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Article

Volatile Profile Characterization of Croatian Commercial Sparkling Wines

by
Ana-Marija Jagatić Korenika
1,
Darko Preiner
1,2,*,
Ivana Tomaz
1,2 and
Ana Jeromel
1
1
Department of Viticulture and Enology, Faculty of Agriculture, University of Zagreb, Svetošimunska 25, 10000 Zagreb, Croatia
2
Center of Excellence for Biodiversity and Molecular Plant Breeding, Svetošimunska 25, 10000 Zagreb, Croatia
*
Author to whom correspondence should be addressed.
Molecules 2020, 25(18), 4349; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25184349
Submission received: 25 August 2020 / Revised: 16 September 2020 / Accepted: 17 September 2020 / Published: 22 September 2020
(This article belongs to the Special Issue Wine Chemistry: The Key behind Wine Quality)
Browse Figure
Versions Notes

Abstract

:
Commercial sparkling wine production represents a relatively low but important part of the Croatian wine production, especially in the Zagreb county. This study presents the results of volatile aroma compounds profile and organic acid composition of commercial sparkling wine samples from three vine-growing regions in Zagreb county. In total, 174 volatile aroma compounds were identified, separated between their chemical classes (aldehydes, higher alcohols, volatile phenols, terpenes, C13-norisoprenoids, lactones, esters, fatty acids, sulfur compounds, other compounds, other alcohols). Higher alcohols such as phenylethyl and isoamyl alcohol as well as 2-methyl-1-butanol, and esters such as diethyl succinate, ethyl hydrogensuccinate, and ethyl lactate had the strongest impact on the volatile compounds profile of Zagreb county sparkling wine. The presence of diethyl glutarate and diethyl malonate, compounds whose concentrations are influenced by yeast autolysis or caused by chemical esterification during the ageing process, was also noted. The influence of every single volatile aroma compound was evaluated by discriminant analysis using forward stepwise model. The volatile profiles of traditional sparkling wines from Croatia were presented for the first time. It is hoped the results will contribute to better understanding the quality potential and to evaluate possible differences on the bases of detected aroma concentrations and multivariate analysis.

1. Introduction

According to International Organisation of Vine and Wine (OIV), in 2018, world sparkling wine production reached 20 million hectoliters with an overall increase of +57% since 2002. In global sparkling wine production, almost half of the total volume produced comes from Italy (27%) and France (22%), followed by Germany (14%), Spain (11%), and USA (6%) [1]. For the past ten years, Croatia has also recorded apparent increase in sparkling wines production, with the Zagreb County as one of the leading wine-growing counties. According to the Croatian Agency for Agriculture and Food data, in 2017, 885.80 hL of sparkling wines were produced in that area with a continuous upward trend. In Croatia almost all sparkling wines are produced by the traditional method, where marked influence can be connected to grape variety. Pjenušac is a quality sparkling wine (Protected Geographical Indication) elaborated by the traditional method that is defined by an excess pressure higher than 3.5 bar, primarily connected with presence of carbon dioxide in solution that is kept at the temperature of 20 °C, and for which alcoholic concentration of the cuvées used for their production have at least 9% volume (Council Regulation (EC), 1308/2013). In Zagreb county, ‘‘Pjenušac’’ is mainly produced from Riesling and Chardonnay grape cultivars and Pinot Noir between the red ones. However, there is also a great diversity of other grape varieties as Manzoni, Portugizer, Muller Thurgau, as well as Kraljevina and Plavec žuti, presenting a quality that can obtain high quality natural sparkling wines with their own personality and sensory profile. However, no work dealing with the influence of these grape cultivars for sparkling wine production have been done. The quality of sparkling wines is mainly influenced by their aroma composition and properties of single aroma compound present [2,3,4]. The sparkling wines aroma composition is formed by the interaction of different factors, such as grape variety and its maturity level, the production technology, the primary and secondary methods of wine fermentation, type of yeast strain used, storage temperature, ageing period, and ingredients used for liqueur d’expedition, level of oxygen during the process of disgorging, type of closure used, and levels of SO2 as well as CO2 [5,6]. According to Kemp et al. [6] wines used in the dosage solutions can have strong impact on volatile compounds concentrations, more than concentration of added sugar. An increase of ethyl esters, such as diethyl succinate, alcohols, and some varietal aromas, such as TDN (1,1,6-trimethyl-1,2-dihydronapthalene) and vitispirane, connected with fermentation in the bottle was noted by several authors [7,8,9], while concentrations of acetic acid esters and fatty acids diminish because of their clevage to the yeast cell walls [7,9]. In the work by Muñoz-Redondo et al. [10] some ester compounds were pointed out as markers of the second fermentation. Aroma changes can be further modified during the ageing on lees, so, therefore, the ageing time can determine the volatile aroma profile present in the sparkling wine [7,11,12]. Loyaux et al. [13] studied the aroma composition changes during the champagne ageing period and detected a slow decrease of isoamyl butyrate and hexyl acetate levels, as well as nerolidol concentrations and an increase in benzaldehyde and vitispirane levels. Over a period of 16 years, the concentrations of benzaldehyde increased up to 4 mg L−1. Environmental factors such as terrain structure, agro- and amphelo-pedological characteristics, climate and viticulture practices used, often described as “terroir”, can also have strong influence on grape composition and wine quality. Geographical origin also has an significant role in the differentiation of wines, since it can indicate the resemblance among wines coming from the one specific vine-growing region and the main differences among the ones coming from several viticultural regions [14,15]. Wine aroma precursors, as well as most wine components, are mainly accumulated during the grape maturation process in the vineyard. They can form a recognizable pattern in the grapes that can enhances the unique nature and specific structure of wines. Studies by Goldner et al. [16] and Vilanova et al. [17] have demonstrated differences in the sensory characteristics of Malbec and Albariño wines from different geographic origins. Robinson et al. [18] noted that the volatile aroma profile of certain type of wine can have marked impact in obtaining a geographical designation by forming a product with characteristics of specific vine-growing area. Nowadays, Voce et al. [19] carried out a comprehensive mapping of sparkling wines samples according to their volatile aroma compounds from Trentodoc and Franciacorta to determine regional features among them. The main target of this research was to define the volatile compounds profile in a relatively significant number of sparkling wine samples from three vine-growing regions in Zagreb county and to evaluate possible differences on the bases of detected aroma concentrations and multivariate analysis. From our experience, this work represents the first definition of the chemical structure of Zagreb county sparkling wines.

