Degradation of ciprofloxacin by the Mn cycle system (MnCS): Construction, characterization and bacterial analysis

The release of Mn(II) occurs in the degradation of organic matters by manganese ore (MnO₂), resulting in a reduced efficiency. During the degradation of ciprofloxacin (CIP), in a biofilter, this paper put forward a novel method that similar to the geo-cycle of Mn (MnCS) on the Earth to regenerate MnO₂. The freshly prepared MnO₂ was suitable for the use in the MnCS. It indicated that the mutual conversion between Mn(II), Mn(III), and Mn(IV) in the MnCS, which was driven by CIP and manganese oxidizing bacteria (MnOB), could maintain the activity of MnO₂. The MnCS showed feasibility in the coexistence of ammonia or humic acid, and provided a kinetic degradation. The physicochemical features of MnO₂ before and after bio-regeneration were characterized by TEM, XRD, BET, and XPS. It was found that the morphological structure of MnO₂ became loose and the maximum peak of pore size distribution became smaller, but the increase of surface area, the change of Mn(III/IV) content, and the decrease of crystallinity favored the bio-regeneration process. Moreover, as a mediator in the MnCS, the group of MnOB was dramatically inhibited by CIP, and the bacterial community had changed significantly. The typical MnOB shared low abundance in the biofilter, while the rarely reported genera (e.g. Sphingomonas) that related to the formation of Mn deposits appeared to be involved in the MnCS.