Activation of peroxymonosulfate by cobalt-impregnated biochar for atrazine degradation: The pivotal roles of persistent free radicals and ecotoxicity assessment

Abstract

Cobalt-mediated activation of peroxymonosulfate (PMS) has been extensively investigated for the degradation of emerging organic pollutants. In this study, PMS activation via cobalt-impregnated biochar towards atrazine (ATZ) degradation was systematically examined, and the underlying reaction mechanism was explicated. It was found that persistent free radicals (PFRs) contained in biochar play a pivotal role in PMS activation process. The PFRs enabled an efficient transfer electron to both cobalt atom and O2, facilitating the recycle of Co(III)/Co(II), and thereby leaded to an excellent catalytic performance. In contrast to oxic condition, the elimination of dissolved oxygen significantly retarded the ATZ degradation efficiency from 0.76 to 0.36 min-1. Radical scavenging experiments and electron paramagnetic resonance (EPR) analysis confirmed that the ATZ degradation was primarily due to SO4·- and, to a lesser extent, ·OH. In addition, dual descriptor (DD) method was carried out to reveal reactive sites on ATZ for radicals attacking and predicted derivatives. Meanwhile, the possible ATZ degradation pathways were accordingly proposed, and the ecotoxicity evaluation of the oxidation intermediates was also conducted by ECOSAR. Consequently, the cobalt-impregnated biochar could be an efficient and environmentally friendly catalyst to activate PMS for abatement and detoxication of ATZ.