Abstract
Widely consumed benzodiazepine drugs are emerging contaminants, some of them being endocrine disruptors. Although many of these drugs remain in wastewater even after conventional treatment, innovative treatability studies are still sparse. The aim of this study was to investigate the efficiency of heterogeneous photocatalysis using synthesized composites based on TiO2 and activated carbon (TiO2/AC) as catalysts under sunlight-simulated irradiation. Different ratios and calcination temperatures were tested for the synthesis, and the composite with the best photocatalytic efficiency (based on methylene blue dye removal from water solution) was the one formed by 10% AC calcined at 400 °C (TiO2/AC10%). This composite was applied in heterogeneous photocatalysis to remove bromazepam, clonazepam, and diazepam at environmentally relevant concentrations (100 μg/L). Such treatment approach has not been reported in the literature to date. Independent variables such as catalyst concentration, pH, and sunlight-simulated irradiation were studied using design of experiments (DoE) to find conditions that provide maximum removal efficiency. TiO2/AC10% powder was characterized by SEM, XRD, BET, and diffuse reflectance. Under feasible optimized conditions, the efficiency of TiO2/AC10% to remove benzodiazepine drugs from water was > 97.5%, which is much higher than the removal obtained with commercial catalyst and all controls.
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References
Ao, C. H., & Lee, S. C. (2003). Enhancement effect of TiO2 immobilized on activated carbon filter for the photodegradation of pollutants at typical indoor air level. Applied Catalysis B: Environmental, 44(3), 191–205. https://doi.org/10.1016/S0926-3373(03)00054-7.
Awfa, D., Ateia, M., Fujii, M., Johnson, M. S., & Yoshimura, C. (2018). Photodegradation of pharmaceuticals and personal care products in water treatment using carbonaceous-TiO2 composites : a critical review of recent literature. Water Research, 142, 26–45. https://doi.org/10.1016/j.watres.2018.05.036.
Bagheri, S., Julkapli, N. M., Bee, S., & Hamid, A. (2015). Functionalized activated carbon derived from biomass for photocatalysis applications perspective functionalized activated carbon derived from biomass for photocatalysis applications perspective. International Journal of Photoenergy, 2015. https://doi.org/10.1155/2015/218743.
Bosio, M., Satyro, S., Bassin, J. P., Saggioro, E., & Dezotti, M. (2019). Removal of pharmaceutically active compounds from synthetic and real aqueous mixtures and simultaneous disinfection by supported TiO2/UV-A, H2O2/UV-A, and TiO2/H2O2/UV-A processes. Environmental Science and Pollution Research, 26(5), 4288–4299. https://doi.org/10.1007/s11356-018-2108-x.
Byrne, C., Subramanian, G., & Pillai, S. C. (2018). Recent advances in photocatalysis for environmental applications. Journal of Environmental Chemical Engineering, 6(3), 3531–3555. https://doi.org/10.1016/j.jece.2017.07.080.
Calisto, V., Ferreira, C. I. A., Oliveira, J. A. B. P., Otero, M., & Esteves, V. I. (2015). Adsorptive removal of pharmaceuticals from water by commercial and waste-based carbons. Journal of Environmental Management, 152, 83–90. https://doi.org/10.1016/j.jenvman.2015.01.019.
Calisto, V., Jaria, G., Silva, C. P., Ferreira, C. I. A., Otero, M., & Esteves, V. I. (2017). Single and multi-component adsorption of psychiatric pharmaceuticals onto alternative and commercial carbons. Journal of Environmental Management, 192, 15–24. https://doi.org/10.1016/j.jenvman.2017.01.029.
Chen, Y., Wang, K., & Lou, L. (2004). Photodegradation of dye pollutants on silica gel supported TiO2 particles under visible light irradiation. Journal of Photochemistry and Photobiology A: Chemistry, 163(1–2), 281–287. https://doi.org/10.1016/j.jphotochem.2003.12.012.
Corrêa, M. D. P. (2015). Solar ultraviolet radiation: properties, characteristics and amounts observed in Brazil and South America. Anais Brasileiros de Dermatologia, 90(3), 297–313.
Cunha, D. L., Araujo, F. G., & Marques, M. (2017). Psychoactive drugs: occurrence in aquatic environment, analytical methods, and ecotoxicity—a review. Environmental Science and Pollution Research, 24, 24076–24091. https://doi.org/10.1007/s11356-017-0170-4.