2. Results and Discussion

2.1. Composition of Organic Acids

Organic acid profile of Croatian sparkling wines from three Zagreb county vine-growing regions is presented in Table 1. There was no significant difference observed among the sparkling wines in terms of main organic acids as well as pH values. The most abundant acid was tartaric with an average concentration between 2.06 and 2.35 g L−1, values similar to ones published by Focea et al., Caliari et al. and Gallardo-Chacón et al. [20,21,22], but much higher compared to results published by Sartor et al. [23]. Conversely, malic acid concentrations were relatively low when compared to literature data by Caliari et al. and Sartor and al. [21,23], and ranged between 0.81 and 1.31 g L−1. It is well known that, in the sparkling wine elaboration process, the grapes must be usually harvested before they are completely matured [24]. The lactic acid concentrations varied according to the region, and could be influenced by grape composition, as well as by yeast activity, formed from malic acid degradation. The concentration of succinic acid, formed during the fermentation process, was lower compared to data obtained in previous studies [21,23]. Citric acid was present in all sparkling wines samples contrary to the data obtained by Caliari et al. and Sartor and al. [21,23] where it was not detected, but in agreement with work by Gallardo-Chacón et al. [22].

2.2. Volatile Compounds

One hundred and seventy-one volatile compounds presented in sparkling wines from three different Zagreb county vine-growing regions were detected, quantified and classified into several chemical classes (aldehydes, higher alcohols, volatile phenols, terpenes, C13-norisoprenoids, lactones, esters, fatty acids, sulfur compounds, other compounds, other alcohols). In Table 2, the average values of main volatile compounds chemical classes are presented, showing a significant difference among vine-growing regions while individual volatile compounds are presented in Table 3. The most abundant class was higher alcohols group with the highest concentrations of isoamyl and phenylethyl alcohol as well as 2-methyl-1-butanol. Comparing these compounds among vine-growing regions shows that sparkling wines from Zelina had significantly the highest concentrations. Data from the work by Torrens et al., Caliari et al., and Torchio et al. [9,25,26] also showed that major aromatic compound was phenylethyl alcohol, with OAV > 1 having influence on the sweet, rose and honey aroma structure of sparkling wines. The concentrations of higher alcohols not exceeding the amount of 300 mg L−1 can positively influenced the formation of wine complexity [27] which was not the case in our samples. Besides above mentioned compounds cis-3-hexene-1-ol, had also an impact on “green grass” odour profile of Zagreb county sparkling wines, especially in some samples from Plešivica vine-growing region. Representatives of alcohols that are also characterized by “green” and “herbaceous” notes, such as trans-1-hexanol, and cis-2-hexene-1-ol, and trans-3-hexen-1-ol, which are mostly synthetized during the pre-fermentation wine production process, were detected, but in concentrations under the defined odour threshold value in all sparkling wines samples analysed. Yeast contact and storage time on lees during sparkling wine production might have been the reason for relatively higher concentrations of 1-hexanol that ranged from 1612 to 2948 µg L−1, concentrations that are in agreement with data reported by [28]. As it can be seen from the Table 3, the presence of 1-hexanol was significantly the highest in sparkling wines from Krašić while there were no marked differences between other two regions. According to Alexandre et al. [29] and Benucci et al. [30], esters are the main class of aroma compounds released by the degradation of yeast cells having low perception thresholds and so positively contributing to the aroma of fruit as well as floral-like aroma of sparkling wine. Significantly, the highest amount of esters was detected in sparkling wines from Zelina while there was no marked difference between the other two vine-growing regions. Also, it can be seen that total esters concentration was more or less similar or something higher when