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Food Chemistry 113 (2009) 1176–1183

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Analytical Methods

Characterisation of apple distillates from native varieties of Sardinia island

and comparison with other Italian products
G. Versini a,*, M.A. Franco b, S. Moser a, P. Barchetti a, G. Manca b,*
a
Agricultural Institute of San Michele all’Adige (IASMA), Research Centre, Agro-Food Department, Via Mach 1, 38010 San Michele all’Adige (Trento), Italy
b
University of Sassari, Department of Chemistry, via Vienna, 2, 07100 Sassari, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this study was to characterise the aroma fraction of Italian distillates from apples typical of the
Received 24 January 2008 Province of Sassari in the northern region of Sardinia (Malus pumila, L. cvs. Miali and Appio) in compar-
Received in revised form 30 July 2008 ison to some international obtained in the northern region of Trentino–Alto Adige (M. pumila, L. cvs. Ren-
Accepted 2 August 2008
etta del Canada (Reinette du Canada or Canadian Rennet), Golden Delicious, Royal Gala, Morgenduft and
Gravenstein). The distillates producted in Sardinia were obtained from the same producer over four years,
while those from Trentino–Alto Adige by two distilleries over one year, both following the same produc-
Keywords:
tion process. Analyses of the aroma fraction were performed by HRGC–FID and HRGC–MS techniques,
Distillates
Apples
with direct injection in GC of full proof distillates. Evaluation of the data by statistical analysis (ANOVA
Aroma analysis and Principal Component Analysis) revealed that the variables ethyl octanoate, hexyl 2-methylbutyrate,
Discrimination 1-hexanol, benzaldehyde and furfural are able to distinguish between the varieties. In the case of the Sar-
dinian varieties the variables 3-methyl-1-butanol, total aldehydes, ethyl acetate and 6-methyl-5-hepten-
2-ol are dependent from the year of production.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Following the studies on the promotion of typical products of
Sardinia, mainly oriented towards the derivates of berries from
Mediterranean scrub (Franco et al., 2002) and local plants/fruits
(Dalla Serra et al., 1999; Ledda, Franco, Sanna, & Manca, 2005),
attention has been focused on the processing of particular varieties
of apples, characteristic of the Province of Sassari, with the aim to
produce fruit brandies. The interest was due in particular to the pe-
culiar fruity/spicy aroma of some types of apple at ripeness which
can be transferred to relevant distillates.
In Italy a certain tradition exists in apple brandy production,
though prevalently in some northern parts of the country, as
acknowledged by EEC Reg. No. 1576/89, in which Attachment II in-
cludes the denomination of origin of apple distillates coming from
the Trentino and Alto Adige provinces and for this latter alone lists
two variety distillates from Golden Delicious and Gravenstein.
For distillates from fermented mashes, the bibliography gives in
particular surveys relating to the volatile compounds during the
production and fermentation steps of the mash and finally to the
distillate, carried out by Schreier, Drawert, and Schmid (1978a)
and Schreier, Drawert, and Steiger (1978b), as well as those of Ver-
sini (1983) and Woidich, Pfannhauser, and Eberhardt (1978), who
compared distillates of various kinds of apple. Deep changes in
* Corresponding authors. Tel./fax: +39 079 229579 (G. Manca).
E-mail addresses: versinig@yahoo.it (G. Versini), gmanca@uniss.it (G. Manca).
the aromatic profile of the fruit have been reported in works of
Schreier et al. (1978a, 1978b) as induced by enzymatic reactions
established at fruit crushing, i.e. at the moment of cell destruction.
For distillates like Calvados from cider obtained from a mixture of
apple varieties, we can quote the researches on aroma performed
by Guichard, Lemesle, Ledauphin, Barillier, and Picoche (2003),
Ledauphin et al. (2004), Mangas, Rodriguez, Moreno, & Blanco
(1996a,1996b), Postel, Adam, and Jäger (1981) and Sponholz, Dit-
trich, and Bausch (1989).
An example of production of distillates from native varieties of
fruit in central-southern Italy has already been reported by Genov-
ese, Ugliano, Pessina, Lamacchia, and Moio (2003) and Genovese
et al. (2004) who characterised the aromas of cider distillate from
the Annurca apple (Malus pumila, Annurca variety) typical of the
Campania region.
In this work the aroma fraction was characterised by gas chro-
matography (GC) coupled either with flame induction detector
(FID) or mass spectrometry (MS) applied on brandies obtained in
different years from apples typical of the Province of Sassari area
(Sardinia) (M. pumila, Miali and Appio varieties) (Mulas & Nieddu,
1994), and those coming from another Italian region, Trentino–Alto
Adige, obtained in a single year from the principal varieties of ap-
ple cultivated (M. pumila, Canadian Rennet, Golden Delicious, Royal
Gala, Morgenduft and Gravenstein varieties). The distillates pro-
duced in Sardinia were obtained from the same producer over four
years, keeping constant both processes of preparation and fermen-
tation of the mash and the system of discontinuous distillation at

0308-8146/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodchem.2008.08.003
 Author's personal copy

