Abstract
The solar photocatalysis has received increasing attention in the last years due to its great potential as eco-friendly technology to detoxify wastewater polluted with estrogenic and/or androgenic chemicals. In this context, this study aims to demonstrate the photocatalyzed degradation of two fungicides (vinclozoline and fenarimol) and four insecticides (malathion, fenotrothion, quinalphos, and dimethoate) all of them with endocrine-disrupting activity, in a wastewater effluent under natural sunlight and pilot plant scale. For this, we have combined hydroxyl radical (HO•)- and sulfate radical (SO4●−)-based advanced oxidation processes (AOPs) by using of ZnO as photocatalyst and Na2S2O8 as oxidant, respectively. Previously, catalyst loading, effect of electron acceptor, and pH conditions were optimized using a lab photoreactor under artificial light. As a result, 200 mg L−1 of ZnO and 250 mg L−1 of Na2S2O8 were used in the further experiment at pilot plant scale at pH around 7. The results show that the use of the tandem ZnO/Na2S2O8 strongly enhances the reaction rate of the studied pesticides as compared with the photolytic test. All pesticides followed an apparent first-order degradation curve. The necessary time for 90% degradation (DT90) under sunlight irradiation ranged from 26 to 1000 min (2–75 min as normalized illumination time, t30W) for malathion and fenarimol, respectively. At the end of the lighting, the remaining percentage of dissolved organic carbon (DOC) was up to 92% lower than its initial content and toxicity (Vibrio fischeri) decreased from 65% of inhibition to an acceptable value of 12% at the end of the treatment. A weak increase in the electrical conductivity (EC) was observed due to the mineralization process. The findings confirm the efficacy of the treatment to remove pesticides from wastewater using natural sunlight as renewable energy source, mainly in sunny areas as Mediterranean basin.
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References
Ahmed, S. N., & Haider, W. (2018). Heterogeneous photocatalysis and its potential applications in water and wastewater treatment: A review. Nanotechnology, 29(34), 342001.
American Public Health Association (APHA). (2005). Standard method for examination of water and wastewater, 21st Edn. APHA, AWWA. In WPCF. Washington: USA.
Amor, C., Marchao, L., Lucas, M. S., & Peres, J. A. (2019). Application of advanced oxidation processes for the treatment of recalcitrant agro-industrial wastewater: A review. Water., 11, 205.
Baxter, J. B., & Aydil, E. S. (2006). Dye-sensitized solar cells based on semiconductor morphologies with ZnO nanowires. Solar Energy Materials and Solar Cells, 90, 607–622.
Birkett, J. W., & Lester, J. N. (2003). Endocrine disruptors in wastewater and sludge treatment processes. Boca Raton, FL: Lewis Publishers.
Cesaro, A., & Belgiorno, V. (2016). Removal of endocrine disruptors from urban wastewater by advanced oxidation processes (AOPs): A review. Open Biotechnology Journal, 10, 151–172.
European Commission, EC. (2000). Directive 2000/60/EC of the European Parliament and of the council of 23 October 2000 establishing a framework for community action in the field of water policy. O.J., 327, 1–69.
European Commission, EC. 2011. Commission Staff Working Paper. SEC (2011) 1001 final: 4th Report on the implementation of the “Community Strategy for Endocrine Disrupters” a range of substances suspected of interfering with the hormone systems of humans and wildlife (COM (1999) 706). Brussels. http://ec.europa.eu/environment/chemicals/ endocrine/ pdf/sec_2011_1001.pdf. Accessed 15 November 2018.
European Environment Agency, EEA. 2012. The impacts of endocrine disrupters on wildlife, people and their environments-The Weybridge+15 (1996-2011) report. Copenhagen, Denmark, European Environment Agency, 112 pp. (Technical Report No. 2/2012).
Esteban, S., Moreno-Merino, L., Matellanes, R., Catalá, M., Gorga, M., Petrovic, M., López de Alda, M., Barceló, D., Silva, A., Durán, J. J., López-Martínez, J., & Valcárcel, Y. (2016). Presence of endocrine disruptors in freshwater in the northern Antarctic peninsula region. Environmental Research, 147, 179–192.
Fenoll, F., Garrido, I., Hellín, P., Vela, N., Flores, N., & Navarro, S. (2016). Photooxidation of three spirocyclic acid derivative insecticides in aqueous suspensions as catalyzed by titanium and zinc oxides. Journal of Photochemistry and Photobiology A: Chemistry, 328, 189–197.
