Insight into the Storage-Related Oxidative/Hydrolytic Degradation of Olive Oil Secoiridoids by Liquid Chromatography and High-Resolution Fourier Transform Mass Spectrometry.

The study of negative effects potentially exerted by the exposure to oxygen and/or light and, thus, also by the type of container on the quality of extra virgin olive oil (EVOO) during its prolonged storage requires an appropriate choice of analytical methods and components to be monitored. Here, reverse-phase liquid chromatography coupled to high-resolution/accuracy Fourier transform mass spectrometry with electrospray ionization was exploited to study oxidative/hydrolytic degradation processes occurring on the important bioactive components of EVOO known as secoiridoids, i.e., oleuropein and ligstroside aglycones, oleacin, and oleocanthal, during storage up to 6 months under controlled conditions. Specifically, isomeric oxidative byproducts resulting from the transformation of a carbonylic group of the original secoiridoids into a carboxylic group and compounds resulting from hydrolysis of the ester linkage of secoiridoids, i.e., elenolic and decarboxymethyl elenolic acids and tyrosol and 3-hydroxytyrosol, were monitored, along with their precursors. Data obtained from EVOO storage at room temperature in glass bottles with/without exposure to light and/or oxygen indicated that, although it was more relevant if a periodical exposure to oxygen was performed, a non-negligible oxidative degradation occurred on secoiridoids also when nitrogen was used to saturate the container headspace. In a parallel experiment, the effects of storage of the same EVOO (250 mL) for up to 6 months in containers manufactured with different materials/shapes were considered. In particular, a square dark glass bottle, a stainless-steel can, and a ceramic jar, typically used for EVOO commercialization, and a clear polyethylene terephthalate bottle, purposely chosen to prompt secoiridoid degradation through exposure to light and oxygen, were compared. Dark glass was found to provide the best combined protection of major secoiridoids from oxidative and hydrolytic degradation, yet the lowest levels of oxidized byproducts were observed when the stainless-steel can was used.