Molecular characterisation of organic material in air fine particles (PM10) using conventional and reactive pyrolysis-gas chromatography-mass spectrometry

Pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was applied to study the composition of organic constituents in air particulate matter (PM10) collected inside an industrial area. A few milligrams of sampling filters containing air particles were pyrolysed at 700 degrees C directly (conventional) or after the addition of a derivatising reagent (tetramethylammonium hydroxide, TMAH, for pyrolysis-methylation; hexamethyldisilazane, HMDS, for pyrolysis-silylation). Py-GC-MS was also applied to synthetic polymers (poly(styrene-co-isoprene), polylimonene and polypinene) and vegetation samples (coniferous pollen, bark and resin) to identify markers indicative of possible precursors. Pyrolysates of PM10 showed the same suite of compounds in all the four seasons, dominated by hydrocarbons like styrene, limonene and clusters of isomeric alkenes with 14, 15 and 16 carbon atoms. Pyrolysis products of natural origin, including furaldehyde, benzeneacetonitrile, dehydroabietin and other diterpenoids were found, while no specific markers of synthetic rubbers were detected. The principal products released from reactive pyrolysis of PM10 were methyl or trimethylsilyl (TMS) derivatives of 1,6-anhydroglucose (levoglucosan), fatty acids, dehydroabietic acid and other resin acids along with hydroxy (di)carboxylic acids. Possible sources of the detected products (e.g. pine forest, biomass combustion) are discussed.