Food Research International 69 (2015) 97–105

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Food Research International

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Freeze-dried grape skins by-products to enhance the quality of white

wines from neutral grape varieties
C. de Torres b, R. Schumacher a, M.E. Alañón c, M.S. Pérez-Coello a, M.C. Díaz-Maroto a,b,⁎
a
Área de Tecnología de Alimentos, Facultad de Ciencias Químicas, Universidad de Castilla La-Mancha, Campus Universitario, s/n, 13071, Ciudad Real Spain
b
IRICA (Instituto Regional de Investigación Científica Aplicada), Universidad de Castilla La-Mancha, Campus Universitario, s/n, 13071, Ciudad Real, Spain
c
Food and Nutritional Sciences Department, School of Chemistry, Food and Pharmacy, University of Reading, Whiteknights, RG6 6AP, Reading, United Kingdom

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

Article history: Wastes generated by the wine industry (grape marc), mainly residues from white wine vinifications, are an
Received 1 October 2014 important source of aroma and phenolic compounds. However, grape marcs are highly perishable and seasonal
Accepted 14 December 2014 products, so they require an adequate conservation method. In this respect, freeze-drying, versus conventional
Available online 20 December 2014
drying methods, is a good alternative since this technique preserves the quality of the raw material. Specifically,
freeze-drying hardly caused losses of characteristic grape variety volatiles, such as terpenes and C6 compounds,
Keywords:
Grape marc
neither increases in the concentration of furan compounds. Furthermore, freeze-dried grape skins obtained from
White wine residues did not presented changes in the amounts of phenolic compounds with respect to the fresh skins. On the
Volatile compounds other hand, skin-contact treatment with Muscat freeze-dried skins enhanced the aroma of white wines made
Phenolic compounds from Airén grapes, a variety considered neutral, without affecting negatively their color. Skin-contact treatment
Sensorial analysis preserved the wine fruity notes, although the only wine that conserved floral notes in its flavor profile was that
macerated with freeze-dried skins. Also, these wines were better rated by the assessors than those macerated
with Muscat fresh skins.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Grape waste management is one of the main problems of winery
industries, mainly in grape producing countries, such as Spain. Accord-
ing to the International Organization of Vine and Wine (OIV, 2011),
Spain ranks first in vineyard area planted, concentrating 50% of it in
the Castilla-La Mancha region. Nowadays, there is a growing interest
in the exploitation of the residues generated by the wine industry.
Once the juice has been extracted, the skin, stalks, and seeds, mixture
known as grape marc or pomace, are all redundant. That grape marc,
if not treated effectively, can initiate a number of environmental
hazards (Spigno & Faveri, 2007).
Furthermore, grape marc is a highly perishable product, and due
to the enormous volumes of grape wastes generated during harvest
season, the utilization of fresh grape marc is unfeasible, and therefore
requires an appropriate method of preservation or appropriate use.
One of the higher value options is the recovery of bioactive plant
food constituents, which could be used in other industries, such as
pharmaceutical or food industry. In particular, winery wastes are an
important source of polyphenols (Alonso, Guillén, Barroso, Puertas, &
⁎ Corresponding author at: Área de Tecnología de Alimentos, Facultad de Ciencias
Químicas, Universidad de Castilla La-Mancha, Campus Universitario, s/n, 13071, Ciudad
Real Spain. Tel.: +34 926 295300x6743; fax: +34 926 295318.
E-mail address: mariaconsuelo.diaz@uclm.es (M.C. Díaz-Maroto).
García, 2002; Makris, Boskou, & Andrikopoulos, 2007). In this regard,
the last year's several studies have been realized, with the aim to recov-
er antioxidant phenolics, mainly on pomace deriving from red wine
production (Lazze et al., 2009; Pinelo, del Fabbro, Manzocco, Nuñez, &
Nicoli, 2005; Spigno & Faveri, 2007), whereas other by-products, such
as white vinification solid wastes have been much less studied
(Casazza, Aliakbarian, Mantegna, Cravotto, & Perego, 2010; Makris
et al., 2007). On the other hand, the high aromatic potential of grapes,
concentrated mainly in the skins cannot be forgotten. Specifically, in
white vinification, this potential, in many cases, is not sufficiently
exploited, since the skins are discarded in the early stages of the
winemaking process, becoming part of the grape wastes.
Although polyphenols are highly reactive, their recovery from grape
wastes is relatively easier than volatile compounds due to their
non-volatile character. The volatility of the compounds responsible
for aroma makes their isolation more costly and complex, and the
extraction conditions could modify the volatile profile profoundly.
In this regard, the drying is one of the methods used to preserve the
aromatic potential of the grape skin wastes (de Torres, Díaz-Maroto,
Hermosín-Gutiérrez, & Pérez-Coello, 2010; Pedroza, Carmona, Salinas, &
Zalacaín, 2011). Different methods of drying have been successfully
applied in the food industry, though it must be noted that the chang-
es in volatile product concentration during the drying process
depend on different factors, such as the drying method, the biological
characteristics of the plants and their volatile composition. For example,

http://dx.doi.org/10.1016/j.foodres.2014.12.016
0963-9969/© 2015 Elsevier Ltd. All rights reserved.
98 C. de Torres et al. / Food Research International 69 (2015) 97–105

