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Application of Gas Chromatography to Analysis of

Spirit-Based Alcoholic Beverages
a a a a
Paulina Wiśniewska , Magdalena Śliwińska , Tomasz Dymerski , Waldemar Wardencki &
a
Jacek Namieśnik
a
Department of Analytical Chemistry, The Chemical Faculty, Gdańsk University of
Technology, Gdańsk, Poland
Accepted author version posted online: 30 Jun 2014.

To cite this article: Paulina Wiśniewska, Magdalena Śliwińska, Tomasz Dymerski, Waldemar Wardencki & Jacek Namieśnik
(2015) Application of Gas Chromatography to Analysis of Spirit-Based Alcoholic Beverages, Critical Reviews in Analytical
Chemistry, 45:3, 201-225, DOI: 10.1080/10408347.2014.904732

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 Critical Reviews in Analytical Chemistry (2015) 45, 201–225
Copyright © Taylor & Francis Group, LLC
ISSN: 1040-8347 print / 1547-6510 online
DOI: 10.1080/10408347.2014.904732

Application of Gas Chromatography to Analysis

of Spirit-Based Alcoholic Beverages


PAULINA WISNIEWSKA,

MAGDALENA SLIWI

NSKA, TOMASZ DYMERSKI, WALDEMAR WARDENCKI,


and JACEK NAMIESNIK
Department of Analytical Chemistry, The Chemical Faculty, Gda

nsk University of Technology, Gda

nsk, Poland

Spirit-based beverages are alcoholic drinks; their production processes are dependent on the type and origin of raw materials. The
Downloaded by [Rutgers University] at 12:11 11 April 2015

composition of this complex matrix is difficult to analyze, and scientists commonly choose gas chromatography techniques for this
reason. With a wide selection of extraction methods and detectors it is possible to provide qualitative and quantitative analysis for
many chemical compounds with various functional groups. This article describes different types of gas chromatography techniques
and their most commonly used associated extraction techniques (e.g., LLE, SPME, SPE, SFE, and SBME) and detectors (MS,
TOFMS, FID, ECD, NPD, AED, O or EPD). Additionally, brief characteristics of internationally popular spirit-based beverages
and application of gas chromatography to the analysis of selected alcoholic drinks are presented.
Keywords: extraction techniques, gas chromatography, spirit-based alcoholic beverages, volatile compounds

Introduction
Spirit-based beverages are alcoholic drinks destined for
human consumption that have specific organoleptic proper-
ties and contain at least 15% ethyl alcohol. Such drinks can
be produced directly or indirectly by the addition of other
spirit-based beverages, ethyl alcohol, or distillate of agricul-
tural origin, other alcoholic beverages, or a nonalcoholic
drink to the spirit-based beverage. Direct production may
include distillation of naturally fermented products with or
without aromatizing substances; maceration or a maceration-
like process for processing plant materials in ethyl alcohol of
agricultural origin, distillates of agricultural origin, and
spirit-based beverages; or the application of aromatizing sub-
stances, sugars, and other sweeteners. There are many catego-
ries of spirit-based beverages with clearly defined
requirements. For example, vodka, whiskey, rum, and
cachaça belong to separate categories based on the produc-
tion type and the raw material used; vodka and whiskey are
produced from grain, while rum and cachaça are from sugar
cane. In addition, some spirit-based beverages are classified
based on their geographical origin as products specific to a
given region.
Due to the large diversity of alcoholic beverages, a number
of articles have been published aimed at investigating the
matrix of such drinks. These studies allowed for a better iden-
tification of the drinks’ composition as well as their authenti-
cation, particularly in the case of alcohols whose
geographical origin has been defined in the standard (Euro-
pean Commission, 2006; Poland, 2002a). At present, gas
chromatography (GC) is most frequently used for analyzing
matrices of spirit-based beverages. This is due to the many
advantages that this technique offers, such as high resolution
and sensitivity, which enable the identification of a large
number of analytes. Moreover, the possibility of coupling
GC to different detectors allows for the application of this
technique to the analysis of a wide spectrum of alcohol prod-
ucts. The vast volume of published articles on related subjects
has inspired us to write a review article that would collate the
maximum amount of information about the usage of gas
chromatography in the analysis of spirit-based beverages.
Sample Preparation Procedures
Depending on the subject of investigation, appropriate sam-
ple preparation is often necessary. The most commonly used
methods of sample preparation in chromatographic analysis
are liquid-liquid extraction (LLE), solid-phase extraction
(SPE), and solid-phase microextraction (SPME) (Barrio-
nuevo and Lanças, 2002).

Address correspondence to Paulina Wi
sniewska, Department of Liquid-Liquid Extraction (LLE)

Analytical Chemistry, The Chemical Faculty, Gdansk Univer-
sity of Technology, 11/12 Narutowicza St., 80-233 Gdansk,
Poland. E-mail: p.m.wisniewska@gmail.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/batc.
The LLE technique is one of the most popular methods of
sample preparation. The condition under which the extrac-
tion can be properly performed is the presence of two phases
that are easily separated by mechanical means after the
 202
finished extraction. The extraction process is based on adding
solvent to the mixture that contains the component to be
extracted (extrahent). The extractant is chosen in such a way
as to secure the highest concentration of extrahent in the sol-
vent and the lowest one in the mixture (raffinate). An equilib-
rium is reached between the two phases. Next, the phases are
separated mechanically (Ebeler et al., 2000). The extraction
is repeated a number of times, and the pooled extracts are
washed with pure liquid that was originally used for dissolv-
ing the sample. The washed extract is dried by applying a dry-
ing agent, e.g., dehydrated sodium sulfate, and then
evaporated (Stepnowski et al., 2010). The main advantages
of this method are simplicity of procedure, low cost of equip-
ment, and the possibility of automating the procedure and
using it to extract samples that are highly contaminated. The
usage of large amounts of expensive, toxic, and highly pure
solvents, and high loss of the obtained material, as well as
a relatively low coefficient of enrichment, are considered
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disadvantageous (Augusto et al., 2000).
Solid-Phase Extraction (SPE)
Solid-phase extraction (SPE) is based on transferring the ana-
lytes from the liquid sample to the solid phase using the
water/solid sorbent partition coefficient for the analyzed
organic compounds (Wasik et al., 2011). The initial develop-
ment of solid-phase extraction techniques started in the 1970s
when durable sorbents became easily accessible. Surface-
modified silicone- and polymer-based materials are applied
as sorbents. It should be remarked that the silicon-based sta-
tionary phases are stable at the pH range between 2 and 7.5.
In an alkaline environment silica gel may dissolve, while
acidic pH may cause the hydrolysis of the bonds between
silane groups and the functional groups modifying the silica
gel (Simpson, 2000). Sample preparation by SPE can be per-
formed in two ways. In one method the analyzed compound
passes through the column, while the remaining substances
are adsorbed by the column packing. This option is used for
high analyte concentrations. In the second method the ana-
lyzed compound is adsorbed by the column packing, while
other substances leave the column; the method is used in
cases when the analyte concentration in the sample is low.
SPE encompasses the following steps:
 Washing of packed column with a solvent that has a higher
value of eluotropic strength than that of the eluent used; in
this way, the substances that may get extracted from ready-
to-use columns (e.g., alkyl phtalates, alkanes, higher
alkenes, silanes, and siloxanes) are removed.
 Conditioning of the column bed, which prepares the sor-
bent surface for an effective analyte isolation and enrich-
ment from the sample.
 Dosing of the analyte-containing sample onto the column
with the solid sorbent.
 Washing out the unbound substances with a small portion
of specifically selected solvent.
 Removing the remnants of solvent by drying in a stream of
air.
P. Wi

sniewska et al.
 Washing out the substances retained by the sorbent.
Organic solvents are mainly used for washing out analytes
from the bed. Instead of washing out, the analytes can be
thermally desorbed or removed by bed mineralization. The
desorbed analytes can be directly introduced into a gas chro-
matograph together with the carrier gas. The disadvantage of
thermal desorption is that its application is limited to sub-
stances that are thermally stable and not too strongly bound
to the adsorbent bed.
SPE has many positive features, inter alia, the possibility
of using this technique in the field; lower usage of solvents
than LLE; the possibility of using SPE for the isolation and
enrichment of volatile and nonvolatile compounds; bypassing
problems connected to emulsification and foaming of the
sample; possible automation of the process; and high selectiv-
ity due to a wide spectrum of solid sorbents to choose from.
Moreover, it is a relatively inexpensive method that can be
performed with simple equipment. The disadvantages of SPE
are high time consumption, necessary bed regeneration
before the next extraction, and clogging of the bed due to the
presence of suspension in the sample (Simpson, 2000).
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 a glass or quartz fiber. The fiber is
placed inside a rust-free tube, which is located in the syringe
needle. Such a setup enables mass exchange during the
enrichment and release of the adsorbed compounds and pre-
vents clogging. The extraction can be conducted by immers-
ing the fiber directly in the liquid (DI-SPME) or by placing it
in the head space above the liquid or solid sample (HS-
SPME). SPME consists of two steps. The first step includes
the partitioning of organic compounds between the station-
ary phase coating the fiber and the matrix. After a specified
time period, the fiber is pulled inside the needle for protec-
tion. Next, the needle is introduced into the injector, and the
fiber is pushed out. Under the influence of high temperature
the partition coefficient of compounds retained in the station-
ary phase changes in favor of desorption to the gaseous
phase, which is a properly selected carrier gas (Augusto et al.,
2000). The released molecules of analyte in the stream of car-
rier gas are dosed onto the chromatographic column. The
extraction efficiency depends on the following factors:
 Type of stationary phase, i.e.,
- Polydimethylsiloxane (PDMS)
- Polydimethylsiloxane/divinylbenzene (PDMS/
DVB)
- Polyacrylate (PA)
- Carboxen/polydimethylsiloxane (Car/PDMS)
- Carbowax/divinylbenzene (CW/DVB)
 Film thickness of stationary phase (7, 30, 65, 85, and
100 mm)
 Sample volume
 Temperature of extraction
 Analysis of Alcoholic Beverages
 Fiber exposure time
 Volume of extraction vial
 Intensity of sample mixing during extraction (Ozcan et al.,
2009).
The advantages of SPME are as follows: possible automa-
tion, the possibility of using portable equipment, simplicity of
performance, relatively low cost, high sensitivity, small size,
and the elimination of solvents; the most important feature is
a relatively short time of sample preparation prior to analy-
sis. In comparison to other techniques, SPME has many dis-
advantages, for example, the partial degradation of
stationary phase during thermal desorption at high tempera-
tures (Augusto et al., 2000).
Stirring Bar Sorbent Extraction (SBSE)
Stirring bar sorbent extraction (SBSE) is based on the adsorp-
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tion of analytes onto a sorbent layer coating the sorptive ele-
ment. In this case, the magnetic stirring bar, which is the
sorbent-coated magnetic rod placed inside the glass housing,
plays the role of a sorptive element (Baltussen et al., 1999).
Polydimethylsiloxane is the most commonly used station-
ary phase because it has specific diffusion-related properties
that allow the analytes to penetrate the entire volume of the
sorbent (Huang et al., 2002). The SBSE technique consists of
the following steps (Ochiai et al., 2011):
 Extraction: the analytes are retained in the entire volume of
sorbent
 Removal of the remnants of the matrix, i.e., salts, sugars,
and proteins, by rinsing with water and careful drying
 Release of analytes from the sorbent by thermal desorption
or solvation in solvent.
The following parameters should be established in order to
secure the proper extraction: sample volume and the volume
of stationary phase, extraction time, stirring intensity, tem-
perature, sample pH, and the type and amount of organic
modifier (Baltussen et al, 1999).
The main advantages of this technique are the possibility
of using PDMS-coated stirring bars multiple times and the
limited use of toxic solvents.
Supercritical Fluid Extraction (SFE)
Supercritical fluid is used as a solvent in supercritical fluid
extraction (SCF) (Augusto et al., 2000). Pure solvent is con-
sidered to be in a supercritical state when its temperature and
pressure is higher than the critical values of both these param-
eters. After these critical values have been exceeded, the sol-
vent properties gradually change. Supercritical fluids are
characterized by viscosity close to that of a gas, their densities
similar to the densities of liquids, and high diffusion capaci-
ties. The density of a supercritical fluid can be manipulated
by changing its pressure and temperature. Usually, supercriti-
cal fluids are nonpolar solvents, therefore they preferentially
dissolve nonpolar substances. Carbon dioxide is the most
203
frequently use solvent (Janiszewska and Witrowa-Rajchert,
2005). Supercritical fluid extraction can be conducted stati-
cally or dynamically. Static SFE consists of placing the liquid
sample in a supercritical fluid and, after a defined period of
time, transferring the fluid together with analytes to the
receiving vessel. Dynamic extraction can be performed by
repeatedly redirecting extrahent back to the sample before it
reaches the receiving vessel, i.e., before the analytes are
extracted from the solution (Lang and Wai, 2001).
The advantages of this method are as follows: the possibil-
ity of adjusting the dissolution of specific components in
dependence on temperature and pressure, the use of nontoxic
solvents, the complete removal of solvent from the extract,
high selectivity, and the possibility of solvent recirculation.
The use of expensive equipment and the costs associated
with energy spent to pressurize the solvent are considered
disadvantageous (Janiszewska and Witrowa-Rajchert, 2005).
Chromatographic Techniques
Chromatography is a technique based on the separation of a
mixture of components or component groups due to the dif-
ferences in the behavior of these substances in a two-phase
system. One of the phases is immobilized (stationary phase),
while the other one moves in a specific direction relative to
the stationary phase (mobile phase). Based on the different
mechanisms of mixture separation, the following types of
chromatographic techniques have been distinguished:
 Adsorption chromatography; liquid is the mobile phase,
while solid with adsorptive properties is the stationary
phase; the separation of a mixture of components is a result
of different coefficients of adsorption.
 Separation chromatography; the mobile phase is liquid,
while another liquid retained on an appropriate carrier con-
stitutes the stationary phase; the separation of components
results from differing coefficients of separation.
 Ion exchange chromatography; liquid is the mobile phase
and the ion exchange resin (bed) is the stationary phase;
the separation of a mixture of components results from dif-
ferent strengths of bonds between these components and
the ion exchange bed.
 Gel chromatography; the mobile phase is liquid, while a
granulated homogeneous swollen gel is the stationary
phase; the component separation is a result of different dif-
fusion capacities into the gel molecules.
Another classification of chromatographic techniques is
based on the separation type, as follows:
 Paper chromatography (PC), in which special absorbent
paper serves as the stationary phase.
 Thin layer chromatography (TLC), where a thin homoge-
neous layer of stationary phase is dispensed onto a glass
plate, or a sheet of aluminum foil or plastic.
 Column chromatography in which a column (mainly made
of glass) is filled with the stationary phase, i.e., adsorbent,
carrier soaked with the liquid stationary phase, ionite or
 204 P. Wi

