In situ measurements of size-dependent water uptake by atmospheric particles made with a tandem differential mobility analyzer (TDMA) and size-resolved chemical composition of aerosol samples collected with cascade impactors in the Smoky Mountains have been examined in order to ascertain the influence of organic carbon compounds on aerosol hygroscopicity. Particles were dried to ∼5% relative humidity (RH) before entering the TDMA, leading us to believe that salts of ammonium and sulfate were in crystalline states for relative humidities below their expected deliquescent points. TDMA-measured water content was found to be in excess of the sulfate-associated water modeled using laboratory data for binary aqueous solutions and the method of Zdanovskii-Stokes-Robinson for multicomponent solutions over a wide range of humidities (RH=5-85%). Furthermore, excess water was observed to increase in proportion to the organic fraction of mass associated with each examined size in the range 0.05 to 0.4 μm. These data are used to obtain an empirical relationship between the amount of water associated with particulate organics and relative humidity. This analysis shows that organic-associated water content is considerably less than that of sulfate compounds, on a volume basis, for high RH, but comparable or greater for low RH. These results are consistent with laboratory data for water absorption by a range of organics vis-à-vis ammonium salts of sulfate.