Microphysics of atmospheric aerosols : phase transitions and cloud formation mechanisms

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003.Vita.Includes bibliographical references (leaves 134-148).Clouds play an extremely important role in our atmosphere, from controlling the local weather, air pollution and chemical balance in the atmosphere to affecting long-term climatic changes at local, regional and global scales. The mechanisms through which tropospheric clouds form are still not fully understood, leading to gross uncertainties in understanding the effect of atmospheric aerosols on the environment. Using laboratory measurements, microphysical properties of typical micro-meter size atmospheric aerosols are investigated in this study. Upper tropospheric ice clouds (cirrus) form when ice is nucleated either homogeneously or heterogeneously in aqueous aerosols. We have investigated the homogeneous and heterogeneous ice nucleation in aqueous particles. Our results for homogeneous nucleation in aqueous ammonium nitrate particles show that the current thermodynamic models do not correctly predict water activities in these particles under super-saturated conditions. High super-saturations are required for ice to nucleate homogeneously in aqueous ammonium nitrate particles. We have also investigated the role of crystallized salt cores, such as solid ammonium sulfate and letovicite, in the heterogeneous nucleation of ice in saturated aqueous ammonium sulfate particles. Our results show that the surface morphology and defects on microcrystals could result in the creation of active sites, leaving the crystallized salt cores as potent ice nuclei under certain conditions. We have also investigated the role of mineral dust and soot, major components of insoluble particulates in the atmosphere, as ice-nuclei. We have found mineral dust to be an effective ice nuclei but both fresh and aged soot do not promote ice nucleation in aqueous particles.(cont.) Soot is the most ubiquitous aerosol in the atmosphere. The lifetime and microphysics of nano-porous soot has a large impact on earth's radiative budget, heterogeneous chemistry, urban and regional air pollution and human health. We have investigated the hydrophilic properties of both fresh and aged soot as a function of relative humidity. Our results show that fresh hydrophobic soot oxidized (aged) by OH/0₃/UV in the presence of water vapor or by exposure to concentrated HNO₃ becomes hydrophilic and exhibits a greater affinity for water. Due to this increased hydrophilicity, aged soot can be easily entrained inside existing liquid cloud droplets, and even activate as cloud condensation nuclei at high super-saturations, thus influencing its heterogeneous chemistry, radiative properties and atmospheric lifetime.by Bilal Zuberi.Ph.D