Ireland’s Rural Environment: Research Highlights from Johnstown Castle

ReportThis booklet gives a flavour of the current research in Teagasc Johnstown Castle Research Centre and introduces you to the staff involved. It covers the areas of Nutrient Efficiency, Gaseous emissions, Agricultural Ecology, Soils and Water quality

Photo-Fenton reaction at mildly acidic conditions: assessing the effect of bio-organic substances of different origin and characteristics through experimental design

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.The authors express their gratitude to CNPq (National Council for Scientific and Technological Development) and to the European Union (PIRSES-GA-2010-269128, EnvironBOS). This study was financed in part by the Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior - Brasil (CAPES) - Finance Code 001.Lastre-Acosta, AM.; Vicente Candela, R.; Mora Carbonell, M.; Jáuregui-Haza, UJ.; Arqués Sanz, A.; Teixeira, ACSC. (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. https://doi.org/10.1080/10934529.2019.1585721S711720548Ikehata, K., Jodeiri Naghashkar, N., & Gamal El-Din, M. (2006). Degradation of Aqueous Pharmaceuticals by Ozonation and Advanced Oxidation Processes: A Review. Ozone: Science & Engineering, 28(6), 353-414. doi:10.1080/01919510600985937Klavarioti, M., Mantzavinos, D., & Kassinos, D. (2009). Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes. Environment International, 35(2), 402-417. doi:10.1016/j.envint.2008.07.009Malato, 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.2009.06.018Pignatello, 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:10.1080/10643380500326564Wu, Y., Passananti, M., Brigante, M., Dong, W., & Mailhot, G. (2014). Fe(III)–EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound. Environmental Science and Pollution Research, 21(21), 12154-12162. doi:10.1007/s11356-014-2945-1Klamerth, 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.2012.11.008Bernabeu, A., Palacios, S., Vicente, R., Vercher, R. F., Malato, S., Arques, A., & Amat, A. M. (2012). Solar photo-Fenton at mild conditions to treat a mixture of six emerging pollutants. Chemical Engineering Journal, 198-199, 65-72. doi:10.1016/j.cej.2012.05.056Gomis, J., Gonçalves, M. G., Vercher, R. F., Sabater, C., Castillo, M.-A., Prevot, A. B., … Arques, A. (2015). Determination of photostability, biocompatibility and efficiency as photo-Fenton auxiliaries of three different types of soluble bio-based substances (SBO). Catalysis Today, 252, 177-183. doi:10.1016/j.cattod.2014.10.015Gomis, 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., 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.2012.08.036Montoneri, E., Boffa, V., Savarino, P., Perrone, D., Ghezzo, M., Montoneri, C., & Mendichi, R. (2011). Acid soluble bio-organic substances isolated from urban bio-waste. Chemical composition and properties of products. Waste Management, 31(1), 10-17. doi:10.1016/j.wasman.2010.08.029Arques, A., & Bianco Prevot, A. (Eds.). (2015). Soluble Bio-based Substances Isolated From Urban Wastes. SpringerBriefs in Molecular Science. doi:10.1007/978-3-319-14744-4Bianco Prevot, A., Fabbri, D., Pramauro, E., Baiocchi, C., Medana, C., Montoneri, E., & Boffa, V. (2010). Sensitizing effect of bio-based chemicals from urban wastes on the photodegradation of azo-dyes. Journal of Photochemistry and Photobiology A: Chemistry, 209(2-3), 224-231. doi:10.1016/j.jphotochem.2009.11.020Bianco Prevot, A., Avetta, P., Fabbri, D., Laurenti, E., Marchis, T., Perrone, D. G., … Boffa, V. (2010). Waste-Derived Bioorganic Substances for Light-Induced Generation of Reactive Oxygenated Species. ChemSusChem, 4(1), 85-90. doi:10.1002/cssc.201000237Carlos, L., Mártire, D. O., Gonzalez, M. C., Gomis, J., Bernabeu, A., Amat, A. M., & Arques, A. (2012). Photochemical fate of a mixture of emerging pollutants in the presence of humic substances. Water Research, 46(15), 4732-4740. doi:10.1016/j.watres.2012.06.022Mohajerani, M., Mehrvar, M., & Ein-Mozaffari, F. (2012). Using an external-loop airlift sonophotoreactor to enhance the biodegradability of aqueous sulfadiazine solution. Separation and Purification Technology, 90, 173-181. doi:10.1016/j.seppur.2012.02.025Conde-Cid, M., Álvarez-Esmorís, C., Paradelo-Núñez, R., Nóvoa-Muñoz, J. C., Arias-Estévez, M., Álvarez-Rodríguez, E., … Núñez-Delgado, A. (2018). Occurrence of tetracyclines and sulfonamides in manures, agricultural soils and crops from different areas in Galicia (NW Spain). Journal of Cleaner Production, 197, 491-500. doi:10.1016/j.jclepro.2018.06.217Amat, A. M., Arques, A., García-Ripoll, A., Santos-Juanes, L., Vicente, R., Oller, I., … Malato, S. (2009). A reliable monitoring of the biocompatibility of an effluent along an oxidative pre-treatment by sequential bioassays and chemical analyses. Water Research, 43(3), 784-792. doi:10.1016/j.watres.2008.11.017Ferreira, S. L. ., dos Santos, W. N. ., Quintella, C. M., Neto, B. B., & Bosque-Sendra, J. M. (2004). Doehlert matrix: a chemometric tool for analytical chemistry—review. Talanta, 63(4), 1061-1067. doi:10.1016/j.talanta.2004.01.015Gomis, J., Bianco Prevot, A., Montoneri, E., González, M. C., Amat, A. M., Mártire, D. O., … Carlos, L. (2014). Waste sourced bio-based substances for solar-driven wastewater remediation: Photodegradation of emerging pollutants. Chemical Engineering Journal, 235, 236-243. doi:10.1016/j.cej.2013.09.009Silva, M. P., Lastre-Acosta, A. M., Mostafa, S., McKay, G., Linden, K. G., Rosario-Ortiz, F. L., & Teixeira, A. C. S. C. (2017). Photochemical generation of reactive intermediates from urban-waste bio-organic substances under UV and solar irradiation. Environmental Science and Pollution Research, 24(22), 18470-18478. doi:10.1007/s11356-017-9310-0Lastre-Acosta, A. M., Barberato, B., Parizi, M. P. S., & Teixeira, A. C. S. C. (2018). Direct and indirect photolysis of the antibiotic enoxacin: kinetics of oxidation by reactive photo-induced species and simulations. Environmental Science and Pollution Research, 26(5), 4337-4347. doi:10.1007/s11356-018-2555-4Helms, J. R., Stubbins, A., Ritchie, J. D., Minor, E. C., Kieber, D. J., & Mopper, K. (2008). Absorption spectral slopes and slope ratios as indicators of molecular weight, source, and photobleaching of chromophoric dissolved organic matter. Limnology and Oceanography, 53(3), 955-969. doi:10.4319/lo.2008.53.3.095

