Biochar-mediated Fenton-like reaction for the degradation of sulfamethazine: Role of environmentally persistent free radicals.

Swine manure biochar (SBC) pyrolyzed at 300 °C, 600 °C and 900 °C were utilized to degrade sulfamethazine (SMT) in heterogeneous Fenton-like systems which achieved excellent degradation efficiency (over 85% in 30 min). Experiments results demonstrated that SBC possessed the poor SMT adsorption capacity but high catalytic performance. Electron Paramagnetic Resonance (EPR) and X-ray photoelectron spectroscopy (XPS) analysis revealed that there were oxygen-centered environmentally persistent free radicals (EPFRs) and carbon-centered EPFRs with an adjacent oxygen atom in SBC. The oxygen-centered EPFRs played a major role in the catalytic process which tended to convert to carbon-centered EPFRs after the reaction. Besides, the electron transfer pathways were the most likely catalytic mechanism of SBC and the contribution of OH was dominant through Electron capture experiments and Linear sweep voltammetry (LSV) measurements. The acidic or alkaline condition can promote the catalytic ability of SBC. The presence of dissolved salts (NaCl) inhibited the catalytic process but the inhibition was slightly weakened at high concentration of NaCl, which showed the high tolerance of Cl in Fenton/Fenton-like systems. Moreover, real wastewater application suggested that SBC600/HO system possessed excellent catalytic efficiency and good adaptability. This research provides a novel swine manure reuse process with high practicability and presents a more explicit perspective about the reaction mechanisms of EPFRs in biochar.