compared to the data published by Benucci et al. [30]. Among esters presented in the analysed sparkling wines, the most common were diethyl succinate, ethyl hydrogensuccinate, and ethyl lactate, which is comparable with the results published in the work by Benucci et al. [30], while the ones with the OAV > 1 were ethyl butanoate, hexanoate, octanoate, ethyl-2-methylbutanoate, ethyl-3-methylbutanoate, isoamyl acetate, and isoamyl lactate. Comparable results were achieved by Voce et al. [19] in Ribolla Gialla sparkling wines where esters had an important role in volatile profile structure. Ethyl decanoate (floral) and 2-phenylethyl acetate (scent of rose) were detected in all sparkling wines in concentrations under the odour threshold values but according to Genovese et al. [31] these compounds can show synergistic effect even at low concentrations. The concentrations of 2-phenylethyl acetate published by Torchio et al. [26] were comparable with our data (23.40 to 28.73 µg L−1). According to Torrens et al. [9] and Riu-Aumatell et al. [11] diethyl succinate and ethyl lactate are considered as “ageing esters” whose concentrations can increase in contact with yeast cells during the second fermentation. For the development of cava, diethyl succinate can be used as a marker, mainly connected with the period of cava storage in the cellar [11]. In Zagreb county sparkling wines its concentrations were between 3917.45 µg L−1 (Krašić) up to 7430.69 µg L−1 (Zelina) which is compared to Ribolla Gialla wines (2555 µg L−1) higher but compared to concentrations published by Martinez-Garcia et al. [32] ranging between 8900 µg L−1 and 15,000 µg L−1 much lower. Among other ester compounds detected in Zagreb county sparkling wines isobutyl lactate, ethyl-2-hydroxy-3-methylbutanoate, diethyl hydroxysuccinate and isobutyl lactate concentrations were significantly higher in Zelina vine-growing region wines while ethyl vanillate, phenyl acetate and ethyl-hydroxyhexanoate concentrations were significantly the highest in wines from Plešivica vine-growing region. In analysed sparkling wines, the presence of diethyl glutarate and diethyl malonate, compounds, whose concentrations are influenced by yeast autolysis or caused by chemical esterification during the ageing process, was detected. By the use of chemometric analysis, diethyl malonate was pointed out as one of the most important compounds having strong influence in the Chardonnay wines differentiation [33]. In the work by Carlin et al. [34], the above mentioned compounds were also reported with concentrations of diethyl glutarate (5.8–7.3 µg L−1) similar to our data (12.0–19.9 µg L−1). Sparkling wines from Krašić stood out with significantly the highest concentration of diethyl malonate, while there was no significant difference in diethyl glutarate concentrations among tested wines. Terpens as a large group of wine aroma compounds primarly characterized by floral aroma are translocated from the grape to the must during the pressing and settling process in free volatile form or bound to sugars. In wines, according to Bordiga et al. [35] the transformation of the monoterpenes is linked to corresponding pyranic and furanic oxides or reduction by yeast membrane incorporation and acetylation [36]. Changes in the aroma characteristics during wine maturation were investigated by Oliveira et al. [37], showing a marked increase in monoterpenic oxides and decrease in monoterpenic alcohols. In our research, the presence of trans and cis linalool oxide, furan as well as geranyl acetate was detected in sparkling wines from all three vine-growing regions. Tetrahydrolinalool was significantly the most abundant terpene in sparkling wines from Plešivica and Zelina vine-growing region, while the significantly highest concentrations of nerol, terpene-4-ol and geraniol were detected in wines from Zelina while terpendiol II and hotrienol was most common in wines from Krašić. According to Caliari et al. [25] the main monoterpenes presented in their work were hotrienol, geraniol, linalool, citronellol, α- terpineol and the oxide forms of linalool. In all sparkling wines, the odour threshold value of linalool was above one. This corresponds to our data pointing out linalool, geraniol and hotrienol as the compounds with