated with Fe3O4 nanoparticles, leading to SiO2@WO3@Fe3O4 photocatalysts. Subsequently, the synthesized photocatalysts have been characterized with several techniques. Finally, the photocatalytic activity of SiO2@WO3 and SiO2@WO3@Fe3O4 pho

[ES] En la presente tesis doctoral se ha estudiado la degradación de diferentes mezclas de contaminantes mediante el proceso de oxidación avanzada foto-Fenton solar, buscando alternativas que lo hagan más eficiente a un pH próximo a la neutralidad. Este proceso oxidativo se ha llevado a cabo a pH 5 mediante la adición de sustancias tipo húmicas (STH) extraídas de diferentes residuos orgánicos. Las STH se han extraído del residuo de la producción del aceite de oliva, del residuo del café y de lodos de depuradora deshidratados del reactor anaerobio de EDAR. Estas STH se han caracterizado por diferentes técnicas analíticas y se han adicionado al proceso foto-Fenton para comprobar su eficacia y eficiencia en el mismo. En el caso del uso de las STH provenientes del residuo de la oliva se han obtenido diferentes tiempos de fermentación y diferentes tamaños de fracciones. El estudio sobre STH preparadas sobre residuos con diferentes tiempos de fermentación, demuestra que los mejores resultados de degradación se obtienen con las muestras fermentada un mes, pero en cualquier caso no son significativas las diferencias, por lo que no sería necesario someter al residuo a ningún tiempo de fermentación previo a la extracción de las STH. En los ensayos con diferentes fracciones de STH, se determina que no es necesario el proceso de separación por membranas ya que las degradaciones obtenidas son muy similares, independientemente del uso de una u otra. Se ha probado su eficiencia en diferentes matrices de agua y se ha comprobado su capacidad para complejar el hierro manteniéndolo en disolución, obteniendo buenos resultados en todos los casos. Se han realizado ensayos de toxicidad sobre diferentes organismos para comprobar la detoxificación de las muestras tratadas. Los ensayos de toxicidad determinan que el compuesto clorfenvinfos es el más tóxico y que las muestras en presencia de las STH son más tóxicas antes de aplicar ningún tratamiento, debido a la capacidad surfactante de las, [CA] En la present tesi doctoral s'ha estudiat la degradació de diferents mescles de contaminants mitjançant el procés d'oxidació avançada foto-Fenton solar, buscant alternatives que ho facen més eficient a un pH pròxim a la neutralitat. Aquest procés oxidatiu s'ha dut a terme a pH 5 mitjançant l'addició de substàncies tipus húmiques (STH) extragudes de diferents tipus de residus orgànics. Les STH s'han extret del residu de la producció de l'oli d'oliva, del residu del café i de lodes de depuradora deshidratats del reactor anaerobi d'EDAR. S¿han caracteritzat per diferents tècniques analítiques i s'han addicionat al procés foto-Fenton per a comprovar la seua eficàcia i eficiència en el mateix. En el cas de les STH provinents del residu de l'oliva s'han obtingut diferents temps de fermentació i diferents tamanys de fraccions. En l'ús de diferents temps de fermentació millors resultats de degradació s'observen en el cas de la mostra fermentada un mes, però, en qualsevol cas no son significatives les diferències, per el que no és necesari sotmetre al residu a cap temps de fermentació abans de l'extracció. Respecte al assatjos en els diferents tamanys de fraccions es determina que no es necessari la separació per membranes, ja que, les degradacions obtenides son molt similars independentment de l'ús d'una fracció o altra. S'ha comprovat l'efectivitat en diferents matrius d'aigua i la capacitat de les mateixes per a complexar el ferro mantenint-lo en disolució, en bons resultats en tots els casos estudiats. Complementàriament s'han realitzat assajos de toxicitat sobre diferents organismes per tal de comprovar la detoxificació de les mostres tractades. Els assatjos de toxicitat determinen que el compost clorfenvinfos és el més tòxic i que les mostres en presència de les STH són més tòxiques, a causa de la capacitat surfactant d'aquestes. El tractament d'una mescla de parabens en STH de diferent procedència milloren els resultats de degradació de contaminants quan es porta, [EN] In the present doctoral thesis, degradation of different pollutant mixtures using the advanced oxidation process called photo-Fenton has been studied, gaining further insight in how this process would take place at circumneutral pHs. Photo-Fenton was carried out at pH 5 by adding humic like substances (HLS) isolated from different organic residues. HLS have been isolated from olive mill wastes, coffee wastes and from wastewater treatment plant sludges. These HLS have been characterized by different analytical techniques and were added to photo-Fenton process to determine their efficacy and efficiency. In the use of HLS isolated from olive mill wastes, different fermentation times and different sizes were obtained. For the HLS from different fermentation times slightly better degradation results were obtained with one month fermentation time, however differences were insignificant to take it into account, and the conclusion of no need of residue fermentation was achieved. In the use of different sizes, the pollutant degradation kinetics were practically the same, concluding that the best option is to use a mixture of them all. Iron complexing ability were studied using different water matrixes with good results in all cases. Toxicity bioassays were carried out using different organisms to know which level of detoxification has achieved. Concluding that these HLS were able to act as iron complexing agents, and that chlorfenvinphos is the most toxic compound, and that water samples containing HLS seems to be more toxic at the end of the treatment time due to their surfactant capacity. A mixture of parabens was treated using different origin HLS at mild photo-Fenton process. HLS isolated from coffee were the most efficient when and extra amount of hydrogen peroxide were added (stoichiometric doble amount). The conclusion reached from toxicology bioassays and endocrine disruption is that the treatment time t30w 30 minutes is not enough to eliminated toxicity, even w

[ES] En la presente tesis doctoral se ha estudiado la degradación de diferentes mezclas de contaminantes mediante el proceso de oxidación avanzada foto-Fenton solar, buscando alternativas que lo hagan más eficiente a un pH próximo a la neutralidad. Este proceso oxidativo se ha llevado a cabo a pH 5 mediante la adición de sustancias tipo húmicas (STH) extraídas de diferentes residuos orgánicos. Las STH se han extraído del residuo de la producción del aceite de oliva, del residuo del café y de lodos de depuradora deshidratados del reactor anaerobio de EDAR. Estas STH se han caracterizado por diferentes técnicas analíticas y se han adicionado al proceso foto-Fenton para comprobar su eficacia y eficiencia en el mismo. En el caso del uso de las STH provenientes del residuo de la oliva se han obtenido diferentes tiempos de fermentación y diferentes tamaños de fracciones. El estudio sobre STH preparadas sobre residuos con diferentes tiempos de fermentación, demuestra que los mejores resultados de degradación se obtienen con las muestras fermentada un mes, pero en cualquier caso no son significativas las diferencias, por lo que no sería necesario someter al residuo a ningún tiempo de fermentación previo a la extracción de las STH. En los ensayos con diferentes fracciones de STH, se determina que no es necesario el proceso de separación por membranas ya que las degradaciones obtenidas son muy similares, independientemente del uso de una u otra. Se ha probado su eficiencia en diferentes matrices de agua y se ha comprobado su capacidad para complejar el hierro manteniéndolo en disolución, obteniendo buenos resultados en todos los casos. Se han realizado ensayos de toxicidad sobre diferentes organismos para comprobar la detoxificación de las muestras tratadas. Los ensayos de toxicidad determinan que el compuesto clorfenvinfos es el más tóxico y que las muestras en presencia de las STH son más tóxicas antes de aplicar ningún tratamiento, debido a la capacidad surfactante de las, [CA] En la present tesi doctoral s'ha estudiat la degradació de diferents mescles de contaminants mitjançant el procés d'oxidació avançada foto-Fenton solar, buscant alternatives que ho facen més eficient a un pH pròxim a la neutralitat. Aquest procés oxidatiu s'ha dut a terme a pH 5 mitjançant l'addició de substàncies tipus húmiques (STH) extragudes de diferents tipus de residus orgànics. Les STH s'han extret del residu de la producció de l'oli d'oliva, del residu del café i de lodes de depuradora deshidratats del reactor anaerobi d'EDAR. S¿han caracteritzat per diferents tècniques analítiques i s'han addicionat al procés foto-Fenton per a comprovar la seua eficàcia i eficiència en el mateix. En el cas de les STH provinents del residu de l'oliva s'han obtingut diferents temps de fermentació i diferents tamanys de fraccions. En l'ús de diferents temps de fermentació millors resultats de degradació s'observen en el cas de la mostra fermentada un mes, però, en qualsevol cas no son significatives les diferències, per el que no és necesari sotmetre al residu a cap temps de fermentació abans de l'extracció. Respecte al assatjos en els diferents tamanys de fraccions es determina que no es necessari la separació per membranes, ja que, les degradacions obtenides son molt similars independentment de l'ús d'una fracció o altra. S'ha comprovat l'efectivitat en diferents matrius d'aigua i la capacitat de les mateixes per a complexar el ferro mantenint-lo en disolució, en bons resultats en tots els casos estudiats. Complementàriament s'han realitzat assajos de toxicitat sobre diferents organismes per tal de comprovar la detoxificació de les mostres tractades. Els assatjos de toxicitat determinen que el compost clorfenvinfos és el més tòxic i que les mostres en presència de les STH són més tòxiques, a causa de la capacitat surfactant d'aquestes. El tractament d'una mescla de parabens en STH de diferent procedència milloren els resultats de degradació de contaminants quan es porta, [EN] In the present doctoral thesis, degradation of different pollutant mixtures using the advanced oxidation process called photo-Fenton has been studied, gaining further insight in how this process would take place at circumneutral pHs. Photo-Fenton was carried out at pH 5 by adding humic like substances (HLS) isolated from different organic residues. HLS have been isolated from olive mill wastes, coffee wastes and from wastewater treatment plant sludges. These HLS have been characterized by different analytical techniques and were added to photo-Fenton process to determine their efficacy and efficiency. In the use of HLS isolated from olive mill wastes, different fermentation times and different sizes were obtained. For the HLS from different fermentation times slightly better degradation results were obtained with one month fermentation time, however differences were insignificant to take it into account, and the conclusion of no need of residue fermentation was achieved. In the use of different sizes, the pollutant degradation kinetics were practically the same, concluding that the best option is to use a mixture of them all. Iron complexing ability were studied using different water matrixes with good results in all cases. Toxicity bioassays were carried out using different organisms to know which level of detoxification has achieved. Concluding that these HLS were able to act as iron complexing agents, and that chlorfenvinphos is the most toxic compound, and that water samples containing HLS seems to be more toxic at the end of the treatment time due to their surfactant capacity. A mixture of parabens was treated using different origin HLS at mild photo-Fenton process. HLS isolated from coffee were the most efficient when and extra amount of hydrogen peroxide were added (stoichiometric doble amount). The conclusion reached from toxicology bioassays and endocrine disruption is that the treatment time t30w 30 minutes is not enough to eliminated toxicity, even w

