Fossil Fuel Combustion-Related Emissions Dominate Atmospheric Ammonia Sources during Severe Haze Episodes: Evidence from ¹⁵N‑Stable Isotope in Size-Resolved Aerosol Ammonium

Abstract

The reduction of ammonia (NH₃) emissions is urgently needed due to its role in aerosol nucleation and growth causing haze formation during its conversion into ammonium (NH₄⁺). However, the relative contributions of individual NH₃ sources are unclear, and debate remains over whether agricultural emissions dominate atmospheric NH₃ in urban areas. Based on the chemical and isotopic measurements of size-resolved aerosols in urban Beijing, China, we find that the natural abundance of ¹⁵N (expressed using δ¹⁵N values) of NH₄⁺ in fine particles varies with the development of haze episodes, ranging from −37.1‰ to −21.7‰ during clean/dusty days (relative humidity: ∼ 40%), to −13.1‰ to +5.8‰ during hazy days (relative humidity: 70–90%). After accounting for the isotope exchange between NH₃ gas and aerosol NH₄⁺, the δ¹⁵N value of the initial NH₃ during hazy days is found to be −14.5‰ to −1.6‰, which indicates fossil fuel-based emissions. These emissions contribute 90% of the total NH₃ during hazy days in urban Beijing. This work demonstrates the analysis of δ¹⁵N values of aerosol NH₄⁺ to be a promising new tool for partitioning atmospheric NH₃ sources, providing policy makers with insights into NH₃ emissions and secondary aerosols for regulation in urban environments