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Characterization of the aromatic prole of the Italia variety of Peruvian pisco by gas
chromatography-olfactometry and gas chromatography coupled with ame
ionization and mass spectrometry detection systems
Juan Cacho a, Liliana Moncayo a, Juan Carlos Palma b, Vicente Ferreira a, Laura Culler a,
a
Laboratory for Aroma Analysis and Enology, Aragn Institute of Engineering Research (I3A), Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza,
Zaragoza 50009, Spain
b
Vitivinicultural Research Center, La Molina National Agrarian, University Lima, Per
a r t i c l e
i n f o
Article history:
Received 15 May 2012
Accepted 17 July 2012
Keywords:
Italia
Peruvian pisco
Aroma
Olfactometry
Quantitative analysis
Aromatic variety
a b s t r a c t
Thirty-three commercial pisco samples made with Italia grapes in ve different regions in Per have been
evaluated by gas chromatography-olfactometry (GC-O) and chemical quantitative analysis for the rst
time. The GC-O study has revealed that the Peruvian pisco made from this aromatic variety of grape (Italia)
has an aroma prole composed of twenty-ve odorants. Only one of them could not be identied (LRIDB-WAX
2313). Most of the odorants are fermentation-related, while guaiacol, -damascenone, geraniol and linalool
come from the grape. A total of sixty-two compounds have been analyzed following two different methods.
As a result of these analyses, a volatile prole quite typical of a wine distillate was obtained. Terpenes play a
relevant aromatic role in piscos elaborated from aromatic varieties of grapes. Italia piscos are particularly
highlighted because of their high levels of linalool. This terpene has exceeded its odor threshold in 28 of
the 33 samples, reaching odor activity value (OAV) up to 10 units. Other terpenes such as geraniol and
-citronellol have presented OAVs higher than 1 in one and ve samples respectively. Compared to the
composition of other aromatic piscos, the Italia variety exhibited considerably higher concentrations of
some volatile compounds (nerol and acetic acid) and lower levels of some ethyl esters (ethyl lactate, diethyl
succinate and ethyl hexanoate). Furthermore, when compared with other distillates it can be concluded that
in general aromatic piscos seem to be characterized by high levels of -phenylethanol and -phenylethyl
acetate (with the exception of some orujo and grappa compositions), and also by low levels of some ethyl
esters, 1-hexanol and ethyl acetate. In general, the chemical differences may be sufcient to classify the
samples by origin. Quantitative data revealed that samples from Ica are the richest in several aromatic
compounds such as terpenes, -damascenone and -phenylethyl acetate and samples from Moquegua are
the poorest in phenol compounds, which can have an impact from a sensory point of view.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Pisco is a common beverage obtained by distillation of wine made
from different varieties of grapes. A distinctly Muscat fruity aroma
distinguishes pisco from other young distillates. Therefore, the avor
and aroma of pisco are dened with fruity and owery descriptors
and can be explained by the variety of grapes used and also by the
presence of some compounds formed during the fermentation and
distillation processes (Palma, 2011).
A comparison of Chilean and Peruvian pisco reveals that the former
is obtained mainly from Muscat grapes while the latter is made with
other grape varieties. It is possible to distinguish between groups of aromatic grapes (Albilla, Italia, Moscatel and Torontel) and nonaromatic
grapes (Mollar, Negra Criolla, Quebranta and Uvina). The most
Corresponding author. Tel.: +34 976 762067; fax: +34 976761292.
E-mail address: lcullere@unizar.es (L. Culler).
0963-9969/$ see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodres.2012.07.065
118
from Per (Agosin et al., 2000; Bordeu, Formas, & Agosin, 2004;
Herraiz, Reglero, Herraiz, & Loyola, 1990; Lillo et al., 2005). Herraiz
et al. (1990) characterized the volatile composition of Chilean Pisco
by a multidimensional gas chromatography strategy. Another study
provided a quantication of the most relevant terpenes and other
aromatic compounds present in the most signicant varieties in the
industry (Moscatel de Alejandra, Moscatel Rosada, Moscatel de
Austria and Torontel) (Agosin et al., 2000). Finally, other two research
studies were carried out in order to provide standardized terminology to describe sensory differences among a wide range of piscos
(Bordeu et al., 2004; Lillo et al., 2005). In both papers, a selection of
a relevant set of attributes was made by well trained assessors. However, to the best of our knowledge, the systematic screening of pisco
odorants by gas chromatography-olfactometry has not been carried
out.