Domingos, R. F., Rafiei, Z., Monteiro, C. E., Khan, M. A. K., & Wilkinson, K. J. (2013). Agglomeration and dissolution of zinc oxide nanoparticles: Role of pH, ionic strength and fulvic acid. Environment and Chemistry, 10, 306–312.
Fechete, I., Wang, Y., & Védrine, C. (2012). The past, present and future of heterogeneous catalysis. Catalysis Today, 189, 2–27.
Gorga, M., Insa, S., Petrovic, M., & Barceló, D. (2015). Occurrence and spatial distribution of EDCs and related compounds in waters and sediments of Iberian rivers. Science of the Total Environment, 503, 69–86.
Herrmann, J. M. (2012). Titania-based true heterogeneous photocatalysis. Environmental Science and Pollution Research, 19, 3655–3665.
Ibhadon, A. O., & Fitzpatrick, P. (2013). Heterogeneous photocatalysis: Recent advances and applications. Catalysts, 3, 189–218.
Ifelebuegu, A. O. (2011). The fate and behavior of selected endocrine disrupting chemicals in full scale wastewater and sludge treatment unit processes. International journal of Environmental Science and Technology, 8, 245–254.
Kitsiou, V., Filippidis, N., Mantzavinos, D., & Poulios, I. (2009). Heterogeneous and homogeneous photocatalytic degradation of the insecticide imidacloprid in aqueous solutions. Applied Catalysis B: Environmental, 86, 27–35.
Kortenkamp, A., Martin, O., Faust, M., Evans, R., McKinlay, R., Orton, F., Rosivatz, E. (2011). State of the art assessment of endocrine disrupters. Final Report, Project Contract Number 070307/2009/550687/SER/D3. European Commission, Brussels. http://ec.europa.eu/environment/chemicals/endocrine/pdf/sota_edc_final_report.pdf. Accessed 15 November 2018.
Kosmulski, M. (2018). The pH dependent surface charging and points of zero charge. VII. Update. Advances in Colloid and Interface Science, 251, 115–138.
Kudo, A., & Miseki, Y. (2009). Heterogeneous photocatalyst materials for water splitting. Chemical Society Reviews, 38, 253–278.
Kushniarou, A., Garrido, I., Fenoll, J., Vela, N., Flores, P., Navarro, G., Hellín, P., & Navarro, S. (2019). Solar photocatalytic reclamation of agro-waste water polluted with twelve pesticides for agricultural reuse. Chemosphere, 214, 839–845.
Lee, K. M., Lai, C. W., Ngai, K. S., & Juan, J. C. (2016). Recent developments of zinc oxide based photocatalyst in water treatment technology: A review. Water Research, 88, 428–448.
Liang, S., Xiao, K., Mo, Y., & Huang, X. (2012). A novel ZnO nanoparticle blended polyvinylidene fluoride membrane for anti-irreversible fouling. Journal of Membrane Science, 394, 184–192.
Liu, B., Zhao, X., Terashima, C., Fujishima, A., & Nakata, K. (2014). Thermodynamic and kinetic analysis of heterogeneous photocatalysis for semiconductor systems. Physical Chemistry Chemical Physics, 16, 8751–8760.
Malato, 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, 1–59.
Matzek, L. W., & Carter, K. E. (2016). Activated persulfate for organic chemical degradation: A review. Chemosphere, 151, 178–188.
Miklos, D. B., Remy, C., Jekel, M., Linden, K. G., Drewes, J. E., & Hubner, U. (2018). Evaluation of advanced oxidation processes for water and astewater treatment - A critical review. Water Research, 139, 118–131.
Mita, D. G. (2016). Endocrine disruptors: A real concern for humans? Open Biotechnology Journal, 10, 13–19.
Mnif, W., Hassine, A. I., Bouaziz, A., Bartegi, A., Thomas, O., & Roig, B. (2011). Effect of endocrine disruptor pesticides: A review. International Journal of Environmental Research and Public Health, 8, 2265–2303.
Ohtani, B., Mahaney, O. O. P., Amano, F., Murakami, N., & Abe, R. (2010). What are titania photocatalysts?: An exploratory correlation of photocatalytic activity and physical properties. Journal of Advanced Oxidation Technologies, 13, 247–261.
Olmez-Hanci, T., & Arslan-Alaton, I. (2013). Comparison of sulfate and hydroxyl radical based advanced oxidation of phenol. Chemical Engineering Journal, 224, 10–16.
