2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: International collaborative study report

Abstract

An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2H/ 1H ratio of the methyl site of acetic acid by SNIF–NMR (site-specific natural isotopic fractionation–nuclear magnetic resonance) and the determination of the 13C/ 12C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18O/ 16O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring δ 13C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability ( r) was 0.45 ‰, and the average reproducibility ( R) was 0.91‰. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2H/ 1H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (δ 13C and δ 18O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring δ 18O were found to be similar to the values previously obtained for other methods applied to wine and fruit juices: the average repeatability was 0.15‰, and the average reproducibility was 0.59‰. The above values are proposed as repeatability and reproducibility limits in the current state of the art. On the basis of this satisfactory inter-laboratory precision and on the accuracy demonstrated by a spiking experiment, the authors recommend the adoption of the three isotopic determinations included in this study as official methods for controlling the authenticity of vinegar.