Cunha, D. L., Kuznetsov, A., Achete, C. A., Machado, A. E. d. H., & Marques, M. (2018). Immobilized TiO2 on glass spheres applied to heterogeneous photocatalysis: photoactivity, leaching and regeneration process. PeerJ, 6, e4464. https://doi.org/10.7717/peerj.4464.
Cunha, D. L., Mendes, M. P., & Marques, M. (2019). Environmental risk assessment of psychoactive drugs in the aquatic environment. Environmental Science and Pollution Research, 26(1), 78–90. https://doi.org/10.1007/s11356-018-3556-z.
El-Sheikh, S. M., Khedr, T. M., Hakki, A., Ismail, A. A., Badawy, W. A., & Bahnemann, D. W. (2017). Visible light activated carbon and nitrogen co-doped mesoporous TiO2 as efficient photocatalyst for degradation of ibuprofen. Separation and Purification Technology, 173, 258–268. https://doi.org/10.1016/j.seppur.2016.09.034.
Finčur, N. L., Krstić, J. B., Šibul, F. S., Šojić, D. V., Despotović, V. N., Banić, N. D., et al. (2017). Removal of alprazolam from aqueous solutions by heterogeneous photocatalysis: Influencing factors, intermediates, and products. Chemical Engineering Journal, 307, 1105–1115. https://doi.org/10.1016/j.cej.2016.09.008.
Gebauer, D. L., Pagnussat, N., Piato, Â. L., Schaefer, I. C., Bonan, C. D., & Lara, D. R. (2011). Effects of anxiolytics in zebrafish: Similarities and differences between benzodiazepines, buspirone and ethanol. Pharmacology Biochemistry and Behavior, 99(3), 480–486. https://doi.org/10.1016/j.pbb.2011.04.021.
Gogoi, A., Mazumder, P., Tyagi, V. K., Tushara Chaminda, G. G., An, A. K., & Kumar, M. (2018). Occurrence and fate of emerging contaminants in water environment: a review. Groundwater for Sustainable Development, 6, 169–180. https://doi.org/10.1016/j.gsd.2017.12.009.
Gulyas, H., Argáez, A. S. O., Kong, F., Jorge, C. L., Eggers, S., & Otterpohl, R. (2013). Combining activated carbon adsorption with heterogeneous photocatalytic oxidation: lack of synergy for biologically treated greywater and tetraethylene glycol dimethyl ether. Environmental Technology, 34(11), 1393–1403. https://doi.org/10.1080/09593330.2012.751129.
Gupta, V. K., Fakhri, A., Agarwal, S., Bharti, A. K., Naji, M., & Tkachev, A. G. (2018). Preparation and characterization of TiO2 nanofibers by hydrothermal method for removal of benzodiazepines (diazepam) from liquids as catalytic ozonation and adsorption processes. Journal of Molecular Liquids, 249, 1033–1038. https://doi.org/10.1016/j.molliq.2017.11.144.
Hansson, H., Kaczala, F., Amaro, A., Marques, M., & Hogland, W. (2015). Advanced oxidation treatment of recalcitrant wastewater from a wood-based industry: a comparative study of O3 and O3/UV. Water, Air, & Soil Pollution, 226(7), 229–241. https://doi.org/10.1007/s11270-015-2468-5.
Herrmann, J.-M., Matos, J., Disdier, J., Guillard, C., Laine, J., Malato, S., & Blanco, J. (1999). Solar photocatalytic degradation of 4-chlorophenol using the synergistic effect between titania and activated carbon in aqueous suspension. Catalysis Today, 54(2–3), 255–265. https://doi.org/10.1016/S0920-5861(99)00187-X.
Holmberg, J. P., Ahlberg, E., Bergenholtz, J., Hassellöv, M., & Abbas, Z. (2013). Surface charge and interfacial potential of titanium dioxide nanoparticles: experimental and theoretical investigations. Journal of Colloid and Interface Science, 407, 168–176. https://doi.org/10.1016/j.jcis.2013.06.015.