Thus, the main goal of this study was to characterize for the rst time
the aromatic prole of Italia piscos belonging to the ve main
pisco-producing regions in Per (Lima, Ica, Arequipa, Tacna and
Moquegua), using gas chromatography-olfactometry (GC-O), GC with
ame ionization detection (GC-FID) and GC with mass spectrometry
detection (GCMS).
Ica
Lima
Moquegua
Tacna
(n = 6)
(n = 9)
(n = 6)
(n = 8)
(n = 4)
Don Maurilio
Majes Tradicin
Sotelo
JH Yanquiza
Don Onorato
Pancho erro
El Mocho
Don Camilo
Cepas de Loro
La Hacienda del
Abuelo
Mi dolo
Cholo Matas
Don Benito
Chumbiauca
Andrs Arias
Biondi
Don Cirilo
Cerro Blanco
El Huerto de
mi Amada
Don Cesar
Carabantes
Cholo Matas
(Rosada)
Viejo Tonel
Bellavista 2006
El Sarcay
Omo Zapata
Gran Cruz
Jimnez
Parras y
Reyes
Paredes
Los Portales
Tunga
Grimaldi
consists of the direct injection of the pure distillate in a gas chromatograph system, after the addition of an internal standard. The calibration of the method was developed using dilute solutions of pure
standards (see Table 2). Then, a volume of 1.6 mL of pisco containing
20 L of internal standard solution (4-methyl-2-pentanol and
4-decanol, 2000 mg L 1) was analyzed by GC with FID detection
under the following conditions. A STAR 3400 CX series gas chromatograph supplied by Varian and equipped with a ame ionization detector (FID) was used. The column was a DB-WAX from Varian,
50 m 0.32 mm ID, with 0.2 m lm thickness. The carrier was H2
at 4 mL min 1. One microliter of the pisco sample was injected in
split mode, with a split ratio of 1/10. Injector and detector were
both kept at 220 C. The temperature program was as follows: 40 C
for 3 min, then raised by 6 C min 1 to 75 C, and by 9 C min 1 to
220 C, and nally held at 220 C for 10 min.
2.5. Chemical quantitative analyses by solid phase extraction (SPE)
followed by injection in a gas chromatograph (GC-ion trapMS)
This analysis was carried out using the method proposed and validated by Lpez, Aznar, Cacho, and Ferreira (2002) with some modications. In accordance with this method, 15 mL of pisco was diluted up to
50 mL with Milli-Q water in order to obtain a 12% (v/v) ethanol. A volume of 26 L of a surrogate standard solution (3-octanone and
-damascone of 200 mg L1) was added to the sample and then passed
through a LiChrolut EN cartridge at about 2 mL min1. The sorbent was
dried by passing air through it (0.6 bar, 10 min). Analytes were recovered by elution with 1.6 mL of dichloromethane. 34 L of internal
standard solution (4-hydroxy-4-methyl-2-pentanone and 2-octanol,
200 mg L 1, in dichloromethane) was added to the eluted sample.
The extract was then analyzed by GC with ion trap MS detection
under the following conditions: the column was a DB-WAX from J&W
(Folsom), 60 m 0.25 mm ID, with 0.25 m lm thickness and was
preceded by a 3 m 0.25 mm ID uncoated (deactivated intermediate
polarity) precolumn from Supelco (Bellefonte, PA, USA). The carrier
gas was He at 1 mL min1. Two microliters was injected in the splitless
mode, with a pulse of 30 psi for 2.60 min. The splitless time was also
2.60 min. The injector was held at 40 C for 0.30 min and then raised
to 250 C at 200 C min1. The chromatographic oven was held at
40 C for 3 min and then raised to 220 C at 2 C min1. A 40220 m/z
ranged was recorded in full scan mode. The MS parameters were MS
transfer line and chamber ionization temperature 200 C and trap
emission current 30 A.
119
Table 2
Linearity data of the methodology based on the direct injection of the pisco samples in a gas chromatograph (GC-FID).
