Unexpected Role of Nitrite in Promoting Transformation of Sulfonamide Antibiotics by Peracetic Acid: Reactive Nitrogen Species Contribution and Harmful Disinfection Byproduct Formation Potential.

Peracetic acid (PAA) is an emerging oxidant and disinfectant for wastewater (WW) treatment due to limited harmful disinfection byproduct (DBP) formation. Nitrite (NO 2 - ) is a ubiquitous anion in water, but the impact of NO 2 - on PAA oxidation and disinfection has been largely overlooked. This work found for the first time that NO 2 - could significantly promote the oxidation of sulfonamide antibiotics (SAs) by PAA. Unexpectedly, the reactive nitrogen species (RNS), for example, peroxynitrite (ONOO - ), rather than conventional organic radicals (R-O • ) or reactive oxygen species (ROS), played major roles in SAs degradation. A kinetic model based on first-principles was developed to elucidate the reaction mechanism and simulate reaction kinetics of the PAA/NO 2 - process. Structural activity assessment and quantum chemical calculations showed that RNS tended to react with an aromatic amine group, resulting in more conversion of NO 2 - -N to organic-N. The formation of nitrated and nitrosated byproducts and the enhancement of trichloronitromethane formation potential might be a prevalent problem in the PAA/NO 2 - process. This study provides new insights into the reaction of PAA with NO 2 - and sheds light on the potential risks of PAA in WW treatment in the presence of NO 2 - .