G. Versini et al. / Food Chemistry 113 (2009) 1176–1183 1177

low steam pressure. The distillates of the Trentino–Alto Adige were
obtained with the same technology. The analytical data of the dis-
tillates were subjected to univariate and multivariate analysis to
define both the variables that mainly contribute to discriminating
both the Sardinian products and possibly the vintages and all the
different types of apple distillates.
2. Materials and methods
2.1. Sampling
Apples of the Miali and Appio varieties were harvested at ripe-
ness for human consumption over the years 2002, 2003, 2004 and
2005 in zones near the town of Sassari, and stored for approxi-
mately 20 days at a temperature not above 25 °C to allow the nat-
ural climateric process at the Rau Distilleries in Sassari.
The apples were crushed and the cores and seeds removed
using the appropriate sieve.
The mash was corrected to approx. pH 3.2 with the addition of a
1:10 diluted solution of sulphuric acid, inoculated with yeasts se-
lected from the Saccharomyces cerevisiae species and fermented
at a controlled temperature in steel recipients of approx. 400 kg.
The mean alcohol level of fermented mashes in the four vintages
was 5.67 ± 0.45 and 5.86 ± 0.43 mL% g for Appio and Miali apples,
respectively.
The mash conserved under the residual CO2 was distilled within
3 weeks after fermentation in a copper pot still at low steam pres-
sure made by the company MetalInox (Trento, Italy), equipped
with an 8-plate rectification column, carrying out the same head
and tail cuts. Annual products from Sardinian distillates are the
mean result for each year from 4 to 12 pot still distillations ob-
tained from 2300 to 6000 kg of apples.
The samples of the Canadian Rennet, Golden Delicious, Royal
Gala, Morgenduft and Gravenstein varieties, harvested in Trentino
in the year 2003, were subjected to the same procedures getting an
alcohol level after fermentation of the mashes acidified at about pH
3.2 of 3.3; 4.6; 5.0; 4.7 and 4.3 mL% g, respectively, and distilled
either at the Agricultural Institute of San Michele all’Adige (IASMA)
in the case of Royal Gala, Golden Delicious and Morgenduft apple
mashes or at the Pilzer s.n.c. Distillery in Faver (Trento) for Cana-
dian Rennet and Gravenstein ones with equipments made by the
same company and very similar to that used for the production
in Sardinia.
2.2. GC–FID and GC–MS analyses
The brandies obtained over various years were submitted to
analysis of the volatile impurities with HRGC–FID and MS tech-
niques, with direct injection of the rough distillate (Versini, Moser,
Carlin, Manca, & Franco, 2002).
Work was carried out using both a packed column (glass col-
umn 2 m  2 mm £ int.; Carbopack C, 60–80 mesh, with 0.2%
CW 1500; Supelco Inc., Bellefonte PA, USA) for GC–FID evaluation
of the macroconstituents (methanol, higher alcohols, acetaldehyde,
acetal and ethyl acetate), and a Supelcowax 10 capillary column
(30 m  0.32 mm  0.25 lm film thickness; Supelco Inc., Belle-
fonte, PA, USA) to measure the minor compounds by HRGC–FID.
With the aim of verifying the FID dosage of some compounds
and determining that of others present in quantities between 50
and 5 lg% mL p.A. (Pure Alcohol) (Versini, 1992; Versini et al.,
2002), HRGC–MS/SIR (Mass Spectrometry/Selected Ion Recording
technique) work was done using a TurboMass Gold equipment
(Perkin Elmer, Norwalk CT, USA) with a DB-WAX column
(60 m  0.32 mm  0.5 lm film thickness; J&W, Folsom CA, USA).
Quantitative evaluation was carried out by the internal stan-
dard method (2-methyl-2-butanol for packed column dosages)
with appropriate calibration based on pure compounds supplied
either by C. Erba (Rodano, Milano, Italy) or Aldrich (Milano, Italy)
or using 2-octanol (internal standard with capillary columns) with
RF = 1 in the case of absence of pure products and in HRGC–MS/SIR
approaches.
Repeatability of the analytical measure (mean, standard devia-
tion and CV% per 10 repetitions) for each compound in the differ-
ent gas chromatographic conditions, in respect of an apple
distillate, is shown in Tables 1 and 2. For the macroconstituents
the standard deviations relating to the repeatability (RSDr%) corre-

Table 1
Analysis by GC–FID (mg% mL p.A.): repeatability of the analytical measure (mean, standard deviation and CV% per 10 repetitions)

1 2 3 4 5 6 7 8 9 10 Mean DS DS% Repeatability = t * 20.5 * DS

Butyl acetate 0.05 0.03 0.03 0.05 0.04 0.04 0.04 0.04 0.04 0.04 0.040 0.007 17.6 0.0227
Isoamyl acetate 0.25 0.28 0.26 0.24 0.25 0.25 0.24 0.25 0.23 0.25 0.250 0.015 5.9 0.0475
n-Hexyl acetate 0.06 0.06 0.07 0.05 0.07 0.07 0.05 0.05 0.05 0.04 0.058 0.009 16.4 0.0302
Hexyl 2-methylbutanoate 1.80 1.92 1.88 1.76 1.88 1.88 1.76 1.88 1.86 1.94 1.856 0.062 3.4 0.1993
Ethyl hexanoate 1.02 1.08 1.03 0.99 1.02 1.04 0.97 1.04 1.03 1.04 1.026 0.030 2.9 0.0945
Ethyl octanoate 2.41 2.50 2.51 2.36 2.46 2.47 2.33 2.44 2.49 2.46 2.444 0.060 2.5 0.1918
Ethyl decanoate 3.28 3.33 3.32 3.17 3.36 3.32 3.15 3.34 3.35 3.35 3.296 0.076 2.3 0.2424
Ethyl dodecanoate 1.66 1.62 1.65 1.56 1.64 1.65 1.56 1.65 1.62 1.69 1.629 0.043 2.6 0.1365
Ethyl tetradecanoate 0.30 0.28 0.30 0.32 0.31 0.25 0.27 0.29 0.31 0.29 0.292 0.020 6.8 0.0640
Ethyl hexadecanoate 2.13 2.13 2.13 2.05 2.09 2.12 2.03 2.13 2.15 2.29 2.126 0.068 3.2 0.2185
Ethyl octadecanoate 0.19 0.16 0.16 0.19 0.16 0.18 0.17 0.16 0.22 0.18 0.175 0.020 11.5 0.0645
Ethyl 9-octadecenoate 0.31 0.23 0.30 0.28 0.28 0.34 0.25 0.24 0.29 0.26 0.279 0.034 12.0 0.1075
Ethyl 9,12-octadecadienoate 1.31 1.37 1.37 1.20 1.39 1.03 1.19 1.12 1.18 1.05 1.221 0.132 10.8 0.4219
Ethyl 9,12,15-octadecatrienoate 0.38 0.20 0.35 0.23 0.23 0.24 0.37 0.26 0.25 0.22 0.272 0.068 24.9 0.2164
Ethyllactate 2.88 2.80 3.04 3.12 2.95 2.91 2.75 3.19 2.98 2.89 2.951 0.136 4.6 0.4362
1-Hexanol 9.24 9.70 9.61 9.14 9.50 9.50 9.04 9.55 9.50 9.61 9.439 0.220 2.3 0.7025
trans 3-Hexenol 0.08 0.09 0.07 0.06 0.07 0.09 0.05 0.07 0.07 0.06 0.071 0.011 16.0 0.0363
cis 3-Hexenol 0.06 0.07 0.03 0.05 0.06 0.05 0.05 0.06 0.06 0.06 0.055 0.011 20.0 0.0350
trans 2-Hexenol <0.03
1-Heptanol 0.07 0.07 0.05 0.03 0.04 0.06 0.04 0.05 0.03 0.07 0.051 0.016 31.7 0.0519
Octanol 0.10 0.06 0.09 0.05 0.05 0.05 0.06 0.05 0.07 0.08 0.065 0.016 25.0 0.0521
Nonanol 0.11 0.12 0.10 0.10 0.07 0.09 0.10 0.08 0.11 0.13 0.100 0.018 18.0 0.0572
Furfural 6.16 6.41 6.51 6.11 6.33 6.33 6.10 6.34 6.38 6.56 6.322 0.156 2.5 0.4998
2-Phenylethanol 1.39 1.42 1.29 1.24 1.44 1.30 1.26 1.44 1.27 1.36 1.341 0.077 5.7 0.2457
Benzaldehyde 2.62 2.69 2.74 2.60 2.70 2.66 2.58 2.74 2.68 2.76 2.678 0.062 2.3 0.1999
a-Farnesene isomer 0.48 0.52 0.48 0.49 0.49 0.44 0.40 0.45 0.46 0.43 0.465 0.034 7.4 0.1103
a-Farnesene 7.26 6.65 6.94 6.71 6.41 6.21 6.24 6.09 6.32 6.94 6.577 0.386 5.9 1.2337
 Author's personal copy