Compound
Slope
Intercept
r2
LD (mg L1)
RSD (%)
Acetaldehydea
Isobutanala
Methyl acetatea
Ethyl acetatea
Propanola
Isobutanola
1-Butanola
2-Methyl-1-butanola
3-Methyl-1-butanola
3-Hydroxy-2-butanonea
Ethyl lactateb
1-Hexanolb
Ethyl octanoateb
Furfuralb
Acetic acidb
2,3-Butanediolb
Diethyl succinateb
-Phenylethanolb
0.0193
0.0350
0.0252
0.0344
0.0526
0.0643
0.0536
0.0838
0.0698
0.0490
0.0323
0.0493
0.0528
0.0289
0.0183
0.0308
0.0836
0.0596
0.1032
0.0434
0.0418
0.670
0.9157
1.1783
0.1217
0.5843
1.2302
0.4688
0.2798
0.1479
0.0038
0.0090
0.1275
0.0115
0.0338
0.2279
0.999
0.997
0.997
0.994
0.994
0.994
0.992
0.996
0.994
0.994
0.996
0.992
0.999
0.996
0.995
0.993
0.999
0.992
0.14850
0.1077
0.03793
0.0461454
0.0035240
0.0151367
0.005298
0.019310
0.0141287
0.01470
0.027309
0.01120
0.003620
0.01120
0.0811688
0.027200
0.003142
0.0054237
0.14
0.10
0.037
0.046
0.0035
0.015
0.0052
0.019
0.014
0.014
0.027
0.011
0.0036
0.011
0.081
0.027
0.0031
0.0054
1.4
4.6
4.9
1.8
3.3
4.8
1.2
2.6
1.5
5.4
3.0
1.7
5.2
2.1
2.7
2.4
4.5
2.1
LD: limit of detection was dened as the concentration which gives a signal to noise ratio of 3. For its calculation, the s/n ratio of samples containing very low amounts was used. aInternal
standard: 4-methyl-2-pentanol; binternal standard: 4-decanol. Relative standard deviation was calculated by means of 16 determinations (4 days4 replicates/day) of three different
pisco samples.
120
Table 3
Calibration data of 23 compounds, which are analyzed by a solid phase extraction followed by and injection in a gas chromatograph and were not quantied in a previous paper
(Lpez et al., 2002).
Compound
m/z
Slope
Intercept
r2
LDa (g L1)
RSD (%)b
Isobutyl acetate
Ethyl butyrate
Ethyl isovalerate
Isoamyl acetate
Ethyl hexanoate
t-Limonene oxide
c-3-Hexenol
c-Linalool oxide
t-Linalool oxide
-Terpinolene
Benzaldehyde
Ethyl furoate
Phenylacetaldehyde
Ethyl decanoate
Neryl acetate
Nerol
Geraniol
Benzyl alcohol
m-Cresol
-Decalactone
-Decalactone
Farnesol
Syringaldehyde
43
71
57
RIC
88
67
67
59
59
93 + 121 + 136
105
95
11 + 120
157 + 201
69 + 93
69
123
108
108
85
99
69
181.0 + 182.0
0.0011
0.00312
0.0005
0.0187
0.00312
0.000937
0.000864
0.000437
0.000443
0.00118
0.00184
0.00125
0.0007
0.00153
0.00625
0.00038
0.0002
0.00052
0.00083
0.00154
0.000795
0.000287
0.00134
0.0447
0.0096
0.0005
0.0061
0.0361
0.0014
0.0015
3.1E05
2.5E05
1.5E06
0.0061
0.0003
0.0011
0.011
0.0002
8.3E06
0.0039
9.3E05
9.00E06
0.0017
3E05
0.00022
0.0237
0.993
0.999
0.998
0.988
0.997
0.987
0.999
0.999
0.999
0.999
0.999
0.992
0.999
0.992
0.995
0.999
0.999
0.998
0.996
0.993
0.995
0.999
0.995
1.301372
11.29395
3.39784
0.442906
0.029395
0.31506
6.0310,000
0.205000
0.105000
0.101000
0.14137
0.6024
0.30997
7.3010,000
0.30147
0.765000
1.0711,962
0.975000
0.083.80
0.0772.5
0.1418.3
3.225000
0.02522
1.30
11.2
3.39
0.44
0.02
0.31
6.03
0.20
0.10
0.10
0.14
0.60
0.30
7.30
0.30
0.76
1.07
0.97
0.08
0.07
0.14
3.22
0.02
6
5
4
4
5
6
5
6
5
6
4
5
4
5
5
6
6
3
5
4
5
6
5
a
b
LD: limit of detection was dened as the concentration which gives a signal to noise ratio of 3. For its calculation, the s/n ratio of samples containing very low amounts was used.
RSD (%): relative standard deviation was calculated by means of 16 determinations (4 days 4 replicates/day) of three different pisco samples.
acetic acid, -phenylethanol and -phenylethyl acetate) were calculated in a 40% ethanol/water (v/v) mixture.
oxidation of the corresponding amino acid precursors during distillation (Ferreira, Barbe, & Bertrand, 2003; Ferreira, Hogg, & de Pinho,
2003).
Table 4
Odorants found by GC-O in the representative sample of Italia pisco. Gas chromatographic retention data, olfactory description, chemical identity and modied frequency
percentage MF (%) for each compound.
