Reduced volatility of aerosols from surface emissions to the top of the planetary boundary layer

Aerosols from surface emission can be transported upwards through convective mixing in the planetary boundary layer (PBL), which subsequently interact with clouds, serving as important sources to nucleate droplets or ice particles. However, the evolution of aerosol composition during this vertical transport has yet to be explicitly understood. In this study, simultaneous measurements of detailed aerosol compositions were conducted at two sites, namely urban Beijing (50m above sea level - a.s.l.) and Haituo mountain (1344ma.s.l.) during wintertime, representing the anthropogenically polluted surface environment and the top of the PBL, respectively. The pollutants from surface emissions were observed to reach the mountain site on daily basis through daytime PBL convective mixing. From the surface to the top of PBL, we found efficient transport or formation of lower-volatility species (black carbon, sulfate, and low-volatile organic aerosol, OA); however, a notable reduction in semivolatile substances, such as the fractions of nitrate and semivolatile OA reduced by 74% and 76%, respectively, during the upward transport. This implies that the mass loss of these semivolatile species was driven by the evaporation process, which repartitioned the condensed semivolatile substances to the gas phase when aerosols were transported and exposed to a cleaner environment. In combination with the oxidation processes, these led to an enhanced oxidation state of OA at the top of the PBL compared to surface environment, with an increase of oxygen to carbon atomic ratio by 0.2. Such a reduction in aerosol volatility during vertical transport may be important in modifying its viscosity, nucleation activity, and atmospheric lifetime.