Copper Inhibition of Triplet-Induced Reactions Involving Natural Organic Matter

The triplet excited state of natural organic matter (³NOM*) is an important reactive intermediate in sensitizing transformation of a wide range of environmentally relevant organic compounds, but the impact of trace metals on the fate and reactivity of ³NOM* is poorly understood. In this study, we investigate the effect of low concentrations of copper on ³NOM*-mediated oxidation (electron transfer) and energy transfer reactions. The oxidative efficiency of ³NOM* from Suwannee River NOM (SRNOM) and the widely used model triplet sensitizer 4-carboxybenzophenone were determined by measuring the photooxidation of 2,4,6-trimethylphenol (TMP). The pseudo-first-order photooxidation rate constants of TMP decreased markedly in the presence of trace amounts of Cu(II) (25-500 nM) with the decrease associated with the continuous reduction of the oxidation intermediates of TMP (i.e., TMP^•_(-H)) by the photochemically produced Cu(I). A kinetic model is developed that adequately describes the Cu inhibition effect in TMP photooxidation in irradiated SRNOM solutions. The ³NOM* energy transfer ability was assessed by measuring the isomerization of sorbic acid with the rate of this process markedly retarded in the presence of significantly higher (micromolar) concentrations of Cu(II) than previously used. This result is attributed to (i) decreased formation of high energy ³NOM* due to formation of Cu-NOM complexes and (ii) increased loss of ³NOM* as a result of quenching by Cu. Since ³NOM* is the precursor to singlet oxygen (¹O₂) formation, the steady-state concentrations of ¹O₂ also decreased in the presence of micromolar concentrations of Cu(II) with the quenching rate constant of ³NOM* by Cu calculated to be 1.08 × 10¹⁰ M^-1 s^-1.