Strategies to Drive Photo-Fenton Process at Mild Conditions for the Removal of Xenobiotics from Aqueous Systems

[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 consideredThis work was performed with the financial of the Marie Sklodowska-Curie Research and Innovation Staff Exchange project funded by the European Commission H2020-MSCA-RISE-2014, within the framework of the research project Mat4treat. Authors also want to thank the financial support of Spanish Ministerio of Economía y Competitividad (TRICERATOPS project and FOTO-CAT excellence network).Santos-Juanes Jordá, L.; Amat Payá, AM.; Arqués Sanz, A. (2017). Strategies to Drive Photo-Fenton Process at Mild Conditions for the Removal of Xenobiotics from Aqueous Systems. Current Organic Chemistry. 21(12):1074-1083. https://doi.org/10.2174/1385272821666170102150337S10741083211

Mild Fenton Processes for the Removal of Preservatives: Interfering Effect of Methylisothiazolinone (MIT) on Paraben Degradation

[EN] The degradation of various preservatives used in the cosmetics industry, including five parabens and their most employed substitute, methylisothiazolinone (MIT), was investigated. A mild photo-Fenton process was applied using low iron concentrations (5 mg/L) at a pH of five, instead of the traditional acidic value of three. At these conditions, the paraben degradation was very low after one hour of reaction and it was necessary to present humic-like substances (HLS) acting as iron chelators to improve the process. Values obtained when MIT was treated were very low, also in the presence of HLS, indicating that their complexing effect was not acting properly. When MIT was added to the mixture of parabens an inhibitory effect was found in the presence of HLS. A possible complex between iron and MIT was suggested and the studies of hydrogen peroxide consumption and Job's plot technique confirmed this hypothesis. Evidence of the formation of this inactive complex, so far never reported, will be essential in future work when dealing with this compound using Fenton processes. Furthermore, this fact points out the importance of using mixtures of model contaminants instead of a single one or a group of the same family, since their ability to form active or inactive complexes with iron can strongly change the behavior of the whole system.Authors want to acknowledge the financial support of Spanish Ministerio de Ciencia, Innovacion y Universidad (RTI 2018-097997-B-C31, Calypsol Project) and Generalitat Valenciana AICO/2021/014.Duarte-Alvarado, V.; Santos-Juanes Jordá, L.; Arqués Sanz, A.; Amat Payá, AM. (2022). Mild Fenton Processes for the Removal of Preservatives: Interfering Effect of Methylisothiazolinone (MIT) on Paraben Degradation. Catalysts. 12(11):1-16. https://doi.org/10.3390/catal12111390116121

Humic like substances for the treatment of scarcely soluble pollutants by mild photo-Fenton process

[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.Authors want to acknowledge the financial support of Spanish Ministerio de Economia y Competitividad (CTQ2015-69832-C04) and European Union (645551-RISE-2014, MAT4TREAT). The present work was partially supported by UNLP (11/X679), ANPCyT (PICT-2015-0374A) and CONICET (PIP: 12-2013-01-00236CO). B. Caram thank the CONICET for his research graduate grant. F. S. Garcia Einschlag is a research member of CONICET.Caram, B.; García-Ballesteros, S.; Santos-Juanes Jordá, L.; Arqués Sanz, A.; Garcia-Einschlag, FS. (2018). Humic like substances for the treatment of scarcely soluble pollutants by mild photo-Fenton process. Chemosphere. 198:139-146. https://doi.org/10.1016/j.chemosphere.2018.01.074S13914619

Unveiling the Dependence between Hydroxyl Radical Generation and Performance of Fenton Systems with Complexed Iron

[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.The authors want to acknowledge the financial support from Ministerio de Ciencia, Innovacion y Universidades (RTI2018-097997-B-C31) and European Union (645551-RISE-2014, MAT4TREAT). P.G.-N. would like to thank Spanish Ministerio de Economia y Competitividad for her fellowship (BES-2016-077962).García-Negueroles, P.; García-Ballesteros, S.; Amat Payá, AM.; Laurenti, E.; Arqués Sanz, A.; Santos-Juanes Jordá, L. (2019). Unveiling the Dependence between Hydroxyl Radical Generation and Performance of Fenton Systems with Complexed Iron. ACS Omega. 4(26):21698-21703. https://doi.org/10.1021/acsomega.9b02241S216982170342

Parabens and Methylisotiazolinone (MIT): Preservatives with Different Behaviors When Subjected to Ozone and Ultraviolet Light Treatments

