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Characterization of Romanian Wines by
Gas Chromatography–Mass Spectrometry
Veronica Avrama, Călin G. Floarea, Anamaria Hosub, Claudia
Cimpoiub, Constantin Măruţoiuc & Zaharie Moldovana
a Mass Spectrometry, Chromatography and Applied Physics
Department, National Institute for Research and Development of
Isotopic and Molecular Technologies, Cluj-Napoca, Romania
b Faculty of Chemistry and Chemical Engineering, Babes-Bolyai
University, Cluj-Napoca, Romania
c Faculty of Orthodox Theology, Babes-Bolyai University, Cluj-
Napoca, Romania
Accepted author version posted online: 31 Dec 2014.Published
online: 09 Feb 2015.
To cite this article: Veronica Avram, Călin G. Floare, Anamaria Hosu, Claudia Cimpoiu,
Constantin Măruţoiu & Zaharie Moldovan (2015) Characterization of Romanian Wines
by Gas Chromatography–Mass Spectrometry, Analytical Letters, 48:7, 1099-1116, DOI:
10.1080/00032719.2014.974054
To link to this article: http://dx.doi.org/10.1080/00032719.2014.974054
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Analytical Letters, 48: 1099–1116, 2015
Copyright © Taylor & Francis Group, LLC
ISSN: 0003-2719 print/1532-236X online
DOI: 10.1080/00032719.2014.974054
Gas Chromatography
CHARACTERIZATION OF ROMANIAN WINES BY GAS
CHROMATOGRAPHY–MASS SPECTROMETRY
Veronica Avram,
1
Călin G. Floare,
1
Anamaria Hosu,
2
Claudia Cimpoiu,
2
Constantin Măruţoiu,
3
and
Zaharie Moldovan
1
1
Mass Spectrometry, Chromatography and Applied Physics Department,
National Institute for Research and Development of Isotopic and Molecular
Technologies, Cluj-Napoca, Romania
2
Faculty of Chemistry and Chemical Engineering, Babes-Bolyai University,
Cluj-Napoca, Romania
3
Faculty of Orthodox Theology, Babes-Bolyai University, Cluj-Napoca,
Romania
This article reports the determination of the volatile composition of commercial Romanian
wines with the goal of identifying characteristic markers. For this purpose, 27 samples from
four wine-producing areas from three consecutive years were investigated. Analysis was
performed by gas chromatography–mass spectrometry with liquid–liquid extraction.
Forty-eight volatile compounds were identified and characterized as alcohols, ethyl
esters, fatty acids, phenyl compounds, aldehydes, ketones, lactones, and terpenes as a
percentage of the total area of volatile compounds. The results are discussed in
relationship to the grape variety, region, and year of production.
Keywords Gas chromatography; GC–MS; Volatile compounds; White wine
INTRODUCTION
The volatile composition of wine is one of the most important factors that deter-
mine its aroma and therefore its quality (Selli et al. 2004; Gil et al. 2006;Câmara,
Alves, and Marques 2006a;Coelhoetal.2008). The aromatic profile of wine results
from the combined effects of several different natural compounds (Alves, Nascimento,
and Nogueira 2005)following the interaction of the original components of the grape
and those produced during the process of wine making, fermentation, and aging
(Gómez-Míguez et al. 2007). Consequently, the wine aroma has been classified into
four groups: aroma variety, characteristic to grape variety; prefermentative aroma
Received 8 July 2014; accepted 28 September 2014.
Address correspondence to Zaharie Moldovan, National Institute for Research and Development
of Isotopic and Molecular Technologies, 65-103 Donath Street, 400293 Cluj-Napoca, Romania, E-mail:
zaha@itim-cj.ro
Color versions of one or more of the figures in the article can be found online at www.tandfonline.
com/lanl.
1099
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derived during processing of grapes; fermentative aroma produced by yeast and bac-
teria during alcoholic and malo-lactic fermentation; and postfermentative aroma
resulting from the changes that occur during storage and aging of wine (Vilanova et
al. 2010). The wine aroma also depends on the climate, region, viticulture practices,
and physiological ripeness (Alves et al. 2005;Gómez García-Carpintero et al.
2012a). The most abundant compounds responsible for the aroma of wine are those
formed during alcoholic fermentation, i.e., alcohols, esters, acids, phenyl compounds,
aldehydes, and ketones (Alves et al. 2005;Sánchez-Palomo et al. 2010). Identification
of these compounds and their relative concentrations can be a useful tool and provide
an isotopic fingerprint (Avram et al. 2014)for the characterization of wines with dif-
ferent geographical origins based on a volatile fraction relationship established with
grape variety, origin, and processing technology used (Gil et al. 2006;Câmara et al.
