Catalytic Ozonation of Ciprofloxacin with Cu–Al Layered Double Hydroxides Based on Response Surface Analysis
Publication: Journal of Environmental Engineering
Volume 148, Issue 4
Abstract
Cu–Al layered double hydroxides (Cu–Al LDHs) were prepared by coprecipitation and used as a catalyst in heterogeneous a catalytic ozonation of ciprofloxacin. The structure of the synthesized Cu–Al LDHs was investigated by X-ray diffraction (XRD) patterns and Fourier-transform infrared spectra. Experimental results showed that the LDHs had the best crystallization structure and the highest catalytic efficiency for ozonation. Response surface methodology (RSM) was used to optimize the operation conditions of ozone dose, ozone dosage, and initial pH. Under the optimal conditions (, LDH dosage , ozone dosage ), the total organic carbon (TOC) removal of ciprofloxacin by catalytic ozonation method can be as high as 72%. In addition, the TOC removal of ozone alone was about 30%, and the adsorption process contributed about 10%. Hydroxyl radicals, superoxide radicals, and singlet oxygen were proved to be involved in this process through electron paramagnetic resonance tests. Several degradation products were determined with LC-MS, suggesting that the pathway for ciprofloxacin degradation might include a substitution reaction, decarboxylation reaction, ring-opening reaction, and oxidation reaction.
Get full access to this article
View all available purchase options and get full access to this article.
Data Availability Statement
All data, models, or code that support the findings of this study are available from the corresponding author upon reasonable request.
Acknowledgments
This work was supported by the National Natural Science Foundation of China (No. 51208299) and the Science and Technology Development Project at the University of Shanghai for Science and Technology (Nos. 2018KJFZ101 and 2020KJFZ112).
References
Acuna, V., D. von Schiller, M. J. Garcia-Galan, S. Rodriguez-Mozaz, L. Corominas, M. Petrovic, M. Poch, D. Barcelo, and S. Sabater. 2015. “Occurrence and in-stream attenuation of wastewater-derived pharmaceuticals in Iberian rivers.” Sci. Total Environ. 503–504 (Jan): 133–141. https://doi.org/10.1016/j.scitotenv.2014.05.067.
Bai, Z., Q. Yang, and J. Wang. 2016. “Catalytic ozonation of sulfamethazine antibiotics using Ce 0.1 Fe 0.9 OOH: Catalyst preparation and performance.” Chemosphere 161 (Oct): 174–180. https://doi.org/10.1016/j.chemosphere.2016.07.012.
Bojer, C., J. Schöbel, T. Martin, M. Ertl, H. Schmalz, and J. Breu. 2017. “Clinical wastewater treatment: Photochemical removal of an anionic antibiotic (ciprofloxacin) by mesostructured high aspect ratio ZnO nanotubes.” Appl. Catal., B 204 (May): 561–565. https://doi.org/10.1016/j.apcatb.2016.12.003.
Cao, L., J. Guo, J. Tian, Y. Xu, M. Hu, M. Wang, and J. Fan. 2018. “Preparation of Ca/Al-layered double hydroxide and the influence of their structure on early strength of cement.” Constr. Build. Mater. 184 (Sep): 203–214. https://doi.org/10.1016/j.conbuildmat.2018.06.186.
Cassini, A., L. D. Högberg, and D. Plachouras. 2019. “Attributable deaths and disability-adjusted life-years caused by infections with antibiotic-resistant bacteria in the EU and the European Economic Area in 2015: A population-level modelling analysis.” Lancet Infect. Dis. 19 (1): 56–66. https://doi.org/10.1016/S1473-3099(18)30605-4.
Chassaing, F. J., R. Mahmudov, C. D. Metcalfe, and V. Yargeau. 2021. “Changes to levels of microcontaminants and biological responses in rainbow trout exposed to extracts from wastewater treated by catalytic ozonation.” J. Hazard. Mater. 404 (Part A): 124110. https://doi.org/10.1016/j.jhazmat.2020.124110.
Chen, M., J. Yao, Y. Huang, H. Gong, and W. Chu. 2018. “Enhanced photocatalytic degradation of ciprofloxacin over heterojunctions: Efficiency, kinetics, pathways, mechanisms and toxicity evaluation.” Chem. Eng. J. 334 (Feb): 453–461. https://doi.org/10.1016/j.cej.2017.10.064.
Cheng, J., D. Wang, B. Wang, H. Ning, Y. Zhang, Y. Li, J. An, and P. Gao. 2020. “Plasma-catalytic degradation of ciprofloxacin in aqueous solution over different nanocrystals in a dielectric barrier discharge system.” Chemosphere 253 (Aug): 126595. https://doi.org/10.1016/j.chemosphere.2020.126595.