[EN] Photo-induced Advanced Oxidation Processes (AOPs) using H2O2 or S2O82- as radical precursors were assessed for the abatement of six different contaminants of emerging concern (CECs). In order to increase the efficiency of these AOPs at a wider pH range, the catechol organic functional compound was studied as a potential assistant in photo-driven iron-based processes. Different salinity regimes were also studied (in terms of Cl- concentration), namely low salt water (1 g center dot L-1) or a salt-water (30 g center dot L-1) matrix. Results obtained revealed that the presence of catechol could efficiently assist the photo-Fenton system and partly promote the photo-induced S2O82- system, which was highly dependent on salinity. Regarding the behavior of individual CECs, the photo-Fenton reaction was able to enhance the degradation of all six CECs, meanwhile the S2O82--based process showed a moderate enhancement for acetaminophen, amoxicillin or clofibric acid. Finally, a response-surface methodology was employed to determine the effect of pH and catechol concentration on the different photo-driven processes. Catechol was removed during the degradation process. According to the results obtained, the presence of catechol in organic macromolecules can bring some advantages in water treatment for either freshwater (wastewater) or seawater (maritime or aquaculture industry).

[EN] In the present work, the treatment of a mixture of six emerging pollutants (acetamiprid, acetaminophen, caffeine, amoxicillin, clofibric acid and carbamazepine) by means of photo-Fenton process has been studied, using simulated sunlight as an irradiation source. Removal of these pollutants has been investigated in three different aqueous matrices distinguished by the amount of chlorides (distilled water, 1 g L-1 of NaCl and 30 g L-1 of NaCl) at a pH of 2.8 and 5.0. Interestingly, the presence of 1 g L-1 was able to slightly accelerate the pollutants removal at pH = 5, although the reverse was true at pH = 2.8. This is attributed to the pH-dependent interference of chlorides on photo-Fenton process, that is more acute in an acidic medium. As a matter of fact, the fastest reaction was obtained at pH = 3.5, in agreement with literature results. Monitoring of hydrogen peroxide consumption and iron in solution indicates that interference with chlorides is due to changes in the interaction between iron and the peroxide, rather than a scavenging effect of chloride for hydroxyl radicals. Experiments were also carried out with real seawater and showed higher inhibition than in the NaCl experiments, probably due to the effect of different dissolved salts present in natural water.

[EN] Photo-induced Advanced Oxidation Processes (AOPs) using H2O2 or S2O82- as radical precursors were assessed for the abatement of six different contaminants of emerging concern (CECs). In order to increase the efficiency of these AOPs at a wider pH range, the catechol organic functional compound was studied as a potential assistant in photo-driven iron-based processes. Different salinity regimes were also studied (in terms of Cl- concentration), namely low salt water (1 g center dot L-1) or a salt-water (30 g center dot L-1) matrix. Results obtained revealed that the presence of catechol could efficiently assist the photo-Fenton system and partly promote the photo-induced S2O82- system, which was highly dependent on salinity. Regarding the behavior of individual CECs, the photo-Fenton reaction was able to enhance the degradation of all six CECs, meanwhile the S2O82--based process showed a moderate enhancement for acetaminophen, amoxicillin or clofibric acid. Finally, a response-surface methodology was employed to determine the effect of pH and catechol concentration on the different photo-driven processes. Catechol was removed during the degradation process. According to the results obtained, the presence of catechol in organic macromolecules can bring some advantages in water treatment for either freshwater (wastewater) or seawater (maritime or aquaculture industry).

[EN] In the present work, the treatment of a mixture of six emerging pollutants (acetamiprid, acetaminophen, caffeine, amoxicillin, clofibric acid and carbamazepine) by means of photo-Fenton process has been studied, using simulated sunlight as an irradiation source. Removal of these pollutants has been investigated in three different aqueous matrices distinguished by the amount of chlorides (distilled water, 1 g L-1 of NaCl and 30 g L-1 of NaCl) at a pH of 2.8 and 5.0. Interestingly, the presence of 1 g L-1 was able to slightly accelerate the pollutants removal at pH = 5, although the reverse was true at pH = 2.8. This is attributed to the pH-dependent interference of chlorides on photo-Fenton process, that is more acute in an acidic medium. As a matter of fact, the fastest reaction was obtained at pH = 3.5, in agreement with literature results. Monitoring of hydrogen peroxide consumption and iron in solution indicates that interference with chlorides is due to changes in the interaction between iron and the peroxide, rather than a scavenging effect of chloride for hydroxyl radicals. Experiments were also carried out with real seawater and showed higher inhibition than in the NaCl experiments, probably due to the effect of different dissolved salts present in natural water.

[EN] In this work, we have tested a photocatalytic material consisting of a core of SiO2/Fe3O4 coated with TiO2 (Magnox) for plausible tertiary wastewater treatment. For this, a pilot plant of 45 L equipped with an Ultraviolet light (UVC) lamp was employed to study the degradation of a model contaminant, enrofloxacin (ENR), as well as water disinfection (elimination of Escherichia coli and Clostridium perfringens). The influence of different operational conditions was explored by means of dye (rhodamine-B) decolorization rates, analyzing the effects of photocatalyst quantity, pH and recirculation flow rates. The magnox/UVC process was also compared with other four Advanced Oxidation Processes (AOPs): (i) UVC irradiation alone, (ii) hydrogen peroxide with UVC (H2O2/UVC), (iii) Fenton, and (iv) photo-Fenton. Although UVC irradiation was efficient enough to produce total water disinfection, only when employing the AOPs, significant degradations of ENR were observed, with photo-Fenton being the most efficient process (total enrofloxacin removal in 5 min and c.a. 80% mineralization in 120 min, at pH(0) 2.8). However, Magnox/UVC has shown great pollutant abatement effectiveness under neutral conditions, with the additional advantage of no acid or H2O2 addition, as well as its plausible reuse and simple separation due to its magnetic properties.

[EN] In this work, we have tested a photocatalytic material consisting of a core of SiO2/Fe3O4 coated with TiO2 (Magnox) for plausible tertiary wastewater treatment. For this, a pilot plant of 45 L equipped with an Ultraviolet light (UVC) lamp was employed to study the degradation of a model contaminant, enrofloxacin (ENR), as well as water disinfection (elimination of Escherichia coli and Clostridium perfringens). The influence of different operational conditions was explored by means of dye (rhodamine-B) decolorization rates, analyzing the effects of photocatalyst quantity, pH and recirculation flow rates. The magnox/UVC process was also compared with other four Advanced Oxidation Processes (AOPs): (i) UVC irradiation alone, (ii) hydrogen peroxide with UVC (H2O2/UVC), (iii) Fenton, and (iv) photo-Fenton. Although UVC irradiation was efficient enough to produce total water disinfection, only when employing the AOPs, significant degradations of ENR were observed, with photo-Fenton being the most efficient process (total enrofloxacin removal in 5 min and c.a. 80% mineralization in 120 min, at pH(0) 2.8). However, Magnox/UVC has shown great pollutant abatement effectiveness under neutral conditions, with the additional advantage of no acid or H2O2 addition, as well as its plausible reuse and simple separation due to its magnetic properties.

