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Aroma compounds in barrel aged apple distillates from two different

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DOI: 10.1002/jib.573

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Received: 4 April 2018 Revised: 2 April 2019 Accepted: 7 April 2019 Published online in Wiley Online Library

(wileyonlinelibrary.com) DOI 10.1002/jib.573

Aroma compounds in barrel aged apple

distillates from two different distillation
techniques
Nermina Spaho,1* Davorka Đukic-Ratković,1,2 Ninoslav Nikićević,3
Milenko Blesić,1 Vele Tešević,4 Branko Mijatović2 and Mirela Smajić Murtić1
The major fermentation and maturation related congeners in apple distillates from two different distillation techniques (alembic
and column), matured in oak for 18 months, were measured by GC-MS and HPLC. Together with a higher ethanol content, column
distillates had higher ethyl acetate, methanol and n-propanol levels compared with alembic distillates. A higher content of acet-
aldehyde was characteristic of the alembic distillates. The concentrations of i-butanol, n-butanol, amyl alcohols and n-hexanol
were not affected by the distillation technique used. Increasing the ageing time of distillates in oak resulted in an increase in
the contents of acetaldehyde, ethyl acetate and amyl alcohols while the content of methanol decreased during ageing. Through-
out ageing, there were no significant changes in the concentrations of n-propanol, i-butanol, n-butanol and n-hexanol. Among
the maturation related compounds, gallic acid, ellagic acid, vanillin and syringaldehyde were determined in apple distillates with
ellagic acid being the most abundant. The contents of gallic acid and ellagic acid increased during ageing whereas vanillin and
syringaldehyde slightly increased throughout the 18 months of maturation. © 2019 The Institute of Brewing & Distilling

Keywords: Charente alembic; batch distillation column; apple spirits; fermentative aroma compounds; maturation aroma compounds

Introduction there are several important differences in spirit production. A

In the Western Balkan countries, traditional fruit liqueur production
still uses a simple distillation pot. During the last two decades,
column distillation has slowly entered the production of spirits in
small distilleries and two different types of distillation equipment
are now commonly used in the production of fruit spirits: the
Charentais alembic pot (French style) and the batch distillation col-
umn (German style). It is clear that different distillation techniques
have an influence on the dynamics of evaporation of volatile
compounds.
A batch distillation column style requires just one distillation to
achieve a high alcohol content (1–3) and consists of a copper pot
fitted with a column with trays and a dephlegmator (reflux con-
denser). For the production of fruit spirits, the column is usually
equipped with three ball trays. Continuous contact of vapour
and liquid with each tray enriches the vapour stream with lighter
components, while the liquid stream becomes saturated with
heavy components. Consequently, as more trays are used in the
distillation, a greater concentration of alcohol and a lower concen-
tration of congeners are obtained. However, some of these conge-
ners are pleasant aroma compounds and rectification must be run
carefully, mindful of what aroma compounds are required in the
distillate (4–7).
Distillation in an alembic pot stills requires multiple distillations
(typically double) to achieve a high content of alcohol. The pur-
pose of the first distillation is to recover as much alcohol as possi-
ble from the fermented mash. The second stage of distillation is
required for the intensification and purification of the alcohol.
The higher the alcohol content, the more neutral the spirit will
be. Although both distillation techniques are performed on the
same theoretical basis and for both three fractions are obtained,
major difference is in the content of alcohol that is distilled. For
alembic distillation, the alcohol strength of the heart fraction
ranges from 50 to 65% v/v, while for column distillation, the
alcohol strength in the heart fraction is higher, ranging from 65
to 85% v/v (8).
The initial concentration of alcohol is very important for the age-
ing of distillates. Macatelli et al. (9) reported that understanding the
behaviour of aqueous ethanol solutions at different concentrations
during maturation is the key challenge of specifying solution prop-
erties and predicting their effects on aroma compounds. Further,
during maturation, the different alcohol content affects the extrac-
tion profile and the process of evaporation in various spirits (10).
Differences between distillates obtained by the two distillation
techniques have been investigated by many authors (3,11–15).
There are also many studies dealing with various influences on
the chemical and sensory changes of the spirits during ageing
(16–25). Indeed, Rodríguez Madrera et al. (26) reported a particu-
* Correspondence to: Nermina Spaho, Faculty of Agriculture and Food Science,
University of Sarajevo, Zmaja od Bosne 8 Sarajevo 71000, Bosnia and
Herzegovina. E-mail: n.spaho@ppf.unsa.ba
1
Faculty of Agriculture and Food Science, University of Sarajevo, Zmaja od
Bosne 8, Sarajevo 71000, Bosnia and Herzegovina
2
Distillery BMB Delta, Jablanica, 173, Gradiška, 78405, Bosnia and Herzegovina
3
Faculty of Agriculture, University of Belgrade, Nemanjina 6, Belgrade 11000,
Serbia
4
Faculty of Chemistry, University of Belgrade, Studentski trg 16, Belgrade
11000, Serbia