De Witte, B., H. Van Langenhove, K. Demeestere, K. Saerens, P. De Wispelaere, and J. Dewulf. 2010. “Ciprofloxacin ozonation in hospital wastewater treatment plant effluent: Effect of pH and .” Chemosphere 78 (9): 1142–1147. https://doi.org/10.1016/j.chemosphere.2009.12.026.
Elmoubarki, R., F. Z. Mahjoubi, A. Elhalil, H. Tounsadi, M. Abdennouri, M. H. Sadiq, S. Qourzal, A. Zouhri, and N. Barka. 2017. “Ni/Fe and Mg/Fe layered double hydroxides and their calcined derivatives: Preparation, characterization and application on textile dyes removal.” J. Mater. Res. Technol. 6 (3): 271–283. https://doi.org/10.1016/j.jmrt.2016.09.007.
Guo, H., N. Jiang, H. Wang, K. Shang, N. Lu, J. Li, and Y. Wu. 2019. “Pulsed discharge plasma induced catalysis for synergetic degradation of ciprofloxacin in water: Synergetic mechanism and degradation pathway.” Chemosphere 230 (Sep): 190–200. https://doi.org/10.1016/j.chemosphere.2019.05.011.
Hai, C., and B. Jwa. 2019. “Catalytic ozonation of sulfamethoxazole over composites.” Chemosphere 234 (Nov): 14–24. https://doi.org/10.1016/j.chemosphere.2019.06.014.
Hosseini, G., A. Maleki, H. Daraei, E. Faez, and Y. D. Shahamat. 2015. “Electrochemical process for diazinon removal from aqueous media: Design of experiments, optimization, and DLLME-GC-FID method for diazinon determination.” Arab. J. Sci. Eng. 40 (11): 3041–3046. https://doi.org/10.1007/s13369-015-1798-3.
Jia, Y., S. K. Khanal, H. Shu, H. Zhang, G. H. Chen, and H. Lu. 2018. “Ciprofloxacin degradation in anaerobic sulfate-reducing bacteria (SRB) sludge system: Mechanism and pathways.” Water Res. 136 (Jun): 64–74. https://doi.org/10.1016/j.watres.2018.02.057.
Karim, A. V., and A. Shriwastav. 2020. “Degradation of ciprofloxacin using photo, sono, and sonophotocatalytic oxidation with visible light and low-frequency ultrasound: Degradation kinetics and pathways.” Chem. Eng. J. 392 (Jul): 124853. https://doi.org/10.1016/j.cej.2020.124853.
Karuppusamy, S., B. Suresh Kumar, M. Ranjith Kumar, K. Raja Guru, and A. M. Rameshbabu. 2020. “Analysis of square threading process by using response surface methodology.” Mater. Today: Proc. 37 (Jan): 3417–3422. https://doi.org/10.1016/j.matpr.2020.09.279.
Li, C., H. Lin, A. Armutlulu, R. Xie, Y. Zhang, and X. Meng. 2019. “Hydroxylamine-assisted catalytic degradation of ciprofloxacin in ferrate/persulfate system.” Chem. Eng. J. 360 (Mar): 612–620. https://doi.org/10.1016/j.cej.2018.11.218.
Li, P., J. Chen, H. Li, Y. Huang, S. Yang, and S. Hu. 2020. “An efficient graphic processing unit parallel optimal point searching approach on complex product response surface.” Adv. Eng. Software 149 (Nov): 102893. https://doi.org/10.1016/j.advengsoft.2020.102893.
Li, S., G. Wang, J. Qiao, Y. Zhou, X. Ma, H. Zhang, G. Li, J. Wang, and Y. Song. 2018a. “Sonocatalytic degradation of norfloxacin in aqueous solution caused by a novel Z-scheme sonocatalyst, composite.” J. Mol. Liq. 254 (Mar): 166–176. https://doi.org/10.1016/j.molliq.2018.01.115.
Li, X., W. Chen, L. Ma, H. Wang, and J. Fan. 2018b. “Industrial wastewater advanced treatment via catalytic ozonation with an Fe-based catalyst.” Chemosphere 195 (Mar): 336–343. https://doi.org/10.1016/j.chemosphere.2017.12.080.
Liao, X., B. Li, R. Zou, Y. Dai, S. Xie, and B. Yuan. 2016. “Biodegradation of antibiotic ciprofloxacin: Pathways, influential factors, and bacterial community structure.” Environ. Sci. Pollut. Res. Int. 23 (8): 7911–7918. https://doi.org/10.1007/s11356-016-6054-1.
Liu, N., J. Wang, J. Wu, Z. Li, W. Huang, Y. Zheng, J. Lei, X. Zhang, and L. Tang. 2020. “Magnetic nanocomposites derived from MIL-53(Fe) for the photocatalytic degradation of ibuprofen under visible light irradiation.” Mater. Res. Bull. 132 (Dec): 111000. https://doi.org/10.1016/j.materresbull.2020.111000.
