Urban biowaste-derived sensitizing materials for caffeine photodegradation

[EN] Caffeine-photosensitized degradation has been studied in the presence of bio-based materials derived from urban biowaste after aerobic aging. A peculiar fraction (namely bio-based substances (BBSs)), soluble in all the pH range, has been used as photosensitizing agent. Several caffeine photodegradation tests have been performed, and positive results have been obtained in the presence of BBSs and H2O2, without and with additional Fe(II) (photo-Fenton-like process). Moreover, hybrid magnetite-BBS nanoparticles have been synthesized and characterized, in order to improve the sensitizer recovery and reuse after the caffeine degradation. In the presence of such nanoparticles and H2O2 and Fe(II), the complete caffeine degradation has been attained in very short time. Both homogeneous and heterogeneous processes were run at pH = 5, milder condition compared to the classic photo-Fenton process.This work was performed with the financial support for academic interchange by 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 (project number 645551). Compagnia di San Paolo and University of Torino are gratefully acknowledged for funding Project Torino_call2014_L2_126 through BBando per il finanziamento di progetti di ricerca di Ateneo – anno 2014 (Project acronym: Microbusters). Additionally, authors would like to acknowledge Dr. Flavio R. Sives (La Plata, Argentina) for magnetization measurements.Prevot, AB.; Baino, F.; Fabbri, D.; Franzoso, F.; Magnacca, G.; Nistico, R.; Arques Sanz, A. (2017). Urban biowaste-derived sensitizing materials for caffeine photodegradation. Environmental Science and Pollution Research. 24(14):12599-12607. https://doi.org/10.1007/s11356-016-7763S1259912607241

Exploring reuse of industrial wastewater from exhaust dyebaths by solar-based photo-Fenton treatment

The aim of the research under discussion in the present paper is to study the decolorization and mineralization of textile industrial wastewaters from exhaust dyebaths by means of a solar photo-Fenton treatment. The exhaust dyebaths were grouped according to the fibers and dyeing recipes used, so as to verify the effectiveness of the photo-Fenton treatment on each dyeing process separately. Next, the results previously achieved were compared to those obtained by mixing all the exhaust baths together, as is common practice when treating the industrial textile effluents from dyeing and finishing procedures. After their neutralization and filtration, photo-Fenton-treated exhaust dyebaths and mixtures were reused to prepare laboratory dyeing samples. These techniques on the reuse of wastewaters were tested on several fibers by using the same dyeing procedure that was originally applied, as well as in different dyeing processes and for most fiber types. The results achieved showed that the reutilization of the aforementioned effluents, either in new exhaust dyebaths or in some other textile industrial operations, was of some considerable importance. Water consumption would be significantly reduced as well as the wastewater levies for the firms. Furthermore, the contaminating effect of the industrial effluents to be dealt with would be also diminished, reaping environmental and economic benefits.Sanz Carbonell, JF.; Monllor Pérez, P.; Vicente Candela, R.; Amat Payá, AM.; Arques Sanz, A.; Bonet Aracil, MA. (2013). Exploring reuse of industrial wastewater from exhaust dyebaths by solar-based photo-Fenton treatment. Textile Research Journal. 83(13):1325-1332. doi:10.1177/0040517512467061S13251332831

Effect of methylisothiazolinone on biological treatments: Efficiency of SBRs and Bioindicative Studies