2006a; Welke et al. 2012). Due to their complexity and sometimes low concentrations
(in some cases <microgram per liter), the use of preconcentration techniques are
essential prior to analysis, performed usually by capillary gas chromatography coupled
to mass spectrometry (GC–MS). Some of the most commonly used methods in the
preconcentration step include liquid–liquid extraction (LLE), solid phase extraction
(SPE), and solid phase microextraction (SPME).
Although LLE is being replaced by more manageable and solvent-free
techniques, this type of extraction is still a reference method for the determination
of wine aroma compounds. The main advantages of this technique are its capacity
to extract a wide range of compounds of different volatilities (as long as they have
an affinity to the solvent), the high repeatability, and the ability to carrying out
simultaneous extractions (Andujar-Ortiz et al. 2009).
The objective of this work was to determine the volatile composition from a
series of commercial Romanian white wines from different regions to identify and
use some of the compounds as markers for geographical origin and processing tech-
nology. The analysis was performed by GC–MS following liquid–liquid extraction.
The results are discussed in relationship to the grape variety, region, and production
year based on classes of compounds and lead the most comprehensive characteriza-
tion of Romanian wines to date.
EXPERIMENTAL
Samples
Twenty-seven commercial white wines from the four most important wine
regions in Romania were characterized: Oltenia (Oprişor and Vânju-Mare
Vineyards), Muntenia (Cramele Halewood and Ceptura Vineyards), Moldova (Huşi
Vineyard), and Transylvania (Jidvei Vineyard). The wine varieties were Sauvignon
Blanc, FeteascăAlbă, and Riesling from 2008, 2009, and 2010 (Table 1).
Liquid–Liquid Extraction
The protocol used in this work for the extraction of volatile compounds from
wine samples was adapted from Andujar-Ortiz et al. (2009). The 25 mL of wine and
5 mL of methylene chloride (Merck, Germany)were stirred at 0°C for 1 h. Sub-
sequently, the mixture was kept for 15 min in an ultrasonic bath at the same
1100 V. AVRAM ET AL.
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temperature to avoid formation of an emulsion. After separation, the organic phase
was collected and centrifuged. In order to remove water, it was filtered through
anhydrous sodium sulfate and concentrated by rotary evaporation to approximately
200 µL. Subsequently 1 µL of extract was analyzed by GC–MS using the splitless
mode.
GC–MS
The wine samples were analyzed using a gas chromatograph (Trace GC)
coupled with a mass spectrometer (Polaris Q, Thermo-Finnigan). An HP 5-MS
capillary column was used with a methyl-phenyl siloxane class (5%)stationary phase
(length of 30 M, inner diameter of 0.25 mM, thickness of stationary phase of
0.25 µL). Helium was used as the carrier gas at a constant flow rate of 1.5 µL/min.
The column temperature was programmed to be: initially, 50°C, maintained for
2 min, and then increased at 10°C/min to 300°C where it was maintained for
10 min. The temperature of the injector was 250°C. The mass spectrometer was
equipped with an electron impact ionization source (EI)at an ionization energy
of 70 electronvolt. The temperatures at the interface and at the ion source were
300°C and 250°C, respectively. Acquisition was performed in the full scan mode
from 50 to 650 amu.
Table 1. White wine samples
Number
Wine
varieties Wine region
Production
year
1 Sauvignon
Blanc
Muntenia (Vineyard I)(Cramele Halewood, Dealurile
Munteniei)
2008
2 2009
3 2010
4 Oltenia (Vineyard I)(Oprişor, Dealurile Olteniei)2008
5 2009
6 2010
7 Oltenia (Vineyard II)(Mehedinţi,Vânju-Mare)2008
8 2009
9 2010
10 Fetească
Albă
Moldova (Dealurile Huşilor)2008
11 2009
12 2010
13 Muntenia (Vineyard I)(Cramele Halewood, Dealurile
Munteniei)
2008
14 2009
15 2010
16 Muntenia (Vineyard II)(Ceptura, Dealurile Munteniei)2008
17 2009
18 2010
19 Riesling Muntenia (Vineyard II)(Ceptura, Dealurile Munteniei)2008
20 2009
21 2010
22 Oltenia (Vineyard II)(Mehedinţi, Vânju-Mare)2008
23 2009
24 2010
25 Transylvania (Jidvei)2008
26 2009
27 2010
CHARACTERIZATION OF ROMANIAN WINES BY GC–MS 1101
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RESULTS AND DISCUSSION
Separation by GC–MS system was performed after optimization of the con-
ditions. Figure 1shows the analysis of FeteascăAlbăfrom Muntenia. Characteristic
chromatograms of 4-vinylguaiacol with the selected ion m/z¼135 (Figure 1b)and
of vanillin derivatives (acetosyringone, acetophenone, ethyl vanillin, and methyl
vanillin)with the selected ion m/z¼151 (Figure 1c)are also shown in Figure 1.