J. Inst. Brew. 2019 © 2019 The Institute of Brewing & Distilling


larly interesting study where different cider brandies were
characterised according to ageing time.
To the best of our knowledge, there are no published studies on
the effects of the Charente alembic pot and batch distillation col-
umn on the fermentation and maturation related compounds in
apple distillates. Accordingly, the purpose of this report is to inves-
tigate whether different distillation techniques have a significant
effect on the concentration of major volatile compounds in the ap-
ple distillates. In addition, the dynamics of fermentation and
maturation related congeners during 18 months of ageing in oak
barrels are discussed, with the aim of detailing the ageing poten-
tial of the two apple distillates produced by different distillation
techniques.
Materials and methods
Apples
Two apple varieties were used for producing the spirits: 6000 kg of
Idared and 4500 kg of Pink Lady. The pH of the Idared mash was
3.4 and the extract was 13° Brix, and the pH of the Pink Lady mash
was 3.5 and the extract was 14° Brix. Apples were collected from
the orchard of the local producer in Gradiska and after harvesting
transported to the commercial distillery BMB Delta.
Fermentation
Milling was performed in a standard apple mill. Whole apples were
crushed and shredded by the rotating rollers with stainless steel
teeth with a mill capacity of 2800 kg/h. Immediately after milling,
the mash was divided into two aliquots. The mash was corrected
to pH 3 with the addition of a 10% (v/v) sulphuric acid. After
10 min, the mash was inoculated with 20 g/100 kg of Saccharomy-
ces cerevisiae var. bayanus, wine yeast (Oenoferme -Freddo,
Geisenheim, Germany). Fermentation was in two stainless steel
vessels of 6000 L at 19 ± 3°C and lasted for 26 days. The rate of al-
cohol fermentation was monitored by density measurements.
When the fermentation reached 3.5° Brix it was considered
complete.
Distillation in an alembic pot
Fermented apple mash (5000 L) was distilled in a 220 L traditional
alembic pot (‘A’) heated directly by flame and equipped with a stir-
rer. Distillation was performed twice. The mash was divided into
appropriate volumes (200 L). A total of 25 first-stage distillations
were performed, and 870 L of raw distillate was collected at 17%
v/v ethanol. The raw distillate was divided into six aliquots of
145 L for the second distillation which was run with separation
Figure 1. The experimental conditions for two distillation techniques to obtain samples for analysis. [Colour figure can be viewed at wileyonlinelibrary.com]
wileyonlinelibrary.com/journal/jib © 2019 The Institute of Brewing & Distilling
N. Spaho et al.
of the fractions. Three fractions – head, heart and tail – were sepa-
rated on the basis of their alcohol content monitored during the
distillation process using an alcoholmeter. The first fraction was
separated from the second using sensorial analysis and ~1.2% of
the raw distillate volume was discarded (head). The distillation
continued to an alcohol concentration of 40 ± 1% v/v (heart), the
remaining fraction being the tail. During the distillation, the flow
was kept constant with a flow rate of ~194 mL/min. Only the heart
fraction was further investigated. From the first three re-
distillations, a portion of the heart fraction was used as a control
representing ‘fresh distillate’. All other heart fractions were com-
bined for ageing with a volume of 289 L at 61% v/v ethanol.
Distillation in batch distillation column
A total amount of 5500 L fermented apple mash was distilled in
the 300 L Holstein batch distillation column (‘C’) which had three
bubble cap tray catalysers on top of the column and a
dephlegmator. Two trays were active and the distillation was con-
ducted once. Mash (220 L) was pumped into the pot of the still and
heated with steam at 0.5 bar until reflux commenced on the third
tray. Claus and Berglund (1) suggested that once reflux begins, the
pressure reduces to between 0.3–0.4 bar on the third tray and is
kept constant for the duration of the distillation. The heating and
partial condenser cooling rates of the distillation column were ad-
justed to obtain a distillate flow rate of 88 mL/min. In all, a total of
25 distillations were performed. The distillates were collected in
three fractions: head, heart and tail. The schemes of the alembic
and column distillations are presented in Figure 1.
The first 1.8 and 2 L were collected as the head. The head cut
was separated using sensory analysis by two tasters and was
<1% of the fermented mash volume. The heart fraction was cut
when the alcohol strength decreased to 50% v/v, the remaining
fraction being the tail. Within the average volume of the heart,
the fraction was 10.5 L with ethanol at 66.7% v/v. The control sam-
ples of fresh distillates were taken from the first three distillations.
All other heart fractions were combined for ageing with 262.5 L
with 66.7% v/v ethanol. The volumes and alcohol strength of heart
fractions in the first three distillations in alembic and column are
presented in Table 1.
Maturation in oak barrels
The heart fractions were filled into new oak barrels (50 L) for each
distillation technique. The oak used in barrel making was Quercus
petraea grown in the Serbia region of Sumadija. The thickness of
the staves was 30 mm. The staves used for barrel making were
not toasted and were thermally treated for bending by the manu-
facturer. All barrels were manufactured at the same time by the
J. Inst. Brew. 2019
Aroma compounds in barrel aged apple distillates from two different distillation techniques

