Laboratory study on the hygroscopic behavior of external and internal C2-C4 dicarboxylic acid-NaCl mixtures.

Atmospheric aerosol is usually found to be a mixture of various inorganic and organic components in field measurements, whereas the effect of this mixing state on the hygroscopicity of aerosol particles has remained unknown. In this study, the hygroscopic behavior of mixtures of C2-C4 dicarboxylic acids and NaCl was investigated. For both externally and internally mixed malonic acid-NaCl and succinic acid-NaCl particles, correlation between water content and chemical composition was observed and the water content of these mixtures at relative humidity (RH) above 80% can be well predicted by the Zdanovskii-Stokes-Robinson (ZSR) method. In contrast, a nonlinear relation between the total water content of the mixtures and the water content of each chemical composition separately was found for oxalic acid-NaCl mixtures. Compared to the values predicted by the ZSR method, the dissolution of oxalic acid in external mixtures resulted in an increase in the total water content, whereas the formation of less hygroscopic disodium oxalate in internal mixtures led to a significant decrease in the total water content. Furthermore, we found that the hygroscopicity of the sodium dicarboxylate plays a critical role in determining the aqueous chemistry of dicarboxylic acid-NaCl mixtures during the humidifying and dehumidifying process. It was also found that the hydration of oxalic acid and the deliquescence of NaCl did not change in external oxalic acid-NaCl mixtures. The deliquescence relative humidity (DRHs) for both malonic acid and NaCl decreased in both external and internal mixtures. These results could help in understanding the conversion processes of dicarboxylic acids to dicarboxylate salts, as well as the substitution of Cl by oxalate in the atmosphere. It was demonstrated that the effect of coexisting components on the hygroscopic behavior of mixed aerosols should not be neglected.