Forty-eight volatile compounds were identified belonging to eight different
classes: alcohols, ethyl esters, fatty acids, phenyl compounds, aldehydes, ketones, ter-
penes, and lactones (Table 2). In most cases, the identification of compounds was
achieved by comparing registered mass spectra with those in the NIST library spectra
and in some cases with those published in the literature (Câmara et al. 2006a; Vichi
et al. 2007). Volatile compounds determined by GC–MS were grouped in classes of
chemical structures and are reported as relative mean concentrations (percentages).
The identified compounds were consistent with other results reported in the literature
(Rocha et al. 2004; González-Marco et al. 2008; Oliveira et al. 2008;Sáenz-Navajas
et al. 2010; Robinson et al. 2011; Losada et al. 2012;Gómez García-Carpintero et al.
2012b; Welke et al. 2012). Quantitative analysis was performed on the basic ion
chromatographic areas of each compound. The identified compounds and main
parameters are shown in Table 2.
Study of Geo-Climatic Influence
To study the geo-climatic influence, on the volatile composition of Sauvignon
Blanc, FeteascăAlbă,and Riesling, wines from Oltenia, Muntenia, Moldova, and
Figure 1. GC–MS of FeteascăAlbăfrom Muntenia: (a)total ion chromatogram (TIC);(b)chromatogram
of 4-vinylguaiacol at m/z¼135; and (c)chromatogram of acetosyringone, acetophenone, ethyl vanillin,
and methyl vanillin at m/z¼151.
1102 V. AVRAM ET AL.
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Table 2. Identified compound, retention time (tr), and ion used for quantification (m/z)
Compounds t
r
Ion (m/z)
Alcohols
3-Methyl-1-butanol 5.89 57
Benzyl alcohol 7.66 79
2-Phenylethanol 9.01 91
Tyrosol 13.71 107
Tryptophol 17.61 130
Acids
Butanoic acid 6.84 60
Hexanoic acid 7.49 60
Octanoic acid 10.54 60
Decanoic acid 12.64 60
Dodecanoic acid 14.95 73
Tetradecanoic acid 17.19 73
Hexadecanoic acid 19.27 73
Esters
2-Furancarboxylic acid, ethyl ester 7.83 95
Hexanoic acid, ethyl ester 6.84 88
Octanoic acid, ethyl ester 9.97 88
Decanoic acid, ethyl ester 12.74 88
Succinic acid, diethyl ester 9.79 101
Succinic acid, monoethyl ester 10.89 101
Butanedioic acid, hydroxyl-, diethyl ester 11.21 71
Succinoic acid, 2-hydroxy-3-methyl-, diethyl ester 10.79 131
Butanedioic acid, 2,3-dihydroxy-, diethyl ester 12.42 104
Butanedioic acid, 2-(1-methoxy-1-methylethoxy)-3-methyl-, diethyl ester 12.69 85
Citric acid, triethyl ester 16.01 157
Isomer of ethyl citrate 16.37 157
Citric acid, tributyl ester, acetate 21.86 185
Phenyl compounds
Styrene 10.98 104
4-Vinylguaiacol 11.88 135
Benzoic acid, 2,6-dihydroxy-, methyl ester 12.03 136
Vanilic acid, methyl ester 14.55 151
Benzoic acid, 2,4-dihydroxy-, methyl ester 14.74 136
Benzeneacetic acid, 4-hydroxy-, ethyl ester 14.95 107
Vanilic acid, ethyl ester 15.35 151
3,4,5-Trimethoxyphenol 15.60 169
3,4,5-Trimethoxybenzyl alcohol 16.26 198
p-Hydroxycinnamic acid, ethyl ester 16.97 147
Ferulic acid, ethyl ester 17.50 222
m-Tolyl ester 17.99 198
oand m-hydroxycinamic acid, ethyl ester 18.17 147
Isomer of ferulic acid, ethyl ester 19.05 222
Aldehydes
Phenylacetaldehyde 12.43 91
Benzaldehyde, 4-hydroxy-2-methoxy- 12.55 151
Benzenebutanal 14.58 104
Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 16.25 182
Ketones
Acetophenone, 4′-hydroxy-3′,5′-dimethoxy- 13.49 181
Acetophenone, 4′-hydroxy-3′-metoxy- 14.22 151
(Continued )
CHARACTERIZATION OF ROMANIAN WINES BY GC–MS 1103
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Transylvania were analyzed. The behavior of each class of compounds is discussed
with reference to the primary influence affecting the chemical composition.