sniewska et al.

granulated gel, and first the analyzed solution and then the
mobile phase (eluent) is introduced into the column head.
 Gas chromatography, where gas is the mobile phase, while
the stationary phase is placed inside the column.
 Liquid chromatography, in which a liquid flowing continu-
ously under a pressure of up to tens of MPa through a col-
umn constitutes the mobile phase.

Capillary gas chromatography, and specifically its one- or

two-dimensional version, is mainly used for analyzing the
volatile fraction of spirit-based beverages (Witkiewicz and
Hetper, 2001).
One-Dimensional Gas Chromatography
Gas chromatography is an analytical method that allows for
separating complex mixtures as well as for conducting quali-
tative and quantitative analysis of substances that occur
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Fig. 1. Schematic representation of a gas chromatograph: 1. car-
rier gas; 2. flowmeter; 3. injector; 4. column; 5. column oven; 6.
detector; 7. waste; 8. data registration system.
characteristic for too slow sample injection or too large sam-
ple volume being injected (Krawczyk, 1999). In order to
avoid such problems, the liquid or solid sample ought to be

in the form of gas or vapor under analytical conditions. The
separation of the analyzed mixture components takes place
due to the partitioning of these compounds between the
mobile and stationary phases of the system. In gas chroma-
tography the mobile phase is gaseous. Depending on the sta-
tionary phase type, one can distinguish the following kinds of
gas chromatography:
 Adsorption chromatography, where gas is the mobile
phase, a solid with adsorptive properties serves as the sta-
tionary phase, and the separation mechanism is based on
the differences between the adsorption coefficients.
 Partition chromatography, where the stationary phase is
the carrier-bound liquid in which the analytes flowing
through the column get dissolved; the partitioning of sub-
stances occurs due to the differences in analyte-specific sol-
vation in the stationary phase.
vaporized inside the injector in the shortest possible time
period. Therefore the injector temperature is usually set 20 C
higher than the boiling point of the sample components. In
gas chromatography there are four basic types of injectors,
namely, split injectors, splitless injectors (Figure 2), Mega-
bore type direct injectors, and on-column inlet, which delivers
the sample directly into the column. In the case of alcohol
analysis, the split and splitless injectors are usually used, and
often one injector with an appropriate control valve for split-
ting the stream of carrier gas is employed (Grob, 1993;
Krawczyk, 1999).
Split injectors are used for processing samples that contain
high analyte concentrations because only a small sample
volume is injected into the chromatographic column. A large
volume of carrier gas pumped into the injector head under-
goes mixing with the volatile fraction of the sample and then

The separation of chemical compounds by gas chromatog-

raphy is carried out by the following steps: sample evapora-
tion in the injector, separation of mixture components on the
specifically prepared column, and detection of each mixture
component in the detector (Witkiewicz and Hetper, 2001).
A gas chromatograph consists of an injector, column oven,
chromatographic column, and detector (Figure 1).

Injectors
The injector enables the introduction of a sample into a
stream of carrier gas that will transfer the injected material to
the column. Hydrogen, nitrogen, argon, and helium are the
most frequently applied carrier gases. The type of carrier gas
used depends on the detector because gas purity influences
the detector’s performance and the condition of column sup-
port, as both can become disabled by impure carrier gas. The
injector temperature should not be too high because some
analytes are not thermally stable (Barrionuevo and Lanças,
2002). The proper choice of an injector is very important Fig. 2. Diagram of split/splitless injector: 1. septum; 2. septum
because it should provide repeatable sample injections into purge outlet; 3. carrier gas inlet; 4. glass tube; 5. split valve; 6.
the system and prevent the occurrence of fuzzy and asymmet- carrier gas outlet; 7. vaporization chamber; 8. heated metal
rical peaks resulting in decreased separation, which is walls; 9. capillary column.
 Analysis of Alcoholic Beverages
transports it further. The introduced stream of carrier gas
flows through the lined injector and exits through two sepa-
rate outlets. A small volume of carrier gas (1–4 mL/min)
enters the column, while the larger part of it (10–100 mL/
min) exits through a split vent (split outlet). Such partition of
carrier gas enables the smaller portion of the sample to reach
the column and the larger one to be purged. Split injectors
are characterized by high efficiency as well as requiring a
small volume of gas to operate; therefore, these devices are
the ideal solution for columns with small diameters.
Another type of injector used for analyzing alcohols is a
splitless injector. It is applied in cases when the analyte con-
centration in samples is very low or even at trace level. A
basic difference between the splitless injector and split injec-
tor is the volume of gas used. Another difference manifests
itself in the shape of the first peaks corresponding to the early
elution of sample components. Moreover, splitless injectors
are wider because the stream of carrier gas does not have to
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be split. Similar to the aforementioned injector, carrier gas is
introduced onto the head of the column. The gas mixes with
the volatile fraction of the sample inside the injector, and the
mixture is transferred to the column. In a splitless injector the
stream of gas is not split, therefore the whole volume of
the introduced carrier gas together with the sample is directly
injected onto the column.
A splitless injector has lower efficiency, however, as has
been mentioned before; it can be used at very low concentra-
tions of analytes, which definitely is a big advantage (Grob,
1993; Krawczyk, 1999).
Chromatographic Columns
A chromatographic column is another element of the chro-
matographic system in which the separation of mixture com-
ponents takes place (G
orecki et al., 2004). There are packed
columns and capillary columns. At present, capillary col-
umns are the most frequently used; they are up to a couple
tens of meters long and have a diameter ranging between 0.2
and 0.6 mm. Capillary columns are made of glass or fused
quartz in the shape of a coil (Liu and Phillips, 1991). Com-
monly used columns have internal diameters of 0.1, 0.25,
0.32, and 0.53 mm. Columns with a diameter of 0.1 mm are
characterized by high resolution and short analysis times;
they are frequently coupled to mass spectrometry.
Columns with diameters of 0.25 and 0.32 mm display simi-
lar properties; they are used in routine procedures and have
high efficiency. Columns with a diameter of 0.53 mm are char-
acterized by high repeatability and can be installed in any
chromatograph. The column efficiency increases with decreas-
ing column diameter, while increased column diameter results
in an increase of column volume without a change of film
thickness (Adahchour et al., 2006). Stationary phases in the
capillary columns can be both solid adsorbent and liquid.
The GC columns are divided into smooth-walled columns
coated with the liquid stationary phase (WCOT); columns
with walls coated with a porous layer, i.e., adsorbent
(PLOT); and columns with walls covered with a carrier satu-
rated with a liquid stationary phase (SCOT). The thickness of
the stationary phase usually ranges between 0.1 and 0.3 mm.
205
When the layer is thinner the column has better efficiency
and short retention time. A thicker layer results in larger
adsorption capacity of the column. Packed columns are filled
with particles of the adsorbent or a carrier that is coated with
the liquid phase. The adsorbent or carrier particles should be
much less than 1 mm in size, spherical or close-to-spherical in
shape, and have a narrow range of particle size distribution.
In this way, the carrier gas flowing through the column
encounters low resistance, and the diffusion-related fuzziness
of the chromatographic bands corresponding to the eluted
substances is limited, which results in narrow and sharp peaks
(Grob, 1993; Krawczyk, 1999).
Detectors
The next element of the equipment is a detector, which is
responsible for the detection of substances separated on a
chromatographic column. The underlying principle of the
majority of GC detectors is based on the differences in phys-
ico-chemical properties of the pure carrier gas and the gas
that contains the substance eluted from the column. The regis-
tered changes may be proportional either to molar concentra-
tion or to the mass flow rate of a substance present in the
carrier gas. Detector should be characterized by high sensitiv-
ity, low detection limit, stability, good repeatability, and the
wide linear range of readings. There are universal detectors
and selective detectors, the latter being used for detecting
only some groups of compounds, e.g., derivatives of halides
and sulfur-containing compounds. The following detectors
are used for analyzing spirit-based beverages: flame ionization
detector (FID), electron capture detector detector (ECD),
atomic emission detector (AED), flame photometric detector
(FPD), nitrogen phosphorus detector (NPD, TID), olfactom-
etry (O), and different types of mass spectrometry (MS).
Flame Ionization Detector (FID)
A flame ionization detector (Figure 3) is a destructive-type
mass spectrometry detector. The analyzed compounds pass
through a column and are subsequently combusted in a
hydrogen-air flame, which results in the formation of H, O,
OH, and HO free radicals. When the analyzed substances
contain carbon a series of reactions occurs, which results in
the creation of CHOC ions.
CH  C O  ! CHO C C e ¡
These ions are collected on the collector electrode and later
counted. The registered ions constitute a signal for the detec-
tor. The FID detector belongs to the selective detectors, i.e.,
the strongest signal is observed for compounds with a CH
bond, a weak response occurs for compounds containing car-
bon without a CH bond, and a signal is lacking for carbon-
free compounds, which do not undergo combustion. The sen-
sitivity of an FID ranges between 0.1 and 10 ng, while its
highest value is reached for hydrogen and an airflow rate of
approximately. 40 and 400 cm3/min, respectively, and a car-
rier gas (usually helium) flow rate of 30–40 cm3/min. The lin-
ear range of FID is 105–107. It normally operates at
temperatures ranging from 250 to 300 C, while in the case
 206 P. Wi

sniewska et al.
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Fig. 4. Schematic representation of ECD: 1. capillary column, 2.

Fig. 3. Schematic representation of FID: 1. capillary column, 2. inlet of purge gas, 3. silicone liner, 4. cathode, 5. nickel source, 6.
air inlet, 3. hydrogen inlet, 4. polarized electrode, 5. burner, 6. anode, 7. outlet, 8. inlet for anode cleaning.
flame, 7. collector electrode, 8. collector electrode, 9. gas outlet.

of determinations performed at higher temperatures, it will specific elements in the sample components. The sample com-
still operate between 400 and 450 C. It is necessary to main- ponents separated on the chromatographic column are intro-
tain the temperature above 100 C in order to avoid moisture duced into microwave-induced helium plasma at a
condensation during combustion inside an FID detector temperature ranging from 3000 to 10000 K that results in the
(Grob, 1993; Krawczyk, 1999). production of excited atoms from the particles. The excited
electrons in the atoms jump back to the lower energy levels
Electron Capture Detector (ECD) while emitting radiation that is specific for a given element.
The radiation hits the optical part of the detector and under-
The operation of an electron capture detector (Figure 4) is
goes diffraction on diffraction grating, and the generated
based on changes in conductivity of the electron gas con-
characteristic wavelengths are registered by the configurable
tained in the ionization chamber, which is due to the presence
matrix of photodiodes (G
orecki et al., 2004).
of electron-acceptor groups. Radioactive 63Ni, a source of
high-energy b particles, is housed in the detector cell where
the current is generated. These particles ionize the carrier gas,
which results in a constant electric current between the elec-
trodes. Negatively charged compounds that leave the column
pick up b particles and thus lower the ionization level of the
carrier gas; this results in a change of electric current between
the electrodes, which is registered by the detector as a signal.
ECD belongs to the selective detectors targeted on registering
the signals that come from halogens, nitrites, and conjugated
carbonyl groups. The sensitivity of ECD depends on the type
of analyzed compounds, i.e., for halogens, nitrites, and car-
bonyl compounds, it is 0.1–10 pg, 1–100 pg, and 0.1–2 ng,
respectively; its linear range is 103–104 (Grob, 1993; Krawc-
zyk, 1999).