oven drying and freeze-drying applied to parsley or spearmint lead
to significant volatile losses (Díaz-Maroto, Pérez-Coello, & Cabezudo,
2002a; Díaz-Maroto, Pérez-Coello, González-Viñas, & Cabezudo, 2003).
However, freeze-dried skins maintained their volatile and phenolic
composition in comparison with the original skins, better than those
which were oven-dried (de Torres et al., 2010). Freeze-drying is based
on the dehydration by sublimation of a frozen product. Due to the
absence of liquid water and the low temperatures required, a final
product of excellent quality is obtained.
The purpose of this study was first to assess the impact of the freeze-
drying process on the aroma and polyphenol potential of white skins
obtained from grape wastes, in order to obtain a stable and quality
product. Grape wastes were obtained after vinification of white wines
from grapes of Vitis vinifera var. Muscat, one of the main white aromatic
varieties. Freeze-drying was chosen after conducting a preliminary
study on the effect of different drying methods (freeze-drying,
oven drying at 45 °C and oven-drying at 30 °C) on the aroma quality
of white grape skins. Then, the freeze-dried skins were used to improve
the aroma of white wines obtained from grapes of Vitis vinifera var.
Airén, a neutral grape variety and the most representative in the
“La Mancha” region, Spain.
2. Materials and methods
2.1. Samples
White vinification by-products of Vitis vinifera (var. Muscat) were
obtained from the experimental winery of the University of Castilla-La
Mancha (Ciudad Real, Spain). They included pomace, a mix of skins
and seeds. Seeds were manually separated from skins immediately
after receipt, and all skins were stored at −78 ° C until dehydrated.
Frozen Muscat skins were freeze-dried under vacuum (2.4 × 10−2 mB)
for 24 h. The condenser temperature was − 49 ± 2 °C. The initial
moisture content of the fresh skins was 73.5% dry weight, and the
dried material had a moisture content of 9.5% dry weight. The freeze-
drying conditions were selected in a preliminary study, where fresh
Muscat skins were divided in four batches. One batch was refrigerated
at 5 °C for analysis in fresh. The other three batches were immediately
dried using different drying methods (freeze-drying, oven drying at
45 °C and oven drying at 30 °C). Three replicates of each treatment
were performed. The drying conditions employed were previously
selected after conducting trials to achieve a percentage moisture
content of less than 10% using the shortest possible time.
White wines were obtained from grapes of Vitis vinifera var. Airén
(a neutral white grape variety, the majority in Castilla-La Mancha).
Laboratory fermentations were performed in 3 L vessels. One of them
contained only Airen must, the other one had Airen must with 500 g
of fresh Muscat skins (25%), and the last one had 145 g of freeze-
died Muscat skins (25%). After 15 h at 18 °C (Sánchez-Palomo,
González-Viñas, Díaz-Maroto, Soriano Pérez, & Pérez-Coello, 2007)
skins were removed, and all the samples were inoculated with
Saccharomyces cerevisiae (CECT no. 10835). Fermentations were
conducted at 18 °C in duplicate.
When fermentation was finished, wines were centrifugated
(5000 rpm, 8 °C, 15 min) and stored under refrigeration until their
analysis.
OIV (1990) Official methods were used for wine conventional
analytical data.
2.2. Analysis of volatile compounds of fresh, oven dried and freeze dried
Muscat grape skins
A microscale simultaneous distillation–extraction apparatus
(Chrompack, Middelburg, The Netherlands) was used as previously
described (Godefroot, Sandra, & Verzele, 1981) to extract skin volatile
compounds. An amount of 5 g of Muscat grape skins in 40 mL of
water with 10 μL of 4-nonanol solution (0.5 g/L) added as an internal
standard was extracted under atmospheric conditions for 2 h using
dichloromethane as the extraction solvent. The extracts obtained were
frozen at −18 °C for gas chromatography analysis.
One microliter (1 μL) of the extract was injected in splitless
mode (0.5 min) for analysis into an Agilent Technology 6890 N
Network GC System equipped with an Agilent Technology 5973
inert mass selective detector. The column used was a BP-21 capillary
column (60 m × 0.25 mm × 0.25 μm). The injector temperature was
250 °C, and the oven temperature was programmed as follows: 70 °C
(5 min) first ramped at 1 °C/min to 95 °C (10 min) and then ramped
at 2 °C/min to 200 °C (40 min). The carrier gas was helium at 1 mL/min
flow rate, and the MS operated in the electron impact mode with elec-
tron energy of 70 eV, ion source temperature of 178 °C and scanning
from 40 to 450 a.m.u.
The identification was based on comparison of the mass spectra with
those provided for authentic standards and by the NBS75K and Wiley A
libraries. Response factor of each volatile compound was calculated by
injection of commercial standards. For compounds which commercial
standards was not available, the response factors of compounds
with similar chemical structures were used (cis-furan-linalool oxide
for trans-furan-linalool oxide, cis-pyran-linalool oxide and trans-
pyran-linalool oxide; linalool for 2,6-dimethyl-3,7-octadiene-2,6-
diol, 2,6-dimethyl-1,7-octadiene-3,6-diol and 3,7-dimethyl-1,7-
octanediol; β-damascenone for vitispirane; (E,E)-2,4-decadienal
for (E,Z)-2,4-decadienal; guaiacol for vinylguaiacol; and furfural for
2-pentyl furan).
2.3. Analysis of volatile compounds of control and macetated wines
For the analysis of the major volatile compounds, 1.5 mL of
wine sample were spiked with 90 μL of 2-pentanol as internal

Table 1
Concentrations of volatile compounds (μg/Kg) extracted from fresh and different dried Muscat skins.

Compounds RI Fresh Muscat skins Freeze-dried Muscat skins Oven-dried Muscat skins at 45 °C Oven-dried Muscat skins at 30 °C

X±SD X±SD X±SD X±SD

Hexanal 1084 535.8a ± 29.3 414.5b ± 39.1 77.7c ± 10.6 106.2d ± 7.6
E-2-Hexenal 1215 687.4a ± 63.3 546.7b ± 56.8 67.5c ± 6.5 94.3d ± 8.4
1-Hexanol 1353 87.2a ± 23.3 42.6b ± 4.2 4.5c ± 0.3 0.0d ± 0.0
Furfural 1447 0.0a ± 0.0 5.7b ± 0.8 227.7c ± 28.5 202.0c ± 14.6
5-Methylfurfural 1540 0.0a ± 0.0 0.0a ± 0.0 6.3b ± 0.9 4.1c ± 0.6
Linalool 1570 2959.7a ± 461.5 3055.2a ± 618.4 2185.2a ± 300.0 2022.6a ± 351.6
Hotrienol 1620 592.5a ± 150.9 616.4a ± 2.3 528.7a ± 107.8 539.6a ± 109.5
α-Terpineol 1646 595.8a ± 23.7 569.4a ± 45.9 549.2a ± 64.1 502.2a ± 57.5
Nerol 1824 332.3a ± 18.6 281.1a ± 56.2 183.1b ± 38.7 194.6b ± 21.3
trans-Geraniol 1849 1125.2a ± 52.9 1056.3a ± 189.6 599.5b ± 96.0 558.4b ± 77.4

Different superscripts (a, b, c, d) in the same row indicate statistical differences at the 0.05 level according to the Student–Newman–Keuls test.
RI, retention index (BP-21, 0.25 μm).
 C. de Torres et al. / Food Research International 69 (2015) 97–105 99