Alcohols
Higher alcohols are produced during alcoholic fermentation from carbohy-
drates and amino acids and play an important role in the flavor of the wine according
to the type and concentration (Câmara, Alves, and Marques 2006b). Quantitatively,
they are the largest group of volatile compounds (more than 50%)in the wines; these
results are confirmed by other published data (Zamúz and Vilanova 2006). However,
their concentrations varies by type and vineyard as shown in Figure 2. The most
important alcohols were aromatic: 2-phenylethanol, tyrosol, triptophol, and benzyl
alcohol. The only aliphatic alcohol present was 3-methylbutanol, but at a low concen-
tration. In some samples, the concentration was less than 1%of the alcohols ident-
ified; a result also reported in the literature (Welke et al. 2012).
Figures 2a and b are very similar due of the high abundance of 2-phenylethanol
relative to total compounds from alcohol family (more than 90%). The 2-Pheny-
lethanol represents 68%of the total volatile fraction. A similar result was reported
by other authors (Vilanova et al. 2010; Sagratini et al. 2012). The compound
2-phenylethanol is formed by chemical degradation of phenylalanine following
transamination, decarboxylation, and reduction reactions (Uzunov et al. 2011)and
has a rose-like odor (Gómez García-Carpintero et al. 2012a).
The concentration of 2-phenylalanine amino acid increased following contact
with the grape skin and yeast. Thus, the wines aging on yeast lees (so called autolysis
of wines)or a longer contact with grape skin during maceration may increase the
concentration of 2-phenylethanol (Selli et al. 2006; Losada et al. 2012). The average
concentrations of the identified alcohols were 64.8%for Sauvignon Blanc, 67.2%for
FeteascăAlbă, and 57%for Riesling.
An increase in alcohol percentage was observed with time. Exceptions include
Sauvignon Blanc from Muntenia (vineyard I)and Riesling from Oltenia (vineyard II)
and Transylvania (Jidvei). This behavior can be explained by an increasing contri-
bution of the esters and other components in wines during maturation. Therefore,
the mentioned exceptions may be due to the specific vinification processes.
For Sauvignon Blanc, the average level of alcohols are 59.9%and 60.7%in
Oltenia I and Muntenia I vineyards but differ significantly in Oltenia II vineyard,
73.8%. This behavior can be attributed to the differences in the vinification process;
a hypothesis which is also sustained by the relative stability of the values obtained
in the Oltenia II vineyard. For FeteascăAlbă, the average values of alcohols from
Muntenia are 64.8%in vineyard I and 62.4%in vineyard II and are different from
Table 2.. Continued
Compounds t
r
Ion (m/z)
Lactones
2(3H)-Furanone, dihydro-3-(phenylmethyl)- 13.57 91
γ-Decalactone 11.78 85
Terpene
2-Acetyl-carene 13.05 163
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the value in the Moldova vineyard, 74.3%. This should indicate that in Muntenia,
the vinification processes and climate were similar but are different from those
in the Moldova vineyard. For Riesling, the average values obtained in Muntenia
and Oltenia vineyards were 53.1%and 50.5%, respectively, but significantly differ-
ent from the value of 67.3%obtained in the Transylvania vineyard. This trend may
be caused by vinification techniques or geo-climate.
The average concentration strongly depended upon the geo-climatic conditions
specific to the grape region. The concentration differences among regions are between
11%and 16%. Also, the vinification process contributes 1–3%. Small quantities of
alcohols are produced by the hydrolysis of esters during maturation in wood (Câmara
et al. 2006b).
Ethyl Esters
Ethyl esters represent a class of compounds that also contribute significantly to
the aroma of the wine. They play a positive role in wine flavor being responsible for
the floral and fruity character. Thirteen esters were identified: three fatty acid ethyl
esters (hexanoic-, octanoic- and decanoic acid), nine esters of dicarboxylic acids (suc-
cinic, malic, citric), and an ethyl ester of a heterocyclic carboxylic acid (2-furoic acid).
The main ester contributors were monoethyl succinate, diethyl succinate, and diethyl
malate with average relative concentrations of 11.3%, 7.0%, and 8.7%, respectively,
with small differences based on grape variety. The maximum of succinic acid esters
was present in Riesling wine.
Figure 2. Relative concentrations of alcohols determined in Sauvignon Blanc, FeteascăAlbă, and
Riesling: (a)total alcohols and (b)2-phenylethanol.
CHARACTERIZATION OF ROMANIAN WINES BY GC–MS 1105
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The following ethyl esters of fatty acids were identified: ethyl hexanoate, ethyl
octanoate, and ethyl decanoate. These compounds are primarily produced in the first
stage of alcoholic fermentation (Gil et al. 2006)and contribute the aromas of green
apples, pears, and pineapple (Noguerol-Pato et al. 2009;Gómez García-Carpintero
et al. 2012b). The levels of these esters were approximately 0.1%in most samples.
