Degradation of the Herbicides Clomazone, Paraquat, and Glyphosate by Thermally Activated Peroxydisulfate

Abstract

Activated sodium peroxydisulfate has the potential to in situ destruct many organic contaminants because of the generation of the stronger oxidant sulfate radical. From photochemical activation of peroxydisulfate in flash-photolysis experiments, the bimolecular rate constants for the reaction of sulfate radical with glyphosate (1.6 × 10(8) M(-1) s(-1)) and paraquat (1.2 × 10(9) M(-1) s(-1)) at 25 °C were obtained. Thermal activation of peroxydisulfate was shown to degrade the herbicides clomazone, paraquat, and glyphosate. Although the herbicide degradation was observed to take place in less than 1 h, the mineralization of the organic carbon required longer reaction times, because of the formation of stable organic intermediates. For similar initial total organic carbon (TOC) values, TOC profiles were similar for experiments with different substrates (the herbicides, humic acids, and a mixture of glyphosate and humic acids), which indicates that the mineralization of all of the samples is limited by the production of SO(4)(•) (-) radicals. A linear correlation between the initial amount of SO(4)(•) (-) needed per mole of C and the average oxidation state was found.