Abstract
In this work, solar photocatalytic degradation of the drug mixture atenolol (ATL), acetaminophen (ACP), and sulfamethoxazole (SMX) in distilled water, tap water, and hospital wastewater was evaluated. The photocatalytic activity of two commercial TiO2-based catalysts, Degussa P25 and KronoClean 7000, was studied at different catalyst amounts, under simulated and natural solar irradiation for the solution of 10 mg L−1 initial concentration of each drug. The results showed complete degradation of the mixture and abatement of 70% of the initial TOC concentration in distilled water with Degussa P25 (1.0 g L−1) using both radiation sources at 400 kJ m−2 of the UV accumulated energy. Thus, to evaluate the matrix effect in the process, the degradation was carried out in hospital wastewater spiked with the drug mixture. Complete degradation of ACP and ATL and 85% of SMX elimination was reached in hospital wastewater, but only 18.1% of the initial TOC reduction was achieved using Degussa P25 catalyst under natural solar radiation at 400 kJ m−2 of accumulated UV energy. Additionally, the process was evaluated in a 20 L semi-pilot plant where degradation near 90% for all drugs was reached in tap water using 0.5 g L−1 of Degussa P25, obtaining a 51.6% of TOC abatement at 38.9 kJ L−1 of accumulated UV energy. Finally, the effluent toxicity during the degradation of the pharmaceuticals in hospital wastewater was evaluated, finding that the natural solar-mediated photocatalysis using TiO2 Degussa P25 is an effective process to obtain a non-toxic effluent.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data Availability
Almost all the data generated or analyzed during this study are included in this published article and its supplementary information file. Additional data are available from the corresponding author (aracely.hernandezrm@uanl.edu.mx).
References
An, Y., De Ridder, D. J., Zhao, C., Schoutteten, K., Bussche, J. V., Zheng, H., et al. (2016). Adsorption and photocatalytic degradation of pharmaceuticals and pesticides by carbon doped-TiO2 coated on zeolites under solar light irradiation. Water Science and Technology, 73(12), 2868–2881. https://doi.org/10.2166/wst.2016.146
Anitha, B., & Khadar, M. A. (2020). Anatase-rutile phase transformation and photocatalysis in peroxide gel route prepared TiO2 nanocrystals: Role of defect states. Solid State Sciences, 108(August), 106392. https://doi.org/10.1016/j.solidstatesciences.2020.106392
Bessa, V. S., Moreira, I. S., Murgolo, S., Mascolo, G., & Castro, P. M. L. (2019). Carbamazepine is degraded by the bacterial strain Labrys portucalensis F11. Science of the Total Environment, 690, 739–747. https://doi.org/10.1016/j.scitotenv.2019.06.461
Bonvin, F., Omlin, J., Rutler, R., Schweizer, W. B., Alaimo, P. J., Strathmann, T. J., et al. (2013). Direct photolysis of human metabolites of the antibiotic sulfamethoxazole: Evidence for abiotic back-transformation. Environmental Science and Technology, 47(13), 6746–6755. https://doi.org/10.1021/es303777k
Cai, Q., & Hu, J. (2017). Decomposition of sulfamethoxazole and trimethoprim by continuous UVA/LED/TiO2 photocatalysis: Decomposition pathways, residual antibacterial activity and toxicity. Journal of Hazardous Materials, 323, 527–536. https://doi.org/10.1016/j.jhazmat.2016.06.006
Calabrese, E. J. (2008). Hormesis: Why it is important to toxicology and toxicologists. Environmental Toxicology and Chemistry, 27(7), 1451–1474. https://doi.org/10.1897/07-541.1
COTEMARNAT (Government of México). (2017). NMX-AA-112-SCFI-2017, water and sediment analysis – Acute toxicity evaluation with Vibrio fischeri – test method. Mexican Norm.