Ethyl hexanoate was slightly higher than for the others, consistent with the literature
(Câmara et al. 2006b). Riesling from the Oltenia region (vineyard II)contained the
highest percentages in all years of production, reaching 0.15%in 2010. Because
the content and composition of the ester fraction is influenced by fermentation
conditions, a possible explanation for the low level may be a higher temperature
and low pH during fermentation (Belitz, Grosch, and Schieberle 2009).
In Figure 3, the total concentrations of ethyl esters for three consecutive years
are shown. An increasing trend of their contribution from year to year that corre-
lated with the downward trend observed for alcohols was present. This correlation
occurred because esters are the second class of compounds in the order of
abundance. Their relative average values were approximately 30%.
The averages were 28.6%for Sauvignon Blanc, 26.5%for FeteascăAlbă, and
35.6%for Riesling. The values of ethyl esters obtained for each vineyard for
Sauvignon Blanc and FeteascăAlbăwere inversely correlated with alcohol abun-
dances as can be seen in Figures 2a and b. An average of 22%was obtained for
Sauvignon Blanc in vineyard II of Oltenia that was significantly smaller compared
with 31.2%in vineyard I of Oltenia and 32.5%in vineyard I of Muntenia. For
FeteascăAlbăfrom Moldova region, an average of 19.1%was obtained that was also
smaller compared with values of 30.5%and 29.9%obtained from vineyards I and II
of Muntenia, respectively. These observations are consistent with the differences
between vinification techniques or geo-climatic conditions that led to this behavior.
Riesling contained the highest values of esters. The average values were 33.3%in
Muntenia (vineyard II), 43.2%in Oltenia (vineyard II), and 27.2%in Transylvania.
Although a similar correlation was expected with the corresponding alcohols levels, a
more pronounced contribution of esters appeared in vineyard II of Oltenia.
The ethyl ester concentration increased with age except for Transylvania
varieties. In addition to the climate contribution, ester concentration may also
increase during aging due to esterification reactions (Câmara et al. 2006b; Coetzee
and du Toit 2012). We assume, therefore, that the levels depend substantially on
Figure 3. Concentrations of ethyl esters in wine.
1106 V. AVRAM ET AL.
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grape variety and on the fermentation conditions in each vineyard. The type of
enzymes and the factors influencing their action, such as temperature, oxygen, pH,
and nitrogen sources, are essential.
Fatty Acids
Wine fatty acids are formed in the first two stages of alcoholic fermentation,
but can be found also in low concentrations in the original composition of the must
before fermentation. The formation of volatile fatty alcohol during fermentation is
relatively low in terms of quantity, but are very important in terms of flavor (Câmara
et al. 2006b)which may be described as having fruity, cheese, fatty, and rancid notes
(Gil et al. 2006; Tufariello, Capone, and Siciliano 2012; Gómez García-Carpintero
et al. 2012a).
Although the presence of C
6
–C
10
fatty acids is linked with the presence of an
unpleasant aroma, they are important to the aromatic equilibrium of wine as they
prevent the hydrolysis of corresponding esters. It was found that concentrations
of 4–10 mg/LofC
6
fatty acids provide a pleasant aroma, while levels above 20 mg/
L have a negative effect (Gil et al. 2006;Muñoz-González et al. 2011; Tufariello
et al. 2012).
Seven fatty acids were identified: butanoic, hexanoic, octanoic, decanoic, dode-
canoic, tetradecanoic, and hexadecanoic. Their levels were low in all types of wine in
concordance with previous studies (Gómez García-Carpintero et al. 2012a). For
butanoic acid, the variation was small: the mean values were approximately 0.15%
for Sauvignon Blanc and FeteascăAlbăand 0.28%for Riesling. The concentrations
of C
10
,C
12
,C
14
, and C
16
acids were approximately 0.01%in all samples. Hexanoic
and octanoic acids accounted for the largest contribution with average values of
0.9%and 1.3%. The higher level of the octanoic acid relative to hexanoic acid is
common as reported in literature (Vilanova et al. 2009; Losada et al. 2012;Gómez
García-Carpintero et al. 2012a). The distribution of fatty acids is shown in Figure 4.
The average acid concentrations were 2.9%for Sauvignon Blanc, 2.1%for
FeteascăAlbă, and 3%for Riesling. The range of the individual values is quite wide
showing a minimum value of 0.74%and a maximum of 5.01%. The acid levels were
affected by the type of yeast, temperature, oxygen, pH, and nitrogen sources. Also,
some technological processes such as skin maceration or clarification of the must
Figure 4. Concentrations of fatty acids in wine.
