Nucleation processes and aerosol chemistry

As the result of many observable optical phenomena, the occasional existence of upper atmospheric aerosols has been known since the beginning of the Century. Nevertheless, it is only during the last two decades that their persistent nature and extent of global distribution have become recognized. This review is addressed to the chemistry of upper atmospheric aerosols with particular attention to the chemical reactions and nucleation mechanisms responsible for their formation.Considering the stratosphere, it is now generally agreed that sulfate, mainly in the form of sulfuric acid, represents the single most abundant constituent of stratospheric aerosols. There is now strong evidence that these aerosols are formed in situ from sulfur bearing gases oxidized by free radicals. The various nucleation processes of atmospheric importance are reviewed, and it is shown that heteromolecular nucleation processes are almost certainly responsible for new particle formation in the stratosphere.The nature, and even existence, of aerosol layers above the stratosphere is less certain. The influx of extraterrestrial materials into the Earth atmosphere is estimated to be in the order of 50 to 500 tons per day. Considerations are given to the possible mechanisms which convert these materials to aerosol size particles. Although these particles provide one possible explanation for the appeareance of noctilucent clouds, nucleation about ions, most probably H₃O⁺ hydrates, is a strong contender as a more plausible formation mechanism. Considerable attention is given to this important atmospheric process, where it is shown that chemical forces contribute to the stability of the prenucleation clusters and the overall height of the energy barrier to nucleation. Finally, the role of aerosols in the sodium and other cycles of trace upper atmospheric constituents, is discussed.This research was performed under the auspices of the U.S. Atomic Energy Commission and partially financed by the Department of Transportation and the National Science Foundation under interagency agreements.