The antioxidant properties of sulfites are still used today, even though the trend is heading towards a decrease in their use. Therefore, it is not uncommon to see winemakers banning the addition of sulfites during winemaking and aging but adding a few milligrams before bottling to preserve the wines from the effect of oxygen intake during this final stage of the process.
In an effort to consider the contribution of sulfites and to control the shelf-life of bottled wines, it is interesting to predict the decline in their concentration over time after bottling. In order to develop a predictive model, we set up a trial of a hundred wines (40 reds, 40 whites, 20 rosés). Each one was bottled with verification of the total oxygen intake (dissolved and gaseous in the headspace). Closures with different OTRs were used for each wine. Their permeability was controlled in parallel of the trials, in equivalent bottles, and at the same temperature conditions to measure accurately the quantity of oxygen delivered by the different closures. For 2 years, the total amount of O2 delivered in the bottle as well as free and total SO2 were tracked. This highlighted that the consumption of 1 mg of O2 by the wine induced, on average, a decrease of 2.5 mg of free SO2. This result differs from the generally accepted 1 to 4 stoichiometry and can be explained by the non-direct reaction of O2 with SO2, and the involvement of numerous molecules in the oxidation mechanism.
These tests finally led us to propose a model for predicting the drop of free SO2 in the bottle, based on the total amount of oxygen intake during bottling, the level of SO2 at bottling, and the contribution of the closure used (Oxygen Ingress = desorption + OTR). This enabled us to predict the decrease in free SO2 levels until it reaches the levels usually associated with the appearance of oxidative taints and thus predicted the shelf-life of the wines. This model has also been integrated into an application available to winemakers.
SO2 is one of the most commonly used additives in the food industry. In wines, SO2 is used for its antimicrobial and antioxidant properties. The antioxidant properties of SO2 play an essential role in controlling the evolution of the wine aromas, its color during the aging process, and the control of its shelf-life. Free SO2 has these antioxidant propertiesthe rest of the total SO2 is present in the form of combined SO2 (SO2 reversibly or irreversibility linked with several wine compounds) and molecular SO2.
The direct reaction between SO2 and molecular oxygen is slow and requires the presence of a catalyst such as iron or copper. Under enological conditions, free SO2 can reduce quinones and oxidation products to phenols (Waterhouse et al. 2006, Danilewicz et al. 2010), which slows down the oxidation process (figure 1). It also reacts with a powerful oxidant, hydrogen peroxide, generated by the oxidation of phenolic compounds (Figure 1) and thus prevents the formation of ethanal (Danilewicz et al. 2010). These two mechanisms lead to a decrease in the concentration of free and total SO2 when storing the wine.
Figure 1: Oxygen interaction mechanism with a polyphenol in the absence and the presence of SO2 (Danilewicz et al., 2010).
Inadequate levels of free SO2 cause the wine aromas and color to deteriorate rapidly. However, because of its toxicity, the SO2 dosage is regulated, and the general trend is to reduce SO2 during winemaking and in bottled wines.
Oxygen control is an important parameter that is becoming more and more relevant in the industry: technological means of measuring oxygen intakes are readily available, and known O2 input tools exist during winemaking (micro-oxygenator, etc.) and bottled storage (closures with controlled oxygen ingress). However, a fundamental aspect of the role of SO2 in wine remains to be defined: the relationship between the amount of O2 consumed by the wine and the amount of SO2 lost. This last aspect is crucial in predicting the decrease in SO2 concentration over time, a key factor in the wine shelf-life.
Materials and methods
Various trials on different grape varieties and different winemaking conditions were performed in collaboration with research institutes including:
All the wines underwent 3 or 4 degrees of exposure to O2 after bottling by using co-extruded closures (Nomacorc) presenting different oxygen transmission rates (OTR), combined with the storage of bottles under atmospheres of varying oxygen concentrations. Oxygen penetration through the closure was measured (NomaSense O2 P6000) in bottles filled with nitrogen, sealed with the closures used for the study, and stored in the same conditions as the experimental wines (Diéval et al. 2011). The resulting levels of oxygen exposure ranged from very low (0.2 mg/year, similar to those of a screw cap) to high (4 mg/year).
A total of 54 red wines, 46 white wines, and 20 rosé wines were followed during these trials.
