Peracetic acid activation by mechanochemically sulfidated zero valent iron for micropollutants degradation: Enhancement mechanism and strategy for extending applicability

In this study, mechanically sulfidated microscale zero valent iron (S-ZVI) was found to effectively activate the peracetic acid (PAA) with a result of almost complete degradation of six micropollutants within 10 min under neutral conditions, and > 95% sulfamethoxazole (SMX) removal after six cycles. Reactive oxidized species (ROS) including HO•, carbon-centered radicals, and Fe(IV) were generated in the S-ZVI/PAA system, while HO• was the main contributor towards micropollutants degradation. This study clearly revealed that enhancement of the electron donating ability of ZVI by the formed conductive iron sulfides was crucial for promoted Fe(II) generation and subsequent PAA activation over several cycles, rather than the ability of sulfides to reduce Fe(III) for Fe(II) regeneration as reported previously. Interestingly, it's discovered that co-existence of Fe(III) would dramatically improve the contaminants removal efficiency of the S-ZVI/PAA system; transform the surfaced Fe(II) dominated ROS generation process to aqueous Fe(II) one; enhance the tolerance of the proposed system to water matrix. The promoting effect of predosed Fe(III) on PAA activation by S-ZVI should be mainly associated with: the greater ability of Fe(III) than H2O to accept electron from Fe0 for obtaining more active sites; slower Fe0 consumption and solid sulfur species release for elevated electron utilization efficiency and PAA activation. Considering the convenient and cost-effective access of Fe(III), the decrease of acute toxicity of treated SMX, excellent stability and good removal of various micropollutants fully demonstrate the superiority of S-ZVI/PAA system for practical application.