CHARACTERIZATION OF ROMANIAN WINES BY GC–MS 1107
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before fermentation may lead to an increase in fatty acids (Pérez Olivero and Pérez
Trujillo 2011). A decrease in acid concentration by variety as a function of age was
observed (Figure 3). This trend is in contrast with the results for ethyl esters (as
shown in Figure 2), confirming that esterification of acids is a continuously process
in presence of ethyl alcohol (Losada et al. 2012).
Phenyl Compounds
The primary phenyl compounds responsible for wine aroma originate from
grapes or can be generated during alcoholic fermentation by degradation of phenolic
acids. Volatile phenols are considered to be characteristic components of wine flavor.
Their influence to the final product can be positive or negative, depending on their
concentration (Tufariello et al. 2012;Gómez García-Carpintero et al. 2012a).
The main phenols in white wines are 4-ethylguaicol, 4-vinylguaicol, and 4-vinyl-
phenol (Tufariello et al. 2012). The presence of these compounds in wines is associated
with Brettanomyces (Dekker)yeast but also may originate from wood barrels in
which maturation occurs (Ortega-Heras, González-Sanjosé, and González-Huerta
2007). In white wines and at high concentrations, vinylphenols may be responsible
for heavy pharmaceutical odors, but at moderate or low concentrations may be asso-
ciated with a pleasant aroma of spice (Gil et al. 2006;Sánchez-Palomo et al. 2010).
Fourteen phenolics were identified including 4-vinylguaiacol, styrene, vanillic
acid methyl ester, ethyl esters of vanilic, ferulic-, p-hydroxycinnamic-, and o- and
m-hydroxycinnamic acids. According to literature, a higher concentration of ethyl
p-coumarate or ethyl ferulate may indicate that the wine was aged in barrels (Hixson
et al. 2012). Also, 4-vinylguaiacol is found only in white wines and its presence in the
red and roséwines serve as an indicator for recognizing a mixture with white wines
(Gil et al. 2006).
A higher concentration of ethyl p-coumarate was observed in Sauvignon Blanc
from Oltenia (vineyard I)in 2008 (1.02%).The 4-Vinylguaiacol level was low, with
average values below 0.1%. The FeteascăAlbăvariety was an exception; in Moldova
and Muntenia (vineyard II)the values were close to 0.2%. Figure 5shows the total
phenyl profile in the three types of wine.
The average values were 1.9%for Sauvignon Blanc, 1.6%for FeteascăAlbă,
and 2%for Riesling. The maximum value was obtained for Riesling wine in vineyard
Figure 5. Concentrations of phenyl compounds in wine.
1108 V. AVRAM ET AL.
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II of Muntenia, which was primarily due to the high values of ethyl o- or m-couma-
rate (1.28%)and of m-tolyl ester (1.6%). A significant difference also appeared
between averages at the vineyards: 4.2%for vineyard II of Muntenia and 0.9%in
vineyard II of Oltenia and Transylvania. Similar results, but not so pronounced,
were observed in Sauvignon Blanc where the vineyard averages were 3.4%for
Oltenia I, 1.3%for Oltenia II, and 1.0%for Muntenia I. For FeteascăAlbă, the
average values were: 1.5%in Moldova, 1.0%in Muntenia I, and 2.2%in Muntenia
II, showing more homogeneous distributions.
No dependence of phenyl compounds concentration was observed for any wine
variety based on year. As the concentrations of phenyl compounds are not dependent
significantly on the type of grape or geo-climatic conditions (variation from a year to
other), the significant differences may be explained by longer times of skin contact used
to produce a floral and fruity wine (Selli et al. 2006;Gómez-Míguez et al. 2007).
Aldehydes
Four aromatic aldehydes were detected: phenylacetaldehyde; benzaldehyde;
4-hydroxy-2-methoxy-, benzenebutanal, and benzaldehyde; and 4-hydroxy-3,5-
dimethoxy- (syringic aldehyde). The most important for wine aroma are phenylacet-
aldehyde and syringic aldehyde. Phenylacetaldehyde is formed during alcoholic
fermentation by decarboxylation of 2-oxo-3-phenylpropanoic acid (Sarrazin,
Dubourdieu, and Darriet 2007)and contributes the note of aged wood (Campo
et al. 2006). Syringic aldehyde is a phenolic aldehyde and together with vanillin
and its derivatives is formed by thermal degradation of lignin during burning oak
wood (Liberatore et al. 2010;Gómez García-Carpintero et al. 2012b). As its concen-
tration is low in the majority of wines, not exceeding 0.01%and absent in some Sau-
vignon Blanc samples, its contribution to total aldehydes is low. Phenylacetaldehyde
was present in all samples at between 0.11%and 0.50%. A large value for Fetească
Albăin 2009 from Moldova was observed due mostly to a higher concentration of
benzenebutanal. This compound was not reported in previous papers. It is likely that
this compound was produced from the container in which the wine was produced.
