Atmos. Chem. Phys. Discuss., 13, 1045-1087, 2013
www.atmos-chem-phys-discuss.net/13/1045/2013/
doi:10.5194/acpd-13-1045-2013
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Measuring and modeling the hygroscopic growth of two humic substances in mixed aerosol particles of atmospheric relevance
I. R. Zamora1 and M. Z. Jacobson2
1Department of Geophysics, Stanford University, Yang & Yamazaki Environment & Energy Building, 473 Via Ortega, Room M05, Stanford, California 94305, USA
2Department of Civil and Environmental Engineering, Stanford University, Yang & Yamazaki Environment & Energy Building, 473 Via Ortega, Room 397, Stanford, California 94305, USA

Abstract. The hygroscopic growth of atmospheric particles affects atmospheric chemistry and Earth's climate. Water-soluble organic carbon (WSOC) constitutes a significant fraction of the dry submicron mass of atmospheric aerosols, thus affecting their water uptake properties. Although the WSOC fraction is comprised of many compounds, a set of model substances can be used to describe its behavior. For this study, mixtures of Nordic Aquatic fulvic acid reference (NAFA) and Fluka humic acid (HA), with various combinations of inorganic salts (sodium chloride and ammonium sulfate) and other representative organic compounds (levoglucosan and succinic acid), were studied. We measured the equilibrium water vapor pressure over bulk solutions of these mixtures as a function of temperature and solute concentration. New water activity (aw) parameterizations and hygroscopic growth curves at 25 °C were calculated from these data for particles of equivalent composition. We examined the effect of temperature on the water activity and found a maximum variation of 9% in the 0–30 °C range, and 2% in the 20–30 °C range. Five two-component mixtures were studied to understand the effect of adding a humic substance (HS), such as NAFA and HA, to an inorganic salt or a saccharide. The deliquescence point at 25 °C for HS-inorganic mixtures did not change significantly from that of the pure inorganic species. However, the hygroscopic growth of HA-inorganic mixtures was lower than that exhibited by the pure salt, in proportion to the added mass of HA. The addition of NAFA to a highly soluble solute (ammonium sulfate, sodium chloride or levoglucosan) in water had the same effect as the addition of HA to the inorganic species for most of the aw range studied. Yet, the water uptake of these NAFA mixtures transitioned to match the growth of the pure salt or saccharide at high aw values. The remaining four mixtures were based on chemical composition data for different aerosol types. As expected, the two solutions representing organic aerosols (40% HS/40% succinic acid/20% levoglucosan) showed lower water uptake than the two solutions representing biomass burning aerosols (25% HS/27% succinic acid/18% levoglucosan/30% ammonium sulfate). However, interactions in multicomponent solutions may be responsible for the differences that arise in relative hygroscopic growth above RH of 95% when comparing three different HS in these two mixtures. The ZSR model was able to predict reasonably well the hygroscopic growth of all the mixtures below aw = 0.95, but produced large deviations for some multicomponent mixtures at higher values.

Citation: Zamora, I. R. and Jacobson, M. Z.: Measuring and modeling the hygroscopic growth of two humic substances in mixed aerosol particles of atmospheric relevance, Atmos. Chem. Phys. Discuss., 13, 1045-1087, doi:10.5194/acpd-13-1045-2013, 2013.
 
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