Water Microdroplets in Air: A Hitherto Unnoticed Natural Source of Nitrogen Oxides

Water microdroplets are widespread in the atmosphere. We report a striking observation that micron-sized water droplets obtained from zero-volt spray sources (sonic spray, humidifier, spray bottle, steamer, etc.) spontaneously generate nitrogen oxides. The mechanistic investigation through the development of custom-designed sampling sources combined with mass spectrometry and isotope labeling experiments confirmed that air nitrogen reacts with the water at the air-water interface, fixing molecular nitrogen to its oxides (NO, NO₂, and N₂O) and acids (HNO₂ and HNO₃) at trace levels without any catalyst. These reactions are attributed to the consequence of an experimentally detected feeble corona discharge (breakdown of air) at the air-water interface, likely driven by the high intrinsic electric field at the surface of water microdroplets. The extent of this corona discharge effect varies depending on the pH, salinity/impurity, size, speed, and lifetime of microdroplets in the air. Thus, this study discloses that the air-water interface of microdroplets breaks the strong chemical bond of nitrogen (N₂), producing nitrogen oxides in the environment, while lightning strikes and microbial processes in soil are considered their dominant natural sources. As nitrogen oxides are toxic air pollutants, their spontaneous formation at the air-water interface should have important implications in atmospheric reactions, requiring further investigations.