Table 2 standard (1 g/L). One microliter (1 μL) was directly injected, on split
Volatile compounds (μg/Kg) in fresh and freeze-dried Muscat skins obtained from grape mode, into a Hewlett Packard 5890 N Series II Gas Chromatograph
wastes.
coupled to a flame ionization detector. A capillary column, CP-Wax 57
Compounds RI Fresh Muscat Freeze-dried CB Chrompack (50.0 m × 0.25 mm × 0.25 μm) was used. The tempera-
skins Muscat skins tures of inlet and detector were 250 and 280 °C, respectively. The
X±SD X±SD column temperature was 40 °C (5 min) ramped at 4 °C/min to 120 °C
δ-Carene 1148 13.6 a ± 0.2 17.6 b ± 0.7
where it was kept during 10 min. Helium was used as carrier gas with
β-Myrcene 1160 57.6a ± 4.9 62.1 a ± 13.4 a flow of 0.7 mL/min. Peak identification was carried out comparing
Limonene 1192 47.6 a ± 3.5 76.0 b ± 1.0 the analyte retention times with those of commercial standards
α-Pinene 1216 34.9 a ± 2.0 29.6 a ± 1.2 (Sigma-Aldrich Chemie GmbH, Steinheim, Germany), and the
α-Terpinolene 1282 51.8 a ± 4.2 52.2 a ± 1.7
quantification process was based on calibration curves made
Alloocimene 1298 16.2 a ± 0.8 17.0 a ± 1.8
cis-furan-Linalool oxide 1420 46.5 a ± 3.4 65.7 b ± 3.6 using pure standards.
trans-furan-Linalool oxide 1449 37.1 a ± 3.2 52.3 a ± 3.4 Minor volatile compounds of wines were extracted by solid phase
Linalool 1570 2914.6 a ± 110.9 2595.4 a ± 185.6 extraction (SPE), with the addition of 40 μL of 4-nonanol as internal
Terpinen-4-ol 1602 8.7 a ± 0.3 9.5 a ± 0.4 standard (1 g/L) to 100 mL of wine. The SPE were carried out using
Hotrienol 1620 188.7 a ± 16.7 229.9 a ± 8.4
Z-Citral 1635 5.1 a ± 0.1 6.2 a ± 0.5
500 mg styrene divinyl benzene cartridges (Lichrolut EN Merck, KGaA,
α-Terpineol 1646 682.2 a ± 29.7 684.8 a ± 31.2 Darmstadt, Germany). The cartridges were previously conditioned by
E-Citral 1661 14.6 a ± 1.8 13.6 a ± 0.0 passing, first 10 mL of dichloromethane, then 5 mL of methanol
cis-pyran-Linalool oxide 1698 37.2 a ± 11.1 41.0 a ± 3.8 and finally 10 mL of 10% (v/v) aqueous ethanol, all at flow rates of
trans-pyran-Linalool oxide 1725 26.1 a ± 10.4 29.7 a ± 3.5
2 mL/min. Non-volatile hydrophilic compounds were washed out
β-Citronellol 1772 23.7 a ± 2.9 19.4 a ± 5.4
Nerol 1824 328.5 a ± 15.7 279.1 b ± 1.6 of the cartridges, using 50 mL of bidistilled Milli Q Plus water, and
trans-Geraniol 1849 1087.8 a ± 83.0 838.8 b ± 8.7 minor volatiles were eluted with 10 mL of dichloromethane. The
Geranyl acetone 1860 46.4 a ± 14.6 38.1 a ± 3.4 extracts were concentrated to 200 μL under a gentle stream of nitrogen
2,6-Dimethyl-3,7-octadiene-2,6-diol 1949 6.0 a ± 2.6 8.3 a ± 0.6 and stored in a freezer (−20 °C) prior to the chromatographic analysis
trans-Farnesol 2044 6.5 a ± 0.6 7.8 a ± 0.4
aforementioned in the previous section.
Geranic acid 2162 298.6 a ± 96.6 543.3 b ± 52.1
Total terpenes 5980.0 a ± 396,7 5717.4.0 a ± 169.5
2.4. Analysis of polyphenolic compounds by HPLC
Vitispirane 1790 3.7 a ± 0.7 6.7 b ± 0.4
β-Damascenone 1813 24.1 a ± 6.3 24.0 a ± 1.1
For the HPLC analysis of the skin polyphenols, an amount of 20 g
β-Ionone 1912 11.6 a ± 2.5 9.2 a ± 0.5
Methyl dihydrojasmonate 1953 1.6 a ± 0.6 5.7 a ± 2.2 of fresh and freeze-dried skins in 150 mL of MeOH/H2O/HCOOH
Total norisoprenoids 41.0 a ± 10.1 45.6 a ± 0.3 (50:48.5:1.5) was beaten by a mixer (Moulinex) for 2 min and then
centrifuged 2500 g for 15 min. The supernatants were stored at −18 °C
Hexanal 1084 261.5 a ± 4.4 178.2 b ± 5.0 until their analysis.
E-2-Hexenal 1215 383.1 a ± 16.1 259.4 b ± 20.9
Wine flavonols and hydroxycinnamic acid derivatives analysis
1-Hexanol 1353 26.3 a ± 1.6 18.0 b ± 0.7
Z-3-Hexen-1-ol 1401 29.6 a ± 8.6 14.7 b ± 1.4 was carried out by direct injection of grape skin extracts or wine
E-2-Hexen-1-ol 1411 26.6 a ± 4.0 28.4 a ± 4.8 samples (control and macerated wines) using the method proposed
Total C6 alcohols and aldehydes 727.1 a ± 6.2 498.7 b ± 13.2 by Castillo-Muñoz et al. (2009). HPLC separation, identification
and quantification of phenolic compounds were performed on an Agilent
Compounds RI Fresh Muscat Freeze-dried
skins Muscat skins
1100 series system (Agilent, Waldbronn, Germany), equipped with a DAD
photodiode detector (G1315B) and an LC/MSD Trap VL (G2445C VL)
X±SD X±SD
electrospray ionization mass spectrometry (ESI/MSn) system. The sam-
Heptanal 1182 13.3 a ± 0.4 3.7 b ± 1.3 ples, after filtration (0.20 μm, polyester membrane, Chromafil PET 20/25,
Octanal 1289 4.5 a ± 0.1 4.6 a ± 0.5 Machery-Nagel, Düren, Germany), were injected (50 μL) on a reversed-
Nonanal 1388 45.2 a ± 2.5 45.5 a ± 4.3
(E,E)-2,4-Hexadienal 1405 6.4 a ± 0.1 8.1 b ± 0.2
phase column Zorbax Eclipse XDB-C18 (4.6 mm × 250 mm × 5 μm
E-2-Octenal 1435 8.4 a ± 0.9 12.5 a ± 4.4 particle; Agilent), thermostatized at 40 °C. The solvents were as follows:
(E,E)-2,4-Heptadienal 1480 5.4 a ± 1.0 14.1 a ± 5.6 solvent A (acetonitrile/water/formic acid, 3:88.5:8.5, v/v/v), solvent
Decanal 1495 12.4 a ± 0.7 15.2 b ± 0.2 B (acetonitrile/water/formic acid, 50:41.5:8.5, v/v/v), and solvent C
(Z)-2-Nonenal 1534 5.2 a ± 0.3 9.1 a ± 3.0
(E,E)-2,6-Nonadienal 1590 2.9 a ± 0.6 4.1 a ± 0.6
(E,E)-2,4-Decadienal 1710 4.7 a ± 0.9 7.4 a ± 2.3 Table 3
(E,Z)-2,4-Decadienal 1795 12.4 a ± 3.9 21.6 a ± 10.5 Phenolic compounds (mg/Kg) in fresh and freeze-dried Muscat skins obtained from
Total aliphatic compounds 120.8 a ± 1.8 145.9 b ± 14.1 grape wastes.