Czech, B., Jośko, I., & Oleszczuk, P. (2014). Ecotoxicological evaluation of selected pharmaceuticals to Vibrio fischeri and Daphnia magna before and after photooxidation process. Ecotoxicology and Environmental Safety, 104(1), 247–253. https://doi.org/10.1016/j.ecoenv.2014.03.024
Czech, B., & Rubinowska, K. (2013). TiO2-assisted photocatalytic degradation of diclofenac, metoprolol, estrone and chloramphenicol as endocrine disruptors in water. Adsorption, 19(2–4), 619–630. https://doi.org/10.1007/s10450-013-9485-8
De Almeida, G. C., Della SantinaMohallem, N., & Viana, M. M. (2022). Ag/GO/TiO2 nanocomposites: The role of the interfacial charge transfer for application in photocatalysis. Nanotechnology, 33(3), 035710. https://doi.org/10.1088/1361-6528/ac2f24
De Witte, B., Van Langenhove, H., Demeestere, K., Saerens, K., De Wispelaere, P., & Dewulf, J. (2010). Ciprofloxacin ozonation in hospital wastewater treatment plant effluent: Effect of pH and H2O2. Chemosphere, 78(9), 1142–1147. https://doi.org/10.1016/j.chemosphere.2009.12.026
Delgado, L. F., Charles, P., Glucina, K., & Morlay, C. (2015). Adsorption of ibuprofen and atenolol at trace concentration on activated carbon. Separation Science and Technology (Philadelphia), 50(10), 1487–1496. https://doi.org/10.1080/01496395.2014.975360
Guo, W. Q., Yin, R. L., Zhou, X. J., Du, J. S., Cao, H. O., Yang, S. S., & Ren, N. Q. (2015). Sulfamethoxazole degradation by ultrasound/ozone oxidation process in water: Kinetics, mechanisms, and pathways. Ultrasonics Sonochemistry, 22, 182–187. https://doi.org/10.1016/j.ultsonch.2014.07.008
Han, J., Liu, Y., Singhal, N., Wang, L., & Gao, W. (2012). Comparative photocatalytic degradation of estrone in water by ZnO and TiO2 under artificial UVA and solar irradiation. Chemical Engineering Journal, 213, 150–162. https://doi.org/10.1016/j.cej.2012.09.066
He, Y., Sutton, N. B., Rijnaarts, H. H. M., & Langenhoff, A. A. M. (2018). Pharmaceutical biodegradation under three anaerobic redox conditions evaluated by chemical and toxicological analyses. Science of the Total Environment, 618, 658–664. https://doi.org/10.1016/j.scitotenv.2017.07.219
Helali, S., Polo-López, M. I., Fernández-Ibáñez, P., Ohtani, B., Amano, F., Malato, S., & Guillard, C. (2014). Solar photocatalysis: A green technology for E. coli contaminated water disinfection. Effect of concentration and different types of suspended catalyst. Journal of Photochemistry and Photobiology A: Chemistry, 276, 31–40. https://doi.org/10.1016/j.jphotochem.2013.11.011
Hernández-Ramírez, A., & Medina-Ramírez, I. (2015). Photocatalytic Semiconductors. (A. Hernández-Ramírez & I. Medina-Ramírez, Eds.) (1st ed.). Suiza: Springer. https://doi.org/10.1007/978–3–319–10999–2
Hernández-Tenorio, R., Guzmán-Mar, J. L., Hinojosa-Reyes, L., Ramos-Delgado, N., & Hernández-Ramírez, A. (2021). Determination of pharmaceuticals discharged in wastewater from a public hospital using lc-ms/ms technique. Journal of the Mexican Chemical Society, 65(1), 94–108. https://doi.org/10.29356/jmcs.v65i1.1439
Ioannou, L. A., Hapeshi, E., Vasquez, M. I., Mantzavinos, D., & Fatta-Kassinos, D. (2011). Solar/TiO2 photocatalytic decomposition of β-blockers atenolol and propranolol in water and wastewater. Solar Energy, 85(9), 1915–1926. https://doi.org/10.1016/j.solener.2011.04.031
Isariebel, Q. P., Carine, J. L., Ulises-Javier, J. H., Anne-Marie, W., & Henri, D. (2009). Sonolysis of levodopa and paracetamol in aqueous solutions. Ultrasonics Sonochemistry, 16(5), 610–616. https://doi.org/10.1016/j.ultsonch.2008.11.008