OAV > 1. Among C13-norisoprenoids compounds detected β-damascenone and TDN were the most common with the significantly highest total concentration above odour detection threshold in sparkling wines from Zelina vine-growing region sparkling wines. TDN originate from carotenoid degradation that is influenced by the ageing process linked to acid-catalysed reactions [9]. Also, according to Marais et al. [38], the TDN levels were remarkably higher in grapes that had more sunlight during maturation than in grapes from shaded locations. So, there is a reason to point out a potential impact of pruning level as well as leaf removal on carotenoid levels [34]. In the work by Francioli et al. [7], TDN was pointed out as a compound that, together with diethyl succinate and vitispirane, can discriminate cavas aged >20 months. A significant difference was also detected in total fatty acids concentrations probably being connected with the different grapes origin, the concentration of lipid substances in the must and differences in winemaking conditions used [19]. The most representative fatty acids similar to data published by Voce et al. [19] were hexanoic, octanoic and decanoic acid with the highest concentrations detected in Plešivica vine-growing region sparkling wines and average concentrations higher than their odour detection threshold. These acids, depending on the concentration, can have negative role in the development of wine sensory profile [9,21], but Shinohara’s [39] data pointed out that, if the concentrations are from 4 to 10 mg L−1, they can positively influenced wine aroma, while if their concentrations are more than 20 mg L−1 they can negatively influence the organoleptic profile of wines what was not the case in our study. Among sulfur compounds detected in analysed sparkling wines 4-methylthio-1-butanol was previously pointed by Rapp [27] as a potential contributor to wine aroma. Its formation can be linked to the degradation of amino acids containing sulfur or as a process connected to sulfur pesticides degradation that are used in the grape protection [40]. Another identified sulfur compound was 3-methylthio-1-propanol which at the contrary has negative influence to aroma mainly due to odour descriptor defined as boiled potatoes, but in our work with no direct impact because of relatively high odour detection threshold. Influence of ageing and storage on lees on the concentration of some fermentative sulfur compounds during sparkling wine production was investigated by Fedrizzi et al. [41], showing significant increments for 4-methylthio-1-butanol as well as 3-methylthio-1-propanol. This result supports the assumption of an analogue synthesis pathway starting from homomethionine as published in the work by Rapp et al. [42]. As can be seen from the results presented in Table 3, wines from Zelina had significantly the highest amount of 4-methylthio-1-butanol while wines from Plešivica stood out with significantly the highest concentrations of 3-methylthio-1-propanol. Among volatile components lactones, mainly γ-lactones and whiskey lactones can influence wine aroma by adding “fruity”, “coconut-like” and “peach-like” notes. Lactones mostly arise from cyclisation of the corresponding γ-hydroxycarboxylic acids, an unstable molecules that can be formed by glutamic acid deamination and decarboxylation process [22,39,43]. Lactones may also come from grapes, as is the case in Riesling, where they contribute to the varietal aroma [24]. The concentration of lactones in thirteen samples of sparkling wine were analysed by Kosmerl and Cegnar [44], with values between 15.0 and 57.5 µg L−1, and γ-nonalactone and γ-decalactone with levels below 4.7 µg L−1. In contrast, in Croatian sparkling wines values were much higher, ranging between 7.58 and 25.44 µg L−1 for γ-nonalactone and 1.93 and 57.19 µg L−1 for γ–decalactone while γ-octalactone concentrations were lower, between 1.06 and 1.80 µg L−1. Comparing average lactones concentrations between vine-growing regions significantly higher values were determined in sparkling wines from Plešivica primarily due to teh presence of γ-butyrolactone. Among others, significantly, the highest concentrations of γ-decalactone and γ-undecalactone were detected in sparkling wines from Krašić.

