Numerous chemical analyses of gaseous and particulate samples from laboratory flames provide a library of data on the polycyclic aromatic hydrocarbon (PAH) species found in diverse flame types burning fuels consisting of pure gaseous hydrocarbons. The diesel fuels utilized by the more complex combustion in compression ignition engines are composed of thousands of hydrocarbon species. Mass spectrometry by the laser microprobe and gas chromatography were used in a complementary manner to distinguish the PAHs originating in the fuel from those produced by engine combustion. The CxHy PAH products of premixed and diffusion flame processes, which also occur in the unsteady diesel combustion, range in mass from 128 u (two rings, x = 10, y = 8) to beyond 350 u (eight rings, x = 28, y = 14). Graphs of the number of hydrogen atoms y vs the number of carbon atoms x for the species found by many investigators of laboratory flames show these pyrogenic PAHs to lie on or near the staircase curve that describes the most stable, pericondensed, benzenoid PAHs. In contrast, samples of diesel fuels from the United Kingdom and the United States contain petrogenic alkyl-PAHs with high hydrogen contents. Samples of diesel particulate emissions typical of the 1990s from two different sources display the full mass range of PAHs from 128 to 350 u, including both the benzenoid PAHs and the alkyl-PAHs. Thus diesel emissions, in general, may contain petrogenic fuel components ranging up to 206 u and also the combustion-generated four- to seven-ring species in the 228 to 302 u mass range that have greater carcinogenic potency. The absence of petrogenic components larger than 206 u facilitates their detection and delineation from pyrogenic PAHs by methods of chemical analysis. (c) 2005 The Combustion Institute. Published by Elsevier Inc. All rights reserved.