Copper Inhibition of Triplet-Sensitized Phototransformation of Phenolic and Amine Contaminants

Excited triplet states of natural organic matter (3NOM*) are important reactive intermediates in phototransformation of organic contaminants in sunlit waters. The main goal of this study was to explore the influence of Cu on triplet-sensitized transformation rates of 20 selected phenolic and amine contaminants. Fourteen of the compounds examined exhibited a marked decrease in their 4-carboxybenzophenone (CBBP)-mediated phototransformation rate in the presence of trace amounts of Cu(II) (25-500 nM). Both mathematical modeling of these rate data and transient absorption spectroscopy measurements support the hypothesis that the decrease in the rate and extent of phototransformation of organic contaminants is due to the reduction of radical intermediates of the contaminants by photochemically formed Cu(I). The Cu-induced inhibition of oxidation of organic contaminants photosensitized by Suwannee River NOM (SRNOM) could also take place in the presence of nanomolar concentrations of Cu. The inhibitory effect of Cu on the oxidation rates of amine contaminants in SRNOM solutions was found to be significantly weaker compared to that in CBBP solutions, but little difference was observed on depletion of phenols. This behavior was attributed to the intrinsic inhibitory effect of the antioxidant moieties present in NOM on phototransformation of amine compounds, partially neutralizing the potential for further Cu inhibition.