Methylisothiazolinone (MIT) is widely used as biocide in hair and skin care products and in high concentrations, more than 150 mg/L, in cooling towers in the paper mill and refinery industry. This product has been recognized as a potent contact allergen and is discharged to the wastewater treatment plants (WWTP) from industrial processes or domestic usages. However, the role of MIT in biological treatment has not been characterized, and therefore, the effect of MIT on the composition and performance of activated sludge has been analyzed. For this purpose, a sequential batch reactor was fed with a synthetic solution containing 5 mg/L of MIT. Addition of MIT had shown no significant effect on organic matter metabolization (dissolved organic carbon [DOC] removal remained constant at 80-90%). On the contrary, a loss of efficiency in the nitrification process occurred (ammonium removal decreased from 90% to 20% per cycle throughout the experiment), first affecting the nitrite oxidizing bacteria and, after around 40 cycles, also the ammonium-oxidizing bacteria disappeared, as shown by fluorescence in situ hybridization analysis. Bioindicative studies based on counts of protozoa and sludge biotic index indicated that, at the end of the process, a stable and well-colonized protozoa community was obtained. Finally, respirometric tests indicated some acclimatization of the heterotrophic bacteria to MIT, as shown by shorter lag periods when the sludge was previously fed with MIT. The role of MIT in biological treatment has been characterized to increase the knowledge about this pollutant effects on activated sludge to improve WWTP performance.We would like to thank the financial support of the Spanish Ministerio de Economia y Competitividad AQUAFOTOX (CTQ2012-38754-C03-02).Amat Payá, AM.; Arques Sanz, A.; López Pérez, MF.; Nácher Pastor, M.; Palacios Guillem, S. (2015). Effect of methylisothiazolinone on biological treatments: Efficiency of SBRs and Bioindicative Studies. Environmental Engineering Science. 32(6):479-485. https://doi.org/10.1089/ees.2014.0283S47948532

Chloride anion effect on the advanced oxidation processes of methidathion and dimethoate: role of Cl2(center dot-) radical

NOTICE: this is the author’s version of a work that was accepted for publication in Water Research. Changes resulting from the publishing process, such as peer review, editing, corrections,structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in WATER RESEARCH [VOL 47, ISSUE 1, (January 2013)] DOI 10.1016/j.watres.2012.10.018¨ IWA Publishing : Set statement to accompany deposit, "©IWA Publishing 2013. The definitive peer-reviewed and edited version of this article is published in Water Research 47 1 351-362 2013 DOI 10.1016/j.watres.2012.10.018 and is available at www.iwapublishing.com."The reaction of phosphor-containing pesticides such as methidathion (MT) and dimethoate (DM) with dichloride radical anions (Cl-2(center dot-)) was investigated. The second order rate constants (1.3 +/- 0.4) x 10(8) and (1.1 0.4) x 10(8) M-1 s(-1) were determined for the reaction of Cl-2(center dot-) with MT and DM, respectively. A reaction mechanism involving an initial charge transfer from the sulfide groups of the insecticides to Cl-2(center dot-) is proposed and supported by the identified transient intermediates and reaction products. The formation of chlorinated byproducts was determined. The unexpected consequences of an efficient Cl-2(center dot-) activity towards MT and DM on the degradation capacity by Advanced Oxidation Procedures applied to polluted waters containing the insecticides and Cl- anions is discussed. (C) 2012 Elsevier Ltd. All rights reserved.This research was financially supported by Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Agencia Nacional de Promocion Cientifica y Tecnologica (Argentina, project PICT 2007 number 00308), and Agencia Espanola de Cooperacion Internacional (project A/8199/07). MCG, JAR and PC are research members of Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Argentina. D.O.M. is a research member of CICPBA, Argentina. This research was supported by the grant PIP 112-200801-00356 from CONICET.Caregnato, P.; Rosso, JA.; Soler Escoda, JM.; Arques Sanz, A.; Martire, DO.; González, MC. (2013). Chloride anion effect on the advanced oxidation processes of methidathion and dimethoate: role of Cl2(center dot-) radical. Water Research. 47(1):351-362. https://doi.org/10.1016/j.watres.2012.10.018S35136247

Humic-like substances from urban waste as auxiliaries for photo-Fenton treatment: a fluorescence EEM-PARAFAC study

