Formation of polycyclic aromatic hydrocarbons from tobacco: the link between low temperature residual solid (char) and PAH formation.

The formation of condensed ring polycyclic aromatic hydrocarbons (PAHs) from the pyrolysis of ground tobacco in helium over the temperature range of 350-600 degrees C was investigated. PAH yields in the ng/g range were detected and the maximum yields of all PAHs studied including benzo[a]pyrene (B[a]P) and benzo[a]anthracene (B[a]A) occurred between 500 and 550 degrees C. The pathway to PAH formation in the 350-600 degrees C temperature range is believed to proceed via a carbonization process where the residual solid (char) undergoes a chemical transformation and rearrangement to give a more condensed polycyclic aromatic structure that upon further heating evolves PAH moieties. Extraction of tobacco with water led to a two fold increase in the yields of most PAHs studied. The extraction process removed low temperature non-PAH-forming components, such as alkaloids, organic acids and inorganic salts, and concentrated instead (on a per unit weight basis) tobacco components such as cell wall bio-polymers and lipids. Hexane extraction of the tobacco removed lipophilic components, previously identified as the main source of PAH precursors, but no change in PAH yields was observed from the hexane-extracted tobacco. Tobacco cell wall components such as cellulose, hemicellulose, and lignin are identified as major low temperature PAH precursors. A link between the formation of a low temperature char that evolves PAHs upon heating is established and the observed ng/g yields of PAHs from tobacco highlights a low temperature solid phase formation mechanism that may be operable in a burning cigarette.