Study on the thermal oxidation of oleic, linoleic and linolenic acids by synchrotron radiation photoionization mass spectrometry

Rationale Cooking oil fumes contain numerous hazardous and carcinogenic chemicals, posing potential threats to human health. However, the sources of these species remain ambiguous, impeding health risk assessment, pollution control and mechanism research. Methods To address this issue, the thermal oxidation of three common unsaturated fatty acids (UFAs), namely oleic, linoleic and linolenic acids, present in vegetable oils was investigated. The volatile and semi‐volatile products were comprehensively characterized by online synchrotron radiation photoionization mass spectrometry (SR‐PIMS) with two modes, which were validated and complemented using offline gas chromatography (GC)/MS methods. Tunable SR‐PIMS combined with photoionization efficiency curve simulation enabled the recognition of isomers/isobars in gaseous fumes. Results SR‐PIMS revealed over 100 products, including aldehydes, alkenes, furans, aromatic hydrocarbons, etc., such as small molecules of formaldehyde, acetaldehyde, acrolein, ethylene and furan, which are not readily detected by conventional GC/MS; and some unreported fractions, e.g. ketene, 4‐ethylcyclohexene and cycloundecene(E), were also observed. Furthermore, real‐time monitoring of product emissions during the thermal oxidation of the three UFAs via SR‐PIMS revealed that linolenic acid may be the major source of acrolein. Conclusion SR‐PIMS has been demonstrated as a powerful technique for online investigation of cooking oil fumes. This study achieved comprehensive characterization of volatile and semi‐volatile products from the thermal oxidation of oleic, linoleic and linolenic acids, facilitating the traceability of species in cooking fumes and aiding in exploring the thermal reactions of different vegetable oils.