Degradation of congo red dye in aqueous solution by using advanced oxidation processes / Alya Nadhira Nasron... [et al.]

Degradation of azo dyes by using advanced oxidation processes (AOPs) was conducted. In this approach, different AOPs, which are Fenton process and titanium dioxide (TiO 2 ) catalyst, were examined and compared for the degradation of an azo dye (i.e., Congo red dye). The sample was tested under UV light and the experiment was conducted for 90 min with 15 min interval. The degradation rate of dye was determined using UV-Vis spectrophotometry. The effect of several parameters on the degradation process such as the concentration of metal ions (Fe 2+ , Cu 2+ , and Mn 2+ ) as the catalyst in Fenton process, the concentration of hydrogen peroxide (H 2 O 2 ), the mass of TiO 2 , and pH value of the dye solution were investigated. The initial Congo red concentration used for both techniques was 5 ppm. The results showed that the percentage degradation followed the sequence of H 2 O 2 /Fe 2+ /UV, H 2 O 2 /Cu 2+ /UV, H 2 O 2 /Mn 2+ /UV, and TiO 2 /UV. The best operating conditions for H 2 O 2 /Fe 2+ /UV were pH 3, 0.2 M concentration of H 2 O 2 , and 0.02 M concentration of metal ion in 15 min, which achieved 99.92% degradation of dye. The Fourier transform infrared (FTIR) spectrum showed the absence of azo bond (N=N) peak after degradation process, which indicates the successful cleavage of azo bond in the chemical structure of Congo red

