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Hybrid process of adsorption and electrochemically based green regeneration of bentonite clay for ofloxacin and ciprofloxacin removal

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Abstract

Removal of emerging contaminants, such as antibiotics, from wastewater by adsorption is a simple, low-cost, and high-performance process; however, regeneration and reuse of the exhausted adsorbent are necessary to make the process economically viable. This study aimed to investigate the possibility of electrochemical-based regeneration of clay-type materials. For this, the calcined Verde-lodo (CVL) clay was saturated with the antibiotics ofloxacin (OFL) and ciprofloxacin (CIP) in one-component systems by an adsorption process and then subjected to photo-assisted electrochemical oxidation (0.45 A, 0.05 mol/L NaCl, UV-254 nm, and 60 min), which promotes both pollutant degradation and adsorbent regeneration. The external surface of the CVL clay was investigated by X-ray photoelectron spectroscopy before and after the adsorption process. The influence of regeneration time was evaluated for the CVL clay/OFL and CVL clay/CIP systems, and the results demonstrate high regeneration efficiencies after 1 h of photo-assisted electrochemical oxidation. Clay stability during regeneration was investigated by four successive cycles in different aqueous matrices (ultrapure water, synthetic urine, and river water). The results indicated that the CVL clay is relatively stable under the photo-assisted electrochemical regeneration process. Furthermore, CVL clay was able to remove antibiotics even in the presence of natural interfering agents. The hybrid adsorption/oxidation process applied here demonstrated the electrochemical-based regeneration potential of CVL clay for the treatment of emerging contaminants, since it can be operated quickly (1h of treatment) and with lower consumption of energy (3.93 kWh kg−1) than the traditional method of thermal regeneration (10 kWh kg−1).

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Acknowledgements

The authors thank Dolomil for donating the Verde-lodo clay, EMS Pharmaceutical for kindly providing us with the antibiotics ofloxacin and ciprofloxacin, Laboratório de Caracterização de Biomassa, Recursos Analíticos e de Calibração (LRAC) for the characterization analyses, and MS. Lucas Queiroz Pinto for collecting water from the river.

Funding

This work was supported by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brazil (CAPES), Fundação de Amparo à Pesquisa do Estado de São Paulo – Brazil (FAPESP) (Proc. 2016/05007-1; 2019/11353-8), Fundação de Amparo à Pesquisa do Estado de Minas Gerais – Brazil (FAPEMIG) (Proc. PPM 00147-17), and Conselho Nacional de Desenvolvimento Científico e Tecnológico – Brazil (CNPq) (Proc. 406193/2018-5; 307836/2018-5; 313447/2021-7, 308046/2019-6).

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All authors contributed to the development and design of the study. Raissa Antonelli developed the experimental methodology, data collection, and analysis and wrote the first draft of the manuscript. Geoffroy R. P. Malpass was responsible for the supervision and revision of the manuscript versions. Melissa G. A. Vieira and Meuris G. C. da Silva were responsible for coordinating the execution of research activities, acquiring financial support, and revising previous versions of the manuscript. All authors reviewed and approved the final version of the manuscript.

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Correspondence to Raissa Antonelli.

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Responsible Editor: Weiming Zhang

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Antonelli, R., Malpass, G.R.P., da Silva, M.G.C. et al. Hybrid process of adsorption and electrochemically based green regeneration of bentonite clay for ofloxacin and ciprofloxacin removal. Environ Sci Pollut Res 30, 53648–53661 (2023). https://doi.org/10.1007/s11356-023-26175-2

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