Optimization and validation of a SPME-GC/MS method for the determination of volatile compounds, including enantiomeric analysis, in northern highbush blueberries (Vaccinium corymbosum L.)

Blueberry aroma is one of the most important quality traits that influences consumer purchasing decisions. This study aimed to optimize and validate a solid-phase microextraction-gas chromatography/mass spectrometry (SPME-GC/MS) method for the quantification of 73 volatile compounds in northern highbush blueberries. A SPME extraction of blueberries with water and specific proportions of sodium chloride, citric acid, and ascorbic acid, for 60 min at 50 °C using a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was optimal. The method was validated for sensitivity, reproducibility, linearity, and accuracy, and used to quantify volatile compounds through matrix-matched calibration curves in six blueberry cultivars (‘Duke’, ‘Draper’, ‘Bluecrop’, ‘Calypso’, ‘Elliott’, and ‘Last Call’). Terpenes represented the most abundant volatile fraction, followed by aldehydes and alcohols. Linalool and 2-(E)-hexenal were key compounds that differentiated blueberry cultivars via Principal Component Analysis (PCA). Enantiomeric analyses revealed an excess of (−)-limonene, (−)-α-pinene, and (+)-linalool for all cultivars with potential impacts on the blueberry aroma.