Traceability of Italian garlic (Allium sativum L.) by means of HRMAS-NMR spectroscopy and multivariate data analysis

1H High Resolution Magic Angle Spinning-Nuclear Magnetic Resonance (HRMAS-NMR) spectroscopy was used to analyse garlic (Allium sativum L.) belonging to red and white varieties and collected in different Italian regions, in order to address the traceability issue. 1D and 2D NMR spectra, performed directly on untreated small pieces of garlic, so without any sample manipulation, allowed the assignment of several compounds: organic acids, sugars, fatty acids, amino acids and the nutritionally important fructo-oligosaccharides and allyl-organosulphur compounds.Application of Partial Least Squares projections to latent structures-Discrimination Analysis provided an excellent model for the discrimination of both the variety and, most important, the place origin, allowing the identification of the metabolites contributing to such classifications.The presence of organosulphurs, allicin and some allyl-organosulphurs found by HRMAS-NMR, was confirmed also by SPME-GC–MS; 11 molecules were identified, containing from one up to three sulphur atoms and with and without allyl moieties.

► Assessment by HRMAS-NMR of the metabolic pattern of garlic. ► Identification of metabolites, i.e. biomarkers, for variety discrimination and traceability classification. ► Determination by means of SPME-GC–MS of organosulphur species.