Table 1. Analysis of control samples of fresh distillates controlled column and DAD. The separation conditions are shown
obtained by two distillation techniques: alembic (A) and in Table 2. Chromatograms were recorded at 280, 320 and 370 nm
column (C) and all spectra were stored in the range of 190–450 nm. A com-
puter system running ChemStation software (Agilent Technolo-
Repetitions (A) (C) gies) was used for data acquisition and processing.

Volume Ethanol (% Volume Ethanol

(L) vol) (L) (% vol) Statistical analysis
First 49.7 61.3 10.5 65.8 Two-way analysis of variance (ANOVA) was performed to establish
Second 51.0 59.8 9.8 68.1 whether a significant difference (p < 0.05) existed between the
Third 50.4 61.6 10.2 66.2 mean concentrations of the compounds in the analysed sample
depending on the distillation technique used and ageing time.
The ANOVA was followed by a least significant difference test to
same cooperage. The barrels were filled to 85% of volume and verify the statistical difference at the 0.05 significance level. Princi-
were stored in a dark, cool room at 18 ± 6°C and a relative humidity pal component analysis was performed for the visualisation of all
of 62 ± 5%. The ageing was monitored over 18 months in three experimental variables in order to determine the differentiation
repetitions. Accordingly, samples of distillates were taken from between the distillation technique employed and the ageing time.
three barrels per distillation technique and bottled in glass bottles All statistical analyses were performed with the statistical package
after ageing periods of 6, 12 and 18 months. The bottles remained StatBox 6.7 (Grimmersoft, Paris, France).
in the dark until chemical analysis. The fresh (unaged) distillates
were used as a control.
Results and discussion
Analytical methods Changes in alcohol content and pH value during maturation
Alcohol concentration was determined with a portable densitom- The maturation process is characterised by changes in the colour
eter type Mettler Toledo Densito 30 PX and the pH value was mea- and flavour of the alcohol as well as by reduction in volume and
sured with the pH meter WTW InoLab pH 720. alcohol content. Owing to the faster evaporation of ethanol and
water, the concentration of most flavouring compounds increases
during maturation. At the same time, during wood maturation, the
GC analysis of the major volatile compounds
organic acid concentration in spirits increases as a result of the ex-
The main volatile constituents were investigated using the Com- traction from cask wood, the oxidation of ethanol and the evapo-
mission Regulation (EC) no. 2870/2000 of 19 December 2000, ration of ethanol and water (28). One of the main reasons for the
which established common reference methods for the analysis acidity increasing in the aged spirits is extraction from stave wood
of alcoholic spirits by gas chromatography (GC) (27) using a flame of fatty acids (octanoic and decanoic acid) from the breakdown of
ionisation detector. The main components including methanol, ac- wood lipids and dicarboxylic adds (succinic, adipic and methyl
etaldehyde, n-propanol, ethyl acetate, i-butanol, n-butanol, amyl succinic acids). Gallic, vanillic, syringic and ellagic acids are also ex-
alcohols (sum of i-amyl and optic active amyl alcohol) and n- tracted from the lignin and tannin components of wood (28).
hexanol were identified by comparing their retention times with Changes in alcohol content and pH of distillates are important
authentic compounds. For quantitative evaluation, 4-methyl-1- for other changes that may occur over the ageing period. Accord-
pentanol was used as an internal standard (IS). Thus, an ethanol so- ingly, changes in ethanol content and pH during ageing are shown
lution containing 5 g/L 4-methyl-1-pentanol was added to 10 mL of in Figure 2.
each sample. The concentration of each volatile constituent was In this work, the ethanol concentration decreased in all samples
determined with respect to the internal standard from the relative regardless of the distillation technique employed. A more rapid
response factors, which were obtained during calibration under the
same chromatographic conditions as those of the sample. The GC
analysis was performed with an HP 5890 gas chromatograph Table 2. Separation conditions: LiChrospher 100 RPC18e
equipped with a flame ionisation detector and a split/splitless injec- column (250 × 4.0 mm i.d., 5 μm) at 40°C using the combina-
tor. A capillary column (30 m × 0.25 mm i.d., 0.25 μm film thickness) tion of isocratic and gradient modes of elution
coated with HP-5 (5% biphenyl and 95% dimethylpolysiloxane)
was used. The column oven temperature was programmed Time A (2% formic acid B (methanol–MilliQ Flow
from 50 to 285°C at a rate of 4.3°C/min, and the injection port (min) in MilliQ water) water–formic (mL/min)
and detector temperatures were maintained at 250°C. Hydrogen acid, 70:28:2)
was used as the carrier gas at a flow rate of l.6 mL min 1 and the 0 100 0 1
split ratio was 60:1. The sample volume was 1 μL. 3 100 0 1
25 60 40 1
LC–DAD analysis of ageing congeners 43 40 60 1
55 40 60 1
Quantification of congeners (syringaldehyde, vanillin, garlic and 60 20 80 1
ellagic acids) during ageing was performed by liquid 65 20 80 1
chromatography–diode array detection (LC–DAD) using an 66 100 0 1
HPLC1100 Series (Agilent Technologies, Germany) equipped with 70 100 0 1
a vacuum degasser, binary pump, autosampler, thermostatically