Atomic Emission Detector (AED) Fig. 5. Schematic representation of AED: 1. capillary column, 2.
An atomic emission detector (AED; Figure 5) is a special inlet of carrier gas, 3. and 4. inlet and outlet of water and the
type of detector that can be used as both a universal and energy source, 5. plasma, 6. mirror, 7. converging lens, 8. diffrac-
selective detector; it allows for analyzing the content of tion grating, 9. set of diodes.
 Analysis of Alcoholic Beverages
Flame Photometric Detector (FPD)
In the case of FPD, the compounds are combusted in a
hydrogen-air flame. The substances containing sulfur and
phosphorus produce particles emitting light (sulfur at
394 nm, and phosphorus at 526 nm).
A monochromatic filter allows for the exiting of only one
wave with a specific wavelength. The photomultiplier column
is used to measure the amount of light and the generated sig-
nal. Different filters are applied for each element being deter-
mined. The flame conditions are very significant as they
influence the correctness of the analysis. Because the detec-
tion zone is above the flame, it is necessary to secure the
appropriate gas flow and burner diameter so the sample com-
ponents combusted in the flame are emitted within the detec-
tion zone (Grob, 1993; Krawczyk, 1999).
Nitrogen Phosphorus Detector (NPD)
A nitrogen phosphorus detector (NPD), also called a therm-
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ionic detector (TID), is a flameless detector used in gas chro-
matography; its sensitivity is due to the presence of an alkali
metal. The detector is sensitive to nitrogen- and phosphorus-
based compounds. Its sensitivity oscillates within 1–10 pg,
while the linear range is 104–106. A mixture of hydrogen gas
and air is used in the combustion process, while the working
temperature is 250 –300 C (Grob, 1993; Krawczyk, 1999).
Olfactometry Detector
Gas chromatography coupled to olfactometry employs con-
ventional detectors such as FID and MS that are connected
to special auxiliary equipment that enables a sensory evalua-
tion of the analyzed sample by a trained person or a group of
evaluators. A stream of eluate is split into two parts at an
appropriate ratio so one part reaches the olfactometry detec-
tor, while the other portion of the eluate ends up in the con-
ventional detector. In this way, the two obtained signals can
be compared. The olfactometry detector has the following
advantages: simplicity, speed, and the possibility of illustrat-
ing the differences in sensory sensitivity of the evaluators. On
the other hand, it also has disadvantages such as a necessity
of training the evaluators and the fact that the result depends
only on the actual intensity of the smell sensed for a given
concentration (Liu and Phillips, 1991).
Mass Spectrometer
A mass spectrometer enables the exact determination of the
mass of each molecule that has been ionized in the ion source.
There is a vacuum inside the detector, therefore the com-
pounds reaching the detector, after leaving the chro-
matographic column, become bombarded by electrons or gas
molecules (Grob, 1993; Krawczyk, 1999). As a result of the
electron bombardment, the following reaction takes place:
M C e ¡ ! M C  C 2e ¡
A molecular ion, in the form of cation radical, is generated
during the aforementioned reaction. Each of such ions may
undergo further fragmentation. Next, the ions are focused
and accelerated in the mass filter, whose selectivity allows all
207
ions with a specific mass-to-charge ratio to pass into the elec-
tron multiplier. After all ions corresponding to a given mass
have been detected and counted, the whole procedure is
repeated for other ions with a different mass-to-charge ratio.
The filter searches the given mass range a couple of times per
second. Such segregated and counted ions are registered by
the detector, and their masses are plotted against their mass
intensity or mass number by the computer to which the detec-
tor sends data after the analysis.
At present, all chromatographs coupled to mass spectrom-
etry are equipped with special libraries that include fragmen-
tation models for some compounds. This is important
because each compound can undergo fragmentation in a
number of possible ways therefore the spectra of different
compounds may look deceivingly alike. Thanks to the library
downloaded to a computer, the analysis of compounds is
based on comparing the obtained spectrum to those available
in the spectra library. A mass spectrometry detector can be a
selective detector depending on the mass range chosen, i.e.,
whether it is a total range or a range specific for selected ions
(SIM). The linear range of this detector is 105–106, while its
sensitivity depends on the mass range; for the full range
search, the sensitivity varies between 1 and 10 ng, and for the
selected ions, from 1 to 10 pg (Krawczyk, 1999; Witkiewicz
and Hetper, 2001).
Two-Dimensional Gas Chromatography
In contrast to one-dimensional gas chromatography, during
comprehensive two-dimensional GC the analytes present in
the mobile phase leave the first chromatographic column
together with the phase to be collected in a modulator and
later to be transported as different fractions to the second col-
umn, which has a different separation mechanism than the
first one (G
orecki et al., 2004). In 1991, John Phillips and
Zaiyou Liu reported that gas chromatography employing
two serial columns allows for obtaining much bigger peaks
and higher resolution than traditional one-dimensional GC;
this statement gave rise to two-dimensional gas chromatogra-
phy (Liu and Phillips, 1991). In order to achieve the separa-
tion of volatile compounds present in the mixture, it is
necessary to apply the orthogonality condition. This means
that the separation mechanisms in serial columns have to be
independent of each other. In the case of comprehensive two-
dimensional gas chromatography, this requirement has been
fulfilled by using columns with different separation mecha-
nisms (G
orecki and Harynuk, 2002).
The GC £ GC system consists of two columns of different
lengths, modulator, detector, and oven and, as an option,
another oven that heats the second column. Considering the
equipment used, the presented system differs only slightly
from the system applied in one-dimensional technique.
Injectors
Similar to one-dimensional gas chromatography, the sample
is introduced into the system by an injector and then
transferred to the first column where the separation of
mixture components takes place. A difference between a
 208
one-dimensional and two-dimensional chromatography is
that in the GC £ GC system the sample leaving the first col-
umn ends up in the modulator instead of the detector; it stays
there together with the mobile phase for a short and constant
period of time. Next, the sample is sent in portions to the sec-
ond column, where it is separated again, and then it reaches
the detector.
A modulator is the main tool and, at the same time, the
beating heart of the system; it retains the fractions leaving the
first column, narrows the band, and introduces the portions
of fractions onto the second column. The modulation period
has to be such as to avoid the contact between the two conse-
cutive bands inside the second column. Therefore the mod-
ulator will not introduce the next sample portion onto the
second column before the band from the previous injection
clears it. Due to different separation mechanisms in both col-
umns, it is possible to separate the analytes that have joined
again after leaving the first column. The components
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separated on the second column reach the detector and are
registered there (G
orecki et al., 2004; Herrero et al., 2009).
Columns
Chromatographic columns used in the GC £ GC system must
differ from each other by their dimensions and separation
mechanisms, which strongly depend on the type of stationary
phase. Therefore if the first column has a nonpolar stationary
phase then the second column should contain a polar station-
ary phase. The first column is longer (15–30 m) and it usually
contains the stationary phase with a thicker film (0.25–1 mm)
than to the stationary phase in the second column. It is rec-
ommended to use the nonpolar stationary phase in the first
column because the separation mechanism for this phase is
mainly based on the volatility of analytes. The sample reten-
tion time during the separation in the second dimension
should be as short as possible and not longer than the modu-
lation time, which usually equals 3–6 s. Because of that the
second column (0.5–1.5 m) is much shorter than the first one,
and the film thickness of the stationary phase usually ranges
between 0.1 and 0.25 mm. Such film thickness shortens the
retention time and increases the efficiency of the stationary
phase. The internal diameters of both columns are compara-
ble, although sometimes a column with a smaller diameter is
used for the separation in the second dimension (Adahchour
et al., 2006; G
orecki et al., 2004). As a rule, both columns
are housed inside the thermostatic cover. However, at times
it is advantageous to place the second column inside an
additional separate oven (Adahchour et al., 2006a; G
orecki
et al., 2004).
Modulators
Modulators used in the GC £ GC system are divided into two
main groups, thermal modulators and flow modulators. In
the case of thermal modulators, cryogenic and heated modu-
lators can be distinguished. The flow modulators are divided
into these equipped with a differential valve and those with a
membrane valve. In the analysis of alcohols cryogenic ther-
mal modulators are the most frequently used.
P. Wi

