Influence of chloride and carbonates on the reactivity of activated persulfate

Chloride and carbonates have the potential to impact pathway, kinetics, and efficiency of oxidation reactions, both as radical scavengers and as metal complexing agents. Traditionally, it is assumed that they have an overall negative impact on the activated persulfate performance. This study investigated the influence of carbonates and chloride on the reactivity of persulfate for three different activation techniques to produce reactive free sulfate radicals; heat, alkaline and iron activation. By using p-nitrosodimethylaniline as model target compound, it was demonstrated that iron activation at neutral pH was not affected by Cl(-) or HCO(3)(-), alkaline activation was enhanced by Cl(-) and even more by CO(3)(2-), and heat activation was enhanced by Cl(-), and no effect from HCO(3)(-) was observed. At pH 2 destruction of perchloroethylene by iron activated persulfate was significantly affected by chloride. Reaction rates decreased, but the overall oxidation efficiency was unaffected up to 28 mM Cl(-). The effect of chloride and carbonates is caused by direct attack of produced reactive chlorine, or carbonate species or by catalysis of the propagation reactions resulting in more sulfate radicals. These results show that carbonate and chloride might play an important role in activated persulfate applications and should not strictly be considered as scavengers.