Effective activation of peroxymonosulfate with natural manganese-containing minerals through a nonradical pathway and the application for the removal of bisphenols

Synthetic manganese oxides had been widely investigated to activate peroxymonosulfate (PMS) for contaminant removal in recent years. The generation of reactive oxygen species (ROS, e.g., radicals) was believed to be the primary PMS activation pathways. In this work, we report that natural manganese-containing minerals (NMMs) were also effective for PMS activation to degrade bisphenols in water. Moreover, a nonradical pathway different from literatures, was confirmed according to scavenging tests, electron paramagnetic resonance (EPR) characterization, chemical probing, solvent exchange, and Raman and electrochemical analysis. It was verified that PMS complexed with the mineral surface via inner-sphere interaction. This surface interaction improved its reactivity towards the probe compounds, bisphenols. Taking bisphenol AF (BPAF) as an example, its degradation rate was related to surface area and dosages of the mineral. Water constituents such as Cl-, HCO3 -, and NOM had negligible impact on BPAF removal. The activity of the mineral was kept in an 80-hour continuous flow test. The PMS/NMM coupled oxidation degraded BPAF through direct electron transfer, and the degradation intermediates further underwent hydroxylation, bond cleavage, H-atom substitution, aromatic ring-opening, and decarboxylation. Consequently, eco-toxicity of BPAF can be reduced during the oxidation.

Automated summary

The study found that natural manganese-containing minerals can effectively activate PMS to degrade bisphenols in water, and the activation process is different from previous literature reports, mainly through inner-sphere complexation to enhance the reactivity of PMS.