The composition and ratio of unsaturated fatty acids in vegetable oils play a crucial role in determining their overall quality. In this study, we present a corona discharge ionization mass spectrometry (MS) method for the rapid differentiation of vegetable oil varieties and their geographical origins under environmental conditions. Abundant water dimer radical cations, (H2O)2+•, were generated by the ionization setup, which effectively activated carbon‑carbon double bonds (C=C) to form epoxidized products. These epoxidation products were analyzed using tandem MS, generating diagnostic fragment ions that precisely identified CC bond positions. Statistical analysis models were subsequently developed using the resulting MS fingerprint data, revealing significant differences between various vegetable oils and olive oils from different origins. Key advantages of this method include minimal sample preparation, rapid analysis, and easily interpretable spectra. This study provides a new MS-based strategy for food quality assessment and offers a promising tool for identifying CC positional isomers in complex systems.
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