Chapter 11 Production of Scotch and Irish whiskies: their history and ...

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160 T.P. Lyonsreport by Mann (1911) published a few yearslater also quoted values for acidity and levels offurfural, aldehydes, esters and alcohols in Scotchwhiskies imported into Australia.Concentrations of organolepticallyimportant compoundsSince the introduction of GLC into distillerylaboratories, several reviews have beenpublished on the composition of the major flavorproducingcompounds in whiskies (namelyhigher alcohols, esters, carbonyl compounds,organic acids, aromatic compounds) and on theidentification of individual compounds that makeup these fractions. Higher alcohols, which arestill routinely determined with GLC using a polarstationary phase (Aylott et al., 1994), arequantitatively the most important. Scotch maltwhiskies are richest in higher alcohols, withcontents often well over 2 g/L. Free fatty acidsare relatively volatile and make a majorcontribution to the organoleptic qualities ofwhiskies. Concentrations of acids in some Scotchmalt whiskies can be as high as 0.4-1.0 g/Labsolute alcohol (Duncan and Philip, 1966).Roughly comparable concentrations of esters arefound in whiskies, although those produced withpot stills generally have higher concentrationsthan those from continuous stills. Esterconcentrations in Scotch and Irish pot stillwhiskies have been reported in the range of 0.27-0.87 g/L absolute alcohol (Valaer, 1940). Lighterwhiskies contain lower concentrations ofcarbonyl compounds, although theconcentration varies with the brand. Grain whiskymay have as little as 20 mg/l of aldehydes, whilein a mature Scotch malt whisky the concentrationmay be as high as 80 mg/L (Duncan and Philip,1966).Chemical nature oforganoleptically-important compoundsDuncan and Philip (1966) reviewed chromatographicand other methods used to separatethe various organoleptically importantcompounds from whiskies. Even thoughanalytical methods such as capillary column gaschromatography linked to a mass selectivedetector (GC-MS) (Aylott et al., 1994) havedeveloped in terms of sensitivity anddiscrimination, a major problem in analyzingwhisky by GLC is the overwhelmingpreponderance of ethanol and water. Only onevolatile compound, namely isoamyl alcohol, islikely to be present in a concentration exceeding0.01%; while most of the others are present inconcentrations that rarely exceed 50 ppm.Indeed many compounds now understood tohave an important impact on whisky flavor arepresent at ppb levels. Carter-Tijmstra (1986)described a technique for measuring dimethyltrisulfide, a compound with a threshold of only0.1 ppb present in whisky at concentrations below50 ppb. Analyses are most convenientlyconducted on extracted fractions of the differentclasses of compounds. When direct analysis ofwhiskies has been employed, only a limitednumber of components have been determined(Morrison, 1962; Bober and Haddaway, 1963;Singer and Stiles, 1965).Recent developments in headspace analysisusing trapping and thermal desorptiontechniques (Pert and Woolfendon, 1986) haveenabled analysis of the more volatilecomponents of whisky flavor whilst avoidinginterference from high concentrations of othercongeners. Headspace analysis using trap andpurge techniques would now be the method ofchoice for measuring highly volatile sulfurcompounds such as dimethyl trisulfide.Some idea of the variety of compoundsdetected in whiskies came from a compilationof both published and unpublished sources(Kahn 1969, Kahn et al., 1969). Of the some 200compounds listed there are 25 higher alcohols,32 acids, 69 esters and 22 phenolic compounds.Undoubtedly, this list could now be extendedquite considerably. Of the higher alcohols,isoamyl alcohol and optically-active amyl alcoholpredominate, accompanied by lowerconcentrations of isobutanol and n-propanol.Characteristically, there are usually only low
Production of Scotch and Irish whiskies: their history and evolution 161concentrations of n-butanol and secbutanol. Theprincipal organic acid in whiskies is acetic acid,which can account for between 50 and 95% ofthe total content of volatile acids determined bytitration. Of the remaining acids, caprylic, capricand lauric are quantitatively the most important(Suomalainen and Nykänen 1970a). Some of thecharacteristic flavor and aroma of Irish whiskiesmay be attributed to somewhat higherconcentrations of the odoriferous butyric acid.Compared with other types of whisky, Scotchwhisky characteristically contains morepalmitoleic acid (and its ethyl ester) than palmiticacid. Suomalainen (1971) has suggested that thetypical stearin-like smell of Scotch malt whiskymay be attributed to long chain fatty acid ethylesters. It is not surprising to find that ethyl acetateis the major whisky ester in view of theprevalence of acetic acid in the distillate.Concentrations of 95 mg/L have been detectedin a blended Scotch whisky (de Becze, 1967).Other esters such as ethyl caprate are presentin much lower concentrations, on the order of2-10 mg/L. Of the carbonyl compounds,acetaldehyde is the principal componenttogether with a range of other short chainaldehydes. Furfural, with an aroma resemblingthat of grain, also occurs with as much as 20-30mg/L in Scotch malt whiskies (Valaer, 1940).Acrolein, a pungent and lachrymatorycompound, is also present; and it has beensuggested that it may contribute to the ‘peppery’smell of whisky.A variety of other organoleptically importantcompounds has also been detected in differentwhiskies, many of which result from maturing thewhisky in charred oak barrels. Scopoletin andother aromatic aldehydes, including vanillin, weredetected in bourbon by Baldwin and hiscolleagues (1967). These compounds werepreviously identified by Black et al. (1953) inethanolic extracts of plain and charred Americanwhite oak from which the bourbon whiskeybarrels subsequently used for the maturation ofScotch and Irish whiskies are constructed. (Itshould be noted that the US regulations forbourbon whiskey production require that newcharred oak barrels be used for maturation; sothere is a continuous supply of once-usedbourbon barrels that are shipped to Ireland andScotland for re-use.) A lactone dubbed ‘whiskylactone’, also appears in whisky followingstorage in oak barrels. This compound, ß-methyloctalactone,was first isolated from Scotch whiskyby Suomalainen and Nykänen (1970b). It hassince been reported that both cis and transdiastereomers of the compound occur in whisky(Nishimura and Masuda, 1971). Othercompounds detected in whisky include phenols(Salo et al., 1976), glycerol and erthritol (Blackand Andreasen, 1974), pyridine, "-picoline andvarious pyrazines (Wobben et al., 1971).Contribution of compounds to organolepticpropertiesPublished information on compoundsresponsible for the organoleptic qualities ofwhiskies is meagre and very largely confined toreports by Suomalainen and his colleagues fromthe State Alcohol Monopoly in Helsinki, Finland.In order to assess the contributions made bywhisky components to the odor of these spirits,Salo et al. (1972) concocted a synthetic whiskywith components that chromatographic analysishad revealed were present in a light-flavoredScotch whisky. The synthetic whisky was madeusing 576 g of a mixture of higher alcohols, 90mg of acids, 129 mg esters and 17.4 mg carbonylcompounds in highly-rectified grain spirit dilutedto 34 o GL in water that had been ion-exchangedand treated with activated charcoal. This imitationwhisky contained 13 alcohols in addition toethanol, 21 acids, 24 esters and 9 carbonylcompounds. Caramel coloring was used to giveit the color of a distilled and matured whisky.Odor thresholds of the individual compoundsand groups of compounds were determined asdescribed by Salo (1970). Experienced tastepanel participants were easily able to distinguishthe imitation whisky from a blended Scotchwhisky; but when the concoction was mixed withan equal amount of the Scotch, only 6% correct
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Chapter 11 Production of Scotch and Irish whiskies: their history and ...

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