[EN] In this work, analysis of excitation-emission-matrices (EEM) has been employed to gain further insight into the characterization of humic like substances (HLS) obtained from urban wastes (soluble bio-organic substances, SBOs). In particular, complexation of these substances with iron and changes along a photo-Fenton process have been studied. Recorded EEMs were decomposed by using parallel factor analysis (PARAFAC). Three fluorescent components were identified by PARAFAC modeling of the entire set of SBO solutions studied. The EEM peak locations (lambda(ex)/lambda(em)) of these components were 310-330 nm/400-420 nm (C1), 340-360 nm/450-500 nm (C2), and 285 nm/335-380 nm (C3). Slight variations of the maximum position of each component with the solution pH were observed. The interaction of SBO with Fe(III) was characterized by determining the stability constants of the components with Fe(III) at different pH values, which were in the order of magnitude of the ones reported for humic substances and reached their highest values at pH = 5. Photochemical experiments employing SBO and Fe(III), with and without H2O2, showed pH-dependent trends for the evolution of the modeled components, which exhibited a strong correlation with the efficiency reported for the photo-Fenton processes in the presence of SBO at different pH values.This work was supported by Generalitat Valenciana, Conselleria d'Ecuacio, Cultura i esport, Spain (GV/2015/074), Spanish Ministerio de Economia y Competitividad (CTQ2015-69832-C4-4-R) and by the Marie Sklodowska-Curie Research and Innovation Staff Exchange project funded by the European Commission H2020-MSCA-RISE-2014 (Project number: 645551). F. S. G. E. and L. C. are researchers from CONICET, Argentina.García-Ballesteros, S.; Constante, M.; Vicente Candela, R.; Mora Carbonell, M.; Amat Payá, AM.; Arques Sanz, A.; Carlos, L.... (2017). Humic-like substances from urban waste as auxiliaries for photo-Fenton treatment: a fluorescence EEM-PARAFAC study. Photochemical & Photobiological Sciences. 16:38-45. https://doi.org/10.1039/c6pp00236fS384516Malato, S., Fernández-Ibáñez, P., Maldonado, M. I., Blanco, J., & Gernjak, W. (2009). Decontamination and disinfection of water by solar photocatalysis: Recent overview and trends. Catalysis Today, 147(1), 1-59. doi:10.1016/j.cattod.2009.06.018WANG, J. L., & XU, L. J. (2012). Advanced Oxidation Processes for Wastewater Treatment: Formation of Hydroxyl Radical and Application. Critical Reviews in Environmental Science and Technology, 42(3), 251-325. doi:10.1080/10643389.2010.507698Pignatello, J. J., Oliveros, E., & MacKay, A. (2006). Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry. Critical Reviews in Environmental Science and Technology, 36(1), 1-84. doi:10.1080/10643380500326564Papoutsakis, S., Miralles-Cuevas, S., Oller, I., Garcia Sanchez, J. L., Pulgarin, C., & Malato, S. (2015). Microcontaminant degradation in municipal wastewater treatment plant secondary effluent by EDDS assisted photo-Fenton at near-neutral pH: An experimental design approach. Catalysis Today, 252, 61-69. doi:10.1016/j.cattod.2015.02.005Klamerth, N., Malato, S., Agüera, A., & Fernández-Alba, A. (2013). Photo-Fenton and modified photo-Fenton at neutral pH for the treatment of emerging contaminants in wastewater treatment plant effluents: A comparison. Water Research, 47(2), 833-840. doi:10.1016/j.watres.2012.11.008De Luca, A., Dantas, R. F., & Esplugas, S. (2015). Study of Fe(III)-NTA chelates stability for applicability in photo-Fenton at neutral pH. 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Degradation of 32 emergent contaminants by UV and neutral photo-fenton in domestic wastewater effluent previously treated by activated sludge. Water Research, 46(6), 1947-1957. doi:10.1016/j.watres.2012.01.014Gomis, J., Vercher, R. F., Amat, A. M., Mártire, D. O., González, M. C., Bianco Prevot, A., … Carlos, L. (2013). Application of soluble bio-organic substances (SBO) as photocatalysts for wastewater treatment: Sensitizing effect and photo-Fenton-like process. Catalysis Today, 209, 176-180. doi:10.1016/j.cattod.2012.08.036Gomis, J., Carlos, L., Prevot, A. B., Teixeira, A. C. S. C., Mora, M., Amat, A. M., … Arques, A. (2015). Bio-based substances from urban waste as auxiliaries for solar photo-Fenton treatment under mild conditions: Optimization of operational variables. Catalysis Today, 240, 39-45. doi:10.1016/j.cattod.2014.03.034Gomis, J., Bianco Prevot, A., Montoneri, E., González, M. C., Amat, A. M., Mártire, D. O., … Carlos, L. (2014). 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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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Solar photocatalytic detoxification of cyanide effluents from metal finishing industry

