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Chemical composition analysis and authentication of whisky

Article  in  Journal of the Science of Food and Agriculture · November 2014

DOI: 10.1002/jsfa.6960

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CHEMICAL COMPOSITION ANALYSIS AND AUTHENTICATION OF

WHISKY

Paulina Wiśniewska*, Tomasz Dymerski, Waldemar Wardencki, Jacek Namieśnik

*
p.m.wisniewska@gmail.com

Department of Analytical Chemistry

The Chemical Faculty

Gdansk University of Technology

11/12 Narutowicza St.

80-233 Gdansk, Poland

This article has been accepted for publication and undergone full peer review but has not
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may lead to differences between this version and the Version of Record. Please cite this
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 ABSTRACT

Whisky (whiskey) is one of the most popular spirit-based drinks made from malted or

saccharified grains, which should mature for at least three years in wooden barrels. High

popularity of products usually cause a potential risk of an adulteration. Regarding to that fact

the authenticity assessment is one of the key elements of food product marketing.

Authenticity of whisky is based on the comparison of composition of this alcohol with other

spirit drinks. This paper summarizes all information about the comparison of whisky and

other alcoholic beverages, the identification of type of whisky or the assessment of its quality

and finally the authentication of whisky. The work also presents the various analytical

techniques for analyzing whisky such as: gas and liquid chromatography with different types

of detectors (FID, AED, UV-Vis), electronic nose, atomic absorption spectroscopy and mass

spectrometry. In some cases the application of chemometric methods there are also described,

namely: PCA, DFA, LDA, ANOVA, SIMCA, PNN, k-NN, CA, and preparation techniques

such SPME or SPE.

Keywords: whisky, authentication, chromatography, food analysis, e-nose

INTRODUCTION

Whisky (whiskey) is one of the most popular spirit-based drinks. Depending on the region,

whisky is defined differently. According to the European definition of whisky, it is a spirit

drink produced via distillation of mash made from malted grains or from grains which have

been saccharified by the diastase of the malt contained therein. Distillation is conducted at

less than 94.8 % vol. in order to retain an aroma and taste derived from the raw materials

used. Whisky should mature for at least three years in wooden barrels of a capacity not

exceeding 700 liters. The final distillate retains its color, aroma and taste derived from the

production process. Only water and plain caramel (for coloring) can be added to the distillate;

no other colorings and flavorings can be added. Scottish whisky is the most popular whisky

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type. It is produced entirely from malted barley via double distillation in large copper pot

stills. The volatile phenolic compounds, inter alia, cresol and guaiacol that form in roasted

barley are responsible for the specific taste of whisky. Whisky originating from the northern

part of the USA is made from the mixture of corn, rye, wheat, barley and other grains. It is

aged in oak barrels for at least two years 1-4.

Allegedly, whisky originated in Ireland where local monks were already producing distilled

alcohol known in Latin as aqua vitae (translated to Gaelic as uisge beatha) in the 7th century.

It was a mixture obtained via distillation of fermented fruits, and used for medicinal purposes

only. In the 17th century, the shortened name uiskie started to be used, while in 1715, the

name was changed to whiskie. The present-day name “whisky” was established in 1736. In

the 9th century, the Irish monks and their medicinal alcohol reached Scotland. Information

about the water of life made from barley appeared in the mid-16th century. At the turn of the

18th century, the British Parliament taxed the production of whisky, which resulted in a

decrease of legal production and, obviously, an increase in illegal production of this spirit.

These circumstances stimulated the development of diverse whisky types produced by small

camouflaged distilleries, and the use of traditional recipes passed on through the Scottish

clans. As a result of this natural diversification, three types of whisky exist presently, i.e.

blended whisky, grain whisky and malt whisky. Blended whisky, produced via mixing of

grain whisky and single malt whisky, is represented by the brands such as, Johnny Walker

and Ballantine's. Grain whisky is made from the mash consisting of different grains, mostly

of barley, wheat and corn. It is produced via continuous distillation in a column still.

Actually, the only difference between grain whisky and vodka is that the former has to be

aged for three years in an oak barrel. Grain whisky made from one type of grain, so-called

single grain whisky, is also produced. In this case, either malted or unmalted barley can be

used. Malt whisky is made from malted barley. Its distillation takes place in copper pot stills,

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followed by maturation in oak barrels usually for over 8 years. Malted whiskies can be

divided into two groups, i.e. single malt whisky (malted whisky originating from one

distillery) and vatted malt whisky (a blend of single malt whiskies originating from different

distilleries) 5.

This article presents the methods for analyzing whisky composition which also enable its

authentication. The chemical composition analysis can be conducted be means of, inter alia,

chromatography and spectrometry as well as other techniques. The application of the

aforementioned methods enable authentication, the determination of exact composition, and

quality evaluation of whisky. Thanks to these procedures, it is possible to remove falsified

products from the market, and to select a whisky which will fulfill expectations.

ANALYSIS OF WHISKY COMPOSITION

Each spirit has a characteristic aromatic profile, which influences the processes of

fermentation, distillation and storage as well as the selection of an appropriate raw material.

