The activation of peroxydisulfate and peroxymonosulfate by Fe(II) (Fe(II)/PDS and Fe(II)/PMS processes) are effective in degrading organic contaminants. Nevertheless, the question of whether Fe(IV) or free radical (SO4●− and HO● ) is the dominant intermediate in these two processes remains unanswered. Therefore, we developed multiple methods to differentiate Fe(IV) and SO4●−/HO● in the Fe(II)/PDS and Fe(II)/PMS processes. Then, we find that Fe(IV), SO4●−, and HO● were generated and contributed differently to the degradation of various organic contaminants in the Fe(II)/PDS process. Meanwhile, both Fe(IV) and SO4●− were the active oxidants in the Fe(II)/PMS process. Moreover, we find that the degradation rates of organic contaminants in the rapid oxidation stage were extremely high in the Fe(II)/PMS process, which has been overlooked before. This work updates the fundamental understanding of the degradation of organic contaminants in the Fe(II)/PDS and Fe(II)/PMS processes.

Both Fe(IV) and free radical are active oxidants in the Fe(II)/persulfate processes

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