[ES] La metilisotiazolinona es un conservante empleado en una gran variedad de industrias, desde la conservación de productos cosméticos, como productos de limpieza o pinturas. En el siguiente proyecto va a estudiarse la degradación de la metilisotiazolinona mediante diferentes procesos de oxidación avanzada (Fenton y foto-Fenton). Además, se observará cuales son las condiciones óptimas de trabajo, variando la cantidad de H2O2 empleado y el pH. La degradación del contaminante será seguida mediante diversas técnicas analíticas como la cromatografía de líquidos de alta precisión (HPLC) o el TOC de líquidos. Una vez determinado el mejor proceso para el tratamiento, se realizará un escalado para poder comprobar su viabilidad a escala industrial, [EN] Methylisothiazolinone is a preservative used in a wide variety of industries, from the preservation of cosmetic products, such as cleaning products or paints. The following project will study the degradation of methylisothiazolinone through different advanced oxidation processes (Fenton and photo-Fenton). In addition, the optimal working conditions will be observed, varying the amount of H2O2 used and the pH. The degradation of the contaminant will be followed by various analytical techniques such as high precision liquid chromatography (HPLC) or liquid TOC. Once the process has been optimized, it will be scaled to verify the feasibility of the process on an industrial scale.

[ES] La metilisotiazolinona es un conservante empleado en una gran variedad de industrias, desde la conservación de productos cosméticos, como productos de limpieza o pinturas. En el siguiente proyecto va a estudiarse la degradación de la metilisotiazolinona mediante diferentes procesos de oxidación avanzada (Fenton y foto-Fenton). Además, se observará cuales son las condiciones óptimas de trabajo, variando la cantidad de H2O2 empleado y el pH. La degradación del contaminante será seguida mediante diversas técnicas analíticas como la cromatografía de líquidos de alta precisión (HPLC) o el TOC de líquidos. Una vez determinado el mejor proceso para el tratamiento, se realizará un escalado para poder comprobar su viabilidad a escala industrial, [EN] Methylisothiazolinone is a preservative used in a wide variety of industries, from the preservation of cosmetic products, such as cleaning products or paints. The following project will study the degradation of methylisothiazolinone through different advanced oxidation processes (Fenton and photo-Fenton). In addition, the optimal working conditions will be observed, varying the amount of H2O2 used and the pH. The degradation of the contaminant will be followed by various analytical techniques such as high precision liquid chromatography (HPLC) or liquid TOC. Once the process has been optimized, it will be scaled to verify the feasibility of the process on an industrial scale.

[EN] The degradation of enrofloxacin (ENR) by direct photolysis, Fenton and solar photo-Fenton processes has been studied in different water matrices, such as ultra-pure water (MQ), tap water (TW) and highly saline water (SW). Reactions have been conducted at initial pH 2.8 and 5.0. At pH = 2.8, HPLC analyses showed a fast removal of ENR by (solar photo)-Fenton treatments in all studied water matrices, whereas a 40% removal was observed after 120 min of photolysis. However, TOC measurements showed that only solar photo-Fenton was able to produce significant mineralization (80% after 120 min of treatment); differences between ENR removal and mineralization can be attributed to the release of important amounts of reaction by-products. Excitation-emission matrices (EEMs) combined with parallel factor analysis (PARAFAC) were employed to gain further insight into the nature of these by-products and their time-course profile, obtaining a 5-component model. EEM-PARAFAC results indicated that photolysis is not able to produce important changes in the fluoroquinolone structure, in sharp contrast with (solar photo)-Fenton, where decrease of the components associated with fluoroquinolone core was observed. Agar diffusion tests employing E. toll and S. aureus showed that the antibiotic activity decreased in parallel with the destruction of the fluoroquinolone core.

[EN] The degradation of enrofloxacin (ENR) by direct photolysis, Fenton and solar photo-Fenton processes has been studied in different water matrices, such as ultra-pure water (MQ), tap water (TW) and highly saline water (SW). Reactions have been conducted at initial pH 2.8 and 5.0. At pH = 2.8, HPLC analyses showed a fast removal of ENR by (solar photo)-Fenton treatments in all studied water matrices, whereas a 40% removal was observed after 120 min of photolysis. However, TOC measurements showed that only solar photo-Fenton was able to produce significant mineralization (80% after 120 min of treatment); differences between ENR removal and mineralization can be attributed to the release of important amounts of reaction by-products. Excitation-emission matrices (EEMs) combined with parallel factor analysis (PARAFAC) were employed to gain further insight into the nature of these by-products and their time-course profile, obtaining a 5-component model. EEM-PARAFAC results indicated that photolysis is not able to produce important changes in the fluoroquinolone structure, in sharp contrast with (solar photo)-Fenton, where decrease of the components associated with fluoroquinolone core was observed. Agar diffusion tests employing E. toll and S. aureus showed that the antibiotic activity decreased in parallel with the destruction of the fluoroquinolone core.

[ES] La metilisotiazolinona es un conservante empleado en una gran variedad de industrias, desde la conservación de productos cosméticos, como productos de limpieza o pinturas. En el siguiente proyecto va a estudiarse la degradación de la metilisotiazolinona mediante diferentes procesos de oxidación avanzada (Fenton y foto-Fenton). Además, se observará cuales son las condiciones óptimas de trabajo, variando la cantidad de H2O2 empleado y el pH. La degradación del contaminante será seguida mediante diversas técnicas analíticas como la cromatografía de líquidos de alta precisión (HPLC) o el TOC de líquidos. Una vez determinado el mejor proceso para el tratamiento, se realizará un escalado para poder comprobar su viabilidad a escala industrial, [EN] Methylisothiazolinone is a preservative used in a wide variety of industries, from the preservation of cosmetic products, such as cleaning products or paints. The following project will study the degradation of methylisothiazolinone through different advanced oxidation processes (Fenton and photo-Fenton). In addition, the optimal working conditions will be observed, varying the amount of H2O2 used and the pH. The degradation of the contaminant will be followed by various analytical techniques such as high precision liquid chromatography (HPLC) or liquid TOC. Once the process has been optimized, it will be scaled to verify the feasibility of the process on an industrial scale.

[ES] La metilisotiazolinona es un conservante empleado en una gran variedad de industrias, desde la conservación de productos cosméticos, como productos de limpieza o pinturas. En el siguiente proyecto va a estudiarse la degradación de la metilisotiazolinona mediante diferentes procesos de oxidación avanzada (Fenton y foto-Fenton). Además, se observará cuales son las condiciones óptimas de trabajo, variando la cantidad de H2O2 empleado y el pH. La degradación del contaminante será seguida mediante diversas técnicas analíticas como la cromatografía de líquidos de alta precisión (HPLC) o el TOC de líquidos. Una vez determinado el mejor proceso para el tratamiento, se realizará un escalado para poder comprobar su viabilidad a escala industrial, [EN] Methylisothiazolinone is a preservative used in a wide variety of industries, from the preservation of cosmetic products, such as cleaning products or paints. The following project will study the degradation of methylisothiazolinone through different advanced oxidation processes (Fenton and photo-Fenton). In addition, the optimal working conditions will be observed, varying the amount of H2O2 used and the pH. The degradation of the contaminant will be followed by various analytical techniques such as high precision liquid chromatography (HPLC) or liquid TOC. Once the process has been optimized, it will be scaled to verify the feasibility of the process on an industrial scale.

[EN] The degradation of enrofloxacin (ENR) by direct photolysis, Fenton and solar photo-Fenton processes has been studied in different water matrices, such as ultra-pure water (MQ), tap water (TW) and highly saline water (SW). Reactions have been conducted at initial pH 2.8 and 5.0. At pH = 2.8, HPLC analyses showed a fast removal of ENR by (solar photo)-Fenton treatments in all studied water matrices, whereas a 40% removal was observed after 120 min of photolysis. However, TOC measurements showed that only solar photo-Fenton was able to produce significant mineralization (80% after 120 min of treatment); differences between ENR removal and mineralization can be attributed to the release of important amounts of reaction by-products. Excitation-emission matrices (EEMs) combined with parallel factor analysis (PARAFAC) were employed to gain further insight into the nature of these by-products and their time-course profile, obtaining a 5-component model. EEM-PARAFAC results indicated that photolysis is not able to produce important changes in the fluoroquinolone structure, in sharp contrast with (solar photo)-Fenton, where decrease of the components associated with fluoroquinolone core was observed. Agar diffusion tests employing E. toll and S. aureus showed that the antibiotic activity decreased in parallel with the destruction of the fluoroquinolone core.