The compounds responsible for the aroma are, e.g. fusel alcohols, fatty acids and esters.

Spirits are a diverse group therefore in order to determine individual qualities of a given

alcoholic beverage, it is necessary to determine its composition. Studies on the exact

composition of whisky are mainly performed by using gas chromatography. Such research

allows for finding characteristic compounds and defining aroma profiles, which can then be
6
used for defining the quality and authenticity of the tested whisky. Fitzgerald et al.

analyzed Scotch and Irish whiskies by means of gas chromatography coupled with a mass

spectrometer (GC-MS). Samples were prepared by solid-phase microextraction (SPME).

Solid-phase microextraction (SPME) is based on the sorption of small amounts of samples

onto a thin cylindrical layer of stationary phase coating the glass or quartz fiber. The fiber is

placed inside the rust-free tube that is located in the syringe needle. Such set-up enables the

mass exchange during the enrichment and release of the adsorbed compounds, and prevents

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clogging. The extraction can be conducted by immersing the fiber directly in the liquid (DI –

SPME) or by placing it in the head space above the liquid or solid sample (HS – SPME) 7, 8.

The applicability of three fiber types was tested, namely, PDMS-DVB, CAR-PDMS and PA,

the latter being the most suitable for the procedure. Seventeen compounds were selected for

the analysis, including fusel alcohols, acetates and esters; however, the concentration levels

of six of them turned out to be below their detection limits in all samples. Despite this

situation, the applied technique was useful for quantitative analysis of the selected

compounds in whisky samples 6. This research allowed for defining a useful method, which

can then be used for analyzing compounds characteristic of whisky. Poisson and Schieberle 8

analyzed the composition of American Bourbon by applying High Resolution Gas

Chromatography – Olfactometry (HRGC-O). This technique allowed the detection of 23

active aroma substances. Based on the review of previously published data, it turned out that

13 of these compounds were never detected before, i.e. ethyl (S)-2-methylbutanoate, (E)-2-

heptenal, (E,E)-2,4-nonadienal, (E)-2-decenal, (E,E)-2,4-decadienal, 2-isopropyl-3-

methoxypyrazine, ethyl phenylacetate,

4-methylacetophenone, α-damascone, 2-phenylethyl propanoate, 3-hydroxy-4,5-dimethyl-

2(5H)-furanone, trans-ethyl cinnamate, and (Z)-6-dodeceno-γ-lactone. Thanks to the use of

olfactometry, it was possible to assign concrete aromas to the identified compounds 9. The
10
next article by Poisson and Schieberle was a continuation of previous research and

included the quantitative analysis of 31 compounds selected from among the substances

which had already been detected via two-dimensional high resolution gas chromatography

coupled with a mass spectrometer (TD-HRGC-MS). The results obtained were used to

formulate the aroma characteristic for American Bourbon by mixing 26 compounds at

10
specified concentrations with the solution of water and ethanol . An aroma profile of this

kind can be used to differentiate American Bourbon from other kinds of whisky.

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Multidimensional gas chromatography coupled with mass spectrometry and olfactometry
11
(MDGC-MS-O) was used by Wanikawa et al. to identify green note compounds in malt

whisky. These compounds are characteristic of some kinds of whisky, which means that they

can be helpful in the assessment of the authenticity of tested products. The applied technique

allowed the detection of two aldehydes (i.e. E-2-nonenal and E,Z-2,6-nonadienal) and three

alcohols (1-octen-3-ol, 4-hepten-1-ol, nonan-2-ol) which are responsible for the green note

aroma. It was demonstrated that the green note whisky contains more aldehydes and nonan-2-
11
ol compared to other whisky types . Besides the attempts of identifying the exact

composition of the volatile fraction in whisky, the investigations of chosen groups of

compounds and single compounds were conducted. It is noted that some groups of

compounds have greater influence on the aroma of whisky. Esters are an example of such a
12
group. Camp et al. used two-dimensional gas chromatography coupled with the mass

spectrometer (GC-GC-MS) in order to analyze ethyl esters in

12
whisky . These compounds mainly form during the fermentation and aging processes.

Esters are characterized by intense aroma and the low value of odor detection threshold.

Depending on the concentration of esters, they may have a positive or negative effect on the

aroma of an alcoholic beverage. For example, ethyl acetate at high concentrations gives

solvent-like or vinegar note to the final product, while at low concentrations, it softens the

sharp aroma of other beverages 13. Because of that it is of utmost importance to quantitatively

analyze this group of compounds. In order to preconcentrate the analyzed compounds in

samples, solid phase extraction was used (SPE) 12.

14
Haloanisoles were another group of compounds studied by Campillo et al. . These

compounds form in whisky aging in oak barrels. Their monitoring may enable an assessment

of the ageing process and, as a result, verification of the authenticity of the age of whisky.

