Thermo-oxidative decomposition of lime, bergamot and cardamom essential oils

• Published in: Journal of analytical and applied pyrolysis 2018-09, Vol.134, p.552-561
• Main Authors: Jakab, E., Blazsó, M., Barta-Rajnai, E., Babinszki, B., Sebestyén, Z., Czégény, Zs, Nicol, J., Clayton, P., McAdam, K., Liu, C.
• Format: Article
• Language: English
• Subjects: Bergamot oil; Cardamom oil; Flavour; Lime oil; Oxidative pyrolysis; Terpene
• ISSN: 0165-2370; 1873-250X
• DOI: 10.1016/j.jaap.2018.08.003

•The decomposition of essential oils was studied at 300 °C using a 9% oxygen in nitrogen atmosphere.•The composition of lime, bergamot, and cardamom oils changed during thermo-oxidative treatment.•The strained rings of bicyclic monoterpenes underwent scission resulting in monocyclic monoterpenes.•Linalyl acetate decomposed via the elimination of acetic acid to β-myrcene and ocimene isomers.•α-Terpinyl acetate decomposed with the release of acetic acid, forming limonene and terpinolene. The thermal decomposition of three essential oils has been studied at 300 °C, using a 9% oxygen in nitrogen atmosphere, to mimic the thermal environment of flavours under low-temperature tobacco heating conditions. The starting compositions of the lime, bergamot and cardamom oils were determined by gas chromatography/mass spectrometry (GC/MS). The thermo-oxidative decomposition was evaluated by applying on-line pyrolysis-GC/MS. The main constituents of the oils studied were cyclic and linear monoterpenoids; however, the relative intensities of these components were characteristically different between oils. Lime oil was dominated by monoterpene hydrocarbons, while the other citrus oil, bergamot oil contained in addition a significant number of esters and alcohols. Oxygen-containing monoterpenoids were the dominant constituents of cardamom oil. The relative proportion of the constituents of all three essential oil samples significantly altered during oxidative pyrolysis at 300 °C. The strained rings of bicyclic monoterpenes (pinenes, sabinene, and thujene) underwent scission, resulting in the formation of monocyclic monoterpenes (limonene etc.). Both linear and cyclic terpene acetates decomposed via elimination of acetic acid, so linalyl acetate produced myrcene and ocimene, while terpinyl acetate formed mostly limonene and terpinolene. The relative intensities of linalool and eucalyptol were reduced during pyrolysis, which can be explained by dehydration reactions resulting in the formation of myrcene and ocimene, or limonene and terpinolene, respectively. The chemical reactions that occurred were explained by bond splitting and intramolecular rearrangement mechanisms, with oxygen playing a role in the initiation processes.