The free and total SO2 was regularly dosed by the Ripper method on each of the wines for 12 to 24 months according to the tests. At the same time, the dissolved and gaseous oxygen in the bottle was measured by luminescence (Dimkou et al. 2011) with the portable NomaSense O2 P6000 oximeter.
The Total Consumed Oxygen (TCO) was calculated as the sum of the oxygen present at bottling, called TPO for Total Package Oxygen (oxygen located in the headspace + dissolved oxygen) and the oxygen entering the bottle through the closure during storage, from which the dissolved oxygen and the oxygen from the headspace measured at each stage are subtracted.
Effects of post-bottling oxygen exposure on the evolution of SO2 when storing wine
Figure 2 shows a characteristic pattern of the decline of free SO2 in wines stored under different degrees of oxygen exposure. These degrees were created using the same closure for each method but by creating:
The highest level of TPO at bottling results in a faster drop in SO2 from the first measurement points, provided they are in equivalent storage conditions.
Given equivalent bottling conditions, storage at 21% of O2 (air) allows for more O2 transfers at a given time than the storage of 1% O2, which is equivalent to the use of a lower OTR closure. A smaller decline in SO2 is observed in the latter case.
Figure 2: Evolution of free SO2 in a Riesling wine. All methods have the same co-extruded closure, but the storage and setting conditions differ.
Correlation between the O2 content of wine and the evolution of SO2.
The correlation between the loss of free SO2 and the decline in dissolved oxygen is the highest in the first few days after bottling (Table 1), even though the correlation coefficient remains around 0.8.
Measuring dissolved O2 does not, therefore, correctly determine the amount of total O2 that was consumed by the wine. For this, a fullassessment must be considered for all sources of O2: Dissolved O2 and O2 from the gaseous headspace taken during bottling as well as the O2 entering the bottle through the closure. For that, it is necessary to substract the dissolved and the gaseous headspace O2 that were not consumed to reach the total consumed O2 (TCO) at each measurement point.
Knowing the total amount of oxygen that can react with wine, it is then possible to establish a correlation with the decline of SO2, one of the most easily measurable antioxidants in wine. It has been demonstrated in the literature that the antioxidant activity of SO2 in wine is not due to a direct reaction between oxygen and HSO3-, the main form of SO2 in wine (Danilewicz 2010) according to equation 1:
2 HSO3- + O2 -----------> 2 SO42- (1)
The reaction mechanism brings into play more complex mechanisms involving quinones and hydrogen peroxide.
It is customary in the industry to consider that the consumption of 1 mg of O2 causes a drop of 4 mg of SO2, in reference to the stochiometry of equation 1.
Figure 3: concentration of free SO2 measured in 16 Riesling methods differing in the degree of exposure to O2 during bottling and storage as a function of total consumed O2 (TCO).
For the 54 red wines, 46 white wines, and 20 rosé wines studied, a linear correlation was observed between the concentration of free SO2 and the TCO. Figure 3 aggregates this correlation of the 16 methods of one of the Riesling wines, followed by the University of Geisenheim. The resulting correlation has a slope coefficient of -2.2, indicating that consumption of 1 mg of O2 causes the loss of 2.2 mg of free SO2. This ratio is well below 4, commonly accepted in the industry.
Of the 120 wines followed, the average loss of SO2 is 2.5 mg per 1 mg of O2 consumed. Ratios higher than 4, sometimes up to 10, have, however, been measured in wines bottled with low OTR closures, suggesting the involvement of SO2 in mechanisms other than oxidation and possibly reduction mechanisms.
Development of a calculator to estimate the wine shelf-life
The average ratio of 2.5 was selected to develop a wine shelf-life calculator, without the appearance of oxidative defects. For that, it was accepted that when the level of free SO2 is less than 10 mg/L, the risk of appearance of aroma oxidation is high, as described by Ferreira (2010). This was corroborated by the tasting of the trials by a trained expert panel.