Huang, S., Lu, X., Li, Z., Ravishankar, H., Wang, J., & Wang, X. (2018). A biomimetic approach towards the synthesis of TiO2/carbon-clay as a highly recoverable photocatalyst. Journal of Photochemistry and Photobiology A: Chemistry, 351, 131–138. https://doi.org/10.1016/j.jphotochem.2017.10.017.
Ivetić, T. B., Dimitrievska, M. R., Finčur, N. L., Crossed D Signačanin, L. R., Gúth, I. O., Abramović, B. F., & Lukić-Petrović, S. R. (2014). Effect of annealing temperature on structural and optical properties of mg-doped ZnO nanoparticles and their photocatalytic efficiency in alprazolam degradation. Ceramics International, 40(1), 1545–1552. https://doi.org/10.1016/j.ceramint.2013.07.041.
Jain, A., Balasubramanian, R., & Srinivasan, M. P. (2016). Hydrothermal conversion of biomass waste to activated carbon with high porosity: a review. Chemical Engineering Journal, 283, 789–805. https://doi.org/10.1016/j.cej.2015.08.014.
Júnior, O. G., Neto, W. B., Machado, A. E. H., Daniel, D., & Trovó, A. G. (2017). Optimization of fipronil degradation by heterogeneous photocatalysis: Identification of transformation products and toxicity assessment. Water Research, 110, 133–140. https://doi.org/10.1016/j.watres.2016.12.017.
Kellner, M., Porseryd, T., Porsch-Hällström, I., Borg, B., Roufidou, C., & Olsén, K. H. (2018). Developmental exposure to the SSRI citalopram causes long-lasting behavioural effects in the three-spined stickleback (Gasterosteus aculeatus). Ecotoxicology, 27(1), 12–22. https://doi.org/10.1007/s10646-017-1866-4.
Leary, R., & Westwood, A. (2011). Carbonaceous nanomaterials for the enhancement of TiO2 photocatalysis. Carbon, 49(3), 741–772. https://doi.org/10.1016/j.carbon.2010.10.010.
Li, Y., Sun, S., Ma, M., Ouyang, Y., & Yan, W. (2008). Kinetic study and model of the photocatalytic degradation of rhodamine B (RhB) by a TiO2-coated activated carbon catalyst: effects of initial RhB content, light intensity and TiO2 content in the catalyst. Chemical Engineering Journal, 142(2), 147–155. https://doi.org/10.1016/j.cej.2008.01.009.
Liu, S. X., Chen, X. Y., & Chen, X. (2007). A TiO2/AC composite photocatalyst with high activity and easy separation prepared by a hydrothermal method. Journal of Hazardous Materials, 143(1–2), 257–263. https://doi.org/10.1016/j.jhazmat.2006.09.026.
Magno, L. D. P., Fontes, A., Gonçalves, B. M. N., & Gouveia, A. (2015). Pharmacological study of the light/dark preference test in zebrafish (Danio rerio): Waterborne administration. Pharmacology Biochemistry and Behavior, 139, 141–148. https://doi.org/10.1016/j.pbb.2015.11.001.
Maletić, M., Vukčević, M., Kalijadis, A., Janković-Častvan, I., Dapčević, A., Laušević, Z., & Laušević, M. (2016). Hydrothermal synthesis of TiO2/carbon composites and their application for removal of organic pollutants. Arabian Journal of Chemistry, in press. https://doi.org/10.1016/j.arabjc.2016.06.020.
Martins, A. C., Cazetta, A. L., Pezoti, O., Souza, J. R. B., Zhang, T., Pilau, E. J., et al. (2017). Sol-gel synthesis of new TiO2/activated carbon photocatalyst and its application for degradation of tetracycline. Ceramics International, 43(5), 4411–4418. https://doi.org/10.1016/j.ceramint.2016.12.088.
Matos, J., Miralles-cuevas, S., Ruíz-delgado, A., Oller, I., & Malato, S. (2017). Development of TiO2-C photocatalysts for solar treatment of polluted water. Carbon, 122, 361–373. https://doi.org/10.1016/j.carbon.2017.06.091.
Noorimotlagh, Z., Kazeminezhad, I., Jaafarzadeh, N., Ahmadi, M., Ramezani, Z., & Silva Martinez, S. (2018). The visible-light photodegradation of nonylphenol in the presence of carbon-doped TiO2 with rutile/anatase ratio coated on GAC: Effect of parameters and degradation mechanism. Journal of Hazardous Materials, 350(15), 108–120. https://doi.org/10.1016/j.jhazmat.2018.02.022.
