Use of Untargeted Liquid Chromatography-Mass Spectrometry Metabolome To Discriminate Italian Monovarietal Red Wines, Produced in Their Different Terroirs

Abstract

The aim of this project was to register, in a liquid chromatography-mass spectrometry-based untargeted single-batch analysis, the metabolome of 11 single-cultivar, single-vintage Italian red wines (Aglianico, Cannonau, Corvina, Montepulciano, Nebbiolo, Nerello, Primitivo, Raboso, Sagrantino, Sangiovese, and Teroldego) from 12 regions across Italy, each one produced in their terroirs under ad hoc legal frameworks to guarantee their quality and origin. The data provided indications regarding the similarity between the cultivars and highlighted a rich list of putative biomarkers of origin wines (pBOWs) characterizing each individual cultivar-terroir combination, where Primitivo, Teroldego, and Nebbiolo had the maximum number of unique pBOWs. The pBOWs included anthocyanins (Teroldego), flavanols (Aglianico, Sangiovese, Nerello, and Nebbiolo), amino acids and N-containing metabolites (Primitivo), hydroxycinnamates (Cannonau), and flavonols (Sangiovese). The raw data generated in this study are publicly available and, therefore, accessible and reusable as a baseline data set for future investigations.

Keywords: amines; biomarkers discovery; mass spectrometry; polyphenols; wine authenticity; wine metabolomics.

Figure 1

Distribution of the wine sample set according to their cultivar (black) and region (red). The principal denomination of origin of each cultivar/region is also shown (light blue). The cultivation area refers to the whole of Italy for each cultivar for the year 2015.

Figure 2

PCA plots of all of the wines in (top) ESI+ and (bottom) ESI–. AGL, Aglianico; PRI, Primitivo; TER, Teroldego; NER, Nerello Mascalese; RAB, Raboso; COR, Corvina; CAN, Cannonau; MON, Montepulciano; SAG, Sagrantino; SAT, Sangiovese Tuscany; SAR, Sangiovese Romagna; NEB, Nebbiolo; and QC, quality control.

Figure 3

Number of pBOW features for each cultivar in ESI+ and ESI–. The pBOWs that help to discriminate the cultivar from all of the others are unique.

Figure 4

Clustering of the wines according to the markers in ESI+ and ESI–.

Figure 5

Biosynthesis and synthesis of N-containing metabolites, hydroxycinnamates, and stilbenoids annotated in this study. The colors refer to the heatmap of Figure S1 of the Supporting Information and provide a comparison of the concentration of each metabolite between the various monocultivar wine groups. The heatmap was constructed using Pareto scaling and Euclidean distance. AGL, Aglianico; PRI, Primitivo; TER, Teroldego; NER, Nerello Mascalese; RAB, Raboso; COR, Corvina; CAN, Cannonau; MON, Montepulciano; SAG, Sagrantino; SAT, Sangiovese Tuscany; SAR, Sangiovese Romagna; and NEB, Nebbiolo.

Figure 6

General pattern for flavonoid biosynthesis, with the metabolites annotated in this study. The colors refer to the heatmap of Figure S1 of the Supporting Information and provide a comparison of the concentration of each metabolite between the various monocultivar wine groups. The heatmap was constructed using Pareto scaling and Euclidean distance. AGL, Aglianico; PRI, Primitivo; TER, Teroldego; NER, Nerello Mascalese; RAB, Raboso; COR, Corvina; CAN, Cannonau; MON, Montepulciano; SAG, Sagrantino; SAT, Sangiovese Tuscany; SAR, Sangiovese Romagna; and NEB, Nebbiolo.

Figure 7

Generic diagram with the major reaction in which anthocyanins participate in wine. The colors refer to the heatmap of Figure S1 of the Supporting Information and provide a comparison of the concentration of each metabolite between the various monocultivar wine groups. The heatmap was constructed using Pareto scaling and Euclidean distance. AGL, Aglianico; PRI, Primitivo; TER, Teroldego; NER, Nerello Mascalese; RAB, Raboso; COR, Corvina; CAN, Cannonau; MON, Montepulciano; SAG, Sagrantino; SAT, Sangiovese Tuscany; SAR, Sangiovese Romagna; and NEB, Nebbiolo.

Figure 8

Variation of the annotated monomeric and oligomeric flavanols according to the various monocultivar wine groups. The classification is based on B-ring substitution. The colors refer to the heatmap of Figure S1 of the Supporting Information and provide a comparison of the average concentration of each metabolite within each of the various monocultivar wine groups. The heatmap was constructed using Pareto scaling and Euclidean distance. AGL, Aglianico; PRI, Primitivo; TER, Teroldego; NER, Nerello Mascalese; RAB, Raboso; COR, Corvina; CAN, Cannonau; MON, Montepulciano; SAG, Sagrantino; SAT, Sangiovese Tuscany; SAR, Sangiovese Romagna; and NEB, Nebbiolo. (a) Two disubstituted and one trisubstituted block. (b) One disubstituted and two trisubstituted block.