[EN] The influence that contaminants exert on the degradation of other substances commonly found in the same water bodies drives this study, which aims to investigate the simultaneous degradation of preservatives such as parabens and methylisothiazolinone (MIT). Mixtures of five parabens, MIT solutions, and mixtures of all five parabens plus MIT (each at 5 mg/L) were treated using 254 nm UV light, ozone treatments, and simultaneous ozone and UV light treatments at three different pH levels (3, 5, and 9). Regardless of pH, UV light is inefficient in degrading parabens, whereas MIT is efficiently degraded under this radiation. On the other hand, ozone treatments rapidly degrade the paraben mixture at any pH, with a basic pH resulting in faster degradation due to the predominance of the indirect mechanism. MIT, due to its structural characteristics, reacts minimally with ozone, and the process is enhanced at basic pH when hydroxyl radicals are involved. The simultaneous treatment with ozone and UV light proves to be the fastest method for eliminating both parabens and MIT at any pH. However, when treating joint mixtures of parabens and MIT, behaviors change notably, particularly for processes involving UV light due to the interfering effect of MIT. Both parabens and MIT require more time to degrade, except at an acidic pH. Only MIT reduces its ozone treatment time when treated alongside parabens due to the distinct degradation mechanisms that each type of contaminant has in the presence of ozone.This research was funded by the Generalitat Valenciana (COSMETICFARMA Project, AICO/2021/014) and Spanish Ministerio de Ciencia e Innovacion (AQUAENAGRI) Project, PID2021-126400OB-C31).López-Timoner, R.; Duarte-Alvarado, V.; Castillo, MÁ.; Santos-Juanes Jordá, L.; Arqués Sanz, A.; Amat Payá, AM. (2023). Parabens and Methylisotiazolinone (MIT): Preservatives with Different Behaviors When Subjected to Ozone and Ultraviolet Light Treatments. Water. 15(21):1-16. https://doi.org/10.3390/w15213837116152

Pentachlorophenol Removal from Water by Soybean Peroxidase and Iron(II) Salts Concerted Action

[EN] Soybean peroxidase (SBP) has been employed for the treatment of aqueous solutions containing pentachlorophenol (PCP) in the presence of hydrogen peroxide at pH range 5-7. Reaction carried out with 1mg/L of PCP, 4mg/L of H2O2, and 1.3x10(-9)M of SBP showed a fast initial elimination of PCP (ca. 30% in 20min), but the reaction does not go beyond the removal of 50% of the initial concentration of PCP. Modification in SBP and PCP amounts did not change the reaction profile and higher amounts of H2O2 were detrimental for the reaction. Addition of Fe(II) to the system resulted in an acceleration of the process to reach nearly complete PCP removal at pH 5 or 6; this is more probably due to a synergetic effect of the enzymatic process and Fenton reaction. However, experiments developed in tap water resulted in a lower PCP elimination, but this inconvenience can be partly overcome by leaving the tap water overnight in an open vessel before reaction.We want to acknowledge Davide Mainero from Acea Pinerolese for his collaboration in this research. The authors want to thank the financial support of the European Union (PIRSES-GA-2010-269128, EnvironBOS and Marie Sklodowska-Curie Research and Innovation Staff Exchange projectH2020-MSCA-RISE-2014, Mat4treaT-project number: 645551) and Spanish Ministerio de Educacion y Ciencia (CTQ2015-69832-C4-4-R). Sara Garcia-Ballesteros would like to thank the Spanish Ministerio de Economia y Competitividad for her fellowship (BES-2013-066201).Tolardo, V.; García-Ballesteros, S.; Santos-Juanes Jordá, L.; Vercher Pérez, RF.; Amat Payá, AM.; Arqués Sanz, A.; Laurenti, E. (2019). Pentachlorophenol Removal from Water by Soybean Peroxidase and Iron(II) Salts Concerted Action. 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Treatment and reuse of textile wastewaters by mild solar photo-Fenton in the presence of humic-like substances

The final publication is available at Springer via http://dx.doi.org/10.1007/s11356-016-7889-1In this paper, the possibility of reusing textile effluents for new dyeing baths has been investigated. For this purpose, different trichromies using Direct Red 80, Direct Blue 106, and Direct Yellow 98 on cotton have been used. Effluents have been treated by means of a photo-Fenton process at pH 5. Addition of humic-like substances isolated form urban wastes is necessary in order to prevent iron deactivation because of the formation of non-active iron hydroxides. Laboratory-scale experiments carried out with synthetic effluents show that comparable results were obtained when using as solvent water treated by photo-Fenton with SBO and fresh deionized water. Experiments were scaled up to pilot plant illuminated under sunlight, using in this case a real textile effluent. Decoloration of the effluent could be achieved after moderate irradiation and cotton dyed with this water presented similar characteristics as when deionized water was used.This work was realized with the financial support of a Marie Sklodowska-Curie Research and Innovation Staff Exchange project funded by the European Commission H2020-MSCA-RISE-2014 within the framework of the research project Mat4treaT (project number 645551). Financial support from Spanish Government (CTQ2015-69832-C4-4-R) is gratefully acknowledged. The authors acknowledge the financial support of the Generalitat Valenciana, Conselleria d’Educació, Cultura i Esport (GV/AICO/2015/124) and CTQ2015-69832-C4-4-R.García-Negueroles, P.; Bou-Belda, E.; Santos-Juanes Jordá, L.; Amat Payá, AM.; Arques Sanz, A.; Vercher Pérez, RF.; Monllor Pérez, P.... (2017). Treatment and reuse of textile wastewaters by mild solar photo-Fenton in the presence of humic-like substances. 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Humic like substances extracted from oil mill wastes in photo-Fenton processes: Characterization, performance and toxicity assesment