1178 G. Versini et al. / Food Chemistry 113 (2009) 1176–1183

Table 2
Analysis by GC–MS (mg% mL p.A.): repeatability of the analytical measure (mean, standard deviation and CV% per 10 repetitions)

1 2 3 4 5 6 7 8 9 10 mean DS DS% Repeatability = t * 20.5 * DS

Ethyl phenylacetate 0.023 0.024 0.023 0.023 0.023 0.024 0.023 0.024 0.023 0.020 0.023 0.001 5.3 0.0039
2-Phenylethyl acetate <0.001
2-Methylbutanoic acid 0.262 0.271 0.250 0.277 0.286 0.287 0.283 0.292 0.265 0.287 0.276 0.014 4.9 0.0434
Hexyl 2-methylbutanoate 1.545 1.601 1.601 1.596 1.632 1.700 1.662 1.570 1.587 1.670 1.616 0.048 3.0 0.1549
Benzaldehyde 1.701 1.774 1.722 1.751 1.736 1.750 1.763 1.710 1.762 1.804 1.747 0.031 1.8 0.0999
Ethyl benzoate 0.253 0.248 0.246 0.256 0.252 0.246 0.251 0.256 0.251 0.293 0.255 0.014 5.4 0.0439
Benzylic alcohol 0.063 0.063 0.063 0.063 0.062 0.063 0.062 0.063 0.063 0.063 0.063 0.000 0.6 0.0012
6-Methyl-5-hepten-2-one 0.062 0.061 0.063 0.063 0.062 0.063 0.062 0.062 0.060 0.063 0.062 0.001 1.6 0.0033
6-Methyl-5-hepten-2-ol 0.060 0.060 0.061 0.062 0.059 0.062 0.060 0.061 0.061 0.075 0.062 0.005 7.6 0.0151
trans Furan linalool oxide 0.013 0.013 0.013 0.013 0.012 0.012 0.012 0.012 0.012 0.011 0.012 0.001 4.8 0.0019
cis Furan linalool oxide 0.009 0.009 0.008 0.009 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.000 2.1 0.0006
Linalool 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.007 0.000 1.9 0.0004
4-Terpineol 0.006 0.007 0.006 0.006 0.007 0.006 0.006 0.006 0.006 0.007 0.006 0.000 2.0 0.0004
a-Terpineol 0.002 0.003 0.002 0.002 0.002 0.003 0.003 0.003 0.003 0.003 0.003 0.000 3.7 0.0003
Citronellol 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 1.003 0.000 4.7 0.0003
Geraniol 0.022 0.022 0.022 0.021 0.022 0.022 0.022 0.022 0.022 0.022 0.022 0.000 1.0 0.0007
Nerolidol 0.044 0.044 0.042 0.045 0.043 0.043 0.044 0.043 0.043 0.041 0.043 0.001 2.2 0.0031
Isoeugenol 0.012 0.012 0.013 0.012 0.012 0.012 0.013 0.012 0.013 0.012 0.012 0.000 1.9 0.0008
Farnesol 0.096 0.095 0.095 0.099 0.099 0.098 0.092 0.091 0.098 0.094 0.096 0.003 3.0 0.0091
Hexyl hexanoate 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.000 2.3 0.0007
Acetophenone 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.000 3.9 0.0003
b-Damascenone 0.010 0.011 0.010 0.010 0.010 0.010 0.011 0.010 0.010 0.010 0.010 0.000 3.6 0.0012

