Fast particulate nitrate formation via N2O5 uptake aloft in winter in Beijing

Particulate nitrate (pNO(3)(-)) is an important component of secondary aerosols in urban areas. Therefore, it is critical to explore its formation mechanism to assist with the planning of haze abatement strategies. Here we report vertical measurements of NOx and O-3 by in situ instruments on a movable carriage on a tower during a winter heavy-haze episode (18 to 20 December 2016) in urban Beijing, China. Based on the box model simulation at different heights, we found that pNO(3)(-) formation via N2O5 heterogeneous uptake was negligible at ground level due to N2O5 concentrations of near zero controlled by high NO emissions and NO concentration. In contrast, the contribution from N2O5 uptake was large at high altitudes (e.g., > 150 m), which was supported by the lower total oxidant (NO2 + O-3) level at high altitudes than at ground level. Modeling results show the specific case that the nighttime integrated production of pNO(3)(-) for the high-altitude air mass above urban Beijing was estimated to be 50 mu gm(-3) and enhanced the surface-layer pNO(3)(-) the next morning by 28 mu gm(-3) through vertical mixing. Sensitivity tests suggested that the nocturnal NOx loss by NO3-N2O5 chemistry was maximized once the N2O5 uptake coefficient was over 2 x 10(-3) on polluted days with S-a at 3000 mu m(2) cm(-3) in wintertime. The case study provided a chance to highlight the fact that pNO(3)(-) formation via N2O5 heterogeneous hydrolysis may be an important source of particulate nitrate in the urban airshed during wintertime.