RIpolar
RInonpolar
DB-WAX
VF 5MS
962
1223
1078
1316
1680
2226
1381
1039
1556
1242
1839
1858
1063
1641
1874
1433
1457
1129
1935
2259
2086
1015
2065
2313
1660
600
719
856
890
898
1114
939
800
1099
999
1392
1350
846
820
1137
1198
600
860
1108
1328
1103
771
1096
1045
Descriptor
Compound
MF (%)
Strawberry, cream
Cheese
Aniseed
Fried
Cheese
Curry, licorice
Floral, green
Aniseed, fruit
Lemon
Aniseed
Apple
Floral, metal
Aniseed
Cheese
Medicinal
Fruit
Vinegar
Banana
Roses, oral
Spicy, phenolic
Leather, animal
Sweet, solvent
Candy
Spicy, phenolic, green
Floral
2,3-Butanedionea
Isoamyl alcohola
Ethyl 3-metylbutyratea
2-Methyl-3-furanthiolb
3-Methylbutyric acid a
Sotolonb
1-Hexanolc
Ethyl butyratea
Linaloola
Ethyl hexanoatea
-Damascenonea
Geraniolc
Ethyl 2-metylbutyratea
Butyric acida
Guaiacolc
Ethyl octanoatea
Acetic acida
Isoamyl acetatea
-Phenylethanola
4-Vinylguaiacola
p-Cresola
Isobutyl acetatea
Furaneolb
Unknown
Phenylacetaldehydeb
85
78
78
66
65
60
58
57
55
49
49
49
45
45
41
33
31
31
27
27
25
24
24
22
20
a
Identication based on the coincidence of gas chromatographic retention indices in
DB-WAX column, olfactory description and mass spectrum.
b
Identication based on the coincidence of gas chromatographic retention indices in
DB-WAX column, and olfactory description but this compound did not produce any
clear signal in the mass spectrometer.
c
Identication based on the coincidence of gas chromatographic retention indices in
DB-WAX column (RIpolar) and VF 5MS column (RInonpolar), olfactory description and
mass spectrum.
*
Duncan's test results are shown with different letters: a,b.
Acetaldehyde
Isobutanal
Methyl acetate
Ethyl acetate
Propanol
Isobutanol
1-Butanol
2-Methyl-1-butanol
3-Methyl-1-butanol
3-Hydroxy-2-butanone
Ethyl lactate
1-Hexanol
Ethyl octanoate
Furfural
Acetic acid
2,3-Butanediol
Diethyl succinate
-Phenylethanol
14.1
1.4
2.5
37.0
43.3
51.2
2.0
38.8
190
9.7
11.1
1.2
0.4
0.7
38.1
13.9
0.5
12.1
66.8
1.8
4.3
319
148
148
3.9
97.6
403
24.6
68.9
4.9
1.3
3.7
251
43.5
2.6
37.5
38.5
1.6
3.1
115
79.4
93.4
3.2
64.8
295
14.7
33.5
2.5
0.7
2.0
126
30.8a
1.3
17.6ab
22.5
0.1
0.7
106
39.4
32.2
0.8
21.1
81.5
5.7
20.3
1.3
0.4
1.1
72.0
10.9
1.0
9.8
12.1
1.5
3.4
76.1
43.4
63.1
2.0
38.6
182
9.7
22.4
1.9
0.3
1.4
102
17.3
0.7
8.0
90.5
3.1
5.7
455
108
235
59.8
87.8
434
40.0
72.9
7.3
0.7
9.2
512
32.9
4.4
30.9
41.1
2.1
4.2
235
64.1
139
10.2
63.7
301
21.4
44.5
3.5
0.5
5.3
206
26.4ab
1.4
17.9ab
23.6
0.6
0.7
128
19.9
58.6
18.9
18.9
95.8
12.8
17.7
1.9
0.1
2.7
123
6.1
1.2
9.3
13.0
1.4
2.8
90.6
35.4
76.8
1.3
40.8
190
9.7
13.2
1.7
0.2
0.5
139
19.8
0.5
11.4
49.1
3.7
5.1
367
60.6
194
3.2
72.5
354
14.1
167
5.1
0.7
8.0
317
37.7
2.0
42.1
30.7
1.9
3.4
209
49.2
114
2.6
55.2
252
11.3
70.3
2.5
0.5
3.1
231
27.4ab
1.0
22.2a
15.0
0.9
0.8
98.1
9.5
46.0
0.7
13.0
69.6
1.6
55.6
1.3
0.2
2.7
80.7
7.8
0.6
10.8
24.0
1.4
2.7
42.8
47.6
64.8
3.4
37.7
160
10.3
16.0
2.0
0.2
1.2
37.6
14.6
0.5
3.7
135
1.7
5.4
407
106
188
5.4
67.2
329
21.9
80.6
6.2
0.8
11.0
325
26.2
0.9
9.2
55.4
1.5
3.8
135
80.1
99.8
4.2
53.2
237
12.6
36.8
3.6
0.4
3.6
133
19.9b
0.6
7.6b
36.5
0.1
1.0
127
26.5
38.9
0.8
11.0
58.1
3.9
23.5
1.3
0.2
3.5
97.2
4.9
0.2
2.0
28.5
1.5
3.0
132
50.1
53.1
3.0
35.5
170
11.0
16.1
1.1
0.3
2.6
156
32.2
0.5
9.0
144
2.5
6.5
218
59.5
189
9.2
93.8
441
12.5
28.6
3.5
1.6
7.7
200
37.9
4.5
39.4
65.4
1.9
4.1
168