The average concentration of aldehydes was only 0.49%of the total volatile com-
pounds identified excluding benzenebutanal.
The minimum measured value for aldehydes was 0.16%and the maximum was
0.78%. The variety averages were 0.43%for Sauvignon Blanc, 0.42%for Fetească
Albă(value calculated excepting the mentioned outlier value), and 0.60%for Riesl-
ing. The average level of aldehydes from each vineyard did not vary significantly
(0.43%). A slightly higher level was observed for the Rieslings, especially in the Trans-
ylvania vineyard, where the average for three years was 0.89%. An explanation is
based on the significant contribution of the benzenebutanal and phenylacetaldehyde.
Additionally, the concentration of phenylacetaldehyde may increase after alcoholic
fermentation by botrytized grapes (Sarrazin et al. 2007).
Ketones
The ketones found were acetovanillone (acetophenone, 4′-hydroxy-3′-
methoxy-)and acetosyringone (Acetophenone, 4′-hydroxy-3′,5′-dimetoxy-)
CHARACTERIZATION OF ROMANIAN WINES BY GC–MS 1109
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(Figure 6). These, together with syringic aldehyde and 4-vinylguaiacol, are produced
during wine aging in oak barrels to enhance the sensory quality of wines (Ortega-
Heras et al. 2007; Liberatore et al. 2010;Gómez García-Carpintero et al. 2012b).
The averages were 0.14%for Sauvignon Blanc, 0.29%for FeteascăAlbă, and
0.23%for Riesling from the total volatile compounds identified. Higher levels for
FeteascăAlbăand Riesling were observed compared to Sauvignon Blanc. However,
this behavior was not associated with the wine type; rather, the values depended to a
greater extent on the vineyard and production year. Thus, for FeteascăAlbă, a signifi-
cant difference between the levels of ketones obtained in the two vineyards in the
region of Muntenia was observed. The averages for the three years were 0.13%in
vineyard I and 0.47%in vineyard II and confirm that the vinification process has a
major influence. Longer contact with wood may have caused the higher values from
vineyard II. Regarding the temporal evolution, although in some cases, there was an
increase in ketones as wine was aged; in other cases, it was almost constant or
decreased in support of this hypothesis.
Lactones
Two lactones were identified: dihydro-3-(phenylmethyl)-2(3H)-furanone and
γ-decalactone (Figure 7). The latter was more abundant. The γ-Decalactons are
among the most important components contributing to sensory characteristics of
wines aged in oak barrels (Perestrelo et al. 2006;Câmara et al. 2006b; Losada
Figure 6. Concentrations of ketones in wine.
Figure 7. Concentrations of total lactones in wine.
1110 V. AVRAM ET AL.
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et al. 2011). The aroma of lactones depends on their chemical structure (functional
group and the side chain length)and are described as “fruity”(γ-hexalactone),
“coconut”(γ-octalactone),“peach, milky”(γ-decalactone),or“sweet floral”
(γ-dodecalactone)(Perestrelo et al. 2006;Câmara et al. 2006b).
The averages were 1.17%for Sauvignon Blanc, 1.23%for FeteascăAlbă, and
1.44%for Riesling. Lactones are the third most important compound class (average
concentration around of 1.25%), following fatty acids and phenolic compounds.
Despite the relatively small differences between the mean values obtained on the types
of wine, a more pronounced difference was present for average lactones from the vine-
yards. Thus, for FeteascăAlbăin the Muntenia region, there was a significant differ-
ence between the levels obtained in the two vineyards. The mean values for the three
years were 0.89%in vineyard I and 1.53%in vineyard II. This is similar to the results
observed for ketones. These results may be due to the different conditions of fermen-
tation or aging. If the wine is fermented on lees or aged in oak barrels, the concentra-
tions of phenols, ketones, phenolic aldehydes, and lactones may increase.
Terpenes
Terpenes are heterogeneous chemical compounds from the structural point of
view and are widely found in nature. In spite of their structural variety, terpenes are
biosynthesized from structural unit of isoprene (2-methyl-1,3-butadiene). The basic
formula of terpenes is a multiple of this structural unit, (C
5
H
8
)
n
, where nis the num-
ber of isoprene units linked. Although developed primarily in conifers, terpenes
appear also in grapes in free form or linked to sugar molecules, when they form a
reserve of odorless aroma. Subsequently, terpenes can be released from sugars
through the action of several enzymes, contributing to the characteristic floral flavor
of wine (Liberatore et al. 2010).