spond to those shown in the EC Regulation No. 2870/2000, in par-
ticular for fruit distillates. For the other compounds using a GC–FID
capillary column, repeatability is certainly good with SD% greater
than 10% only for the compounds at a level lower than 0.3 mg% mL
p.A. except for ethyl 9,12,15-octadecatrienoate eluted at a higher
RT and with a SD of 25% for a level of 0.38 mg% mL p.A.). SD%
decidedly lower at low quantities were found in the GC–MS anal-
yses where 7% is not exceeded even up to levels of 0.002 mg% mL
p.A.
2.3. Statistical analyses
Univariate statistical analysis (ANOVA) was used to evaluate
whether significant differences exist between the Sardinian sam-
ples depending on year and between the Sardinian and Trentino
ones depending on variety. The variables that showed high signif-
icance were used in the Principal Component Analysis (PCA). This
analysis is an unsupervised method of pattern recognition which
shows the relationship between the samples (objects) on the basis
of their distribution in the multidimensional space described from
all the variables and also makes it possible to determine which
variables are principally responsible for the separation of the ob-
jects. PCA produces linear combinations of original variables which
represent, in decreasing order, the directions of the maximum var-
iance in the experimental space under consideration. The main
objective is to identify a reduced number of principal components
which sufficiently explain most of the information in the starting
data. All statistical analyses were performed with the software
package SPSS 14.0 (SPSS Inc., Chicago, IL).
3. Results and discussion
The compounds measured in both distillates of mashes from
Sardinian and Trentinian varieties are shown in Tables 3 and 4.
The significance of discrimination among varieties or years ob-
tained by ANOVA analysis is also indicated with different symbols.
As regards the macroconstituents in Table 3, we observe among
the alcohols that the methanol content never exceeds the legal lim-
it of 1.20 g% mL p.A. established by EC Reg. No. 1014/90 and subse-
quent amendments. A certain variability is observed that is
attributable to the year and varieties. In particular, Appio apple dis-
tillates have a content that is 17% higher on average than that of
Miali apples. The comparisons made among the years for the same
distillates show that productions of 2002 and 2003 have lower val-
ues than those of 2004 and 2005. Trentino brandies present a sim-
ilar range of variability, likely induced by the variety of apple.
Also the level of 1-butanol may be associated prevalently with
varietal aspects as shown in apple ciders by Reinhard (1968) and
Williams (1975). In the Sardinian varietal brandies significant dif-
ferences do not appear depending on year with the exception of
2003, where the distillates presented a greater content (max value
of 16 mg% mL p.A.). In the Trentino distillates high values are ob-
served compared with the Sardinian varieties, decreasing from
the Royal Gala variety (116 mg% mL p.A.), Canadian Rennet
(46 mg% mL p.A.) to the others (values between 13 and 19 mg% mL
p.A.).
The higher alcohols show a different level depending on the
variety and year, respectively. 1-Propanol is present in fact in the
Appio distillates with a mean value of 50 and in the Miali ones at
37 mg% mL p.A. There are notable variations also among the Tren-
tino products, where the maximum value of 74 is found for the
Gravenstein distillate. Also the 2-methyl-1-propanol shows ten-
dentially higher values for the Appio products compared with the
Miali ones. Great variations between varieties are also to be noted
among the Trentino distillates with the higher level in the Graven-
stein brandy. For both isoamylic alcohols, variety and year differ-
ences are not observed in the Sardinian products, whereas the
Trentino distillates present remarkable differences probably due
to variety effects. Rapp and Versini (1991) put in evidence that iso-
amylic alcohols in wines are significantly correlated with the yeast
assimilable nitrogen level in the matrix. We can also observe that
the two isomers, the 2-methyl and 3-methyl-1-butanol, are line-
arly highly correlated. The higher alcohols as a sum generally are
at higher levels in the Sardinian distillates (between 370 and
600 mg% mL p.A.) compared with those of Trentino. As from the lit-
erature referred both to distillates (Genovese et al., 2003; Salo,
1970), and to fermented products like beer (Meilgaard, 1975),
these macro compounds are responsible for a so-called sweet-
alcoholic-floral basic aroma on which interact other sensory active
substances typical of the beverages.
Ethyl acetate shows a variable concentration with an upper lim-
it not higher than 130 mg% mL p.A., a value corresponding to the
mean contents for commercial fruit/apple distillates like ‘Obstwas-
ser’ and Calvados (Postel, Drawert, & Adam, 1975). This upper
 Author's personal copy

G. Versini et al. / Food Chemistry 113 (2009) 1176–1183 1179

value is still considered as sensorially acceptable according to Gui-

ANOVA

chard et al. (2003) for Calvados distillates. In the 2002 harvest year

ns
ns

ns
ns

ns

ns

ns
ns
2

+
distillates from Sardinia presented higher values respect to the

148.9
successive three harvest years, likely for a casual microbiological

43 3
23.1
42.9

69.8

37.2
0.16

20.3

9.0
SD

events. The sum of acetaldehyde + acetal, defined as total acetalde-

hyde, shows rather low values that confirms a mostly correct tech-
Mean

223.2

435.8
42 2
66.6
0.68
37.0

67.0

21.0
67.0
nological process, with a regular fermentation without oxidative
events.
Gravenstein

With regard to minor components fundamental for determining

peculiar aroma of distillates and reported in Table 4, we observe
135.0

278.0

597.0

118.0
2003

that the acetates of higher alcohols and of 1-hexanol, responsible

0.92
73.0

19.0
91.0

12.0
for apple–banana fruity scents of fermentative origin (Salo,
1970), are usually on rather moderate levels according to Postel
116.0

227.0
Royal

503.0

et al. (1975) and Schreier et al. (1978a). Evaluated as a sum, differ-

2003
Gala

0.67
44.0
49.0

68.0

15.0
61.0

ences are observed for the Sardinian products with higher levels
than the Trentinian distillates. In particular, variations relating to
Morgenduft

butyl acetate can be traced back to the different alcohol contents.

The ethyl esters of fatty acids from hexanoate to ethyl decano-
512.0
300.0
2003

17 0
0.83
33.0
81.0

82.0

17.0
90.0

ate with a ripe fruits aroma (Salo, 1970) are usually at medium-low
levels if compared with similar distillates, like those from Annurca
apple produced with the same equipment (Genovese et al., 2003).
Delicious

The esters at higher molecular weight from ethyl dodecanoate to

Golden

129.0

229.0
2003

ethyl 9,12,15-octadecatrienoate with a waxy-rancid hint (Salo,

0.54
15.0

13.0
42.0

28.0
28.0
30.0

ANOVA 2: significance depending on variety (comparison between averages for Appio, Miali and Trentino samples); ns = not significant, +p 6 0.05.