J. Inst. Brew. 2019 © 2019 The Institute of Brewing & Distilling wileyonlinelibrary.com/journal/jib

Figure 2. Changes in alcohol content and pH value of apple distillates obtained by
alembic (A) and column device (C) during ageing time.
decline was observed in column distillates, which had a higher ini-
tial content of alcohol than alembic distillates (Figure 2). For the
18 months of ageing, the concentration of ethanol decreased by
about 4% in the alembic distillates and about 5% in the column
distillates achieving, respectively, 57 and 61.7% v/v at the end of
the ageing period. The decrease in alcoholic strength was the
highest from 6 to 12 months during the summer when the ambi-
ent temperature was higher. During ageing in oak barrels of apple
distillates, the pH decreased owing to the extraction of acids from
the wood and oxidation of ethanol and other congeners. Over the
18 month period, the pH decreased from 4.6 and 4.5 to from 4.0
and 3.9 in alembic and column distillates, respectively.
Fermentative aroma compounds, distillation technique and
ageing
During alcoholic fermentation, yeast converts sugar into ethanol
and carbon dioxide but also produces numerous minor but senso-
rially important aromatic compounds (29). Hundreds of different
compounds, termed congeners, have been identified in fruit spirits
which are present at low concentrations but are important for bev-
erage quality. Some of the aroma compounds that are formed dur-
ing alcohol fermentation include acetaldehyde, ethyl acetate,
methanol and higher alcohols including i-butanol (2-methyl-1-
propanol), amylic alcohols that include active amyl alcohol (2-
methyl-1-butanol) and i-amyl alcohol (3-methyl-1-butanol), n-
propanol and n-butanol and n-hexanol. In Figure 3, the average
concentration of the volatile compounds in apple distillates and
the results of the ANOVA test are shown to establish whether the
distillation technique and ageing time resulted in any significant
compositional differences in apple distillates. The concentrations
of all compounds in the analysed apple distillates were broadly
similar to those reported by other authors in the apple distillates
(21,23,30,31) with the exception of n-butanol and n-hexanol, which
were higher in the work reported here.
As can be seen in Figure 3, significant differences were observed
between apple distillates depending on the distillation technique
and ageing time. The concentrations of acetaldehyde, ethyl ace-
tate and methanol were influenced by experimental factors; fur-
thermore, the effect of interaction was observed in the case of
acetaldehyde and methanol. The concentration of n-propanol
was influenced by the distillation technique, while ageing time af-
fected the concentration of amyl alcohols. There was no significant
wileyonlinelibrary.com/journal/jib © 2019 The Institute of Brewing & Distilling
N. Spaho et al.
difference from ageing time and distillation technique for the
levels of i-butanol, n-butanol and n-hexanol.
Acetaldehyde is a major carbonyl compound found in apple
spirits (21), and has been reported to have variable effects depend-
ing on the concentration. At low concentrations it gives a pleasant,
hazelnut, cherry and overripe apple aroma while at high concen-
trations it is responsible for pungent and irritating odours. Silva
et al. (32) established 1200 mg/L ethanol of total aldehydes (mainly
acetaldehyde) as the limiting value before the spirit aroma was sig-
