Review

Received: 19 May 2013 Revised: 13 August 2013 Accepted article published: 28 August 2013 Published online in Wiley Online Library: 2 October 2013

(wileyonlinelibrary.com) DOI 10.1002/jsfa.6377

Grape brandy production, composition

and sensory evaluation
Argyrios Tsakiris,a∗ Stamatina Kallithrakab and Yiannis Kourkoutasc

Abstract
Grape brandy is a spirit drink produced by wine distillation and is matured in wooden casks. According to legislation, it can be
characterised by the geographical area where the grapes were produced, the grape variety used and the selected distillation
and ageing techniques. Distillation increases ethanol concentration and aromatic constituents which are already present in
grapes or are developed during fermentation and distillation. During maturation in wooden casks, compounds that contribute
to the aroma and taste are extracted from the wood. Hence the spirit acquires the desired softer mouth feel, aromatic complexity
and overall quality. Different methods of analysis are used in order to pursuit this process by analysing volatile and non-volatile
substances and correlate composition with quality. Analysis can also be useful in identification of brandy safety, potential
adulterations, provenance and differentiation from other spirits drinks.

c 2013 Society of Chemical Industry

Keywords: brandy; grape; wine; distillation; ageing; quality

INTRODUCTION regional wine grapes and are mainly produced by column stills,
Geographical origin and legislation although there are also a number of low-scale producers which
Brandy is produced in several regions of the world. Globally, employ pot stills. German brandy, which is called weinbrand
brandy (with 1.2 billion litres) is the fifth largest category of (‘burnt wine’), is made from imported wine. Contemporary United
spirits drink (20.0 billion litres in total). Today, the biggest selling State brandies in California are made mostly by column stills.
brandies in the world come from India and the Philippines. It can be According to U.S. legislation,2 fruit brandies, derived from grapes,
characterised according to the geographical area where the grapes are labelled as ‘grape brandy’ or ‘brandy’. When brandy has been
are produced, the grape variety used and the selected distillation stored in oak containers for less than 2 years, it must be labelled
and ageing techniques employed. According to the European as ‘immature’. It is obvious that, worldwide, there are various legal
Union legislation1 brandy is a spirit drink (alcoholic beverage) definitions according to the national traditions and commercial
interests.
produced from wine spirit, whether or not wine distillate has
been added, distilled at less than 94.8% (v/v), provided that the
distillate does not exceed a maximum of 50% of the alcoholic Grapes and treatments before fermentations
content of the finished product. It should be matured for at least In order to produce 1 L of brandy, about 4.5 L of wine are required.
1 year in oak receptacles or for at least 6 months in oak casks The condensation which takes place during the distillation process
with a capacity of less than 1000 L. It must also contain a quantity causes a significant increase of aromatic compounds, which is
of volatile substances equal to or exceeding 1.25 g L−1 of pure responsible for the intense and strong flavour of brandy. For this
alcohol (125 grams per hectolitre of 100% vol alcohol) and must reason, in brandy production, the usage of neutral flavour grapes,
possess a maximum methanol content of 2.0 g L−1 of pure alcohol such as Ugni blanc, is favoured.3 The utilisation of such grapes
(200 grams per hectolitre of 100% vol alcohol). According to the ensures a satisfactory yield of production in combination with
same regulations, wine spirits are produced exclusively by the
distillation at less than 86% (v/v) of wine or wine fortified for
∗ Correspondence to: Argyrios Tsakiris, Department of Enology & Beverage
distillation or by the re-distillation of a wine distillate at less than
86% (v/v). The most famous French wine spirits are those of the Technology, Faculty of Food Technology and Nutrition, Technological
Educational Institute (T.E.I.) of Athens, Ag. Spiridonos Str, Egaleo, 12210 Athens,
regions of Cognac and Armagnac. Cognac is a double-distilled Greece. E-mail: atsakiris@teiath.gr
spirit in pot still. In Armagnac, distillation takes place in alembic
Armagnacais, a continuous column still with 5–15 plates. Well- a DepartmentofEnology&BeverageTechnology,FacultyofFoodTechnologyand
Nutrition, Technological Educational Institute (T.E.I.) of Athens, Ag. Spiridonos
known Spanish brandies are those originating from the region of
Str, Egaleo, 12210 Athens, Greece
Jeres, which have aged in used sherry casks. A solera system is
followed similar to that used for sherry wine. The most known b Department of Food Science and Technology, Agricultural University of Athens,
South American brandy is Pisco. In Peru it is made mainly from Iera Odos 75, 11855 Athens, Greece
Muscat grapes. In Chile it is made from different varieties, and c Applied Microbiology and Molecular Biotechnology Research Group,
is distilled in pot stills. Italian brandies are not produced within Department of Molecular Biology & Genetics, Democritus University of Thrace,
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the borders of specified geographical areas. They are made from Dragana, 68100 Alexandroupolis, Greece

