Abstract
The increasing presence of pharmaceutical products in municipality wastewaters has raised serious environmental concerns. Ozonation is one of the advanced oxidation processes that can degrade these substances, instead of simply transferring them from aqueous to another phase. Treatability studies applying ozonation to degrade benzodiazepine drugs are scarce. The aim of this investigation was to apply design of experiments (DoE) to optimize ozonation processes for removal of bromazepam, clonazepam, and diazepam from two effluents of municipal wastewater treatment plants (WWTP1 and WWTP2) both located in Rio de Janeiro City, Brazil. During a preliminary study using ultrapure water, OHº radicals were more efficient (removal efficiency greater than 99% (< LOQ) at pH = 10, 15 min) than O3 in degrading all psychoactive drugs (removal efficiency from 46 to 85% at pH = 4, 15 min). The optimum values for the tested variables were pH = 8.03; O3 specific dose = 4.8 mgO3.mgDOC−1; and O3 mass flow rate = 22.07 mgO3.min−1. The WWTP1 and WWTP2 effluents were treated under optimized conditions by ozonation in two effluent volumes (5L and 8L). When 8 L effluent was treated, the degradation of all benzodiazepine drugs was improved, due to the higher water column used, which favors the mass transfer of O3 from the gas phase to the liquid phase, promoting greater contact between oxidant and target compounds. Using a specific dose of 1.8 mgO3.mgDOC−1, more than 93% of all anxiolytic drugs were removed from 8 L of WWTP2 effluent, whereas for the WWTP1, more than 90% were removed using 2.7 times higher specific dose (4.8 mgO3.mgDOC−1).
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All data generated or analyzed during this study are included in this manuscript and its supplementary information file.
References
Andreozzi, R., Insola, A., Caprio, V., & D’Amore, M. G. (1991). Ozonation of pyridine in aqueous solution: Mechanistic and kinetic aspects. Water Research, 25(6), 655–659. https://doi.org/10.1016/0043-1354(91)90040-W
APHA, AWWA, & WEF. (2017). Standard methods for the examination of water and wastewater (23rd ed.). Washington, DC
Bourgin, M., Beck, B., Boehler, M., Borowska, E., Fleiner, J., Salhi, E., et al. (2018). Evaluation of a full-scale wastewater treatment plant upgraded with ozonation and biological post-treatments: Abatement of micropollutants, formation of transformation products and oxidation by-products. Water Research, 129, 486–498. https://doi.org/10.1016/j.watres.2017.10.036
Buxton, G. V., Greenstock, C. L., Helman, W. P., & Ross, A. B. (1988). Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O− in aqueous solution. Journal of Physical and Chemical Reference Data, 17(2), 513–886. https://doi.org/10.1063/1.555805
Calisto, V., & Esteves, V. I. (2009). Psychiatric pharmaceuticals in the environment. Chemosphere, 77(10), 1257–1274. https://doi.org/10.1016/j.chemosphere.2009.09.021
Carpinteiro, I., Rodil, R., Quintana, J. B., & Cela, R. (2017). Reaction of diazepam and related benzodiazepines with chlorine. Kinetics, transformation products and in-silico toxicological assessment. Water Research, 120, 280–289. https://doi.org/10.1016/j.watres.2017.04.063
Chen, W. R., Sharpless, C. M., Linden, K. G., & Suffet, I. H. (2006). Treatment of volatile organic chemicals on the EPA contaminant candidate list using ozonation and. Environmental Science and Technology, 40(8), 2734–2739.