The study results demonstrated that solid-phase microextraction coupled with gas

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chromatography and atomic emission detection (SPME-GC-AED) is a perfect system for
14
monitoring the contents of 12 selected haloanisoles . A class of phenols is among the

compounds investigated in whisky. This is connected with their different contents in

individual types of whisky. Twelve substances belonging to phenols were analyzed in the

samples of whisky originating from Scotland (15), Ireland (1), USA (4), Canada (1), Japan

(5), Spain (1), Argentina (1), New Zealand (2) and India (1) by using GC-MS. As a result,

2,4-dimethylphenol was detected in the volatile fraction of whisky for the first time. The

main difference between the samples from specific countries was in the concentration of o-,

m- and p-cresol. The highest concentration of these compounds was determined in whisky

from Scotland. Moreover, the samples of Scottish, Canadian and Bourbon whisky were

compared. The highest concentration of phenols was found in Scottish whisky, while the

lowest one, in Canadian whisky. On the other hand, the highest concentration of eugenol was
15
observed in Bourbon whisky . It is concluded from this article that an analysis of the

presence of selected phenols and their total amount can be used for distinguishing whisky

according to its geographical origin. Apart from selected groups, also individual compounds

are analyzed with the presence being characteristic of selected spirits. Among the analyzed

single compounds were γ-lactone 16, ethyl carbamate 17, 18 and methanol 19. Lactones are well-

known organic compounds which display diverse biological effects, e.g. anticancer, antiviral,

antibacterial and anti-inflammatory activities, etc. Lactones have also been recognized as the

components of taste and aroma in alcoholic beverages, mainly in whisky, wine and cognac.

The characteristic odor of the famous Japanese sake results from the presence of sotolon 20. γ-
16
lactones are responsible, to a large extent, for the aroma of whisky. Wanikawa et al.

conducted a study whose aim was to identify the compounds responsible for “sweet” and

“fatty” aromas in malt whisky from Scotland. The analysis was performed by using GC-MS

and GC-O. It has been determined that γ-decalactone and γ-dodecalactone are responsible for

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 16
“sweet” and “fatty” aromas, respectively . Ethyl carbamate is another compound which

should be analyzed in alcoholic beverages. This is needed due to its influence on the quality

of the product. Ethyl carbamate (EC) is a natural compound that occurs in fermented foods

and alcoholic beverages such as, bread, yoghurt, soy sauce, wine, beer, and particularly in

spirits made from stone fruits and stone-fruit pomace (e.g. cherry, plum, mirabelle plum and

apricots). Research has demonstrated that ethyl carbamate has a carcinogenic effect in

laboratory animals. The International Agency for Research on Cancer has classified EC as

possibly carcinogenic to humans 21, 22. Ethyl carbamate was analyzed in alcoholic beverages,

inter alia, in whisky by means of gas chromatography coupled with tandem mass

spectrometry (GC/MS-MS). The technique was tested for its suitability to determine low

concentrations of EC. Five samples of whisky were analyzed; the detected level of ethyl

carbamate varied from 60 to 330 ppb 17. EC was also analyzed in Scottish whisky by using

GC-MS. Five types of blended whisky, including two deluxe and two malt whiskies, were

investigated. A total of 229 samples were processed. The mean concentrations of ethyl

carbamate in specific whisky types were similar, except for deluxe whisky which had higher

EC content 18. Methanol is similar in this respect. This is also a toxic compound, which must

be monitored due to its influence on the quality of whisky. The presence of methanol was
19
investigated by means of an electronic nose . The electronic nose is an analytical device

used for the fast detection and identification of odorant mixtures; its mode of operation

mimics the human sense of smell. The electronic nose employs specific chemical sensors

which generate a characteristic aroma profile, a so-called fingerprint, in response to being

exposed to the investigated gaseous mixture. The identification of mixture components is

based on the comparison with reference profiles 23. Wongchoosuk et al. 19 used the electronic

nose equipped with carbon nanotubes (CNT) to investigate the samples of whisky tainted

with different amounts of methanol. Principal component analysis (PCA) was used to analyze

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the obtained data. The principal component analysis (PCA) is based on transformation of the

original variables to new variables. The PCA provides a rotation of the coordinate system to

maximize the variance of the all the coordinates. The PCA is mainly used to model, compress
24
and visualize data . The applied method allowed the graphical identification of methanol-

free whisky and whisky containing methanol at four different methanol concentrations.

Distinguishing among specific methanol concentrations in the samples was also possible
19
thanks to the application of PCA . Besides the concentrations of organic compounds, the

contents of zinc, lead and copper ions was also determined. The presence of inorganic

compounds is tested in connection with the quality of whisky as they can also influence its

aroma. Anodic stripping voltammetry (ASV) and atomic absorption spectrometry (AAS)

were employed in this study. In the case of whisky samples, ASV turned out to be a more

suitable method because it allowed the detection of all analyzed ions in all samples 25.

