Formation of oxidation byproducts during electrochemical treatment of simulated produced water

Electrochemical oxidation (EO) can effectively remove recalcitrant organic contaminants from produced water (PW) but the formation of toxic oxidation byproducts (OBPs) is an unintended consequence. This study has rigorously investigated the OBPs formation during the EO treatment of a simulated PW containing phenol - a common organic contaminant existing in PW, as a model contaminant. In the absence of ammonia, free chlorine was generated from Cl^- oxidation to serve as the main oxidant for phenol oxidation. During the EO process, 2,4,6-trichlorophenol and 2,6-dichlorobenzoquinone were identified as the critical intermediates that led to the formation of carbonaceous OBPs (C-OBPs). Some C-OBPs like chloroform (TCM), chloral hydrate (CH), and trichloroacetic acid (TCAA) reached their peak concentrations of 15 - 180 μM that were then reduced to 1 - 115 μM via volatilization and/or electrochemical reduction. When ammonia was present, nitrogenous OBPs (N-OBPs) were formed with the peak levels of 1 - 10 μM at the chlorination breakpoint (when ammonia was completely removed) that were subsequently reduced below 1 uM via volatilization and/or hydrolysis. It was observed that ammonia significantly decreased the formation of both C-OBPs and chlorate due to the consumption of free chlorine. A higher current density accelerated OBPs formation rates with different effects on volatile and non-volatile OBPs. The results of this study will enhance our understanding of OBPs formation precursors and mechanisms during electrochemical process and help develop strategies for proper control of OBPs to achieve safer electrochemical wastewater treatment.