[En] Wastewaters from metal fi nishing industry contain, among other pollutants, high amounts of cyanide and heavy metals, which results in a high toxicity of the effl uent. Therefore, it is necessary to detoxify the effl uent before discharging to a sewage treatment plant which commonly consists in a biological treatment. In this study, we analyzed different photocatalytic methods for cyanide removal: photo-Fenton, Fenton-like with metals such as manganese, zinc, silver, cobalt, chromium and copper and photocatalysis with addition of other oxidants such as persulfate. Initially, we performed a study on synthetic water prepared with contaminants found in real wastewater. In order to better simulate real conditions, the possible interferences from ions usually present in water, such as carbonates, sulfates, fl uorides or nitrates has been studied. The best treatment (Fenton-Like) was applied to real wastewaters from a metallurgical industry of the east of Spain, containg high amounts of copper. The global analysis of the treatments determined that the best results were obtained by applying solar photo-Fenton process and photo-Fenton-like processes with copper. The total degradation of cyanide and copper precipitation was achieved, improving the characteristics of the treated effl uent.[ES] Las aguas procedentes de la industria metalúrgica contienen, entre otros contaminantes, grandes cantidades de cianuro y metales pesados que les confieren elevadas toxicidades; por ello se hace necesario detoxificar estos efluentes antes de verterlos a una Estación de Depuración de Aguas Residuales Urbanas (EDARU) con tratamientos biológicos. En este estudio se analizan distintos métodos fotocatalíticos para la eliminación de cianuro: proceso foto-Fenton, Fentonlike con diferentes metales frecuentes en aguas reales, como manganeso, cinc, plata, cobalto, cromo y cobre y fotocatálisis solar con adición de oxidantes adicionales como persulfato. Inicialmente, se realiza un estudio sobre aguas preparadas con contaminantes encontrados en las analíticas de aguas de empresa. Con objeto de acercarnos más a condiciones reales, se determinan posibles interferencias causadas por iones presentes en aguas de forma habitual: carbonatos, sulfatos, fluoruros y nitratos. El tratamiento que proporciona mejores resultados (proceso similares al fotoFenton: ¿foto-Like-Fenton¿) se aplica en las aguas procedentes de una industria metalúrgica de la Comunidad Valenciana, cuyas aguas contienen cobre en cantidad suficiente como para influir de manera beneficiosa en el proceso. El análisis global de los tratamientos aplicados determina que los mejores resultados se obtienen con la aplicación del proceso foto-Fenton solar y procesos fotocatalíticos similares con cobre; se consigue la total degradación del cianuro y la precipitación final del cobre que favorece su eliminación del efluente mediante aplicación de un filtro prensa.Silvestre Mira, M.; Vercher Pérez, RF.; Palacios Guillem, S.; Arqués Sanz, A.; Amat Payá, AM.; Añó Montalvá, EJ. (2012). Detoxificación por fotocatálisis solar de efl uentes cianurados provenientes de una industria metalúrgica. Dyna Ingeniería e Industria. 87(6):698-706. doi:10.6036/4676S69870687