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the relatively low cost of the raw material. Since the flavour of Fermentation
brandy derives mainly from compounds that are formed during Wine for brandy production is produced from the must by yeast
alcoholic fermentation, quality grapes are not suitable for brandy fermentation. Brandy production is a traditional process and,
production. For example, aromatic grape varieties with strong therefore, few innovations are employed as far as fermentation,
and persistent flavour, such as Sauvignon blanc or Chardonnay, distillation and ageing processes are concerned. Alcoholic
with low yield and high cost, produce wines of high quality but fermentation of must occurs mainly by spontaneous fermentation
are unsuitable for brandy production. For some Pisco brandy, by indigenous Saccharomyces serevisiae yeasts. Immobilised yeast
producers use varieties such as Muscat with more intense varietal cells have also been employed for base wine production due to
aromas due to the presence of terpenes4 since their concentration their higher productivity and the reduced cost of the final product.
diminishes during distillation.5 Loukatos et al.11 proposed that delignified cellulose, gluten and
Sometimes, in order to enhance vine defence, the application kissiris-supported biocatalysis may have a different effect on the
of pesticides is necessary. Although pesticides may have an concentration of amyl alcohols of the distillate. Immobilised cell
influence on the fermentation process, they do not affect the reactor was also used to produce ethanol.12 The reactor was
sensory quality of the wine. In contrast, the addition of sulfur by coupled with a distillation column for recycling the effluent from
spraying or dusting on vine can produce nasty reduction odours.6 the bottom of the column.
Pesticides applied in vineyards may remain on grapes and during The presence of lactic acid bacteria also influences the quality
distillation they may be transferred into the distillate. This can only of wine and brandy.13 Different strains of lactic acid bacteria
happen when their concentration is high enough since they are were isolated from grape must at different stages of brandy base
characterised by low transfer rates.7 The Botrytis cinerea infection wine production in South African vineyards and wineries. The
of grapes has a negative effect on the quality of both wines and presence of Lactobacillus spp. was correlated with a decrease in
spirits since mould odours can be detected even after distillation base wine and distillate quality. In contrast, Oenococcus oeni strains
and ageing. Measurement of the concentration of selected were found to have a more favourable influence on base wine and
volatile compounds, such as 1-octen-3-ol, is often employed in distillate flavour.
order to monitor the growth of Botrytis cinerea during grape
maturation.8
Between fermentation and distillation
The harvest should be done mechanically or by hand at the
During the period between fermentation and distillation, which
proper time, not necessarily coinciding with the maximum of
may last up to 5 months, several chemical reactions take place
sugars. Grapes must be transported as quickly as possible to the
and the wine composition alters. Care should be taken to keep
winery for must extraction and the putrid grapes are removed with
this period as short as possible. Distillation can immediately occur
careful screening. Must extraction and vilification is similar to the
after the end of fermentation. Wine higher alcohol and polyol
white wine making.
content is not influenced by the time that elapses after the end of
The stalks are removed from grapes which are then crushed
fermentation, in contrast with its ester content which can decrease
and pressed. The must production should be made in such
significantly. The most affected esters are those which possess the
a way as to extract as few as possible phenolic compounds,
aromatic properties of interest (such as isoamyl, hexyl acetate,
especially tannins. For this reason, discontinuous presses are
phenylethyl acetate, ethyl caproate, ethyl caprylate, ethyl caprate
used. Continuous presses have the disadvantage of increasing
and ethyl laurate). An undesirable increase in ethyl acetate, ethyl
the sediment of grapes and release undesirable compounds. In
lactate, diethyl succinate, acetaldehyde (ethanal) and acetic acid
contrast to modern white wine making, must is not clarified by
of the base wine content is usually observed simultaneously.14
racking of the lees. The presence and the proportion of lees
affects the composition of wine and consequently the quality
of distillates since it increases their aromatic complexity.9 The Distillation
time that elapses between pressing and the start of fermentation Either batch or continuous processing is used for base wine
should be the minimum possible. This is due to the absence distillation. In batch distillation by pot still, the first distillation
of sulfur dioxide which protects must and wine from oxidation or distillation of the wine takes place until almost all ethanol is
and microbial spoilage. Only the must which is produced by the distilled. In the second distillation, about 1% of total volume is
application of low pressure (about 80% of the total must) is used for collected separately and constitutes the ‘head’, while the distillate
brandy production. Must which is extracted using high pressure which contains less than 86% (v/v), about 70% (v/v) of ethanol,
is usually fermented separately and is distilled in a continuous constitutes the ‘heart’. It is the ‘wine spirit’. Finally, the distillate
column still to produce pure alcohol. The addition of pectolytic which then runs out, the ‘tail’, is collected separately until almost
enzymes to musts to aid clarification increases the methanol all ethanol is distilled.
content of the distillate10 and thus it should be avoided. Moreover, In a small continuous still, distillation is performed in column
the concentration of higher alcohols increases when no racking of stills consisting of 5–15 plates in order to produce the ‘wine spirit’.
the lees takes place. Distillation towers (30–40 plates) are used in order to produce
In general, musts and wines are not treated with sulfur dioxide ‘wine distillates’ with less than 94.8% (v/v). This type of distillate
since the latter could be transferred into the distillate and thus contains only a small portion of the volatile substances. This is
decrease its quality by neutralising the aromatic perception. In the reason brandies produced with the addition of such distillates
certain cases, however, where the hygienic condition of the grapes are less aromatic. In continuous distillation process, wine lees are
is not adequate, 0.01 g L−1 sulfur dioxide could be added to must removed just before distillation since their presence could block
in order to avoid the appearance of ethyl acetate and ethyl lactate. the distillation equipment and delay the whole process.
The above-mentioned volatile compounds could be synthesised Wine is a colloidal suspension that contains several hundred
by certain strains of bacteria which can grow in the absence of components in small proportions. Among these, some trace
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sulfur dioxide.9 components are considered as positive quality factors in contrast

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 www.soci.org A Tsakiris, S Kallithraka, Y Kourkoutas

