Vacuum-assisted and multi-cumulative trapping in headspace solid-phase microextraction combined with comprehensive multidimensional chromatography-mass spectrometry for profiling virgin olive oil aroma

: In the present work vacuum (Vac) and multiple cumulative trapping (MCT) headspace solid phase microextraction (HS-SPME) were evaluated as alternative or combined techniques for the volatile profiling. A higher extraction performance for semi-volatiles was shown by all three techniques. Synergic combination of Vac and MCT showed up to 5-times extraction power for less volatile compounds. The hyphenation of said techniques with comprehensive two-dimensional gas chromatography (GC × GC) enabled a comprehensive analysis of the volatilome. Firstly, 18 targeted quality markers, previously defined by means of classical HS-SPME, were explored for their ability to classify commercial categories. The applicability of such markers proved to be limited with the alternative sampling techniques. An untargeted approach enables the selection of specific features for each technique showing a better classification capacity of the commercial categories. No misclassifications were observed, except for one extra virgin olive oil classified as virgin olive oil in 3 × 10 min Vac-MCT-HS-SPME.