Measurement report: Investigation of pH- and particle-size-dependent chemical and optical properties of water-soluble organic carbon: implications for its sources and aging processes

Knowledge of the chemical structures and optical properties of water-soluble organic carbon (WSOC) is critical considering its involvement in many key aerosol-associated chemical reactions and its potential impacts on climate radiative forcing. This study investigates the coupled effects of pH and particle size on the chemical structures (functional groups) and optical properties (UV/fluorescence properties) of WSOC and further explores the source and aging of WSOC constituents. The results showed that the specific UV absorbance at a wavelength of 254 nm (SUVA(254)) and mass absorption efficiency at a wavelength of 365 nm (MAE(365)) were higher in smaller than larger particles, revealing the relatively higher aromaticity/molecular weight and more freshness of WSOC in smaller particles. A decrease in aromaticity/molecular weight of WSOC in larger particles was caused by the degradation reaction that occurred during the aging process. The carboxylic groups tend to be enriched in larger particles, whereas the contribution of phenolic groups was generally higher in smaller particles. The changes in the fluorescence peak position suggested that hydroxyl groups play a leading role in pH-responsive fluorescence in summer, while carboxylic and nitro groups play a dominant role in winter. Overall, the chromophores in smaller particles showed a more pronounced pH dependence, which might be related to the higher content of aromatic species in WSOC in these particle size ranges. Specifically, the climate impact of WSOC would be enhanced with increasing pH. The pH- and particle-size-dependent chemical and optical properties of WSOC provide insights into the structure, source, and aging of WSOC, which will ultimately improve the accuracy of assessing the climate effects of WSOC.

Automated summary

Knowledge of the chemical structures and optical properties of water-soluble organic carbon (WSOC) is critical for understanding its impact on aerosol-associated chemical reactions and climate radiative forcing. This study investigates the effects of pH and particle size on the chemical structure and optical properties of WSOC, as well as the aging process. The results show that WSOC in smaller particles has higher aromaticity and molecular weight, while WSOC in larger particles undergoes degradation during aging. Carboxylic groups are enriched in larger particles, while phenolic groups are more dominant in smaller particles. The fluorescence peak position suggests that hydroxyl groups play a leading role in pH-responsive fluorescence in summer, while carboxylic and nitro groups dominate in winter. Overall, smaller particles show a more pronounced pH dependence, which is related to the higher content of aromatic species in WSOC. The findings provide insights into the structure, source, and aging of WSOC, improving the accuracy of assessing its climate effects.