to some other compounds that are deleterious to distillate quality. derivatives) have important sensory properties. These compounds
In fact, all substances contribute to the complexity and quality of have been significantly correlated with several olfactory attributes,
the distillate when they do not exceed a certain concentration. such as vanilla, smoke, toasted and dried fruits, which are positively
During the distillation process, volatile components are extracted correlated with the overall brandy quality.24
from wine and are concentrated into the distillate. The aim of the The aged distillates can be classified according to their aroma
distillation is to recover the maximum amount of ethanol and the and taste, by the use of adequate and reliable expert systems
positive characteristic aromas, while minimising the off-flavours in based on fuzzy logic and neural networks. Fuzzy classifier and a
the distillate. neural network was used25 for the classification of wine distillates.
Lately, modelling and simulation of the distillation process have The fuzzy classifier was based on the fuzzy algorithm, while the
been employed in order to apply the optimal operation policies neural system was a feed-forward sigmoidal multilayer network.
and to maximise both the production and the quality of brandy.
Osorio et al.5 developed a model by the use of neural networks
Mixing and bottling
which describes wine distillation as a multi-component reactive
In order to obtain the final product, various distillates of different
batch distillation process.
age from different casks are mixed and pure water is added
During the process of distillation, a number of chemical reactions
to accomplish an alcoholic degree of 40% (v/v). In most cases,
take place together with the extraction of the volatile compounds.
caramel is also added since it contributes to the development of
These reactions, which involve15 esterifications, acetalisations,
the colour. Cold stabilisation usually follows to ensure the removal
Maillard reactions and Strecker degradations, can greatly affect
of the excess quantity of ingredients, such as tannins, which could
spirit quality. Thus, in order to modify the spirit composition,
develop turbidity and thus affect the quality of the final product.19
the distillers mainly control two parameters: wine flow rate and
Brandy is stabilised after 2 days at −4◦ C. Finally, filtration and
temperature of distillation.
bottling follow. The presence of the fatty acid ethyl esters in
Wine distillation is a traditional technique which has been
quantities higher than 5 mg L−l may cause deterioration in the
intensively investigated. Some researchers focussed on the
quality of the bottled spirit,26 depending on the alcoholic degree
partial or total removal of ethanol from the spirits in order to
of the product and the storage temperature.
produce reduced-alcohol or alcohol-free drinks. The processes
employed for the production of such alcoholic drinks include
distillation, membrane separation, reverse osmosis, solvent Hazard analysis of critical control points
extraction and supercritical fluid extraction using a counter- Alcoholic beverages control and safety can be assured within
current supercritical fluid extraction system.16 In addition, air- the frame of strict adherence to quality and safety systems,
gap membrane distillation was studied as a possible technique such as ISO 9000 series, hazard analysis of critical control points
for ethanol–water separation using polyvinylidene difluoride (HACCP) and total quality management (TQM).23 Although the
membranes.17 alcoholic beverages are comparatively safer than other foods and
Several books18 – 22 describe the equipment, processes and drinks because of their high alcohol content, identification of
particularities applied in distillation, depending on the country potential hazards and resumption of preventive and corrective
and place of production. actions (when required) is of primary importance. In recent years,
adulteration (e.g. use of low-cost inappropriate alcohol) has made
Ageing of distillates in wooden casks rapid progress in this field.
Maturation and ageing of the distillates (‘wine distillate’ or ‘wine Efstratiadis and Arvanitogiannis27 implemented HACCP for a
spirit’) is carried out in wooden, mostly oak, casks. This process may large-scale brandy-producing company, as part of the total quality
last from several months to several years. Relatively new distillates system. In such a way, it was possible to produce a safer product,
are placed in casks with maximum capacity of 225–1000 L, while free of heavy metals and methanol.
more aged distillates can be stored in 5000-L casks. During this
period, there is a loss of 2–3.5% of the distillate per year due to
evaporation. COMPOSITION
During the ageing process, the brandy acquires a very Since brandy is a product of wine distillation, it does not contain
characteristic flavour distinctly different from that of the fresh the non-distillable wine organic and inorganic compounds. The
distillate. The sensory attributes of the distillates such as colour, absence of non-volatile organic acids in the distillate affects the
flavour and taste are greatly influenced by the botanical species balance of the taste. The brandy’s high alcohol content, about 40%
of the wood, the different heat treatments applied to wooden (v/v), ‘burns’ the mouth and simultaneously augments the sweet
barrels, the times that the wooden barrel has been used and taste.
the ageing time. The complexity of brandy aroma increases Brandies, which are usually matured in oak casks for several
due to the extraction of certain wood compounds (volatile and years, present a very complex aroma profile. In fact, hundreds
non-volatile) into the distillate. For instance, tannins, which are of volatile compounds have been identified in grape brandies.
polymeric phenolic substances, are extracted from the wood Some of these volatiles are already present in grapes (primary
and contribute to the flavour of brandy. In addition, some other aromas) and in wines (fermentation aromas), while some others are
reactions between the components of wood and distillates may formed during the distillation process (specific aromas produced
also occur during barrel ageing which can also contribute to the by the heating process) or they are extracted from the oak wood.
brandy complexity. The presence of scopoletin [determined with Among them, acetaldehyde, ethyl acetate, methanol, 1-propanol,
high-performance liquid chromatography (HPLC)] is considered as isobutanol, and isoamyl alcohol are present in relatively large
proof of maturation in oak barrels.23 amounts, generally between 50 and 2000 mg L−l , and they can be
The different volatile compounds extracted from the wood easily determined directly by gas chromatography (GC) employing
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(lactones, furanic compounds, vanillin derivatives and phenol internal standards. Usually GC is coupled with mass spectrometry

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(MS) where a simultaneous search of a library database is also Terpenes

