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Characterization of Romanian Wines by Gas

Chromatography-Mass Spectrometry
a a b b c
Veronica Avram , Călin G. Floare , Anamaria Hosu , Claudia Cimpoiu , Constantin Măruţoiu
a
& Zaharie Moldovan
a
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 Ortodox Theology, Babes-Bolyai University, Cluj-Napoca, Romania
Accepted author version posted online: 31 Dec 2014.

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To cite this article: Veronica Avram, Călin G. Floare, Anamaria Hosu, Claudia Cimpoiu, Constantin Măruţoiu & Zaharie
Moldovan (2014): Characterization of Romanian Wines by Gas Chromatography-Mass Spectrometry, Analytical Letters, DOI:
10.1080/00032719.2014.974054

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 Characterization of Romanian Wines by Gas

Chromatography-Mass Spectrometry

Veronica Avram1, Călin G. Floare1, Anamaria Hosu2, Claudia Cimpoiu2, Constantin Măruţoiu3,

and Zaharie Moldovan1*

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1
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 Ortodox Theology, Babes-Bolyai University, Cluj-Napoca, Romania

*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: [email protected]

Received 08 July 2014; revised XX YYY ZZZZ; accepted 28 September 2014.

Abstract

The paper reports the determination of the volatile composition of commercial Romanian wines

with the goal of identifying characteristic markers. For this purpose, twenty-seven 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-

1
 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

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Introduction

The volatile composition of wine is one of the most important factors that determine its aroma

and therefore its quality (Selli et al. 2004; Gil et al. 2006; Camara, Alves, and Marques 2006a;

Coelho et al. 2008). The aromatic profile of wine results from the combined effects of several

different natural compounds (Alves et al. 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; pre-fermentative aroma derived

during processing of grapes; fermentative aroma produced by yeast and bacteria during alcoholic

and malo-lactic fermentation; and post-fermentative 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

2
 different geographical origins based on a volatile fraction relationship established with grape

variety, origin, and processing technology used (Gil et al. 2006; Camara, Alves, and Marques

2006a; Welke et al. 2012). Due to their complexity and sometimes very low concentrations (in

some cases (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
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compounds as markers for geographical origin and processing technology. The analysis was

done 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 leads the most

comprehensive characterization of Romanian wines to date.

Experimental

Samples

Twenty-seven commercial white wines from the four most important wine regions in Romania:

Oltenia (Oprişor and Vânju-Mare Vineyards), Muntenia (Cramele Halewood and Ceptura

Vineyards), Moldova (Huşi Vineyard), and Transylvania (Jidvei Vineyard) were characterized.

The wine varieties were Sauvignon Blanc, Fetească Albă, and Riesling from 2008, 2009 and

2010 (Table 1).

Liquid-liquid Extraction

3
 The protocol used in this work for the extraction of volatile compounds from wine samples was

adapted from Andujar-Ortiz et al. (2009). 25 milliliter of wine and 5 milliliter of methylene

chloride (Merck, Germany) were stirred at 0 degree celsius for one hour. Subsequently, the

mixture was kept for fifteen minutes in an ultrasonic bath at the same 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 microliter. Subsequently 1 microliter of extract was

analyzed by GC-MS using the splitless mode.

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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 percent) stationary phase (length of 30 meter, inner diameter of

0.25 millimeter, thickness of stationary phase of 0.25 micrometer). Helium was used as the

carrier gas at a constant flow rate of 1.5 microliter per minute. The column temperature was

programmed to be: initially 50 degree celsius, maintained for two minutes, and then increased at

10 degree celsius per minute to 300 degree celsius where it was maintained for ten minutes. The

temperature of the injector was 250 degree celsius. 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 and 250 degree celsius, respectively.

Acquisition was performed in the full scan mode from 50 to 650 Daltons.

Results and Discussion

4
 Separation by GC-MS system was performed after optimization of the conditions. Figure 1

shows the analysis of Fetească Albă from Muntenia. Characteristic chromatograms of 4-

vinylguaiacol with the selected ion m/z = 135 (Figure 1b) and of vanillin derivatives

(acetosyringone, acetophenone, ethyl vanillin, and methyl vanillin) with the selected ion

m/z = 151 (Figure 1c) are also shown in Figure 1.