sniewska et al.
The first thermal modulator, invented in 1991 by Phillips
and Ledford, consisted of gold-coated capillary column,
which had been filled with a thick film of stationary phase for
retaining and collecting the analytes at the end of the first
dimension separation. This construction allowed for narrow-
ing the sample band and extended the time of analyte migra-
tion. Gold secured good conductance along the capillary so
the moment the electric current was applied to the tube’s sur-
face fast heating of the modulator occurred (Adahchour
et al., 2006b). The current was run through the capillary at
constant intervals in order to desorb the analytes from the
stationary phase and then transfer them into the second col-
umn. The next band-specific portion of the sample was intro-
duced after the capillary had cooled down, which was a
difficult task to perform. Therefore the analytes leaving the
first column when the modulator was still hot were directed
to the second column.
The problem related to the long cooling time of the capil-
lary column was solved by the same scientists; they designed
another modulator in which a rotary heater traveling along
the length of the column forced the thermal desorption of
analytes. The heater maintained the temperature at a level
100 C higher than that of the chromatographic oven
(G
orecki et al., 2004). However, similar to its predecessor, it
had moving parts, which was sometimes disadvantageous.
The first modulator without moving parts was developed
by G
orecki, Harynuk, and Pani
c (2004). It consisted of two
rust-free serially connected microtraps containing porous sor-
bent. Heat to the microtraps was delivered by means of the
alternating electrical current from discharging capacitors.
Cryogenic modulators operate on the principle of a cold
trap, while in the second dimension a constant temperature is
maintained (Dalluge et al., 2002). The first cryogenic mod-
ulator was a so-called longitudinal modulation cryogenic sys-
tem (LMCS) designed by Marriot and his collaborators in
1997 (Figure 6.). Liquid carbon dioxide is used in LMCS to
cool the part of column that is placed inside a radiator. Thus
the very volatile analytes are not retained, and fuzzy chroma-
tograms may result. The radiator moves along the length of
the capillary from T position (Trap) to R position (Release).
In T position the radiator cools a certain part of the column,
which results in the retention of analytes. Next, the radiator
moves to R position and releases the analytes that had been
Fig. 6. Diagram of LCMS modulator: 1. injector, 2. first column,
3. LCMS modulator, 4. inlet of liquid carbon dioxide, 5. second
column, 6. detector, 7. oven.
 Analysis of Alcoholic Beverages
retained in T position, while at the same time it retains the
analytes in R position. Consequently, the radiator moves to
T position again and the analytes trapped in R position are
released into the second column, while some analytes are
retained in T position. This procedure is repeated until the
entire sample has been processed (Adahchour et al., 2006b;
G
orecki et al., 2004).
The moving parts have been eliminated from cryogenic
modulators developed in recent years. The first new design
employed two rust-free capillaries that were cooled with liq-
uid nitrogen, which allowed for retaining even highly volatile
analytes. In this case, the analyte bands were retained in the
traps not by sorption onto the stationary phase, but by freez-
ing. The release of analytes was achieved by heating the capil-
lary by means of an electrical current from discharging
capacitors. The fault of this modulator was the leakage of
liquid nitrogen into the system.
Another modulator was built from (1) four nozzles that
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alternately delivered liquid CO2 for cooling the first and then
the second part of the column, and (2) two nozzles that, in
the same way, transported hot air for heating the same parts
of the column. In this way, the stream of the mobile phase
with the analytes leaving the first column could be stopped
twice, i.e., in the column part that was cooled first and then
in the second part of the column together with the next por-
tion of analytes. In order to avoid exceeding the sorption
capacity, the flow of hot air was directed to the first nozzle. In
this way, the stream retained in the second part of the column
could be introduced into the second column. The first valve
modulator was developed by Bruckner and coworkers in
1998.
The principle of the operation of a diaphragm valve mod-
ulator (DVM) is based on concurrently directing one stream
of carrier gas from column I into the atmosphere, and
another stream of the same gas delivered from a separate
source to column II. All the operations were controlled
by switching the valve in order to introduce a small band of
the sample from the one-dimension column to the second
dimension; the consecutive switching of the valve allowed for
producing a chromatogram. Such a procedure was continued
until the entire sample was analyzed (Edwards et al., 2011;
G
orecki et al., 2004).
In 2000, Seeley constructed a valve modulator with closed-
loop dispensing that consisted of six membrane valves and a
closed-loop dispenser. A volume of 20 mL of carrier gas, con-
taining the analytes that had left column I, flows through the
closed-loop dispensing system. The valve is switched at spe-
cific time intervals to turn on the closed-loop dispensing sys-
tem in the direction of column II, which results in the
introduction of a narrow sample band into the second col-
umn. Despite many improvements in this device (i.e., increas-
ing the amount of sample reaching the second column), the
entire sample is still not analyzed (Edwards et al., 2011;
G
orecki et al., 2004).
Valve modulators have the following advantages: no
exceeding of sorption capacity, no large differences in
temperature, the possibility of being used in fast two-
dimensional analysis (1 s or less; due to fast switching of
the valve, the narrow bands are obtained at the moment
209
of injection), low cost, and simplicity of operation com-
pared to thermal modules. The fact that only a part of
the sample stream from one dimension is directed to the
second dimension (2–90%) is the main disadvantage of
valve modulators (Adahchour et al., 2006b; G
orecki and
Harynuk, 2002; G
orecki et al., 2004).
Detectors
An electrical signal is produced by the detector as a result of
the presence of analytes leaving the chromatographic col-
umn. The signal is sent to the data registration system in the
form of a series of chromatograms from the second dimen-
sion separation. A requirement that has to be fulfilled by the
detectors used in the GC £ GC technique is high-frequency
data acquisition because the second dimension separation is
fast and the gas stream is introduced into the second column
as a narrow band. The detectors used in classical gas chroma-
tography (which are described in a previous section) are also
applied in GC £ GC systems. A flame ionization detector
(FID) is most commonly used, while an electron capture
detector (ECD), atomic emission detector (AED), and mass
spectrometer coupled to time-of-flight detector (TOF-MS)
are less frequently employed (Adahchour et al., 2006b;
G
orecki et al., 2004).
At present, it seems that the best detector for this tech-
nique is TOF-MS as it is characterized by a much higher sen-
sitivity level than other detectors and by high resolution. The
time-of-flight analyzers are based on the relationship between
the time-of-flight and the mass/charge ratio of the ions. Ions
produced in the ionizer are accelerated in the electric field. It
is the lighter ions that first reach the detector located at the
end of analyzer. The time-of-flight has been defined as time
elapsed from the moment an electrical impulse reaches the
ionization chamber until the ions are registered by the detec-
tor. Next, time-of-flight is recalculated as a ratio of mass-to-
charge (m/z) for a given ion (Adahchour et al., 2006b;
Rochat et al., 2007).
Characteristics of Selected Spirit-Based Beverages
Distillates of Agricultural Origin
A distillate of agricultural origin (raw spirit of agricultural
origin) is an alcoholic liquid obtained from the distillation
process of agricultural products after alcohol fermenta-
tion. It has the properties of neither agricultural ethyl
alcohol nor spirit-based beverages. However, it retains the
smell and flavor of the raw materials used in its produc-
tion. A distillate of agricultural origin should fulfill spe-
cific requirements in relation to its transparency, color,
smell, and the volume percent of ethyl alcohol (not less
than 88%) as well as other impurities such as fusel, alde-
hydes, acetates, and acids. The raw spirit is produced by
fermentation of (1) starch-containing raw materials,
mainly potatoes and grain, (2) sugar-containing products
such as sugar cane, sugar beets, molasses, and fruits, and
(3) cellulose raw materials (Poland, 2002a, 2002b).
 210
Alcohol production consists of the following steps:
 Washing and cleaning of raw materials
 Thermal treatment with water vapor at approximately
140 C and under high pressure
 Preparation of malt, i.e., germinated cereal grain
 Mashing
 Alcohol fermentation; in alcohol production a yeast strain,
Saccharomyces cerevisiae, is used because these organisms
decompose sugars quickly and are resistant to organic acids
and temperature, even above 35 C at times
 Distillation, which results in the production of agricultural
distillate
 Rectification, which results in the production of rectified
spirit; this procedure is conducted in order to obtain con-
centrated spirit, free of by-products (Bednarski and Reps,
2003; Jaroci
nski and Jarosz, 1980 28, 29).
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Thai Spirits
The traditional Thai spirit is produced from sticky rice or
sugar cane molasses. These two raw materials are essential in
the production of bio-ethanol. The origin of Thai spirit dates
back to ancient times. The spirit, which comes from the
northwest part of Thailand, is the most popular alcohol
among the inhabitants of this country. Unfortunately, the
Thai spirit produced from rice does not have any characteris-
tic flavor compounds (Wechgama et al., 2008a).
Vodkas
Vodka is the most popular spirit-based beverage in Poland,
Russia, and other East European countries. It is made from
ethyl alcohol of agricultural origin that is obtained during the
fermentation of potatoes, grains, or other agricultural raw
materials. Such ethyl alcohol is distilled and rectified to assure
the selective reduction of organoleptic properties of the raw
materials used and the by-products of fermentation (stan-
dard). Grain vodka is produced by distillation of grain mash;
it exclusively displays organoleptic properties of the raw mate-
rial used. In Russia vodka is mainly produced from wheat,
while in Poland rye mash is most commonly used. The distilla-
tion process takes place in distillation columns. Vodka’s neu-
tral character is achieved by the separation of forerunnings
(higher alcohols) from fusel oil (the least volatile esters).
The soft taste of vodka is obtained by multiple filtering of
alcohol through charcoal, which is followed by dilution with
water (Christoph and Bauer-Christoph, 2006; European
Commission, 2008). The minimum ethanol content in vodka
is 37.5% by volume.
Fruit-Based Vodkas
According to European Council regulations, flavored vodkas
should be produced exclusively by alcohol fermentation and
distillation of fleshy fruits or fruit must. In order to improve
the distillate’s aroma and taste, only 86% of the original vol-
ume should be distilled at the most. The content of toxic
methanol cannot exceed 1000 g/hL. In the case of pit-con-
taining fruits, the content of hydrogen cyanide should not be
P. Wi

sniewska et al.
higher than 10 g/hL. The fruits that are the most commonly
used in the production of alcohol are pit-containing fruits
(cherries, prunes, and apricots) and fleshy fruits (apples,
pears, and oranges). Quince fruits and strawberries are used
less frequently.
Pear distillates are most popular in France, Germany, and
Eastern Europe. The middle distillation fraction is collected in
order to avoid the presence of toxic compounds and undesired
flavorants. It has been scientifically proven that the characteris-
tic pear taste is caused by ethyl hexanoate, ethyl decanoate,
and etyl-2-trans-4-cis-decanodien. In the case of Bartlett pear,
a-farrnezen is generated during the ripening and storage of the
fruits. Thanks to this finding, it has been demonstrated that
the intensity of pear distillate mainly depends on fruit ripeness
(Christoph and Bauer-Christoph, 2006; European Commis-
sion, 2008; García-Llobodanin et al., 2008).
France is the major producer of a cider known by the
name of Calvados, which is an alcoholic beverage made of
fermented ripe apples. The apples are specifically selected
because their size and ripeness influence the taste of this fruit
spirit. The fermentation of must continues for two months at
low temperatures (10 –15 C) to limit the loss of volatile esters
that influence the beverage aroma. Next, the alcohol is sub-
jected to double distillation in a copper kettle called an alqui-
tara. The last and the most important step is maturation in
small oak barrels, which should add vanilla flavor to the dis-
tillate. The aging period should not be too long in order to
retain the taste of apples. After a specific time, the distillate is
poured into sequentially older barrels. It has been demon-
strated that 169 volatile compounds are responsible for the
aroma of cider, including, first of all, unsaturated alcohols,
aldehydes, phenol, and phenol derivatives (Christoph and
Bauer-Christoph, 2006; García-Llobodanin et al., 2008).
Distillates from pit-containing fruits, inter alia, cherries
(kirschwasser, cherry, and kirsch) and prunes (Zwetschgen-