Benzaldehyde 1515 7.7 a ± 0.9 11.5 a ± 2.2 Compounds Fresh Muscat skins Freeze-dried Muscat skins
Benzeneacetaldehyde 1625 28.4 a ± 0.6 41.9 a ± 8.5 X±SD X±SD
Benzyl alcohol 1869 20.7 a ± 8.1 20.8 a ± 1.2
Phenylethyl alcohol 1940 31.9 a ± 7.7 33.4 a ± 6.6 Flavonols 11.58a ± 0.52 12.75 a ± 0.03
Vinylguaiacol 2134 3.7 a ± 0.3 8.0 b ± 0.1 Quercetin-glucoside 9.36 a ± 1.52 10.39 a ± 0.52
Total benzenic compounds 92.4 a ± 15.7 115.6 a ± 15.1 Kaempferol-galactoside 1.06 a ± 0.27 1.18 a ± 0.08
Kaempferol-glucuronide 0.33 a ± 0.04 0.33 a ± 0.02
2-Pentylfuran 1231 n.d. 6.8 b ± 1.8 Kaempferol-glucoside 3.83 a ± 0.96 4.32 a ± 0.37
Furfural 1447 60.5 a ± 2.2 95.7 b ± 14.3 Total 26.16 a ± 1.31 28.97 a ± 0.96
5-Methylfurfural 1540 n.d. 4.0 b ± 0.1
Furanmethanol 1659 1.8 a ± 0.4 3.3 b ± 0.2 Hydroxycinamic acids
2,3-Dihydrobenzofuran 1748 2.9 a ± 1.4 7.3 a ± 3.3 GRP 8.55 a ± 0.61 8.92 a ± 0.07
Total furan and pyran compounds 65.3 a ± 0.4 117.2 b ± 13.2 trans-Caftaric acid 4.48 a ± 0.30 4.82 a ± 0.26
trans-Cutaric acid 0.20 a ± 0.00 0.21 a ± 0.02
Different superscripts (a, b) in the same row indicate statistical differences at the 0.05 level Total 13.23 a ± 0.19 13.95 a ± 0.31
according to the Student's t-test.
n.d.: not detected. Different letters (a, b) in the same row indicate statistical differences at the 0.05 level
RI, retention index (BP-21, 0.25 μm). according to the Student's t-test.
100 C. de Torres et al. / Food Research International 69 (2015) 97–105

Table 4 52.5 min, 30% A, 40% B and 30% C; 57 min, 50% B and 50% C; and
Major volatile compounds (mg/L) in control and macerated wines with fresh and 65 min, 96% B and 4% C. For identification DAD and MSn data were
freeze-dried Muscat skins obtained from grape wastes.
used as previously described by Castillo-Muñoz et al., 2009. DAD-
Compounds RI Control wine Macerated wine Macerated wine chromatograms were extracted at 360 nm and 320 nm, for flavonols
with fresh with freeze-dried and hydroxycinnamic acid derivatives quantification, respectively,
Muscat skins Muscat skins
using commercial standards from Extrasynthese (Genay, France), and
Χ ± SD X ± SD X ± SD non-commercial flavonol standards kindly supplied by the Institute of
Acetaldehyde 1420 14.7 a ± 0.6 8.1 b ± 0.5 10.6 c ± 0.1 Food Chemistry from the Technical University of Braunschweig
Ethyl acetate 1545 11.0 a ± 0.0 19.9 b ± 1.0 26.1 c ± 1.6 (Germany). Flavonols for which standards were not available were
Methanol 1623 9.2 a ± 0.3 20.1 b ± 1.4 18.5 b ± 4.7 quantified as thir respective 3-glucoside derivative.
Isobutanol 1698 31.0 a ± 0.7 39.6 b ± 0.5 44.2 c ± 0.3
2-methyl-1-Butanol 1725 26.6 a ± 0.1 38.0 b ± 0.4 41.1 c ± 0.6
3-methyl-1-Butanol 1772 149.9 a ± 0.9 197.8 b ± 0.7 210.4 c ± 1.3 2.5. Analysis of the color parameters of control and macerated wines
Total higher alcohols 242.4 a ± 1.0 323.5 b ± 0.5 350.8 c ± 7.4

Different superscripts (a, b, c, d) in the same row indicate statistical differences at the 0.05
level according to the Student–Newman–Keuls test.
RI, retention index (CP-Wax 57, 0.25 μm).
(methanol/ware/formic acid, 90:1.5:8.5, v/v/v). The flow rate was
0.63 mL/min. The linear solvents gradient was: 0 min, 96% A and 4%
B; 38 min, 70% A, 17% B and 13% C; 52 min, 50% A, 30% B and 20% C;
Chromatic characteristics of wine samples in the CIELAB space were
obtained using the simplified method proposed by Ayala, Echávarri, and
Negueruela (1999), from absorbance measures at 450, 520, 570, and
630 nm for wine samples after adjusting the pH values to 3.6. Necessary
calculations to obtain the values for chromatic parameters L*, a*, b*, C*,
and h* were made using a computer application (Ayala et al., 1999).
Total polyphenols were measured by Folin-Ciocalteu method.

