Rapid determination of free sulfur dioxide in wine and cider by capillary electrophoresis

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 (alpha-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 so-lution 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 re-sults 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 cor-related 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.(c) 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ )

Automated summary

A novel method using CE-UV/vis was developed for the determination of free SO2 in wine and cider. The CE method showed significant differences with conventional methods, especially in the presence of anthocyanins. The CE method was found to be rapid, sensitive, robust, and repeatable, overcoming the issue of over-reporting free SO2 in pigmented samples.