Collins, J., & Bolton, J. R. (2016). Advanced Oxidation Handbook (1a.). American Water Work Asspciation
Couto, C. F., Lange, L. C., & Amaral, M. C. S. (2019). Occurrence, fate and removal of pharmaceutically active compounds (PhACs) in water and wastewater treatment plants—A review. Journal of Water Process Engineering, 32(August), 100927. https://doi.org/10.1016/j.jwpe.2019.100927
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., Mendes, M. P., & Marques, M. (2019a). 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
Cunha, D. L., Kuznetsov, A., Araujo, J. R., Neves, R. S., Archanjo, B. S., Canela, M. C., & Marques, M. (2019b). Optimization of benzodiazepine drugs removal from water by heterogeneous photocatalysis using TiO2/activated carbon composite. Water, Air, & Soil Pollution, 230(7), 141. https://doi.org/10.1007/s11270-019-4202-1
do Amaral, A. F., da Silva, A. S. A., Coutinho, R., Cunha, D. L., & Marques, M. (2021). Benzophenone and diethyl phthalate removal from real wastewater by a multi-stage hybrid reactor. Water, Air, and Soil Pollution, 232(10), 1–14. https://doi.org/10.1007/s11270-021-05388-6
Erden, G., & Filibeli, A. (2010). Ozone oxidation of biological sludge: Effects on disintegration, anaerobic biodegradability, and filterability. Environmental Progress & Sustainable Energy, 30(3), 377–383. https://doi.org/10.1002/ep.10494
Fall, C., Silva-Hernández, B. C., Hooijmans, C. M., Lopez-Vazquez, C. M., Esparza-Soto, M., Lucero-Chávez, M., & van Loosdrecht, M. C. M. (2018). Sludge reduction by ozone: Insights and modeling of the dose-response effects. Journal of Environmental Management, 206, 103–112. https://doi.org/10.1016/j.jenvman.2017.10.023
Fernandes, M. J., Paíga, P., Silva, A., Llaguno, C. P., Carvalho, M., Vázquez, F. M., & Delerue-Matos, C. (2020). Antibiotics and antidepressants occurrence in surface waters and sediments collected in the north of Portugal. Chemosphere, 239, 124729. https://doi.org/10.1016/j.chemosphere.2019.124729
García, J., García-Galán, M. J., Day, J. W., Boopathy, R., White, J. R., Wallace, S., & Hunter, R. G. (2020). A review of emerging organic contaminants (EOCs), antibiotic resistant bacteria (ARB), and antibiotic resistance genes (ARGs) in the environment: Increasing removal with wetlands and reducing environmental impacts. Bioresource Technology, 307(March), 123228. https://doi.org/10.1016/j.biortech.2020.123228
Gil, A., Galeano, L. A., & Vicente, M. A. (2019). The Handbook of Environmental Chemistry 67: Applications of Advanced Oxidation Processes (AOPs) in Drinking Water Treatment (1a.). Springer
Gottschalk, C., Libra, J., & Saupe, A. (2010). Ozonation of Water and Waste Water: A Practical Guide to Understanding Ozone and its Applications (2nd ed.). Wiley-VCH.
Hansen, K. M. S., Spiliotopoulou, A., Chhetri, R. K., Escolà Casas, M., Bester, K., & Andersen, H. R. (2016). Ozonation for source treatment of pharmaceuticals in hospital wastewater - Ozone lifetime and required ozone dose. Chemical Engineering Journal, 290, 507–514. https://doi.org/10.1016/j.cej.2016.01.027
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
Hoigné, J., & Bader, H. (1976). The role of hydroxyl radical reactions in ozonation processes in aqueous solutions. Water Research, 10(5), 377–386. https://doi.org/10.1016/0043-1354(76)90055-5
Hoigné, J., & Bader, H. (1983a). Rate constants of reactions of ozone with organic and inorganic compounds in water-I. Non-dissociating organic compounds. Water Research, 17(2), 173–183. https://doi.org/10.1016/0043-1354(83)90098-2
Hoigné, J., & Bader, H. (1983b). Rate constants of reactions of ozone with organic and inorganic compounds in water –II. Dissociating organic compounds. Water Research, 17, 185–194.
Huber, M. M., Canonica, S., Park, G. Y., & Von Gunten, U. (2003). Oxidation of pharmaceuticals during ozonation and advanced oxidation processes. Environmental Science and Technology, 37(5), 1016–1024. https://doi.org/10.1021/es025896h
Huber, M. M., Korhonen, S., Ternes, T., & a., & Von Gunten, U. (2005). Oxidation of pharmaceuticals during water treatment with chlorine dioxide. Water Research, 39(15), 3607–3617. https://doi.org/10.1016/j.watres.2005.05.040
Huerta-Fontela, M., Galceran, M. T., & Ventura, F. (2011). Occurrence and removal of pharmaceuticals and hormones through drinking water treatment. Water Research, 45(3), 1432–1442. https://doi.org/10.1016/j.watres.2010.10.036
ICH. (2005). ICH Topic Q2 (R1) Validation of analytical procedures : Text and methodology. International Conference on Harmonization 17. http://www.ich.org/fileadmin/Public_Web_Site/ICH_Products/Guidelines/Quality/Q2_R1/Step4/Q2_R1__Guideline.pdf. Accessed 20 Aug 2020.
