Determination of molecular and free sulphur dioxide in foods by headspace gas chromatography

A study was made of the equilibria between SO2 in packaged liquid foods and gaseous SO2 in their headspace atmospheres as a basis for a new analytical method for the determination of molecular and free SO,. Using a gas-chromatographic method developed previously to determine SO2 at the 1 × 10⁻³ mg/l level in atmospheres saturated with water vapour, studies with aqueous solutions showed that headspace SO2 was directly proportional to molecular SOz in accordance with Henry's law.
Using the Henry's law constant for the S02/H20 system, determinations of molecular SOz were made on a white and a red wine and a fruit juice, each adjusted to five levels of pH to achieve different concentrations of molecular SO,. The results observed by the headspace method showed good agreement with those determined by a reference analytical method with white wine and fruit juice, but with red wine the reference method gave values which were more than 45% higher. Free SO2 was determined in a range of white wines by the headspace and reference methods, and the results showed high correlations.
The headspace method is rapid, precise and non-destructive. A major advantage is that, during the analysis, it does not change the complicated equilibria between SO, and its ionised species, hence complexes of SO2 and food constituents are not disturbed.