Abstract
This study explores the utilization of adsorption and advanced oxidation processes for the degradation of ofloxacin (OFL) and ciprofloxacin (CIP) using a green functionalized carbon nanotube (MWCNT-OH/COOH-E) as adsorbent and catalyst material. The stability and catalytic activity of the solid material were proved by FT-IR and TG/DTG, which also helped to elucidate the reaction mechanisms. In adsorption kinetic studies, both antibiotics showed similar behavior, with an equilibrium at 30 min and 60% removal. The adsorption kinetic data of both antibiotics were well described by the pseudo-first-order (PFO) model. Different advanced oxidation processes (AOPs) were used, and the photolytic degradation was not satisfactory, whereas heterogeneous photocatalysis showed high degradation (⁓ 70%), both processes with 30 min of reaction. Nevertheless, ozonation and catalytic ozonation have resulted in the highest efficiencies, 90%, and 70%, respectively, after 30-min reaction. For AOP data modeling, the first-order model better described CIP and OFL in photocatalytic and ozonation process. Intermediates were detected by MS–MS analysis, such as P313, P330, and P277 for ciprofloxacin and P391 and P332 for ofloxacin. The toxicity test demonstrated that a lower acute toxicity was observed for the photocatalysis method samples, with only 3.1 and 1.5 TU for CIP and OFL, respectively, thus being a promising method for its degradation, due to its lower risk of inducing the proliferation of bacterial resistance in an aquatic environment. Ultimately, the analysis of MWCNT reusability showed good performance for 2 cycles and regeneration of MWCNT with ozone confirmed its effectiveness up to 3 cycles.
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Acknowledgements
The authors would like to thank the material donation of Usina do Eucalipto and EMS Pharmaceuticals (Brazil).
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This work was supported by the Brazilian National Research Council (CNPq, grant no. 406193/2018–5 and no. 308046/2019–6), the Research Supporting Foundation of the State of São Paulo (FAPESP, grant no. 2020/16004–9), and Nacional Institute of Sciences and Technology Midas (INCT Midas//CNPq, grant no. 465594/2014–0).
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Mariana Gomes Oliveira: conceptualization and writing—original draft; Daniela Gier Della Rocca: conceptualization and writing—original draft; Regina de Fátima Peralta Muniz Moreira: resources, supervision, and writing—review and editing; Meuris Gurgel Carlos da Silva: resources, supervision, and writing—review and editing; Melissa Gurgel Adeodato Vieira: resources, supervision, and writing—review and editing.
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Oliveira, M.G., Rocca, D.G.D., Moreira, R.d.F.P.M. et al. Enhanced degradation and removal of ciprofloxacin and ofloxacin through advanced oxidation and adsorption processes using environmentally friendly modified carbon nanotubes. Environ Sci Pollut Res 31, 29957–29970 (2024). https://doi.org/10.1007/s11356-024-33252-7
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DOI: https://doi.org/10.1007/s11356-024-33252-7