Comparative analysis of UV-initiated ARPs for degradation of the emerging substitute of perfluorinated compounds: Does defluorination mean the sole factor?

Abstract

Due to the increasing attention for the residual of per- and polyfluorinated compounds in environmental water, Sodium p-Perfluorous Nonenoxybenzenesulfonate (OBS) have been considered as an alternative solution for perfluorooctane sulfonic acid (PFOS). However, recent detections of elevated OBS concentrations in oil fields and Frontal polymerization foams have raised environmental concerns leading to the decontamination exploration for this compound. In this study, three advanced reduction processes including UV-Sulfate (UV-SF), UV-Iodide (UV-KI) and UV-Nitrilotriacetic acid (UV-NTA) were selected to evaluate the removal for OBS. Results revealed that hydrated electrons (eaq−) dominated the degradation and defluorination of OBS. Remarkably, the UV-KI exhibited the highest removal rate (0.005 s−1) and defluorination efficiency (35 %) along with the highest concentration of eaq− (K = −4.651). Despite that nucleophilic attack from eaq− on sp2 carbon and H/F exchange were discovered as the general mechanism, high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC/Q-TOF-MS) analysis with density functional theory (DFT) calculations revealed the diversified products and routes. Intermediates with lowest fluorine content for UV-KI were identified, the presence nitrogen-containing intermediates were revealed in the UV-NTA. Notably, the nitrogen-containing intermediates displayed the enhanced toxicity, and the iodine poly-fluorinated intermediates could be a potential-threat compared to the superior defluorination performance for UV-KI.