The combined synergistic effects of copper (Cu2+) and sulfur dioxide (SO2) on the formation of hydrogen sulfide (H2S) in Verdelho and Shiraz wine samples post-bottling was studied over a 12-month period. The combined treatment of Cu2+ and SO2 significantly increased H2S formation in Verdelho wines samples that were not previously treated with either Cu2+ or SO2. The formation of H2S produced through Cu2+ mediated reactions was likely either: (a) directly through the interaction of SO2 with either Cu2+ or H2S; or (b) indirectly through the interaction of SO2 with other wine matrix compounds. To gain better understanding of the mechanisms responsible for the significant increases in H2S concentration in the Verdelho samples, the interaction between Cu2+ and SO2 was studied in a model wine matrix with and without the presence of a representative thiol quenching compound (4-methylbenzoquinone, 4MBQ). In these model studies, the importance of naturally occurring wine compounds and wine additives, such as quinones, SO2, and metal ions, in modulating the formation of H2S post-bottling was demonstrated. When present in equimolar concentrations a 1:1 ratio of H2S- and SO2-catechol adducts were produced. At wine relevant concentrations, however, only SO2-adducts were produced, reinforcing that the competition reactions of sulfur nucleophiles, such as H2S and SO2, with wine matrix compounds play a critical role in modulating final H2S concentrations in wines.
The impact of oxygen exposure during winemaking on metal ion concentrations in wine were investigated throughout the winemaking process in a Chardonnay wine. The concentrations of Al, Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Sn, and Zn were determined using inductively coupled plasma-mass spectrometry. Oxygen exposure significantly impacted 13 metal ions at different phases of winemaking. However, only the concentrations of Cr, Cu, and Fe were impacted by early oxygen exposure during pressing, with lower Cr and Cu concentrations in wines that were aerobically pressed and lower concentrations of Fe in wines that were inertly pressed. The sequestering of Al, Cu, Ni, and Zn by wine lees was significantly affected by oxygen treatment, with lees collected from wines that were treated oxidatively sequestering significantly greater amounts of Cu and Zn and removing these metals from the wine supernatant. The metal ion that was most affected by oxygen exposure during pressing and handling was Cu, with significantly lower Cu measured in wines that were produced under oxidative conditions. It is known that elevated Cu concentrations have negative implications for wine aroma and flavour. This study demonstrated that oxygen management during winemaking significantly impacts metal ion concentrations in lees and wine, which may decrease the risk of developing taints and faults.