Why dry hopping may lower iso-alpha acids but boost bitterness

Recent research related to hops and brewing is not making life easier for the people who write brewing software.

Exhibit A: A peer-reviewed paper in the Master Brewers Association of the Americas Technical Quarterly titled, “Humulinone Formation in Hops and Hop Pellets and its implications for Dry Hopped Beers.” (A condensed version of the results of the S.S. Steiner experiments described in the Technical Quarterly is available at the Hopsteiner website.)

Exhibit B: Research going on at Urban Chestnut Brewing in St. Louis related to the impact of dry hopping on pH, then the impact of pH on perceived bitternes.

We’re not talking about changes in International Bitterness Units (IBU) that result from dry hopping, so I pretty much made up that part about problems for brewing software. But the changes in bitterness are real. So ripped from the headlines:

– Humulinones are formed by the oxidation of alpha acids within the hop. They are not a recent discovery, but there was little reason to pay attention to them before brewers began dry hopping at the rate some do today. Yes, you may blame IPAs.

– They are about two-thirds as bitter as alpha acids that are isomerized by boiling (becoming iso-alpha acids, the primary bittering component in beer), but — here is the key — they are more soluble and will dissolve into beer during dry hopping to increase bitterness.

The devil is in the details:

– Baled hops (which is what almost all brewers previously used) contain less than 0.3% w/w (which basically means by weight), but the concentration can increase to .5% w/w after hop pelleting.

– Hops with a higher hop storage index (HSI – and when that is higher it means the hop loses its alpha acids more quickly) have a higher concentration of humulinones. This is variety dependent.

– Comparing a low-IBU beer to a high-IBU beer in order to understand the solubility characteristics of humulinones produced a surprising result. Increasing the dry hopping dose from 0 to 0.5, 1.0, and 2.0 pounds per barrel resulted in progressively lower iso-alpha acid concentrations, from 48 to 39, 35, and 30 ppm, respectively. “This significant loss in bitterness was offset, however, by the large increase in humulinones that dissolved in the beer.”

And the bitterness was different. I had to read this explanation slowly (I could feel my lips move): “Sensory evaluation of a very low IBU beer spiked with 22 ppm of humulinones was compared with the same beer spiked with 14.5 ppm of iso-alpha acids. The bitterness intensity of the two beers appeared to be similar, confirming that humulinones are about 66% as bitter as iso-alpha acids. The bitterness profile of the humulinone beer, however, appeared smoother, and there was less lingering on the tongue than with the iso-alpha acid beer. This smooth bitterness makes sense given humulinones are more polar than iso-alpha acids and should therefore not stick or linger on the tongue as long as iso-alpha acids.”

Moving on to pH.

Kurt Driesner, quality assurance manager at Urban Chestnut, discussed some of the early results of the brewery’s research at a MBAA meeting at UCB last month. Expect more information in a few months, but right now: typical dry hopping at UCBC increases pH between 0.1 and 0.25 units; preliminary data suggests that every 0.1 increase in pH is equivalent to a 2 IBU increase in perceived bitterness; and the perceived difference can be observed through pH adjustments independent of any dry hop addition.

S.S. Steiner also observed that pH increased as the dry hop dosage increased, so took five commercial beers with different IBUs and different pHs and dry hopped them with with Cascade hop pellets. The results showed that regardless of starting IBU or pH dry hopping had a linear impact on pH, with the pH rising by about 0.14 units per pound of hops used per barrel.

8 thoughts on “Why dry hopping may lower iso-alpha acids but boost bitterness”

  1. Amazing info, Stan. I miss your regular blogging, and this is a great reminder of why. Apropos of my recent AAB post, I’m now reconsidering whether that perceived bitterness really does come (or all come) from higher-that-expected post-kettle utilization. This technique is almost always conjoined with dry-hopping, so maybe brewers have misidentified the key causal agent for unnexpectedly high BUs.

    Fascinating.

    • So you are shaming me into posting more often ;>)

      When the IBU measurement was created/agreed upon most brewers used baled hops as opposed to pellets, they were not stored as carefully (cold) as today, there were no hops with the alpha and oil levels of today, alpha/beta ratios were lower, and – as you wrote about in the magazine and online – breweries make a heck of a lot more late and post-fermentation additions. Might be time for a new formula.

  2. “So you are shaming me into posting more often.” Yes! Was that unclear?

    I’m sure you’ve written about it somewhere, but isn’t there a “total bitterness” calculation some breweries do instead of IBUs? I ran across that recently, but my leaky old brain has forgotten from where.

    • I’ve talked to brewers who have have done of in-house reconfiguring, but no formal formula (trying saying the three comes quick after a couple of beers).

  3. Are humulinones picked up by IBU testing? If dry-hopping increases humulinones, but decreases iso-AA concentrations, what would the net effect be on IBU’s measured by spectroscopy?

    • Sorry not to get to this quicker. Humulinone has an IBU spectrophotometric response factor similar to iso-alpha-acids.

      “That means, for example, if one performs the spectrophotometric IBU test on the 2 lb/bbl dry hopped beer the instrument results would measure just under 57 IBU for 27 ppm of humulinone + 30 ppm of iso-alpha-acids (not taking into account other IBU absorbing compounds); however, the organoleptic bitterness will taste more like 47 IBU beer (27 ~ 0.66 + 30), or about 17% less bitter than the instrument results would suggest.”

      • Thanks for the response, Stan!

        Has there been any testing to determine if more humulinone is retained from whirlpool additions compared to boil additions? I’ve been noticing that my beers with extensive whirlpool additions seem to have a smoother bitterness than those that get the majority of their bitterness from traditional 60-minute additions. I have also noticed that the bitterness seems to dissipate from the tongue a lot sooner in these examples as well.

        I had a beer with only whirlpool and dry hop additions measure 98 IBU’s in the lab, but tasted a lot lower to my palate. I’m guessing that humulinone was probably a large factor in that experience.

        • Eric – Haven’t seen anything related to humulinone and whirlpool hops. It would be interesting to see the HPLC analysis for that beer.

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