Efficient co-removal of aqueous Cr(VI) and ciprofloxacin by alkali lignin-derived carbon supported nanoscale zero-valent iron via adsorption and redox synergistic mechanisms

Abstract

Developing an efficient co-removal strategy is crucial for the treatment of combined contaminants with heavy metals and antibiotics due to their great threat to sustainable advancement and ecological preservation. Herein, the efficient co-removal of aqueous hexavalent chromium (Cr(VI)) and ciprofloxacin (CIP) is achieved via a newly developed composite of nanoscale zero-valent iron particles embedded into alkali lignin-derived carbon (nZVI/ALC) without external assistance (such as light, advanced oxidants). nZVl/ALC demonstrates superior co-removal efficiencies of Cr(VI) (99.9 %) and CIP (89.9 %) with high removal kinetic rate constants of 1.595 and 0.779 min−1, respectively. The underlying mechanisms involving the co-removal of Cr(VI) and CIP verify that Cr(VI) ions are adsorbed onto the skeleton of nZVI/ALC originating from the electrostatic interaction, and CIP molecules adsorbed on nZVl/ALC act as a bridge, complexing with the Cr(VI) ions to promote Cr(VI) removal. Meanwhile, the CIP adsorption by nZVI/ALC involves hydrogen bonding, π-π interaction, and complexation. The coexisting Cr(VI) ions are transformed into Cr(III) components with abundant electron transfer, leading to the generation of more •O2– radicals, thus the self-generating reactive oxygen species (•OH, •O2– and 1O2) in ambient-air condition promote CIP degradation in the binary system. The CIP molecules’ degradation pathways mainly include piperazine ring cracking, piperazine epoxidation, quinolone ring opening and defluorination according to the analysis of HPLC-MS and FuKui function, along with the gradual reduction in toxicity throughout the degradation process of CIP molecules. This study offers a new insight on the co-removal of Cr(VI) and CIP, which would provide promising guidance for the remediation of compound wastewater with heavy metals and antibiotics.