Monoterpenes are particularly abundant in aromatic grape varieties such as:
Muscat, Riesling, and Gewürztraminer (Masa and Vilanova 2008; Dziadas and Jeleń
2010). As most terpenoids occur in micro-concentrations in grapes, must, and wine,
their quantification is often difficult (Câmara, Alves, and Marques 2006c). Thus, in
these samples, only one terpene was determined, 2-acetyl-carene, a bicyclic monoter-
pene. Its percentage in the three types of wine was small (under 0.3%)but consistent
with the literature (Welke et al. 2012). The variation of 2-acetyl-carene in wine is
shown in Figure 8.
Figure 8. Concentrations of 2-acetyl-carene in wine.
CHARACTERIZATION OF ROMANIAN WINES BY GC–MS 1111
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The averages based on variety are close: 0.11%for Sauvignon Blanc, 0.11%for
FeteascăAlbă, and 0.16%for Riesling. The maximum level of 2-acetyl-carene was
obtained for FeteascăAlbăin 2008 in Muntenia region. Wine from 2008 had the
highest concentrations of 2-acetyl-carene for many wine samples. This observation
is consistent with climatic conditions. Because one of the most important factors that
influence the characteristic aroma of a particular variety of grape is ripening stage, a
possible explanation for the higher concentration of 2-acetyl-carene in 2008 is that in
this year the weather conditions allowed a delayed harvest and the grapes reached
full maturity. Terpenoids are higher in wine produced from ripe grapes (Sánchez
Palomo et al. 2007).
Effect of the Variety on the Volatile Fraction
To determine the influence of grape variety on the volatile composition,
Sauvignon Blanc, Riesling, and FeteascăAlbăproduced in the Muntenia region were
analyzed. Thus, the behavior of the major volatile compounds (higher alcohols and
ethyl esters)was studied in these assortments. The values by compound family
showed a downward trend of alcohol contribution to the total volatile compounds
as the wines were aged. This behavior is, as mentioned, correlated with the increased
contribution of ethyl esters. As alcohols and esters are major components of wine
(the totality of minor compounds are about 10%), their correlation is evident and
an increase of ethyl esters content in older wines was observed. This correlation
supports the idea that ethyl esters are formed from acids and alcohols present in wine
during aging.
The alcohol averages over the three years were 53.1%for Riesling, 60.7%for
Sauvignon Blanc, and 64.8%for FeteascăAlbăin vineyard I and 62.4%in vineyard
II. The averages over the three years for ethyl esters were 36.3%for Riesling, 32.5%
for Sauvignon, and 30.5%for FeteascăAlbăin vineyard I and 29.9%in vineyard II.
The concentrations of alcohols were close for Sauvignon Blanc and FeteascăAlbă
but significantly lower for Riesling. A similar situation was observed for ethyl esters
but the quantities were higher for Riesling.
CONCLUSIONS
LLE GC–MS was robust and rapid for the determination of volatiles in wine.
Forty-eight compounds were determined from 0.001%to 75%. Detailed analyses of
the compounds allow correlation with the technology used at a vineyard, region, and
production year. Average concentration of alcohols strongly depended upon the
geo-climatic conditions specific to the cultivation region. The range of total alcohols
was between 53.10%and 67.33%. A decrease in the alcohol percentage was observed
with time due to a higher contribution by esters during maturation. Ester concen-
tration showed a strong dependence on grape variety. For example, the average
value for FeteascăAlbăwas 26.5%but for Riesling the average was 35.6%.A
n
increase was observed from year to year and the values correlated with the down-
ward trend observed for alcohols.
The concentrations of acids depended primarily on vineyard processing (type
of yeast and specific technology). In the same region (Oltenia)for the same type
1112 V. AVRAM ET AL.
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of grape (Sauvignon Blanc)but in different vineyards, the average of the acids was of
1.33%in vineyard Oltenia II but 3.7%in vineyard Oltenia I. The main factor influ-
encing phenolic levels was vinification technology (longer time of skin contact during
the preparation of the must). The maximum level was found to be 6.61%(Riesling
sort, Muntenia II).
The concentrations of ketones and lactones depended upon the contact time
with wood during the aging in oak barrels. Thus, for FeteascăAlbă, significant
differences were observed between the levels of ketones obtained in two vineyards
from Muntenia: 0.13%at vineyard I and 0.47%at vineyard II. A similar result
was obtained for lactones: the concentrations were 0.89%in vineyard I and
1.53%in vineyard II from the same region. The levels of terpenes were characteristic
of climatic condition (ripening stage of the grape). The highest level was observed for
all varieties in 2008 because weather conditions allowed a delayed harvest.
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