CCN activity of organic aerosols observed downwind of urban emissions during CARES

During the Carbonaceous Aerosols and Radiative Effects Study (CARES), activation fraction of size-resolved aerosol particles and aerosol chemical composition were characterized at the T1 site (similar to 60 km downwind of Sacramento, California) from 10 June to 28 June 2010. The hygroscopicity of cloud condensation nuclei (CCN)-active particles (kappa(CCN)) with diameter from 100 to 170 nm, derived from the size-resolved activated fraction, varied from 0.10 to 0.21, with an average of 0.15, which was substantially lower than that proposed for continental sites. The low kappa(CCN) value was due to the high organic volume fraction, averaged over 80% at the T1 site. The derived kappa(CCN) exhibited little diurnal variation, consistent with the relatively constant organic volume fraction observed. At any time, over 90% of the size-selected particles with diameter between 100 and 171 nm were CCN active, suggesting most particles within this size range were aged background particles. Due to the large organic volume fraction, organic hygroscopicity (kappa(org)) strongly impacted particle hygroscopicity and therefore calculated CCN concentration. For the vast majority of the cases, an increase of kappa(org) from 0.03 to 0.18, which are within the typical range, doubled the calculated CCN concentration. Organic hygroscopicity was derived from kappa(CCN) and aerosol chemical composition, and its variations with the fraction of total organic mass spectral signal at m/z 44 (f(44)) and O : C were compared to results from previous studies. Overall, the relationships between kappa(org) and f(44) are quite consistent for organic aerosol (OA) observed during field studies and those formed in a smog chamber. Compared to the relationship between kappa(org) and f(44), the relationship between kappa(org) and O: C exhibits more significant differences among different studies, suggesting kappa(org) may be better parameterized using f44. A least squares fit yielded kappa(org) = 2.10(+/- 0.07) x f(44) - 0.11(+/- 0.01) with a Pearson R-2 value of 0.71. One possible explanation for the stronger correlation between kappa(org) and f(44) is that the m/z 44 signal (mostly contributed by the CO2+ ion) is more closely related to organic acids, which may dominate the overall kappa(org) due to their relatively high water solubility and hygroscopicity.