55.6
107
6.1
65.4
298
11.5
23.8
2.3
0.7
4.5
178
35.1a
1.6
21.5
52.9
0.4
1.6
37.6
4.0
58.7
3.1
28.9
130
0.7
5.4
1.0
0.6
2.3
18.2
2.5
2.0
12.9
ANOVA
s
Av
Max
Tacna (n = 4)
Min
s
Av
Max
Moquegua (n = 8)
Min
s
Av
Max
Min
Ica (n = 9)
Min
Max
Av
s
Min
Max
Av
Lima (n = 6)
121
Arequipa (n = 6)
Table 5
Compounds analyzed by direct injection of pisco samples in a GC-FID: average concentration levels and standard deviation found in different Italia samples belonging to different regions (Arequipa, Ica, Lima, Moquegua and Tacna). Compounds that differed signicantly in ANOVA analyses are marked with an asterisk (*).
Two different analytical methods were used to characterize the volatile chemical composition of the Italia pisco samples. Eighteen major
volatile compounds were determined by direct injection of the pisco
samples in a GC-FID system. Analytical details of this procedure are
given in Table 2 and quantitative results of the samples, grouped by
geographical origin, are given in Table 5. Another 44 different compounds were determined by the GCMS analysis of extracts obtained
by solid phase extraction from diluted pisco, and the results are given
in Table 6. Five relevant odorants reported in Table 4 (GC-O data)
could not be quantied: 2,3-butanedione because it could not be separated from ethanol in the direct injection method, and sotolon,
2-methyl-3-furanthiol, butyric and 3-methylbutyric acids because
their concentrations were below the method detection limits. Another
two compounds (2,6-dimethoxyphenol and syringaldehyde) were
also not detected in any pisco samples.
The quantitative results are in accordance with the nature of a wine
distillate. The major compounds are major fermentation metabolites,
such as 3-methyl-1-butanol, acetic acid, ethyl acetate, isobutanol,
2-methyl-1-butanol and propanol. Leaving aside these major compounds found at typical levels in distillates, some results in Tables 5
and 6 merit attention. It should be emphasized that piscos from the
Ica region exhibited signicantly high levels of some terpenes such as
t-limonene oxide, c- and t-linalool oxide and -terpineol. Furthermore,
linalool and -citronellol were also at their maximum levels in samples
from Ica, although not in a signicant manner. In fact, the sum of these
compounds reached more than 15 mg L1 as the average level in these
samples, while Lima, Moquegua and Arequipa presented lower average
levels (between 9 and 11 mg L 1) and Tacna piscos did not reach
8 mg L 1. It is important to take this high level of terpenes into account
because it may explain some notes perceived during the sensory analysis. For this reason, individual odor thresholds of this family of compounds have been estimated, as explained in Section 3.3.
The Ica samples also were characterized by signicantly higher
levels of -damascenona than in other regions (reaching an average
level of 76.1 g L 1) and by exhibiting the maximum levels of aromatic
compounds such as cis-3-hexenol and -phenylethyl acetate. On the
other hand, Arequipa piscos stood out because of the presence of vanillins, although at very low levels compared to the levels obtained in aged
alcoholic distillates. Finally, piscos from the Tacna region exhibited
signicantly higher levels of ethyl cinnamate, whose aroma is dened
by oral notes.