possible.28 However, some other important aroma compounds Terpenes are mainly present in the grape skins. Their concentration
generated during grape ripening (varietal aroma compounds is particularly high in Muscat grape varieties. About 40 terpene
such as monoterpenes), and during alcoholic fermentation compounds have been identified in grapes. Some of the
(fermentation aroma compounds, such as higher alcohols, middle- monoterpene alcohols, which posse a characteristic floral aroma,
chain mono-carboxylic acids and mono-carboxylic acids), are are among the most odoriferous, especially linalool, α-terpineol,
usually present at concentrations ranging from 0 to 50 mg L−l nerol, geraniol, citronellol and hotrienol. The olfactory perception
and their determination requires the use of an isolation and thresholds of these compounds are rather low (a few hundred
pre-concentration technique.29 For the quantification of such micrograms per litre). In Muscat wines, terpenes are found either
compounds several authors used liquid–liquid extraction followed free or bound to sugars as glycosides. The latter are also called
by a concentration step, prior to analysis by GC, but other aroma precursors, as they are unable to express their aromatic
techniques have also been proposed, i.e. headspace with solid- character. However, upon hydrolysation, which occurs during
phase micro-extraction (SPME). SPME is actually one of the most distillation, these precursors liberate free terpenes. High distillation
used methods for the analysis of a very wide range of compounds. temperature and low pH may, however, oxidise terpenes, leading
The SPME method was successfully applied30 to determine the to less positive or negative odorant forms.5
differences in volatile concentration of grape distillates produced
by crushed, pressed and fermented grapes. In addition, a stir bar
sorptive extraction method coupled to gas chromatography–mass Alcohols
spectrometry (GC-MS) has been developed for the analysis of Ethanol (ethyl alcohol) is the most abundant compound in wine,
volatile compounds in brandy. A rapid extraction of aroma after water. In wine it is produced by the alcoholic fermentation
compounds from grape brandies was proposed31 by using of glucose and fructose. Under standard fermentation conditions
ultrasonication. All classic analytical methods concerning spirits ethanol may accumulate up to 14% (v/v). The ethanol content of
are described by Bertrand.32 the wine spirit is habitually 70% (v/v) with a recovery of 99%, while
Although the volatile composition of brandies is qualitatively brandy’s ethanol content, after addition of pure water, is about
rather similar, their organoleptic characteristics are often quite 40% (v/v).
distinct. This can be attributed to the slight differences that The accurate and rapid determination of ethanol in alcoholic
exist between their volatile concentrations.33 Wine distillates beverages is very important for economic reasons. The techniques
authentication, mainly in terms of varieties and regions of used for this purpose can be grouped into chemical, physical,
geographical origin, is rather difficult.34 However, differentiation enzymatic and instrumental physico-chemical methods. A
can be realised by the utilisation of statistical methods, such as reagentless amperometric biosensor, which is sensitive to ethanol,
principal component analysis. was developed by Santos et al.38 This sensor was comprised of a
carbon paste electrode modified with alcohol dehydrogenase,
Volatile compounds nicotinamide adenine dinucleotide co-factor and Meldola’s
The flavourful distilled beverages are highly complex mixtures con- blue adsorbed on silica gel coated with niobium oxide. The
taining hundreds of individual compounds in an ethanol–water proposed biosensor presented good sensitivity allowing ethanol
matrix, enhanced or modified by synergistic or masking effects. quantification at levels down to 8.0 × 10−6 mol L−l . Another
Their role in the formation of wine flavour is dependent upon method based on infrared spectrophotometry was developed for
their abundance and odour thresholds.35 The odour threshold is the determination of ethanol in alcoholic beverages39 where
defined as the minimum amount of odorant which must be added satisfactory results were obtained with the help of Glenn’s
to a reference matrix to cause a significant sensory difference. It orthogonal and first-derivative functions to correct for water
is different in pure water and in model dilute alcohol solutions absorption. In addition, a spectrophotometric procedure was
ranging 10–40% ethanol–water (v/v). For example, linalool cor- developed40 for the ethanol determination in alcoholic beverages
responding thresholds are 5, 50, 1000 µg L−l for water, 10 and by employing a flow system based on a multi-commutation and
40% ethanol/water (v/v). Odour activity value is a measure of the binary sampling approach. The method was based on ethanol
importance of a specific compound to the odour.36 It is calculated oxidation by dichromate in sulfuric acid medium and detection by
as the ratio between the concentration of the individual substance spectrophotometry.
and its threshold concentration. Aroma extract dilution analysis Methanol (methyl alcohol) is not produced by alcoholic
can also be used to identify the most important aroma compounds fermentation. It is formed exclusively from the enzymatic
and determine the highest flavour dilution factor.37 hydrolysis of the methoxyl groups of pectins during fermentation.
More than 500 substances have been detected in spirits14 that It is always present in very small quantities, 40–60 mg L−l in
belong to a large number of chemical classes, such as terpenes, wine. However, in distillates and brandy it is found in higher
alcohols, esters, aldeydes, ketones, acids and phenols. However, concentrations 0.30–0.70 g L−1 of pure alcohol with a recovery
only a few of these substances are important for its contribution of 90%. Its taste is similar to ethanol and it does not affect the
to the brandy sensory characteristics. Quite recently, the use of organoleptic quality of the spirits. However, it affects the safety of
chemical markers has been employed for tracking the sensory brandy because its toxicity is well known.41 Following ingestion, it
contribution of each the three post-fermentation stages of a oxidises to formaldehyde and formic acid, both of which are toxic
Chilean spirit. Peña y Lillo et al.,4 using multivariable statistical to the central nervous system. Formaldehyde causes deterioration
methods and applying heuristics for matching the sensory and of the optical nerve, leading to blindness.42 European Union
chemical differentiation of brandy samples, managed to determine legislation requires a limit lower than 2.0 g L−1 of pure alcohol.
the main sensory contribution of blended and aged wine distillates Methanol is reduced during ageing in casks.43
by following the concentration of just one corresponding chemical Fermentation alcohols with more than two carbon atoms are
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marker. known as higher or fusel alcohols. They are synthesised by

