Rising Alkali-to-Acid Ratios in the Atmosphere May Correspond to Increased Aerosol Acidity.

Aerosol acidity (or pH) is one central parameter in determining the health, climate, and ecological effects of aerosols. While it is traditionally assumed that the long-term aerosol pH levels are determined by the relative abundances of atmospheric alkaline to acidic substances (referred to as RC/A hereinafter), we observed contrasting pH─RC/A trends at different sites globally, i.e., rising alkali-to-acid ratios in the atmosphere may unexpectedly lead to increased aerosol acidity. Here, we examined this apparently counterintuitive phenomenon using the multiphase buffer theory. We show that the aerosol water content (AWC) set a pH "baseline" as the peak buffer pH, while the RC/A and particle-phase chemical compositions determine the deviation of pH from this baseline within the buffer ranges. Therefore, contrasting long-term pH trends may emerge when RC/A increases while the AWC or nitrate fraction decreases, or vice versa. Our results provided a theoretical framework for a quantitative understanding of the response of aerosol pH to variations in SO2, NOx versus NH3, and dust emissions, offering broad applications in studies on aerosol pH and the associated environmental and health effects.

Light absorption enhancement of black carbon and its impact factors during winter in a megacity of the Sichuan Basin, China.

Carbonaceous aerosols play a vital role in global climate patterns due to their potent light absorption capabilities. However, the light absorption enhancement effect (Eabs) of black carbon (BC) is still subject to great uncertainties due to factors such as the mixing state, coating material, and particle size distribution. In this study, fine particulate matter (PM2.5) samples were collected in Chengdu, a megacity in the Sichuan Basin, during the winter of 2020 and 2021. The chemical components of PM2.5 and the light absorption properties of BC were investigated. The results revealed that secondary inorganic aerosols and carbonaceous aerosols were the dominant components in PM2.5. Additionally, the aerosol filter filtration-dissolution (AFD) treatment could improve the accuracy of measuring elemental carbon (EC) through thermal/optical analysis. During winter in Chengdu, the absorption enhancement values of BC ranged between 1.56 and 2.27, depending on the absorption wavelength and the mixing state of BC and non-BC materials. The presence of internally mixed BC and non-BC materials significantly contributed to Eabs, accounting for an average of 68 % at 405 nm and 100 % at 635 nm. The thickness of the BC coating influenced Eabs, displaying an increasing-then-decreasing trend. This trend was primarily attributed to the hygroscopic growth and dehydration shrinkage of particulate matter. Nitrate, as the major component of BC coating, played a crucial role in the lensing effect and exhibited fast growth during variation in Eabs. By combining the results from PMF, we identified the secondary formation and vehicle emission as the primary contributors to Eabs. Consequently, this study can provide valuable insights into the optical parameters, which are essential for assessing the environmental quality, improving regional atmospheric conditions, and formulating effective air pollution control strategies.