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. Applied Catalysis B: Environmental, 179, 372-379. doi:10.1016/j.apcatb.2015.05.025Bernabeu, A., Palacios, S., Vicente, R., Vercher, R. F., Malato, S., Arques, A., & Amat, A. M. (2012). Solar photo-Fenton at mild conditions to treat a mixture of six emerging pollutants. Chemical Engineering Journal, 198-199, 65-72. doi:10.1016/j.cej.2012.05.056Klamerth, N., Malato, S., Maldonado, M. I., Agüera, A., & Fernández-Alba, A. (2011). Modified photo-Fenton for degradation of emerging contaminants in municipal wastewater effluents. Catalysis Today, 161(1), 241-246. doi:10.1016/j.cattod.2010.10.074Voelker, B. M., Morel, F. M. M., & Sulzberger, B. (1997). Iron Redox Cycling in Surface Waters:  Effects of Humic Substances and Light. Environmental Science & Technology, 31(4), 1004-1011. doi:10.1021/es9604018De la Cruz, N., Giménez, J., Esplugas, S., Grandjean, D., de Alencastro, L. F., & Pulgarín, C. (2012). 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). Waste sourced bio-based substances for solar-driven wastewater remediation: Photodegradation of emerging pollutants. Chemical Engineering Journal, 235, 236-243. doi:10.1016/j.cej.2013.09.009Avetta, P., Berto, S., Bianco Prevot, A., Minella, M., Montoneri, E., Persico, D., … Arques, A. (2015). Photoinduced transformation of waste-derived soluble bio-based substances. Chemical Engineering Journal, 274, 247-255. doi:10.1016/j.cej.2015.03.126Gomis, J., Gonçalves, M. G., Vercher, R. F., Sabater, C., Castillo, M.-A., Prevot, A. B., … Arques, A. (2015). Determination of photostability, biocompatibility and efficiency as photo-Fenton auxiliaries of three different types of soluble bio-based substances (SBO). Catalysis Today, 252, 177-183. doi:10.1016/j.cattod.2014.10.015Berkovic, A. M., García Einschlag, F. S., Gonzalez, M. C., Pis Diez, R., & Mártire, D. O. (2013). Evaluation of the Hg2+binding potential of fulvic acids from fluorescence excitation–emission matrices. Photochem. Photobiol. Sci., 12(2), 384-392. doi:10.1039/c2pp25280eStedmon, C. A., & Bro, R. (2008). Characterizing dissolved organic matter fluorescence with parallel factor analysis: a tutorial. Limnology and Oceanography: Methods, 6(11), 572-579. doi:10.4319/lom.2008.6.572Ishii, S. K. L., & Boyer, T. H. (2012). Behavior of Reoccurring PARAFAC Components in Fluorescent Dissolved Organic Matter in Natural and Engineered Systems: A Critical Review. Environmental Science & Technology, 46(4), 2006-2017. doi:10.1021/es2043504Su, Y., Chen, F., & Liu, Z. (2015). Comparison of optical properties of chromophoric dissolved organic matter (CDOM) in alpine lakes above or below the tree line: insights into sources of CDOM. Photochemical & Photobiological Sciences, 14(5), 1047-1062. doi:10.1039/c4pp00478gYang, X., Meng, F., Huang, G., Sun, L., & Lin, Z. (2014). Sunlight-induced changes in chromophores and fluorophores of wastewater-derived organic matter in receiving waters – The role of salinity. 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INVESTIGAÇÃO DO USO DO PROCESSO INTEGRADO FENTON - COAGULAÇÃO NO TRATAMENTO TERCIÁRIO DE EFLUENTE FRIGORÍFICO

Os Processos de Oxidação Avançada (POAs), como o Fenton, têm se apresentado como métodos eficientes e promissores na degradação e remoção de compostos orgânicos resistentes aos tratamentos convencionais, podendo ser utilizado para o polimento do efluente tratado biologicamente. O presente trabalho teve como objetivo avaliar os efeitos dos parâmetros operacionais do processo integrado Fenton - Coagulação no tratamento terciário de um efluente frigorífico. Com base em estudos na literatura, as variáveis investigadas foram: pHREAÇÃO, razão [H2O2]/[DQO], razão [Fe+2]/[H2O2] e pHCOAGULAÇÃO. Os ensaios foram conduzidos em triplicata de acordo com o planejamento fatorial fracionário 24-1 com três repetições no ponto central, totalizando em 11 ensaios. A eficiência do processo proposto foi determinada em cada ensaio experimental em função da eficiência de remoção da demanda química de oxigênio (DQO). A máxima remoção de DQO, 65,81%, ocorreu nas condições de pHREAÇÃO 4,0, razão [H2O2]/[DQO] 1,5, razão [Fe+2]/[ H2O2] 0,5 e pHCOAGULAÇÃO 6,0. Os resultados obtidos comprovaram a eficiência do processo integrado Fenton - Coagulação no tratamento terciário de efluentes agroindustriais.&nbsp

