Constant oxidation of atrazine in Fe(III)/PDS system by enhancing Fe(III)/Fe(II) cycle with quinones: Reaction mechanism, degradation pathway and DFT calculation

Quinones are potential pollutants and redox active compounds widely distributed in environmental media. In this study, methyl-p-benzoquinone (MBQ) was introduced into Fe(III)/peroxydisulfate system (Fe(III)/PDS) to expedite the conversion of Fe(III) to Fe(II) and the degradation of atrazine (ATZ), ultimately establishing an environmentally friendly system of "treating pollution with pollution". MBQ/Fe(III)/PDS system showed superior performance to traditional Fe(II)/PDS system in pH range of 2-7. Sulfate radical (SO₄^•-) and hydroxyl radical (^•OH) were confirmed to exist in MBQ/Fe(III)/PDS system according to alcohol quenching experiments and ESR tests. Meanwhile, stable 80% of η[PMSO₂] (i.e., the molar ratio of PMSO₂ generation to PMSO consumption) was achieved and manifested that highly reactive substance Fe(IV) also participated in MBQ/Fe(III)/PDS system. The spontaneous transformation of MBQ and methyl-hydroquinone (MHQ) drove Fe(III)/Fe(II) cycle, during which MHQ induced Fe(III) reduction and Fe(II) regeneration. Transformation pathways of ATZ were proposed based on HPLC-MS detection and DFT calculation and ATZ degradation could be initiated by lateral chain oxidation and dechlorination-hydroxylation. The acute toxicity, bioaccumulation factor, developmental toxicity and mutagenicity of ATZ and its degradation intermediates were evaluated by Toxicity Estimation Software Tool, and the luminescent bacteria test was conducted to investigate the acute toxicity variation of the reaction solution. Cl^- obviously inhibited ATZ degradation and three main by-products generation, while humic acid (HA) had little effect on them probably due to the established balance between inhibition (some components in HA competed to consume reactive species) and acceleration (quinone units in HA also facilitated Fe(III)/Fe(II) cycle).