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yeasts during fermentation, either directly from sugars or from are often considered to give wine much of its vinous fragrance.
grape amino acids via the Ehrlich reaction. In wine, the higher The ethyl ester content of brandies increases during ageing, as a
alcohol content remains almost unaffected before distillation. consequence of the slow esterification of different organic acids
Quantitatively, the most important higher alcohols are the straight- with ethanol. Preserving wines before distillation in the presence
chain alcohols: 1-propanol, isobutyl alcohol (methyl-2-propanol-1) of lees has been connected with increased content of ethyl esters,
and amyl alcohols (a mixture of 2-methyl-1-butanol and 3-methyl- since they are generally retained within yeast cells, rather than
1-butanol). Most straight-chain alcohols and their esters have a being released into the fermenting must during fermentation.
strong pungent smell. At low concentrations, they contribute to It has been found3 that there are about four times less ethyl esters
the aromatic complexity but at higher levels are characterised by of fatty acids with 8, 10 and 12 carbon atoms in Armagnac than
penetrating odours which mask the aromatic finesse. In distilled in Cognac. Some brandies contain noticeably lower quantities of
spirits, such as brandies, rum and whisky, fusel alcohols provide esters than others. This can be attributed to the utilisation of ‘wine
most of their common aromatic character. distillate’, which results in poorer distillates concerning volatile
They reach concentrations in the range of 150–550 mg L−l in substances.
wine and 2.5–5.0 g L−1 of pure alcohol in distillates. Recovery is Ethyl butyrate concentration increases with ageing, with the
about 90% with the exception of 2-phenyl-ethanol which is 10% absence of antioxidant and antimicrobial agents, and mainly with
recovered. increased temperature. In general, wines pressed by continuous
The herbaceous odour of brandies is due to grape-derived presses contain higher amounts of ethyl esters of long chain fatty
carbonyl compounds with six carbon atoms. Unripe grapes and acids (14–18), due to the fact that they contain relatively lower
continuous presses may induce herbaceous tastes by liberating oxygen which affects their synthesis by yeasts.44 Distillates of wines
compounds, such as hexanols (hexanol-1 and hexanol-2) and which have remained in contact with lees contain greater amounts
hexenols (cis-3-hexene-1-ol, trans-2-hexen-1-ol, cis-2-hexen-1-ol). of ethyl decanoate and ethyl laurate.9 Recent research has shown
1-Octen-3-ol is characterised by a mushroom odour and it is that some brandies contain naturally rare ethyl esters, which may
produced in grapes infected by Botrytis cinerea.42 have some impact on their aroma. Such compounds are ethyl 2-, 3-
and 4-methylpentanoate, and ethyl cyclohexanoate, which exhibit
pleasant strawberry–liquorices-like odours.45 As brandy matures,
Volatile acids
ethyl esters become less flavour-active,46 due to an increase in their
Acetic acid is the main volatile acid and contributes greatly solubility in aqueous ethanol by the wood-extracted materials.
to the volatile acidity. It has a vinegar-like intense odour and The most prevalent ester in wine is ethyl acetate. A small quantity
its concentration is significantly increased during wine ageing. is produced by yeasts during fermentation, but it is mainly formed
Although it commonly occurs in wine, it typically occurs at by the activity of the aerobic acetic bacteria. Wines normally
detectable levels only in wines spoiled by acetic acid. During wine contain below 40 to 120 mg L−l , while distillates and brandies
maturation in barrels, a small quantity of acetic acid, however, can contain about 0.4 to 0.8 g L−l of pure alcohol. Ethyl acetate has
be produced from ethanol oxidation or it can be extracted from a recovery of 100% in continuous distillation and 60% in batch
wood hemicelluloses. In wine, it is found in concentrations ranging distillation.
from 300 to 700 mg L−l , while in distillates the concentration ranges
from 0.20 to 1.0 g L−1 of pure alcohol. Recovery is as low as 2–5% Higher alcohol acetates
due to the removal of the distillation ‘heads’. However, distillates
The formation of esters between acetic acid and higher alcohols is
produced by continuous distillation may contain higher amounts
also important since they may provide a fruity character. For
of acetic acid due to the absence of the removal of the distillation
example, isoamyl acetate, which has a characteristic banana
heads.
odour, positively influences brandy’s aroma. Low fermentation
Other carboxylic acids, such as propionic acid and butyric acids
temperatures favour synthesis of fruity esters, such as isoamyl,
may also be present and they are also associated with bacterial
isobutyl and hexyl acetates, while higher temperatures favour the
activity. Butyric acid is characterised by unpleasant buttery and
production of higher molecular weight esters. Both low SO2 levels
cheesy aromas and its concentration is increased during ageing.
and juice clarification favour ester synthesis and retention. The
Hexanoic, octanoic, decanoic, dodecanoic, myristic (14 carbon absence of oxygen during yeast fermentation enhances further
atoms), palmitic (16 carbon atoms), and stearic (18 carbon atoms) ester formation.47
acids are formed by yeasts. Ester synthesis as well hydrolytic breakdown continue non-
enzymatically during ageing based on the chemical composition
Ethyl esters and storage conditions of the brandy.
Esters are condensation products of the carboxyl group of an
organic acid and the hydroxyl group of an alcohol or a phenol. Aldehydes and ketones
Esters are produced by yeasts after cell division has ceased. Acetaldehyde (ethanal) is the major aldehyde found in wine. It
They can also be present in grapes, but their amount and is one of the early metabolic by-products of yeast fermentation.
sensory importance are often negligible. Esters are present in More acetaldehyde is produced through autoxidation of ethanol.
fresh brandies and since they have fruity aspects, they have an An important quantity is bound to sulfur dioxide in cases where
important contribution to the development of their aroma. Over it is has been added to the base wine. The toxicity associated
160 esters have been identified in wines and most of them are also with acetaldeyde is well known and its presence in the alcoholic
present in brandies. Recovery varies from 40 to 60% depending beverages is quite often related to nausea and vomiting. In
on the distillation technique. distillates and brandies it is found in concentrations ranging
Of the monocarboxylic acid esters, the most important are those from 0.20 to 0.25 g L−1 of pure alcohol.
based on ethanol and saturated carboxylic acids, such as hexanoic Other aldehydes which may be found in brandies are
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(caproic), octanoic (caprylic) and decanoic (capric) acids. These formaldeyde, 5-hydroxymethylfyrfural, acrolein, propionaldehyde,