Graphenes as Efficient Metal-Free Fenton Catalysts

[EN] Reduced graphene oxide exhibits high activity as Fenton catalyst with HO. radical generation efficiency over 82 % and turnover nos. of 4540 and 15023 for phenol degrdn. and H2O2 consumption, resp. These values compare favorably with those achieved with transition metals, showing the potential of carbocatalysts for the Fenton reaction.Financial support by Generalidad Valenciana (GV/2013/040 and Prometeo 2012/2013) is gratefully acknowledged. Spanish Ministry of Economy and Competitiveness is also thanked for funding (Severo Ochoa and CTQ2012-32315).Espinosa, JC.; Navalón Oltra, S.; Primo Arnau, AM.; Moral, M.; Fernandez Sanz, J.; Alvaro Rodríguez, MM.; García Gómez, H. (2015). Graphenes as Efficient Metal-Free Fenton Catalysts. Chemistry - A European Journal. 21(34):11966-11971. https://doi.org/10.1002/chem.201501533S11966119712134Stratakis, M., & Garcia, H. (2012). Catalysis by Supported Gold Nanoparticles: Beyond Aerobic Oxidative Processes. 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R., Park, S., Bielawski, C. W., & Ruoff, R. S. (2010). The chemistry of graphene oxide. Chem. Soc. Rev., 39(1), 228-240. doi:10.1039/b917103gSchaetz, A., Zeltner, M., & Stark, W. J. (2012). Carbon Modifications and Surfaces for Catalytic Organic Transformations. ACS Catalysis, 2(6), 1267-1284. doi:10.1021/cs300014kDreyer, D. R., Jia, H.-P., & Bielawski, C. W. (2010). Graphene Oxide: A Convenient Carbocatalyst for Facilitating Oxidation and Hydration Reactions. Angewandte Chemie, 122(38), 6965-6968. doi:10.1002/ange.201002160Primo, A., Navalón, S., Asiri, A. M., & García, H. (2014). Chitosan-Templated Synthesis of Few-Layers Boron Nitride and its Unforeseen Activity as a Fenton Catalyst. Chemistry - A European Journal, 21(1), 324-330. doi:10.1002/chem.201405469Zhao, Y., Chen, W., Yuan, C., Zhu, Z., & Yan, L. (2012). Hydrogenated Graphene as Metal-free Catalyst for Fenton-like Reaction. Chinese Journal of Chemical Physics, 25(3), 335-338. doi:10.1088/1674-0068/25/03/335-338Pignatello, 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:10.1080/10643380500326564Neyens, E., & Baeyens, J. (2003). A review of classic Fenton’s peroxidation as an advanced oxidation technique. Journal of Hazardous Materials, 98(1-3), 33-50. doi:10.1016/s0304-3894(02)00282-0Pera-Titus, M., Garcı́a-Molina, V., Baños, M. A., Giménez, J., & Esplugas, S. (2004). Degradation of chlorophenols by means of advanced oxidation processes: a general review. Applied Catalysis B: Environmental, 47(4), 219-256. doi:10.1016/j.apcatb.2003.09.010Navalon, S., Alvaro, M., & Garcia, H. (2010). Heterogeneous Fenton catalysts based on clays, silicas and zeolites. 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D. (2010). Preparation and Evaluation of Graphite Oxide Reduced at 220 °C. Chemistry of Materials, 22(19), 5625-5629. doi:10.1021/cm102005mJin, M., Jeong, H.-K., Kim, T.-H., So, K. P., Cui, Y., Yu, W. J., … Lee, Y. H. (2010). Synthesis and systematic characterization of functionalized graphene sheets generated by thermal exfoliation at low temperature. Journal of Physics D: Applied Physics, 43(27), 275402. doi:10.1088/0022-3727/43/27/275402Primo, A., Atienzar, P., Sanchez, E., Delgado, J. M., & García, H. (2012). From biomass wastes to large-area, high-quality, N-doped graphene: catalyst-free carbonization of chitosan coatings on arbitrary substrates. Chemical Communications, 48(74), 9254. doi:10.1039/c2cc34978gPrimo, A., Sánchez, E., Delgado, J. M., & García, H. (2014). High-yield production of N-doped graphitic platelets by aqueous exfoliation of pyrolyzed chitosan. Carbon, 68, 777-783. doi:10.1016/j.carbon.2013.11.068Konios, D., Stylianakis, M. M., Stratakis, E., & Kymakis, E. (2014). Dispersion behaviour of graphene oxide and reduced graphene oxide. Journal of Colloid and Interface Science, 430, 108-112. doi:10.1016/j.jcis.2014.05.033Dreyer, D. R., Todd, A. D., & Bielawski, C. W. (2014). Harnessing the chemistry of graphene oxide. Chemical Society Reviews, 43(15), 5288. doi:10.1039/c4cs00060aSilva, C. M., Silva, P. L., & Pliego, J. R. (2013). Prediction of the pH-rate profile for dimethyl sulfide oxidation by hydrogen peroxide: The role of elusive H3O2+Ion. International Journal of Quantum Chemistry, 114(8), 501-507. doi:10.1002/qua.24594Sun, J.-H., Sun, S.-P., Wang, G.-L., & Qiao, L.-P. (2007). Degradation of azo dye Amido black 10B in aqueous solution by Fenton oxidation process. Dyes and Pigments, 74(3), 647-652. doi:10.1016/j.dyepig.2006.04.006Bagri, A., Mattevi, C., Acik, M., Chabal, Y. J., Chhowalla, M., & Shenoy, V. B. (2010). Structural evolution during the reduction of chemically derived graphene oxide. Nature Chemistry, 2(7), 581-587. doi:10.1038/nchem.686Choudhary, S., Mungse, H. P., & Khatri, O. P. (2013). Hydrothermal Deoxygenation of Graphene Oxide: Chemical and Structural Evolution. Chemistry - An Asian Journal, 8(9), 2070-2078. doi:10.1002/asia.201300553Navalon, S., Martin, R., Alvaro, M., & Garcia, H. (2010). Gold on Diamond Nanoparticles as a Highly Efficient Fenton Catalyst. Angewandte Chemie International Edition, 49(45), 8403-8407. doi:10.1002/anie.201003216Navalon, S., Martin, R., Alvaro, M., & Garcia, H. (2010). Gold on Diamond Nanoparticles as a Highly Efficient Fenton Catalyst. Angewandte Chemie, 122(45), 8581-8585. doi:10.1002/ange.201003216Martin, R., Navalon, S., Delgado, J. J., Calvino, J. J., Alvaro, M., & Garcia, H. (2011). Influence of the Preparation Procedure on the Catalytic Activity of Gold Supported on Diamond Nanoparticles for Phenol Peroxidation. Chemistry - A European Journal, 17(34), 9494-9502. doi:10.1002/chem.201100955Wu, P., Du, P., Zhang, H., & Cai, C. (2013). Microscopic effects of the bonding configuration of nitrogen-doped graphene on its reactivity toward hydrogen peroxide reduction reaction. Physical Chemistry Chemical Physics, 15(18), 6920. doi:10.1039/c3cp50900aBurkitt, M. J., & Mason, R. P. (1991). Direct evidence for in vivo hydroxyl-radical generation in experimental iron overload: an ESR spin-trapping investigation. Proceedings of the National Academy of Sciences, 88(19), 8440-8444. doi:10.1073/pnas.88.19.8440Navalon, S., Martin, R., Alvaro, M., & Garcia, H. (2011). Sunlight-Assisted Fenton Reaction Catalyzed by Gold Supported on Diamond Nanoparticles as Pretreatment for Biological Degradation of Aqueous Phenol Solutions. ChemSusChem, 4(5), 650-657. doi:10.1002/cssc.201000453Navalon, S., Sempere, D., Alvaro, M., & Garcia, H. (2013). 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Effect of the air pressure on electro-Fenton process