nificantly affected. In all of the samples analysed, the concentra-
tion of acetaldehyde was low and ranged between 0.03 and
0.12 g/L ethanol. The low concentration of acetaldehyde in the
samples is confirmation of the separation of the head from heart
fraction as acetaldehyde is a typical congener of the head fraction.
Also, the low concentration of this compound indicates a con-
trolled fermentation without unnecessary ethanol oxidation. As
can be seen in Figure 3, the ANOVA showed a higher content of
acetaldehyde in alembic distillates than in column distillates. The
results of this study are in agreement with the results reported
previously (3,33,34). According to Matias-Guiu et al. (34), alembic
distillations have much lower levels of compounds in the head
owing to low rectification. However, compound levels in the
head decreased steadily throughout alembic distillation and this
increased the acetaldehyde, acetal and ethyl acetate levels in
the heart. Arrieta-Garay et al. (6) and Balcerek et al. (35) reported
a higher concentration of acetaldehyde in distillates obtained
by rectification column. These differences in the published results
are supported by the content of acetaldehyde corresponding
more to the head/heart cut than the distillation equipment
used (36).
Considering the influence of ageing time on the concentration
of acetaldehyde, it was shown that acetaldehyde significantly in-
creased during 12 months of ageing (Figure 3). This result was in
agreement with the work previously reported by Rodríguez
Madrera et al. (23). Indeed, Vivas and Glories (37) explained this
as a consequence of the capacity of ellagic tannins (derived from
the staves) to consume oxygen, which in turn causes a large quan-
tity of acetaldehyde to be produced (through ethanol oxidation).
Differences between alembic and column samples were observed
during the last six months of maturation, from 12 to 18 months.
While the concentration of acetaldehyde in alembic samples con-
tinued to increase, the concentration of acetaldehyde in column
samples was reduced after 12 months.
Ethyl acetate is the major ester in cider and other fruit brandies
(38,39). Its contribution to flavour is strongly influenced by its con-
centration. In small quantities, ethyl acetate contributes to the
pleasant smell of distillates, giving them a fruity character. Indeed,
the perception threshold of ethyl acetate (180 g/hL a.a.) gives the
spirit an acidic character (40) and it is perceived as having a solvent
character (41). Guichard et al. (30) noted that ethyl acetate in a con-
centration of 388.77 g/hL a.a. was acceptable in the Calvados
sample.
As shown in Figure 3, the content of ethyl acetate in fresh alem-
bic distillates was two times lower than in fresh column distillates.
The same result was reported by Garcia-Llobodanin et al. (3),
Cortes et al. (12) and Balcerek et al. (35). Differences were observed
in the content of ethyl acetate according to maturation. However,
the content evolved very differently over time. An increase was de-
tected for the first six months of ageing, followed by a decrease for
the next six months. After one year, the content of ethyl acetate in-
creased progressively, especially in alembic samples, and attained
a maximum level of 2.33 g/L of ethanol. Its concentration increased
J. Inst. Brew. 2019
Aroma compounds in barrel aged apple distillates from two different distillation techniques

