Techniques for the Analysis of Minor Lipid Oxidation Products Derived from Triacylglycerols: Epoxides, Alcohols, and Ketones

Abstract Lipid oxidation can lead to flavor and safety issues in fat‐containing foods. In order to measure the extent of lipid oxidation, hydroperoxides and their scission products are normally targeted for analytical purposes. In recent years, the formation of rarely monitored oxygenated products, including epoxides, alcohols, and ketones, has also raised concerns. These products are thought to form from alternative pathways that compete with chain scissions, and should not be neglected. In this review, a number of instrumental techniques and approaches to determine epoxides, alcohols, and ketones are discussed, with a focus on their selectivity and sensitivity in applications to food lipids and oils. Special attention is given to methods employing gas chromatography (GC), high‐performance liquid chromatography (HPLC), and nuclear magnetic resonance (NMR). For characterization purposes, GC‐mass spectrometry (GC‐MS) provides valuable information regarding the structures of individual oxygenated fatty acids, typically as methyl esters, isolated from oxygenated triacylglycerols (TAGs), while the use of liquid chromatography–MS (LC‐MS) techniques allows analysis of intact oxygenated TAGs and offers information about the position of the oxygenated acyl chain on the glycerol backbone. For quantitative purposes, traditional chromatography methods have exhibited excellent sensitivity, while spectroscopic methods, including NMR, are superior to chromatography for their rapid analytical cycles. Future studies should focus on the development of a routine quantitative method that is both selective and sensitive.