This is an Author's Accepted Manuscript of an article published in Arlen Mabel Lastre-Acosta, Rafael Vicente, Margarita Mora, Ulises Javier Jáuregui-Haza, Antonio Arques & Antonio Carlos Silva Costa Teixeira (2019) Photo-Fenton reaction at mildly acidic conditions: assessing the effect of bio-organic substances of different origin and characteristics through experimental design, Journal of Environmental Science and Health, Part A, 54:8, 711-720 [copyright Taylor & Francis], available online at: http://www.tandfonline.com/10.1080/10934529.2019.1585721, [EN] Urban-waste bio-organic substances (UW-BOS) have been shown to be capable of extending the photo-Fenton reaction to mildly acidic conditions. In this study, the effects of pH (3-7), UW-BOS, H2O2 and iron concentrations on the photo-Fenton process were systematically assessed using a Doehlert experimental design and response surface methodology for two UW-BOS (CVT230 and FORSUD). Solutions of the model antibiotic sulfadiazine (SDZ) were irradiated in a solar simulator equipped with a 550W Xenon lamp. The results showed that for UW-BOS contents below 30mg L-1, SDZ removal proceeds at pH 5 with similar rates for both CVT230 and FORSUD, regardless of Fe(III) concentration. For 50mg L-1 of UW-BOS or higher, CVT230 performs better than FORSUD, even for low Fe(III) content (1-3mg L-1). In contrast, half-life times of 35-40min can only be achieved under mildly acidic conditions with FORSUD for iron concentrations higher than 10mg L-1. The better performance of CVT230 can be associated with its high hydrophilic/hydrophobic ratio, low E2:E3, higher iron content and possibly higher yields of triplet reactive species generation upon solar irradiation. The most appropriate conditions for each UW-BOS studied are discussed for the first time, which are advantageous for possible engineered applications.

[EN] In the present work, the photo-Fenton degradation of pentachlorophenol (PCP, 1 mg/L) has been studied under simulated and natural solar irradiation; moreover, the effect on the process efficiency of urban waste-derived soluble bio-based substances (SBO), structurally comparable to humic acids, has been investigated. Experiments showed a crucial role of PCP photolysis, present in the solar pilot plant and hindered by the Pyrex (R) filter present in the solar simulator. Indeed, the SBO screen negatively affects PCP degradation when working under natural solar light, where the photolysis of PCP is relevant. In contrast, in the absence of PCP photolysis, a significant improvement of the photo-Fenton process was observed when added to SBO. Furthermore, SBO were able to extend the application of the photo-Fenton process at circumneutral pH values, due to their ability to complex iron, avoiding its precipitation as oxides or hydroxides. This positive effect has been observed at higher concentration of Fe(II) (4 mg/L), whereas at 1 mg/L, the degradation rates of PCP were comparable in the presence and absence of SBO.

[EN] Humiclike substances (HLS) have been demonstrated to be useful auxiliaries to drive the (photo)-Fenton process at mild pH, by avoiding iron inactivation via formation of active complexes. However, the actual performance of the process is affected by a manifold of opposite processes. In this work, the generation of hydroxyl radical-like reactive species in the Fentonlike process has been investigated using electron paramagnetic resonance, employing 5,5-dimethyl-1-pyrroline-N-oxide as a probe molecule. The signal obtained with the Fe(II)-HLS-H2O2 system at pH = was very intense but decreased with time, in line with the difficult reduction of the formed Fe(III) to Fe(II). On the contrary, the signal of the Fe(III)-HLS-H2O2 system was weak but stable. The most intense signal was observed at HLS concentration of ca. 30 mg/L. Interestingly, the performance of the Fenton system at pH = 5 to degrade caffeine followed the same trends, although caffeine removal was very low after 1 h of irradiation. The results were more evident in a solar simulated photo-Fenton process, where an increase in the abatement of caffeine was observed until an HLS concentration of 30 mg/L, where 98% removal was reached after 1 h.

[EN] Pentachlorophenol solutions in tap water were treated with a combined process of zero valent iron (ZVI) reduction followed by a photo-Fenton oxidation. Commercial steel wool was used as ZVI source, demonstrating its effectivity for pentachlorophenol de-chlorination at acidic pH values. The reductive pathway was monitored by the use of excitation emission matrices, showing the transformation of the initial compound into the fluorescent species 4-chlorophenol and phenol. While the use of tap water represented a drawback in photo-Fenton oxidative reactions (at least half kinetic constants values) an improvement was achieved when the reductive stage was applied in the studied pH range. The transformation of pentachlorophenol into phenol produced an increase in oxidative stage rate of about 8 times. This fact could be related to the treatment time and hydrogen peroxide consumption of the photo-Fenton process, enhancing the economic viability. Furthermore, the de-chlorination of the pentachlorophenol minimized the possibility of releasing toxic by-products in the photo-Fenton process.

This is an Author's Accepted Manuscript of an article published in Arlen Mabel Lastre-Acosta, Rafael Vicente, Margarita Mora, Ulises Javier Jáuregui-Haza, Antonio Arques & Antonio Carlos Silva Costa Teixeira (2019) Photo-Fenton reaction at mildly acidic conditions: assessing the effect of bio-organic substances of different origin and characteristics through experimental design, Journal of Environmental Science and Health, Part A, 54:8, 711-720 [copyright Taylor & Francis], available online at: http://www.tandfonline.com/10.1080/10934529.2019.1585721, [EN] Urban-waste bio-organic substances (UW-BOS) have been shown to be capable of extending the photo-Fenton reaction to mildly acidic conditions. In this study, the effects of pH (3-7), UW-BOS, H2O2 and iron concentrations on the photo-Fenton process were systematically assessed using a Doehlert experimental design and response surface methodology for two UW-BOS (CVT230 and FORSUD). Solutions of the model antibiotic sulfadiazine (SDZ) were irradiated in a solar simulator equipped with a 550W Xenon lamp. The results showed that for UW-BOS contents below 30mg L-1, SDZ removal proceeds at pH 5 with similar rates for both CVT230 and FORSUD, regardless of Fe(III) concentration. For 50mg L-1 of UW-BOS or higher, CVT230 performs better than FORSUD, even for low Fe(III) content (1-3mg L-1). In contrast, half-life times of 35-40min can only be achieved under mildly acidic conditions with FORSUD for iron concentrations higher than 10mg L-1. The better performance of CVT230 can be associated with its high hydrophilic/hydrophobic ratio, low E2:E3, higher iron content and possibly higher yields of triplet reactive species generation upon solar irradiation. The most appropriate conditions for each UW-BOS studied are discussed for the first time, which are advantageous for possible engineered applications.

[EN] In the present work, the photo-Fenton degradation of pentachlorophenol (PCP, 1 mg/L) has been studied under simulated and natural solar irradiation; moreover, the effect on the process efficiency of urban waste-derived soluble bio-based substances (SBO), structurally comparable to humic acids, has been investigated. Experiments showed a crucial role of PCP photolysis, present in the solar pilot plant and hindered by the Pyrex (R) filter present in the solar simulator. Indeed, the SBO screen negatively affects PCP degradation when working under natural solar light, where the photolysis of PCP is relevant. In contrast, in the absence of PCP photolysis, a significant improvement of the photo-Fenton process was observed when added to SBO. Furthermore, SBO were able to extend the application of the photo-Fenton process at circumneutral pH values, due to their ability to complex iron, avoiding its precipitation as oxides or hydroxides. This positive effect has been observed at higher concentration of Fe(II) (4 mg/L), whereas at 1 mg/L, the degradation rates of PCP were comparable in the presence and absence of SBO.

[EN] Humiclike substances (HLS) have been demonstrated to be useful auxiliaries to drive the (photo)-Fenton process at mild pH, by avoiding iron inactivation via formation of active complexes. However, the actual performance of the process is affected by a manifold of opposite processes. In this work, the generation of hydroxyl radical-like reactive species in the Fentonlike process has been investigated using electron paramagnetic resonance, employing 5,5-dimethyl-1-pyrroline-N-oxide as a probe molecule. The signal obtained with the Fe(II)-HLS-H2O2 system at pH = was very intense but decreased with time, in line with the difficult reduction of the formed Fe(III) to Fe(II). On the contrary, the signal of the Fe(III)-HLS-H2O2 system was weak but stable. The most intense signal was observed at HLS concentration of ca. 30 mg/L. Interestingly, the performance of the Fenton system at pH = 5 to degrade caffeine followed the same trends, although caffeine removal was very low after 1 h of irradiation. The results were more evident in a solar simulated photo-Fenton process, where an increase in the abatement of caffeine was observed until an HLS concentration of 30 mg/L, where 98% removal was reached after 1 h.