Forty eight volatile compounds were identified belonging to eight different classes: alcohols,
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ethyl esters, fatty acids, phenyl compounds, aldehydes, ketones, terpenes, 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 (Camara, Alves, and Marques 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 (percent). 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, Fetească

Albă, and Riesling, wines from Oltenia, Muntenia, Moldova, and Transylvania were analyzed.

The behavior of each class of compounds compounds is discussed with reference to the primary

influence affecting the chemical composition.

5
 Alcohols

Higher alcohols are produced during alcoholic fermentation from carbohydrates 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 percent) in the wines; these results are confirmed by other published

data (Zamúz and Vilanova 2006). However, their concentrations varies by type and vineyard as
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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 concentration. In some samples, the concentration was less than 1 percent of the alcohols

identified, 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 percent). 2-Phenylethanol represents 68 percent

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, lie aging of wines on the grape and/or yeast lees (so called, autolysis of wines)

or a longer contact 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

percent for Sauvignon Blanc, 67.2 percent for Fetească Albă, and 57 percent for Riesling.

6
 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 contribution of the esters and other components

in wines during maturation. Therefore the mentioned exceptions may be due to the specific

vinification processes.
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For Sauvignon Blanc, the average level of alcohols are 59.9 and 60.7 percent in Oltenia I and

Muntenia I vineyards but differ significantly in Oltenia II vineyard, 73.8 percent. 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 Fetească

Albă, the average values of alcohols from Muntenia are 64.8 percent in vineyard I and 62.4

percent in vineyard II and are different from the value in the Moldova vineyard, 74.3 percent.

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 percent, respectively, but significantly

different from the value of 67.3 percent 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 percent. Also,

the vinification process contributes 1–3 percent. Small quantities of alcohols are produced by the

hydrolysis of esters during maturation in wood (Câmara, Alves, and Marques 2006b).

7
 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 (succinic, 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,
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and 8.7 percent, respectively, with small differences on grape variety. The maximum of succinic

acid esters was present in Riesling wine.

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 percent in most samples. Ethyl hexanoate was slightly higher than for

the others, consistent with the literature (Câmara, Alves, and Marques 2006b). Riesling from the

Oltenia region (vineyard II) contained the highest percentages in all years of production,

reaching 0.15 percent 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 et al. 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 correlated with the downward trend

observed for alcohols was present. This correlation occurred because esters are the second class

8
 of compounds in the order of abundance. Their relative average values were approximately 30

percent.

The averages were 28.6 percent for Sauvignon Blanc, 26.5 percent for Fetească Albă, and 35.6

percent for Riesling. The values of ethyl esters obtained for each vineyard for Sauvignon Blanc

and Fetească Albă were inversely correlated with alcohol abundances as can be seen in Figures

2a and b. An average of 22 percent was obtained for Sauvignon Blanc in vineyard II of Oltenia
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that was significantly smaller compared with 31.2 percent in vineyard I of Oltenia and 32.5

percent in vineyard I of Muntenia. For Fetească Albă from Moldova region, an average of 19.1

percent was obtained that was also smaller compared with values of 30.5 and 29.9 percent

obtained from vineyards I and II of Muntenia. These observations are consistent that the

difference between vinification techniques or geo-climate conditions led to this behavior.

Riesling contained the highest values of esters. The average values were 33.3 percent in

Muntenia (vineyard II), 43.2 percent in Oltenia (vineyard II), and 27.2 percent 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, Alves, and Marques 2006b; Coetzee and du Toit 2012). We assume,

therefore, that the levels depend substantially on 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.

9
 Fatty Acids

Wine fatty acids are formed in the first two stages of alcoholic fermentation, but can be found

also in very 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, Alves, and Marques 2006b) which may be

described as having fruity, cheese, fatty, and rancid notes (Gil et al. 2006; Tufariello et al. 2012;

Gómez García-Carpintero et al. 2012a).

