Quantifying Hydrated Electron Transformation Kinetics in UV-Advanced Reduction Processes Using the Re-,UV Method.

Abstract

Ultraviolet advanced reduction processes (UV-ARP) have garnered significant attention recently for the degradation of several hard to treat contaminants, including recalcitrant per- and polyfluoroalkyl substances (PFAS). The rate of contaminant degradation in UV-ARP is directly related to the available hydrated electron concentration ([eaq-]). However, reports of [eaq-] and other parameters typically used to characterize photochemical systems are not widely reported in the UV-ARP literature. Deploying monochloroacetate as a probe compound, we developed a method (Re-,UV) to quantify the time-based hydrated electron concentration ([eaq]t) available for contaminant degradation relative to inputted UV fluence. Measured [eaq]t was then used to understand the impact of eaq- rate of formation and scavenging capacity on the degradation of two contaminants─nitrate and perfluorooctane sulfonate (PFOS)─in four source waters with varying background water quality. The results show that the long-term treatability of PFOS by UV-ARP is not significantly impacted by the initial eaq- scavenging conditions but rather is influenced by the presence of eaq- scavengers like dissolved organic carbon and bicarbonate. Lastly, using [eaq]t, degradation of nitrate and PFOS was modeled in the source waters. We demonstrate that the Re-,UV method provides an effective tool to assess UV-ARP treatment performance in a variety of source waters.