Secondary aerosol formation alters CCN activity in the North China Plain

Secondary aerosols (SAs, including secondary organic and inorganic aerosols, SOAs and SIAs) are predominant components of aerosol particles in the North China Plain (NCP), and their formation has significant impacts on the evolution of particle size distribution (PNSD) and hygroscopicity. Previous studies have shown that distinct SA formation mechanisms can dominate under different relative humidity (RH). This would lead to different influences of SA formation on the aerosol hygroscopicity and PNSD under different RH conditions. Based on the measurements of size-resolved particle activation ratio (SPAR), hygroscopicity distribution (GF-PDF), PM2.5 chemical composition, PNSD, meteorology and gaseous pollutants in a recent field campaign, McFAN (Multiphase chemistry experiment in Fogs and Aerosols in the North China Plain), conducted during the autumn-winter transition period in 2018 at a polluted rural site in the NCP, the influences of SA formation on cloud condensation nuclei (CCN) activity and CCN number concentration (N-CCN) calculation under different RH conditions were studied. Results suggest that during daytime, SA formation could lead to a significant increase in N-CCN and a strong diurnal variation in SPAR at supersaturations lower than 0.07 %. During periods with daytime minimum RH exceeding 50% (high RH conditions), SA formation significantly contributed to the particle mass and size changes in a broad size range of 150 to 1000 nm, leading to N-CCN (0.05 %) increases within the size range of 200 to 500 nm and mass concentration growth mainly for particles larger than 300 nm. During periods with daytime minimum RH below 30% (low RH conditions), SA formation mainly contributed to the particle mass and size and N-CCN changes for particles smaller than 300 nm. As a result, under the same amount of mass increase induced by SA formation, the increase of N-CCN (0.05 %) was stronger under low RH conditions and weaker under high RH conditions. Moreover, the diurnal variations of the SPAR parameter (inferred from CCN measurements) due to SA formation varied with RH conditions, which was one of the largest uncertainties within N-CCN predictions. After considering the SPAR parameter (estimated through the number fraction of hygroscopic particles or mass fraction of SA), the relative deviation of N-CCN (0.05 %) predictions was reduced to within 30 %. This study highlights the impact of SA formation on CCN activity and N-CCN calculation and provides guidance for future improvements of CCN predictions in chemical-transport models and climate models.