화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.115, No.5, 762-773, 2011
Homogeneous Ice Nucleation From Aqueous Inorganic/Organic Particles Representative of Biomass Burning: Water Activity, Freezing Temperatures, Nucleation Rates
Homogeneous ice nucleation plays an important role in the formation of cirrus clouds with subsequent effects on the global radiative budget. Here we report on homogeneous ice nucleation temperatures and corresponding nucleation rate coefficients of aqueous droplets serving as surrogates of biomass burning aerosol. Micrometer-sized (NH4)(2)SO4/levoglucosan droplets with mass ratios of 10:1, 1:1, 1:5, and 1:10 and aqueous multicomponent organic droplets with and without (NH4)(2)SO4 under typical tropospheric temperatures and relative humidities are investigated experimentally using a droplet conditioning and ice nucleation apparatus coupled to an optical microscope with image analysis. Homogeneous freezing was determined as a function of temperature and water activity, a(w), which was set at droplet preparation conditions. The ice nucleation data indicate that minor addition of (NH4)(2)SO4 to the aqueous organic droplets renders the temperature dependency of water activity negligible in contrast to the case of aqueous organic solution droplets. The mean homogeneous ice nucleation rate coefficient derived from 8 different aqueous droplet compositions with average diameters of similar to 60 mu m for temperatures as low as 195 K and a(w) of 0.82-1 is 2.18 x 10(6) cm(-3) s(-1). The experimentally derived freezing temperatures and homogeneous ice nucleation rate coefficients are in agreement with predictions of the water activity-based homogeneous ice nucleatioritheory when taking predictive uncertainties into account. However, the presented ice nucleation data indicate that the water activity-based homogeneous ice nucleation theory overpredicts the freezing temperatures by up to 3 K and corresponding ice nucleation rate coefficients by up to similar to 2 orders of magnitude. A shift of 0.01 in a(w), which is well within the uncertainty of typical field and laboratory relative humidity measurements, brings experimental and predicted freezing temperatures and homogeneous ice nucleation rate coefficients into agreement. The experimentally derived ice nucleation data are applied to constrain the water activity-based homogeneous ice nucleation theory to smaller than +/-1 order of magnitude compared to the predictive uncertainty of larger than +/-6 orders of magnitude. The atmospheric implications of these findings are discussed.