Liquid Chromatography–Mass Spectrometry-Based Metabolomics for Understanding the Compositional Changes Induced by Oxidative or Anoxic Storage of Red Wines

Abstract

The aim of this work was to study the physicochemical changes of eight red wines stored under conditions differing in O₂ exposure and temperature and time under anoxia. The methods used to analyze the wines included the measurement of volatile sulfur compounds, color, tannin (T) polymerization, and liquid chromatography-mass spectrometry untargeted metabolomic fingerprint. After 3 months, the color of the oxidized samples evolved 4-5 times more intensively than in wines stored under anoxia. The major metabolomic differences between oxidative and anoxic conditions were linked to reactions of acetaldehyde (favored in oxidative) and SO₂ (favored in anoxia). In the presence of oxygen, the C-4 carbocation of flavanols delivered ethyl-linked tannin-anthocyanin (T-A) and tannin-tannin (T-T) adducts, pyranoanthocyanins, and sulfonated indoles, while under reduction, the C-4 carbocation delivered direct linked T-A adducts, rearranged T-T adducts, and sulfonated tannins. Some of these last reactions could be related to the accumulation of reduced species, eventually ending with reductive off-odors.