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Hans Falk (Falk et al., 1956; 1960) published the first papers demonstrating that polycyclic aromatic hydrocarbons underwent a transformation when exposed to ultraviolet light and oxidants. His experiments, in which concentrated spots of individual PAH were irradiated under UV light and exposed to ozone, suggested that PAH were oxidized to unknown products at a very slow rate of about 1 to 5% per hour. However, in 1977, it was shown (Lane & Katz, 1977) that PAH were, indeed, very sensitive to ozone by exposing monolayer distributions of PAH adsorbed on glass plates to ozone and irradiation which closely matched solar irradiation in the 2500A to 5000A region of the spectrum from a quartz lamp. Under lamp irradiation and 0.19 ppm O3, the half lives of Benzo[a]pyrene, Benzo[k]fluoranthene and Benzo[b]fluoranthene were 0.58 h, 3.9 h, and 4.2 h respectively (Lane, 1975). They also were the first to describe how multi-layering of PAH on particles could influence the apparent reaction rate of the PAH in Falk’s experiment, and demonstrated that a rapid surface oxidation reaction formed a “crust” of oxidized products and was then followed by a slower penetration reaction involving the ozone accessing the subsurface material by penetrating the surface oxidized material – much like passing through a crust of bread. In the 1980s the group at the University of California, lead by Roger Atkinson began smog chamber studies to determine the rate of decomposition of a wide variety of PAH and PAH-related compounds when exposed to various oxidants. Their work clearly indicated that the OH radical was the dominant oxidant in the atmosphere (Atkinson et al., 1984; Atkinson, 1988). Most subsequent smog chamber studies to investigate the decomposition of PAH have utilized the OH radical as the oxidant of choice. The first report of a variety of oxidized products of the reaction of Naphthalene with the OH radical in a smog chamber was published in 1994 (Lane & Tang, 1994). Numerous publications have followed, describing the products of the OH radical reactions with naphthalene (Atkinson & Arey, 1994; Bunce et al., 1997; Sasaki et al., 1997; Mihele et al., 2002; Wang et al., 2007; Lee & Lane, 2009; Nishino & Arey, 2009); with acenaphene (SauretSzczepanski & Lane, 2004); with Alkylated naphthalenes (Banceu et al., 2001; Wang et al., 2007) and with phenanthrene (Helmig & Harger, 1994; Esteve et al., 2003; Lee & Lane, 2010).

Multidimensional Gas Chromatography - Time of Flight Mass Spectrometry of PAH in Smog Chamber Studies and in Smog Samples