A COMPARISON BETWEEN WHISKY AND OTHER ALCOHOLIC BEVERAGES

Being one of the most popular alcoholic beverages, whisky is often compared with other

known spirits in relation to chemical composition. Such studies aim at establishing whether

different types of spirits can be identified by means of analytical techniques. For example,
26
Cardeal and Marriott describe how cachaça, whisky, rum, vodka, gin, tequila and selected

liqueurs were identified by using two-dimensional gas chromatography. The specification of

compounds present in the sample matrix was prepared for cachaça and rum only. Whisky and

other spirits were compared based on the obtained chromatograms. In comparison to other

spirit-based beverages, whisky and vodka had the poorest chromatographic profiles.

Compounds belonging to alcohols, aldehydes, ketones, terpenes, aromatic compounds, esters

and acids were detected in the samples of whisky. The chromatogram representing whisky is
26
very poor in comparison to other obtained chromatograms . The electronic nose was also

used to compare different alcoholic beverages 27. There are electronic noses which combine

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the features of fast gas chromatography with the properties of an electronic nose. One

analysis conducted with such device supplies concurrent information about the sample

composition and the profiles of volatile fractions. Thanks to this, complete information about

the similarity between the given sample and reference sample is obtained. The electronic nose

coupled with fast gas chromatography was used to distinguish among vodka, tequila, whisky,

beer and wine. The statistical analysis was performed by using principal component (PCA)

and discriminant function analysis (DFA). Discriminant function analysis is used for

determining which variables allow for the best division of a given group of cases on naturally

occurring groups. Discriminant function analysis is used for classification of samples to

28
previously defined groups . The DFA method gave better results because it allowed for

distinguishing the types of alcoholic beverages, including four whisky brands 27. Apart from

comparing alcohols in relation to entire matrices, research was also conducted as regards the

comparison of the content of only some groups of compounds. Ng et al. 29 analyzed selected

acids and phenols (a total of 19 compounds) in whisky and cognac samples by means of GC-

MS. Moreover, five compounds, i.e. vanillin, syringaldehyde, coniferaldehyde, gallic acid

and vanillic acid were determined in samples of spirits of different age. In the case of Scotch

whisky, the chosen samples were 12, 17 and 30 years old. The other sampled whiskies were 6

and 12 years old. In general, the samples of oldest whiskies contained the highest

concentrations of the analyzed compounds. However, in the case of Scotch whisky, one

sample of 17-yr old spirit has lower concentration of coniferaldehyde than that measured in

the sample of 12-yr old spirit. This indicates that the relationship between the age of whisky

and the content of phenolic compounds is not a simple one 29.

IDENTIFICATION OF WHISKY WITH REGARD TO ITS TYPE, QUALITY, BRAND

AND ORIGIN

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Due to the high diversity of alcoholic products, the assessment of whisky with regard to its

brand, quality and origin is necessary. The study conducted by Lehtonen et al. 30 by means of

GC-FID and UV-Vis can serve as an example here. The obtained data were analyzed by PCA

method. The investigations were conducted twice by using different UV-Vis techniques. At

first, HPLC with UV-Vis detection was applied; the absorbance was measured in the

wavelength range from 220 to 520 nm. The concentrations of propanol, isobutanol, 2-methyl-

1-butanol and 3-methyl-1-butanol were determined by means of GC-FID. The samples of

whisky originating from Canada (2), Finland (3), Ireland (1) and Scotland (8) were analyzed.

Besides whisky, the samples of rum and brandy were also investigated. The results of UV-

Vis measurements did not supply sufficient information to distinguish among the whisky

samples with regard to the country of their origin. The second set of measurements

encompassed the absorbance determinations at a wavelength of 380, 440 and 500 nm made

with a spectrophotometer, and the concentration measurements of the aforementioned

compounds and methanol. The samples of whisky from Canada (2), Ireland (10) and Scotland

(15) were analyzed. As in the previous case, the UV-Vis analysis alone was not sufficient to

distinguish among the processed samples. This has become possible thanks to the application

of PCA to the results of GC-FID analysis 30. Gas chromatography combined with numerous

chemometric analyses is used for the analysis of whisky according to its geographical origin.

Three types of whisky, i.e. Scottish, Irish and Bourbon were distinguished by means of GC-
31
MS and different statistical methods. González-Arjona et al. stated that the best results

were achieved with kNN, PDA, MLP and PNN methods. The kNN algorithm belongs to the

group of algorithms, in which the description of the classifier's target function is not

performed during the classifier's training, but at the stage of assigning an object to the

specific classes. The underlying principle of the classifier's operation is that the object

belonging to a specific class has in its close proximity other objects belonging to the same

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class. Classification in performed by comparing the fitted object to all objects stored in the

training set and then choosing from among the key defined k objects that are most alike 32, 33.

Artificial neural network involving multilayer perceptrons (MLP) is a multilayer one-

directional neural network. They are the most frequently used kind of ANN. An artificial

neural network mimics a biological neural network, which collects and transfers signals to the

central nervous system, processes the data, and makes specific decisions depending on the

identified objects. The basic elements of artificial neural networks are artificial neurons 33, 34.

