Getting inside on virgin olive oil (VOO) photooxidation kinetics through combined generalized 2D correlation analysis and moving window 2D correlation analysis of ATR-FTIR spectra.

The generalized two-dimensional correlation spectroscopy (g2D-COR spectroscopy) analysis combined with its extended version moving-window 2D-COR (MW-2D-COR) was performed on a set of kinetic ATR-FTIR spectral data. The former is a mathematical method that is applied to a set of spectra collected for a sample exposed to an external perturbation (e.g. storage time). Virgin olive oils (VOOs) of similar fatty acid composition, chlorophyll, and a-tocopherol content were photooxidized (10,912 Lx, no headspace, 24 h). The proposed approach revealed hidden information under specific ATR-FTIR bands and the order of events was established using appropriate rules. MW-2D-COR analysis displayed the evolution of changes during storage. In this way, the detection of the time interval upon which spectral changes are observed was evidenced. As an overview, MW plots of the analyzed samples revealed three time-zones in which changes tend to maximize, with the first one to reach a peak at ~2.5 h. The area around 2850-2930 cm including bands assigned to the symmetric and asymmetric stretching vibration of the aliphatic -CH- bonds, was the one found to be affected in all VOOs. The time interval upon which spectral changes are first detected in the corresponding area could serve as an index for the commencement of the loss of freshness. Present findings highlight the need to combine the two types of correlation analyses to obtain meaningful information on VOO photooxidation kinetics. Lipid scientists may gain an extra tool in their efforts to understand oxidation phenomena.