This is an Author's Accepted Manuscript of an article published in Arlen Mabel Lastre-Acosta, Rafael Vicente, Margarita Mora, Ulises Javier Jáuregui-Haza, Antonio Arques & Antonio Carlos Silva Costa Teixeira (2019) Photo-Fenton reaction at mildly acidic conditions: assessing the effect of bio-organic substances of different origin and characteristics through experimental design, Journal of Environmental Science and Health, Part A, 54:8, 711-720 [copyright Taylor & Francis], available online at: http://www.tandfonline.com/10.1080/10934529.2019.1585721, [EN] Urban-waste bio-organic substances (UW-BOS) have been shown to be capable of extending the photo-Fenton reaction to mildly acidic conditions. In this study, the effects of pH (3-7), UW-BOS, H2O2 and iron concentrations on the photo-Fenton process were systematically assessed using a Doehlert experimental design and response surface methodology for two UW-BOS (CVT230 and FORSUD). Solutions of the model antibiotic sulfadiazine (SDZ) were irradiated in a solar simulator equipped with a 550W Xenon lamp. The results showed that for UW-BOS contents below 30mg L-1, SDZ removal proceeds at pH 5 with similar rates for both CVT230 and FORSUD, regardless of Fe(III) concentration. For 50mg L-1 of UW-BOS or higher, CVT230 performs better than FORSUD, even for low Fe(III) content (1-3mg L-1). In contrast, half-life times of 35-40min can only be achieved under mildly acidic conditions with FORSUD for iron concentrations higher than 10mg L-1. The better performance of CVT230 can be associated with its high hydrophilic/hydrophobic ratio, low E2:E3, higher iron content and possibly higher yields of triplet reactive species generation upon solar irradiation. The most appropriate conditions for each UW-BOS studied are discussed for the first time, which are advantageous for possible engineered applications.

[EN] Humiclike substances (HLS) have been demonstrated to be useful auxiliaries to drive the (photo)-Fenton process at mild pH, by avoiding iron inactivation via formation of active complexes. However, the actual performance of the process is affected by a manifold of opposite processes. In this work, the generation of hydroxyl radical-like reactive species in the Fentonlike process has been investigated using electron paramagnetic resonance, employing 5,5-dimethyl-1-pyrroline-N-oxide as a probe molecule. The signal obtained with the Fe(II)-HLS-H2O2 system at pH = was very intense but decreased with time, in line with the difficult reduction of the formed Fe(III) to Fe(II). On the contrary, the signal of the Fe(III)-HLS-H2O2 system was weak but stable. The most intense signal was observed at HLS concentration of ca. 30 mg/L. Interestingly, the performance of the Fenton system at pH = 5 to degrade caffeine followed the same trends, although caffeine removal was very low after 1 h of irradiation. The results were more evident in a solar simulated photo-Fenton process, where an increase in the abatement of caffeine was observed until an HLS concentration of 30 mg/L, where 98% removal was reached after 1 h.

[EN] In the present work, the photo-Fenton degradation of pentachlorophenol (PCP, 1 mg/L) has been studied under simulated and natural solar irradiation; moreover, the effect on the process efficiency of urban waste-derived soluble bio-based substances (SBO), structurally comparable to humic acids, has been investigated. Experiments showed a crucial role of PCP photolysis, present in the solar pilot plant and hindered by the Pyrex (R) filter present in the solar simulator. Indeed, the SBO screen negatively affects PCP degradation when working under natural solar light, where the photolysis of PCP is relevant. In contrast, in the absence of PCP photolysis, a significant improvement of the photo-Fenton process was observed when added to SBO. Furthermore, SBO were able to extend the application of the photo-Fenton process at circumneutral pH values, due to their ability to complex iron, avoiding its precipitation as oxides or hydroxides. This positive effect has been observed at higher concentration of Fe(II) (4 mg/L), whereas at 1 mg/L, the degradation rates of PCP were comparable in the presence and absence of SBO.

[EN] Pentachlorophenol solutions in tap water were treated with a combined process of zero valent iron (ZVI) reduction followed by a photo-Fenton oxidation. Commercial steel wool was used as ZVI source, demonstrating its effectivity for pentachlorophenol de-chlorination at acidic pH values. The reductive pathway was monitored by the use of excitation emission matrices, showing the transformation of the initial compound into the fluorescent species 4-chlorophenol and phenol. While the use of tap water represented a drawback in photo-Fenton oxidative reactions (at least half kinetic constants values) an improvement was achieved when the reductive stage was applied in the studied pH range. The transformation of pentachlorophenol into phenol produced an increase in oxidative stage rate of about 8 times. This fact could be related to the treatment time and hydrogen peroxide consumption of the photo-Fenton process, enhancing the economic viability. Furthermore, the de-chlorination of the pentachlorophenol minimized the possibility of releasing toxic by-products in the photo-Fenton process.

[EN] Pentachlorophenol solutions in tap water were treated with a combined process of zero valent iron (ZVI) reduction followed by a photo-Fenton oxidation. Commercial steel wool was used as ZVI source, demonstrating its effectivity for pentachlorophenol de-chlorination at acidic pH values. The reductive pathway was monitored by the use of excitation emission matrices, showing the transformation of the initial compound into the fluorescent species 4-chlorophenol and phenol. While the use of tap water represented a drawback in photo-Fenton oxidative reactions (at least half kinetic constants values) an improvement was achieved when the reductive stage was applied in the studied pH range. The transformation of pentachlorophenol into phenol produced an increase in oxidative stage rate of about 8 times. This fact could be related to the treatment time and hydrogen peroxide consumption of the photo-Fenton process, enhancing the economic viability. Furthermore, the de-chlorination of the pentachlorophenol minimized the possibility of releasing toxic by-products in the photo-Fenton process.

[ES] Los contaminantes emergentes son un problema creciente en las aguas residuales de las industrias, así como en la vida de los humanos. Dentro de estos residuos, se puede destacar a la cafeína, un compuesto que está presente en la gran mayoría de la población del planeta y que, justo por esto, no le prestamos la importancia que merece. Por ello, para realizar la eliminación de este componente, se estudian diferentes tipos de depuración de aguas, como es el caso del método Foto-Fenton, un proceso por el cual los contaminantes son eliminados utilizando luz solar, un catalizador y un oxidante. Así conseguiremos en este trabajo conocer cómo funciona este proceso, así como qué método dentro del proceso Foto-Fenton será mejor y más efectivo para suprimir de un agua contaminada por cafeína a diferentes concentraciones y con diferentes cantidades de reactivos., [EN] Emerging pollutants are a growing problem in the wastewater of industries, as well as in the lives of humans. Among these residues, caffeine, a compound that is present in the vast majority of the population of the planet and that, just for this, we do not give it the importance it deserves. Therefore, to carry out the elimination of this component, different types of water purification are studied, as is the case of the Photo-Fenton method, a process by which the contaminants are eliminated using sunlight, a catalyst and an oxidant. In this work we will get to know how this process works, as well as what method within the Photo process-Fenton will be better and more effective in suppressing water contaminated by caffeine at different concentrations and with different amounts of reagents., [CA] Els contaminants emergents són un problema creixent en les aigües residuals de les indústries, així com en la vida dels humans. Dins d'aquests residus, es pot destacar a la cafeïna, un compost que està present en la gran majoria de la població del planeta i que, just per això, no li prestem la importància que mereix. Per això, per a realitzar l'eliminació d'aquest component, s'estudien diferents tipus de depuració d'aigües, com és el cas del mètode Foto-Fenton, un procés pel qual els contaminants són eliminats utilitzant llum solar, un catalitzador i un oxidant. Així aconseguirem en aquest treball conèixer com funciona aquest procés, així com quin mètode dins del procés Foto-Fenton serà millor i més efectiu per a suprimir d'una aigua contaminada per cafeïna a diferents concentracions i amb diferents quantitats de reactius.

[ES] Los contaminantes emergentes son un problema creciente en las aguas residuales de las industrias, así como en la vida de los humanos. Dentro de estos residuos, se puede destacar a la cafeína, un compuesto que está presente en la gran mayoría de la población del planeta y que, justo por esto, no le prestamos la importancia que merece. Por ello, para realizar la eliminación de este componente, se estudian diferentes tipos de depuración de aguas, como es el caso del método Foto-Fenton, un proceso por el cual los contaminantes son eliminados utilizando luz solar, un catalizador y un oxidante. Así conseguiremos en este trabajo conocer cómo funciona este proceso, así como qué método dentro del proceso Foto-Fenton será mejor y más efectivo para suprimir de un agua contaminada por cafeína a diferentes concentraciones y con diferentes cantidades de reactivos., [EN] Emerging pollutants are a growing problem in the wastewater of industries, as well as in the lives of humans. Among these residues, caffeine, a compound that is present in the vast majority of the population of the planet and that, just for this, we do not give it the importance it deserves. Therefore, to carry out the elimination of this component, different types of water purification are studied, as is the case of the Photo-Fenton method, a process by which the contaminants are eliminated using sunlight, a catalyst and an oxidant. In this work we will get to know how this process works, as well as what method within the Photo process-Fenton will be better and more effective in suppressing water contaminated by caffeine at different concentrations and with different amounts of reagents., [CA] Els contaminants emergents són un problema creixent en les aigües residuals de les indústries, així com en la vida dels humans. Dins d'aquests residus, es pot destacar a la cafeïna, un compost que està present en la gran majoria de la població del planeta i que, just per això, no li prestem la importància que mereix. Per això, per a realitzar l'eliminació d'aquest component, s'estudien diferents tipus de depuració d'aigües, com és el cas del mètode Foto-Fenton, un procés pel qual els contaminants són eliminats utilitzant llum solar, un catalitzador i un oxidant. Així aconseguirem en aquest treball conèixer com funciona aquest procés, així com quin mètode dins del procés Foto-Fenton serà millor i més efectiu per a suprimir d'una aigua contaminada per cafeïna a diferents concentracions i amb diferents quantitats de reactius.

