Odorants comprising the hop aromas of beers were examined. Strongly hopped beers with Saazer, Hersbrucker, and Cascade hops were compared with unhopped beer by gas chromatography-olfactometry (CharmAnalysis) and sensory evaluation. Twenty-seven odorants were revealed as hop-derived, which derived either directly from hops or via metabolization, and 19 components were identified. Of the components, linalool, geraniol, ethyl 2-methylbutanoate, ethyl 3-methylbutanoate, and ethyl 2-methylpropanoate were determined as odor-active components from their Charm values and aroma values. The muscat-like aroma of Cascade beer and the spicy aroma of Hersbrucker beer were predominant in sensory evaluation, and the contributors to these characteristics were investigated.
Hop aroma components, which mainly comprise terpenoids, contribute to the character of beers. However, pretreatments are necessary before analyzing these components because of their trace levels and complicated matrixes. Here, the stir bar-sorptive extraction (SBSE) method was used to detect and quantify many terpenoids simultaneously from small samples. This simple technique showed low coefficients of variation, high accuracy, and low detection limits. An investigation of the behavior of terpenoids identified two distinct patterns of decreasing concentration during wort boiling. The first, which was seen in myrcene and linalool, involved a rapid decrease that was best fitted by a quadratic curve. The second, which was observed in beta-eudesmol, humulene, humulene epoxide I, beta-farnesene, caryophyllene, and geraniol, involved a gentle linear decrease. Conversely, the concentration of beta-damascenone increased after boiling. As the aroma composition depended on the hop variety, we also examined the relationship between terpenoid content and sensory analysis in beer.
Contributions of hop-derived thiols were examined. Extremely strong fruity, black currant-like aromas were detected in beers hopped with some U.S. cultivars. 4-Mercapto-4-methylpentan-2-one (4MMP) was supposed to be the main contributor to the fruity aroma, and the contents between cultivars were investigated. In hop pellets, a negative correlation between 4MMP concentration and copper ion content in hops was observed. 4MMP was detected only in U.S., Australian, and New Zealand cultivars, but no European ones, which are treated with copper-containing fungicides (Bordeaux mixture) and therefore have a high content of copper ions. The 4MMP content was highest in Simcoe cultivars, followed by Summit, Apollo, Topaz, Cascade pellets, and also differed between crop years. It was indicated that most 4MMP exists freely in wort or in hop pellets with only small amounts formed from precursors and that the amounts increased during the fermentation process.
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