Comparing the volatile composition of Peruvian Italia pisco with
Chilean piscos elaborated from different Muscat grape varieties
(Agosin et al., 2000; Herraiz et al., 1990) and other distillates such
as orujo (Cortes, Gil, & Fernandez, 2005; Cortes, Rodriguez, Salgado,
& Dominguez, 2011; Diguez, de la Pena, & Gomez, 2005; Diguez,
de la Pea, & Gmez, 2003; Lpez-Vzquez et al., 2010; Pea,
Barciela, Herrero, & Garca-Martn, 2008), grappa (Cortes et al.,
2011; Masino, Montevecchi, Riponi, & Antonelli, 2009), grape marc
distillate (Lukic et al., 2010) or different brandies (Nyknen &
Nyknen, 1991; Nyknen & Suomalainen, 1983), it can be concluded
that in general the levels of the majority of compounds in all these
beverages are very similar. However, some differences in their composition are noticeable, considering the limited quantitative data
available in the literature relating to these kinds of distillates. Italia
piscos differ from other distillates for several reasons: 1) compounds
such as 1-butanol, 3-hydroxy-2-butanone, and acetic acid were present at the highest levels in Italia piscos. However, both 1-butanol and
3-hydroxy-2-butanone appear at very high levels in only a few samples. 2) In contrast, this variety of pisco was characterized by the lowest levels of other compounds such as 2- and 3methyl-1-butanol,
diethyl succinate and ethyl hexanoate. However, one of the most relevant ndings is that -phenylethanol and its acetate derivative
-phenylethyl acetate, which are usually described in the literature
122
Table 6
Compounds analyzed by SPE and GC-ion trapMS: average concentration levels and standard deviation found in different Italia samples belonging to different regions (Arequipa, Ica, Lima, Moquegua and Tacna). Compounds that differed
signicantly in ANOVA analyses are marked with an asterisk (*).
g L1
Arequipa (n = 6)
Min
Ica (n = 9)
Av
43.7
42.3
3.8
13.7
350
325
12.1
201
36.4
55.6
60.2
4.6
144
79.1
54.7
8.0
64.2
170
9.8
3.4
352
74.4
494
1110
163
77.5
2356
1645
930
466
97.1
10,425
28.9
17.1
1734
4290
47.1
29.4
22.5
25.7
44.0
2.6
120
0.6
1507
2024
89.4
1787
3262
9.9
1007
4.5
687
892
52.9b
647
1592
6.7
518
2.2
521
838
31.2
651
1370
2.6
293
1.5
12.8
9.0
259
10.0
4.3
0.2
5.3
12.1
25.2
0.7
46.3
9.0
6.0
125
2.8
2.4
0.1
2.3b
6.4
13.1
0.2
20.2
4.0
3.1
91.1
4.4
1.9
0.1
1.9
2.9
9.8
0.2
15.2
633
493
4.3
0.2
1.4
0.6
b0.02
345
213
2.9a
0.1
0.6
0.2
223
169
1.1
0.1
0.6
0.3
3.4
b0.1
40.1
b0.1
b0.1
b0.02
b0.1
4.7
3.2
b0.1
5.3
b0.1
88.4
31.9
1.6
b0.04
b0.05
b0.03
170
177
7.5
74.3a
Min
121
108
3.2
79.5
Lima (n = 6)
Max
125
62.2
9.1
8.0
920
1141
78.1
58.4
171
182
21.5
409
383
170
a
118
40.4
48.9
39.7ab
28.7
44.6
639
845
288
928a
618
1115
577ab
353
548
150
163
44.3
b
87.0
13.6
29.3
3977
4344
3766
a
18.6
7.5
10.6
7.6
5.0
2.1
838
519
252
2778ab
1502
2312
168
535
140
113
1499
2492
1105
293
543
8780
39.3
10.1
1274
5597
b0.2
1307
1227
90.8
3262
2053
7.6
856
8.6
383
282
60.2
250
554
3.0
139
b0.1
5.9
3.0
18.5
1.5
b0.1
b0.02
b0.1
1.6
2.0
b0.1
2.7
b0.1
90.9
32.7
0.3
Av
304
244
20.6
25.5b
Min
241
349
22.1
15.7
Max
74.3
34.9
2.2
8.0
633
207
13.4
53.1
43.7
20.4
68.6ab
315
143
84.3
b
83.6
28.1
40.0
a
71.6
23.4
2.4
845
425
72.2
1701a
517
48.6
