Activation of persulfate by humic substances: Stoichiometry and changes in the optical properties of the humic substances

Abstract

Persulfate activation through electron transfer from humic substances (HS) was investigated. Persulfate consumption in the presence of standard HS and HS model compounds linearly correlated with the phenol contents of the HS. Redox-active carbonyl groups such as aromatic ketones and quinone also contributed to persulfate consumption by donating electrons while being reduced. Phenols activated persulfate through direct electron transfer from the phenolate forms but reduced ketones activated persulfate through reactions between their organic radicals and persulfate. Persulfate was activated more by terrestrially derived aquatic HS containing large numbers of phenol groups than by other species, and this caused more benzene oxidation to occur in the presence of terrestrially derived aquatic HS than in the presence of other species. Larger amounts of sulfate radicals were scavenged by soil-derived HS than other types of HS because soil-derived HS were composed of larger molecules than other types of HS. The fluorescence regional integration volume for HS reacted with persulfate linearly correlated with persulfate consumption. Decreases in the fluorescence regional integration value could be used to predict persulfate activation through electron transfer from HS to persulfate if the electron-donating capacity cannot be determined. Persulfate activation by HS is expected to be stoichiometrically more advantageous than conventional persulfate–Fe2+ processes when treating an aquifer containing large amounts of electron-rich HS.