Calcium isotopes in wine

The δ ^44/40Ca values of bottled wine vary between -0.76% to -1.55% on the seawater scale and correlate weakly with inverse Ca concentration and Mg/Ca ratio, such that the lowest δ ^44/40Ca values have the highest Ca concentrations and lowest Mg/Ca ratios. The correlation is notable in the sense that the measured wines include both whites and reds sampled from different wine growing regions of the world, and cover a wide range of quality. Trends among the data yield clues regarding the cause of the observed isotopic fractionation. White wines, and wines generally perceived to be of lower quality, have lower δ ^44/40Ca values compared to red wines and wines of generally perceived higher quality. Quality was assessed qualitatively through sensory evaluation, price, and scores assigned by critics. The relationship between δ ^44/40Ca and wine quality was most apparent when comparing wines of one varietal from one producer from the same growing region. In the vineyard, wine quality is related to factors such as the tonnage of the crop and the ripeness of the grapes at the time of harvesting, the thickness of the skins for reds, the age of the vines, as well as the place where the grapes were grown (terroir). Quality is also influenced by winemaking practices such as fermentation temperature, duration of skin contact, and barrel ageing. Accordingly, the relationship between δ ^44/40Ca and wine quality may originate during grape ripening in the vineyard or during winemaking in the cellar. We tested the grape ripening hypothesis using Merlot grapes sampled from a vineyard in the Okanagan, British Columbia, using sugar content (degrees Brix) as an indicator of ripeness. The grapes were separated into pulp, skin, and pip fractions and were analyzed separately. Thus far, there is no clear evidence for a systematic change in δ ^44/40Ca values associated with progressive ripening of grapes in the vineyard. On the day of harvesting, the δ ^44/40Ca value of juice squeezed from Merlot grapes was -1.94%, which is lower than any of the bottled wines measured, thus far, whether white or red. The wine made from this juice yielded -1.16%, which points to fermentation being the principal source of isotopic variability found in bottled wine. The working hypothesis is that light isotopes of Ca are preferentially stripped from the juice during maceration, fermentation, and lees contact, by ion exchange sites on solid organic-matter comprising the skins and yeast and/or by Ca-tartrate precipitation. High quality wines (especially reds) tend to involve longer contact times between juice and skins in order to increase the extraction of color and phenolic compounds (tannins) from the grape skins, a practice that might also result in greater losses of light isotopes of Ca from the juice, thus explaining the isotopic pattern in bottled wine.