Oller, I., Malato, S., & Sánchez-Pérez, J. A. (2011). Combination of advanced oxidation processes and biological treatments for wastewater decontamination-A review. Science of The Total Environment, 409, 4141–4166.
Ong, C. B., Ng, L. Y., & Mohammad, A. W. (2018). A review of ZnO nanoparticles as solar photocatalysts: Synthesis, mechanisms and applications. Renewable and Sustainable Energy Reviews, 81, 536–551.
Prieto-Rodríguez, L., Miralles-Cuevas, S., Oller, I., Agüera, A., Li Puma, G., & Malato, S. (2012). Treatment of emerging contaminants in wastewater treatment plants (WWTP) effluents by solar photocatalysis using low TiO2 concentrations. Journal of Hazardous Materials, 211-212, 131–137.
Rani, C. N., & Karthikeyan, S. (2016). Endocrine disrupting compounds in water and wastewater and their treatment options-a review. International Journal of Environmental Technology and Management, 19, 392–431.
Ribeiro, A. R., Nunes, O. C., Pereira, M. F. R., & Silva, A. M. T. (2015). An overview on the advanced oxidation processes applied for the treatment of water pollutants defined in the recently launched Directive 2013/39/EU. Environment International, 75, 33–51.
Rodríguez-Chueca, J., Laski, E., García-Cañibano, C., Martín de Vidales, M. J., Encinas, A., Kuch, B., & Marugán, J. (2018). Micropollutants removal by full-scale UV-C/sulfate radical based advanced oxidation processes. Science of the Total Environment, 630, 1216–1225.
Salgueiro-González, N., Turnes-Carou, I., Besada, V., Muniategui-Lorenzo, S., López-Mahía, P., & Prada-Rodríguez, D. (2015). Occurrence, distribution and bioaccumulation of endocrine disrupting compounds in water, sediment and biota samples from a European river basin. Science of the Total Environment, 529, 121–130.
Tsydenova, O., Batoev, V., & Batoeva, A. (2015). Solar-enhanced advanced oxidation processes for water treatment: Simultaneous removal of pathogens and chemical pollutants. International Journal of Environmental Research and Public Health, 12, 9542–9561.
US Environmental Protection Agency, US EPA. (2000). Environmental protection agency-Endocrine disruptor screening program. In Report to Congress. Washington, DC, USA: USEPA.
Vela, N., Fenoll, J., Garrido, I., Navarro, G., Gambín, M., & Navarro, S. (2015). Photocatalytic mitigation of triazinone herbicide residues using titanium dioxide in slurry photoreactor. Catalysis Today, 252, 70–77.
Vela, N., Pérez-Lucas, G., Fenoll, J., & Navarro, S. (2017). Recent overview on the abatement of pesticide residues in water by photocatalytic treatment using TiO2. In M. Janus (Ed.), Applications of titanium dioxide (pp. 147–177). Croatia: Intech.
Vela, N., Calín, M., Yáñez-Gascón, M. J., Garrido, I., Pérez-Lucas, G., Fenoll, J., & Navarro, S. (2018). Photocatalytic oxidation of six pesticides listed as endocrine disruptor chemicals from wastewater using two different TiO2 samples at pilot plant scale under sunlight irradiation. Journal of Photochemistry and Photobiology A: Chemistry, 353, 271–278.
Vilela, C. L. S., Bassin, J. P., & Peixoto, R. S. (2018). Water contamination by endocrine disruptors: Impacts, microbiological aspects and trends for environmental protection. Environmental Pollution, 235, 546–559.
Wallacem, B., Purcell, M., & Furlong, J. (2002). Total organic carbon analysis as a precursor to disinfection by-products in potable water: Oxidation technique considerations. Journal of Environmental Monitoring, 4, 35–42.
Wee, S. Y., & Aris, A. Z. (2017). Endocrine disrupting compounds in drinking water supply system and human health risk implication. Environment International, 106, 207–233.
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The Catholic University of Murcia (Project PMAFI 27/14) supported this research.
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Vela, N., Calín, M., Yáñez-Gascón, M.J. et al. Removal of Pesticides with Endocrine Disruptor Activity in Wastewater Effluent by Solar Heterogeneous Photocatalysis Using ZnO/Na2S2O8. Water Air Soil Pollut 230, 134 (2019). https://doi.org/10.1007/s11270-019-4185-y
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DOI: https://doi.org/10.1007/s11270-019-4185-y