Enhanced transformation of aquatic organic compounds by long-lived photooxidants (LLPO) produced from dissolved organic matter

Dissolved organic matter (DOM) plays a crucial role in the photochemical transformation of organic contaminants in natural aquatic systems. The present study focuses on the characterization of a specific effect previously observed for electron-rich phenols, consisting in an acceleration of the DOM-photosensitized transformation of target compounds at low concentrations (< 1 mu M). This effect was hypothesized to be caused by DOM-derived "long-lived" photooxidants (LLPO). Pseudo-first-order rate constants for the transformation of several phenols, anilines, sulfonamide antibiotics and phenylureas photosensitized by Suwannee River fulvic acid were determined under steady-state irradiation using the UVA and visible wavelengths from a medium-pressure mercury lamp. A significant enhancement (by a factor of 2.4 - 16) of the first-order transformation rate constant of various electron-rich target compounds was observed for an initial concentration of 0.1 mu M compared to 5 mu M. This effect points to a relevant reactivity of these compounds with LLPO. For phenols and anilines the enhancement effect occurred only above certain standard one-electron oxidation potentials. From these data series the standard one-electron reduction potential of LLPO was estimated to be in the range of 1.0 - 1.3 V versus the standard hydrogen electrode. LLPO are proposed to mainly consist of phenoxyl radicals formed by photooxidation of electronpoor phenolic moieties of the DOM. The plausibility of this hypothesis was successfully tested by studying the photosensitized transformation kinetics of 3,4-dimethoxyphenol in aqueous solutions containing a model photosensitizer (2-acetonaphthone) and a model electron-poor phenol (4-cyanophenol) as DOM surrogates. (c) 2020 The Authors. Published by Elsevier Ltd.