2.3. Multivariate Analysis

Discriminant analysis using forward stepwise model for all volatile compounds showed that 21 volatile compounds were selected and ranked based on their discrimination efficiency of three vine-growing regions (Table 4), while other compounds were not included by the model as the threshold to enter was set to 0.05.
Three vine-growing regions can be clearly separated, and that Fisher distances between all of them are significant (Table 5).
Scatter plot presented in Figure 1 obtained on the basis of the discriminant analysis showed the distribution of the sparkling wines in the space defined with two discrimination factors. Based on the vector diagram of ten highest ranked volatile compounds selected using forward stepwise model in discriminant analysis we can conclude that due to the position of the plot, samples from Plešivica vine-growing region are specific for high content of hexanoic acid, octanoic acid, 4-hydroxy−4-methyl-2-pentanon, 1,4-butandiol, and acetylfurane, samples from Zelina are specific for a higher content of 2-methylpropionic acid, while Krašić samples have higher level of methyl hexanoate and isobutyl acetate. After the series of discriminant analyses were performed starting with two variables with the highest rank based on stepwise discriminant analysis, followed by the introduction of one new variable in each new analysis, we have discovered that using first two variables (methyl hexanoate and hexanoic acid) 100% correct classification was achieved for Krašić and Zelina while 95% correct classification was achieved for Plešivica samples. After one additional variable (4-hydroxy-4-methyl-2-pentanone) was included, all samples were classified within the corresponding vine-growing region. Significant Fisher distances were detected (Table 5) among all three groups using these three variables (methyl hexanoate, hexanoic acid, and 4-hydroxy-4-methyl-2-pentanone).
In the past years’ classification of musts and/or wines by multivariate analysis were carried on on the basis of their geographical origin or viticultural region [14], based on their chemical attributes [74] and aroma profile [66]. In the work by Arozarena et al. [76] discriminant selection process showed that correct classification by grape cultivar was achieved in the 94% of the training wines and 85% of the test wines. These percentages were very similar when the separation model was used to test the differences between regions, achieving 89% in training sample set and 92% in test wines samples. Similar results were achieved by Marais et al. [77] where stepwise discriminant analysis was applied for the separation based on the aroma compounds data of dry white table wine. The highest discriminatory value components were isoamyl and hexyl acetate and isobutanol, in the Colombar wines while in the Chenin blanc wines they were 2-phenyl ethanol and hexanol.

2.4. Odour Active Values (OAV) and Relative Odour Contribution (ROC)

To evaluate the influence of individual volatile compounds on overall aroma of sparkling wines from three vine-growing regions, OAV values and ROC indexes were calculated and presented in Table 6. From the total of 174 compounds only 26 exceeded the treshold values (OAV > 1). Between them, the most abundand were esters with seven individual compounds and aldehydes with five compounds. The highest OAV was noted in Krašić samples where isoamly lactate OAV value was notably higher compared to other two vine-growing regions. Among others hexanal and β-damascenone stood up in Zelina samples while in the sparkling wines from Plešivica vine-growing region hexanoic acid OAV was the highest. ROC index pointed out pronounced influence of volatile compounds belonging to esters and aldehydes in all sparkling wine samples.

3. Materials and Methods

3.1. Samples

Commercial Croatian sparkling wines samples (n = 30), were obtained from the wineries located in Plešivica, Zelina and Krašić vine-growing regions, all within Zagreb County. In Plešivica vine-growing region the dominant grape varieties were Chardonnay, Pinot noir and Portugizer, in Zelina beside Pinot noir and Chardonnay the presence of Kraljevina (autohotnous Croatian variety) was notable while in Krašić for all the sparkling wines Manzoni bianco grape variety was used. Grapes used for the sparkling wines production were manually harvested while second fermentation was conducted in bottles for the period of 9 months. The first step, before chemical analysis, was to degas sparkling wines by use of Sonorex Ultrasonic bath (Bandelin ElectronicGmbH & Co. KG, Berlin, Germany). To eliminate carbon dioxide, approximately 50 mL of sparkling wines sample was put in a centrifuge tube and degassed for around 2 min.

3.2. Volatile Compounds Determination

Wine sample volatile compounds analysis was performed according to the described method [78]. Isolation of analytes was performed by solid phase extraction on LiChrolut EN cartridges (200 mg/3 mL, Merck, Darmstadt, Germany). In the column which was previously conditioned by successive washing with 3 mL dichloromethane (UHPLC gradient grade J.T.Baker, Deventar, The Netherland), methanol (UHPLC gradient grade J.T.Baker, Deventar, The Netherland) and a 13% aqueous ethanol (LiChrosolv, Merck, Darmstadt, Germany) solution 50 mL of sample was loaded. After the passage of the sample through column, residual sugars and other polar compounds were washed out by 3 mL of water. The column was dried by passing the air. The eluation of analytes was done by 1 mL of dichloromethane. As a quality control, 50 mL of water was injected to the SPE column instead of the sample. Quantitative and qualitative analysis was performed on an Agilent 6890 system coupled with 5973N mass spectrometer with the column ZB-WAX (60 m × 0.32 mm i.d., with 0.5 µm film thickness, Phenomenex, Torrance, USA). The temperature program was as follow 40 °C for 15 min, from 40 to 250 °C with increments of 2 °C per minute and 250 °C for 15 min. Transfer line was set to 250 °C, the flow rate of helium was 1 mL min−1. The MS was operated in electron ionization (EI) mode at 70 eV with a total ion current (TIC) monitoring. Identification was done by comparing retention times and mass spectra with those of standards. List of used standards, linear retention indices and other parameters for identification and quantification is presented in Table 7. Quantification was done by calibration curves. The curves (based on quantification ions) were constructed with software Enhanced ChemStation (Agilent Technologies, Santa Clara, CA, USA, SAD). For all available standards (172) six different concentrations were prepared. For two compounds (Terpendiol I and II) semi-quantitative analysis was performed. Their concentrations were expressed in equivalents of similar compounds with assumption that a response factor was equal to one.

