Reactive Nitrogen Species Generated from Far-UVC Photolysis of Nitrate Contribute to Pesticide Degradation and Nitrogenous Byproduct Formation

Climate change has resulted in increased use of pesticides and fertilizers in agriculture, leading to elevated pesticide and nitrate levels in aquatic ecosystems that receive agricultural runoff. In this study, we demonstrate that far-UVC (UV222) photolysis of nitrate rapidly degrades four pesticides in surface water, with a degradation rate constant 37.1-144.75 times higher than that achieved by UV254 photolysis of nitrate. The improved pesticide degradation is due not only to the enhanced direct photolysis by UV222 compared to UV254 but also to the increased generation of hydroxyl radicals (HO center dot) and reactive nitrogen species (e.g., NO2 center dot and ONOO-) in the UV222/nitrate process. We determined the innate quantum yields of nitrate photolysis at 222 nm and incorporated these values into a kinetic model, allowing for the accurate prediction of nitrate photodecay and reactive species generation. While reactive nitrogen species predominantly contribute to pesticide degradation in the UV222/nitrate process, they also lead to the formation of nitration byproducts. Using stable isotope-labeled nitrate (15NO3 -) combined with mass spectrometry, we confirmed that the nitration byproducts are formed from the reactive nitrogen species generated from nitrate photolysis. Additionally, we demonstrate that the UV222/nitrate process increases the formation potential of highly toxic nitrogenous chlorinated products (e.g., trichloronitromethane) during postchlorination in real surface water.