[ES] Los contaminantes emergentes son un problema creciente en las aguas residuales de las industrias, así como en la vida de los humanos. Dentro de estos residuos, se puede destacar a la cafeína, un compuesto que está presente en la gran mayoría de la población del planeta y que, justo por esto, no le prestamos la importancia que merece. Por ello, para realizar la eliminación de este componente, se estudian diferentes tipos de depuración de aguas, como es el caso del método Foto-Fenton, un proceso por el cual los contaminantes son eliminados utilizando luz solar, un catalizador y un oxidante. Así conseguiremos en este trabajo conocer cómo funciona este proceso, así como qué método dentro del proceso Foto-Fenton será mejor y más efectivo para suprimir de un agua contaminada por cafeína a diferentes concentraciones y con diferentes cantidades de reactivos., [EN] Emerging pollutants are a growing problem in the wastewater of industries, as well as in the lives of humans. Among these residues, caffeine, a compound that is present in the vast majority of the population of the planet and that, just for this, we do not give it the importance it deserves. Therefore, to carry out the elimination of this component, different types of water purification are studied, as is the case of the Photo-Fenton method, a process by which the contaminants are eliminated using sunlight, a catalyst and an oxidant. In this work we will get to know how this process works, as well as what method within the Photo process-Fenton will be better and more effective in suppressing water contaminated by caffeine at different concentrations and with different amounts of reagents., [CA] Els contaminants emergents són un problema creixent en les aigües residuals de les indústries, així com en la vida dels humans. Dins d'aquests residus, es pot destacar a la cafeïna, un compost que està present en la gran majoria de la població del planeta i que, just per això, no li prestem la importància que mereix. Per això, per a realitzar l'eliminació d'aquest component, s'estudien diferents tipus de depuració d'aigües, com és el cas del mètode Foto-Fenton, un procés pel qual els contaminants són eliminats utilitzant llum solar, un catalitzador i un oxidant. Així aconseguirem en aquest treball conèixer com funciona aquest procés, així com quin mètode dins del procés Foto-Fenton serà millor i més efectiu per a suprimir d'una aigua contaminada per cafeïna a diferents concentracions i amb diferents quantitats de reactius.

[EN] Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 x 10(9) s(-1)M(-1) for the reaction of the fungicide with HO center dot and 4.6 x 10(8) s(-1) M-1 for the same reaction with SO4 center dot- radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S2O82- with flusilazole, were identified as alpha-aminoallcyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively. (C) 2017 Published by Elsevier Ltd.

[EN] Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 x 10(9) s(-1)M(-1) for the reaction of the fungicide with HO center dot and 4.6 x 10(8) s(-1) M-1 for the same reaction with SO4 center dot- radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S2O82- with flusilazole, were identified as alpha-aminoallcyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively. (C) 2017 Published by Elsevier Ltd.

[ES] El agua es un recurso esencial para la vida en este planeta, pero no es un bien ilimitado. Debido al calentamiento global, hoy en día existen situaciones de escasez en zonas donde antes era abundante. A esto hay que sumarle el continuo desarrollo de la sociedad, el cual va acompañado de un aumento de las actividades urbanas, industriales y agrícolas, junto a los residuos que estos generan. Aunque el principal objetivo es minimizar su producción, esto no siempre es posible, por lo que la valorización de estos residuos para ser reutilizados en otros procesos, debe ser un objetivo alternativo. En este contexto, se ha dedicado mucho esfuerzo en los últimos años para obtener productos valiosos a partir de residuos agrícolas biodegradables. Durante los últimos años las sustancias bio-orgánicas (SBO) aisladas de la fracción húmeda de los residuos urbanos se han mostrado útiles en gran cantidad de aplicaciones. El uso de este tipo de materiales se hace interesante debido a las ventajas económicas y medioambientales que implican. Las SBO tienen diversas similitudes estructurales básicas con las materia orgánica presente en aguas naturales, en especial con los ácidos húmicos y fúlvicos. Debido a estas similitudes, cabría esperar que estas sustancias muestren propiedades fotoquímicas, y en especial la capacidad de generar especies altamente reactivas, favoreciendo, a su vez, reacciones de oxidación con el fin de degradar sustancias contaminantes presentes en aguas. En este trabajo de investigación se parte de aguas contaminadas en las que se estudia el poder fotosensibilizador de tres SBO obtenidos a partir de residuos agrícolas. Las aguas han sido contaminadas con cuatro compuestos de interés (clorfenvinfos, diclofenaco, pentaclorofenol y terbutrina) y tratadas con foto-Fenton. Para evaluar la eficacia de los SBO y del tratamiento foto-Fenton no sólo hay que asegurar la degradación completa de los contaminantes sino también valorar una detoxificación total de la muestra., [EN] Water is an essential resource for life on this planet, but it is not an unlimited good. Due to global warming, today there are situations of scarcity in areas where it was previously abundant. To this, must be added the continuous development of society, which is accompanied by an increase in urban, industrial and agricultural activities, together with the waste that these generate. Although the main objective is to minimize production, this is not always possible, so the recovery of these waste to be reused in other processes should be an alternative objective. In this context, much effort has been devoted in recent years to obtain valuable products from biodegradable agricultural waste. In recent years bio-organic substances (SBO) isolated from the humid fraction of urban waste have proved useful in a large number of applications. The use of this type of materials becomes interesting due to the economic and environmental advantages they imply. The SBOs have several basic structural similarities with the organic fraction present in natural waters, especially with humic and fulvic acids. Due to these similarities, it would be expected that these substances show photochemical properties, and especially the ability to generate highly reactive species, favoringoxidation reactions in order to degrade polluting substances present in water. In this research work, we start with contaminated water in which the photosensitizing power of three SBO obtained from agricultural waste is studied. The waters have been contaminated with four compounds of interest (chlorfenvinphos, diclofenac, pentachlorophenol and terbutrine) and treated with photo-Fenton. To evaluate the effectiveness of the SBO and the photo-Fenton treatment, we have to evaluate the complete degradation of these contaminants and assess a total detoxification of the sample. For this purpose, an evaluation of the toxicity of the sample is sought before, during and after treatment by a battery of bioassays at t

[EN] Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 x 10(9) s(-1)M(-1) for the reaction of the fungicide with HO center dot and 4.6 x 10(8) s(-1) M-1 for the same reaction with SO4 center dot- radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S2O82- with flusilazole, were identified as alpha-aminoallcyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively. (C) 2017 Published by Elsevier Ltd.

[ES] El agua es un recurso esencial para la vida en este planeta, pero no es un bien ilimitado. Debido al calentamiento global, hoy en día existen situaciones de escasez en zonas donde antes era abundante. A esto hay que sumarle el continuo desarrollo de la sociedad, el cual va acompañado de un aumento de las actividades urbanas, industriales y agrícolas, junto a los residuos que estos generan. Aunque el principal objetivo es minimizar su producción, esto no siempre es posible, por lo que la valorización de estos residuos para ser reutilizados en otros procesos, debe ser un objetivo alternativo. En este contexto, se ha dedicado mucho esfuerzo en los últimos años para obtener productos valiosos a partir de residuos agrícolas biodegradables. Durante los últimos años las sustancias bio-orgánicas (SBO) aisladas de la fracción húmeda de los residuos urbanos se han mostrado útiles en gran cantidad de aplicaciones. El uso de este tipo de materiales se hace interesante debido a las ventajas económicas y medioambientales que implican. Las SBO tienen diversas similitudes estructurales básicas con las materia orgánica presente en aguas naturales, en especial con los ácidos húmicos y fúlvicos. Debido a estas similitudes, cabría esperar que estas sustancias muestren propiedades fotoquímicas, y en especial la capacidad de generar especies altamente reactivas, favoreciendo, a su vez, reacciones de oxidación con el fin de degradar sustancias contaminantes presentes en aguas. En este trabajo de investigación se parte de aguas contaminadas en las que se estudia el poder fotosensibilizador de tres SBO obtenidos a partir de residuos agrícolas. Las aguas han sido contaminadas con cuatro compuestos de interés (clorfenvinfos, diclofenaco, pentaclorofenol y terbutrina) y tratadas con foto-Fenton. Para evaluar la eficacia de los SBO y del tratamiento foto-Fenton no sólo hay que asegurar la degradación completa de los contaminantes sino también valorar una detoxificación total de la muestra., [EN] Water is an essential resource for life on this planet, but it is not an unlimited good. Due to global warming, today there are situations of scarcity in areas where it was previously abundant. To this, must be added the continuous development of society, which is accompanied by an increase in urban, industrial and agricultural activities, together with the waste that these generate. Although the main objective is to minimize production, this is not always possible, so the recovery of these waste to be reused in other processes should be an alternative objective. In this context, much effort has been devoted in recent years to obtain valuable products from biodegradable agricultural waste. In recent years bio-organic substances (SBO) isolated from the humid fraction of urban waste have proved useful in a large number of applications. The use of this type of materials becomes interesting due to the economic and environmental advantages they imply. The SBOs have several basic structural similarities with the organic fraction present in natural waters, especially with humic and fulvic acids. Due to these similarities, it would be expected that these substances show photochemical properties, and especially the ability to generate highly reactive species, favoringoxidation reactions in order to degrade polluting substances present in water. In this research work, we start with contaminated water in which the photosensitizing power of three SBO obtained from agricultural waste is studied. The waters have been contaminated with four compounds of interest (chlorfenvinphos, diclofenac, pentachlorophenol and terbutrine) and treated with photo-Fenton. To evaluate the effectiveness of the SBO and the photo-Fenton treatment, we have to evaluate the complete degradation of these contaminants and assess a total detoxification of the sample. For this purpose, an evaluation of the toxicity of the sample is sought before, during and after treatment by a battery of bioassays at t