This calculator (Figure 4) estimates the time it takes to reach the 10 mg/L threshold of free SO2 by providing:
the model has been refined by incorporating additional parameters such as:
Figure 4: Application for the prediction of the lifespan of a wine
At first, this study was able to demonstrate that the simple measurement of dissolved oxygen does not predict the evolution of wines and that it is necessary to consider the oxygen contribution as a whole (dissolved, headspace, contribution of the closure systems) to be able to find any correlation with changes in the concentrations of wine constituent molecules. In addition, this study of the link between consumed O2 and the drop in free SO2 in bottled wines showed that, on average, 1 mg of O2 consumed results in the loss of 2.5 mg of free SO2. This ratio has been integrated into a calculator that estimates the potential losses of free SO2 in the wine during its life in the bottle and thus estimates the wine shelf-life before the development of oxidation taints. However, this ratio can vary from one wine to another, so the result of the calculator provides only an estimate, and above all has an educational purpose of showing the importance of certain factors in the evolution of wines and of guiding improvements in production.
Caillé S, Samson A, Wirth J et al. Sensory characteristics changes of red Grenache wines submitted to different oxygen exposures pre and post bottling. Analytica Chimica Acta 2010; 660: 35-42.
Danilewicz J.C., Wallbridge P.J. Further Studies on the Mechanism of Interaction of Polyphenols, Oxygen, and Sulfite in Wine Am J Enol Vitic. 2010, 61: 166-175
Dieval, J.-B.; Vidal, S.; Aagaard, O. Measurement of the oxygen transmission rate of co-extruded wine bottle closures using a luminescence-based technique. Packag. Technol. Sci. 2011, 24, 375-385. Dimkou, E., Ugliano, M.,
Dieval, J-B., Vidal, S. Aagard, O., Rauhut, D. Jung, R. Impact of headspace oxygen and closure on sulfur dioxide, color, and hydrogen sulfide levels in a Riesling wine. Am. J. Enol. Vitic., 2011, 62, 261-269
Dimkou, E., Ugliano, M., Dieval, J-B., Vidal,. Jung, R. Impact of dissolved oxygen at bottling on sulfur dioxide and sensory properties of a Riesling wine. Am. J. Enol. Vitic. 2013, 4, 325-332
Ferreira V., Bueno M., Franco-Luesma E., Culleré L., Fernández-Zurbano P. Key Changes in Wine Aroma Active Compounds during Bottle Storage of Spanish Red Wines under Different Oxygen Levels. J. Agric. Food Chem. 2014, 62, 10015-10027
Han, G., Ugliano, M., Currie, B., Vidal, S., Diéval, J. B., & Waterhouse, A. L. Influence of closure, phenolic levels and microoxygenation on Cabernet Sauvignon wine composition after 5 years' bottle storage. J. Sci. Food Agric., 2015, 95, 36-43.
Ugliano M, Dieval JB, Siebert TE, Kwiatkowski M, Aagaard O, Vidal S, Waters EJ. Oxygen consumption and development of volatile sulfur compounds during bottle aging of two Shiraz wines. Influence of pre and post-bottling controlled oxygen exposure. J. Agric. Food Chem. 2012, 60, 8561-8570
Ugliano, M., Kwiatkowski, M., Vidal, S., Capone, D., Siebert, T., Dieval, JB., Aagaard, O., Waters, E.J. Evolution of 3-mercaptohexanol, hydrogen sulfide, and methyl mercaptan during bottle storage of Sauvignon blanc wines. Effect of glutathione, copper, oxygen exposure, and closure-derived oxygen. J. Agric. Food Chem., 2011, 59, 2564–2572.
Waterhouse A.L., Laurie V.F. Oxidation of Wine Phenolics: A Critical Evaluation and Hypotheses Am J Enol Vitic. 2006, 57: 306-313
Waterhouse, A. L., Frost, S., Ugliano, M., Cantu, A. R., Currie, B. L., Anderson, M., ... & Heymann, H. Sulfur Dioxide–Oxygen Consumption Ratio Reveals Differences in Bottled Wine Oxidation. Am. J. Enol. Vitic, 2016, 67: 449-459.
Wirth J, Morel-Salmi C, Souquet JM et al. The impact of oxygen exposure before and after bottling on the polyphenolic composition of red wines. Food Chemistry 2010; 123: 107-116.
Wirth, J.; Caillé, S.; Souquet, J.-M.; Samson, A.; Dieval, J.-B.; Vidal, S.; Fulcrand, H.; Cheynier, V. Impact of post-bottling oxygen on the sensory characteristics and phenolic composition of Grenache rosé wines. Food Chem. 2012, 132, 1671−1681