3.3. Determination of Organic Acids

Analysis of individual acids (tartaric, malic and citric acid) were done by HPLC system Agilent Series 1100 equipped with Diode Array Detector (Agilent, Palo Alto, CA, USA). In brief, the determination was performed isocratically with a flow rate set to 0.6 mL min−1 with 0.065 % phosphoric acid (p.a. Merck, Darmstadt, Germany) as a mobile phase. Column Aminex HPX-87H 300 × 7.8 mm i.d (Bio-Rad Laboratories, Hercules, CA, USA) was heated at 65 °C, while the detector was set to 210 nm.

3.4. Determination of Odour Activity Values and Relative Odour Contributions

Each chemical substance can have specific influence on the wine aroma. It can be presented by the odour activity value (OAV) and relative odour contributions (ROC). So they can be used as a markers in determining the role of a specific compound in the sample aroma composition. OAV is calculated as the quotients of their concentration (c) and the corresponding odour detection threshold (t) reported in the literature [79]. Volatile aroma substances with an OAV ≥ 1 can have direct impact on aroma and they are usually marked as one of the most significant volatile substances or the most active odours [80]. The volatiles with an OAV < 1 can also positively influence the wine aroma complexity and aromatic intensity of other compounds through synergistic effects. The ROC of each aroma compound is calculated as the ratio of the OAV of the respective compound to the total OAV of each wine [81].

3.5. Statistical Analysis

The analysis of variance was used for the statistical assessment of the data and Duncan’s multiple range test was used to determine significant differences (p < 0.05) among means. Multivariate analysis was carried out with XLSTAT software v.2020.3.1. (Addinsoft, New York, NY, USA). The forward stepwise model was used to select and rank the variables based on contribution to the discrimination of the groups. The selection process starts by using the variable with the largest contribution to the model and then the following variable is added with an enter probability greater than the threshold value. When the third and all the following variables are being added, model then evaluate the impact of removing each previously present variable in contrast to the removal threshold. To test the minimal number of dependent variables required to achieve the 100% correct classification using cross-validation of the samples within the belonging group, i.e., vine-growing region, a series of discriminant analyses were performed using all of the samples, starting with two variables with the highest rank based on stepwise discriminant analyses, and in each new analysis, one new variable was added as a differentiating factor among cultivars. This determined the cumulative efficiency of the parameters applied in the correct classification of wine samples in the corresponding vine-growing region.

4. Conclusions

Even though in the current work little was known about the enological steps used in the production of the wines studied, differences were clearly demonstrated and wines classified according to the vine-growing regions, indicating that future studies using greater control over enological factors are likely to demonstrate an even stronger role of the site in the sparkling wine composition. As can be seen from the results, in all sparkling wines, esters had an important role, among them especially the once with the OAV > 1 as ethyl butanoate, hexanoate, octanoate, ethyl-2-methylbutanoate, ethyl-3-methylbutanoate, isoamyl acetate, and isoamyl lactate. The presence of diethyl succinate as well as diethyl glutarate, compounds whose presence can be used as an ageing marker was detected. Another compound that could be used as discriminate marker is TDN whose concentrations were notably higher in sparkling wines from Zelina vine-growing region. Such data could lead to a better understanding of what defines sparkling wines of a specific vine-growing region. However, this work provides a basis for the future research variations of volatile aroma compounds within Croatian sparkling wines from Zagreb County and for the development of models that better explain these variations due to the geographic origin that is associated with similar climatic conditions or soil.

Author Contributions

Conceptualization, A.-M.J.K. and A.J.; methodology, I.T.; formal analysis, I.T.; data curation, D.P.; writing—original draft preparation, AM.J.K.; writing—review and editing, AM.J.K. and D.P.; supervision, A.J. All authors have read and agreed to the published version of the manuscript.

Funding

Financial support for this work is attributed to the project, KK.01.1.1.04.0031, New Start for Croatian Grapevine Varieties (CroVitiRestart) funded by European Structural and Investment Funds and Croatian Ministry of Science and Education.