Table 5
Minor volatile compounds (μg/L) in control and macerated wines with fresh and freeze-dried Muscat skins obtained from grape wastes.

Compounds RI Control wine Macerated wine with fresh Muscat skins Macerated wine with freeze-dried Muscat skins

X±SD X±SD X±SD

cis-furan-Linalool oxide 1420 n.d. 5.2 a ± 0.5 5.4 a ± 0.1

Linalool 1570 Tr 305.9 a ± 31.3 273.4 a ± 13.7
Hotrienol 1620 n.d. 7.8 a ± 1.2 6.8 a ± 1.1
α-Terpineol 1646 Tr 151.4 a ± 9.3 163.0 a ± 4.1
cis-pyran-Linalool oxide 1698 n.d. 32.0 a ± 2.8 35.7 a ± 2.4
trans-pyran-Linalool oxide 1725 n.d. 19.5 a ± 1.6 19.2 a ± 0.6
β-Citronellol 1772 n.d. 107.9 a ± 6.9 107.8 a ± 5.3
Nerol 1824 n.d. 74.7 a ± 5.2 84.3 a ± 2.2
trans-Geraniol 1849 Tr 129.9 a ± 4.5 124.1 a ± 14.2
2,6-Dimethyl-3,7-octadiene-2,6-diol 1949 n.d. 218.0 a ± 17.1 220.2 a ± 25.7
2,6-Dimethyl-1,7-octadiene-3,6-diol 2134 n.d. 25.0 a ± 3.0 29.2 a ± 2.9
3,7-Dimethyl-1,7-octanediol 2004 n.d. 34.9 a ± 5.5 42.0 a ± 0.4
Neryl acetate 2098 n.d. 95.2 a ± 11.3 104.2 a ± 2.3
Geranic acid 2162 n.d. 434.3 a ± 38.8 429.0 a ± 9.1
Total terpenes 1641.6 a ± 138.8 1644.3 a ± 69.4

1-Hexanol 1353 894.1 a ± 85.9 1007.7 a ± 70.6 955.9 a ± 28.3

E-3-Hexen-1-ol 1378 18.1 a ± 1.4 22.4 a ± 1.4 23.1 a ± 1.2
Z-3-Hexen-1-ol 1401 314.4 a ± 30.6 333.2 a ± 26.4 313.2 a ± 20.1
Z-2-Hexen-1-ol 1411 3.7 a ± 0.0 3.2 b ± 0.1 3.6 a ± 0.0
Total C6 alcohols 1230.3 a ± 117.9 1366.5 a ± 98.6 1295.7 a ± 49.6

Ethyl butyrate 1047 67.1 a ± 4.6 174.7 b ± 20.1 217.5 c ± 8.3

Isoamyl acetate 1147 1428.4 a ± 160.8 1129.6 a ± 122.6 1395.2 a ± 45.8
Ethyl hexanoate 1229 610.0 a ± 42.0 875.3 b ± 33.2 945.6 b ± 27.5
Hexyl acetate 1270 131.3 a ± 9.7 18.2 b ± 1.2 25.3 b ± 0.9
Ethyl lactate 1358 55.4 a ± 5.4 65.1 b ± 2.3 56.2 b ± 4.7
Ethyl octanoate 1444 1055.0 a ± 73.4 1160.8 b ± 0.2 1198.2 b ± 21.1
Ethyl 3-hydroxybutyrate 1483 39.8 a ± 0.1 60.8 b ± 3.9 61.4 b ± 5.1
Ethyl decanoate 1630 425.6 a ± 71.3 252.6 b ± 4.2 259.9 b ± 1.8
Ethyl 3-hydroxyhexanoate 1664 3.0 a ± 0.4 4.9 b ± 0.4 5.7 b ± 0.4
Diethyl-succinate 1690 55.8 a ± 2.9 101.0 b ± 1.8 126.9 b ± 8.5
2-Phenylethyl acetate 1803 213.4 a ± 2.9 62.9 b ± 6.6 97.5 b ± 7.2
Total esters 4084.7 a ± 83.0 3905.9 a,b ± 156.0 4389.3 b ± 130.6

Compounds Control wine Macerated wine with fresh Muscat skins Macerated wine with freeze-dried Muscat skins

X±SD X±SD X±SD

Benzaldehyde 1515 2.6 a ± 0.2 3.0 a ± 0.1 3.6 a ± 0.5

Guaiacol 1848 8.6 a ± 2.2 8.3 a ± 1.6 7.0 a ± 0.1
Benzyl alcohol 1869 25.9 a ± 1.0 104.8 b ± 12.5 106.0 b ± 13.7
Phenylethyl alcohol 1940 13544.1 a ± 466.1 17466.3 a ±1723.1 16938.3 a ± 196.5
Vinylguaiacol 2134 350.1 a ± 5.3 215.8 b ± 26.2 218.3 b ± 8.2
Total benzenic compounds 13931.3 a ± 470.4 17798.3 b ± 1763.5 17273.1 b ± 218.9

Different letters (a, b, c) in the same row indicate statistical differences at the 0.05 level according to the Student–Newman–Keuls test.
n.d.: not detected; Tr: traces.
RI, retention index (BP-21, 0.25 μm).
 C. de Torres et al. / Food Research International 69 (2015) 97–105 101