[ES] El agua es un recurso esencial para la vida en este planeta, pero no es un bien ilimitado. Debido al calentamiento global, hoy en día existen situaciones de escasez en zonas donde antes era abundante. A esto hay que sumarle el continuo desarrollo de la sociedad, el cual va acompañado de un aumento de las actividades urbanas, industriales y agrícolas, junto a los residuos que estos generan. Aunque el principal objetivo es minimizar su producción, esto no siempre es posible, por lo que la valorización de estos residuos para ser reutilizados en otros procesos, debe ser un objetivo alternativo. En este contexto, se ha dedicado mucho esfuerzo en los últimos años para obtener productos valiosos a partir de residuos agrícolas biodegradables. Durante los últimos años las sustancias bio-orgánicas (SBO) aisladas de la fracción húmeda de los residuos urbanos se han mostrado útiles en gran cantidad de aplicaciones. El uso de este tipo de materiales se hace interesante debido a las ventajas económicas y medioambientales que implican. Las SBO tienen diversas similitudes estructurales básicas con las materia orgánica presente en aguas naturales, en especial con los ácidos húmicos y fúlvicos. Debido a estas similitudes, cabría esperar que estas sustancias muestren propiedades fotoquímicas, y en especial la capacidad de generar especies altamente reactivas, favoreciendo, a su vez, reacciones de oxidación con el fin de degradar sustancias contaminantes presentes en aguas. En este trabajo de investigación se parte de aguas contaminadas en las que se estudia el poder fotosensibilizador de tres SBO obtenidos a partir de residuos agrícolas. Las aguas han sido contaminadas con cuatro compuestos de interés (clorfenvinfos, diclofenaco, pentaclorofenol y terbutrina) y tratadas con foto-Fenton. Para evaluar la eficacia de los SBO y del tratamiento foto-Fenton no sólo hay que asegurar la degradación completa de los contaminantes sino también valorar una detoxificación total de la muestra., [EN] Water is an essential resource for life on this planet, but it is not an unlimited good. Due to global warming, today there are situations of scarcity in areas where it was previously abundant. To this, must be added the continuous development of society, which is accompanied by an increase in urban, industrial and agricultural activities, together with the waste that these generate. Although the main objective is to minimize production, this is not always possible, so the recovery of these waste to be reused in other processes should be an alternative objective. In this context, much effort has been devoted in recent years to obtain valuable products from biodegradable agricultural waste. In recent years bio-organic substances (SBO) isolated from the humid fraction of urban waste have proved useful in a large number of applications. The use of this type of materials becomes interesting due to the economic and environmental advantages they imply. The SBOs have several basic structural similarities with the organic fraction present in natural waters, especially with humic and fulvic acids. Due to these similarities, it would be expected that these substances show photochemical properties, and especially the ability to generate highly reactive species, favoringoxidation reactions in order to degrade polluting substances present in water. In this research work, we start with contaminated water in which the photosensitizing power of three SBO obtained from agricultural waste is studied. The waters have been contaminated with four compounds of interest (chlorfenvinphos, diclofenac, pentachlorophenol and terbutrine) and treated with photo-Fenton. To evaluate the effectiveness of the SBO and the photo-Fenton treatment, we have to evaluate the complete degradation of these contaminants and assess a total detoxification of the sample. For this purpose, an evaluation of the toxicity of the sample is sought before, during and after treatment by a battery of bioassays at t

[EN] Humic-like substances (HLS) extracted from urban wastes have been tested as auxiliaries for the photo Fenton removal of thiabendazole (TBZ) under simulated sunlight. Experimental design methodology based on Doehlert matrices was employed to check the effects of hydrogen peroxide concentration, HLS amount as well as TBZ loading; this last parameter was studied in the range 25-100 mg/L, to include values below and above the limit of solubility at pH = 5. Very satisfactory results were reached when TBZ was above solubility if HLS and H2O2 amounts were high. This could be attributed to an interaction of HLS-TBZ that enhances the solubility of the pollutant. Additional evidence supporting the latter interaction was obtained by fluorescence measurements (excitation emission matrices) and parallel factor analysis (PARAFAC). (C) 2018 Elsevier Ltd. All rights reserved.

[ES] En este proyecto se han sintetizado nuevos fotocatalizadores para estudiar la fotodegradación de contaminantes representativos de aguas residuales. Los fotocatalizadores que se sintetizarán estarán formados por nanopartículas de magnetita soportados directa o indirectamente sobre microesferas de sílice. Con estos catalizadores se estudiará la eficiencia de la oxidación de contaminantes fenólicos mediante reacciones foto-Fenton (generación de radicales hidroxilo). En primer lugar el alumno se familiarizará con la síntesis de materiales, micropartículas de sílice y nanopartículas de magnetita y los métodos de ensamblaje entre ellos. Además de realizar las tareas de síntesis en el laboratorio, usará técnicas de microscopía electrónica (TEM, SEM, etc) para analizar los materiales tanto a nivel de su estructura como en la de su composición. A continuación, el alumno se entrenará en el manejo y diseño de dos tipos de fotorreactores utilizando diferentes tipos de fuentes de luz y finalmente, para los estudios de fotodegradación utilizará el fenol y el 2-fenilfenolcomo representantes de los derivados fenólicos contaminantes de aguas residuales del tratamiento post-cosecha de frutas. Para los estudios de degradación se utilizarán técnicas de análisis y monitorización de reacciones así como la cromatografía de gases y/o el HPLC., [EN] In this project two new photocatalysts have been synthesized, all of them formed by magnetite nanoparticles supported on silica microspheres, and also one of them by using aluminiun. Therefore, the photocatalysts synthesized are SiAlFe and SiFe. Electron microscopy techniques (TEM, SEM and FESEM), X-ray diffraction (XRD) and infrared spectrophotometry have been used to characterize the new materials both at the level of their structure and their composition. With these catalysts, the efficiency of the photooxidation of phenolic contaminants representative of wastewater, such as phenol and 2-phenylphenol, has been studied. Photodegradation studies of these pesticides have been carried out using a photoreactor equipped with lamps emitting at 350 nm. To follow the kinetics of degradation, the technique of column chromatography (HPLC) has been used., [CA] En este projecte s’han sintetitzat nous fotocatalitzadors per a estudiar la fotodegradación de contaminants representatius d’aigües residuals. Els fotocatalitzadors que se sintetitzaran estarán formats per nanopartículas de magnetita suportats directament o indirectament sobre microesferes de sílice. Amb estos catalitzadors s’estudiarà l’eficiéncia de l’oxidació de contaminants fenòlics per mitjà de reaccions foto-Fenton (generació de radicals hidroxil). En primer lloc l’alumne es familiaritzarà amb la síntesi de materials, micropartícules de sílice i nanopartículas de magnetita i els mètodes d’acoblament entre ells. A més de realizar les tasques de síntesi en el laboratori, usarà tècniques de microscòpia electrónica (TEM, SEM, etc) per a analitzar els materials tant a nivell de la seua estructura com en la de la seua composició. A continuación, l’alumne s’entrenarà en el maneig i disseny de dos tipus de fotorreactores utilitzant diferents tipus de fonts de llum i finalment, per als estudis de fotodegradación utilizarà el fenol i el 2-fenilfenol com representats dels derivats fenòlics contaminants d’aigües residuals del tractament post-collita de fruites. Per als estudis de degradació s’utilitzaran tècniques d’anàlisi i monitorització de reaccions així com la cromatografía de gasos y/o el HPLC.

[EN] Humic-like substances (HLS) extracted from urban wastes have been tested as auxiliaries for the photo Fenton removal of thiabendazole (TBZ) under simulated sunlight. Experimental design methodology based on Doehlert matrices was employed to check the effects of hydrogen peroxide concentration, HLS amount as well as TBZ loading; this last parameter was studied in the range 25-100 mg/L, to include values below and above the limit of solubility at pH = 5. Very satisfactory results were reached when TBZ was above solubility if HLS and H2O2 amounts were high. This could be attributed to an interaction of HLS-TBZ that enhances the solubility of the pollutant. Additional evidence supporting the latter interaction was obtained by fluorescence measurements (excitation emission matrices) and parallel factor analysis (PARAFAC). (C) 2018 Elsevier Ltd. All rights reserved.

