ABSTRACT
An "omics"-style approach was used to evaluate the complex relationship between whisky aroma and dilution with water, typically suggested as a way to better appreciate whisky. A set of 25 samples, including Bourbons, ryes, single-malt and blended Scotches, and Irish whiskies were chemically profiled at six dilution levels (100, 90, 80, 70, 60, and 50% whisky/water), while a subset of six whiskies (three Bourbons, three Scotches) at four dilution levels (100, 80, 60, and 40% whisky/water) were chemically profiled and subjected to sensory analysis by a trained panel (n = 20). Untargeted volatile analysis was performed using headspace solid-phase microextraction gas chromatography coupled with mass spectrometry (HS-SPME-GC-MS) and sensory analysis was performed using descriptive analysis (DA). Results were evaluated using multivariate statistical techniques, including multifactor analysis (MFA) and partial least squares discriminant analysis (PLS-DA). Dilution decreased headspace concentration of hydrophilic aroma compounds and increased concentration of more hydrophobic compounds, which agreed with DA results. Dilution above 80% whisky/20% water reduced differences within whisky styles, though differences between American (Bourbon, rye) and Scotch styles (single malt, blended) continued to increase with further dilution. This provides important insight into how dilution of whisky during consumption changes consumer perception, as well as the usefulness of HS-SPME-GC-MS as a proxy for human olfaction.
ABSTRACT
A novel method for the determination of "true" free sulfur dioxide (SO2) in wine and cider was developed using capillary electrophoresis with direct ultraviolet-visible spectrophotometric detection (CE-UV/vis). Free SO2 was measured in model solutions with different SO2-binding agents present (α-ketoglutarate, pyruvate, acetaldehyde, glucose, fructose, and malvidin-3-glucoside) as well as a variety of white and red wines and ciders. The CE method was compared to three conventional methods for measuring free SO2, the Ripper method, Aeration-Oxidation (AO), and pararosaniline by discrete analyzer (DA). While some statistically significant differences (p<0.05) were found between the four methods in unpigmented model solutions and samples, the values generally agreed. In the presence of anthocyanins in model solution and red wines, free SO2 values found by CE were significantly lower than the other three methods (p<0.05). The difference in values found by Ripper and CE correlated strongly with anthocyanin content (R2 = 0.8854) and even more strongly when accounting for polymeric pigments (R2 = 0.9251). The results in red ciders differed from those in red wines, while the CE measured significantly lower free SO2 values than the other three methods, the difference in free SO2 values measured by CE and Ripper correlated more closely with anthocyanin concentration (R2 = 0.8802) than absorbance due to bleachable pigment (R2 = 0.7770). The CE method was found to be rapid (4 min/injection), sensitive (LOD=0.5 mg/L, LOQ=1.6 mg/L free SO2 in wine, 0.8 and 2.8 mg/L, respectively, in cider), robust, and repeatable (average RSD = 4.9%) and did not suffer from the issue of over-reporting free SO2 in pigmented samples often observed with currently accepted methods.
