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A number of samples which eluted at unexpectedly short retention times during size exclusion chromatography have been characterized. Soot and tar samples likely to show similar behavior have been examined. Distinct peaks from about 6 min were observed, compared to 9−10 min for more usual samples. Molecular masses of the early eluting material appear to be large, although extrapolation of existing calibrations does not seem appropriate. A naphthalene mesophase pitch also gave peaks at short elution times. It appears reasonable to interpret chromatograms of this nonpolar material as a direct indication of the presence of large molecular mass material, and to infer that excluded peaks of SEC chromatograms do not necessarily result from the presence of clusters of polar molecules. GC-MS and probe-MS examination of the samples showed only very limited proportions of the samples to have small molecular masses. MALDI-MS spectra of the samples indicated the presence of signal up to 20 000 u. Taken together, data from SEC and the three MS techniques indicated the presence of very large molecular mass materials in this set of samples. Tar deposits recovered from entrained, combusting coal particles have also been examined, providing direct evidence for the presence of large molecular mass material in combustion environments. The observation contrasts with mathematical models of coal burners, where rates of combustion of volatiles are assumed similar to rates of combustion of methane. The nature of the early-eluting material is not known but repeated microfiltration and TEM indicate that it may correspond to molecular diameters in the region of 20 nm. The soots and other samples appear to be in true solution rather than in colloidal suspension.

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