Sorbic Acid as a Triplet Probe: Reactivity of Oxidizing Triplets in Dissolved Organic Matter by Direct Observation of Aromatic Amine Oxidation

Abstract

Sorbic acid (2,4-hexadienoic acid; HDA) isomerization is frequently used to probe triplet-state dissolved organic matter (³CDOM*) reactivity, but there remain open questions about the reaction kinetics of ³CDOM* with HDA due to the difficulties of directly measuring ³CDOM* quenching rate constants. Using our recently developed approach based on observing the radical cation of <i>N</i>,<i>N</i>,<i>N</i>',<i>N</i>'-tetramethyl-<i>p</i>-phenylenediamine (TMPD) formed through oxidation of TMPD by ³CDOM*, we studied ³CDOM* quenching kinetics with HDA monitored via transient absorption spectroscopy. A competition kinetics-based approach utilizing formation yields of TMPD^•+ was developed, validated with model sensitizers, and used to determine bimolecular rate constants between ³CDOM* oxidants and HDA for diverse DOM isolates and natural waters samples, yielding values in the range of (2.4-7.7) × 10⁸ M^-1 s^-1. The unquenchable fraction of TMPD-oxidizing triplets showed that, on average, 41% of ³CDOM* oxidants cannot be quenched by HDA. Conversely, cycloheptatriene quenched nearly all TMPD^•+-forming triplets in CDOM, suggesting that most ³CDOM* oxidants possess energies greater than 150 kJ mol^-1. Comparing results with our companion study, we found slight, but noticeable differences in the ³CDOM* quenching rate constants by HDA and unquenchable triplet fractions determined by oxidation of TMPD and energy transfer to O₂ (¹O₂ formation) methods.