Effects of Chemical Aging on the Ice Nucleation Activity of Soot and Polycyclic Aromatic Hydrocarbon Aerosols

The role of soot particles as ice nuclei (IN) in heterogeneous freezing processes in the atmosphere remains uncertain. Determination of the freezing efficiency of soot is complicated by the changing properties of soot particles undergoing atmospheric aging processes. In this study, the heterogeneous freezing temperatures of droplets in contact with fresh and oxidized soot particles were determined using an optical microscope apparatus equipped with a sealed cooling stage and a CCD video camera. Experiments were also conducted using fresh and oxidized polycyclic aromatic hydrocarbons (PAHs), including anthracene, pyrene, and phenanthrene, as potential ice nuclei. Chemical changes at the surface of the aerosols caused by exposure to ozone were characterized using Fourier transform infrared spectroscopy with horizontal attenuated total reflectance (FTIR-HATR). In addition, Brunauer-Emmett-Teller (BET) measurements were used to determine the specific surface areas of the soot particles. Mean freezing temperatures on fresh particles ranged from -19 to -24 degrees C, depending on the IN composition and size. In all cases, exposure to ozone facilitated ice nucleation at warmer temperatures, by 2-3 degrees C, on average. In addition, nucleation rate coefficients for a single temperature and IN type increased by as much as 4 orders of magnitude because of oxidation. Furthermore, a fraction of the oxidized soot particles froze at temperatures above -10 degrees C. A modified version of classical nucleation theory that accounts for a range of contact angles on nucleation sites within an IN population was used to derive the probability of freezing as a function of temperature for each type of IN. In summary, our results suggest that atmospheric oxidation processes may both extend the range over which particles can act as ice nuclei to warmer temperatures and increase heterogeneous nucleation rates on soot and pollutant aerosols.