wasser, Sliwowica), are also produced outside Europe; how-
ever, Germany, Switzerland, Italy, Austria, Poland,
Hungary, Czech Republic, and Romania are the biggest
manufacturers of such distillates. Occasionally, distillates
made from figs can be found. Fig distillates are characterized
by intense aroma due to the presence of ethyl hexanoate,
eugenol, and g-decalactone. Particularly aromatic are distil-
lates made from apricots, peaches, blackberries, and rowan
berries, however, they do not contain enough sugar for pro-
ducing ethanol. Therefore in some countries ethyl alcohol of
agricultural origin is added to vodkas produced from these
fruits (Christoph and Bauer-Christoph, 2006; European
Commission, 2008; Galego et al., 2011; Postel and Adam,
1989; Satora and Tuszy
nski, 2008).
A distillate made from oranges is a novel fruit liqueur. The
aroma of orange juice changes during the fermentation pro-
cess because of the interaction with yeast, metabolic processes
in oranges, and the reaction with ethanol during distillation
(Da Porto et al., 2003, 2006).
Anise Alcohols
Absinthe is a spirit-based beverage with a dominant bitter
taste that belongs to the group of anise-flavored alcohols
 Analysis of Alcoholic Beverages
with high ethanol content. It is produced by aromatizing
ethyl alcohol of agricultural origin with anise and the flowers
and leaves of Artemisia absinthium L. (a medicinal plant
known as wormwood). The main aromatic compounds that
occur in absinthe are, inter alia, a- and b-thujones. The collo-
quial name of absinthe is “green fairy” because of its color
and psychoactive properties. Other popular anise-flavored
alcohols include ouzo (Greece), rakı (Turkey), pastis
(France), sambuca (Italy), and anis (Spain). The production
of these alcohols is based on aromatizing the agricultural
ethyl alcohol with plant extracts that contain trans-anethole
and other aromatic compounds, i.e., cis-anethole, estragole,
and anisaldehyde. Star anise (Illicium verum), anise (Pimpi-
nella anisum), and fennel (Foeniculum vulgare) are most fre-
quently used in the production of anise-flavored alcohols.
Pastis, which originated in the south of France, specifically in
Marseille, must additionally contain natural extracts of lico-
rice (the root of Glycyrrhiza glabra), which implies the pres-
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ence of dyes, so-called chalcones, and glycyrrhizic acid at
concentrations of 0.005 or 0.5 g/L. For ouzo production, the
seeds of the mastic tree grown on Chios (Pistacia lentiscus
var. Chia or latifolia) are also added. The final product has to
be colorless and should contain, at the most, 50 g/L of sugar
and 1 g/L of anethole. Both alcohols become turbid when
diluted with water due to anethole precipitation. Because of
this phenomenon, Frenchmen call their liqueur “the milk of
Provence,” while Greeks consider it to be the “ouzo effect”
(Christoph and Bauer-Christoph, 2006; European Commis-
sion, 2008; Jurado et al., 2007; Yucesoy and Ozen, 2013)
Gin
Gin is a dry alcoholic beverage that is popular in England.
Distilled gin is made from rectified rye alcohol that has been
subjected to additional distillation. During the second distil-
lation the evaporated spirit permeates through a cotton sack
hung inside the apparatus or into a chamber containing dried
juniper berries (Juniperus communis) and other aromatic sub-
stances, e.g., anise, cardamon, and orange and lemon peel.
The alcohol prepared this way has a very delicate aroma and
taste of juniper. A medium-quality gin (compound gin) is
produced by adding juniper oil and other plant materials to
regular rectified alcohol. The most popular type of gin is Lon-
don gin, or dry gin, which has a sugar content of less than
0.1 g/L. The main compounds identified in gin are monoter-
penes, i.e., a-pinene, b-mircen, limonene, g-terpinene, and
p-cymen, that originate from the juniper berries (European
Commission, 2008; Vichi et al., 2007).
Rum and Cachaça
Rum is an alcoholic beverage made by distillation of either
fermented sugar cane juice, molasses, or a mixture of both
these raw materials. The majority of rum is manufactured
from molasses, which mostly comes from Brazil. The French-
speaking territories are an exception because there sugar cane
juice constitutes the basic raw material. Yeast and water are
the components that enable the onset of fermentation.
211
Depending on the targeted final product, fermentation may
take 24 hours (light rum) or even a couple of weeks (heavy
rum). There is no one method of rum distillation, however,
choosing the right distillation equipment influences the final
taste of the alcohol. The aging process lasts at least one year
and takes place in oak barrels as well as stainless steel tanks.
The choice of material in which rum is stored influences the
final color of the beverage. Aging in wooden barrels causes
darkening of rum, while stainless steel tanks do not have an
effect of the rum’s color. The last step of rum production is
mixing in order to secure homogeneous taste and color of the
product.
There are three basic types of rum, namely, white rum with
a soft and light taste, gold rum of amber color, and dark rum,
which has the most intense taste and color due to the longest
aging process. Dark rum contains large concentrations of
fusel alcohol and ethyl esters, which influences the pro-
nounced aroma of the drink (Christoph and Bauer-Chris-
toph, 2006; Pino, 2007).
Cachaça is a Brazilian spirit-based beverage produced
from sugar cane that has been known since colonial times.
Juice prepared from raw materials is decanted, diluted, and
fermented. The next step is distillation in a copper alembic
followed by aging of the liqueur in wooden or steel tanks. As
in the case of other alcohols, the taste of cachaça is influenced
by the fermentation by-products, inter alia, higher alcohols,
carboxylic acids, and carbonyl compounds (Aquino et al.,
2008; Baffa J
unior et al., 2011; Cardeal and Marriott, 2009;
Christoph and Bauer-Christoph, 2006).
Whiskey
Whiskey is a spirit-based beverage distilled from mash con-
sisting of malted grain or grain that has been malted by dia-
stase of the starch. Distillation is conducted until the
distillate volume reaches 94.5% or less in order to retain the
flavor and taste of the raw materials used. Whiskey has to be
aged for at least three years in oak barrels with an individual
volume of less than 700 L. The final distillate retains the
color, smell, and taste that has formed during the production
process. Only water and pure caramel (coloring agent) can be
added to the distillate. It is forbidden to add any other color-
ing and aromatizing agents. Scotch whiskey is a popular type
of whiskey. It is produced 100% from malted barley and
undergoes double distillation in large copper containers. Vol-
atile phenolic compounds that form during the burning of
malt, inter alia, cresol and guaiacol, are responsible for whis-
key’s typical taste. Whiskey originating from the northern
U.S. is produced from a mixture of corn, rye, wheat, barley,
and other grains. After distillation, it is aged in oak barrels
for at least two years (Christoph and Bauer-Christoph, 2006;
European Commission, 2008; Rhodes et al., 2009).
Tequila and Mezcal
Traditional spirit-based alcohols made in Mexico are tequila
and mezcal. They are produced from fermented agave nectar.
In accordance with Mexican law, tequila can be made only
 212
from the fruits of the agave species Agave tequilana, which is
also known as “blue agave.” Moreover, these legal regula-
tions specify a region in Mexico where the production of
tequila is allowed. The alcohol was named after the city of
Tequila in the Jalisco region, in western Mexico (Christoph
and Bauer-Christoph, 2006; Lachance, 1995). Mezcal can be
produced from other agave species, among others, A. sal-
mina, A. angustifolia, and A. patatorum (De Le
on-Rodríguez
et al., 2006). Tequila and mezcal are made from the fruits of
agave called pi~ na, which are baked in large ovens, or auto-
claves, until the starch has been converted to sugar. Pi~na used
for producing mezcal is baked in the presence of charcoal,
which gives the beverage a smoky flavor. Next, the fruits are
mashed and ground in order to separate the sweet juice called
aquamiel (honey water). The last production stage is fermen-
tation of the juice. In the case of tequila and mezcal, two
products are manufactured, one based on 100% agave juice
and another that is a “mix” consisting of 49% sugar cane
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sugar (Christoph and Bauer-Christoph, 2006). Besides this
division, there are five types of tequila: silver, blanco/white,
gold, reposado, and a~ nejo. The first two types are pure tequi-
las that mature in stainless steel tanks not longer than
60 days. Gold tequila is made from silver tequila that under-
goes aging and coloring with caramel. Tequila reposado is
aged in wooden barrels for a minimum of 2 months, however,
the best quality is achieved after 3 to 9 months. The fifth type
of tequila, the so-called a~nejo, has to be aged for a minimum
of 12 months (Aguilar-Cisneros et al., 2002; Christoph and
Bauer-Christoph, 2006). Mezcal’s three varieties are white,
reposado, and a~ nejo. White mezcal is bottled immediately
after distillation, while reposado is aged in oak barrels from 2
to 6 months, and tequila a~ nejo, up to 12 months. It is worth
mentioning that one to four larvae of the butterfly feeding on
agave are added to white and reposado tequilas. That is the
reason mezcal is sometimes called a “worm drink” (De Le
on-
Rodríguez et al., 2006).
Spirit-Based Alcohols from Grape Pomace
According to the EU norm, orujo should be produced from
grape pomace of a specific grape variety and exclusively in
Galicia (northwest Spain). The concentration limits of differ-
ent volatile compounds, e.g., ethanol (50–37, 5%, v/v), meth-
anol (1000–200 g/hL a.a.), higher alcohols (600–225 g/hL a.
a.), ethyl acetate (250 g/hL a.a.), and copper content (maxi-
mum 10 mg/L) are also defined in order to assure the high
quality of the product. Grape pomace is subjected to sponta-
neous fermentation. To this end, it is stored for a couple of
days in closed containers. Depending on the storage condi-
tions, characteristic compounds form that are responsible for
the product’s quality. Next, the fermented fruits are distilled
in copper vats. The following spirit-based alcohols are also
produced from grape pomace: grappa (Italy), eau-de-vie de
marc (France), bagaçeira (Portugal), and tsipouro (Greece)
(Christoph and Bauer-Christoph, 2006; Cortes et al., 2005;
García-Martín et al., 2010; L
opez-V
azquez et al., 2010).
Brandy is defined as an alcohol produced from distilled
wine. The name has Dutch roots, from “brandewijn,”
P. Wi

sniewska et al.
meaning “burnt wine,” because in the 16th century wine was
burned or boiled during distillation. In the case of high qual-
ity brandy, it should be kept in mind that the distillation pro-
cess has to be slow and gentle in order to extract the aroma
compounds from raw material in the best possible way.
Aging is the most critical process. Brandy is aged in oak bar-
rels, which results in change of the color, taste, and smell of
this beverage. At times, aromatizing agents are added, e.g.,
extract of dried prunes, almonds, and walnuts. In many coun-
tries region-specific brandy varieties are produced, for exam-
ple, Weinbrand in Germany, and brandy de Jerez in Spain.
However, cognac is considered the most popular alcohol pro-
duced from grape pomace. The name originated from the
town of Cognac in the Charente region, France. Three types
of white grapes are used in cognac production, although the
ugnic blans variety is preferred. Grapes are mashed and
pressed and then fermented for about one week. Next, the
obtained wine undergoes double distillation in copper alem-
bics. After the first stage, a distillate containing 30% of etha-
nol is produced. The second distillation results in a 70%
distillate. The final product is called eau-de-vie in French,
which means “water of life.” The most important step in the
production of cognac is aging in new barrels made from
French oak. The wood porosity and moisture level in the
storage room influence the quality of cognac. The interac-
tions between the wood and alcohol continue for three years,
which results in the lightly yellow color of the beverage.
Next, the drink is transferred into older barrels to gain an
amber color, while its ethanol content is decreased to 50%.
The aging of cognac takes over 25 years. The last and the
most critical stage of production is blending of eaux-de-vie
from different barrels. The mixture obtained this way is
called cognac (Christoph and Bauer-Christoph, 2006; L
eaut
e,
1990).
Liqueurs
Liqueur is a spirit-based beverage produced by aromatization
of ethyl alcohol of agricultural origin, agricultural distillate,
or one or more spirit-based beverages; it is sweetened and
mixed with agricultural or food products such as, cream,
milk, other milk products, fruits, wine, and aromatized wine.
The minimum ethanol content in a liqueur should be 15%.
Fruit liqueurs made of cherries, black currants, blueberries,
pineapples, and citrus fruits are prepared by adding natural
aromas and juices. The produced bitter liqueurs contain
added spices, herbs, or medicines. The legally regulated con-
tent of artificial aromas is not higher than 0.1% (2, Christoph
and Bauer-Christoph, 2006; European Commission, 2008).
Application of Chromatographic Techniques
to the Analysis of Spirit-Based Beverages
Chromatographic techniques are often used for analyzing
spirit-based beverages. This is due to the fact that such drinks
have complex matrices and the specific groups of compounds
play different roles.
 Analysis of Alcoholic Beverages
Examples of the application of gas chromatography in
studies of spirit-based beverages are presented in Table 1. The
first described group of alcohols is raw spirits, which have
been analyzed mostly in order to identify their botanical char-
acteristics (Bauer-Christoph et al., 1997; Jele
n et al., 2010; Liu
and Jiang, 2002; Zi
o»kowska and Jele
n, 2012). The matrix
composition of the spirits was also investigated to detect aro-
matic compounds (Plutowska and Wardencki, 2009; Plutow-
ska et al., 2010) and determine fatty acids (Plutowska and
Wardencki, 2008). Also, the influence of mycotoxin contami-
nation in the used raw materials on the presence of aldehydes
and higher alcohols was researched (Kloskowski and Mikul-
ski, 2010). Most commonly, the SPME (Plutowska and War-
dencki, 2009; Zi
o»kowska and Jele
n, 2012) and HS-SPME
(Biernacka and Wardencki, 2012; Wardencki, 2008; Plutowska
et al., 2010) techniques were employed to analyze volatile frac-
tions. Information related to the studies of volatile compounds
in Thai spirits made from sticky rice can be found in the pub-
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lished literature (Wechgama et al., 2008a, 2006b). In both
cases, the compounds responsible for the aroma of alcohols,
among others, were identified. For example, in Wechgama
et al. (2008a) 11 main compounds that influence the smell of
beverages were identified, i.e., ethyl acetate, ethyl butyrate,
ethyl decanoate, acetaldehyde, ethyl caprylate, 2-phenethyl
acetate, ethyl laureate, 1-hexanol, phenethyl alcohol, isoamyl
alcohol, and 2-furaldehyde. In the aforementioned research
the methods of GC-FID and GC-MS were used (Wechgama
et al., 2008a, 2006b).
In the case of vodkas, carbonyl compounds (Sowi
nski
et al., 2005; Wardencki et al., 2003) and alcohols (inter alia,
ethanol, methanol, and 2-propanol) were investigated (Char-
apitsa et al., 2013; Savchuk et al., 2006). Mostly, SPME was
used (Cardoso et al., 2004a; Sowi
nski et al., 2005); however,
there also are reports on the application of liquid-liquid
extraction (Sowi
nski et al., 2005). GC-MS (Savchuk et al.,
2006), GC-FID (Charapitsa et al., 2013; Savchuk et al.,
2006), and GC-ECD (Sowi
nski et al., 2005; Wardencki et al.,
2003) systems were used for the analysis. The GC-ECD tech-
nique was employed in investigations of carbonyl com-
pounds, and particularly of aldehydes such as methanal,
ethanal, propanal, isobutanal, propenal, butanal, isopenta-
nal, 2-butenal, pentanal, and hexanal ((Sowi
nski et al., 2005;
Wardencki et al., 2003).
The next presented group of alcohols is whiskey, which has
been analyzed in relation to ethanol content and ethanol
derivatives (Rhodes et al., 2008). In addition, the aroma pro-
files of different whiskey varieties were determined (C^amara
et al., 2007; Fitzgerald et al., 2000); volatile congeners were
identified (Fitzgerald et al., 2000); and the quantitative analy-
sis of ethyl carbamate was performed (Brumley et al., 1988).
Haloanisoles, inter alia, 4-chloroanisole, 2-chloroanisole, 4-
bromoanisole, pentachloroanisole, and 5-bromo-4-chloroani-
sole were also identified by applying GC-AED on samples
prepared by using SPME. Different fibers were employed,
and DVB/Car/PDMS fiber (Campillo et al., 2008) turned
out to be the best choice. For identifying green note com-
pounds, specifically for detecting two aldehydes (E,Z-2,6,
nonenal and E-2-nonenal) and three compounds belonging to
the group of alcohols (1-octen-3-ol, 4-hepten-1-ol, and
213
nonanal-2-ol), multidimensional gas chromatography with
mass spectrometer coupled with olfactometry (MDGC-MS-
O) was used. This technique enabled the identification of
compounds present at low concentration levels (Wanikawa
et al., 2002).
In comparative studies of whiskey, rum, and cachaça,
quantitative and qualitative analysis of selected esters (among
others, ethyl acetate, ethyl butyrate, ethyl lactate, and ethyl
decanoate) was conducted; these esters are responsible for the
aroma of the aforementioned alcohols (Nascimento et al.,
2008). The applicability of two extraction methods, i.e.,
SPME and SBSE, for identifying the highest possible number
of volatile compounds in samples of whiskey was compared
(Demyttenaere et al., 2003). Often rum and cachaça were ana-
lyzed simultaneously because of the type of raw material used
in their production. In this case, aromatic compounds (de
Souza et al., 2006) and, among others, alcohols, esters, and
metals (Cardoso et al., 2004b) were analyzed. In Cardoso
et al. (2004b) the authors presented the analysis of results by
means of statistical methods such as principal component
analysis (PCA), hierarchical cluster analysis (HCA), partial
least squares-discriminant analysis (PLS-DA), and k-nearest
neighbors algorithm (KNN). For example, thanks to the use
of PCA, it was possible to identify the compounds, inter alia,
propanol, izobutanol, and protocatechuic acid (Cardoso et al.,
2004b), which are used for discriminating between rum and
cachaça. The analysis of cachaça matrix allowed determining
the changes taking place in the matrix composition during spe-
cific stages of distillation (de Souza et al., 2009). In addition,
content analysis of compounds belonging to alcohols (Nonato
et al., 2001; Timmer et al., 1971), higher fatty acids (Pino
et al., 2002), and dimethyl sulfides (Fitzgerald et al., 2000)
was also performed. The conducted analysis allowed for distin-
guishing rums of different age (three and seven years old)
(Pino, 2007) as well as determining the concentration of higher
fatty acids (Pino et al., 2002). The techniques used during the
aforementioned analysis were GC-MS (Baffa J
unior et al.,
2011; Cardoso et al., 2004a, 2004b; de Souza et al., 2006; Nas-
cimento et al., 2008; Nonato et al., 2001), GC-FID (Cardoso
et al., 2004b; Pino, 2007; Pino et al., 2002), and GC-GC/
TOF-MS (Cardeal et al., 2009).
The volatile fraction of orujo was analyzed to identify its
botanical characteristics (Di
eguez et al., 2005; García-Martín
et al., 2010) and selected volatile compounds (L
opez-
V
azquez et al., 2010; Pe~ na et al., 2008), for example, 1-prop-
anol, 2-methyl-1propanol, 3-methyl butanol, ethyl hexa-
noate, geraniol (Pe~ na et al., 2008), methanol, ethyl butyrate,
1-butanol, and allylic alcohol (L
opez-V
azquez et al., 2010).
In addition, analysis aimed at distinguishing between home-
made and commercial orujo was performed. It was demon-
strated that the concentrations of, among others, ethanol and
methanol in commercially available orujo are a couple times
higher than in the homemade orujo. It was also proven that
allyl alcohol occurs only in commercial orujo. In order to
interpret the obtained results, analysis of variance (ANOVA)
́
was applied (Cortes et al., 2005). HS-SPME with CW/DVB
fiber (García-Martín et al., 2010; Pe~ na et al., 2008) and direct
́
injection (Cortes et al., 2005; Di
eguez et al., 2005; L
opez-
V
azquez et al., 2010) was used to conduct chemical analysis.
 214 P. Wi