[EN] Humic-like substances (HLS) extracted from urban wastes have been tested as auxiliaries for the photo Fenton removal of thiabendazole (TBZ) under simulated sunlight. Experimental design methodology based on Doehlert matrices was employed to check the effects of hydrogen peroxide concentration, HLS amount as well as TBZ loading; this last parameter was studied in the range 25-100 mg/L, to include values below and above the limit of solubility at pH = 5. Very satisfactory results were reached when TBZ was above solubility if HLS and H2O2 amounts were high. This could be attributed to an interaction of HLS-TBZ that enhances the solubility of the pollutant. Additional evidence supporting the latter interaction was obtained by fluorescence measurements (excitation emission matrices) and parallel factor analysis (PARAFAC). (C) 2018 Elsevier Ltd. All rights reserved.

[ES] En este proyecto se han sintetizado nuevos fotocatalizadores para estudiar la fotodegradación de contaminantes representativos de aguas residuales. Los fotocatalizadores que se sintetizarán estarán formados por nanopartículas de magnetita soportados directa o indirectamente sobre microesferas de sílice. Con estos catalizadores se estudiará la eficiencia de la oxidación de contaminantes fenólicos mediante reacciones foto-Fenton (generación de radicales hidroxilo). En primer lugar el alumno se familiarizará con la síntesis de materiales, micropartículas de sílice y nanopartículas de magnetita y los métodos de ensamblaje entre ellos. Además de realizar las tareas de síntesis en el laboratorio, usará técnicas de microscopía electrónica (TEM, SEM, etc) para analizar los materiales tanto a nivel de su estructura como en la de su composición. A continuación, el alumno se entrenará en el manejo y diseño de dos tipos de fotorreactores utilizando diferentes tipos de fuentes de luz y finalmente, para los estudios de fotodegradación utilizará el fenol y el 2-fenilfenolcomo representantes de los derivados fenólicos contaminantes de aguas residuales del tratamiento post-cosecha de frutas. Para los estudios de degradación se utilizarán técnicas de análisis y monitorización de reacciones así como la cromatografía de gases y/o el HPLC., [EN] In this project two new photocatalysts have been synthesized, all of them formed by magnetite nanoparticles supported on silica microspheres, and also one of them by using aluminiun. Therefore, the photocatalysts synthesized are SiAlFe and SiFe. Electron microscopy techniques (TEM, SEM and FESEM), X-ray diffraction (XRD) and infrared spectrophotometry have been used to characterize the new materials both at the level of their structure and their composition. With these catalysts, the efficiency of the photooxidation of phenolic contaminants representative of wastewater, such as phenol and 2-phenylphenol, has been studied. Photodegradation studies of these pesticides have been carried out using a photoreactor equipped with lamps emitting at 350 nm. To follow the kinetics of degradation, the technique of column chromatography (HPLC) has been used., [CA] En este projecte s’han sintetitzat nous fotocatalitzadors per a estudiar la fotodegradación de contaminants representatius d’aigües residuals. Els fotocatalitzadors que se sintetitzaran estarán formats per nanopartículas de magnetita suportats directament o indirectament sobre microesferes de sílice. Amb estos catalitzadors s’estudiarà l’eficiéncia de l’oxidació de contaminants fenòlics per mitjà de reaccions foto-Fenton (generació de radicals hidroxil). En primer lloc l’alumne es familiaritzarà amb la síntesi de materials, micropartícules de sílice i nanopartículas de magnetita i els mètodes d’acoblament entre ells. A més de realizar les tasques de síntesi en el laboratori, usarà tècniques de microscòpia electrónica (TEM, SEM, etc) per a analitzar els materials tant a nivell de la seua estructura com en la de la seua composició. A continuación, l’alumne s’entrenarà en el maneig i disseny de dos tipus de fotorreactores utilitzant diferents tipus de fonts de llum i finalment, per als estudis de fotodegradación utilizarà el fenol i el 2-fenilfenol com representats dels derivats fenòlics contaminants d’aigües residuals del tractament post-collita de fruites. Per als estudis de degradació s’utilitzaran tècniques d’anàlisi i monitorització de reaccions així com la cromatografía de gasos y/o el HPLC.

[EN] The aim of this paper is to provide an overview on the different approaches that can be employed to drive a photo-Fenton process under mild conditions, using both heterogeneous and homogeneous iron sources. For this purpose, sections are devoted to the following strategies: a) addition of iron at low concentrations; b) using the matrix of the effluent in order to avoid deactivation of iron; c) addition of chemical auxiliaries to form photoactive complexes with iron, such as carboxylates, chelating agents and humic-like macromolecules; d) strategies leading to the application of heterogeneous photo-Fenton process, by using iron-based solid particles or by hosting iron on different supports and; e) using heterogeneous iron sources as a reservoir for constant dosing of homogeneous iron photocatalyst. In particular, the review will focus on the elimination of emerging pollutants (e.g. drugs, personal care products or pesticides at low concentrations) which are the effluents where applying neutral photo-Fenton seems especially meaningful, although relevant works with other families of pollutants are also considered

[EN] The aim of this paper is to provide an overview on the different approaches that can be employed to drive a photo-Fenton process under mild conditions, using both heterogeneous and homogeneous iron sources. For this purpose, sections are devoted to the following strategies: a) addition of iron at low concentrations; b) using the matrix of the effluent in order to avoid deactivation of iron; c) addition of chemical auxiliaries to form photoactive complexes with iron, such as carboxylates, chelating agents and humic-like macromolecules; d) strategies leading to the application of heterogeneous photo-Fenton process, by using iron-based solid particles or by hosting iron on different supports and; e) using heterogeneous iron sources as a reservoir for constant dosing of homogeneous iron photocatalyst. In particular, the review will focus on the elimination of emerging pollutants (e.g. drugs, personal care products or pesticides at low concentrations) which are the effluents where applying neutral photo-Fenton seems especially meaningful, although relevant works with other families of pollutants are also considered

[EN] An iron-based photochemical process able to act via reductive and oxidative stages by tuning experimental conditions has been explored. In a first step, zero-valent iron (ZVI), added as steel wool, was used to reduce those pollutants reluctant to oxidative processes. Then, the iron released in the solution was employed, upon addition of hydrogen peroxide, to drive a photo-Fenton process. This procedure has been checked with a mixture of five chemicals, namely p-toluenesulfonic acid, benzoic acid, p-nitrobenzoic acid, acetaminophen and caffeic. p-Nitrobenzoic acid resulted to be the most reluctant against oxidation but it was reduced in the absence of H2O2 to form 4-aminobenzoic acid; the presence of salts (e.g. tap water) was required and best results were reached at neutral pH. As p-aminobenzoic acid can be more easily oxidized than p-nitrobenzoic, combination of both stages is meaningful: a ZVI-based reduction followed by a photo-Fenton like-oxidation was employed to remove this pollutant from tested solutions. (C) 2016 Elsevier B.V. All rights reserved.

[EN] An iron-based photochemical process able to act via reductive and oxidative stages by tuning experimental conditions has been explored. In a first step, zero-valent iron (ZVI), added as steel wool, was used to reduce those pollutants reluctant to oxidative processes. Then, the iron released in the solution was employed, upon addition of hydrogen peroxide, to drive a photo-Fenton process. This procedure has been checked with a mixture of five chemicals, namely p-toluenesulfonic acid, benzoic acid, p-nitrobenzoic acid, acetaminophen and caffeic. p-Nitrobenzoic acid resulted to be the most reluctant against oxidation but it was reduced in the absence of H2O2 to form 4-aminobenzoic acid; the presence of salts (e.g. tap water) was required and best results were reached at neutral pH. As p-aminobenzoic acid can be more easily oxidized than p-nitrobenzoic, combination of both stages is meaningful: a ZVI-based reduction followed by a photo-Fenton like-oxidation was employed to remove this pollutant from tested solutions. (C) 2016 Elsevier B.V. All rights reserved.

[EN] The aim of this paper is to provide an overview on the different approaches that can be employed to drive a photo-Fenton process under mild conditions, using both heterogeneous and homogeneous iron sources. For this purpose, sections are devoted to the following strategies: a) addition of iron at low concentrations; b) using the matrix of the effluent in order to avoid deactivation of iron; c) addition of chemical auxiliaries to form photoactive complexes with iron, such as carboxylates, chelating agents and humic-like macromolecules; d) strategies leading to the application of heterogeneous photo-Fenton process, by using iron-based solid particles or by hosting iron on different supports and; e) using heterogeneous iron sources as a reservoir for constant dosing of homogeneous iron photocatalyst. In particular, the review will focus on the elimination of emerging pollutants (e.g. drugs, personal care products or pesticides at low concentrations) which are the effluents where applying neutral photo-Fenton seems especially meaningful, although relevant works with other families of pollutants are also considered