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Although the presence of C6–C10 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 milligram per liter of C6 fatty

acids provide a pleasant aroma, while levels above 20 milligram per liter 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, dodecanoic,

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

very small: the mean values were approximately 0.15 percent for Sauvignon Blanc and Fetească

Albă and 0.28 percent for Riesling. The concentrations of C10, C12, C14, and C16 acids were

approximately 0.01 percent in all samples. Hexanoic and octanoic acids accounted for the largest

contribution with average values of 0.9 and 1.3 percent. The higher level of the octanoic acid

relative to hexanoic acid is common as reported in the 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.

10
 The average acid concentrations were 2.9 percent for Sauvignon Blanc, 2.1 percent for Fetească

Albă, and 3 percent for Riesling. The range of the individual values is quite wide showing a

minimum value of 0.74 percent and a maximum of 5.01 percent. 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 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
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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-vinylphenol

(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 et al. 2007). In white wines and at high concentrations, vinylphenols may

be responsible for heavy pharmaceutical odors, but at moderate or low concentrations may be

associated with a pleasant aroma of spice (Gil et al. 2006; Sánchez-Palomo et al. 2010).

11
 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 the 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 rosé wines serve as an indicator for

recognizing a mixture with white wines (Gil et al. 2006).

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A higher concentration of ethyl p-coumarate was observed in Sauvignon Blanc from Oltenia

(vineyard I) in 2008 (1.02 percent). 4-Vinylguaiacol level was low, with average values below

0.1 percent. The Fetească Albă variety was an exception; in Moldova and Muntenia (vineyard II)

the values were close to 0.2 percent. Figure 5 shows the total phenyl profile in the three types of

wine.

The average values were 1.9 percent for Sauvignon Blanc, 1.6 percent for Fetească Albă, and 2

percent for Riesling. The maximum value was obtained for Riesling wine in vineyard II of

Muntenia which was primarily due to the high values of ethyl o- or m-coumarate (1.28 percent)

and of m-tolyl ester (1.6 percent). A significantive difference also appeared between averages at

the vineyards: 4.2 percent for vineyard II of Muntenia and 0.9 percent 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 percent for Oltenia I, 1.3 percent for Oltenia II, and 1.0

percent for Muntenia I. For Fetească Albă, the average values were: 1.5 percent in Moldova, 1.0

percent in Muntenia I, and 2.2 percent in Muntenia II, showing more homogeneous distributions.

12
 No dependence of phenyl compounds concentration was observed for any wine variety based on

year. Since 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
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Four aromatic aldehydes were detected: phenylacetaldehyde, benzaldehyde, 4-hydroxy-2-

methoxy-, benzenebutanal and benzaldehyde, 4-hydroxy-3,5-dimethoxy- (syringic aldehyde).

The most important for wine aroma are phenylacetaldehyde and syringic aldehyde.

Phenylacetaldehyde is formed during alcoholic fermentation by decarboxylation of 2-oxo-3-

phenylpropanoic acid (Sarrazin et al. 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). Since its concentration is low in the majority of wines,

not exceeding 0.01 percent and absent in some Sauvignon Blanc samples, its contribution to total

aldehydes is low. Phenylacetaldehyde was present in all samples at between 0.11 and 0.50

percent. A large value for Fetească Albă in 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 concentrations of aldehydes was only 0.49 percent of the total volatile compounds

identified excluding benzenebutanal.

13
 The minimum measured value for aldehydes was 0.16 percent and the maximum was 0.78

percent. The variety averages were 0.43 percent for Sauvignon Blanc, 0.42 percent for Fetească

Albă (value calculated excepting the mentioned outlier value), and 0.60 percent for Riesling. The

average level of aldehydes from each vineyard did not vary significantly (0.43 percent). A

slightly higher level was observed for the Rieslings, especially in the Transylvania vineyard,

where the average for three years was 0.89 percent. An explanation is based on the significant

contribution of the bezenebutanal and phenylacetaldehyde. Additionally, the concentration of

phenylacetaldehyde may increase after alcoholic fermentation by botrytized grapes (Sarrazin et

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al. 2007).

