The role of nitrite in sulfate radical-based degradation of phenolic compounds: An unexpected nitration process relevant to groundwater remediation by in-situ chemical oxidation (ISCO).

As promising in-situ chemical oxidation (ISCO) technologies, sulfate radical-based advanced oxidation processes (SR-AOPs) are applied in wastewater treatment and groundwater remediation in recent years. In this contribution, we report for the first time that, thermally activated persulfate oxidation of phenol in the presence of nitrite (NO2-), an anion widely present in natural waters, could lead to the formation of nitrated by-products including 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2,4-dinitrophenol (2,4-DNP), and 2,6-dinitrophenol (2,6-DNP). Nitrogen dioxide radical (NO2•), arising from SO4•- scavenging by NO2-, was proposed to be involved in the formation of nitrophenols as a nitrating agent. It was observed that nitrophenols accounted for approximately 70% of the phenol transformed under reaction conditions of [NO2-] = 200 μM, [PS] = 2 mM and temperature of 50 °C. Increasing the concentration of NO2- remarkably enhanced the formation of nitrophenols but did not affect the transformation rate of phenol significantly. The degradation of phenol and the formation of nitrophenols were significantly influenced by persulfate dosage, solution pH and natural organic matter (NOM). Further studies on the degradation of other phenolic compounds, including 4-chlorophenol (4-CP), 4-hydroxybenzoic acid (4-HBA), and acetaminophen (ATP), verified the formation of their corresponding nitrated by-products as well. Therefore, formation of nitrated by-products is probably a common but overlooked phenomenon during SO4•--based oxidation of phenolic compounds in the presence of NO2-. Nitroaromatic compounds are well known for their carcinogenicity, mutagenicity and genotoxicity, and are potentially persistent in the environment. The formation of nitrated organic by-products in SR-AOPs should be carefully scrutinized, and risk assessment should be carried out to assess possible health and ecological impacts.