Solar Light-Assisted Oxidative Degradation of Ciprofloxacin in Aqueous Solution by Iron(III) Chelated Cross-Linked Chitosan Immobilized on a Glass Plate

Abstract

The massive worldwide use of antibiotics leads to water pollution and increasing microbial resistance. Hence, the removal of antibiotic residues is a key issue in water remediation. Here, we report the solar light-assisted oxidative degradation of ciprofloxacin (CPF), using H2O2 in aqueous solution, catalyzed by iron(III) chelated cross-linked chitosan (FeIII-CS-GLA) immobilized on a glass plate. The FeIII-CS-GLA catalyst was characterized by FTIR and 57Fe-Mössbauer spectroscopies as well as X-ray diffraction, revealing key structural motifs and a high-spin ferric character of the metal. Catalytic degradation of CPF was investigated as a function of solar light irradiation time, solution pH, concentration of H2O2 and CPF, as well as cross-linker dosage and iron(III) content in FeIII-CS-GLA. The system was found to serve as an efficient catalyst with maximum CPF degradation at pH 3. The specific ·OH scavenger mannitol significantly reduces the degradation rate, indicating that hydroxyl radicals play a key role. The mechanism of catalytic CPF degradation was evaluated in terms of pseudo-first-order and Langmuir-Hinshelwood kinetic models; adsorption of CPF onto the FeIII-CS-GLA surface was evidenced by field emission scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. FeIII-CS-GLA can be reused multiple times with only minor loss of catalytic efficiency. Antimicrobial activity tests performed against both Gram-negative (Escherichia coli DH5α, Salmonella typhi AF4500) and Gram-positive bacteria (Bacillus subtilis RBW) before and after treatment confirmed complete degradation of CPF. These results establish the immobilized FeIII-CS-GLA as a rugged catalyst system for efficient photo-Fenton type degradation of antibiotics in aqueous solutions.