Liu, Y., Y. Zhao, and J. L. Wang. 2021. “Fenton/Fenton-like processes with in-situ production of hydrogen peroxide/hydroxyl radical for degradation of emerging contaminants: Advances and prospects.” J. Hazard. Mater. 404 (Feb): 124191. https://doi.org/10.1016/j.jhazmat.2020.124191.
Lv, J., Y. Li, and Y. Song. 2013. “Reinvestigation on the ozonation of N-nitrosodimethylamine: Influencing factors and degradation mechanism.” Water Res. 47 (14): 4993–5002. https://doi.org/10.1016/j.watres.2013.05.035.
Naseem, S., B. Gevers, R. Boldt, F. J. W. J. Labuschagné, and A. Leuteritz. 2019. “Comparison of transition metal (Fe, Co, Ni, Cu, and Zn) containing tri-metal layered double hydroxides (LDHs) prepared by urea hydrolysis.” RSC Adv. 9 (6): 3030–3040. https://doi.org/10.1039/C8RA10165E.
Nie, Y., N. Li, and C. Hu. 2015. “Enhanced inhibition of bromate formation in catalytic ozonation of organic pollutants over Fe–Al .” Sep. Purif. Technol. 151 (Sep): 256–261. https://doi.org/10.1016/j.seppur.2015.07.057.
Ou, H.-S., J.-S. Ye, S. Ma, C.-H. Wei, N.-Y. Gao, and J.-Z. He. 2016. “Degradation of ciprofloxacin by UV and via multiple-wavelength ultraviolet light-emitting diodes: Effectiveness, intermediates and antibacterial activity.” Chem. Eng. J. 289 (Apr): 391–401. https://doi.org/10.1016/j.cej.2016.01.006.
Perini, J. A. L., A. L. Tonetti, C. Vidal, C. C. Montagner, and R. F. P. Nogueira. 2018. “Simultaneous degradation of ciprofloxacin, amoxicillin, sulfathiazole and sulfamethazine, and disinfection of hospital effluent after biological treatment via photo-Fenton process under ultraviolet germicidal irradiation.” Appl. Catal., B 224 (May): 761–771. https://doi.org/10.1016/j.apcatb.2017.11.021.
Ren, J., J. Li, N. Jiang, K. Shang, N. Lu, and Y. Wu. 2020. “Degradation of trans-ferulic acid in aqueous solution by a water falling film DBD reactor: Degradation performance, response surface methodology, reactive species analysis and toxicity evaluation.” Sep. Purif. Technol. 235 (Mar): 116226. https://doi.org/10.1016/j.seppur.2019.116226.
Shahmahdi, N., R. Dehghanzadeh, H. Aslani, and S. Bakht Shokouhi. 2020. “Performance evaluation of waste iron shavings (Fe0) for catalytic ozonation in removal of sulfamethoxazole from municipal wastewater treatment plant effluent in a batch mode pilot plant.” Chem. Eng. J. 383 (Mar): 123093. https://doi.org/10.1016/j.cej.2019.123093.
Tian, X., J. Zhu, M. Tang, D. Wang, Y. Nie, L. Yang, C. Dai, C. Yang, and L. Lu. 2021. “Surface acidity and basicity of Mg/Al hydrotalcite for 2, 4-dichlorophenoxyacetic acid degradation with ozone: Mineralization, mechanism, and implications to practical water treatment.” J. Hazard. Mater. 402 (Jan): 123475. https://doi.org/10.1016/j.jhazmat.2020.123475.
Vasconcelos, T. G., K. Kummerer, D. M. Henriques, and A. F. Martins. 2009. “Ciprofloxacin in hospital effluent: Degradation by ozone and photoprocesses.” J. Hazard. Mater. 169 (1–3): 1154–1158. https://doi.org/10.1016/j.jhazmat.2009.03.143.
Veloso, C. O., C. N. Pérez, B. M. de Souza, E. C. Lima, A. G. Dias, J. L. F. Monteiro, and C. A. Henriques. 2008. “Condensation of glyceraldehyde acetonide with ethyl acetoacetate over Mg,Al-mixed oxides derived from hydrotalcites.” Microporous Mesoporous Mater. 107 (1–2): 23–30. https://doi.org/10.1016/j.micromeso.2007.05.036.
Wang, B., X. M. Liu, X. N. Fu, Y. L. Li, P. X. Huang, Q. Zhang, W. G. Li, L. Ma, F. Lai, and P. F. Wang. 2018. “Thermal stability and safety of dimethoxymethane oxidation at low temperature.” Fuel 234 (Dec): 207–217. https://doi.org/10.1016/j.fuel.2018.07.034.