Conflicts of Interest

Authors declare no conflict of interest

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Sample Availability: Samples from the described study are not available from the authors.
Molecules 25 04349 g001 550
Figure 1. Discriminant analysis of 30 sparkling wines (left) based on the concentrations of ten volatile compounds (right)) with highest rank after forward stepwise model applied on total number of volatile compounds detected. The vector diagram indicates the direction and intensity of the effect of nine variables on the distribution of wine samples in the space defined by two discrimination factors (F1 and F2).
Figure 1. Discriminant analysis of 30 sparkling wines (left) based on the concentrations of ten volatile compounds (right)) with highest rank after forward stepwise model applied on total number of volatile compounds detected. The vector diagram indicates the direction and intensity of the effect of nine variables on the distribution of wine samples in the space defined by two discrimination factors (F1 and F2).
Molecules 25 04349 g001
Table
Table 1. Organic acid composition (g L−1) of sparkling wines from different vine-growing regions.
Table 1. Organic acid composition (g L−1) of sparkling wines from different vine-growing regions.
Parameters Vine Growing Regions
Plešivica (n = 19)Zelina (n = 8)Krašić (n = 3)
MINMAXMean ± SDMINMAXMean ± SDMINMAXMean ± SD
Tartaric acid1.283.772.35 ± 0.701.722.912.23 ± 0.401.612.502.06 ± 0.62
Malic acid0.121.610.81 ± 0.430.432.021.20 ± 0.550.991.621.31 ± 0.44
Citric acid0.040.510.18 ± 0.120.060.590.26 ± 0.150.060.080.07 ± 0.01
Succinic acid0.010.500.13 ± 0.140.010.280.11 ± 0.080.030.070.05 ± 0.02
Lactic acid0.010.270.10 ± 0.090.070.360.16 ± 0.090.100.130.12 ± 0.09
pH value2.893.563.16 ± 0.173.053.393.16 ± 0.103.203.453.33 ± 0.10
MIN-minimum value, MAX-maximum value, SD-standard deviation.
Table
Table 2. Average volatile compound concentrations (µg L−1) of sparkling wines produced in different vine-growing regions.
Table 2. Average volatile compound concentrations (µg L−1) of sparkling wines produced in different vine-growing regions.
Parameters Vine Growing Regions
Plešivica (n = 19)Zelina (n = 8)Krašić (n = 3)
MINMAXMean ± SDMINMAXMean ± SDMINMAXMean ± SD
∑ Aldehydes356.261902842 ± 62 ab281.361161546.77 ± 88.03 c978.0211001039 ± 172 a
∑ Higher alcohols383385996449531 ± 5846 b443349775475423 ± 20673 a 422234370642965 ± 1048 b
∑ Volatile phenols84.0448.1181.6 ± 89.0 b17.1257.184.5 ± 76.1 c304.5458.0381.3 ± 108.5 a
∑ Terpenes188.61270475.3 ± 242.0 b481.81044760.0 ± 219.8 a609.9800.6705.3 ± 134.8 ab
∑ C13-norisoprenoides0.313.13.9 ± 4.7 b4.113.28.1 ± 2.7 a0.11.50.84 ± 1.0 c
∑ Lactones16.97740.33158.96 ± 218.0 a15.83472.28133.34 ± 179.8 b22.09180.32101.20 ± 111.8 b
∑ Esters149903021521658 ± 4660 b156048505048045 ± 29098 a164562397720217.3 ± 5318 b
∑ Fatty acids68152503515244 ± 5327 a183.889702137 ± 3324 b6915103638639 ± 2438 ab
∑ Other alcohols419.62381.8947.1 ± 478.1 a140.2815.0302.4 ± 241.9 b637.0769.0703.0 ± 93.3 ab
∑ Sulfur compounds27.64195.5103.8 ± 40.3 b96.4932.9574.9 ± 302.5 a30.265.547.9 ± 24.9 b
∑ Other compounds102.693025553.4 ± 750.0 a82.3291.6162.6 ± 79.9 a269.3332.3300.9 ± 44.5 a