2.6. Descriptive sensory analysis
Control and macerated wines were evaluated, in duplicate, by a
panel of eight expert assessors with experience in wine sensory analy-
sis. Assessment took place in a standard sensory-analysis chamber
(ISO, 1998), equipped with separate booths and wine-testing glasses
(ISO, 1997) covered with a watch-glass to minimize the escape of
volatile compounds. Wines were sniffed and tasted.
The panelists used a 10 cm unstructured scale to rate the intensity
of each attribute. The left-hand end of the scale was “attribute not per-
ceptible,” and the right-hand end was “attribute strongly perceptible.”
All wine samples were evaluated in duplicate.
2.7. Statistical analysis
Statistical analysis was carried out by using the SPSS version 22.0 for
Windows statistical package. The Student's t-test was used to assess the
significance of differences between the fresh and freeze-dried skins, and
the Student–Newman–Keuls test was used to assess the significance of
differences among wines.
3. Results and discussion
3.1. Effect of drying on the aroma quality of Muscat skins: preliminary study
A preliminary study on the effect of different drying methods on
the aroma of Muscat skins was conducted, in order to select a suitable
method for drying fresh white grapes skins. The results are shown in
Table 1. The mean values (μg/kg dry weight) and the standard deviation
(SD) for each compound and each treatment are given. The table also
shows the results of the Student–Newman–Keuls test for comparison
of the means. Ten volatile compounds were selected belonging to
three different chemical families, C6 alcohols and aldehydes, furan
compounds and terpenes. The total quantity of volatile compounds in
the fresh skins decreased considerably during oven-drying at 45 °C
and 30 °C, with losses of 35.9% and 38.9%, respectively. However, in
the freeze-dried samples, volatile compound losses were smaller
(4.7%). Similar losses of volatiles have been observed in red grape vari-
eties, such as Cabernet sauvignon or Carmènére (de Torres et al., 2010).
On the one hand, there were substantial losses in C6 alcohols and
aldehydes in dried samples, mainly in oven-dried skins. With regard
to the terpenes, no significant differences were generally found in
the amount of these compounds in the freeze-dried skins, but they
appeared in the oven-dried samples at 45 °C and at 30 °C for nerol
and trans-geraniol. Analogous results were found when freeze-drying
and oven-drying processes were used to dehydrate two red grape
variety skins (de Torres et al., 2010).
Fresh samples did not present furan derivatives; however these
volatile compounds were detected in dried skins, mainly in oven-
dried skins. Freeze-drying only produced a little amount of furfural.
This fact, together with the results found for C6 alcohols and aldehydes
and terpenes, highlights the great potential of freeze-drying for drying
white grape skins.
3.2. Effect of freeze-drying on the volatile and phenolic compounds of
Muscat skins obtained from grape wastes
In order to known the real potential of the freeze-drying to obtain
quality dried skins, a larger study on the effect of freeze-drying on the
volatile and phenolic compounds of white grape skins was conducted.
Table 2 shows the volatile components identified in fresh and
freeze-dried Muscat skins obtained from grape wastes after vinification.
A total of 53 compounds were identified, including monoterpenoids,
sesquiterpenoids, norisoprenoids, C6 alcohols and aldehydes, aliphatic,
benzenic and, furan compounds. As in the preliminary study, the total
quantity of volatile compounds in the fresh skins decreased slightly
during freeze-drying, with losses of 5.5%.
High amount of terpenic compounds were found in fresh skins as
it is common in Muscat variety (Ribereau-Gayon, Glories, Maujean, &
Dubourdieu, 2000), and no significant losses were detected after
dehydrated process in that type of compounds as well as norisoprenoids,
except for nerol and trans-geraniol. On the other hand, an increase was
observed in the content in some terpenic and norisoprenoid compounds,
such as geranic acid, δ-carene and vitispirane. The increases observed
may be attributable to rupture of the plant cells in which the volatiles
are stored. Increases in certain compounds have been recorded in
skins from other grape varieties (de Torres et al., 2010) and in other
vegetal materials by some other researchers after freeze-drying
(Díaz-Maroto, Pérez-Coello, & Cabezudo, 2002b; Díaz-Maroto,

Table 6
Phenolic compounds (mg/L) and color parameters in control and macerated wines with fresh and freeze-dried Muscat grape skins obtained from grape wastes.

Compounds Control wine Macerated wine with fresh Muscat grape skins Macerated wine with freeze-dried Muscat grape skins

X±SD X±SD X±SD

Quercetin-glucuronide 2.21 a ± 0.03 10.93 b ± 0.70 10.94 b ± 0.41

Quercetin-glucoside n.d. n.d. 0.12 a ± 0.01
Kaempferol-galactoside n.d. 0.50 a ± 0.08 0.58 a ± 0.01
Kaempferol-glucuronide 0.10 a ± 0.00 0.39 b ± 0.03 0.43 b ± 0.02
Total flavonols 2.30 a ± 0.03 11.83 b ± 0.81 12.07 b ± 0.44

GRP 22.55 a ± 0.94 28.60 b ± 0.94 23.28 a ± 2.20

trans-Caftaric acid 13.94 a ± 0.04 9.11 b ± 0.04 9.28 b ± 0.32
trans-Cutaric acid 1.05 a ± 0.09 0.45 b ± 0.02 0.45 b ± 0.02
cis-Cutaric acid 2.97 a ± 0.03 1.75 b ± 0.06 1.87 b ± 0.07
Caffeic acid 2.91 a ± 0.00 2.60 b ± 0.00 2.64 c ± 0.00
trans-Fertaric acid 4.48 a ± 0.01 4.20 a ± 0.02 4.76 a ± 0.43
Total hydroxycinamic acids 47.89 a ± 1.02 46.72 a ± 1.00 42.27 b ± 2.99

Color parameters
L* 96.25 a ± 0.07 96.05 a ± 0.49 95.75 a ± 0.21
C* 9.74 a ± 0.06 7.73 b ± 0.65 8.21 a ± 0.49
h* 92.52 a ± 0.63 94.02 a ± 1.15 94.81 a ± 1.26
a* −0.43 a ± 0.11 −0.54 a ± 0.11 −0.69 a ± 0.13
b* 9.72 a ± 0.07 7.71 a ± 0.66 8.18 a ± 0.51
Total polyphenols 214.03 a ± 0.01 220.51 b ± 0.02 223.74 c ± 0.01

Different letters (a, b, c) in the same row indicate statistical differences at the .005 level according to the Student–Newman–Keuls test.
n.d.: not detected.
102 C. de Torres et al. / Food Research International 69 (2015) 97–105

