ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-8-5589-2008 A combined particle trap/HTDMA hygroscopicity study of mixed inorganic/organic aerosol particles Zardini A. A. 1 Sjogren S. 2 Marcolli C. 1 Krieger U. K. 1 Gysel M. 2 Weingartner E. 2 Baltensperger U. 2 Peter T. 1 Institute for Atmospheric and Climate Science, ETH-Zurich, 8092 Zurich, Switzerland Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, 5232 Villigen, Switzerland 19 09 2008 8 18 5589 5601 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/8/5589/2008/acp-8-5589-2008.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/5589/2008/acp-8-5589-2008.pdf

Atmospheric aerosols are often mixtures of inorganic and organic material. Organics can represent a large fraction of the total aerosol mass and are comprised of water-soluble and insoluble compounds. Increasing attention was paid in the last decade to the capability of mixed inorganic/organic aerosol particles to take up water (hygroscopicity). We performed hygroscopicity measurements of internally mixed particles containing ammonium sulfate and carboxylic acids (citric, glutaric, adipic acid) in parallel with an electrodynamic balance (EDB) and a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds were chosen to represent three distinct physical states. During hygroscopicity cycles covering hydration and dehydration measured by the EDB and the HTDMA, pure citric acid remained always liquid, adipic acid remained always solid, while glutaric acid could be either. We show that the hygroscopicity of mixtures of the above compounds is well described by the Zdanovskii-Stokes-Robinson (ZSR) relationship as long as the two-component particle is completely liquid in the ammonium sulfate/glutaric acid system; deviations up to 10% in mass growth factor (corresponding to deviations up to 3.5% in size growth factor) are observed for the ammonium sulfate/citric acid 1:1 mixture at 80% RH. We observe even more significant discrepancies compared to what is expected from bulk thermodynamics when a solid component is present. We explain this in terms of a complex morphology resulting from the crystallization process leading to veins, pores, and grain boundaries which allow for water sorption in excess of bulk thermodynamic predictions caused by the inverse Kelvin effect on concave surfaces.

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