1970), are also usually at rather low levels, but these compounds
ANOVA 1: significance depending on year (comparison between averages for Appio and Miali samples); ns = not significant, *p 6 0.05; **p 6 0.01.

are removed during the finishing process of distillates (Postel &

Adam, 1985; Versini, Dell’Eva, & Inama, 1989).
Rennet of

Ethyl lactate is present with rather low values in Sardinian

Canada

182.0

338.0
2003

46 0

33.0
38.0
0.54

38.0

52.0
20.0

brandies, a fact that indicates a reduced presence of lactic or malo-

lactic fermentation in the mashes. Contents quite higher are in-
ANOVA

stead present among the Trentinian products.

The level of 1-hexanol, considered of sensory relevance in apple
ns
ns
ns

ns
ns





1

ciders by Reinhard (1968) and associated with a grassy scent in

16.4

13.9

42.5

67.2

37.9
0.12
Content of macroconstituents present in the aromatic fraction of distillates obtained from apples of different varieties

distillates as proved by Salo (1970) for whisky and by Bertrand

4.7

4.7

9.6
SD

(1989) for Armagnac brandy but not by Guichard et al. (2003) in

Mean

491.4
300.5

Calvados, is higher in Appio than in Miali apple distillates of Sardi-

0 86
37.1
68.3

75.8

38.3
24.0
9.5

nia. In the Trentinian products higher values are found for the
Canadian Rennet and Royal Gala distillates, resulting the values
399.3
240.0
2005

36.7
0.96
44.0

58.0

17.0
50.0

of the Annurca apple distillates in the same range of variability

6.3

(Genovese et al., 2003). Trans and cis 3-hexenol and trans 2-hexe-
304.5

484.0
2004

nol, the so-called ‘‘leaf alcohols”, are somewhat low compared with
72.5

24.7
0.97
35.0
65.0

20.0
7.0

values measured for some of these by Schreier et al. (1978a,

1978b), and by Genovese et al. (2004), in any case with poor sen-
545.5
337.0
2003

33.5
68.5

16.5
0.74

20.4
21.0
90.0

sorial relevance (Bertrand, 1989; Salo, 1970). The linear alcohols

from C7 to C10 – rather fruity-floral compounds at the level here
536.9
320.5
Miali

2002

found (Salo, 1970) and derived from the decomposition of fatty

35.8
89.7

82.7
0.78

14.0
95.0
8.2

acids during the fermentative processes – show similar values in

all distillates analysed with the exception of the Appio ones with
108.2
21.1

64.8

14.9
48.4
0.12

29.0

11
4.6
SD

the highest values.

2-Phenylethanol, quite exclusively of fermentative origin
Mean

533.8
307.9
49.9
82.6

84.6

23.3
55.8
1.01

according to Williams (1975) and Schreier et al. (1978a) as com-

8.7

paring the level of cider apples juices to that of relevant fermented

372.1
213.0

ciders, results at higher levels in the Sardinian distillates of 2002.

2005

45.5
1.08
52.0

53.0

45.0
25.0
8.1

Its content may be affected by the dominant yeast type during

the mash fermentation (Di Stefano & Ciolfi, 1985), but mostly by
331.5

578.5
2004
1.14

91.5

19.5
53.0

95.0

36.0

the intensity of the tail cut at the distillation (Postel, 1984; Versini,
7.5

Values expressed in mg% mL p.A.

1978). The possible contribution to distillates content of bound

Values expressed in g% mL p.A.
584.5
359.0
2003

forms of 2-phenylethanol as glycosides which are present e.g. in

78.5

17.2
43.0

94.0

34.0
0.90

10.0

grape of Vitis vinifera (Strauss, Williams, Wilson, & Massy-Wes-

tropp, 1983) up to about 0.5 ppm (Günata, 1984) and in other fruits
Appio

114.9

328.2

128.0
600.2
2002

51.6

96.5

11.5
0.91

9.0

like nectarines (Takeoka et al., 1992) in traces, can be very scarce as

demonstrated in the latter research applying chemical hydrolysis
Total aldehydesb

of bound fraction at pH 3 by 2 hours long SDE (Simultaneous Dis-

Ethyl acetateb
propanolb

tillation and Extraction) technique. This fact can be justified being

2-Methyl-1-

2-Methyl-1-

3-Methyl-1-

Total higher
alcoholsb
1-Propanolb

butanolb

butanolb
1-Butanolb
Methanola

the bound forms referred to a non-allylic primary alcohol (Flanzy,

Table 3

Variety

1998). In any case, the level found in the apple distillates can deter-
Year

mine a contribution to the floral scent (Salo, 1970).

 Author's personal copy

1180
Table 4
Content of microconstituents present in the aromatic fraction of distillates obtained from apples of different varieties

Variety Appio Miali ANOVA 1 Rennet of Golden Morgenduft Royal Gravenstein Mean SD ANOVA 2
Canada Delicious Gala
Year 2002 2003 2004 2005 Mean SD 2002 2003 2004 2005 Mean SD 2003 2003 2003 2003 2003
Butyl acetateb 0.07 0.16 0.05 0.05 0.08 0.05 0.10 0.12 0.04 0.04 0.08 0.04 * 0.10 0.05 0.07 0.16 0.05 0.11 0.05 ns
Isoamyl acetateb 1.40 0.85 0.54 0.52 0.83 0.41 0.71 1.07 0.56 0.38 0.68 0.29 ns 0.33 0.24 0.33 0.25 0.23 0.27 0.05 +
n-Hexyl acetateb 0.10 0.08 0.07 0.05 0.08 0.02 0.04 0.10 0.04 0.04 0.06 0.03 ns 0.10 0.04 0.06 0.05 0.05 0.06 0.03 ns
Phenylethyl acetate 0.12 0.15 0.08 0.06 0.10 0.04 0.12 0.03 0.08 0.04 0.07 0.04 ns 0.06 0.05 0.06 0.06 0.05 0.06 0.01 ns
Ethyl hexanoateb 0.37 0.25 0.50 1.39 0.63 0.2 0.21 0.51 0.56 0.89 0.54 0.28 * 0.79 0.72 0.81 0.64 0.72 0.74 0.07 ns
Ethyl octanoateb 1.71 2.34 1.60 1.86 1.88 0.32 0.89 1.86 1.96 1.81 1.63 0.50 ns 2.50 3.08 3.35 2.84 4.66 3.29 0.83 ++
Ethyl decanoateb 2.66 14.15 2.12 2.00 5.23 5.95 1.43 3.59 3.26 2.27 2.64 0.98 ns 3.12 3.76 4.40 4.32 6.95 4.51 1.46 ns
P
esters C6–C10b 4.74 16.74 4.22 5.26 7.74 6.01 2.53 5.96 5.79 4.97 4.81 1.58 ns 6.42 7.56 8.56 7.80 12.33 8.53 0.89 ns
P
esters C12–C18(3=)b 8.87 23.20 4.27 12.00 12.08 8.06 29.99 5.47 11.10 12.60 14.79 10.59 ns 5.46 5.34 5.72 3.26 5.97 5.15 1.08 ns
Ethyl lactateb 3.48 0.77 6.17 0.24 2.66 2.73 22.89 0.52 1.78 0.24 6.35 11.04 ns 1.16 2.36 54.33 15.29 46.08 23.85 24.86 ns

