Influence of microplastics and environmentally persistent free radicals on the ability of biochar components to promote degradation of antibiotics by activated peroxymonosulfate

Microplastics (MPs) in sludge can affect the ability of biochar-activated peroxymonosulfate (PMS) to degrade antibiotics. In this work, biochar was prepared by mixing sludge and polystyrene (PS) through hydrothermal carbonization (HTC) and high-temperature pyrolysis processes. The resulting biochar was used to activate PMS to degrade ofloxacin (OFX), levofloxacin (LEV), and pefloxacin (PFX). The addition of PS significantly enhanced the ability of biochar/PMS to degrade antibiotics and the levels of environmentally persistent free radicals (EPFRs, 4.59 × 1020 spin/g) due to the decomposition of PS. The addition of PS resulted in a slight decrease in the specific surface area of biochar (2-3 m2/g on average), but a significant increase in the concentration of EPFRs increased the removal efficiency. The activation of PMS by biochar is dominated by free radicals, accounting for about 70%, in which SO4•- and •OH contribute the most and O2•- the least. However, 1O2 contributes 15-20% to the degradation of antibiotics in non-free radical processes. Overall, the process of biochar/PMS degradation of antibiotics is mainly dominated by free radicals, and the effect of non-free radicals is not obvious. Both hydrochar and pyrocarbon samples showed good hydrophilicity, and this property should improve the ability of active sites on biochar to degrade antibiotics. In the HTC process, PS can decompose during hydrochar preparation, with a maximum reduction value of 40.09%. The three-dimension excitation emission matrix fluorescence spectroscopy (3D-EEM) and total organic carbon (TOC) results show that the protein content in sludge plays a major role in reducing PS, with little effect of polysaccharide and SiO2. There are six to seven degradation intermediates of quinolone antibiotics, which are eventually degraded into CO2, H2O, and inorganic substances. The regeneration experiment showed good reusability of hydrochar and pyrocarbon, further demonstrating the suitability of biochar for the degradation of antibiotics.