sniewska et al.

Table 1. Application of gas chromatography to the analysis of selected alcoholic beverages

Alcohol Subject of Extraction and
type investigation equipment Columns Reference

Raw spirit Identification of SPME Car/PDMS/ CP Wax 57B (0.2 mm, Jele

n et al., 2010
botanical DVD; GC-FID 50 m, 0.25 mm)
characteristics
Raw spirit Investigation of the HS-SPME; GC-MS Stabilwax-DA (0.5 mm, Plutowska et al., 2001
volatile fraction 30 m, 0.25 mm), HP-
(aromatic 5MS (0.25 mm,
compounds) 30 m, 0.25 mm)
composition in spirits
in relation to
organoleptic qualities
of grains
Raw spirits, brandy, Identification of GC-MS DB-WAX i DB5 Bauer-Christoph et al.,
and whiskey characteristics typical (0.5 mm, 30 m, 1997
for a given raw 0.32 mm)
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material
Corn distillates Influence of mycotoxins GC-FID CP WAX 57 (50 m, Kloskowski and
on the presence of 0.32 mm) Mikulski, 2010
aldehydes and higher
alcohols
Raw spirits made from Comparison of HS-SPME (DVB/Car/ DB-WAX (0.5 mm, Biernackaand
different raw distillates’ PDMS); GC-MS 30 m, 0.25 mm) Wardencki, 2012
materials, i.e., corn, composition
wheat, and rye obtained from
different raw
materials
Raw spirits Detection of aromatic SPME (DVB/Car/ Stabilwax-DA (0.5 mm, Plutowska and
compound PDMS); GC-O, 30 m, 0.32 mm) Wardencki, 2009
GC-MS
Raw spirits Determination of fatty HS-SPME (PDMS); SPB-20 (1 mm, 30 m, Plutowska and
acids GC-FID, GC-MS 0.25 mm) Wardencki, 2008
Raw spirits Discrimination of SPME (PDMS/PA/ GC-FID CP-Wax 57B o»kowska and Jele

Zi
n,
spirits based on their Car, Car/PDMS, (20 mm, 50 m, 2012
origin DVB/PDMS, Car/ 0.25 mm), GC-MS
DVB/PDMS); Supelcowax-10 (0.25
GC-MS, GC-FID v, 30 m, 0.25 mm)
Thai spirit made of Identification of volatile GC-FID Stabiwax (Restek) Wechgama et al.,
sticky rice compounds (0.2 mm, 60 m, 2008b
responsible for the 0.25 mm)
spirit’s aroma
Spirits made of Thai Analysis of selected GC-MS Stabiwax and Wechgama et al., 2008a
rice compounds Stabiwax-DA
0.25 mm, 60 m,
0.25 mm)
Vodkas and rectified Determination of LLE, HS-SPME; DB 1301 (0.25 mm, Sowi

nski et al., 2005
spirits carbonyl compounds GC-ECD 30 m, 0.32 mm)
Vodka Detection and the GC-FID, GC-MS HP-FFAP (0.52 mm, Savchuk et al., 2006
concentration 50 m, 0.32 mm)
measurement of
selected compounds
Vodka Analysis of volatile SPME (100 mm Rtx-5 (3 mm, 30 m, Wardencki et al., 2003
carbonyl compounds PDMS) GC-ECD 0.32 mm)
“Krystal super-luxury” Content determination GC-FID Rt Wax 60 m Savchuk et al., 2006
rectified ethyl alcohol of selected
compounds

(Continued on next page)

 Analysis of Alcoholic Beverages 215

Table 1. Application of gas chromatography to the analysis of selected alcoholic beverages (Continued)
Alcohol Subject of Extraction and
type investigation equipment Columns Reference

Whiskey Comparison of two SPME (PDMS, DVB/ HP-5MS (0.25 mm, Demyttenaere et al.,
extraction methods, Car/PDMS SBME; 30 m, 0.25 mm) 2003
i.e., SPME and SBSE GC-MS
for identifying the
largest possible
number of volatile
compounds
Whiskey Analysis of ethanol and GC-C-IRMS CP WAX 57 CB (1 mm, Rhodes et al., 2009
related compounds 30 m, 0.53 mm)
Whiskey (Irish and Identification of 17 SPME (PA), GC-MS CP Wax 57CB (50 m, Fitzgerald et al., 2000
Scotch varieties) taste congeners 0.2 mm, 0.25 mm)
containing fusel
alcohols, acetates,
and esters
Investigation of flavor
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Scotch whiskey SPME (Car/PDMS), DB Waxter (30 m, C^

amara et al., 2007
profiles in different GC-MS 0.25 mm, 0.5 mm)
kinds of whiskey
Whiskey Identification of green MDGC-MS-O DB-1701 (30 m, 1 mm, Wanikawa et al., 2002
note compounds in 0.25 mm), DB-Wax
malt whiskey (25 m, 0.25 mm,
0.25 mm)
Whiskey Quantitative analysis of GC/MS/MS SP-10 (60 m, 0.25 mm, Brumley et al., 1988
ethyl carbamate 0.25 mm)
Whiskey and brandy Detection of 12 SPME (DVB/Car/ HP-5 (0.25 mm, 30 m, Campillo et al., 2008
haloanisoles PDMS); GC-AED 0.32 mm)
Cachaça, whisky, and Quantitative and GC-MS HP-FFAP (0.33 mm, Nascimento et al., 2008
rum qualitative analysis 50 m, 0.2 mm)
of selected esters that
are responsible for an
aroma in chosen
spirit-based
beverages
Cachaça Determination of ethyl GC-MS DB-Wax (0.50 mm, Baffa J

unior et al., 2011
carbamate content at 60 m, 0.25 mm)
different stages of
alcohol production
Rum Possibility of SPME (PDMS); GC- SPB-5 (0.25 mm, 30 m, Pino, 2007
distinguishing rum FID 0.25 mm)
samples in relation to
their age, namely, 3-
and 7-year-old rums
Cachaça Determination of the SPME (PA), LLE; GC- HP-INNOWAX Nonato et al., 2001
content of FID, GC-MS (0.4 mm, 50 m,
compounds 0.2 mm)
belonging to 1-
propyl, isobutyl, 1-
butyl, and isoamyl
alcohols
White rum Determination of HS-SPME (PDMS), SPB-5 (30 m, 0.25 mm, Pino et al., 2002
higher fatty acids GC-FID 0.25 mm)
Rum and cachaça Determination of LLE, GC-O, GC-MS HP5-MS (30 m, de Souza et al., 2006
aromatic compounds 0.2 mm), DB-5
(13.5 m, 0.32 mm)

(Continued on next page)

 216 P. Wi

sniewska et al.

Table 1. Application of gas chromatography to the analysis of selected alcoholic beverages (Continued)
Alcohol Subject of Extraction and
type investigation equipment Columns Reference

Rum and cachaça Comparison of the GC-MS, GC-FID Among others, HP- Cardoso et al., 2004b
composition of FFAD (50 m,
alcohol matrices; 0.33 mm, 0.2 mm)
analysis of selected
compounds and
metals
Cachaca, tiquira, Sample analysis with GC-MS HP-FFAP (0.3 mm, Fitzgerald et al., 2000
grappa, whiskey, regard to the 50 m, 0.20 mm)
rum, brandy, tequila, presence of dimethyl
and vodka sulfide
Cachaca, rum, fruit Comparison of the SPME (85 mm PA); BPX5 (0.25 mm, 30 m, Cardeal and Marriott,
liqueurs, gin, composition of GC £ GC/TOF-MS 0.25 mm) and 2009
whiskey, tequila, and alcohol matrices BPX20 (0.1 mm,
vodka 1.5 m, 0.1 mm)
BPX5 (0.25 mm, 30 m,
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Cachaça Comparison of the HS-SPME (PA); Timmer et al., 1971

composition of GC £ GC/TOF-MS 0.25 mm) and BP20
alcohols from (0.1 mm, 1.5 m,
different distillation 0.1 mm)
processes
Orujo Analysis of volatile HS-SPME (65 mm HP-Innowax (0.25 mm, García-Martín et al.,
compounds CW/DVB); GC-MS 30 m, 0.25 mm) 2010
characterized by their
botanical and
geographical origin
and the distillation
type
Orujo Quantitative analysis of HS-SPME (CW/DVB); HP-Innowax (0.25 mm, Pe~
na et al., 2008
selected volatile GC-MS 30 m, 0.25 mm)
compounds
Orujo Discrimination of GC-FID Chrompack CP-Wax Di
eguez et al., 2005
varieties based on the 57CB (0.25 mm,
quantitative and 50 m, 0.25 mm)
qualitative analysis
of selected
compounds
Orujo Quantitative analysis of GC-FID CP-WAX-57 CB L

opez-V

azquez et al.,
33 volatile (2 mm, 50 m, 2010
compounds in order 0.32 mm)
to distinguish the
orujo varieties
́
Orujo Analysis of the main GC-FID CHROMPACK CP- Cortes et al., 2005
volatile compounds WAX 57CB
in order to (0.25 mm, 50 m,
discriminate between 0.25 mm)
homemade and
industrial alcohols
Orujo Quantitative analysis of GC-MS CHROMPACK CP- Di
eguez et al., 2003
selected aromatic WAX 57B (0.25 mm,
compounds 50 m, 0.25 mm)
Chinese liqueur Content analysis of HS-SPME (PDMS) Do GD-FPD – HP-1 Liu and Jiang, 2002
mono-, di-, and 100 mm, LLE; GC- (0.17 mm, 25 m,
tributyltin FPD, GC-MS 0.32 mm) Do GC-
MS HP-5 (30 m,
0.25 mm, 0.25 mm)

(Continued on next page)

 Analysis of Alcoholic Beverages 217

Table 1. Application of gas chromatography to the analysis of selected alcoholic beverages (Continued)
Alcohol Subject of Extraction and
type investigation equipment Columns Reference

