The quantitative determination of volatile compounds of Chardonnay wines using HS-SPME-GC × GC/TOFMS along with the determination of odor activity value (OAV) and relative odor contribution (ROC) of volatiles are reported for the first time. The use of GC × GC/TOFMS for the analysis of Chardonnay wine of Serra Gaucha resulted in the tentative identification of 243 compounds, showing the superior performance of this analytical technique for this specific varietal wine, considering that the number of compounds usually separated by 1D-GC for this type of wine is lower. Furthermore, 42 compounds co-eluted in the first dimension and 34 of them were separated in the second dimension, while the others were resolved by spectral deconvolution (8), which indicates that the conventional 1D-GC/MS may result in misleading results. The calculation of OAV and ROC allowed the determination of the volatile compounds that presented the greater contribution to wine aroma. Ethyl octanoate, ethyl hexanoate, ethyl butanoate, and beta-damascenone showed the highest OAV and ROC values, although other 43 compounds showed also potential to contribute to wine aroma. Figures of merit of the developed method were: accuracies from 92.4 to 102.6%, repeatability from 1.2% to 13.4%, LOD from 0.001 ?g L?1 (ethyl isovalerate and hexanoic acid) to 2.554 ?g L?1 (ethyl 3-hydroxybutanoate), LOQ from 0.003 ?g L?1 (ethyl isovalerate and hexanoic acid) to 7.582 ?g L?1 (ethyl 3-hydroxybutanoate).2014DOI 10.1016/j.foodres.2014.02.00

Wine aroma is an important characteristic and may be related to certain specific parameters, such as raw material and production process. The complexity of Merlot wine aroma was considered suitable for comprehensive two-dimensional gas chromatography (GC×GC), as this technique offers superior performance when compared to one-dimensional gas chromatography (1D-GC). The profile of volatile compounds of Merlot wine was, for the first time, qualitatively analyzed by HS-SPME-GC×GC with a time-of-flight mass spectrometric detector (TOFMS), resulting in 179 compounds tentatively identified by comparison of experimental GC×GC retention indices and mass spectra with literature 1D-GC data and 155 compounds tentatively identified only by mass spectra comparison. A set of GC×GC experimental retention indices was also, for the first time, presented for a specific inverse set of columns. Esters were present in higher number (94), followed by alcohols (80), ketones (29), acids (29), aldehydes (23), terpenes (23), lactones (16), furans (14), sulfur compounds (9), phenols (7), pyrroles (5), C13-norisoprenoids (3), and pyrans (2). GC×GC/TOFMS parameters were improved and optimal conditions were: a polar (polyethylene glycol)/medium polar (50% phenyl 50% dimethyl arylene siloxane) column set, oven temperature offset of 10 °C, 7s as modulation period and 1.4s of hot pulse duration. Co-elutions came up to 138 compounds in 1D and some of them were resolved in 2D. Among the co-eluted compounds, thirty-three volatiles co-eluted in both 1D and 2D and their tentative identification was possible only due to spectral deconvolution. Some compounds that might have important contribution to aroma notes were included in these superimposed peaks. Structurally organized distribution of compounds in the 2D space was observed for esters, aldehydes and ketones, alcohols, thiols, lactones, acids and also inside subgroups, as occurred with esters and alcohols. The Fischer Ratio was useful for establishing the analytes responsible for the main differences between Merlot and non-Merlot wines. Differentiation among Merlot wines and wines of other grape varieties were mainly perceived through the following components: ethyl dodecanoate, 1-hexanol, ethyl nonanoate, ethyl hexanoate, ethyl decanoate, dehydro-2-methyl-3(2H)thiophenone, 3-methyl butanoic acid, ethyl tetradecanoate, methyl octanoate, 1,4 butanediol, and 6-methyloctan-1-ol.