Aerosol‐planetary boundary layer (PBL) interactions have been found to enhance air pollution in megacities in China. We show that black carbon (BC) aerosols play the key role in modifying the PBL meteorology and hence enhancing the haze pollution. With model simulations and data analysis from various field observations in December 2013, we demonstrate that BC induces heating in the PBL, particularly in the upper PBL, and the resulting decreased surface heat flux substantially depresses the development of PBL and consequently enhances the occurrences of extreme haze pollution episodes. We define this process as the “dome effect” of BC and suggest an urgent need for reducing BC emissions as an efficient way to mitigate the extreme haze pollution in megacities of China.

Light-absorbing organic carbon (i.e., brown carbon or BrC) in the atmospheric aerosol has significant contribution to light absorption and radiative forcing. However, the link between BrC optical properties and chemical composition remains poorly constrained. In this study, we combine spectrophotometric measurements and chemical analyses of BrC samples collected from July 2008 to June 2009 in urban Xi'an, Northwest China. Elevated BrC was observed in winter (5 times higher than in summer), largely due to increased emissions from wintertime domestic biomass burning. The light absorption coefficient of methanol-soluble BrC at 365 nm (on average approximately twice that of water-soluble BrC) was found to correlate strongly with both parent polycyclic aromatic hydrocarbons (parent-PAHs, 27 species) and their carbonyl oxygenated derivatives (carbonyl-OPAHs, 15 species) in all seasons ( r > 0.61). These measured parent-PAHs and carbonyl-OPAHs account for on average ∼1.7% of the overall absorption of methanol-soluble BrC, about 5 times higher than their mass fraction in total organic carbon (OC, ∼0.35%). The fractional solar absorption by BrC relative to element carbon (EC) in the ultraviolet range (300-400 nm) is significant during winter (42 ± 18% for water-soluble BrC and 76 ± 29% for methanol-soluble BrC), which may greatly affect the radiative balance and tropospheric photochemistry and therefore the climate and air quality.

The chromophores responsible for light absorption in atmospheric brown carbon (BrC) are not well characterized, which hinders our understanding of BrC chemistry, the links with optical properties, and accurate model representations of BrC to global climate and atmospheric oxidative capacity. In this study, the light absorption properties and chromophore composition of three BrC fractions of different polarities were characterized for urban aerosol collected in Xi'an and Beijing in winter 2013−2014. These three BrC fractions show large differences in light absorption and chromophore composition, but the chromophores responsible for light absorption are similar in Xi'an and Beijing. Water-insoluble BrC (WI-BrC) fraction dominates the total BrC absorption at 365 nm in both Xi'an (51 ± 5%) and Beijing (62 ± 13%), followed by a humic-like fraction (HULIS-BrC) and high-polarity water-soluble BrC. The major chromophores identified in HULIS-BrC are nitrophenols and carbonyl oxygenated polycyclic aromatic hydrocarbons (OPAHs) with 2−3 aromatic rings (in total 18 species), accounting for 10% and 14% of the light absorption of HULIS-BrC at 365 nm in Xi'an and Beijing, respectively. In comparison, the major chromophores identified in WI-BrC are PAHs and OPAHs with 4−6 aromatic rings (in total 16 species), contributing 6% and 8% of the light absorption of WI-BrC at 365 nm in Xi'an and Beijing, respectively.