Chinese liqueur Characterization of GC £ GC-FID, DB-Petro, DB-1701 Zhu et al., 2007

volatile fraction GC £ GC-TOFMS
Chinese Yangue Daqu Investigation of HS-SPME (DVB/Car/ DB-Wax (0.25 mm, Fan and Qian, 2005
liqueur aromatic compounds PDMS 50/30 mm); 30 m, 0.32 mm) DB-
GC/O, GC-MS 5 (0.25 mm, 30 m,
0.32 mm)
Chinese Yanghe Dary Analysis of 70 aromatic LLE; GC-O, GC-FID, GC-O, GC-FID (DB- Fan and Qian, 2006a
compounds GC-MS Wax (0.25 mm,
30 m, 0.32 mm) and
DB-5 (0.25 mm,
30 m, 0.32 mm) GC-
MS the same
Chinese liqueur Analysis of aromatic GC-MS, GC-O, GC- GC-MS: DB-wax I DB- Fan and Qian, 2006b
compounds and the FID 5 (30 m, 0.25 mm,
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comparison of 0.25 mm) GC-FID:

matrices in DB-wax (30 m,
Wuliangye and 0.25 mm, 0.32 mm) I
Jiannanchum DB-5 (30 m, 1 mm,
liqueurs 0.32 mm)
Chinese liqueur Detection of pyrazine LLE, GC-MS DB-Wax (30 m, Fan et al., 2007
compounds 0.25 mm, 0.25 mm),
HP-5 (30 m,
0.25 mm, 0.25 mm)
Spirits, whiskey, and Investigation of GC-FID CP-Wax 58 CB Wang et al., 2004
Chinese medicinal methanol (1.5 mm, 30 m,
liqueur concentration in 0.53 mm)
samples
Cognac Investigation of aroma GC-O, GC-MS CP Wax (50 m, Lablanquie et al., 2002
profiles 0.2 mm, 0.25 mm)
Cognac and calvados Identification of GC-MS ZB-Wax (30 m, Ledauphin et al., 2006
carbonyl volatile 1.5 mm, 0.25 mm)
compounds at trace-
level and sulfur in
fresh distillates
Cognac Analysis of selected GC-MS HP-INNOWAX (60 m, Panosyan et al., 2001
volatile compounds 0.5 mm, 0.25 mm)
French brandy Comparison of the GC-MS BP-20 (50 m, 0.25 mm, Yilmaztekin et al., 2011
(armagnac, cognac, volatile fraction 0.25 mm), BP-5
calvados, and composition in (60 m, 0.25 mm,
mirabelle) different brandy 0.25 mm)
varieties
Cognac Investigation of the HS-SPME (PDMS/ HP-5ms (30 m, Watts and Butzke, 2003
relationship between DVB), GC-MS 0.25 mm, 0.25 mm)
the concentration of
methylketones and
aging time in cognac
Cognac Identification of aroma GC-O, GC-MS CP-WAX57CB (50 m, Ferrari et al., 2004
compounds in fresh 0.2 mm, 0.25 mm)
cognac not aged in a
barrel
Calvados Analysis of volatile LLE, GC-MS, GC- SPB-5 (30 m, 0.25 mm, Ledauphin et al., 2004
fraction in order to FID, GC-O 0.32 mm), BP-10
identify the (25 m, 0.25 mm,
compounds 0.25 mm)
influencing the
aroma of alcohol

(Continued on next page)

 218 P. Wi

sniewska et al.

Table 1. Application of gas chromatography to the analysis of selected alcoholic beverages (Continued)
Alcohol Subject of Extraction and
type investigation equipment Columns Reference

Anise-flavored alcohols Analysis of volatile HS-SPME (Car/ ZB-5 (0.25 mm, 30 m, Jurado et al., 2007
(anis, pastis, fraction based on PDMS); GC-MS 0.25 mm)
sambuca, raki) selected compounds,
aimed at
discriminating
different types of
anise alcohols
Turkish raki Investigation of HS-SPME (Car/ DB-WAX (30 m, Yilmaztekin et al., 2011
differences in raki PDMS); GC-MS 0.32 mm, 0.5 mm)
composition
Whiskey, anisette, and Analysis of sulfur and HS-SPME (Car/ DB-624 (1.8 mm, 30 m, Campillo et al., 2009
vermouth selenium compounds PDMS); GC-AED 0.32 mm)
Gin Investigation of volatile SPME (DVB/Car/ HP-5MS (0.25 mm, Vichi et al., 2007
compounds in the PDMS), SDE; GC- 30 m, 0.25 mm)
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berries of J. MS
communis
Tequila Authentication of GC-IRMS SE 54 (1 mm, 25 m, Bauer-Christoph et al.,
tequila 0.32 mm) 2003
Tequila, rum, and Authentication of HS-SPME (PDMS/ HP-PLOT Q (0.32 mm, Aguilar-Cisneros et al.,
vodka tequila DVB); HRGC- 30 m, 0.32 mm) 2002
IRMS
Tequila Discrimination of SPME (PDMS); GC- HP-5 (0.25 mm, 30 m, Vallejo-Cordoba et al.,
tequila types by MS 0.32 mm) 2004
quantitative analysis
of ethyl esters
Tequila Investigation of GC-FID, GC-MS GC-FID: DB-WAX Benn and Peppard,
aromatic compounds (30 m, 0.25 mm, 1996
0.32 mm); GC-MS:
DB-WAX (50 m,
0.25 mm, 0.25 mm),
DB-1 (30 m, 0.1 mm,
0.25 mm)
Tequila Determination of SPME (PDMS/DVB), ZB-5M (30 m, Pe~
na-Alvarez et al.,
terpenes GC-MS 0.25 mm, 0.32 mm) 2006
Mezcal Analysis of fatty acids GC-MS, GC-FID (GC-FID) Carbowax/ Martínez-Aguilar and
BTR (0.25 mm, Pe~

na-Alvarez, 2009
30 m, 0.25 mm),
GC-MS ZB-5HT
Zebron (0.1 mm,
15 m, 0.25 mm)
Mezcal Analysis of compounds SPME (Car/DVB) GC- GC-MS: HP-FFAP De Le
on-Rodríguez
found in mezcal MS GC-FID (25 m, 0.25 mm, et al., 2006
made from Agave 0.25 mm), GC-FID:
salmina HP-Innowax (30 m,
0.25 mm, 0.25 mm)
Mezcal Quantitative and GC-FID HP-INNOWAX Vera-Guzm

an et al.,
qualitative analysis (0.25 mm, 30 m, 2010
of the main 0.25 mm)
compounds present
in alcohols made
from two different
agaves
Tequila, mezcal, sotol, Analysis of selected GC-FID CP-WAX 52CB Lachenmeier et al.,
and bacanora compounds in order (0.5 mm, 60 m, 2006
to compare the 0.32 m)
alcohols

(Continued on next page)

 Analysis of Alcoholic Beverages 219

Table 1. Application of gas chromatography to the analysis of selected alcoholic beverages (Continued)
Alcohol Subject of Extraction and
type investigation equipment Columns Reference

Spirit made from Investigation of the SPME (DVB/Car/ GC-FID Supelcowax Da Porto et al., 2003
oranges matrix and its PDMS); GC-FID, 10 (0.3 mm, 30 m,
composition in GC-MS 0.32 mm) and GC-
dependency on MS EC-WAX
ethanol (0.25 mm, 30 m,
concentration 0.25 mm)
Spirit made from The influence of SPME (DVB/Car/ GC-FID Supelcowax Da Porto et al., 2006
oranges sweeteners on PDMS); GC-FID, 10 (0.3 mm, 30 m,
volatile compounds GC-MS 0.32 mm) and GC-
in spirits MS EC-WAX
(0.25 mm, 30 m,
0.25 mm)
Pear distillate Identification and GC-FID TR-MetaWax (0.5 mm, García-Llobodanin
quantitative analysis 30 m, 0.25 mm) et al., 2008
Downloaded by [Rutgers University] at 12:11 11 April 2015

of methanol, ethanol,
and the main
aromatic compounds
Fig spirit Identification and HS-SPME (PDMS/ GC-MS AT-WAX MS Galego et al., 20011
quantitative analysis DVB); GC-MS, GC- (0.25 mm, 30 m,
of the main aromatic FID 0.25 mm) GC-FID
compounds DB-WAX (0.25 mm,
30 m, 0.25 mm)
Mulberry spirit Analysis of volatile GC-FID CP-Wax 57 CB (50 m, Soufleros et al., 2004
compounds 0.22 mm)
Melon distillate Comparison of volatile GC-MS BP21 (50 m, 0.25 mm, Hern
andez-G
omez
fractions in 0.31 mm) et al., 2005
homemade and
commercial
distillates
Fruit-based spirits Analysis of selected SPME (Car/PDMS); GC-FID CP-WAX Spaho et al., 2013
(brandy) volatile compounds GC-FID, GC-MS 57CB (0.2 mm, 50 m,
in order to 0.32 mm) GC-MSD
distinguish different DB-WAX (0.25 mm,
brandy types 30 m, 0.25 mm)
Slivovitz Determination of GC-FID Carbowax 20 M (4 m Caldeira et al., 2004
ethanol, higher £ 2 mm) Carbopack
alcohols, and esters B80/120
Slivovitz and prune Determination of the GC-MS HP-INNOVAX (1 mm, Satora and Tuszy

nski,
brandy composition of 30 m, 0.53 mm) 2008
ºacka
˛

Sliwowica and
a comparison with
other types of
slivovitz
Cider Detection of volatile LLE; GC-MS FFAP (0.33 mm, 50 m, Mangas et al., 1996
compounds 0.22 mm)
originated during the
aging process in oak
barrels
Cider Investigation of the GC-FID TR-FFAP (1 mm, Rodriguez Madrera
influence of cider 30 m, 0.53 mm) et al., 2010
aging on its
composition
Cider Analysis of volatile GC-FID MetaWax (30 m, Rodríguez Madrera
compounds 0.5 mm, 0.25 mm) and Su

arez Valles,
2007

(Continued on next page)

 220 P. Wi

sniewska et al.

Table 1. Application of gas chromatography to the analysis of selected alcoholic beverages (Continued)
Alcohol Subject of Extraction and
type investigation equipment Columns Reference

Cider Analysis of volatile HS-SPME Car/PDMS; DB-Wax (0.5 mm, Villiere et al., 2012
compounds that are GC-O, GC-FID, 30 m, 0.32 mm) I
responsible for cider GC £ GC-TOF-MS DB-5MS (0.25 mm,
aroma 2 m, 0.25 mm)
Cider Analysis of volatile GC-FID TR-FFAP (30 m, Picinelli et al., 2000
compounds 1 mm, 0.53 mm)
Lemon liqueur Quantitative analysis of GC-MS SE 52 (25 m, 0.25 mm, Se~
nor

ans et al., 2001
(limoncello) volatile compounds 0.25 mm)
Brandy Quantitative and SPME (DVB/Car/ DB-Wax (30 m, Zhao et al., 2009
qualitative analysis PDMS) GC-MS 0.25 mm, 0.25 mm)
of volatile
compounds
Brandy Determination of GC-SFE, GC-FID Carbowax 20M (30 m, Se~
nor

ans et al., 2001
ethanol content 0.25 mm, 0.25 mm)
DB-5 (30 m, 0.25 mm,
Downloaded by [Rutgers University] at 12:11 11 April 2015

Brandy and whiskey Analysis of organic SPE, GC-MS Park et al., 1999
acids 0.25 mm)
Brandy Analysis of main GC-IR-MS HP-20M (Carbowax Laber et al., 1995
groups of volatile 20 M)
compounds
Brandy Analysis of aromatic GC-FID, GC-MS GC-FID: DB-WAX Caldeira et al., 2004
compounds (30 m, 0.25 mm,
0.32 mm); GC-MS:
DB-WAX (30 m,
0.25 mm, 0.25 mm)
Brandy Analysis of volatile LLE, SPME (PDMS); DB-Wax (30 m, Ebeler et al., 2000
compounds GC-FID, GC-MS, 0.25 mm, 0.32 mm)
GC-O
Cupuassu liqueur Identification of volatile Different SPME fibers HP-1 (0.17 mm, 25 m, De Oliveira et al., 2004
compounds and (PDMS, Car/ 0.32 mm), HP-Wax
quantitative PDMS, PDMS/ (0.3 mm, 25 m,
determination of DVB); GC-AED 0.32 mm)
alkyl pyrazine
Tsipouro Quantitative analysis of GC-MS DB-Wax (0.25 mm, Apostolopoulou et al.,
main volatile 30 m, 0.32 mm) 2005
compounds

