Enhanced Adsorption of Aqueous Ciprofloxacin Hydrochloride by a Manganese-Modified Magnetic Dual-Sludge Biochar

In this study, an effective composite material, manganese-modified magnetic dual-sludge biochar (Mn@MDSBC), was developed for the adsorption of ciprofloxacin hydrochloride (CIP). This composite was prepared by means of a simple one-pot method, which involved the pyrolysis of iron-based waterworks sludge (IBWS) and paper mill sludge (PMS) loaded with manganese (Mn) under controlled conditions in a nitrogen atmosphere. The synthesized Mn@MDSBC was subjected to a comprehensive suite of characterization approaches, which included N2 adsorption–desorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). Subsequently, static adsorption tests were conducted to investigate how different factors, including the initial solution pH, reaction time and temperature, CIP concentration, and ionic strength influence the adsorption of CIP by Mn@MDSBC. Mn@MDSBC had the maximum CIP adsorption capacity of 75.86 mg/g at pH 5, among the pH values ranging from 3 to 9. The pseudo-second order model provided the best description of the adsorption process, while the experimental data aligned more closely with the Langmuir equation than with the Freundlich model, indicating monolayer adsorption. The adsorption process was found to be non-spontaneous and exothermic according to thermodynamic analysis. The presence of Cl− and SO42− enhanced CIP adsorption, while PO43− weakened it. After five cycles of reuse, Mn@MDSBC experienced a 17.17% loss in CIP adsorption capacity. The primary mechanisms for CIP removal by Mn@MDSBC were identified as physical and chemical adsorption, hydrogen bonding, and π-π stacking interactions. In summary, the study underscores the high efficiency of Mn@MDSBC as a composite material for CIP adsorption, highlighting its potential for application in wastewater treatment processes.