Figure 3. Changes in the average content (g/L a.a., absolute alcohol) of the fermentative volatile compounds in apple distillates depending on distillation technique used and
ageing time of distillates.

as a result of esterification in the presence of ethanol in distillates.
Lee et al. (42) noted that, in maturation, esterification of fatty acids
occurs and ethyl acetate becomes abundant originating from
acetic acid from the hydrolysis of hemicellulose acetyl groups,
oxidation of ethanol and wood charring.
Among the congeners in fruit spirts, methanol is often the most
abundant (43), which is supported by this study. Although it has a
limited sensory impact (15), its presence in spirits is important due
to its toxicity. The concentration of methanol in all distillates in
this study was <1200 g/hL of ethanol, which is the official limit
of the European Council (N-110/2008) (44) for apple spirits. The
concentration of methanol was influenced by both experimental
factors and their interaction. Its content was considerably higher
in distillates obtained by column distillation (Figure 3) in agree-
ment with the work reported by Cortes et al. (12). In their study,
the concentration of methanol was seven times higher in the case
of industrial distillation than the concentration of methanol in the
distillates obtained by a simple pot still. It is very difficult to sepa-
rate the methanol from the ethanol–water mixture owing to the
formation of azeotropic mixtures. It appears that ethanol is
followed by methanol throughout distillation and concentrates
together with ethanol. Further, Matias-Guiu et al. (34) state that