Probabilistic neural networks (PNN) are a kind of artificial neural networks capable of

independent learning. When a new teaching standard, which may introduce additional

information of very important nature, becomes available, it is not necessary to start the

learning process from the beginning. It is possible to introduce such a new standard directly

into the network in the form of another radial neuron. This feature is very significant as it
32,
allows the continuous operation of a PNN without any breaks for a long learning process
33 35
. The same whisky types were analyzed by González-Arjona et al. by means of GC-MS.

The data were processed by PCA and CA methods. Cluster analysis is a method, which

allows for grouping elements described by more than one feature into relatively homogenous

classes. The most important part of CA is the formation of clusters, that is, the sets of objects

where the similarity between any two objects from the same set is higher than that between

any other object from the same set and any object not belonging to the set. The clusters do

not overlap, i.e. none of the objects can belong to more than one class. The clusters are

separated by a precisely determined distance, which can be defined in a number of ways 33, 36.

The contents of 1-propanol, 2-methyl-1-propanol, 3-methyl-1-butanol and 2-methyl-1-

butanol were determined in the samples of 12 Irish whiskies, 20 Bourbons, and 26 single malt

Scottish whiskies. Thanks to the combined use of GC-MS technique and PCA method, it was

possible to distinguish among all the analyzed samples. Irish whiskies were the most compact

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group in the PCA graph which demonstrates that the four compounds selected for the analysis

are enough to distinguish Irish whisky from other whisky 35. Apart from verifying, whether it

is possible to define the county, from which whisky originates, tests were performed aimed at

verification as to whether it is possible to determine the region of origin of a given whisky.

Mignani et al. 37 analyzed 18 samples of Scotch whisky, which included 15 samples of single

malt whisky (10 samples from the uplands, and six samples from the islands) and three

samples of blended whisky. Each analyzed whisky was of different brand identity. The

samples were investigated by means of optical spectroscopy, while the obtained data were

analyzed by PCA and LDA methods. Linear Discriminant Analysis (LDA) is a statistical

method, which allows division into border areas by means of linear functions and works well

in data analysis. This is one of the data classification methods. Such methods are aimed at

determining class allocation of other tested objects described by the same or similar chemical
33, 38
structural features . The applied methodology allowed distinguishing among various

whisky types, i.e. blended whisky was distinguished from single malt whisky. However, it

was problematic to divide the samples based on the region of their origin. In the case of

whiskies originating from the uplands and islands, one sample in each region poorly fitted to

the model 37. In order to determine the region of sample origin and sample type, Adam et al.
39
attempted to use atomic absorption spectroscopy (AAS). Thirty-five samples of whisky

were analyzed; the samples differed with regard to distillery, the region of origin, whisky

type and vintage. The contents of copper, zinc, lead, nickel, iron, calcium, magnesium and

sodium were determined in the samples. The obtained data were statistically analyzed by

means of CA. It was demonstrated that the origin of whisky cannot be identified based on the

contents of the aforementioned compounds. However, malt whisky had much higher

concentration of copper than blended Scotch and pure grain whisky. This finding shows that

a simple analysis of copper content may allow distinguishing malt whisky from other whisky

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 39
types . Various kinds of whisky and brandy were compared based on the ratio

of 2-methylbutanol to 3-methylbutanol by using the GC-FID technique. The analyzed whisky

samples included blended whisky (14), malt whisky (14), Bourbon (2), Canadian whisky (2)

and whisky originating from Denmark (3). The highest and the lowest content of both

analyzed compounds was determined in Bourbon and Danish whisky, respectively. The ratio

of 2-methylbutanol to 3-methylbutanol ranged from 0.32 to 0.44. Only two samples had

ratios of 0.32 and 0.33, while the ratio values for the remaining samples were greater than

0.36. This allowed distinguishing whisky from brandy because the ratio values in brandy
40
ranged from 0.19 to 0.33 . Apart from testing the origin and kind of whisky, tests were

performed to distinguish between whiskies of the same kind produced by various brands.

Three well-known whisky brands, i.e. Black Label, Ballantine's and West Highlands were

analyzed by means of GC-MS, including sample preparation by SPME technique. The

microextraction technique was optimized with regard to the fiber type; CAR/PDMS fiber has

been selected from among the five evaluated fibers. The compounds detected in whisky

samples belonged to monoterpenes, higher alcohols, esters, fatty acids, carbonyl compounds

and phenols. Differences detected between specific whisky brands were mainly of

quantitative nature. In all analyzed samples ethyl esters were the most numerous group of

compounds. In the case of higher alcohols, it was observed that the concentration of 3-

methyl-1-butanol in Black Label whisky was definitely higher than that in other whisky

brands. The concentration of carbonyl compounds showed a similar pattern. The lowest

concentration of terpenes was determined in Ballantine's whisky. By using the sum of the

areas under the peaks attributable to specific compounds, it was possible to distinguish
41
among specific whisky brands . Apart from the aforementioned research, it was also

checked as to whether it was possible to distinguish between whiskies of different quality.

