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.

Efficient activation of PAA by FeS for fast removal of pharmaceuticals: The dual role of sulfur species in regulating the reactive oxidized species.

As peracetic acid (PAA) is being increasingly used as an alternative disinfectant, efficient activation of PAA by low-cost and environmentally friendly catalysts over a wide pH range is potentially useful for simultaneous sterilization and pharmaceutical degradation in wastewater, such as hospital wastewater. In this study, peracetic acid (PAA) was successfully activated by low-cost and environmental-friendly FeS (25 mg/L) for efficient oxidative removal of three pharmaceuticals over a wide pH range (3.0∼9.0) as indicated by 80∼100% removal rate within 5 min. As expected, Fe(II) rather than sulfur species was the primary reactive site for PAA activation, while unlike the homogeneous Fe2+/PAA system with organic radicals (R-O·) and ·OH as the dominant reactive oxidized species (ROS), ·OH is the key reactive species in the FeS/PAA system. Interestingly and surprisingly, in-depth investigation revealed the dual role of sulfur species in regulating the reactive oxidized species: (1) S(-II) and its conversion product H2S (aq) played a significant role in Fe(II) regeneration with a result of accelerated PAA activation; (2) however, the R-O· generated in the initial seconds of the FeS/PAA process was supposed to be quickly consumed by sulfur species, resulting in ·OH as the dominant ROS over the whole process. The selective reaction of sulfur species with R-O· instead of ·OH was supported by the obviously lower Gibbs free energy of CH3COO· and sulfur species than ·OH, suggesting the preference of CH3COO· to react with sulfur species with electron transfer. After treatment with the FeS/PAA system, the products obtained from the three pharmaceuticals were detoxified and even facilitated the growth of E. coli probably due to the supply of numerous carbon sources by activated PAA. This study significantly advances the understanding of the reaction between PAA and sulfur-containing catalysts and suggests the practical application potential of the FeS/PAA process combined with biotreatment processes.