J. Inst. Brew. 2019 © 2019 The Institute of Brewing & Distilling wileyonlinelibrary.com/journal/jib
 N. Spaho et al.

methanol was the only head compound which maintained a sim-
ilar concentration through the distillation. In contrast to our results,
the results of Arrieta-Garay et al. (44), there is no difference in
methanol content (in grape pomace spirits) depending on the dis-
tillation system employed (alembic pot still or packed column dis-
tillations) while Léauté (8) and Garcia-Llobodanin et al. (3) observed
that the methanol content was higher in alembic distillates than
column distillates.
The behaviour of methanol was interesting, considering its
changes throughout ageing. The methanol content significantly
decreased during two maturation levels, but just for the column
distillates. Since the column distillates had a higher ethanol con-
tent, the ethanol evaporation was more pronounced than in alem-
bic distillates (Figure 3) with the associated evaporation of
methanol. In the case of alembic distillates, a slight increase in
methanol content was detected during the first six months
followed by a considerable decrease. After one year, concentration
of methanol was stable in all samples. The reduction in methanol
occurs owing to its evaporation and adsorption, but also as a result
of other simultaneous processes occurring during maturation in
oak barrels, such as oxidation of methanol to formaldehyde, ester-
ification and acetal transformation (17).
Higher alcohols are produced by yeast during fermentation.
They make an important contribution to the aroma profile of the
distillate, imparting aroma and essential character (40). Among
the higher alcohols, the largest were the amyl alcohols followed
by i-butanol and n-propanol. The quantities of the n-butanol and
n-hexanol were considerably lower. A significantly higher amount
of n-propanol was found only in the fresh column distillates in
comparison with fresh alembic distillates. Among all higher alco-
hols, n-propanol has the lowest boiling point, which makes it more
likely to be in the head compared with the other higher alcohols.
Owing to the low rectification capacity of the alembic pot and its
solubility in ethanol, n-propanol was pulled at the beginning of dis-
tillations when the vapour was rich in ethanol. During the column
distillation, a high level of ethanol was maintained in the heart frac-
tion together with some of the n-propanol. After six months of
ageing, the concentration of n-propanol reached the same value
in all samples, which was maintained throughout the ageing
period.
Although higher concentrations of i-butanol and n-butanol
were found in alembic distillates than in column distillate, these
differences were not significant. Also, the concentration of amyl al-
cohols and n-hexanol did not vary depending on the distillation
technique used. These results agree with those reported by
Arrieta-Garay et al. (6) and partially agree with the results reported
by Cortes et al. (12), who did not find significant differences in the
concentration of n-butanol and both amyl alcohols (2-methyl-1-
butanol and 3-methyl-1-butanol) between industrial and tradi-
tional samples. Regarding the influence of maturation level on
the above higher alcohols (Figure 3), a slight increase in those
compounds was observed during ageing. Nevertheless, the differ-
ences among samples were not statistically significant with the ex-
ception of the amyl alcohols. The concentration of amyl alcohols
increased statistically during 12 months of ageing, followed by a
stable level.
Changes in aroma compounds from maturation in an oak
barrel
During spirit maturation in a wood barrel, oxidation, hydrolysis and
ethanolysis occur in the distillate and simultaneously a variety of
compounds are extracted from the barrels, modifying the chemi-
cal and sensory profile of the spirit. The majority of these chemical
reactions have a positive effect on the quality of beverages. Ac-
cording to many authors (24,45–47), the major compounds that
originate from wood are syringaldehyde, vanillin and gallic and
ellagic acids. Vanillin and syringaldehyde together with gallic and
ellagic acids are considered as important compounds for wine
and distillates (18). Table 3 shows the average concentration of
four compounds in aged apple distillates from the two different
distillation techniques.
Gallic acid is a phenolic compound originating from wood tan-
nins and is the product of the hydrolysis of tannins in the oak
wood. Gallic acid is a non-volatile substance and is responsible
for the viscosity and texture of the aged beverages. Although it
has no effect on the aroma profile of the spirits, gallic acid contrib-
utes to the quality of the beverage related to the visual and
textural attributes (24). In this study, the concentration of gallic
acid ranged from 2.1 to 8.0 mg/L. This is in agreement with work

Table 3. Average content (mg/L) of major maturation related congeners in the two types of apple distillates analysed over the
18 months of ageing

Maturation Method Effect of distillation Aging time (months) Effect of

related technique maturation level
congeners 6 12 18

Gallic acid A * 3.3a 5.8b 8.0c *

C 2.3a 3.0a 3.9ab
Vanillin A n.s. 2.9 3.4 3.8 n.s.
C 3.2 3.7 3.9
Syring aldehyde A n.s. 3.8 4.7 5.4 n.s.
C 3.6 5.4 6.3
Ellagic acid A n.s. 24.1a 29.4b 36.5c *
C 26.7a 31.3b 35.2c
A, Alembic distillate; C, column distillate; n.s., Not significant.
* Statistically significant influence at 95%, confidence for the distillation technique used and ageing time; different letters within all
treatments per compounds indicate statistically significant differences (p ≤ 0.05) according to least significant difference test.

wileyonlinelibrary.com/journal/jib © 2019 The Institute of Brewing & Distilling J. Inst. Brew. 2019
Aroma compounds in barrel aged apple distillates from two different distillation techniques