758a
163
32.5
122
75.8
5.9
b
186
154
40.9
5851
1880
128
24.8a
10.2
16.5
4.9ab
2.3
3.3
510
312
44.6
3814a
1252
55.9
b0.2
821
344
36.9
804
313
27.8
a
76.1
11.5
20.5
982
900
130
1424
492
38.2
5.0
1.4
3.4
355
221
232
2.7
2.6
1.6
134
279
82.4
105
1045
1800
585
158
419
6684
24.5
16.3
1485
4229
2.5
806
1012
66.7
2539
2094
21.3
704
22.0
13.3
6.9
536
486
4.1
0.7
3.7
25.7
317
15.9
62.0
8.0
4.7
126
65.4
2.0
0.1
0.8b
7.9
47.1
5.6
12.7
2.4
1.5
156
158
1.7
0.2
1.3
7.1
101.9
7.2
18.6
375
272
3.4
b0.04
b0.05b
b0.03b
b0.02
259
117
1.2b
97.4
88.4
1.0
3.1
8.7
2.9
25.3
38.5
250
6.1
1176
b0.1
8.6
b0.02
7.8
b0.1
4.7
3.0
16.3
18.7
2771
b1.0
12.2
5.3
31.6
b0.1
60.8
544
97.6
467
0.5
1.6
b0.04
b0.05b
b0.03b
b0.02
Moquegua (n = 8)
Av
s
206
80.3
5.5
28.9b
Min
213
63.8
4.3
19.7
Max
Tacna (n = 4)
Av
Min
Max
ANOVA
Av
20.2
23.4
1.0
2.8
162
142
5.6
14.7
80.8
65.2
3.2
8.8b
44.5
44.9
1.7
3.8
95.6
49.8
7.1
34.4
452
351
8.9
69.3
71.7ab
48.0
9.1
205
72.0
40.0
bc
61.3
18.4
15.7
41.1ab
41.0
16.9
399
369
193
853b
723
339
326b
234
175
82.6
62.7
56.4
b
135
142
13.3
3510
2864
3476
20.6a
3.4
4.0
6.6a
4.8
0.5
447
525
72.8
2328ab
1791
1250
1.0
1.0
b0.2
472
338
440
573
472
642
36.6b
16.4
29.4
791
974
54.2
1046
902
993
8.6
6.7
2.9
415
174
106
7.3
8.1
0.6
38.3
343
77.8
60.4
1733
1155
415
195
108
6508
8.9
2.4
1011
3856
1.9
688
1257
71.9
759
2413
4.5
843
6.0
22.9b
131
39.6c
29.0b
571
625b
314b
111
49.5b
4821
6.8b
1.4c
242
2098b
0.4
575
885
44.3b
263
1451
3.6
261
2.0
9.6
115
22.1
15.1
498
267
91.1
45.1
36.3
959
1.5
0.8
313
905
0.6
77.6
237
14.6
255
477
0.5
253
1.8
79.8
147
68.0
3.7
67.3
61.9
39.6
6.3
69.4
128
5.3
2.4
242
55.8
b0.2
36.9
28.5
21.0
133
38.2
3.6
139
2.1
265
2132
97.8
45.9
541
977
556
271
2482
6195
18.3
14.0
1485
2527
2.0
975
1273
52.3
2515
2431
7.4
371
11.9
149a
707
79.6b
23.4b
241
562b
324b
128
831a
3087
10.2b
6.8a
691
1301b
0.6
555
629
31.0b
885
1031
5.5
248
5.8
12.3
6.9
250
67.9
3.6
0.1
3.3
10.1
64.8
4.4
33.0
7.0
5.0
106
19.5
2.0
0.03
1.8b
4.4
21.7
3.3
9.9
10.8
4.2
140
424
3.0
3.0
12.3
9.1
409
4.1
51.9
7.6
3.3
68.2
183
1.9
0.9
7.0a
5.0
208
2.6
19.8
2.2
0.9
48.1
208
0.9
1.4
5.1 *
2.8
224
1.8
22.2
393
263
2.6
b0.04
b0.05b
b0.03b
b0.02
192
126
1.0b
5.6
2.1
38.5
2.9
0.9
0.2
1.9
3.3
8.1
b0.1
4.4
b0.1
188
23.0
0.03
528
1375
0.8
b0.04
b0.05b
b0.03b
b0.02
306
413
0.3b
153
644
0.4 *
6.1
8.2
109
242
3.2
1.6
2.7b
7.2
665
5.4
15.0
2.1
8.5
86.4
465
3.0
3.1
1.9
5.0
1053
4.1
9.6
233
209
1.0b
206
134
0.4
3.2
3.4
32.9
0.5
b0.1
b0.02
b0.1
1.3
1.5
2.5
1.1
b0.1
68.8
26.7
0.3
Statistically signicant differences measured by ANOVA at p b 0.05 according to region of origin. Duncan's test results are showed with different letters:
a,b,c
2.9
1.3
72.3
27.3
1.2
0.02
1.1
2.9
26.2
0.7
9.7
114
98.4
0.7
222
229
7.9
50.1ab
s
157
134
0.8
16.5 *
87.1
952
13.7
17.7
213
388
218
110
1135
2478
5.7
5.0
561
1009
0.9
387
509
14.3
1097
1006
1.9
113
4.4
*
*
*
*
*
*
*
*
*
*
*
Isobutyl acetate
Ethyl butyrate
Butyl acetate
Ethyl
2-methylbutyrate
Ethyl isovalerate
Isoamyl acetate
Ethyl hexanoate
t-Limonene oxide
c-3-Hexenol
c-Linalool oxide
t-Linalool oxide
-Terpinolene
Benzaldehyde
Linalool
Ethyl furoate
Phenylacetaldehyde
Ethyl decanoate
-Terpineol
Neryl acetate
-Citronellol
Nerol
-Damascenone
