Formation of Nitrophenolic Byproducts during Heat-Activated Peroxydisulfate Oxidation in the Presence of Natural Organic Matter and Nitrite

Sulfate radical (SO₄^•–)-based advanced oxidation is a viable in situ remediation technology for degrading organic contaminants in the subsurface. In this study, we demonstrated that SO₄^•– could induce the activation of nitrite, an anion commonly present in the subsurface environment, leading to the formation of nitrophenolic byproducts. Fourier-transform infrared spectroscope and ¹⁵N nuclear magnetic resonance analysis revealed that the inorganic nitrite was incorporated into natural organic matter (NOM) to form organic nitrogen upon SO₄^•– oxidation. Nitrophenolic byproducts, including 2-hydroxy-5-nitrobenzoic acid, 4-nitrophenol, and 2,4-dinitrophenol, were identified using high-resolution mass spectrometry in combination with a ¹⁵N labeling technique. Formation of nitrated byproducts was ascribed to the scavenging of SO₄^•– by nitrite, which not only generated the nitrating agent NO₂^• but also inhibited the degradation of organic compounds, making them more available to the reactions with NO₂^•. The phenolic moieties in NOM served as the main reactive sites for NO₂^• attack. The nitration begins with H abstraction on the phenoxy oxygen, followed by the addition of another NO₂^• to its ortho or para site. Decarboxylation followed by NO₂^• addition can also generate nitrophenolic byproducts. To the best of our knowledge, this is the first study reporting the nitration of NOM and formation of toxic nitrophenolic byproducts during SO₄^•–-based oxidation. It sheds light on the potential risks of this technology in subsurface remediation practices.