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

Combined nanofiltration and photo-Fenton treatment of water containing micropollutants

[EN] The purpose of this study was to find out whether the use of a combination of nanofiltration (NF) and solar photo-Fenton is more efficient than photo-Fenton alone as a tertiary treatment. Five different pharmaceuticals (carbamazepine, flumequine, ibuprofen, ofloxacin, and sulfamethoxazole) dissolved (100 mu g L-1) in natural water were preconcentrated by NF and treated by solar photo-Fenton. Photo-Fenton was operated at pH 5 with 5 mg L-1 of Fe2+. The NF system consists of two membranes operating simultaneously with a total surface area of 5.2 m(2). The photo-Fenton experiments were carried out in a 3 m(2) CPC solar pilot plant with a 35 L total volume. Hydrogen peroxide consumption and the pharmaceutical removal rate were used as the key evaluation parameters. It was demonstrated that at higher initial concentrations of microcontaminants, hydrogen peroxide is used more efficiently and NF pretreatment also reduced the photo-Fenton treatment time. Combined NF and photo-Fenton treatment was therefore found to be a promising approach for wastewater containing extremely low concentrations of microcontaminants. (C) 2012 Elsevier B.V. All rights reserved.Pentair Water Process Technology BV/X-Flow BV (Enschede, The Netherlands) are kindly acknowledged for providing the nanofiltration unit. The authors wish to thank the Spanish Ministry of Science and Innovation for financial support under the EDARSOL Project (Reference: CTQ2009-13459-C05-01).Miralles Cuevas, S.; Arqués Sanz, A.; Maldonado, MI.; Sánchez Pérez, JA.; Rodríguez, SM. (2013). Combined nanofiltration and photo-Fenton treatment of water containing micropollutants. Chemical Engineering Journal. 224:89-95. doi:10.1016/j.cej.2012.09.068S899522

A mechanistic study on photocatalysis by thiapyrylium salts. Photodegradationof dimethoate, alachlor and pyrimethanil under simulated sunlight

Photodegradation of dimethoate, alachlor, and pyrimethanil using a thiapyrilium salt (TPTP+) as photocatalyst was performed under simulated sunlight. The photocatalyst removes preferentially pyrimethanil (45% after 60 min of irradiation), followed by dimethoate (20%) and alachlor (13%). In the three cases, an important to moderate decrease of the fluorescence intensity upon addition of the pollutants was observed. The active participation of the singlet excited state in the photodegradation of the pollutants was demonstrated; the corresponding dynamic quenching rate constants were found to be 1.9 x 10(10) M-1 s(-1) (pyrimethanil), 6.7 x 10(9) M-1 s(-1) (dimethoate) and 9.1 x 10(9) M-1 s(-1) Moreover, a decrease in the signal corresponding to the triplet excited state was observed immediately after the laser pulse; again a good correlation was observed between the missing fraction of triplets and the photodegradation rates under solar light. Detection of TPT+, the reduced species derived from the photocatalyst, as well as Rehm-Weller calculations on the free energy changes, strongly support an electron transfer mechanism occurring from the singlet excited state. (C) 2012 Published by Elsevier B.V.Financial support from the Spanish Government (CTQ200913699, CTQ2009-13459-C05-03/PPQ and RIRAAF RETICS), and the Generalitat Valenciana (Prometeo Program and ACOM/2011/173) is gratefully acknowledged.Gomis Vicens, J.; Arques Sanz, A.; Amat Payá, AM.; Marín García, ML.; Miranda Alonso, MÁ. (2012). A mechanistic study on photocatalysis by thiapyrylium salts. Photodegradationof dimethoate, alachlor and pyrimethanil under simulated sunlight. Applied Catalysis B: Environmental. 123-124:208-213. https://doi.org/10.1016/j.apcatb.2012.04.025S208213123-12