Wang, J. L., and Z. Y. Bai. 2017. “Fe-based catalysts for heterogeneous catalytic ozonation of emerging contaminants in water and wastewater.” Chem. Eng. J. 312 (Mar): 79–98. https://doi.org/10.1016/j.cej.2016.11.118.
Wang, J. L., and H. Chen. 2020. “Catalytic ozonation for water and wastewater treatment: Recent advances and perspective.” Sci. Total Environ. 704 (Feb): 17. https://doi.org/10.1016/j.scitotenv.2019.135249.
Wang, J. L., L. B. Chu, L. Wojnarovits, and E. Takacs. 2020. “Occurrence and fate of antibiotics, antibiotic resistant genes (ARGs) and antibiotic resistant bacteria (ARB) in municipal wastewater treatment plant: An overview.” Sci. Total Environ. 744 (Jul): 12. https://doi.org/10.1016/j.scitotenv.2020.140997.
Wang, J. L., and S. Z. Wang. 2016. “Removal of pharmaceuticals and personal care products (PPCPs) from wastewater: A review.” J. Environ. Manage. 182 (Nov): 620–640. https://doi.org/10.1016/j.jenvman.2016.07.049.
Wang, J. L., and L. J. Xu. 2012. “Advanced oxidation processes for wastewater treatment: Formation of hydroxyl radical and application.” Crit. Rev. Environ. Sci. Technol. 42 (3): 251–325. https://doi.org/10.1080/10643389.2010.507698.
Wang, J. L., and R. Zhuan. 2020. “Degradation of antibiotics by advanced oxidation processes: An overview.” Sci. Total Environ. 701 (Jan): 135023. https://doi.org/10.1016/j.scitotenv.2019.135023.
Wu, J., L. Ma, Y. Chen, Y. Cheng, Y. Liu, and X. Zha. 2016. “Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst: Removal and pathways.” Water Res. 92 (Apr): 140–148. https://doi.org/10.1016/j.watres.2016.01.053.
Yahya, M., N. Oturan, K. El Kacemi, M. El Karbane, C. T. Aravindakumar, and M. A. Oturan. 2014. “Oxidative degradation study on antimicrobial agent ciprofloxacin by electro-Fenton process: Kinetics and oxidation products.” Chemosphere 117 (Dec): 447–454. https://doi.org/10.1016/j.chemosphere.2014.08.016.
Zhang, J., K. Zhu, Y. Zhu, C. Qin, L. Liu, D. Liu, Y. Wang, W. Gan, X. Fu, and H. Hao. 2020. “Enhanced photocatalytic degradation of tetracycline hydrochloride by Al-doped BiOCl microspheres under simulated sunlight irradiation.” Chem. Phys. Lett. 750 (Jul): 137486. https://doi.org/10.1016/j.cplett.2020.137483.
Zhou, H., Z. Cao, M. Zhang, Z. Ying, and L. Ma. 2021. “Zero-valent iron enhanced in-situ advanced anaerobic digestion for the removal of antibiotics and antibiotic resistance genes in sewage sludge.” Sci. Total Environ. 754 (Feb): 142077. https://doi.org/10.1016/j.scitotenv.2020.142077.
Information & Authors
Information
Published In
Journal of Environmental Engineering
Volume 148 • Issue 4 • April 2022
Copyright
© 2022 American Society of Civil Engineers.
History
Received: Oct 18, 2021
Accepted: Dec 14, 2021
Published online: Feb 10, 2022
Published in print: Apr 1, 2022
Discussion open until: Jul 10, 2022
Authors
Metrics & Citations
Metrics
Citations
Download citation
If you have the appropriate software installed, you can download article citation data to the citation manager of your choice. Simply select your manager software from the list below and click Download.
Cited by
- Xianyong Hong, Mingzhu Xia, Mingxing Shi, Chun Liu, Yanghao Yan, Yu Tao, Yongqiang Zhang, Yulei Zhang, Ping Du, Fengyun Wang, Investigation of the adsorption performance and mechanism of 2-mercaptoethane sulfonic acid intercalated modified layered double hydroxide on heavy metal ions, Journal of Colloid and Interface Science, 10.1016/j.jcis.2022.09.088, 629, (948-959), (2023).
- Sera Budi Verinda, Muflihatul Muniroh, Eko Yulianto, Nani Maharani, Gunawan Gunawan, Nur Farida Amalia, Jonathan Hobley, Anwar Usman, Muhammad Nur, Degradation of ciprofloxacin in aqueous solution using ozone microbubbles: spectroscopic, kinetics, and antibacterial analysis, Heliyon, 10.1016/j.heliyon.2022.e10137, 8, 8, (e10137), (2022).