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butyraldeyde, benzaldehyde, isovaleraldeyde and n-valeraldeyde. beverages in amounts ranging from undetectable levels to 534
The aldehydic content of brandy can be analysed by reversed- mg L−l . RP-HPLC with fluorescence detection and GC-MS were
phase HPLC.48 used for its identification.
Isobutanal at concentrations higher than 25 mg L−l could give
a herbaceous character to the brandy. However, during ageing its
Trichloroanisole
content declines due to acetylysation and selective evaporation.
Fortunately, cork taint in wines is very rare. It produces a very
trans-Nonenal is characterised by a paper-like sense, while octanal
unpleasant, putrid smell that causes wine quality to deteriorate.
contributes to the aroma complexity by adding an orange
Their origins are certainly related to wine corks, but it may appear
flavour. Although concentration of both the above aldehydes
also in brandies. In brandy, 2,4,6-trichloroanisole was described as
is increased during ageing, it generally remains below the
possessing a walnut-like aroma. In brandy, 2,4,6-trichloroanisole
perception threshold. However, significant statistical correlations
can be perceptible 5–30 min after consumption.57
have been obtained among the herbaceous odour and aldehyde
concentration.49
β-Damascenone is a isoprenoid ketone which is present in Furfural and furanic compounds
grapes. Since it is a highly odoriferous compound with a powerful Another aldehyde having a sensory impact of ‘baked’ in brandy
and pleasant fragrance, it is an important compound in the is furfural (0.5–82.5 mg L−l of pure alcohol). Its synthesis involves
perfume and flavouring industries. As it has a very low sensory sugar oxidation and it is activated by heat. It is mainly produced
threshold, β-damascenone is considered to be a key odour during distillation from the remaining pentose content of the lees
compound in brandy, imparting a ‘stewed apple’, ‘fruity–flowery’ and consequently it is highly influenced by the distillation system
and honey-like character.50 Diacetyl (2,3-dioxobutane), is a ketone employed. For this reason, the concentration of furfural in brandy
produced during wine fermentation through oxidation of acetoin, shows high fluctuation. Furfural and its derivatives may also derive
a degradation product of citric acid.51 It has an important sensory from both the wooden cask and the possible addition of caramel.
influence on brandy since its odour is characterised as sweet, Double distillation enhances the amount of all furanic species.
buttery or butterscotch-like. Thus, Cognac can be differentiated from Armagnac, since Cognac
contains higher contents of furan derivatives.33
Sulfur derivatives
Brandy may contain extremely low concentrations of different Non-volatile substances in brandy
unpleasant (rotten eggs, garlic) volatile sulfur compounds, such Total acidity
as hydrogen sulfide, carbonyl sulfide, sulfur dioxide, thiols, Total acidity in brandies is initially due to the presence of volatile
sulfides, polysulfides and thiosterols. The determination of these acids, such as acetic acid. Acetic acid content increases during
compounds in wines and spirits is difficult because of their volatility ageing by oxidation of ethyl alcohol. In addition, total acidity
and their very low concentrations, which require the use of highly progressively increases due to the extraction of phenols from oak
sensitive detectors. Among the different analytical techniques, casks. Phenols are weak acids that gradually create a fixed acidity.
gas chromatographic separation coupled with sulfur-specific New brandies have pH values between 4 and 5, while during
detection, namely flame photometric detection, is the most widely maturation pH falls to 3.5.
used method. Nedjma and Maujean52 used a static headspace
technique and a chemiluminescence detector. Counter-current
supercritical fluid extraction could also be used as it permits Metal content
maximum extraction of aroma compounds in brandy. Although wine contains different metals, they are not volatile and
therefore they cannot be found in the distillates. Brandy acquires
its metallic content by contact with different metals of stills during
Ethyl carbamate
distillation.
Ethyl carbamate is a potential carcinogenic compound and its Aluminium is widespread throughout nature – in air, water and
presence is strictly monitored in wines and spirits. Yeasts may be plants – and consequently in all the food chain. Also, packing
involved in ethyl carbamate synthesis through the production of materials and containers may contaminate alcoholic beverages.
carbamyl phosphate and by the synthesis and degradation of urea. A reliable and rapid method for the determination of aluminium
The official determination method of ethyl carbamate in alcoholic in alcoholic beverages by graphite furnace is atomic absorption
beverages is GC-MS. However, other methods such as HPLC53 and spectrometry.58 The mean aluminium concentrations in alcoholic
HPLC with post-column fluorescence derivatisation have also been beverages ranged from 15.7 to 739.6 mg L−l .
employed.54 The cadmium content of alcoholic beverages was measured by
electrothermal atomisation–atomic absorption spectrometry.59
Organo-tin compounds The mean values measured ranged from undetectable levels to
Organo-tin compounds are widely used in agriculture and industry. 11.52 µg L−l . The wide variability of the results emphasised the
They can also be present in brandies and wines. Because of multiplicity of factors that can influence the presence of cadmium
their high toxicity, even at very low concentrations, sensitive and in these products.
selective analytical procedures must be employed for their analysis. Calcium, copper, iron, magnesium, manganese and zinc can be
Recently, these compounds were detected in wine samples, with measured by flame atomic absorption spectrometry in brandies.
concentrations varying55 from 50 to 80 000 ng L−l . Heroult et al.55 Potassium and sodium content can be determined by atomic
developed an analytical method for determination of ethylated emission spectrometry, while aluminium, cadmium and lead by
organo-tins in brandies based on solid-phase microextraction. graphite furnace atomic absorption spectrometry.60
A tetrahydro-β-carboline (1-methyl-1,2,3,4-tetrahydro-β-carbo Copper is a very important trace element due to its heat
409

line-3-carboxylic acid ethyl ester) was identified56 in alcoholic conducting and chemical properties. Most of the copper found in