Most frequently applied techniques in the analysis of orujo
́
were GC-FID (Cortes et al., 2005; Di
eguez et al., 2005;
L
opez-V
azquez et al., 2010) and GC-MS (García-Martín
et al., 2010; Pe~
na et al., 2008). In some cases, the data analy-
sis was conducted by using statistical methods such as
́
ANOVA (Cortes et al., 2005; Di
eguez et al., 2005), PCA, lin-
ear discriminant analysis (LDA), and cluster analysis (CA)
(García-Martín et al., 2010).
Chinese liqueur was also the subject of investigation. Its
volatile fraction was analyzed to investigate aromatic sub-
stances (Fan and Qian, 2005, 2006a, 2006b) and compare the
compositions of different Chinese liqueurs, i.e., Wuliangue
and Jiannunchum (Fan and Qian, 2006b). The contents of
mono-, di-, and tributyltin (Liu and Jiang, 2002), pyrazine
compounds (Fan and Zhang, 2007), and methanol (Wang
et al., 2004) were also investigated. Two types of extraction
were applied, HS-SPME (Fan and Qian, 2005; Liu and Jiang,
2002) and LLE (Fan and Qian, 2006a; Fan and Zhang,
2007). GC-MS (Fan and Qian, 2005, 2006b; Liu and Jiang,
2002; Wang et al., 2004) and GC-FID (Campillo et al., 2008;
Fan and Qian, 2006b; Wang et al., 2004; Zhu et al., 2007)
were mainly employed. In addition, GC-O (Fan and Qian,
2005, 2006a, 2006b) was used to analyze volatile compounds.
Moreover, as reported in Liu and Jiang (2002), GC-FPD was
used to analyze the contents of mono-, di-, and tributyltin. It
was shown that the aforementioned compounds are present
in Chinese liqueurs at low concentration levels that are com-
parable to those measured in dry wines (Liu and Jiang, 2002).
Moreover, the modern technique of GC £ GC-TOF-MS was
used in the analysis, which allowed for identifying 528 com-
pounds (Zhu et al., 2007).
The volatile fraction of cognac was analyzed in order to
determine the aroma profile (Ferrari et al., 2004; Lablanquie
et al., 2002) and the concentration of methylketones (Watts
and Butzke, 2003). Calvados was analyzed together with
cognac to identify the trace amounts of carbonyl and sulfur
 Analysis of Alcoholic Beverages
compounds (Ledauphin et al., 2006). The compounds influ-
encing the aroma of calvados were investigated (Ledauphin
et al., 2003). The matrices of French alcohols such as, arma-
gnac, cognac, calvados, and mirabelle were comparatively
analyzed. A total of 207 volatile compounds was identified.
The statistical method PLS-DA was applied to perform data
analysis. It was demonstrated that aldehydes occur at higher
concentration levels in mirabelle, while the high concentra-
tion of butan-2-ol is characteristic for calvados. On the other
hand, many furan compounds are present in cognac, and
armagnac is characterized by the presence of 1-(ethoxye-
thoxy)-2-methylbutane and g-eudesmol (Ledauphin et al.,
2010). For analyzing these beverages, GC-MS (Ferrari et al.,
2004; Ledauphin et al., 2003, 2002, 2006, 2010; Panosyan
et al., 2001; Watts and Butzke, 2003) and GC-O (Ferrari
et al., 2004; Ledauphin et al., 2002, 2003) were mostly
employed. In particular, the GC-O method was used to ana-
lyze aromatic compounds.
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The application of gas chromatography also allows for
distinguishing the volatile fraction of anise alcohols (Jurado
et al., 2007; Yilmaztekin et al., 2011). In Jurado et al. (2007)
and Yilmaztekin et al. (2011) the compounds characteristic
for anise alcohols, e.g., b-himachalene, b-pinene, b-elemene,
and ledene, were collated in tables. All the obtained results
were analyzed by means of statistical methods such as PCA
(Jurado et al., 2007; Yilmaztekin et al., 2011), LDA, and
artificial neural network (ANN) (Jurado et al., 2007). In
Campillo et al. (2009) the authors presented the results of
analysis of the sulfur and selenium compounds present in
anisette, whiskey, and vermouth. It was demonstrated that
the combination of HS-SPME with GC-AED is reliable in
the case of analyzing, inter alia, dimethyl sulfide, ethyl methyl
sulfide, diethyl sulfide, and methionol. In the aforementioned
articles the previously mentioned HS-SPME method with
Car/PDMS fiber (Campillo et al., 2009; Jurado et al., 2007;
Yilmaztekin et al., 2011), and GC-MS technique (Jurado
et al., 2007; Yilmaztekin et al., 2011) was employed.
For gin samples, analysis of only the volatile fraction in
J. communis berries, used in gin production, has been per-
formed. Two extraction methods, i.e., SPME with DVB/
Car/PDMS fiber and single drop extraction (SDE), and GC-
MS technique were employed in these investigations. The
numbers of compounds identified by means of the two extrac-
tion methods were similar. The following compounds were
included: monoterpenes (among others, tricyclene, a-pinene,
a-terpinene, limonene, o-cymene, and b-myrcene), oxidized
monoterpenes (among others, camphor, cuminal, myrtenal,
linalool, and verbenone), and sesquiterpenes (among others,
a-cubebene, a-humulene, a-selinene, g-elemene, and g-muur-
olene) (Vichy et al., 2007).
There are numerous published studies on volatile fraction
analysis in tequila and mezcal. Mostly the investigations con-
sidered the authentication of tequila (Aguilar-Cisneros et al.,
2002; Bauer-Christoph et al., 2003) and discrimination of its
varieties based on the quantitative analysis of ethyl esters (Val-
lejo-Cordoba et al., 2004). Terpenes (Pe~ na-Alvarez et al.,
2006) and aromatic compounds (Benn and Peppard, 1996)
were also determined. For mezcal, fatty acids (Martínez-Agui-
lar and Pe~

na-Alvarez, 2009) were analyzed, and qualitative
221
and quantitative analysis was conductedfor the main volatile
compounds, inter alia, esters (De Le
on-Rodríguez et al., 2006,
104). In order to discriminate volatile fractions of mezcal alco-
hol made from two different agave species, ANOVA was
used. The analysis was conducted by GC-FID technique using
direct injection (Vera-Guzm
an et al., 2010). A comparative
analysis of the volatile fractions of selected Spanish alcohols
(tequila, mezcal, stool, and bacanora) was performed (Lachen-
meier et al., 2006). Differences between the two varieties of
tequila were demonstrated. In “100% agave” tequila com-
pounds such as methanol, 2-methyl-1-butanol, 3-methyl-1-
butanol and 2-phenylethanol are present at concentration lev-
els lower than those in “mixed” tequila. In the samples of sotol
the measured concentrations of nitrogen compounds were
higher, while the concentrations of 2-methyl-1-butanol and 3-
methyl-1-butanol were lower. High concentrations of acetalde-
hyde were characteristic for samples of bacarole, while the
composition of mezcal did not show significant differences
(Lachenmeier et al., 2006). The SPME (Benn and Peppard,
1996; De Le
on-Rodríguez et al., 2006; Vallejo-Cordoba et al.,
2004) and HS-SPME (Vallejo-Cordoba et al., 2004) techni-
ques were used in the analysis of Spanish alcohols. Mostly the
GC-MS (Benn and Peppard, 1996; De Le
on-Rodríguez et al.,
2006; Pe~ na-Alvarez et al., 2006; Vallejo-Cordoba et al., 2004)
and GC-FID (De Le
on-Rodríguez et al., 2006; Kloskowski
and Mikulski, 2010; Martínez-Aguilar et al., 2009; Vera-
Guzm
an et al., 2010) systems were applied. Moreover, in Val-
lejo-Cordoba et al. (2004) the use of GC-IRMS (isotope ratio
mass spectrometry) to authenticate tequila from the Jalisco
region was reported.
Fruit alcohols are a very large group of spirit-based bever-
ages. The matrix composition, in particular ethanol content,
was investigated in orange spirits (Da Porto et al., 2003). In
addition, the influence of added sweeteners on volatile com-
pounds was also researched (Da Porto et al., 2006). In both
aforementioned cases, the SPME method with DVB/Car/
PDMS fiber was applied. The GC-MS and GC-FID techni-
ques were employed (Da Porto et al., 2003, 2006). Pear distil-
lates were analyzed for their identification and the
quantitative analysis of methanol, ethanol, and the main aro-
matic compounds, inter alia, ethyl hexanoate, ethyl dec-
anoate, and ethyl-2-trans-4-cis-decadienoate; the latter are
responsible for a pleasant fruity flavor of the alcohol. The
results were analyzed by using ANOVA, PCA, and LDS
(García-Llobodanin et al., 2008). In fig spirits the main com-
pounds, e.g., ethanol, ethyl acetate, methanol, isopentanol,
and ethyl laureate were identified and quantitatively deter-
mined. The analysis was performed by HS-SPME with
PDMS/DVB fiber, and by means of GC-MS and GC-FID
techniques (Galego et al., 2011). On the other hand, samples
of mulberry spirit were analyzed for volatile compounds
exclusively by GC-FID (Soufleros et al., 2004). Researchers
also compared different volatile fractions of homemade and
commercial distillates produced from melon by applying the
GC-MS technique (Hern
andez-G
omez et al., 2005). In addi-
tion, compounds such as acetaldehyde, ethyl acetate, metha-
nol, and higher alcohols were analyzed in order to
discriminate among fruit spirits. To this end, SPME with
Car/PDMS fiber together with the GC-MS and GC-FID
 222
techniques were employed (Winterov
a et al., 2008). For slivo-
vitz samples originating from various countries, the contents
of methanol, esters, and higher alcohols were determined
(Spaho et al., 2013), and the matrix composition was identi-


fied in order to discriminate among Polish Sliwowica ºacka,
˛ matography is dynamic, as confirmed by numerous publica-
Slovak Prav
a Bosacka Slivovica, and Romanian Tzuica from
Clej-Napoca (Spaho et al., 2013). To identify the differences
in slivovitz composition, the statistical method ANOVA was
applied. It was demonstrated that Polish slivovitz has the
highest ethanol concentration; the lowest methanol concen-
tration was determined in the Slovak variety of slivovitz.
Moreover, a distinct characteristic of Romanian slivovitz
was detected, namely, the highest concentration of ethyl ace-
tate (Satora and Tuszy
nski, 2008). The techniques of GC-MS
(Mangas et al., 1996; Versari et al., 2003), GC-FID (Picinelli
et al., 2000; Rodriguez Madrera et al., 2007, 2010; Villiere
et al., 2012), GC-O (Villiere et al., 2012), and GC £ GC-
TOF-MS (Villiere et al., 2012) were used to analyze volatile
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fractions in samples of different ciders in relation to volatile
compounds (Picinelli et al., 2000; Rodriguez Madrera et al.,
2007; Villiere et al., 2012), aromatic compounds (Villiere
et al., 2012), and the influence of the aging process on cider
composition (Mangas et al., 1996; Rodriguez Madrera et al.,
2010). For the Italian lemon liqueur limoncello, the quantita-
tive analysis of volatile compounds, inter alia, linalol, neral,
octanal terpinolene, neryl acetate, and geranial was con-
ducted. Additionally, the concentrations of compounds
belonging to acids and polyalcohols were also determined. In
the analysis of limoncello the GC-MS technique was
employed (Versari et al., 2003). Volatile (Ebeler et al., 2000;
Laber et al., 1995; Zhao et al., 2009) and aromatic (Caldeira
et al., 2004) compounds as well as organic acids (Park et al.,
1999) were also analyzed in brandy. To this end, LLE and
SPME with PDMS (Ebeler et al., 2000) and DVB/Car/
PDMS (Zhao et al., 2009) fibers were used. In Se~ nor
ans et al.
(2001) the application of a less popular extraction method,
i.e., CC-SFE, for analyzing spirit-based beverages was
reported. Thanks to CC-SFE, the determination of ethanol
concentration was possible (Se~ nor
ans et al., 2001). A liqueur
called capassu was the subject of investigation aimed at iden-
tifying volatile compounds and the quantitative determina-
tion of alkylpyrazine. In this analysis different SPME fibers
were used, such as PDMS, Car/PDMS, and PDMS/DVB.
Capassu liqueur was analyzed by means of GC-AED and
GC-IT-MS (Timmer et al., 1971). A Greek brandy made
from grapes was quantitatively analyzed for the main volatile
compounds, i.e., 1-hexanol, furfural, 2-phenyl ethanol, 2-
methyl-1-propanol, amyl alcohols, and ethyl lactate. In this
study it was proven that, among others, ethyl lactate has a
positive effect on the alcohol’s aroma only when it is present
at low concentration levels. Such low levels mostly occurred
in homemade alcohols of this type. The pertinent analysis
was performed with GC-MS (Apostolopoulou et al., 2005).
Summary
In this article a wide use of gas chromatography in studies
of alcoholic beverages is presented. Due to numerous
P. Wi

sniewska et al.
advantages such as good resolution and high sensitivity GC
is becoming increasingly more popular in the analysis of sam-
ples with complex matrices. Despite high costs and the need
to have well-trained personnel, the development of gas chro-
tions. At present, scientists more frequently employ 2-D gas
chromatography, which allows the identification of a couple
of hundreds of compounds. The following alcohols have been
analyzed: vodka, whiskey, cachaça, tequila, mezcal, brandy,
cognac, cider, spirits of plant and fruit origin, anise alcohols,
gin, calvados, and liqueurs. Mostly esters and alcohols were
determined in the spirit-based beverages. The most popular
extraction method was SPME due to its high sensitivity and
small size of equipment, but primarily because of the short
time needed for sample preparation prior to analysis. The
GC-MS and GC-FID techniques were most frequently
applied in the analysis of spirit-based alcohols. Undoubtedly,
gas chromatography will continue to be widely used in the
analysis of spirit-based beverages in the future.
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