A novel diagnostic method for distinguishing between Fe(IV) and OH by using atrazine as a probe: Clarifying the nature of reactive intermediates formed by nitrilotriacetic acid assisted Fenton-like reaction.

In this work, we found that the distribution of two specific atrazine (ATZ) oxidation products (desethyl-atrazine (DEA) and desisopropyl-atrazine (DIA)) was different in oxidation processes involving aqueous ferryl ion (Fe(IV)) species and OH. Specifically, the molar ratio of produced DEA to DIA (i.e., [DEA]/[DIA]) increased from 7.5 to 13 with increasing pH from 3 to 6 when ATZ was oxidized by Fe(IV), while the treatment of ATZ by OH led to the [DEA]/[DIA] value of 2 which was independent of pH. Moreover, ATZ showed high reactivity towards Fe(IV) over a wide pH range, especially at near-neutral pH, at which ATZ oxidation in Fe(II)/peroxydisulfate system was even much faster than another well-defined Fe(IV) scavenger, the sulfoxides. By using this approach, it was obtained that the [DEA]/[DIA] value remained at 2 during ATZ transformation by the nitrilotriacetic acid (NTA) assisted Fenton-like (Fe(III)/HO) system, which was independent of solution pH and reactants dosage. This result clarified that OH was the primary reactive intermediate formed in the NTA assisted Fe(III)/HO system. This study not only developed a novel sensitive diagnostic tool for distinguishing Fe(IV) from OH, but also provided more credible evidence to the nature of reactive intermediate in a commonly controversial system.