previously reported by Rodríguez-Madrera et al. (26) and
Bortoletto and Alcarde (46). Alembic distillates showed a signifi-
cantly higher concentration of gallic acid than column distillates.
Alembic distillates had lower alcohol strength (61% v/v) than col-
umn distillate (66.7% v/v – Figure 2) and the lower alcohol strength
of alembic distillates favours tannin extraction and hydrolysis. Lee
et al. (42) observed that ethanol activity is greatest at cask strength
(60% v/v). Table 3 shows that the content of gallic acid was signif-
icantly increased during ageing. The changes in gallic acid content
were significant in the distillates obtained by the alembic device,
while an increase in gallic acid in the column samples was not
found to be significant. The increase during apple distillation
maturation was caused by hydrolysis of gallotannins (17). This is
in agreement with Rodríguez-Madrera et al. (26), who noted that
gallic acid is important in distinguishing cider brandy according
to age.
Vanillin and syringaldehyde are aromatic phenolic aldehydes
which are formed throughout lignin degradation during cooper-
ing and are extracted from the wood into spirits. These aldehydes
are suggested to enrich the sensorial attributes of the spirits (20).
According to Pannossian et al. (48), aromatic phenolic aldehydes
can be used for the identification of spirits on the basis of raw ma-
terial and ageing in cask. Vanillin and syringaldehyde are markers
of good spirit quality because they are responsible for enhancing
smooth, vanillin, sweet, malty, spicy, fruity, floral, black chocolate
or smoked notes of beverages (49). From a sensory point of view,
these compounds are among the most important extractable
components with a low sensory perception threshold.
The concentration of vanillin in the samples ranged from 2.9 to
3.9 mg/L, in accordance with the vanillin content of cider brandy
(23). The concentration of syringaldehyde was higher than the
content of vanillin in all samples. The important practical signifi-
cance of these oak extracts is because they can be used as markers
to distinguish between counterfeit alcoholic beverages and real
brandy (48). In fake brandy, the amount of syringaldehyde is lower
than that of vanillin. Interestingly, the effect of distillation tech-
niques and the effect of ageing time on the concentration of van-
illin and syringaldehyde was not observed. Although, the content
of these aldehydes increased during ageing, the difference was
not significant at p ≤ 0.05.
The most abundant maturation related compound in the
analysed samples was ellagic acid, ranging from 24.1 to 36.5 mg/L
(Table 3). Also, in the study of Goldberg et al. (50), ellagic acid was
present in highest concentration in whisky, brandy and rum, but
the concentration of ellagic acid together with that of Viriot et al.
(51) was lower than in the work reported here. Ellagic acid is
present in spirits owing to the hydrolysis of ellagic tannins. These
tannins play an important role in beverage oxidation processes,
quickly absorbing dissolved oxygen and facilitating the hydro-
peroxidation of beverage constituents (42). Hale et al. (52) reported
that major changes during maturation take place in the structure
and amount of oak tannins. The ellagic acid together with the
gallic acid of a spirit provide indicators of maturation, but their in-
fluences on spirit flavour are not fully understood (42). As can be
seen in Table 3, the content of ellagic acid increased significantly
during ageing. No effect of distillation equipment applied was
observed.
Principal component analysis
Principal component analysis was applied to the aroma com-
pounds with the aim of interpreting the relationships between
apple distillates. An overview of the similarities and differences
amongst the eight samples of apple distillates based on distillation
technique (A and C), and ageing time (6, 12 and 18 months) is
shown in Figure 4. The final data matrix showed three principal

Figure 4. Principal component analysis of the fermentation- and maturation related aroma compounds, showing the distribution of the samples obtained by different distillation
techniques (A, alembic, and C, column) and matured in oak barrels for 6, 12 and 18 months.

J. Inst. Brew. 2019 © 2019 The Institute of Brewing & Distilling wileyonlinelibrary.com/journal/jib

components (eigenvalues >1) which accounted for 93% of the
variance, but just one plot was constructed (PC1 × PC2) with the
aim of separating samples. The distillate sample sites on the plot
clearly show the distribution of alembic and column distillates to
be opposite. The column distillates were characterised by a lower
content of fermentable aroma compounds with the exception of
n-propanol and methanol. The young distillates (six months of
ageing) exhibited a higher content of methanol. As expected,
older distillates (12 and 18 months of ageing) were determined
by a higher content of maturation related compounds. However,
the contents of vanilla, syringaldehyde and ellagic acid were more
characteristic for aged column distillates than alembic distillates.
Those distillates had a higher content of alcohol. The opposite
was true for gallic acid, which is more characteristic of older alem-
bic distillates.
Conclusion
Different distillation techniques affect the concentration of major
volatile compounds in apple distillates. However, the higher etha-
nol content is less dependent on the distillation technique and
more dependent on the distillation cutting than the equipment
used. Alcohol concentrations above 65% v/v can increase the ex-
traction rate of vanilla, syringaldehyde and ellagic acid. In contrast,
the comparatively low alcohol strength of alembic distillates
favours tannin extraction and hydrolysis, resulting in a higher gallic
acid content.
Acknowledgements
We are grateful for the technical support of the owner and
employees of distillery BMB Delta, Gradiška.
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