G. Versini et al. / Food Chemistry 113 (2009) 1176–1183

Hexyl 2-methylbutanoateb 1.84 2.53 2.07 2.07 2.13 0.29 0.61 0.42 0.38 0.48 0.47 0.10 ns 0.76 0.76 1.32 0.61 0.24 0.74 0.39 +++
Hexyl hexanoateb 0.02 0.09 0.03 0.05 0.05 0.03 0.02 0.01 0.04 0.01 0.02 0.01 ns 0.40 0.14 0.02 0.05 0.01 0.12 0.16 ns
1-Hexanolb 11.44 11.35 9.62 11.89 11.07 1.00 8.30 8.29 5.34 5.32 6.81 1.71 ns 15.18 9.54 11.02 15.33 13.00 12.81 2.54 ++
trans 3-Hexenolb 0.10 0.100 0.05 0.11 0.07 0.05 0.09 0.05 0.04 0.04 0.06 0.03 ns 0.00 0.05 0.08 0.03 0.10 0.05 0.04 ns
cis 3-Hexenolb 0.08 0.08 0.06 0.14 0.09 0.04 0.12 0.08 0.03 0.08 0.08 0.04 ns 0.07 0.08 0.15 0.05 0.21 0.11 0.07 ns
1-Heptanolb 0.10 0.11 0.05 0.05 0.08 0.03 0.08 0.05 0.03 0.04 0.05 0.02 ns 0.06 0.06 0.08 0.06 0.09 0.07 0.02 ns
Octanolb 0.20 0.16 0.06 0.14 0.14 0.06 0.11 0.06 0.05 0.05 0.07 0.03 ns 0.07 0.07 0.13 0.07 0.14 0.10 0.03 ns
Nonanolb 0.18 0.43 0.17 0.78 0.39 0.29 0.160 0.08 0.13 0.16 0.14 0.05 ns 0.20 0.14 0.11 0.16 0.11 0.15 0.04 ns
Benzylic alcohol b 0.16 0.07 0.08 0.20 0.13 0.06 0.16 0.11 0.11 0.14 0.13 0.02 ns 0.02 0.01 0.05 0.06 0.10 0.05 0.04 +
2-Phenylethanolb 2.36 0.48 1.36 1.25 1.36 0.77 1.87 1.26 0.83 1.67 1.41 0.46 ns 0.81 0.70 3.11 1.36 1.67 1.53 0.97 ns
Benzaldehydeb 5.97 4.10 2.65 4.34 4.34 1.37 2.89 1.40 2.43 2.78 2.37 0.68 ns 0.53 0.42 0.88 1.11 1.00 0.79 0.30 +++
Ethyl benzoate 0.06 0.32 0.34 0.97 0.42 0.39 0.210 0.02 0.16 0.46 0.21 0.18 ns 0.02 0.02 0.13 0.06 0.16 0.08 0.06 ns
4-Ethylguaiacola 130.00 17.20 10.00 8.71 41.48 59.13 100.00 66.22 10.00 6.15 45.59 45.49 ns 49.75 88.58 5.41 20.09 3.49 33.46 35.94 ns
4-Ethylphenola 290.00 103.21 1.89 15.99 102.77 132.62 710.00 110.37 10.00 55.30 221.42 328.30 ns 37.31 179.93 135.15 8.04 3.49 72.79 80.04 ns
Eugenolb 0.03 0.01 0.03 0.03 0.03 0.01 0.04 0.03 0.05 0.01 0.03 0.02 ns 0.22 0.06 0.04 0.46 0.03 0.16 0.18 ns
Furfuralb 2.77 2.79 6.23 5.39 4.29 1.79 1.31 3.23 4.41 4.40 3.34 1.46 ns 0.93 1.34 1.20 0.23 1.17 0.98 0.44 ++
6-Methyl-5-hepten-2-oneb 0.03 0.16 0.07 0.12 0.09 0.06 0.03 0.04 0.10 0.22 0.10 0.09 ns 0.14 0.08 0.03 0.06 0.08 0.08 0.04 ns
6-Methyl-5-hepten-2-olb 0.15 0.06 0.05 0.08 0.08 0.05 0.14 0.02 0.04 0.09 0.07 0.05  0.17 0.09 0.05 0.12 0.04 0.09 0.05 ns
trans Furan linalool oxidea 32.27 24.95 14.94 19.96 23.03 23.03 11.79 4.23 19.58 15.06 12.67 6.47 ns 19.77 34.41 10.29 11.22 9.71 17.08 10.51 ns
cis Furan linalool oxidea 16.31 13.40 26.52 4.24 17.62 14.82 6.92 2.93 17.62 2.53 7.50 7.03 ns 14.66 21.55 21.74 7.19 6.86 14.40 7.31 ns
Linaloolb 0.02 0.03 0.01 0.01 0.02 0.01 0.02 0.01 0.02 0.02 0.02 0.01 ns 0.01 0.02 0.01 0.01 0.01 0.01 0.00 ns
a-Terpineola 8.04 21.47 11.90 12.16 13.39 14.73 9.98 4.60 10.00 16.76 11.39 5.32 ns 8.17 10.45 3.76 3.91 3.01 5.86 3.27 ns
Citronellolb 0.01 0.03 0.02 0.01 0.02 0.01 0.02 0.01 0.02 0.02 0.01 0.00 ns 0.01 0.01 0.01 0.01 0.01 0.01 0.00 ns
Geraniolb 0.02 0.02 0.05 0.05 0.03 0.02 0.01 0.01 0.06 0.05 0.03 0.03 ns 0.02 0.02 0.01 0.01 0.01 0.01 0.00 ns
Nerolidolb 0.17 0.14 0.09 0.09 0.12 0.04 0.44 0.18 0.56 0.45 0.41 0.16 ns 0.19 0.54 0.08 0.16 0.17 0.23 0.18 ns
Farnesolb 0.25 0.17 0.17 0.19 0.20 0.04 190 0.23 0.69 0.72 0.66 0.32 ns 0.22 0.47 0.43 0.76 0.88 0.55 0.27 ns
a-Farnesene (E,E?)b 12.87 7.61 6.58 11.98 9.76 3.13 5.29 1.23 7.80 8.37 5.67 3.25 ns 10.33 6.05 3.36 6.07 3.17 5.79 2.89 ns
a-farnesene(Z,E?)b 1.07 0.58 0.30 0.44 0.60 0.33 0.50 0.16 0.43 0.37 0.36 0.14 ns 0.75 0.71 0.15 0.37 0.15 0.43 0.29 ns
b-damascenoneb 0.03 0.02 0.03 0.02 0.03 0.01 0.03 0.02 0.03 0.01 0.02 0.01  0.02 0.03 0.02 0.03 0.02 0.02 0.00 ns

