Molecular fingerprint of the alcoholic Grappa beverage by mass spectrometry techniques

•A molecular characterization of Grappa is proposed.•Grappa “fingerprint” was studied by MALDI-TOF/MS and MALDI-TOF/TOF.•Grappa volatile profile was achieved by HS-SPME-GC-MS.•Main non-volatile components from Grappa were identified.

Grappa is the traditional Italian spirit derived from marc. The molecular characterization of volatile compounds in the liquid Grappa, responsible of its bouquet, has been achieved by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography–mass spectrometry (GC-MS). Of these, 12 compounds represent more than 1% of Grappa volatile fraction.In addition, a molecular fingerprint of Grappa samples was performed by MALDI-TOF and MALDI-TOF/TOF MS, allowing the identification of molecular structures of major compounds within the non-volatile fraction of Grappa. The − 82 Da shifts on precursor ion masses due to the loss of 5-methylfuran ion also allowed the identification of some heterocyclic compounds, such as furan derivatives, formed during the Grappa aging within barrels. Overall, by integrating different mass spec techniques, we obtained a comprehensive molecular fingerprint of selected Grappa samples.