In Wine Chemistry

One of the reasons that grapes have been used to make wine for thousands of years is that they are one of the few fruits in the world that contain large concentrations of tartaric acid. The strength of acids is measured by their ability to shed protons – or more specifically, hydrogen ions (H+). Without going too deep into a chemistry lecture (which I’m sure will lose most of you in a few sentences), when you measure the pH of your wine, you are measuring the concentration of these ions – that’s what the big ‘H’ in pH stands for. The tricky thing to remember is that while pH is a measurement of H+, the formula for its calculation causes the pH to be inversely proportional to the H+ concentration. Thus, as the H+ concentration increases, your pH decreases.

So what is the big deal about pH? Because tartaric acid is relatively strong, it works to keep a wine’s pH near 3.0, which in turn keeps the wine stable against microbes. This is one of the reasons why wine made from grapes has flourished around the world: it doesn’t spoil easily, and acts as an antiseptic. The combination of ethanol and the acidic environment are extremely inhospitable to most microbes. In an indigenous yeast fermentation, after the wine hits 5-6% alcohol, one yeast will dominate the fermentation: Saccharomyces cerevisiae or S. bayanus. After the sugar is depleted, there isn’t much left in the wine to act as a food source for microbes that are capable of surviving in those harsh conditions. Lactic Acid bacteria, if present, will begin to consume the malic acid (transforming it to lactic acid), while Acetobacter species are capable of turning ethanol into acetic acid (vinegar). However, Acetobacter needs oxygen in order to do this, so as long as you keep your containers full, you don’t need to worry much about them.

This year, like in 2010, we saw problems with high pH in many of our wines, but we saw it especially in Marquette. The most likely explanation is that Marquette grown under certain conditions has an excess of potassium, which can drive up the pH. Malic acid concentration likely also plays a role in increasing the pH, since it is a weaker acid that in turn is converted to an even weaker acid (lactic acid) in red wine vinification. In any case, the high pH is worrisome and steps need to be taken to ensure that the wine remains stable.

Sulfur Dioxide Addition. While it is still possible to limit microbes with sulfur addition when the pH creeps up to 3.8, you need to use substantially more SO2 as your pH increases. Most of the sulfur you add to wine becomes bound to sugars and other compounds in your wine. The rest of the sulfur exists as “free” or unbound SO2. At a pH of 3.4, you should aim for 35 mg/L of free sulfur in your wine in order to be sure that it’s protecting your wine against microbial spoilage. However, at a pH of 3.8, you’d need nearly 90 mg/L of free sulfur to get the same protection. Considering that the legal limit for TOTAL sulfur in your wine cannot exceed 400 ppm, one can see how maintaining a high free SO2 rate can quickly make it possible to exceed that limit. Though it’s possible to keep your wine clean with a high pH, it isn’t easy. One should consider a pH greater than 3.8 the breaking point where acidification becomes necessary.

Wine Sensory. The pH has a huge effect on the color of red wine, as it affects the colored pigments. If you start to keep track of your wine color and corresponding pH, it becomes almost possible to predict your wine’s pH based on color alone. A high pH wine will lose the vibrant red tones, and become more of an eggplant purple color. Low pH wines will have a bright pink rim and vibrant red hue. Differences occur between grape cultivar, of course, but generally if you observe the rim of color at the edge of the wine when you tilt your glass, if it’s purple then the pH is high. High pH wines also have a tendency to be described as “flabby” or “flat,” however it is difficult to say whether or not that holds true when the wine has a corresponding high total acidity, like we often see in Marquette. In Riesling, wines with equal sugar/acid ratios can taste sweeter at a higher pH.

Cold Stabilization. Wines with a pH greater than 3.65 should not be cold stabilized. When wines are cold-stabilized, the goal is to precipitate potassium bitartrate crystals so that they don’t fall out of solution in the bottle. Above pH 3.65, this salt acts like an acid. So, by removing an acid from the solution, it causes your pH to increase. However, if the wine’s pH is LESS THAN 3.65, cold stabilization will help to LOWER your pH. Below this point, potassium bitartrate acts as a base, so removing from solution causes the solution to become more acidic. Pretty cool, huh?

What we were faced with this year. The Marquette grapes that were harvested this year arrived at the winery with a pH of 3.6, but also had a total acidity of almost 1.0%! Knowing that the pH would increase during skin maceration (potassium is extracted from the skins), and again during malolactic fermentation, I acidified the must at harvest with tartaric acid at a rate of 0.2%. This brought the pH below 3.5. During Malolactic fermentation, we saw the pH creep up again to 4.0, so we were forced to once more acidify the wine to make it stable.

So here’s where a decision needed to be made: how much tartaric acid should we add? The total acidity was around 0.65%, which is pretty good for a red wine. Adding too much tartaric acid would make the wine tart and unpalatable. If I was working in a commercial winery, these are the options I’d see:

1) Acidify with Tartaric Acid. Aim to get the pH to 3.8, and hope that the tartaric acid additions didn’t make the wine too tart, then avoid cold-stabilization. A rule of thumb to use when acidifying:  1.0 g/L of tartaric acid will generally lower the pH by 0.1 (this is a guideline, of course… to be accurate, always perform bench trials before making a large addition).

2) Acidify with Tartaric Acid. Aim to get the pH below 3.65 and KNOW the wine was going to be very tart, but then cold-stabilize. With this option, the cold-stabilization will further lower the pH another 0.1 to 0.2 points (depending on the potassium bitartrate concentration). Then, working at a pH of 3.4-3.5, we will have room to remove the tartaric acid using chemical deacidification methods. Chemical deacidification comes with the worry of losing some of the aromatics, so bench trials should be performed to determine the amount of additive works best for the individual wine.

3) Blend the wine with a lower pH wine (of course do bench trials to see if you like the blend). This of course is still an option if you choose option 1 or 2, especially if you find the wine is still too tart. Blending is one of the the real arts in winemaking.

4) Use an anion exchanger. However, while an ion exchanger is available on the commercial scale for wineries, the cost of the equipment isn’t practical unless your last name is Mondavi.

We went with option #2. Since we are an experimental winery, blending is not an option. If I went with the first option, the amount of tartaric acid needed to get the wine under a pH of 3.8 made the wine too tart.  The wines were acidified with 4 g/L of tartaric acid, which brought the pH down below 3.6 (and the TA above 1.0%), and they are now chilling  at 28°F. I’m hoping that cold stabilization removes 1-2 g/L of total acidity, and we can use potassium bicarbonate to remove an additional 1-2 g/L.  In the end, I’m hoping that nearly all of the added tartaric acid that was added to the wine can be removed, and we’ll be left with a wine that has a healthy pH between 3.6-3.8, with a palatable TA around 0.6%.

Katie Cook, Enology Project Leader of University of Minnesota, Horticulture Research Center

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