Volatilomic Differentiation of Protected-Origin Italian Balsamic Vinegars by HS-SPME-GC×GC-TOFMS

Area of Science:

• Food Chemistry
• Analytical Chemistry
• Volatilomics

Background:

• Balsamic vinegars with Protected Designation of Origin (PDO) and Protected Geographical Indication (PGI) have distinct production methods and raw materials.
• Chemical characterization to differentiate these balsamic vinegars is analytically challenging due to complex volatile profiles.

Purpose of the Study:

• To comprehensively characterize the volatile composition of PDO and PGI balsamic vinegars.
• To evaluate the feasibility of using volatilomics for reliable differentiation between PDO and PGI balsamic vinegars.
• To establish a robust analytical workflow for authenticity and quality control.

Main Methods:

• Headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS).
• Optimization of SPME fiber coatings and extraction conditions (salting-out effect).
• Statistical analysis including Mann-Whitney U testing and multivariate analysis for feature selection and sample discrimination.

Main Results:

• A total of 227 volatile features were identified after filtering, with 100 statistically significant features differentiating the samples.
• PDO balsamic vinegars showed higher levels of furanoids, lactones, esters, aldehydes, acids, phenols, ketones, and alcohols.
• PGI balsamic vinegars exhibited comparatively higher levels of terpenoids.
• Multivariate analysis clearly separated PDO and PGI samples based on their volatile profiles.

Conclusions:

• The integrated HS-SPME-GC×GC-TOFMS workflow successfully differentiated PDO and PGI balsamic vinegars.
• The identified volatile compounds correlate with the distinct production processes of PDO and PGI vinegars.
• This study provides a methodological framework for large-scale authenticity and quality control of balsamic vinegars.