Singlet Oxygen Phosphorescence as a Probe for Triplet-State Dissolved Organic Matter Reactivity

Triplet-state chromophoric dissolved organic matter (³CDOM*) plays an important role in aquatic photochemistry, yet much remains unknown about the reactivity of these intermediates. To better understand the kinetic behavior and reactivity of ³CDOM*, we have developed an indirect observation method based on monitoring time-resolved singlet oxygen (¹O₂) phosphorescence kinetics. The underpinning principle of our approach relies on the fact that O₂ quenches almost all triplets with near diffusion limited rate constants, resulting in the formation of ¹O₂, which is kinetically linked to the precursors. A kinetic model relating ¹O₂ phosphorescence kinetics to triplet excited states produced from isolated humic substances and in whole natural-water samples (hereafter referred to as ³CDOM*) was developed and used to determine rate constants governing ³CDOM* natural lifetimes and quenching by oxygen and 2,4,6-trimethylphenol (TMP), a common triplet probe molecule. ³CDOM* was found to exhibit smaller O₂ and TMP quenching rate constants, ∼9 × 10⁸ and ∼8 × 10⁸ M^-1 s^-1, respectively, compared with model sensitizers, such as aromatic ketones. Findings from this report shed light on the fundamental photochemical properties of CDOM in organic matter isolates and whole waters and will help refine photochemical models to more accurately predict pollutant fate in the environment.