Electro-Fenton process is considered a very promising tool for the treatment of waste waters contaminated by organic pollutants refractant or toxic for microorganisms used in biological processes [1-6]. In these processes H2O2 is continuously supplied to an acidic aqueous solution contained in an electrolytic cell from the two-electron reduction of oxygen gas, directly injected as pure gas or bubbled air. Due to the poor solubility of O2 in aqueous solutions, two dimensional cheap graphite or carbon felt electrodes give quite slow generation of H2O2, thus resulting in a slow abatement of organics. In this context, we report here a series of studies [7-9] on the effect of air pressure on the electro-generation of H2O2 and the abatement of organic pollutants in water by electro-Fenton process. The effect of air pressure, current density, mixing and nature of the organic pollutant was evaluated. [1] E. Brillas, I. Sirés, M.A. Oturan, Chem. Rev., 109 (2009) 6570-6631. [2] C.A. Martínez-Huitle, M.A. Rodrigo, I. Sirés, O. Scialdone, Chem. Rev. 115 (2015) 13362–13407. [3] M. Panizza, G. Cerisola, Chem. Rev. 109 (2009) 6541–6569. [4] I. Sirés, E. Brillas, M.A. Oturan, M.A. Rodrigo, M. Panizza, Environ. Sci. Pollut. Res. 21 (2014) 8336–8367. [5] C.A. Martínez-Huitle, S. Ferro, Chem. Soc. Rev. 35 (2006) 1324–1340. [6] B.P.P. Chaplin, Environ. Sci. Process. Impacts. 16 (2014) 1182–1203. [7] O. Scialdone, A. Galia, C. Gattuso, S. Sabatino, B. Schiavo, Electrochim. Acta, 182 (2015) 775-780. [8] J.F. Pérez, A. Galia, M.A. Rodrigo, J. Llanos, S. Sabatino, C. Sáez, B. Schiavo, O. Scialdone, Electrochim. Acta, 248 (2017) 169-177. [9] A.H. Ltaïef, S. Sabatino, F. Proietto, A. Galia, O. Scialdone, O. 2018, Chemosphere, 202, 111-118

