Biochar composite derived from cellulase hydrolysis apple branch for quinolone antibiotics enhanced removal: Precursor pyrolysis performance, functional group introduction and adsorption mechanisms.

In this study, magnetic biochar (MAB) and humic acid (HA)-coated magnetic biochar produced from apple branches without and after cellulase hydrolysis (HMAB and CHMAB, respectively) were prepared and tested as adsorbents of enrofloxacin (ENR) and moxifloxacin (MFX) in aqueous solution. Compared with MAB and HMAB, novel adsorbent CHMAB possessed a superior mesoporous structure, greater graphitization degree and abundant functional groups. When antibiotic solutions ranged from 2 to 20 mg L, the theoretical maximum adsorption capacities of CHMAB for ENR and MFX were 48.3 and 61.5 mg g at 35 °C with adsorbent dosage of 0.4 g L, respectively, while those of MAB and HMAB were 39.6 and 54.4 mg g, and 44.7 and 59.0 mg g, respectively. The pseudo-second-order kinetic model and Langmuir model presented a better fitting to the spontaneous and endothermic adsorption process. The maximum adsorption capacity of ENR and MFX onto CHMAB was achieved at initial pH values of 5 and 8, respectively. Additionally, the adsorption capacity of ENR and MFX decreased with increasing concentrations of K and Ca (0.02-0.1 mol L). Synergism between the pore-filling effect, π-π electron-donor-acceptor interactions, regular and negative charge-assisted H-bonding, surface complexation, electrostatic interactions and hydrophobic interactions may dominate the adsorption process. This study demonstrated that a novel magnetic biochar composite prepared through pyrolysis of agricultural waste lignocellulose hydrolyzed by cellulase in combination with HA coating was a promising adsorbent for eliminating quinolone antibiotics from aqueous media.