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wines originates from sprays based on the disinfectant properties The first year of ageing of Cognac and Armagnac takes place
of copper sulfate, used to treat vines for mildew. Copper could in new oak casks, while after that period they may be placed in
combine with caprylic, caproic and lauric fatty acids, whose used casks. Sherry brandies (brandies de Jerez) are aged in casks
odour resembles that of cheese, as well as with long-chain fatty of American oak (Quercus alba), which previously contained sherry
acids which could produce insoluble soaps. As far as distillation wine. This prior procedure is known as the ‘wining’ of the casks.
is concerned, its presence is connected with higher quality The characteristics of each brandy de Jerez will vary according to
distillates. Distillation in stainless-steel distillers results in poor- the type of sherry which the oak-wood casks previously contained.
quality brandies. The process can be improved by the addition of Brandies de Jerez age according to the traditional dynamic system
turnings of copper or copper sulfate.3 known as ‘Soleras y Criaderas’. In this system, only a proportion
of the brandy contained in the oldest barrel (situated at ground
Caramel level, hence the name: solera) is drawn off for bottling. Then that
barrel is refilled from the next oldest cask (the first criadera) and
The addition of caramel is quite common in the production of
that, in turn, is refilled from the third oldest, and so on to the
aged spirit beverages since it gives them an amber coloration
youngest cask, which contains the newly distilled product. The
that is attractive to the consumer. The chemical composition
quantities of the younger product transferred in this way mix
of caramel is complex, due to the large number of substances
with the older product in the corresponding barrel, thus acquiring
produced as a result of pyrolysis of carbohydrates, such as sucrose,
the desirable characteristics.30 Phenolic and furanic content of
glucose or starch. However, furanic compounds are also present,
brandies de Jerez, increases considerably during ageing.24
such as furfural or 5-hydroxylmethyl furfural, of which the latter
Most casks are made by oak wood and rarely by chestnut
is found in much higher concentrations. In cases where caramel
wood. Caldeira et al.64 confirmed the strong influence of the barrel
colour has been added to brandies, it influences the furfural/5-
toasting degree on the sensory profile of the aged brandies. The
hydroxylmethyl furfural ratio, as it is higher than 1 in brandies
brandies that had been aged in strong toasted chestnut barrels
without caramel and lower than 1 in those with the addition of
presented sensory properties more closely related to the older
caramel.61
brandies than the brandies aged in medium or light toasting
The colour characteristics of a brandy can be estimated by
barrels. The cis-β-methyl-γ -octalactone content of the brandies is
calculating a trichromatic value at wavelengths between 400 and
an important chemical marker to distinguish chestnut from oak
700 nm every 5 nm.32 A simplified method to calculate colour
wood.66 Brandies matured in barrels made with American white
coordinates by measuring only three wavelengths was proposed
oak contained higher amounts of (3S,4S)-oak lactone than those
by Ayala et al.62
matured in barrels made with Quercus robur from Europe.67
In spite of their wide acceptance, the use of wooden barrels
Maturation in casks is prone to some problems, such as the high cost and the
Oak wood consists of 40–45% cellulose, 20–25% hemi-cellulose, difficulty of their handling. Therefore, recently, the use of wood
25–30% lignin and 8–15% tannins. These components are best fragments in order to promote an accelerated ageing process
extracted by wine spirits with an ethanol concentration of 55% became an interesting economic alternative to the wooden
(v/v).31 The natural colour of the brandy is due to the presence barrels. Alternative wood ageing systems (staves and tablets)
of tannins. The phenolic composition of distillates that have been were compared66 with wooden barrels after an ageing period
aged in barrels can be analysed by HPLC.63 of 6 months. The brandies aged in wooden barrels contained
the highest levels of several ethyl esters, acids, furanic aldehydes
Volatile compounds from casks and the lowest levels of volatile phenols. Regarding eugenol
Volatile compounds extracted from the barrel wood are mainly and vanillin levels, the lowest values were found in the brandies
furanic and phenolic compounds. Concentration of furanic aged with tablets. The smoky and toasted odour notes associated
compounds, such as furfuryl ethyl ether, furfural, 2-acetylfuran and with some volatile phenols could explain the higher toasted
5-methylfurfural, varies according to the type of cask and ageing notes reported for the brandies aged with tablets. In fact, a
time. Furanic aldehydes derive from the thermal degradation of positive linear correlation was found between the levels of
wood polysaccharides of wooden casks. guaiacol, 4-methylguaiacol and syringol and the toasted attribute.
Eugenol, cis-β-methyl-c-octalactone, furfural, 4-hydroxy-2- Considering the overall quality of the brandies, the results obtained
butenoic acid lactone, hexanoic acid and guaiacol seemed to suggested the use of wood fragments to be an interesting
be important compounds, which could be related with the wood alternative technology. On the other hand, the chemical analysis
origin. The toasting process can modify strongly the volatile of the brandies showed the possibility of discriminating the ageing
composition of the different types of wood, particularly the levels of technologies based on odorant compound levels.
furanic aldehydes (furfural, 5-methylfurfural with toasted almond
aromas, 5-hydroxylmethyl furfural), volatile phenols (syringol Non-volatile compounds from casks
and 4-allyl-syringol), propanoic acid, 4-hydroxy-2-butenoic acid The ageing of spirits in oak barrels is a complex process. Direct
lactone and vanillin.64 When wood is not toasted, the extraction extraction of wood components or degradation products of
during ageing is limited. After three consecutive uses (3 years) the macromolecules of the wood may occur, as well as reactions
wood will no longer liberate fatty acids, coniferaldeyde, furfural, 5- between the components of the distillate itself and/or those
methylfurfural and 5-hydroxymethyl-furfural into the wine spirits. originating from the oak wood (polymerisations, esterifications,
However, it is still an important source (30–50%) of polyphenols, acetylysations, and hydrolysis), in addition to major oxidation
ellagic acid, gallic acid, vanilline, methyl-octalactone and eugenol. processes. Apart from ellagitannins, oak releases a certain number
During the first use, the barrel wood contributes mainly to the of other compounds into brandies, mainly lignins. Depending
toast aroma of spirits, while during the second and third it offers on conditions, oak may also release polysaccharides, mostly
410

more vanilla flavour.65 consisting of hemicelluloses, that contribute to spirit flavour.