ANOVA 1: significance depending on year (comparison between averages for Appio and Miali samples); ns = not significant, *p 6 0.05; **p 6 0.01.
ANOVA 2: significance depending on variety (comparison between averages for Appio, Miali and Trentino samples); ns = not significant, +p 6 0.05; ++
p 6 0.01; +++
p 6 0.0005.
a
Values expressed in lg% mL p.A.
b
Values expressed in mg% mL p.A.
 Author's personal copy
G. Versini et al. / Food Chemistry 113 (2009) 1176–1183
Differences resulted among the Sardinian products for farnesol
and nerolidol, alcohols which prove to be tendentially correlated
with each other as derivates of sterolic metabolism of the yeasts
with floral sensorial influences (Ledauphin et al., 2004). Differences
of furfural are not noted between the distillates considered except,
in the case of the Sardinian ones, depending on the year. Furfural
formation in distillation is basically due to the presence of pen-
toses residue in the mash as well as to a possible Amadori decom-
position product via 1,2-enolisation (Eichner, Lange-Aperdannier,
& Vossmann, 1998), but its final level in distillate is above all deter-
mined by tail cut intensity at the distillation (Versini, 1978).
Among other compounds of possible sensorial interest, we
quote 4-ethylphenol and 4-ethylguaiacol (Woidich et al., 1978),
whose level is probably linked with limited bacterial processes or
Brettanomyces metabolism in the mash departing from p-coumaric
and ferulic acids (Chatonnet, Dubourdieu, Boidron, & Pons, 1992).
Only the Sardinian apple distillates of 2002 show higher values
and a phenolic-medicinal off-flavour could derive from those con-
tents. Levels generating defects e.g. in wine distillates like Cognac
seem however not affect the quality in apple distillates like Calva-
dos (Ledauphin et al., 2004). Finally, we observe that no significant
correlation results for both ethylphenols with the level of ethyl lac-
tate, another metabolite of bacterial fermentation.
Benzaldehyde shows a noticeably higher tenor in products of
the Sardinian apple varieties, more close to that of Annurca apple
cider distillate (Genovese et al., 2004) than to the mean level of ap-
ple distillates investigated by Postel et al. (1975). In particular, the
distillates of Appio variety show greater concentrations than those
of Miali, certainly in both cases with an organoleptic contribution
towards a spicy, almond-like scent (Meilgaard, 1975) as typical
of stone-fruit distillates to which mean level is more similar (Postel
et al., 1975). Ethyl benzoate does not characterise the different
products or varieties so much, nevertheless it is tendentially higher
in the Appio apple distillates and above all in the produce of the
year 2005. Benzylic alcohol does not appear to have varietal
correlations.
In the field of monoterpenes, correspondence is seen for the list
of possible compounds in apple distillates (Ledauphin et al., 2004),
as well as with some values reported in the literature (Postel et al.,
1975; Schreier et al., 1978a, 1978b). Their level can derive from the
free forms often after acid catalysed rearrangements during the
distillation, as well as from bound forms present in the mash (Flan-
zy, 1998; Otha, 1992; Skouroumounis & Sefton, 2000) taking how-
ever into account the difficulty of hydrolysis of primary alcohols
glycosides at the usual mash pH. Cis and trans furanic linalool oxi-
des dominate, even if sensorially not active; values no greater than
30 lg% mL p.A. result for linalool, alfa-terpineol, 4-terpineol, citro-
nellol and geraniol, which altogether do not exceed 100 lg% ml
p.A. The value of this sum for compounds at rather similar sensory
thresholds and similar floral scents e.g. in wine (Terrier, 1972) is
however interesting because possibly determining a floral contri-
bution to the aroma.
The 6-methyl-5-hepten-2-one and respective alcohol, 6-
methyl-5-hepten-2-ol, fruity derivatives from possible oxidative
decomposition of a-farnesene (Mehinagic, Royer, Symoneaux, Jou-
rion, & Prost, 2006; Whitaker & Saftner, 2000), are present both in
the Appio and the Miali apple distillates, but with great variations
depending on the year, and in the Trentinian distillates. The pres-
ence of ketone was reported in apple distillates by Schreier et al.
(1978a, 1978b), while that of the alcohol by Versini (1983) and
Ledauphin et al. (2004). The contents of distillates in a-farnesenes,
where the E,E isomer is notably dominant, are particularly abun-
dant in the Appio compared with the Miali and in that of the Cana-
dian Rennet for the Trentino products. Their important removal in
the filtration process during the fining step should be carefully
controlled and limited with adequate operative conditions e.g. by
1181
a filtration at not to low temperature (Versini et al., 1989), since
these compounds are likely responsible for an important ‘apple-
like quality’ scent (Murray, 1969) and, generally, for a ‘fresh floral
terpenyl topnote’ (Ziegler & Ziegler, 1998).
We highlight, amongst the compounds with an intense, delicate
fruity scent, hexyl 2-methylbutanoate and hexyl hexanoate (Schre-
ier et al., 1978a). The Appio apple distillate is particularly rich in
the first component, as it is in that of Morgenduft apples among
the Trentinian products. Hexyl hexanoate proves particularly
important in the product from Canadian Rennet apples.
Among the Sardinian products an appreciable presence of euge-
nol also emerges, responsible for a spicy tone, with variable levels
depending on the year rather than the variety. Quite high contents
are observed in the Canadian Rennet apple products and secondly
in Royal Gala among the Trentinian brandies.
Finally, there are no evident differences between the single vari-
ety apple distillates for the level of beta-damascenone, a norisopr-
enoidic compound with honey-like, flowery, tea hints and a very
low sensory threshold at about 40 ppt in a 23 Vol.% hydroalcoholic
solution even if not qualifying the aroma of distillates like whisky
at 0.1 ppm likely for masking odours (Perry, 1989). The alfa and
beta-ionone and the beta-cyclocitral are not detected even if the
literature indicates them in certain apple distillates (Schreier
et al., 1978a; Woidich et al., 1978).
3.1. Multivariate statistical analysis
The complete data set obtained from the analysis of distillates
from Sardinian apples (Miali and Appio) for four different years
and from Trentinian varieties (Canadian Rennet, Golden Delicious,
Royal Gala, Morgenduft and Gravenstein) was analysed using the
SPSS statistic package. At a preliminary stage, the data set com-
posed of 51 variables and 13 samples was subjected to ANOVA
analysis (Tables 3 and 4) to test the possible differences between
the varieties with the aim of selecting a small number of significant
variables. The variables with a P 6 0.01 were ethyl octanoate, ethyl
2-methylbutanoate, 1-hexanol, benzaldehyde and furfural. The
new data set selected, composed of these 5 variables and 13 sam-
ples, was subjected to principal component analysis (PCA). The first
two components account for about 80% of total variance. In partic-
ular the first component is negatively correlated with ethyl octano-
ate and positively with benzaldehyde and furfural (loading values
are 0.788, 0.829 and 0.835, respectively). The second component
is positively correlated with hexyl 2-methylbutanoate and 1-hexa-
nol (loading values are 0.724 and 0.801, respectively). The individ-
ual plan of the projection of the first and second components
(Fig. 1) shows the excellent separation between the Trentino and
Sardinian distillates and among the latter the differences between
the Appio and Miali varieties. This shows that the variables se-
lected are able to explain the differences observed between the
groups.
With the aim of highlighting whether there was an influence
deriving from the year of production among the Sardinian varie-
ties, the data set made up still of 51 variables and 8 samples (4
of Miali apples and 4 of Appio) was again subjected to ANOVA anal-
ysis. The variables selected with P 6 0.01 were 3-methyl-1-buta-
nol, total aldehydes, ethyl acetate and 6-methyl-5-hepten-2-ol
(Tables 3 and 4). The PCA carried out using these 4 variables and
8 samples highlighted that the first two components take charge
of about 99% of total variance and that the first component is pos-
itively correlated with 3-methyl-1-butanol and ethyl acetate and
negatively with total aldehydes (loading values are 0.720, 0.882
and 0.919, respectively). The second component is positively cor-
related with 6-methyl-5-hepten-2-ol (loading value is 0.919).
The individual plane of the first two principal components
(Fig. 2) shows good separation carried out by the second compo-
 Author's personal copy

