Dual solid-phase and stir bar sorptive extraction combined with gas chromatography-mass spectrometry analysis provides a suitable tool for assaying limonene-derived mint aroma compounds in red wine.

A novel analytical method was developed for quantitative determination of eight limonene-derived monoterpenes responsible for the mint aroma in red wine. As these aromatic compounds are present at trace levels, a new dual extraction approach was proposed, combining solid-phase extraction (SPE) and stir bar sorptive extraction (SBSE), followed by gas chromatography-mass spectrometry analysis. The various parameters affecting the efficiency of extracting the analytes from wine samples in both the SPE and SBSE steps were first investigated, to determine the best compromise for the simultaneous analysis of the compounds studied. Following preliminary optimization of the dilution factor, phase ratio, and methanol content in the SBSE sample, cartridge sorbent mass, type of solvent, elution volume, and wine sample volume in the pre-concentration SPE step were studied. Highest response values were obtained when a 90 mL wine sample was extracted on a 500 mg SPE C18 cartridge and eluted with 1.5 mL methanol. The wine extract was then diluted in 10 mL water to obtain a final methanol content of 15% before the SBSE step. Good linearity, repeatability, reproducibility, accuracy and the required low detection and quantification limits were obtained under the conditions described, making this SPE-SBSE combination a suitable, powerful tool for routine analysis of the selected limonene-derived mint aroma compounds in large series of wine samples. Finally, the validated method was applied to 15 commercial red Bordeaux wines, aged from 3 to 23 years. Most of the compounds studied, present within the ng.L-1 range, were easily quantified for the first time in wine.