Such tests would be helpful in verifying the authenticity of high-quality whisky, which is

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often counterfeited with poorer-quality whiskies. In order to distinguish among Scottish

whiskies of different quality, a sensory evaluation and various statistical methods (PCA,
42
ANOVA and PLS regression) were employed by Lee et al. . Analysis of variance

(ANOVA) is a parametric tool that allows for comparing more than two groups, which had

been categorized based on one variable (one-way ANOVA). The underlying idea is to

compare the variance of dependent variables within the groups that had been created, based

on the values of independent variables 33, 43. The partial least squares method (PLS) combines

features of principal component analysis and multiple regression. First, a set of latent

variables is distinguished, which explain as much covariance as possible between

independent and dependent variables. Next, at the regression phase, values of dependent

variables are predicted using independent variable decomposition 44. The samples of blended

whisky were divided in the following categories: deluxe (11), standard (22), multiple retailer

(4), and West Highland (3). PLS regression turned out to be the best method for data analysis

because it correctly grouped all types of whisky, except for the West Highland type. The

dominant aroma of Deluxe whisky was described as fruity, buttery, malty and nutty, and also

vanilla, floral, pungent, sweet and smooth. The aroma of retailer whisky was evaluated as

solventy, soapy, rancid, grassy, mouldy, pungent, grainy, oily and spicy. The dominant

organoleptic qualities of standard whisky were characterized as oily, sulfury, rancid, grainy,

smooth, soapy, vanilla, solvent and sweet. West Highlands whisky was described as woody,
42
smoky, spicy, medicinal and sulphurs, mouldy, pungent, soapy and malty notes . Similar

research aimed at distinguishing among blended whiskies of different quality was conducted
45
by Lee et al. . The whisky samples were analyzed by using SPME-HRGC-MS, while the

obtained data were processed with the same statistical methods as before, i.e. PCA, ANOVA

and PLS regression. A total of 38 compounds was analyzed. Deluxe whisky was identified

based on the contents of ethyl hexanoate, ethyl heptanoate, ethyl acetate, ethyl nonanoate,

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ethyl decanoate, isoamyl decanoate and isoamyl hexanoate. The content of acetate esters

(dodecyl and phenylethyl esters, and 3-methylbutyl acetate) was used to identify standard

whisky. In the case of retailer whisky, ethyl hexadecanoate, ethyl octadecanoate, ethyl

tetradecanoate and propyl decanoate were the markers. West Highlands whisky was

identified by the presence of furfural, isobutyl octanoate and ethyl benzoate 45.

AUTHENTICATION OF SCOTCH WHISKY

Scotch whisky the most highly valued of spirits that is preferentially chosen by consumers. It

is produced almost exclusively in Scotland from malted barley or barley; Scotch whisky is

aged in wooden barrels for three years. The most popular scotch brands are Johnie Walker,

Teacher’s, The Famous Grouse, Chivas Regal, Laphroaig, The Balvenie and Ballantine’s.

The name “Scotch whisky” is a geographical indication assigned to Scotland; the term is

protected by international law. Genuine Scotch whisky has to be produced in Scotland

therefore the authentication of this spirit is of utmost importance. Scotch is the most

frequently falsified whisky thusScotch numerous studies on the methods of its authentication

have been published. Parker et al. 46 used gas chromatography-combustion-isotope ratio mass

spectrometry (GC-C-IRMS) to authenticate whisky. Eight samples of popular Scottish

whisky and two samples of other whisky types were compared. The carbon isotopic ratios

were analyzed for selected congeners, i.e. acetaldehyde, ethyl acetate, n-propanol, isobutanol

and amyl alcohol. The plotted graphs allowed distinguishing among the analyzed samples,

and finding the samples of falsified spirits 46. Scotch whisky was also authenticated by means

of GC-MS and HPLC 47, 48. It became apparent that the analysis of higher alcohols is the most

important part of such authentication procedures. Higher alcohols are the most representative
47
group attributable to whisky, particularly n-propanol, isobutanol and amyl alcohol . In the

second article 48, a number of qualities had been defined which scotch whisky should posses.

These qualities include, inter alia, the alcohol content not lower than 40%; methanol content

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lower than 25 g / 100 l; the sum of the contents of n-propanol and isobutanol at least 97 g/100

l; the ratio (sum of 2-methylbutanol and 3-methylbutanol)/ 2-methylbutanol not lower than

1.9 and not higher than 3.5; and the ratio of 3-methylbutanol to 2-methylbutanol not lower

than 2.2 and not higher than 3.5. All the aforementioned properties allow the authentication
48 49
of Scottish whisky . MacKenzie and Aylott decided to check whether the UV-Vis

technique can be used to authenticate whisky produced in Scotland. To this end, 35 samples

were analyzed of which 20 were suspected to be Scottish whisky and the remaining 15

samples to be other whisky types. In order to confirm the UV-Vis results, gas

chromatography was also used as it has been previously assessed as suitable for the

authentication of Scottish whisky. According to chromatographic analysis, only eight samples

were classified as Scotch whisky and one sample was considered suspicious. Based on the

