Isotopic imprints of aerosol ammonium over the north China plain

Atmospheric PM_2.5 poses a variety of health and environmental risks to urban environments. Ammonium is one of the main components of PM_2.5, and its role in PM_2.5 pollution will likely increase in the coming years as NH₃ emissions are still unregulated and rising in many cities worldwide. However, partitioning urban NH₄⁺ sources remains challenging. Although the ¹⁵N natural abundance (δ¹⁵N) analysis is a promising approach for this purpose, it has seldom been applied across multiple cities within a given region. This limits our understanding of the regional patterns and controls of NH₄⁺ sources in urban environments. Here, we collected PM_2.5 samples using an active sampling technique during winter at six cities in the North China Plain to characterize the concentrations, δ¹⁵N and sources of NH₄⁺ in PM_2.5. We found substantial variations in both the concentrations and δ¹⁵N of NH₄⁺ among the sites. The mean NH₄⁺ concentrations across the six cities ranged from 3.6 to 12.1 μg m^-3 on polluted days and from 0.9 to 10.6 μg m^-3 on non-polluted days. The δ¹⁵N ranged from 6.5‰ to 13.9‰ on polluted days and from 8.7‰ to 13.5‰ on non-polluted days. The δ¹⁵N decreased with increasing NH₄⁺ concentrations at all six sites. We found that non-agricultural sources (vehicle exhaust, ammonia slip and urban wastes) contributed 72%-94% and 56%-86% of the NH₄⁺ on polluted and non-polluted days, respectively, and that during polluted days, combustion-related emissions (vehicle exhaust and ammonia slip) were positively associated with the proportion of urban area, population density and number of vehicles, highlighting the importance of local sources of particulate pollution. This study suggests that the analysis of ¹⁵N in aerosol NH₄⁺ is a promising approach for apportioning atmospheric NH₃ sources over a large region, and this approach has potential for mapping rapidly and precisely the sources of NH₃ emissions.