Electrogenerated oxychlorides induced overlooked negative effects on electro-oxidation wastewater treatment in terms of over-evaluated COD removal efficiency and biotoxicity

The high-efficiency and environmentally-friendly electro-oxidation (EO) would lose its competitive edge because of the production of oxychloride by-products (ClOx-), which has not yet drawn significant attention in academic and engineering communities. In this study, the negative effects of the electrogenerated ClOx- were compared among four commonly used anode materials (BDD, Ti4O7, PbO2 and Ru-IrO2) in terms of ClOx(- i)nterference on the evaluation of electrochemical COD removal performance and biotoxicity. Apparently, the COD removal performance of various EO systems were highly enhanced with increasing current density in the presence of Cl-, e.g., the amounts of COD removed by various EO systems from the phenol solution with an initial COD content of 280 mg L-1 at 40 mA cm(-2) within 120 min decreased in the order: Ti4O7 of 265 mg L-1 > BDD of 257 mg L-1 > PbO2 of 202 mg L-1 > Ru-IrO2 of 118 mg L-1, which was different from the case with the absence of Cl- (BDD of 200 mg L-1 > Ti4O7 of 112 mg L-1 > PbO2 of 108 mg L-1 > Ru-IrO2 of 80 mg L-1) and the results after removing ClOx- by anoxic sulfite-based method (BDD of 205 mg L-1 > Ti4O7 of 160 mg L-1 > PbO2 of 153 mg L-1 > Ru-IrO2 of 99 mg L-1). These results can be ascribed to the ClOx- interference on COD evaluation, the extent of which decreased in the order: ClO3- > ClO- (where ClO4- cannot impact COD test). The highest overrated electro-chemical COD removal performance of Ti4O7 may be associated with its relatively high production of ClO3- and the low mineralization extent. The chlorella inhibition ratio of ClOx(-) decreased in the order: ClO- > ClO3- >> ClO4-, which accounted for the biotoxicity increasement of the treated water (PbO2 68%, Ti4O7 56%, BDD 53%, Ru-IrO2 25%). Generally, the inevitable problems of overrated electrochemical COD removal performance and biotoxicity increasement induced by ClOx(-) should deserve significant attention and effective countermeasures should be also developed when employing EO process for wastewater treatment.