UV-Vis analysis, seven samples were classified as Scotch whisky (agreement with GC

analysis), one as falsified (disagreement with GC), and one sample as suspicious (different

sample than the one pointed to by GC) 49. Ashok et al. and Backhaus et al. undertook the task

of assessing whether near-infrared spectroscopy (NIRS) is suitable for analyzing Scotch

whisky 50, 51. Different brands of Scottish whisky were analyzed with regard to taste, age and

barrels in which they had been aged. The data obtained were processed by PCA and PLS

regression. The spectroscopic spectrum of whisky mainly represents ethanol due to the high

content of this compound in the sample. Besides ethanol, whisky contains other alcohols,

esters, aldehydes and organic acids, called congeners. The presence of these compounds

allows the identification of the brand, age and quality of a given sample. However, it is only

possible based on the comparative analysis of fluorescence background of the spectra. This

technique combined with chemometric analysis enables the fast evaluation of whisky quality.

The samples differing with regard to brand, age and barrel type can be properly grouped by
50
using NIRS and PCA . The falsified Scotch whisky was also detected by employing mid-

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infrared spectrometry. A total of 17 samples analyzed which included falsified and genuine

Scotch whisky. The study concerned the ethanol concentration and colorants used. The

obtained data were statistically analyzed by PCA and PLS regression. Seven samples were

classified as falsified because their ethanol content was below the required standard value of

40%. One sample was on the borderline of statistical significance therefore it had been

temporarily classified as genuine. The next stage of the study dealt with testing for the

presence of commercially available colorants among which only one is authorized. Based on

the obtained results, eight samples were classified as genuine Scotch whisky, while the rest of

the samples were recognized as falsified. A comparative analysis of both data sets

demonstrated that only seven samples fulfilled both requirements and thus could be
52
considered genuine Scotch whisky . As previously mentioned, only whisky produced in
53
Scotland can be called Scotch whisky. Meier-Augenstein et al. undertook the task of

evaluating the applicability of High Temperature Conversion-Isotope Ratio Mass

Spectrometry (TC/EA-IRMS) technique for determining the origin of whisky. To that end,

the samples of water used in the whisky production and genuine whisky from all Scottish

distilleries as well as samples of falsified Scotch, the latter supplied by the Scottish Whisky

Research Institute (SWRI), were analyzed. TC/EA-IRMS allowed for distinguishing between

the falsified and genuine whisky which suggests that the applied analytical technique can be

used for confirming the authenticity of geographical origin in whisky samples 53. Garcia et al.
54
analyzed 80 samples of whisky, namely, 50 samples of authentic brands of Scottish whisky

and 30 samples of falsified Scotch by using Fourier transform ion cyclotron resonance mass

spectrometry (FT-ICR MS). The obtained data were statistically analyzed by the PCA

method. At first, a comparative analysis of authentic whisky brands was performed to

determine whether it is possible to distinguish among them. Two brands, i.e. Buchanan’s and

J&B were found to be easily identifiable. Red Label, Black Label and White Horse were

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located closely together and even slightly overlapping in the graph which can cause problems

with a very precise identification of these brands. The second part of the analysis, described

in the same article, dealt with distinguishing between the authentic and falsified whisky

samples. The application of the FT-ICR MS technique and the PCA method demonstrated

that all authentic whiskies were grouped together in the graph, while the falsified whiskies

were farther away from them. These findings prove that the applied technique is also suitable

for the authentication of Scottish whisky 54. Yet another method capillary electrophoresis was

evaluated as a possible technique for the authentication of Scottish whisky; LC-MS/MS was

employed as a comparative technique in this study. A total of 32 samples was analyzed which

included 10 reference samples, 21 samples of possibly falsified spirits, and one sample of

whisky purchased in the local supermarket. The samples were of different vintage. The

contents of syringaldehyde, vanillin, sinapaldehyde and coniferaldehyde were determined.

For all samples classified as falsified, syringaldehyde, sinapaldehyde and coniferaldehyde

were present at concentrations below the detection limit, while vanillin concentration was
55
lower than in the samples of authentic whisky . The samples of genuine Scottish (11

samples) and American (2 samples) whisky were compared to the falsified Brazilian whisky

(2 samples) by means of electrospray ionization mass spectrometry (EI-MS). The obtained

data were analyzed by discriminant partial least square (D-PLS) regression. The analysis

demonstrated that the used technique allowed for distinguishing among Sottish, American

and Brazilian whiskies. However, a distinction between Scotch blended whisky and Scotch

single malt whisky was questionable 56.

SUMMARY

Whisky, being one of the most popular alcoholic beverages, is researched very often. Such

investigations are conducted as a result of high diversity and widespread production of this

spirit. Scotch whisky is widely appreciated by consumers. Due to this popularity, Scotch is

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the most frequently sold and analyzed whisky type. The aim of the conducted investigations

is to determine the chemical composition of this alcoholic beverage. Besides gaining

knowledge, such research allows for comparing whisky with other popular spirits. This, in

turn, allows determining the specific qualities of whisky for which it is preferentially chosen

by consumers. Due to significant diversity of brands, resulting from the type and quality of

raw materials, production location and production type, scientists often compare certain types

of whisky. The conducted studies also aim at relative quality comparisons and the

determination of features that are characteristic for a given product. Moreover, whisky is

analyzed in order to authenticate it. Because many whisky brands of different quality are

present on the market the occurrence of falsified products, made from substandard raw

materials or by cheaper methods, is frequent. Another issue is aging of whisky. Older whisky

has its own distinctly different taste which translates into different, usually higher price.

