Hygroscopic Properties of Two Model Humic-like Substances and Their Mixtures with Inorganics of Atmospheric Importance

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Abstract
Water-soluble macromolecular polyacids can play a potentially important role in the hygroscopic properties of atmospheric aerosols. These acids have molecular structures similar to natural fulvic acids (FA) (or humic acids) and are referred to as humic-like substances (HULIS). In this study, the hygroscopicity of HULIS and the mixture of HULIS and sodium chloride (NaCl) and that of HULIS and ammonium sulfate (AS) aerosols at a mass ratio of 1:1 are studied using two natural FA: the Nordic Aquatic Fulvic Acid (NAFA) and the Suwannee River Fulvic Acid (SRFA) as model compounds in an electrodynamic balance. NAFA and SRFA both absorbed and desorbed water reversibly without crystallization and retained water at a relative humidity (RH) < 10%. NAFA and SRFA have a mass growth ratio of 1.25 and 1.45 from RH = 10% to RH = 90%, respectively. However, these results are different from those of another natural FA (the Nordic River Fulvic Acid Reference) in the literature. The differences are possibly due to the differences in the chemical composition of the natural FA, which depends on their sources and the isolation methods. These results suggest that a standardization of the isolation methods of HULIS is needed for better understanding of their atmospheric properties and environmental impacts. In general, the deliquescence and crystallization RH of FA−inorganic mixtures are comparable with those of their respective pure inorganic species. Since FA are less hygroscopic than NaCl and AS, all mixtures absorb less water compared to their respective pure inorganic species of equal particle mass. The FA−AS mixtures have a larger water uptake than the sum of those of the FA and AS individually following a simple additivity rule as noninteracting species at RH = 90%. This enhancement effect increases as the RH decreases. There is no such enhancement effect for the FA−NaCl mixtures until RH is below 90%. These results reveal that the effect of the interactions between FA and inorganic species on the water uptake of the mixtures, in general, is a function of RH.

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