New Volatile Molecular Markers of Rancidity in Virgin Olive Oils under Nonaccelerated Oxidative Storage Conditions

Evolution of the volatile profile of two extra-virgin olive oils with very different fatty acid composition (monounsaturated fatty acid/polyunsaturated fatty acid ratio) stored in several nonaccelerated oxidative conditions was studied by a validated headspace solid-phase microextraction-gas chromatography–mass spectrometry (HS-SPME-GC–MS) method. The role of C8 volatile compounds in oxidative processes was highlighted, and controversial aspects regarding the origin of some volatiles were clarified. Specific volatile markers for rancidity were proposed: sum of pentanal, hexanal, nonanal, E -2-heptenal, propanoic acid, and hexanoic acid for oils stored in the dark; sum of pentanal, heptanal, nonanal, decanal, E -2-heptenal, E -2-decenal, E, E -hepta-2,4-dienal, and E, E -deca-2,4-dienal, octane for oils stored under light exposure; sum of pentanal, nonanal, decanal, E -2-heptenal, E -2-decenal, E, E -hepta-2,4-dienal, nonan-1-ol, propanoic acid, octane, 6-methylhept-5-en-2-one, and oct-1-en-3-ol for oils stored under light exposure with oxygen in headspace. A simplified marker (sum of pentanal, nonanal and E -2-heptenal) suitable for all conditions was also proposed.