-Phenylethyl acetate
Geraniol
Guaiacol
Benzyl alcohol
Ethyl
dihydrocinnamate
c-Whiskylactone
o-Cresol
-Nonalactone
4-Ethylguaiacol
m-Cresol
4-Propylguaiacol
Ethyl cinnamate
-Decalactone
4-Ethylphenol
-Decalactone
4-Vinylguaiacol
2,6-Dimethoxyphenol
Farnesol
4-Vinylphenol
Vanillin
Methyl vanillate
Ethyl vanillate
Acetovanillone
Syringaldehyde
Max
123
Table 7
Odor thresholds (mg L1) and odor activity values (OAVs) of some aromatic compounds which highlight because of their high levels in Italia piscos.
Odor threshold (mg L1)
Terpenes
Linalool
Geraniol
Nerol
-Terpineol
Terpinolene
-Citronellol
t-Limonene oxide
c-Linalol oxide
t-Linalool oxide
OAV (min)
OAV (max)
1
3
40
300
2.5
1
5
5
5
0.13
b0.10
b0.10
b0.10
b0.10
b0.10
b0.10
b0.10
b0.10
10.4
1.09
b0.10
b0.10
0.19
1.51
b0.10
0.50
0.22
b0.10
0.19
b0.10
0.85
2.11
1.31
Ica (n = 9)
Lima (n = 6)
Moquegua (n = 8)
Tacna (n = 4)
4
1
3
1
3
1
2
1
124
Fig. 1. Score plot of Principal Component Analysis (PCA) applied to quantitative data of Pisco Quebranta varieties from four regions.
were found between the ve regions. It can be appreciated that in accordance to quantitative data of linalool compound (see Table 6), linalool
descriptor received high scores of modied frequency in the ve samples, irrespective of their origin. However, it should be noted that the
Ica prototype was characterized by a much higher sweet descriptor
(38 vs. less than 20). This sensory difference could be attributed to the
higher levels of terpenes present in these samples from Ica, as
commented previously. On the other hand, Moquegua sample seems
to be characterized from a sensory point of view by a low intensity in
the spicy note, which could be justied by the low levels of phenols
obtained quantitatively (guaiacol, 4-ethylguaiacol, 4-propylguaiacol,
4-vinylguaiacol and 4-vinylphenol among others). Considering Tacna
samples, it could be concluded that the high concentrations of ethyl
cinnamate found in these samples do not seem to be responsible for
any sensory difference.
4. Conclusions
This study provides a complete characterization of the aromatic prole of Italia piscos from Per for the rst time. For this, GC-O study and
different analytical methodologies based on GC-FID and GCMS have
been applied. The GC-O study has revealed that this aromatic prole is
typical of a naturally fermented alcoholic beverage, with 2,3-butanedione,
isoamyl alcohol and some ethyl esters as some of the most important
odorants. Furthermore, a total of sixty-two compounds, including many
of the relevant odorants according to GC-O analysis, have been analyzed
following the two different methods.
Generally speaking, aromatic piscos are marked by their high concentrations of -phenylethanol, -phenylethyl acetate and terpenes.
The Italia variety is particularly highlighted because of their high
levels of linalool, which exceeded its odor threshold in 28 of the 33
Raisin
45
40
Oxidized
Fresh fruit
35
30
25
20
15
Linalool
Floral
10
5
0
Nuts
Cut grass
Spicy
Wood
Sweet
Arequipa
Ica
Lima
Moquegua
Tacna
Fig. 2. Graph of mean sensory ratings MF (%) of the piscos from the region studied.
125
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