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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The kinetics of the reaction of superoxide radical with Fe(III) complexes of EDTA, DETAPAC and HEDTA

AbstractTo gain an understanding of the mechanism by which the hydroxyl free radical can arise in superoxide generating systems and learn how different chelaters of iron can inhibit this reaction, a pulse radiolysis kinetic study of the reaction of O−2 with Fe(III)EDTA, Fe(III)HEDTA and Fe(III)DETAPAC (or DTPA) was undertaken. Superoxide reacts readily with Fe(III)EDTA and Fe(III)HEDTA with a pH-dependent second-order rate constant having values of 1.9 × 106 M−1.s−1 and 7.6 × 105 M−1.s−1 at pH 7, respectively. However, the rate constant for the reaction of O−2 with Fe(III)DETAPAC was found to be much slower, the upper limit for the rate constant being 104 M−1.s−1. These results in conjunction with spin-trapping experiments with Fe(II)EDTA, Fe(II)HEDTA, Fe(II)DETAPAC and H2O2 suggests that DETAPAC inhibits the formation of OH by slowing the reduction of Fe(III) to Fe(II) and not by inhibiting the Fenton reaction

Acetaminophen oxidation under solar light using Fe-BiOBr as a mild Photo-Fenton catalyst

Acetaminophen is an analgesic used as a first-choice treatment for pain and fever. When individuals consume acetaminophen, a portion of the drug is excreted through urine and can end up in wastewater. Water remediation from pharmaceuticals, such as acetaminophen, is required before reaching the environment. This work demonstrates that Fe–BiOBr using the solar photo-Fenton process eliminates acetaminophen at mild pH in aqueous media. Fe-BiOBr is produced using microwave-assisted solvothermal synthesis, and the formation of the BiOBr phase is confirmed with XRD. SEM and TEM demonstrated the flower-like morphology, in which crystallite size reduces as a function of the Fe loading. The chemical environment at the surface of Fe–BiOBr is investigated with XPS. The results are connected with Raman analysis, which suggests the presence of oxygen vacancies in Fe–BiOBr. Furthermore, the effect of Fe in BiOBr is assessed by determining the optical band gap with UV–Vis. The Fe-BiOBr functionality is assessed during acetaminophen degradation. Fe-BiOBr revealed excellent performance in degrading acetaminophen in the first minutes (Q = 10 kJ m −2) under natural sunlight. Results reveal that 1% Fe content in BiOBr can degrade acetaminophen and its main byproduct (30 min, Q = 50 kJ m −2) at pH 5 and using 0.25 gL -1 of catalyst. A synergistic mechanism between heterogeneous photocatalysis and Fenton processes with primary superoxide ( •O 2 –) radical, followed by hydroxyl ( •OH) radical and photogenerated holes (h +), is proposed. Our research contributes to the degradation of pharmaceuticals under mild conditions and sunlight irradiation.</p