Anthropogenic Emission Largely Enhances Nocturnal Oxidation Chemistry in the Upper Mixing Layer of Megacities

Nitrate radicals (NO 3 ) are the dominant oxidants at night, shaping air quality, the climate, and ecosystems. However, the vertical variations of NO 3 chemistry within the nocturnal boundary layer remain poorly understood, owing to the stratification of air masses and complex vertical chemistry. Here, we combined vertical and ground-based measurements of NO 3 precursors from diverse atmospheric environments with model simulations to investigate the vertical structure of nocturnal NO 3 oxidation and its long-term trend. Our results indicate that the nocturnal enhanced NO 3 chemistry aloft event occurs far more frequently in megacities (64–72%) than in representative clean areas (16%), with a median enhancement factor of 2.7 relative to the surface. The event largely promotes the formation of secondary pollutants aloft rather than at the surface. We further show the event is more prevalent in China and India, attributed to intense ground-level NO x emissions, than in the United States and Europe. However, its frequency has declined rapidly in China in recent years, closely linked to the implementation of NO x emission controls. These findings highlight the critical role of vertical gradients in nocturnal NO 3 chemistry on surface air pollution and underscore the need for comprehensive vertical measurements to support further improvement of urban air quality.