Vehicular Emissions Enhanced Ammonia Concentrations in Winter Mornings: Insights from Diurnal Nitrogen Isotopic Signatures.

ABSTRACT

A general feature in the diurnal cycle of atmospheric ammonia (NH3) concentrations is a morning spike that typically occurs around 0700 to 1000 (LST). Current hypotheses to explain this morning's NH3 increase remain elusive, and there is still no consensus whether traffic emissions are among the major sources of urban NH3. Here, we confirmed that the NH3 morning pulse in urban Beijing is a universal feature, with an annual occurrence frequency of 73.0% and a rapid growth rate (>20%) in winter. The stable nitrogen isotopic composition of NH3 (δ15N-NH3) in winter also exhibited a significant diurnal variation with an obvious morning peak at 0700 to 1000 (-18.6‰, mass-weighted mean), higher than other times of the day (-26.3‰). This diurnal pattern suggests that a large fraction of NH3 in the morning originated from nonagricultural sources, for example, power plants, vehicles, and coal combustion that tend to have higher δ15N-NH3 emission signatures relative to agricultural emissions. In particular, the contribution from vehicular emissions increased from 18% (0000 to 0700) to 40% (0700 to 1000), while the contribution of fertilizer sources to NH3 was reduced from 15.8% at 0000 to 0700 to 5.2% at 0700 to 1000. We concluded that NH3 concentrations in winter mornings in urban Beijing were indeed enhanced by vehicle emissions, which should be considered in air pollution regulations.