[EN] Olive mill waste has been used as sourcing materials for the isolation of humic like substances (OMW-HLS) which have demonstrated its capacity to expand the range of applicability of photo-Fenton process to pH= 5. During the isolation process, membranes of three different pore sizes (300 kDa, 150 kDa and 50 kDa) were employed in order to obtain three batches of OMW-HLS. Four pollutants contained in 2013/39/EC were used as target substances: terbutryn (TBT), diclofenac (DCF), chlorfenvinphos (CVF) and pentachlorophenol (PCP). Results showed that OMW-HLS was able to enhance photo-Fenton at pH = 5, but differences were not significant, either among fractions or with commercial humic substances. Reactions were scaled-up and driven under real sunlight and pollutants removal was faster in the presence of OMW-HLS. Toxicity was monitored according to bioassays based on different organisms or cell lines. Detoxification was observed with and without OMW-HLS, although higher toxicity was detected in the presence of humic acids, most probably due to the surfactant effect, that allows a better contact between pollutant and organism.The authors thank the financial support of the European Union H2020 (2018-2022) (Ref. 776816) Proyect O, and Spanish Ministerio de Ciencia, Innovacion y Universidad (RTI 2018-097997-B-C31) . Paula Garcia Negueroles thanks Spanish Ministerio de Ciencia, Innovacion y Universidades for providing their fellowships BES-2016-0777962.García-Negueroles, P.; García-Ballesteros, S.; Santos-Juanes Jordá, L.; Sabater Marco, C.; Castillo López, M.; López Pérez, MF.; Vicente Candela, R.... (2021). Humic like substances extracted from oil mill wastes in photo-Fenton processes: Characterization, performance and toxicity assesment. Journal of Environmental Chemical Engineering. 9(6):1-8. https://doi.org/10.1016/j.jece.2021.106862189

Compuestos orgánicos como fotocatalizadores solares para la eliminación de contaminantes en medios acuosos: aplicaciones y estudios fotofísicos

Como consecuencia de los problemas derivados de la escasez de agua, se está despertando un gran interés en el desarrollo de nuevas técnicas para la depuración de aguas. Una de estas novedosas técnicas es la fotocatálisis que puede emplear la radiación solar como fuente de energía. Con intención de ampliar las posibilidades en la aplicación de la fotocatálisis se va ha estudiar la posibilidad de emplear sensibilizadores orgánicos como fotocatalizadores: el catión 2,4,6-trifeniltiopirilio y el amarillo de acridina G. Ambos fotocatalizadores han conseguido importantes porcentajes de degradación (entre 60 y 80 %) de contaminantes fenólicos modelo como los ácidos ferúlico y cafeico logrando incluso mejores resultados que el dióxido de titanio. Se han escalado estas reacciones a planta piloto empleando la radiación solar directa demostrando la efectividad de estos procesos a escala pre-industrial. Además, los estudios de toxicidad y biodegradabilidad demuestran la total detoxificación del efluente e importantes aumentos en su biodegradabilidad; del orden de entre 6 y 10 veces. Se ha descartado la participación de especies transitorias como el radical hidroxilo o el oxígeno singlete en la oxidación de los contaminantes tratados, mientras que los estudios fotofísicos han demostrado la desactivación de los estados excitados singlete y triplete de los fotocatalizadores a estudio. Conocidos los rendimientos cuánticos de cada estado se han calculado las constantes de desactivación que están en todos los casos limitadas por la difusión en el disolvente. La termodinámica desde cada uno de los estados excitados ha demostrado que el proceso de transferencia electrónica es favorable. Se ha comprobado que la oxidación de los compuestos se lleva a cabo mediante un proceso de transferencia electrónica mayoritariamente desde los estados excitados triplete de los fotocatalizadores.Santos-Juanes Jordá, L. (2008). Compuestos orgánicos como fotocatalizadores solares para la eliminación de contaminantes en medios acuosos: aplicaciones y estudios fotofísicos [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/2642Palanci

Evaluación de la competencia transversal ‘Comunicación Efectiva’ mediante presentaciones en vídeo

Resumen de los autoresGrado en Ingeniería Mecánica (Universidad Politécnica de Valencia)La comunicación efectiva es una de las competencias transversales que se trabajan y evalúan en la Universistat Politècnica de Valencia (UPV). En dicha competencia se valora la capacidad de transmitir conocimientos e ideas con claridad y utilizando los recursos necesarios para ello. Se decidió evaluar esta competencia con la realización de presentaciones orales individuales grabadas en formato video para que se permitiera su visionado y evaluación fuera del horario docente. Durante las clases de esta asignatura (Máquinas Térmicas 3º Grado Ingeniería Mecánica) se suele recurrir al visionado de vídeos de pequeña duración para poder entender el funcionamiento de estas máquinas. Por este motivo, este tipo de vídeos no resultan extraños al alumno y en esta actividad se les propuso que hicieran uno explicando las características, funcionamiento, aplicaciones etc., de una máquina térmica comercial. El resultado obtenido fue muy positivo ya que los alumnos fueron receptivos a realizar este tipo de presentaciones y la habilidad y creatividad de algunos alumnos fue enormemente sorprendente y gratificante.ES