Sánchez-Palomo, Castro-Vázquez, González-Viñas, & Pérez-Coello,
2004; Venskutonis, 1997).
No significant losses were also recorded in aliphatic and benzenic
compounds. However, high losses of volatiles occurred in C6 alcohols
and aldehydes as was observed in the preliminary study and when
freeze-drying and oven-drying processes were used to dehydrate two
red grape variety skins (de Torres et al., 2010).
Finally, it was observed an increase in the concentration of some
furan compounds from browning reactions. This increase was similar
to that recorded in freeze-dried skins from red grape varieties,
and much less than that occurred when the oven-drying is used as
dehydration method (de Torres et al., 2010). Two furan compounds,
2-pentylfuran and 5-methylfurfural, were detected only in freeze-
dried samples, although the more significant increase was produced
in furfural content, however it did not exceed its olfactive threshold
(3000–23.000 ppb in water (Buttery, Turnbaugh, & Ling, 1988).
Respect to the content of phenolic compounds, Table 3 shows the
flavonols and hydroxycinamic acids identified in fresh and freeze-
dried Muscat skins. In the flavonol family, quercetin and kaempferol de-
rivatives were determined in both grape skins, fresh and freeze-dried,
and quercetin-glucoside was found in greater proportion. The freeze-
drying did not generate significant drops in the amounts of these com-
pounds, unlike what happened in the skins of two red grape varieties,
Cabernet Sauvignon and Carmenère (de Torres et al., 2010). The
flavonols are stored in the cellular vacuoles, but, they are often found
in the external areas of vacuoles (Chism & Haard, 1996). Thus, if the
cellular structure deteriorates during freeze-drying, the compounds
stored outside of the organelles are more sensitive to degradation,

(a) Fresh
8.0
7.0
6.0
Citric
Banana 5.0
4.0
3.0
2.0
1.0
0.0

Tropical fruit Green apple

Apricot, peach Flower

Control wine
Macerated wine with fresh Muscat grape skins
Macerated wine with freeze-dried Muscat grape skins

(b) Green apple

8.0
Overall impression 7.0
Apricot, peach
6.0
5.0
4.0
3.0
2.0
Aftertaste quality 1.0 Tropical fruit
0.0

Aftertaste intensity Acidity

Body Flower
Control wine
Macerated wine with fresh Muscat grape skins
Macerated wine with freeze-dried Muscat grape skins