Ketones

The ketones found were acetovanillone (acetophenone, 4 -hydroxy-3 -methoxy-) and

acetosyringone (Acetophenone, 4 -hydroxy-3 ,5 -dimetoxy-) (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 percent for Sauvignon Blanc, 0.29 percent for Fetească Albă, and 0.23

percent for Riesling from the total volatile compounds identified. Higher levels for Fetească Albă

and 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 Fetească Albă, a significantly differences between the levels of

ketones obtained in the two vineyards in the region of Muntenia was observed. The average for

the three years was 0.13 percent in vineyard I and 0.47 percent in vineyard II and confirm that

14
 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 -decalactone

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(Figure 7). The latter was more abundant. -Decalactons are among the most important

components contributing to sensory characteristics of wines aged in oak barrels (Perestrelo et al.

2006; Câmara, Alves, and Marques 2006b; Losada et al. 2011). The aroma of lactones depends

on their chemical structure (functional group and the side chain length) and are described as

“fruity” ( -hexalactone), “coconut” ( -octalactone), “peach, milky” ( -decalactone), or “sweet

floral” ( -dodecalactone) (Perestrelo et al. 2006; Câmara, Alves, and Marques 2006b).

The averages were 1.17 percent for Sauvignon Blanc, 1.23 percent for Fetească Albă, and 1.44

percent for Riesling. Lactones are the third most important compound class (average

concentration around of 1.25 percent), 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 vineyards. Thus, for Fetească

Albă in the Muntenia region, there was a significant difference between the levels obtained in the

two vineyards. The mean values for the three years was 0.89 percent in vineyard I and 1.53

percent in vineyard II. This is similar to the results observed for ketones. These results may be

due to the different conditions of fermentation or aging. If the wine is fermented on lees or aged

15
 in oak barrels, the concentrations 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 biosynthesised from

structural unit of isoprene (2-methyl-1,3-butadiene). The basic formula of terpenes is a multiple

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of this structural unit, (C5H8)n, where n is the number 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). Since 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 monoterpene. Its percentage in the three types of wine was very small

(under 0.3 percent) but consistent with the literature (Welke et al. 2012). The variation of 2-

acetyl-carene in wine is shown in Figure 8.

The averages based on variety are close: 0.11 percent for Sauvignon Blanc, 0.11 percent for

Fetească Albă, and 0.16 percent for Riesling. The maximum level of 2-acetyl-carene was

obtained for Fetească Albă in 2008 in Muntenia region. Wine from 2008 had the highest

16
 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).

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Effect of the Variety on the Volatile Fraction

To determine the influence of grape variety on the volatile composition, Sauvignon Blanc,

Riesling, and Fetească Albă produced in 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 shown 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. Since alcohols and esters are major components of wine

(the totality of minor compounds are about 10 percent), their correlation is evident and an

increase of ethyl esters content in older wines is 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 percent for Riesling, 60.7 percent for

Sauvignon Blanc, and 64.8 percent for Fetească Albă in vineyard I and 62.4 percent in vineyard

II. The averages over the three years for ethyl esters were 36.3 percent for Riesling, 32.5 percent

for Sauvignon, and 30.5 percent for Fetească Albă in vineyard I and 29.9 percent in vineyard II.

The concentrations of alcohols were close for Sauvignon Blanc and Fetească Albă but

17
 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 percent. Detailed analyses of the compounds

allow correlation with the technology used at a vineyard, region, and production year. Average
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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 percent. A decrease

in the alcohol percentage was observed with time due to a higher contribution by esters during

maturation. Ester concentration showed a strong dependence on grape variety. For example, the

average value for Fetească Albă was 26.5 percent but for Riesling the average was 35.6 percent.

An increase was observed from year to year and the values correlated with the downward 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 of grape (Sauvignon Blanc)

but in different vineyards, the average of the acids was of 1.33 percent in vineyard Oltenia II but

3.7 percent in vineyard Oltenia I. The main factor influencing 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 percent (Riesling sort, Muntenia II).