Therefore the confirmation of whisky age is of utmost importance. Among the whisky types,

Scotch whisky is falsified most often. Different types of gas chromatography are

preferentially employed to analyze whisky. The more advanced analysis is conducted by

means of two-dimensional gas chromatography, while one-dimensional gas chromatography

is used in the other analysis types. Mass spectrometry, FID and AED are mostly chosen as

detectors. The sample preparation is usually performed by using SPME technique, with

different commercially available fibers. The obtained data are statistically processed by PCA,

PLS regression, ANOVA and DFA methods. Besides chromatographic analysis, other

techniques are also used such as, liquid chromatography, spectroscopy, electronic nose, and

spectrometry. The presently applied methods allowed a relatively good determination of

whisky composition as well as distinguishing whisky from other spirits and falsified whisky.

Thanks to the development of analytical techniques, the acquisition of other interesting

information about spirit-based beverages has become possible. Despite the fact that whisky

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types have been so far researched in detail, the development of chromatographic techniques

coupled with detectors may allow for even more detailed determination of whisky

composition, while the application of analytical devices such as the electronic nose and the

electronic tongue will enable rapid identification of these spirits. Information about markers

characteristic for raw materials and geographic localities of produced whisky are still lacking.

Based on the information reviewed in this paper, the methods described above have proved to

be suitable for analyzing whisky. However, there are still undiscovered areas related to spirit-

based beverages which, when properly researched, would improve the quality of the

produced goods.

Table 1. Examples of analysis of whisky

"Acknowledgments

The authors acknowledge the financial support for this study by the Grant No.

2012/05/B/ST4/01984 from National Science Centre of Poland."

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Table 1. Examples of analysis of whisky

Sample Object of study Apparatus Lit.

American bourbon detection of 23 active aroma substances HRGC-O 9

American bourbon quantitative analysis of 31 compounds TD-HRGC-MS 10

Malt whisky identify green note compounds in malt whisky MDGC-MS-O 11

Scotch and Irish quantitative analysis of the selected compounds GC-MS, SPME 6

whisky

Scotch whisky analysis of ethyl esters GC-GC-MS, SPE 12

Whisky bought in monitoring the contents of 12 selected haloanizoles SPME-GC-AED 14

local market in

Spain

Whisky from 9 analysis of phenols GC-MS 15

countries

Malt whisky from analysis of γ-decalaktone and γ-dodecalactone GC-MS, GC-O 16

Scotland

whisky analysis of ethyl carbamate GC/MS-MS 17

Scotch whisky analysis of ethyl carbamate GC-MS 18

whisky analysis of methanol e-nose 19

whisky analysis of zinc, lead and copper ions ASV, AAS 25

whisky comparison of cachaça, whisky, rum, vodka, gin, GCxGC-TOFMS 26

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 tequila and selected liqueurs

Scotch whisky comparison of whisky and cognac GC-MS 29

whisky distinguishing the types of alcoholic beverages e-nose 27

Whisky from distinguish among the whisky samples with regard GC-FID, UV-Vis 30

Canada, Finland, to the country of their origin

Ireland, Scotland

Scotch and Irish distinguish among Scotch and Irish whisky and GC-MS 31,

whisky and bourbon bourbon 34

blended and malt comparison of whisky and brandy GC-FID 40

whisky, bourbon,

Canadian and

Danish whisky

Scotch whisky distinguishing among various whisky types, i.e. optical 37

blended from single malt spectroscopy

Scotch whisky distinguish among Scottish whiskies of different sensory 42

quality evaluation

Scotch whisky distinguishing among blended whiskies of different SPME-HRGC- 45

quality MS

Black Label, distinguish among specific whisky brands GC-MS, SPME 41

Ballantine's and

West Highlands

Scotch whisky samples differing with regard to brand, age and NIRS 50

barrel type

Blended, malt and determine the region of sample origin and sample AAS 39

grain whisky type

Scotch whisky distinguishing among the analyzed samples, and GC-C-IRMS 46

finding the samples of falsified spirits

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 Scotch whisky authentication of Scottish whisky GC-MS 47,

48

Scotch whisky authentication of Scottish whisky UV-Vis 49

Scotch whisky detection of falsified scotch whisky mid-infrared 52

spectrometry

Scotch whisky determining the origin of whisky TC/EA-IRMS 53

Scotch whisky authentication of Scottish whisky FT-ICR MS 54

Scotch whisky authentication of Scottish whisky Capillary 55

electrophoresis

Scotch, American distinguishing among Sottish, American and EI-MS 56

and falsified Brazilian whiskies.

Brazilian whisky

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