Mechanism of nitro-byproducts formation during persulfate-based electrokinetic in situ oxidation for remediation of anthracene contaminated soil

Persulfate-based electrokinetic (EK) chemical oxidation appears to be a novel and viable strategy for the in situ remediation of polycyclic aromatic hydrocarbons (PAHs) polluted soil; however, the possible toxic byproducts of PAHs have been overlooked. In this study, we systematically investigated the formation mechanism of the nitro byproducts of anthracene (ANT) during the EK process. Electrochemical experiments revealed that NH4+ and NO2- originating from nitrate electrolyte or soil substrates were oxidized to NO2 & BULL; and NO & BULL; in the presence of SO4 & BULL;-. Liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS/MS) analysis with 15N labeling revealed the formation of nitro-byproducts (14 kinds), including 1-hydroxy-4-nitro-anthraquinone and its similar derivatives, 4-nitrophenol, and 2,4-dinitrophenol. The nitration pathways of ANT have been proposed and described, mainly including the formation of hydroxyl-anthraquinone-oxygen and phenoxy radicals and the subsequent addition of NO2 & BULL; and NO & BULL;. ANT-based formation of nitro-byproducts during EK, which is usually underestimated, should be further investigated due to their enhanced acute toxicity, mutagenic effects, and potential threat to the ecosystem.