Mechanisms and Factors for Edible Oil Oxidation

TLDR

Edible oil oxidation occurs through autoxidation by triplet oxygen and photosensitized oxidation by singlet oxygen, and is influenced by temperature, light, oxygen levels, processing, and fatty acid composition. Autoxidation of oils depends on radical acylglycerols and is accelerated by free fatty acids, mono‑ and diacylglycerols, metals, and thermally oxidized compounds, whereas photosensitized oxidation proceeds without lipid radicals via singlet oxygen reacting directly with double bonds. Hydroperoxides generated by triplet oxygen are conjugated dienes that decompose into off‑flavor compounds, while singlet oxygen produces both conjugated and nonconjugated dienes; antioxidants such as chlorophylls, phenolics, carotenoids, tocopherols, and phospholipids modulate oxidation, with chlorophyll acting as a photosensitizer and carotenoids/tocopherols quenching singlet oxygen, thereby affecting oil quality.

Abstract

ABSTRACT: Edible oil is oxidized during processing and storage via autoxidation and photosensitized oxidation, in which triplet oxygen ( 3 O 2 ) and singlet oxygen ( 1 O 2 ) react with the oil, respectively. Autoxidation of oils requires radical forms of acylglycerols, whereas photosensitized oxidation does not require lipid radicals since 1 O 2 reacts directly with double bonds. Lipid hydroperoxides formed by 3 O 2 are conjugated dienes, whereas 1 O 2 produces both conjugated and nonconjugated dienes. The hydroperoxides are decomposed to produce off‐flavor compounds and the oil quality decreases. Autoxidation of oil is accelerated by the presence of free fatty acids, mono‐ and diacylglycerols, metals such as iron, and thermally oxidized compounds. Chlorophylls and phenolic compounds decrease the autoxidation of oil in the dark, and carotenoids, tocopherols, and phospholipids demonstrate both antioxidant and prooxidant activity depending on the oil system. In photosensitized oxidation chlorophyll acts as a photosensitizer for the formation of 1 O 2 ; however, carotenoids and tocopherols decrease the oxidation through 1 O 2 quenching. Temperature, light, oxygen concentration, oil processing, and fatty acid composition also affect the oxidative stability of edible oil.