1182 G. Versini et al. / Food Chemistry 113 (2009) 1176–1183

2003
4. Conclusions
1.50000

2002
The study carried out shows a vast picture of volatile com-
2005
pounds in apple distillates produced in the northern part of the
1.00000
southern Italian Sardinia region from native varieties (Miali and
2003
Appio) and from international ones (Canadian Rennet, Golden Deli-
2003

0.50000
cious, Royal Gala, Morgenduft and Gravenstein), produced and dis-
Principal component 2

2003
2003 2004
tilled in the northern Trentino region. The comparison shows clear
differences between the products, often on a varietal base and
0.00000 sometimes also due to limited variations in the process. The statis-
tical analyses performed on both monovariate (ANOVA) and multi-
2003 variate (PCA) data sets highlighted that ethyl octanoate, hexyl 2-
-0.50000 methylbutanoate, 1-hexanol, benzaldehyde and furfural are corre-
2002 lated with the varieties and able to differentiate them. Whereas the
3-methyl-1-butanol, total aldehydes, ethyl acetate and 6-methyl-
-1.00000 Type of Apple 2003
5-hepten-2-ol variables, in the case of the Sardinian varieties, are
Appio strongly correlated with the year of production. Finally, many of
Miali 2005 the compounds investigated confirm the sensorial evidence
-1.50000 Trentino observed.
varieties 2004
As for the variables selected, we observe that hexyl 2-methyl-
-2.00000
butanoate, 1-hexanol and benzaldehyde may effectively be quali-
fied as compounds derived from variety, whereas the ethyl
-2.00000 -1.50000 -1.00000 -0.50000 0.00000 0.50000 1.00000 1.50000 octanoate may constitute an index of more or less favourable mul-
Principal component 1 tiplicative activity of the yeasts in the substrate (Postel & Adam,
1989). Furfural may be considered a parameter linked both with
Fig. 1. Scatter plot of the scores on the first 2 principal components obtained with the distillation (tail-cutting) and with different sugar residues in
data set of 5 variables and 13 objects (4 Miali, 4 Appio and 5 Trentino samples).
the fermented mash.

Acknowledgements

1.50000
The F.lli Rau S.n.c. Company – Sassari, Italy, and the Pilzer S.n.c.
2005 Distillery – Faver, Italy, are thanked for their helpful cooperation.

2002
1.00000
2005
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