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Liquid chromatography with diode array detection and liquid predicting the aroma from the odour profile, shortening thus
chromatography–mass spectrometry has been used for their the evaluation time. A second aim was the assessment of the
analysis. Capillary electrophoresis is a simple and useful method sensory contribution of each post-fermentation production stage
which has been employed for the analysis of tannins and other of Muscat wine distillates by the use of chemical markers. They
polyphenolic compounds of brandies.68 formed sample clusters of sensory and chemical data employing
principal component analysis and revealed the potential chemical
markers. The chemical markers which were characteristic of the
Antioxidant activities
‘head’ fraction were ethyl hexanoate, ethyl octanoate and ethyl
Brandies contain polyphenols which are well-known antioxidants
decanoate. The possible chemical markers of the first part of the
having a protective effect on human health. They acquire their
‘heart’, included linalool, ethyl hexanoate, ethyl octanoate, and
polyphenolic content and thus their antioxidant activity during
ethyl decanoate while of the second part 2-phenylethanol, ethyl
ageing through contact with the barrel wood.
lactate and decanoic acid. Oak ageing was correlated with eugenol
A significant correlation between the antioxidant activity and
and whisky lactones, while 5-hydroxy-methyl-2-furfural accounted
the total polyphenolic content of the spirits has been found.69
for added caramel.
In respect of the compounds considered individually, each
Ferrari et al.73 used gas chromatography–olfactometry to
polyphenol had a different antioxidant power depending on its
identify odorant compounds responsible for the typical sensory
chemical structure. The compounds which were present in greater
descriptors attributed to freshly distilled Cognac spirits, not
concentrations were not necessarily those better correlated with
matured in barrels. They demonstrated that many odorant
the antioxidant power of the samples. When brandies had been
molecules were already present in freshly distilled Cognac,
in contact with wood, a significant amount of polyphenols was thereby providing the spirit with its specific aroma. Among
extracted resulting in an important contribution to the antioxidant more than 150 organic compounds identified in Cognacs not
power. aged in wooden casks, only 34 were responsible for odours. The
Schwarz et al.70 studied the antioxidant activity of commercial ‘butter’ descriptor was explained by the presence of diacetyl,
sherry brandies obtained from an experimental ageing system the ‘hay’ descriptor by nerolidol, the ‘grass’ descriptor mainly by
(Solera, Solera Reserva and Solera Gran Reserva). They concluded (Z)-3-hexen-1-ol, the ‘pear’ and ‘banana’ descriptors by 2- and
that this parameter was correlated with the total phenolic content. 3-methylbutyl acetates, the ‘rose’ descriptor by 2-phenylethyl
The results also suggested that addition of caramel may also acetate and the ‘lime tree’ descriptor by linalool. Moreover, gas
contribute to the antioxidant activity of the brandies. It was also chromatography–olfactometry followed by GC-MS analysis was
found that Solera Gran Reserva samples showed the highest used74 to identify and characterise aroma compounds responsible
antioxidant activity of all the products studied. for distinctive odours of brandies produced in Slovakia. It
was found that the presence of olfactive zones described by
Sensory evaluation olfactory attributes, such as fruity (including vegetable), floral and
Sensory evaluation of brandy is similar to wine tasting since it herbal depended on maturation time. Caldeira et al.66 studied
includes colour, smell, mouth feel and after-taste examination. odorant compounds in different aged brandies from Lourinhã.
The main difference is that brandy contains lower quantities of These compounds presented important correlations with several
acids and a much higher quantity of ethyl alcohol that provides an olfactory attributes, such as vanilla, woody, spicy, burned/toasted,
alcohol burning sensation known as ‘rime’. dried fruits, smoke, fruity, green and tails.
Ségur and Chassin71 proposed the use of description forms
in order to characterise Armagnac by sensory evaluation. The Authentication
first form was related with the acceptance or not of the product GC, GC-MS and ultraviolet–visible spectrophotometry have been
based on the detection of sulfur, alcohol burning, butter–putrid, employed for identifying the adulteration of strong alcoholic
winey–vinous, bitter and drying aspects. They also proposed a beverages including brandies. Multi-component analysis of spirits
second form of a more detailed examination of the final product can reveal the replacement of spirit with alcohol produced from
which included visual, nose and mouth evaluation of selected non-grape raw materials, determine whether the spirit was in
sensory attributes. contact with oak wood and how long was the duration of
A special form is used by the Office International du Vin its ageing, and detect the acceleration of the ageing process
(O.I.V.) for the evaluation of the international spirituous beverages by adding certain ingredients.75 Lehtonen et al.76 developed
of vitivinicultural origin (www.oiv.int). In more detail, visual a method based on the determination of higher fermentation
evaluation concerns limpidity and colour. Nose examination alcohols (propanol, isobutanol, 2-methyl-1-butanol, 3-methyl-1-
involves typicality, quality and positive aromatic intensity. Finally, butanol), ethyl acetate, pH and UV–visible absorbance to identify
mouth evaluation focusses on typicality, quality and harmonious the types and/or brands of matured distilled beverages.
persistence. It is difficult to define precisely these sensory attributes A common adulteration is the addition of inappropriate (for
and correlate them with brandy chemical composition and sensory food purposes) ethanol, such as synthetic ethyl alcohol produced
evaluation data. It depends on the personal evaluation abilities of by the hydration of ethylene or of industrial ethyl alcohol prepared
the tasters since it is, to some extent, a subjective judgment. from wood raw materials. It is possible to determine whether
Thus, in recent years research has focused on possible ethanol derives from fermentation or it has been synthesised by
correlations between the sensory data and the results of the using a set of characteristic impurity markers of alcoholic nature,
chemical analyses. Precise sensory measurements of both odour which are present in a certain ratio and can be determined by
(orthonasal) and aroma (retronasal olfactory perception) are time GC or GC-MS analysis. Acetone, 2-butanol, crotonaldehyde and
and resource consuming. An improved olfactory tasting procedure some other impurity substances typical of synthetic alcohol and
was developed by Pena y Lillo et al.72 based on the comparison atypical of alcohols produced by fermentation can be used as such
411

of odour and aroma profiles of Pisco spirits and aiming at markers. Furthermore, vanillin and syringaldehyde could be used

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 www.soci.org A Tsakiris, S Kallithraka, Y Kourkoutas

as age markers. The dilution of Cognac with rectified alcohol or a 4 Peña y Lillo M, Agosin E, Belancic A and Latrille E, Chemical markers for
water–alcohol mixture can also be detected since it results in a tracking the sensory contribution of production stages in Muscat
wine distillates. J Food Sci 70:432–441 (2005).
proportional decrease in the concentrations of all components.75
5 Osorio D, Péerez-Correa R, Belancic A and Agosin E, Rigorous
Fourier transform infrared spectroscopy was employed77 for the dynamic modeling and simulation of wine distillations. Food Control
differentiation and classification of brandies during their ageing 15:515–521 (2004).
process, as well as for the characterisation and differentiation of 6 Estregueil S, Galy B, Loiseau B and Lutron L. Maı̂trise des risques liés
the origin of distilled drinks from several producing countries. à l’utilization de specialités phytosanitaires dans le vignoble de
Cognac, in Les Eaux-de-Vie Traditionnelles d’Origine Viticole, ed. by
An alcoholic beverage is a complex mixture consisting of a large Bertrand A. Lavoisier TEC & DOC, Paris, pp. 65–67 (2007).
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of alcoholic beverages based on the measurement of the sulfureux et de la lie sur la qualité du Brandy distillé à la Chaudiere,
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mixing conditions which made possible to create gradients of des pectinases pour la vinification charentaise des vins destinés
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