Efficient degradation of benzalkonium chloride (BAC) by zero-valent iron activated persulfate: Kinetics, reaction mechanisms, theoretical calculations and toxicity evolution

The present study systematically investigated the elimination of benzalkonium chloride (BAC) in the zero valent iron activated persulfate (Fe 0 /PS) system. The influence of operational parameters, including PS concentration, Fe 0 dosage and pH, were investigated through a series of kinetic experiments. When the Fe 0 dosage was 5.0 mM, the initial ratio of [PS]: [BAC] was 10:1, the degradation efficiency could achieve 91.7% at pH 7.0 within 60 min. Common inorganic anions and humic acid did not significantly affect BAC degradation, implying that Fe 0 /PS system had a potential application prospect in the actual wastewater remediation. Based on the electron paramagnetic resonance test and quenching experiments, the BAC degradation was found to be contributed by •OH, SO 4 • - and Fe(IV). A total of 23 intermediates were identified by the liquid chromatography-mass spectrometry, and the degradation pathways were proposed accordingly, including dealkylation and demethylation, hydroxylation, sulfate substitution and benzyl C-N cleavage reactions. Density functional theory based calculations were conducted to realize the rationality of the proposed reaction mechanisms. The toxicity of transformation products was predicted by ECOSAR program. This work demonstrated the possibility of BAC removal in hospital and municipal wastewater by Fe 0 /PS treatment, and also provides a safe choice for deep treatment of quaternary ammonium salt wastewater.