Tag Archives: defects

Say “Cheese”! Isovaleric acid in beer.

Cracking cheese, Gromit!

Have you ever smelled cheese in your beer? How about dirty sweatsocks? It’s more common than you may think. If you’re a homebrewer and you don’t use your hop supply as fast as you should, or if you store them improperly, you may be familiar with this aroma. This is isovaleric acid, and it’s a short-chain fatty acid commonly found in cheese, the valerian herb, foot odor, and sometimes beer. Now that’s an interesting selection of sources!

The commonly accepted threshold for isovaleric acid is about 1ppm, but like most other aromatic compounds, this can vary greatly depending on your genetics. This brief article gives some information about the genetic component of isovaleric acid receptors, exploring some of the sources of variability in how subjects perceive this compound. One of the more interesting things mentioned is that its detection threshold can apparently differ between individuals by up to 10,000 times. Personally, I think my nose has what I call an “acquired anosmia” to this compound. To be anosmic to a particular compound means you can not detect it at any concentration. While my case isn’t that dramatic, I think my sensitivity has dropped due to being frequently exposed to the purified compound when I spike it into my samples (despite using a fume hood and taking protective measures, it’s still possible to get it on you). If you get this stuff on your hands, you’ll stink for the rest of the day, if not longer. For this reason, I often have a hard time being able to tell if my spiked samples are at an appropriate level for the panel. Many times, I have to trust my math more than my nose.

So, how does isovaleric acid get into beer? Most of the time, it’s formed when hops get old, particularly when the alpha acids degrade. I’ve discussed hop acids already in the bitterness article, so if you need a quick overview, head over there and it might clarify some things. This image (from the above-linked article) shows the basic structure of the alpha acids (on the left) and the iso-alpha acids (right) that they isomerize into during boiling in the brewing kettle (at which time they become the source of bitterness in beer). Basically, there are 3 main types of alpha acid (and the 3 corresponding iso-alpha acids) and while they have the same basic structure as each other, there are differences at the “R-group” (top right of the molecule in the images). The differences are minor, but these minor differences can be interesting and influential nonetheless. One of these 3 alpha acids (humulone) has an R-group which is called an isovaleryl group. When this alpha acid oxidizes (due to age and/or improper storage), this R-group can be removed from the molecule and becomes flavor-active, leading to the cheesy/sweatsock flavor I’m on about.

Another way isovaleric acid can get into beer is through a Brettanomyces infection. It’s not the most common source in beer, but infection by this yeast genus can produce cheesy aromas, as well as a host of other undesirable flavor-active compounds like acetic acid (vinegar), 4-ethylphenol (bandages), and 4-ethylguaiacol (smoky). Some breweries intentionally “pitch” Brett into their fermentors as they try to achieve a certain flavor profile or match a particular Belgian style, but more often than not a Brett infection is a bad thing. Brett is also used in winemaking to achieve certain flavors, but it can also be a spoilage organism here depending on the intent of the oenologist.

So limiting undesirable isovaleric acid levels in your beer comes down to using fresh and high-quality raw materials (store hops in a cool, dark environment and, if possible, oxygen-free), and maintaining sanitary brewing conditions and using plentiful and healthy yeast to limit the potential for beer spoilage.

Diacetyl – “Who put butter in my beer?”

Diacetyl (dye-assa-TEEL, or dye-ASS-itle) is probably one of the most well-known flavors related to brewing.  It’s buttery aroma is easily recognized at levels above threshold but, as much as is known and recognized about this compound, I’m constantly amazed and disappointed by how much “butter-beer” is still being produced. This post will briefly explore the various ways that diacetyl arises in beer.

Background

Diacetyl (2,3-butanedione) is one of a class of compounds called “vicinal diketones” (VDK). In chemistry-speak, “vicinal” essentially means “adjacent”, and “diketone” means that there are two ketone functional groups (a ketone is an oxygen double-bonded to a carbon in the middle of a carbon chain). If you look at the molecular structure in the link above, you’ll see that it is a 4-carbon chain (hence the “butane” root in the name), and the two ketones are on the vicinal positions of the #2 and #3 carbons (ergo, 2,3-butanedione: two ketones on #2/3 carbons of a 4-carbon chain). The other main VDK in beer is 2,3-pentanedione (pentane – can you guess what this one looks like?), but it is usually found in beer at levels below that of diacetyl.

Diacetyl, as mentioned already, has a buttery or butterscotch-like aroma. Open a bag of microwave buttered popcorn and you’re hit in the face with diacetyl. At very high levels it can even start to affect the mouthfeel of the beer, causing a slick or oily mouthfeel.  The detection threshold of diacetyl in beer is typically between 10 and 40ppb, although I have determined the personal thresholds for 11 of my panelists and they range from 7-190ppb, with an average of about 60ppb. Personally, my threshold is about 20ppb and beers with higher levels are so offensive to me that any beer with detectable diacetyl usually goes down the drain. Many times you may be served a beer which appears to have no hint of diacetyl, but as you work your way down to the bottom of the glass you begin to detect it. This is because the beer is warming up, which allows more diacetyl to volatilize into the headspace of the glass (and your nose). Too many times have I started in on a good and cold beer only to dump the second half because the “Big D” had begun to show its stinky face.

Common levels for diacetyl in beer range from 30ppb to over 1ppm [1]. Until recently, I would have had a hard time believing that there was packaged beer out there with 1ppm diacetyl. That is, until my panel tasted a beer from a local micro-brewery which was so high in diacetyl that we just had to run it through our gas chromatograph to find out how much was actually in there: almost 900ppb. Nearly all of our beers that we make here at The Company are below 30ppb or so, with most falling easily below 20ppb. I would hazard a guess that the big American Lagers/Pilsners are about 10ppb or less, but I don’t know for sure.

There are a few different sources of diacetyl in beer, only two of which are widely discussed.  The first is during fermentation, where it’s created by the brewer’s yeast.   The other well-known source is from bacterial infection.  The third source is probably the least known:  beer aging.  Below, we’ll examine each of these sources.

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