Overturf, C. L., Overturf, M. D., & Huggett, D. B. (2016). Bioconcentration and endocrine disruption effects of diazepam in channel catfish, Ictalurus punctatus. Comparative Biochemistry and Physiology Part C: Toxicology & Pharmacology, 183–184, 46–52. https://doi.org/10.1016/j.cbpc.2016.02.001.
Ragupathy, S., Raghu, K., & Prabu, P. (2015). Synthesis and characterization of TiO2 loaded cashew nut shell activated carbon and photocatalytic activity on BG and MB dyes under sunlight radiation. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 138, 314–320. https://doi.org/10.1016/j.saa.2014.11.087.
Rajamanickam, D., & Shanthi, M. (2014). Photocatalytic degradation of an azo dye sunset yellow under UV-A light using TiO2/CAC composite catalysts. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 128, 100–108. https://doi.org/10.1016/j.saa.2014.02.126.
Rivetti, C., Campos, B., & Barata, C. (2016). Low environmental levels of neuro-active pharmaceuticals alter phototactic behaviour and reproduction in Daphnia magna. Aquatic Toxicology, 170, 289–296. https://doi.org/10.1016/j.aquatox.2015.07.019.
Rodrigues, M. I., & Iemma, A. F. (2015). Experimental Design and Process Optimization (1 a .). Boca Raton, United States: CRC Press.
Romeiro, A., Freitas, D., Emília Azenha, M., Canle, M., & Burrows, H. D. (2017). Effect of the calcination temperature on the photocatalytic efficiency of acidic sol–gel synthesized TiO2 nanoparticles in the degradation of alprazolam. Photochemical & Photobiological Sciences, 16(6), 935–945. https://doi.org/10.1039/C6PP00447D.
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. https://doi.org/10.1016/j.scitotenv.2015.05.048.
Seiler, J. P. (2002). Pharmacodynamic activity of drugs and ecotoxicology - can the two be connected? Toxicology Letters, 131(1–2), 105–115. https://doi.org/10.1016/S0378-4274(02)00045-0.
Silva, R. V. S., Tessarolo, N. S., Pereira, V. B., Ximenes, V. L., Mendes, F. L., de Almeida, M. B. B., & Azevedo, D. A. (2017). Quantification of real thermal, catalytic, and hydrodeoxygenated bio-oils via comprehensive two-dimensional gas chromatography with mass spectrometry. Talanta, 164, 626–635. https://doi.org/10.1016/j.talanta.2016.11.005.
Sodré, F. F., Locatelli, M. A. F., & Jardim, W. F. (2010). Occurrence of emerging contaminants in Brazilian drinking waters: a sewage-to-tap issue. Water, Air, and Soil Pollution, 206(1–4), 57–67. https://doi.org/10.1007/s11270-009-0086-9.
Sousa, M. A., Gonçalves, C., Vilar, V. J. P., Boaventura, R. a. R., & Alpendurada, M. F. (2012). Suspended TiO2-assisted photocatalytic degradation of emerging contaminants in a municipal WWTP effluent using a solar pilot plant with CPCs. Chemical Engineering Journal, 198–199, 301–309. https://doi.org/10.1016/j.cej.2012.05.060.
Sousa, M. A., Lacina, O., Hrádková, P., Pulkrabová, J., Vilar, V. J. P., Gonçalves, C., et al. (2013). Lorazepam photofate under photolysis and TiO2-assisted photocatalysis: identification and evolution profiles of by-products formed during phototreatment of a WWTP effluent. Water Research, 47(15), 5584–5593. https://doi.org/10.1016/j.watres.2013.06.029.
Spasiano, D., Marotta, R., Malato, S., Fernandez-Ibañez, P., & Di Somma, I. (2015). Solar photocatalysis: materials, reactors, some commercial, and pre-industrialized applications. A comprehensive approach. Applied Catalysis B: Environmental, 170–171, 90–123. https://doi.org/10.1016/j.apcatb.2014.12.050.