Jallouli, N., Pastrana-Martínez, L. M., Ribeiro, A. R., Moreira, N. F. F., Faria, J. L., Hentati, O., et al. (2018). Heterogeneous photocatalytic degradation of ibuprofen in ultrapure water, municipal and pharmaceutical industry wastewaters using a TiO2/UV-LED system. Chemical Engineering Journal, 334, 976–984. https://doi.org/10.1016/j.cej.2017.10.045
Kanakaraju, D., Glass, B. D., & Oelgemöller, M. (2014). Titanium dioxide photocatalysis for pharmaceutical wastewater treatment. Environmental Chemistry Letters, 12(1), 27–47. https://doi.org/10.1007/s10311-013-0428-0
Kete, M., Pavlica, E., Fresno, F., Bratina, G., & Štangar, U. L. (2014). Highly active photocatalytic coatings prepared by a low-temperature method. Environmental Science and Pollution Research, 21(19), 11238–11249. https://doi.org/10.1007/s11356-014-3077-3
Klauson, D., Babkina, J., Stepanova, K., Krichevskaya, M., & Preis, S. (2010). Aqueous photocatalytic oxidation of amoxicillin. Catalysis Today, 151(1–2), 39–45. https://doi.org/10.1016/j.cattod.2010.01.015
Konstas, P.-S., Kosma, C., Konstantinou, I., & Albanis, T. (2019). Photocatalytic treatment of pharmaceuticals in real hospital wastewaters for effluent quality amelioration. Water, 11(10), 2165. https://doi.org/10.3390/w11102165
Kosma, C. I., Lambropoulou, D. A., & Albanis, T. A. (2010). Occurrence and removal of PPCPs in municipal and hospital wastewaters in Greece. Journal of Hazardous Materials, 179(1–3), 804–817. https://doi.org/10.1016/j.jhazmat.2010.03.075
Kowalska, K., Maniakova, G., Carotenuto, M., Sacco, O., Vaiano, V., Lofrano, G., & Rizzo, L. (2020). Removal of carbamazepine, diclofenac and trimethoprim by solar driven advanced oxidation processes in a compound triangular collector based reactor: A comparison between homogeneous and heterogeneous processes. Chemosphere, 238, 124665. https://doi.org/10.1016/j.chemosphere.2019.124665
Krzeminski, P., Tomei, M. C., Karaolia, P., Langenhoff, A., Almeida, C. M. R., Felis, E., et al. (2019). Performance of secondary wastewater treatment methods for the removal of contaminants of emerging concern implicated in crop uptake and antibiotic resistance spread: A review. Science of the Total Environment, 648, 1052–1081. https://doi.org/10.1016/j.scitotenv.2018.08.130
Kusiak-Nejman, E., Wanag, A., Kowalczyk, L., Tryba, B., Kapica-Kozar, J., & Morawski, A. W. (2015). The photocatalytic performance of benzene- modified TiO2 photocatalysts under UV-vis light irradiation. Journal Of Advanced Oxidation Technologies, 18(2), 204–210. https://doi.org/10.1515/jaots-2015-0204
Mendiola-Alvarez, S., Guzmán-Mar, J. L., Turnes-Palomino, G., Hinojosa-Reyes, L., & Hernández-Ramírez, A. (2017). UV and visible activation of Cr ( III ) -doped TiO2 catalyst prepared by a microwave-assisted sol – gel method during MCPA degradation. Environmental Science and Pollution Research, 24, 12673–12682. https://doi.org/10.1007/s11356-016-8034-x
Le Minh Tri, N., Kim, J., Giang, B. L., Al Tahtamouni, T. M., Huong, P. T., Lee, C., et al. (2019). Ag-doped graphitic carbon nitride photocatalyst with remarkably enhanced photocatalytic activity towards antibiotic in hospital wastewater under solar light. Journal of Industrial and Engineering Chemistry, 80, 597–605. https://doi.org/10.1016/j.jiec.2019.08.037
Mirzaei, A., Chen, Z., Haghighat, F., & Yerushalmi, L. (2016). Removal of pharmaceuticals and endocrine disrupting compounds from water by zinc oxide-based photocatalytic degradation: A review. Sustainable Cities and Society, 27, 407–418. https://doi.org/10.1016/j.scs.2016.08.004