18
 The concentrations of ketones and lactones depended upon the contact time with wood during

the aging in oak barrels. Thus, for Fetească Albă, significant differences were observed between

the levels of ketones obtained in two vineyards from Muntenia: 0.13 percent at vineyard I and

0.47 percent at vineyard II. A similar result was obtained for lactones: the concentrations were

0.89 percent in vineyard I and 1.53 percent 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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 Table 1. White wine samples

Numbe Wine Wine region Productio

r varieties n year

1 Sauvigno Muntenia 2008

n Blanc (Vineyard I)
2 2009
(Cramele
3 2010
Halewood,

Dealurile
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Munteniei)

4 Oltenia 2008

(Vineyard I)
5 2009
(Oprişor,
6 2010
Dealurile

Olteniei)

7 Oltenia 2008

(Vineyard II)
8 2009
(Mehedinţi,Vânj
9 2010
u-Mare)

10 Fetească Moldova 2008

Albă (Dealurile
11 2009
Huşilor)
12 2010

13 Muntenia 2008

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 14 (Vineyard I) 2009

(Cramele
15 2010
Halewood,

Dealurile

Munteniei)

16 Muntenia 2008

(Vineyard II)
17 2009
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(Ceptura,
18 2010
Dealurile

Munteniei)

19 Riesling Muntenia 2008

(Vineyard II)
20 2009
(Ceptura,
21 2010
Dealurile

Munteniei)

22 Oltenia 2008

(Vineyard II)
23 2009
(Mehedinţi,
24 2010
Vânju-Mare)

25 Transylvania 2008

(Jidvei)
26 2009

27 2010

24
 Table 2. Identified compound, retention time (tr), and ion used for quantification (m/z)

Compounds tr Ion (m/z)

Alcohols

3-Methyl-1-butanol 5.89 57

Benzyl alcohol 7.66 79

2-Phenylethanol 9.01 91
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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

25
 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 11.21 71

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ester

Succinoic acid, 2-hydroxy-3-methyl-, 10.79 131

diethyl ester

Butanedioic acid, 2,3-dihydroxy-, 12.42 104

diethyl ester

Butanedioic acid, 2-(1-methoxy-1- 12.69 85

methylethoxy)-3-methyl-, diethyl ester

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

26
 Benzoic acid, 2,6-dihydroxy-, methyl 12.03 136

ester

Vanilic acid, methyl ester 14.55 151

Benzoic acid, 2,4-dihydroxy-, methyl 14.74 136

ester

Benzeneacetic acid, 4-hydroxy-, ethyl 14.95 107

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ester

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

o and m-hydroxycinamic acid, ethyl 18.17 147

ester

Isomer of ferulic acid, ethyl ester 19.05 222

Aldehydes

Phenylacetaldehyde 12.43 91

Benzaldehyde, 4-hydroxy-2-methoxy- 12.55 151

27
 Benzenebutanal 14.58 104

Benzaldehyde, 4-hydroxy-3,5- 16.25 182

dimethoxy-

Ketones

Acetophenone, 4 -hydroxy-3 ,5 - 13.49 181

dimethoxy-
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Acetophenone, 4 -hydroxy-3 -metoxy- 14.22 151

Lactones

2(3H)-Furanone, dihydro-3- 13.57 91

(phenylmethyl)-

γ-Decalactone 11.78 85

Terpene

2-Acetyl-carene 13.05 163

28
 Figure 1. GC-MS of Fetească Albă from Muntenia: (a) total ion chromatogram (TIC); (b)
chromatogram of 4-vinylguaiacol at m/z = 135; and (c) chromatogram of acetosyringone,
acetophenone, ethyl vanillin, and methyl vanillin at m/z = 151.
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 Figure 2. Relative concentrations of alcohols determined in Sauvignon Blanc, Fetească Albă, and
Riesling: (a) total alcohols and (b) 2-phenylethanol.
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Figure 3. Concentrations of ethyl esters in wine.

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Figure 4. Concentrations of fatty acids in wine.

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Figure 5. Concentrations of phenyl compounds in wine.
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Figure 6. Concentrations of ketones in wine.

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Figure 7. Concentrations of total lactones in wine.

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Figure 8. Concentrations of 2-acetyl-carene in wine.