Degradation of ciprofloxacin using CoFe2O4@three-dimensional TiO2@graphene aerogels composite: kinetic, reusability, mineralization, degradation pathway, and toxicity assessment

Fatemeh Zisti; Irwanjot Kaur; Sameer A Awad; Nizomiddin Juraev; Dmitry Olegovich Bokov; Hamad AlMohamadi; Carlos Rodriguez-Benites; Merwa Alhadrawi; Salah Hassan Zain Al-Abdeen; Davoud Balarak

doi:10.1007/s11356-024-35787-1

Degradation of ciprofloxacin using CoFe₂O₄@three-dimensional TiO₂@graphene aerogels composite: kinetic, reusability, mineralization, degradation pathway, and toxicity assessment

Environ Sci Pollut Res Int. 2025 Jan 6. doi: 10.1007/s11356-024-35787-1. Online ahead of print.

Authors

Fatemeh Zisti¹, Irwanjot Kaur^{2

3}, Sameer A Awad⁴, Nizomiddin Juraev^{5

6}, Dmitry Olegovich Bokov^{7

8}, Hamad AlMohamadi⁹, Carlos Rodriguez-Benites¹⁰, Merwa Alhadrawi^{11

12

13}, Salah Hassan Zain Al-Abdeen¹⁴, Davoud Balarak¹⁵

Affiliations

¹ Department of Chemistry, University of Brock, St. Catharines, ON, Canada.
² Department of Biotechnology and Genetics, Jain (Deemed-to-Be) University, Bengaluru, Karnataka, 560069, India.
³ Department of Allied Healthcare and Sciences, Vivekananda Global University, Jaipur, Rajasthan, 303012, India.
⁴ Department of Medical Laboratories Techniques, College of Health and Medical Techniques, Al-Maarif University, Ramadi, Al-Anbar Governorate, 31001, Iraq.
⁵ Faculty of Chemical Engineering, New Uzbekistan University, Tashkent, Uzbekistan.
⁶ Scientific and Innovation Department, Tashkent State Pedagogical University, Tashkent, Uzbekistan.
⁷ Laboratory of Food Chemistry, Federal Research Center of Nutrition, Biotechnology and Food Safety, 2/14 Ustyinsky Pr, Moscow, 109240, Russian Federation.
⁸ Institute of Pharmacy Named After A.P. Nelyubin, Sechenov First Moscow State Medical University, 8 Trubetskaya St., Bldg. 2, Moscow, 119991, Russian Federation.
⁹ Department of Chemical Engineering, Faculty of Engineering, Islamic University of Madinah, Madinah, Saudi Arabia.
¹⁰ Universidad César Vallejo, Trujillo, Peru.
¹¹ Department of Refrigeration and Air Conditioning Techniques, College of Technical Engineering, the Islamic University, Najaf, Iraq.
¹² Department of Refrigeration and Air Conditioning Techniques, College of Technical Engineering, the Islamic University of Al Diwaniyah, Al Diwaniyah, Iraq.
¹³ Department of Refrigeration and Air Conditioning Techniques, College of Technical Engineering, the Islamic University of Babylon, Babylon, Iraq.
¹⁴ Department of Medical Laboratories Technology, Al-Nisour University College, Baghdad, Iraq.
¹⁵ Department of Environmental Health, Health Promotion Research Center, Zahedan University of Medical Sciences, Zahedan, Iran. [email protected].

PMID: 39760836
DOI: 10.1007/s11356-024-35787-1

Abstract

An investigation into the degradation of ciprofloxacin (CIP) under visible light was carried out using an efficient photocatalyst, i.e., CoFe₂O₄@3D-TiO₂@GA, synthesized by doping CoFe₂O₄@three-dimensional-TiO₂ into a hierarchical porous graphene aerogel. Optimal conditions for achieving complete removal of CIP involved a reaction time of 60 min, a catalyst dose of 0.6 g/L, an initial CIP concentration of 25 mg/L, and a solution pH range of 3-5. The reusability of CoFe₂O₄@3D-TiO₂@GA was observed to remain high even after four consecutive cycles, as the CIP degradation only slightly decreased from 94.3 to 87.1%. Following a 2-h photocatalytic degradation process, the intermediate products within the CIP solution no longer posed a threat to E. coli. The TOC analysis confirmed that CIP achieved 86% total mineralization. In the raw sewage, the BOD₅/COD and BOD₅/TOC ratios were 0.774 and 0.232, respectively. However, after a 120-min photocatalytic reaction, these ratios increased to 1.38 and 0.754, respectively. These findings suggest that non-biological sewage can be successfully transformed into biodegradable effluent through photocatalytic degradation. The photocatalytic process has a reaction rate coefficient that is 8.7 to 20.7 times higher than the adsorption process, depending on the concentration. The half-life constant is 117.4 min for the optimal concentration of 10 mg/L for the adsorption process, while for the photocatalytic process, it is 6.24 min. The research has highlighted the importance of integrating adsorption and photocatalysis, whereby primary reactive oxidative species, including superoxide and hydroxyl radicals, were identified. The study presents a pioneering approach for producing CoFe₂O₄@3D-TiO₂@GA, which has promising potential for environmental applications utilizing visible light.

Keywords: Ciprofloxacin; CoFe2O4@3D-TiO2@GA; Degradation pathway; Toxicity.