Fig. 1. Sensory profile of control and macerated wines with fresh and freeze-dried Muscat grape skins obtained from grape wastes. (a) Aroma profile, (b) gustative profile.
 C. de Torres et al. / Food Research International 69 (2015) 97–105
which could explain the higher losses of flavonols observed in the skins
from red grape varieties.
With regard to GRP (grape reaction product or 2-S-glutathionyl
caffeoyl tartaric acid) and the two hydroxycinamic acids determined
at 320 nm no significant differences were observed. The levels of these
compounds decrease markedly under oxidative conditions, such as the
prefermentative steps of wine making (Cheynier, Trousdale, Singleton,
Salgues, & Wilde, 1986), however freeze-drying treatment did not
produce any change in their concentrations, because it is performed in
the absence of oxygen and at low temperatures. It shows the advantages
of freeze-drying process to obtain a product of similar quality to the
original one.
3.3. Use of freeze-dried Muscat skins to improve the quality of white wines
obtained from neutral grape varieties
Freeze-dried Muscat skins, obtained from grape wastes, were used
to improve the aroma of white wines obtained from grapes of Vitis vinif-
era var. Airén, a neutral grape variety. Control and macerated wines
(with fresh and freeze-dried Muscat skins) did not show significant dif-
ferences in their conventional parameters, except for alcohol content,
which was higher for macerated wines than control wine (12.9° control
wine, 13.6° fresh skin macerated wine, 13.9° freeze-dried skin macerat-
ed wine) probably due to the sugar added by the skins. All wines had
values of pH and volatile acidity of 3.6 and 0.2 g/L, respectively.
Respect to the volatile compounds, Table 4 shows the major volatile
compounds quantified in control wines and those macerated with fresh
and freeze-dried Muscat skins, together with the results of Student–
Newman–Keuls test for comparison of means. The concentrations of
the major volatile compounds increased during fresh and freeze-dried
skin contact, but in no case concentrations which could adversely affect
the aroma of the wines were obtained. The increase in the content of
higher alcohols observed in the macerated wines could be due to the
enrichment in amino acids of the must from the skins. While the in-
crease of methanol in the macerated wines is the result of the enzymatic
hydrolysis of the methoxyl groups of the skin pectins produced during
alcoholic fermentation. Normally the methanol content of wines is
low, and only increases are observed when a maceration with the
skins is done, but in any case are higher than 30 or 35 mg/L
(Ribereau-Gayon et al., 2000).
The minor volatile compounds are presented in Table 5. Thirty four
compounds were identified, including those previously identified in
the skins and ceded to Muscat wine, and other formed during alcoholic
fermentation.
Both wines macerated with fresh and freeze-dried skins showed a
high content in terpene compounds characteristic of Muscat variety,
while, as expected, in the control wine only appeared some terpene
alcohols, linalool, nerol and geraniol in trace amounts. As in the
case of the skins, no significant differences in the concentrations of
terpenes between wines macerated with fresh and freeze-dried
skins were found.
The most abundant terpene compounds in macerated wines were
geranic acid, linalool, 3,7-dimethyl-1,5-octadiene-3,7-diol (Diendiol I),
trans-geraniol and β-citronellol. In general, the concentrations of
terpenes in macerated wines were lower than that identified in fresh
and freeze-dried skins, except in some cases such as β-citronellol. Also
some compounds that were not transferred to the wines and new
terpenes, previously unidentified in the skins, were detected such
as 3,7-dimethyl-1,5-octadiene-3,7-diol (Diendiol I), 3,7-dimethyl-
1,7-octadiene-3,6-diol (Diendiol II), 3,7-dimethyl-1,7-octanediol
and neryl acetate.
β-citronellol could be formed from nerol and geraniol by yeast
metabolism (Dugelay, Günata, Sapis, Baumes, & Bayonove, 1992),
whereas 3,7-dimethyl-1,7-octanediol is a derivative of β-citronellol
(Ribereau-Gayon et al., 2000). Moreover, the diendioles are derivatives
of linalool, which was the major terpene component in the fresh and
103
freeze-dried skins, and neryl acetate is formed from nerol during
alcoholic fermentation (Ribereau-Gayon et al., 2000).
The influence of maceration with Muscat skins in the content of C6
alcohols and aldehydes of Airén wines was minimal. This is logical
because these compounds are mainly formed during the prefermentation
treatments from polyunsaturated fatty acids, linoleic and linolenic
(Drawert, Heimann, Enberger, & Tressi, 1966). There are certain grape
varieties like Chardonnay whose skins are rich in polyunsaturated fatty
acids, which causes the amount of C6 alcohols and aldehydes in wines
to increase with the contact time of the must with the skins (Ferreira
et al., 1995). This behavior was not observed in our study as Muscat vari-
ety was not particularly rich in such compounds.
In control and macerated wines, the majority C6 compounds were
1-hexanol and E-2-hexenal, both with green and herbaceous aromatic
notes (Joslin & Ough, 1978).
Within the group of esters formed during alcoholic fermentation,
a slight increase in some compounds was observed in wines macerated
with fresh and freeze-dried skins. Particularly, major increases occurred
in those esters formed from fatty acids and alcohol. Contact with skins
can produce an enrichment of wine in fatty acids, which would justify
the observed increase in the content of esters in macerated wines.
These compounds can play an important role in wine aroma, such as
ethyl butyrate or ethyl hexanoate. Both compounds are of particular
importance in the aroma of white wines made from neutral varieties, due
to its influence on their fruity aromatic notes (Bertrand, Anocibar-Beloqui,
Guesdes de Pinho, & Kotséridis, 1995; Kotséridis, 1999).
Another compound, whose concentration was higher in macerated
wines, was benzyl alcohol. This increase has been previously described
by other authors during skin-contact treatment with different grape va-
rieties (Sánchez-Palomo, Pérez-Coello, Díaz-Maroto, González Viñas, &
Cabezudo, 2006).
Although in the skins, both fresh and freeze-dried, furan compounds
were identified, they were not given to wine during maceration, proba-
bly to the low concentration at which these compounds were found in
the skins.
Also, flavonoids (flavonols) and no flavonoids (hydroxycinamic acids)
compounds were indentified in the three wines analyzed (Table 6).
Regarding flavonols, in control wines only quercetin and kaempferol
glucuronides derivatives were found, while macerated wines also
present kaempferol galactoside and quercetin glucoside, the latter
only in wine macerated with freeze dried skins. The kaempferol-
glucoside previously quantified in fresh and freeze-dried skins was
not identified in wines. The disappearance or significant decrease
in the concentration of glycosylated derivatives in macerated wines
could be due to their hydrolysis during the fermentation stage.
Flavonol profiles of wines differ from the original grapes due to
the hydrolysis of the flavonol 3-O-glycosides (Castillo-Muñoz, Gómez-
Alonso, García-Romero, & Hermosín-Gutiérrez, 2007). Therefore,
flavonol profiles of wine consist of a mixture of 3-O-flavonol glycosides
and free flavonol aglycones liberated from them. The causes of such
hydrolysis in wine have not yet been revealed, however, Castillo-
Muñoz et al. (2007) suggest that the hydrolysis of the flavonol 3-O-
glycosides develops either in young and aged wines and, also, the
degree of hydrolysis appears to be dependent on the flavonoid structure
and type of 3-O-glucoside.
Moreover, the GRP and hydroxycinnamic acids were found in
highest concentration and variety in wines than in skins, due to the con-
tribution of the control wine. In addition to the compounds identified in
fresh and freeze-dried skins (GRP, trans-caftaric acid and trans-cutaric
acid), cis-cutaric acid, caffeic acid and trans-fertaric acid were quantified
in control and macerated wines. The differences between the three
types of wines were low.
Table 6 shows the color parameters and the total polyphenol content
of wines. In the first case no significant differences between the control
wine and wines macerated with fresh and freeze-dried skins were
obtained, which shows that the skin-contact treatment do not produce
104 C. de Torres et al. / Food Research International 69 (2015) 97–105
any change in the color of white wines. As to the content of total poly-
phenols, only a small increase in the macerated wines was observed,
due to the contribution of the skins.
Finally, wines were analyzed by expert tasters. In Fig. 1 the results
of the quantitative descriptive sensory analysis of wines in form of
“spider-web” diagrams are shown. Fig. 1a shows the mean values of
the scores given to the olfactory attributes, while in Fig. 1b gustatory
attributes are observed along with the overall impression of each of
the wines.
The flavor profile of the control wine, obtained from Airén grapes,
was characterized by an intense fresh aroma and green apple odor,
with moderate citrus and fruity notes, mainly peach, apricot and
banana. It also presented a slight floral and tropical fruit aroma.
Muscat skin-contact treatment, both fresh and freeze-dried skins,
produced a moderate increase of the fruity notes (apricot, peach) and
fresh aroma, with a greater contribution to the floral aroma and citrus
notes. Floral and fruity olfactory attributes are mainly attributed to ter-
pene compounds and ethyl esters of short chain fatty acids, respectively
(Guth, 1997; Kotséridis, 1999), whose concentration was higher in
macerated wines.
On the other hand, a decrease in the characteristic aroma of Airén
wines, such green apple, banana and tropical fruit notes, was observed.
As for the comparison between the wines macerated with fresh
and freeze-dried skins, no differences were observed, which demon-
strates the potential of freeze-drying technique for the dehydration
of grape skins.
Differences in taste profiles were also found between macerated
wines and control wine. However, in this case the wines macerated
with freeze-dried skins were slightly better rated than the wines
macerated with fresh skins, and both obtained higher scores on
overall impression and quality aftertaste than control wine.
Airén control wine was mainly characterized by its acidity and green
apple flavor, with light gustatory notes of peach, apricot and tropical
fruit. Skin-contact treatment preserved the wine fruity notes, although
produced a light decrease in the green apple flavor and acidity. Similar
results have been obtained by other authors for wines obtained by
skin-contact treatment (García Romero, Pérez-Coello, Cabezudo,
Sánchez-Muñoz, & Martín Álvarez, 1999; Sánchez-Palomo et al.,
2006, 2007). It could be due to the neutralization of the main acids
of wines produced during the maceration of the must. The only
wine that conserved floral notes in its flavor profile was that macerated
with freeze-dried skins.
4. Conclusions
Freeze-drying, versus conventional drying methods, is a good
technique to preserve the quality of grape skins, obtained from wine
industry wastes. Freeze-drying hardly cause losses of characteristic
grape variety volatiles, neither increases in the concentration of furan
compounds. Moreover, freeze-dried grape skins obtained from residues
do not present changes in the amounts of phenolic compounds with
respect to the fresh skins. Among other applications, freeze-dried
skins obtained from by-products of an aromatic grape variety as
Muscat could be used to enhance the flavor of white wines made
from neutral grape varieties. Naturally, this study is a first step or
proposal to revalue waste from wineries. However, future work
about cost evaluation or other potential applications are required.
Acknowledgements
The authors thank to Junta de Comunidades de Castilla-La
Mancha for the project POII-2014-009-A. M. E. Alañón would like
to thank Fundación Alfonso Martín Escudero for the post-doctoral
fellowship awarded.
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