INMETRO. (2010). Orientação sobre validação de métodos analíticos. DOC-CGCRE-008. Rio de Janeiro.
Jakimska, A., Śliwka, K. M., Nagórski, P., Kot, W. A., & Namieśnik, J. (2014). Environmental fate of two psychiatric drugs, diazepam and sertraline : Phototransformation and investigation of their photoproducts in natural waters. Chromatography Separation Techniques, 5(6), 1–12. https://doi.org/10.4172/2157-7064.1000253
Khan, A. H., Khan, N. A., Ahmed, S., Dhingra, A., Singh, C. P., Khan, S. U., et al. (2020). Application of advanced oxidation processes followed by different treatment technologies for hospital wastewater treatment. Journal of Cleaner Production, 269.https://doi.org/10.1016/j.jclepro.2020.122411
Kovalakova, P., Cizmas, L., McDonald, T. J., Marsalek, B., Feng, M., & Sharma, V. K. (2020). Occurrence and toxicity of antibiotics in the aquatic environment: A review. Chemosphere, 251, 126351. https://doi.org/10.1016/j.chemosphere.2020.126351
Lee, Y., Kovalova, L., McArdell, C. S., & von Gunten, U. (2014). Prediction of micropollutant elimination during ozonation of a hospital wastewater effluent. Water Research, 64, 134–148. https://doi.org/10.1016/j.watres.2014.06.027
Mathon, B., Choubert, J. M., Miege, C., & Coquery, M. (2016). A review of the photodegradability and transformation products of 13 pharmaceuticals and pesticides relevant to sewage polishing treatment. Science of the Total Environment, 551–552, 712–724. https://doi.org/10.1016/j.scitotenv.2016.02.009
Mathon, B., Coquery, M., Liu, Z., Penru, Y., Guillon, A., Esperanza, M., et al. (2021). Ozonation of 47 organic micropollutants in secondary treated municipal effluents: Direct and indirect kinetic reaction rates and modelling. Chemosphere, 262, 127969. https://doi.org/10.1016/j.chemosphere.2020.127969
Merga, G., Schuchmann, H. P., Rao, B. S. M., & von Sonntag, C. (1996). Solution in the absence and presence of oxygen M. Journal of the Chemical Society, Perkin Transactions 2, 91(7), 1097–1103.
Mezzelani, M., Gorbi, S., & Regoli, F. (2018). Pharmaceuticals in the aquatic environments: Evidence of emerged threat and future challenges for marine organisms. Marine Environmental Research, 140(May), 41–60. https://doi.org/10.1016/j.marenvres.2018.05.001
Montagner, C. C., Sodré, F. F., Acayaba, R. D., Vidal, C., Campestrini, I., Locatelli, M. A., et al. (2019). Ten years-snapshot of the occurrence of emerging contaminants in drinking, surface and ground waters and wastewaters from São Paulo State, Brazil. Journal of the Brazilian Chemical Society, 30(3), 614–632. https://doi.org/10.21577/0103-5053.20180232
Neves, A. C., & Mol, M. P. G. (2019). Theoretical environmental risk assessment of ten used pharmaceuticals in Belo Horizonte, Brazil. Environmental Monitoring and Assessment, 191(5), 275. https://doi.org/10.1007/s10661-019-7386-3
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. review-article. https://doi.org/10.1021/acs.chemrev.8b00299
Pivetta, R. C., Rodrigues-Silva, C., Ribeiro, A. R., & Rath, S. (2020). Tracking the occurrence of psychotropic pharmaceuticals in Brazilian wastewater treatment plants and surface water, with assessment of environmental risks. Science of the Total Environment, 727, 138661. https://doi.org/10.1016/j.scitotenv.2020.138661
Qi, W., Zhang, H., Hu, C., Liu, H., & Qu, J. (2018). Effect of ozonation on the characteristics of effluent organic matter fractions and subsequent associations with disinfection by-products formation. Science of the Total Environment, 610–611, 1057–1064. https://doi.org/10.1016/j.scitotenv.2017.08.194
Ramírez-Malule, H., Quiñones-Murillo, D. H., & Manotas-Duque, D. (2020). Emerging contaminants as global environmental hazards. A bibliometric analysis. Emerging Contaminants, 6, 179–193. https://doi.org/10.1016/j.emcon.2020.05.001
Reungoat, J., Escher, B. I., Macova, M., & Keller, J. (2011). Biofiltration of wastewater treatment plant effluent: Effective removal of pharmaceuticals and personal care products and reduction of toxicity. Water Research, 45(9), 2751–2762. https://doi.org/10.1016/j.watres.2011.02.013
Ribani, M., GrespanBottoli, C. B., Collins, C. H., Fontes Jardim, I. C. S., & Costa Melo, L. F. (2004). Validation for chromatographic and electrophoretic methods. Quimica Nova, 27(5), 771–780. https://doi.org/10.1590/S0100-40422004000500017
Rodrigues, M. I., & Iemma, A. F. (2015).Experimental Design and Process Optimization (1a.). CRC Press.