Morawski, A. W., Kusiak-Nejman, E., Wanag, A., Kapica-Kozar, J., Wróbel, R. J., Ohtani, B., et al. (2017). Photocatalytic degradation of acetic acid in the presence of visible light-active TiO2-reduced graphene oxide photocatalysts. Catalysis Today, 280, 108–113. https://doi.org/10.1016/j.cattod.2016.05.055
Mousset, E., Loh, W. H., Lim, W. S., Jarry, L., Wang, Z., & Lefebvre, O. (2021). Cost comparison of advanced oxidation processes for wastewater treatment using accumulated oxygen-equivalent criteria. Water Research, 200, 117234. https://doi.org/10.1016/j.watres.2021.117234
Nasuhoglu, D., Yargeau, V., & Berk, D. (2011). Photo-removal of sulfamethoxazole (SMX) by photolytic and photocatalytic processes in a batch reactor under UV-C radiation (λmax=254nm). Journal of Hazardous Materials, 186(1), 67–75. https://doi.org/10.1016/j.jhazmat.2010.10.080
Oliveira, T. S., Murphy, M., Mendola, N., Wong, V., Carlson, D., & Waring, L. (2015). Characterization of pharmaceuticals and personal care products in hospital effluent and waste water influent/effluent by direct-injection LC-MS-MS. Science of the Total Environment, 518–519, 459–478. https://doi.org/10.1016/j.scitotenv.2015.02.104
Olvera-Vargas, H., Oturan, N., Buisson, D., & Oturan, M. A. (2016). A coupled Bio-EF process for mineralization of the pharmaceuticals furosemide and ranitidine: Feasibility assessment. Chemosphere, 155, 606–613. https://doi.org/10.1016/j.chemosphere.2016.04.091
Patel, M., Kumar, R., Kishor, K., Mlsna, T., Pittman, C. U., & Mohan, D. (2019). Pharmaceuticals of emerging concern in aquatic systems: Chemistry, occurrence, effects, and removal methods. Chemical Reviews, 119(6), 3510–3673. https://doi.org/10.1021/acs.chemrev.8b00299
Pereira, J. H. O. S., Vilar, V. J. P., Borges, M. T., González, O., Esplugas, S., & Boaventura, R. A. R. (2011). Photocatalytic degradation of oxytetracycline using TiO2 under natural and simulated solar radiation. Solar Energy, 85(11), 2732–2740. https://doi.org/10.1016/j.solener.2011.08.012
Qi, C., Liu, X., Lin, C., Zhang, X., Ma, J., Tan, H., & Ye, W. (2014). Degradation of sulfamethoxazole by microwave-activated persulfate: Kinetics, mechanism and acute toxicity. Chemical Engineering Journal, 249, 6–14. https://doi.org/10.1016/j.cej.2014.03.086
Reina, A. C., Martínez-Piernas, A. B., Bertakis, Y., Brebou, C., Xekoukoulotakis, N. P., Agüera, A., & Sánchez Pérez, J. A. (2018). Photochemical degradation of the carbapenem antibiotics imipenem and meropenem in aqueous solutions under solar radiation. Water Research, 128, 61–70. https://doi.org/10.1016/j.watres.2017.10.047
Rivera-Utrilla, J., Sánchez-Polo, M., Ferro-García, M. Á., Prados-Joya, G., & Ocampo-Pérez, R. (2013). Pharmaceuticals as emerging contaminants and their removal from water. A review. Chemosphere, 93(7), 1268–1287. https://doi.org/10.1016/j.chemosphere.2013.07.059
Rizzo, L., Malato, S., Antakyali, D., Beretsou, V. G., Đolić, M. B., Gernjak, W., et al. (2019). Consolidated vs new advanced treatment methods for the removal of contaminants of emerging concern from urban wastewater. Science of the Total Environment, 655(2018), 986–1008. https://doi.org/10.1016/j.scitotenv.2018.11.265
Rokicka-Konieczna, P., Markowska-Szczupak, A., Kusiak-Nejman, E., & Morawski, A. W. (2019). Photocatalytic water disinfection under the artificial solar light by fructose-modified TiO2. Chemical Engineering Journal, 372(April), 203–215. https://doi.org/10.1016/j.cej.2019.04.113