Tahar, A., Choubert, J. M., Miège, C., Esperanza, M., Le Menach, K., Budzinski, H., et al. (2014). Removal of xenobiotics from effluent discharge by adsorption on zeolite and expanded clay: an alternative to activated carbon? Environmental Science and Pollution Research, 21(8), 5660–5668. https://doi.org/10.1007/s11356-013-2439-6.
Tomić, N., Grujić-Brojčin, M., Finčur, N., Abramović, B., Simović, B., Krstić, J., et al. (2015). Photocatalytic degradation of alprazolam in water suspension of brookite type TiO2 nanopowders prepared using hydrothermal route. Materials Chemistry and Physics, 163, 518–528. https://doi.org/10.1016/j.matchemphys.2015.08.008.
Uchida, H., Itoh, S., & Yoneyama, H. (1993). Photocatalytic decomposition of propyzamide using TiO2 supported on activated carbon. Chemistry Letters, 22(12), 1995–1998. https://doi.org/10.1246/cl.1993.1995.
Velasco, L. F., Parra, J. B., & Ania, C. O. (2010). Role of activated carbon features on the photocatalytic degradation of phenol. Applied Surface Science, 256(17), 5254–5258. https://doi.org/10.1016/j.apsusc.2009.12.113.
Vona, A., Garcia-ivars, J., & Picó, Y. (2015). Comparison of different removal techniques for selected pharmaceuticals. Journal of Water Process Engineering, 5, 48–57. https://doi.org/10.1016/j.jwpe.2014.12.011.
Wang, X., Hu, Z., Chen, Y., Zhao, G., Liu, Y., & Wen, Z. (2009). A novel approach towards high-performance composite photocatalyst of TiO2 deposited on activated carbon. Applied Surface Science, 255(7), 3953–3958. https://doi.org/10.1016/j.apsusc.2008.10.083.
Wang, G., Xu, L., Zhang, J., Yin, T., & Han, D. (2012). Enhanced photocatalytic activity of TiO2 powders (P25) via calcination treatment. International Journal of Photoenergy, 2012, 1–9. https://doi.org/10.1155/2012/265760.
Yahya, M. A., Al-Qodah, Z., & Ngah, C. W. Z. (2015). Agricultural bio-waste materials as potential sustainable precursors used for activated carbon production: a review. Renewable and Sustainable Energy Reviews, 46, 218–235. https://doi.org/10.1016/j.rser.2015.02.051.
Yang, H., Zhou, S., Liu, H., Yan, W., Yang, L., & Yi, B. (2013). Photocatalytic degradation of carbofuran in TiO2 aqueous solution: kinetics using design of experiments and mechanism by HPLC/MS/MS. Journal of Environmental Sciences, 25(8), 1680–1686. https://doi.org/10.1016/S1001-0742(12)60217-4.
Yuan, R., Zheng, J., Guan, R., & Zhao, Y. (2005). Surface characteristics and photocatalytic activity of TiO2 loaded on activated carbon fibers. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 254(1–3), 131–136. https://doi.org/10.1016/j.colsurfa.2004.11.027.
Zhang, X., Zhou, M., & Lei, L. (2005). Preparation of photocatalytic TiO2 coatings of nanosized particles on activated carbon by AP-MOCVD. Carbon, 43(8), 1700–1708. https://doi.org/10.1016/j.carbon.2005.02.013.
Acknowledgments
The support of Dr. Antonio E.H. Machado with diffuse reflectance analyses, Rodrigo Coutinho with UPLC-MS/MS analyses, and Carlos A. Senna with SEM images were highly appreciated.
Funding
The authors acknowledge the financial support given to the first and last authors by the Carlos Chagas Filho Research Support Foundation of Rio de Janeiro State (FAPERJ) (E-26/202.261/2018 and E-26/202.262/2018), respectively). To the last author by the National Council for Scientific and Technological Development (CNPq 308335/2017-1), and the Financing Agency of Studies and Project (FINEP) (Conv.01.14.0081.00).
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Cunha, D.L., Kuznetsov, A., Araujo, J.R. et al. Optimization of Benzodiazepine Drugs Removal from Water by Heterogeneous Photocatalysis Using TiO2/Activated Carbon Composite. Water Air Soil Pollut 230, 141 (2019). https://doi.org/10.1007/s11270-019-4202-1
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DOI: https://doi.org/10.1007/s11270-019-4202-1