Sales Junior, S. F., Vallerie, Q., de Farias Araujo, G., Soares, L. O. S., Oliveira da Silva, E., Correia, F. V., & Saggioro, E. M. (2020). Triclocarban affects earthworms during long-term exposure: Behavior, cytotoxicity, oxidative stress and genotoxicity assessments. Environmental Pollution, 267, 115570. https://doi.org/10.1016/j.envpol.2020.115570
Schaar, H., Clara, M., Gans, O., & Kreuzinger, N. (2010). Micropollutant removal during biological wastewater treatment and a subsequent ozonation step. Environmental Pollution, 158(5), 1399–1404. https://doi.org/10.1016/j.envpol.2009.12.038
Schindler Wildhaber, Y., Mestankova, H., Schärer, M., Schirmer, K., Salhi, E., & von Gunten, U. (2015). Novel test procedure to evaluate the treatability of wastewater with ozone. Water Research, 75, 324–335. https://doi.org/10.1016/j.watres.2015.02.030
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
Thoré, E. S. J., Philippe, C., Brendonck, L., & Pinceel, T. (2020). Antidepressant exposure reduces body size, increases fecundity and alters social behavior in the short-lived killifish Nothobranchius furzeri. Environmental Pollution, 265, 115068. https://doi.org/10.1016/j.envpol.2020.115068
Verlicchi, P., Galletti, A., Petrovic, M., & Barceló, D. (2010). Hospital effluents as a source of emerging pollutants: An overview of micropollutants and sustainable treatment options. Journal of Hydrology, 389(3–4), 416–428. https://doi.org/10.1016/j.jhydrol.2010.06.005
von Sonntag, C., & von Gunten, U. (2012). Chemistry of ozone in water and wastewater treatment: From basic principles to applications. IWA Publishing. https://doi.org/10.2166/9781780400839
Wang, Z., Gao, S., Dai, Q., Zhao, M., & Yang, F. (2020). Occurrence and risk assessment of psychoactive substances in tap water from China. Environmental Pollution, 261, 114163. https://doi.org/10.1016/j.envpol.2020.114163
Wert, E. C., Rosario-Ortiz, F. L., & Snyder, S. A. (2009). Effect of ozone exposure on the oxidation of trace organic contaminants in wastewater. Water Research, 43(4), 1005–1014. https://doi.org/10.1016/j.watres.2008.11.050
West, C. E., & Rowland, S. J. (2012). Aqueous phototransformation of diazepam and related human metabolites under simulated sunlight. Environmental Science and Technology, 46(9), 4749–4756. https://doi.org/10.1021/es203529z
Yang, B., Xu, C., Kookana, R. S., Williams, M., Du, J., Ying, G., & Gu, F. (2018). Aqueous chlorination of benzodiazepines diazepam and oxazepam: Kinetics, transformation products and reaction pathways. Chemical Engineering Journal, 354(April), 1100–1109. https://doi.org/10.1016/j.cej.2018.08.082
Funding
This study was financially supported by the Research Support Foundation of the State of Rio de Janeiro (FAPERJ) to the first author (E-26/202.261/2018, E-26/202.262/2018) and to the last author (E-26/202.894/2018). The Brazilian National Council for Scientific and Technological Development (CNPq) has also supported the last author (435883/2018–6; 308.335/2017–1).
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Cunha, D.L., da Silva, A.S.A., Coutinho, R. et al. Optimization of Ozonation Process to Remove Psychoactive Drugs from Two Municipal Wastewater Treatment Plants. Water Air Soil Pollut 233, 67 (2022). https://doi.org/10.1007/s11270-022-05541-9
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DOI: https://doi.org/10.1007/s11270-022-05541-9