Sanganyado, E., Lu, Z., Fu, Q., Schlenk, D., & Gan, J. (2017). Chiral pharmaceuticals: A review on their environmental occurrence and fate processes. Water Research, 124, 527–542. https://doi.org/10.1016/j.watres.2017.08.003
Seck, E. I., Doña-Rodríguez, J. M., Fernández-Rodríguez, C., Portillo-Carrizo, D., Hernández-Rodríguez, M. J., González-Díaz, O. M., & Pérez-Peña, J. (2013). Solar photocatalytic removal of herbicides from real water by using sol-gel synthesized nanocrystalline TiO2: Operational parameters optimization and toxicity studies. Solar Energy, 87(1), 150–157. https://doi.org/10.1016/j.solener.2012.10.015
Spina, M., Venâncio, W., Rodrigues-Silva, C., Pivetta, R. C., Diniz, V., Rath, S., & Guimarães, J. R. (2021). Degradation of antidepressant pharmaceuticals by photoperoxidation in diverse water matrices: A highlight in the evaluation of acute and chronic toxicity. Environmental Science and Pollution Research, 28(19), 24034–24045. https://doi.org/10.1007/s11356-020-11657-4
Tang, K., Spiliotopoulou, A., Chhetri, R. K., Ooi, G. T. H., Kaarsholm, K. M. S., Sundmark, K., et al. (2019). Removal of pharmaceuticals, toxicity and natural fluorescence through the ozonation of biologically-treated hospital wastewater, with further polishing via a suspended biofilm. Chemical Engineering Journal, 359, 321–330. https://doi.org/10.1016/j.cej.2018.11.112
Tobaldi, D. M., Lajaunie, L., Rozman, N., Caetano, A. P. F., Seabra, M. P., Sever Škapin, A., et al. (2019). Impact of the absolute rutile fraction on TiO2 visible-light absorption and visible-light-promoted photocatalytic activity. Journal of Photochemistry and Photobiology A: Chemistry, 382, 111940. https://doi.org/10.1016/j.jphotochem.2019.111940
Tobaldi, D. M., Seabra, M. P., Otero-Irurueta, G., de Miguel, Y. R., Ball, R. J., Singh, M. K., et al. (2015). Quantitative XRD characterisation and gas-phase photocatalytic activity testing for visible-light (indoor applications) of KRONOClean 7000®. RSC Advances, 5(124), 102911–102918. https://doi.org/10.1039/C5RA22816F
Van Doorslaer, X., Dewulf, J., De Maerschalk, J., Van Langenhove, H., & Demeestere, K. (2015). Heterogeneous photocatalysis of moxifloxacin in hospital effluent: Effect of selected matrix constituents. Chemical Engineering Journal, 261, 9–16. https://doi.org/10.1016/j.cej.2014.06.079
Wilde, M. L., Montipó, S., & Martins, A. F. (2014). Degradation of B-blockers in hospital wastewater by means of ozonation and Fe2+/ozonation. Water Research, 48(1), 280–295. https://doi.org/10.1016/j.watres.2013.09.039
Zou, X., Lin, Z., Deng, Z., & Yin, D. (2013). Novel approach to predicting hormetic effects of antibiotic mixtures on Vibrio fischeri. Chemosphere, 90(7), 2070–2076. https://doi.org/10.1016/j.chemosphere.2012.09.042
Acknowledgements
Pino-Sandoval (606780) thanks CONACyT for the scholarship granted.
Funding
This work received financial support from the National Council of Science and Technology, Mexico (CONACyT, project 181057), Facultad de Ciencias Químicas, UANL, and UANL Foundation.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Confict of Interest
The authors declare no competing interests.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Pino-Sandoval, D.A., Hinojosa-Reyes, L., Guzmán-Mar, J.L. et al. Solar Photocatalysis for Degradation of Pharmaceuticals in Hospital Wastewater: Influence of the Type of Catalyst, Aqueous Matrix, and Toxicity Evaluation. Water Air Soil Pollut 233, 14 (2022). https://doi.org/10.1007/s11270-021-05484-7
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11270-021-05484-7