MIN-minimum value, MAX-maximum value, SD-standard deviation; Means mean ± S.D. are calculated only from samples in which analytes were quantified; Means with different superscript letters in the same row differ significantly (p ≤ 0.05).
Table
Table 3. Individual volatile compound concentrations (µg L−1) of sparkling wines produced in different vine growing regions.
Table 3. Individual volatile compound concentrations (µg L−1) of sparkling wines produced in different vine growing regions.
Parameters ODT (µg L−1)Odour DescriptorOAVVine-Growing Regions
PlešivicaZelinaKrašić
MINMAXMean ± SDMINMAXMean ± SDMINMAXMean ± SD
Aldehydes
2,4-Decadienal270 [45]floral [46] 0.038.802.19 ab ± 1.89n.d.3.671.47 b ± 1.232.723.283.00 a ± 0.23
2,4-Heptadienal (E,E) 0.0523.616.30 a ± 5.70n.d.11.114.0 a ± 4.948.959.909.43 a ± 0.39
2,4-Heptadienal (Z,Z) 0.079.353.75 a ± 2.52n.d.12.0611.30 a ± 19.696.3116.9811.65 a ± 4.36
2,4-Nonadienal0.09 [47]cucumber [46]>10.124.731.70 a ± 1.26n.d.5.740.70 a ± 1.780.223.561.89 a ± 1.36
2-Heptenal4.6 [48]green [46]>1n.d.383.08215.13 a ± 92.35n.d.153.4617.1 b ± 48.23147.88156.95152.42 a ± 3.70
5-Hydroxymethylfurfural100,000 [48]almond [49] 1.30789.4567.40 b ± 166.440.2635.447.98 b ± 12.0657.87453.56255.72 a ± 161.54
5-Methyl-furfural16,000 [48] bitter, almond, spice [49] 2.3835.4510.28 a ± 7.292.7513.967.57 b ± 3.407.2115.6911.45 a ± 3.46
Benzeneacetaldehyde4 [50] 81.5246.35142.60 a ± 49.27n.d.318.170.92 a ± 109.14110.87202.25156.56 a ± 37.31
Benzaldehyde350 [51]bitter, almond [52] 8.7178.5627.23 a ± 17.872.9150.9620.38 a ± 14.5030.935.2533.08 a ± 1.78
Decanal0.1–2 [53] >1n.d.138.2525.71 a ± 42.020.89117.5855.23 a ± 34.390.2551.7726.01 a ± 21.03
Furfural770 [54]burn, almond, yeast [55] 5.24423.08125.89 a ± 108.98n.d.279.63164.93 a ± 87.47154.58291.47223.03 a ± 55.89
Heptanal3 [53] n.d.3.050.84 a ± 0.75n.d.2.790.75 a ± 0.980.810.930.87 a ± 0.05
Hexanal5 [56]herbaceous [51]>190.13428.31203.69 b ± 90.81221.77433.73315.25 a ± 64.33100.29173.01136.65 b ± 29.69
Nonanal1 [50] >1n.d.19.4510.04 a ± 7.29n.d.17.383.65 b ± 2.7715.1219.8217.47 a ± 6.77
Higher alcohols
1-Butanol150,000 [57]medicinal [51] 43.07186.43112.11 a ± 42.2028.4878.6457.75 b ± 14.9893.06109.75101.41 ab ± 6.81
1-Decanol5000 [58]pear, waxy, violet [58] 0.441.750.69 b ± 0.320.466.173.83 a ± 2.080.420.670.55 b ± 0.10
1-Heptanol425 [50]oily [46] 2.7264.4719.21 a ± 18.050.9813.194.37 b ± 4.6426.9131.3129.11 a ± 1.80
1-Hexanol2500 [55]grass just cut [51]>167737071874 b ± 78847132601612 b ± 848271931772948 a ± 186
1-Methoxy-2-propanol 8.3482.2619.82 a ± 15.70n.d.17.244.78 b ± 6.4213.5425.9619.75 ab ± 5.07
1-Octadecanol 0.410.810.59 a ± 0.100.583.172.24 a ± 1.090.715.948.32 a ± 6.22
1-Octanol110–130 [53]chemical [51] 3.208.375.29 b ± 1.475.168.656.74 a ± 1.235.435.925.68 ab ± 0.20
1-Pentanol64,000 [39]bitter, almond, balsamic [39] 9.3431.9215.82 a ± 5.090.3024.36.90 b ± 9.3015.9518.0717.01 a ± 0.87
2-Heptanol70 [59]fruity, herbaceous [46] 2.8524.477.66 a ± 4.560.4010.076.66 a ± 4.896.516.746.63 a ± 0.09
trans-2-Hexene-1-ol100 [59]herbaceous, green [46] 0.5910.312.96 b ± 2.861.8615.258.53 a ± 5.491.142.151.65 b ± 0.41
cis-2-Hexene-1-ol green [46] 9.2129.5815.74 b ± 5.944.1817.9511.19 b ± 4.4720.832.5626.68 a ± 4.80
2-Methyl-1-butanol30,000 [60]whiskey, burnt, nail polish [61] 924513,17110835 b ± 11806898.2272017390 a ± 6395803191478589 b ± 455
2-Pentadecanol n.d.4.500.80 b ± 1.31n.d.3.521.90 a ± 1.39--n.d.
2-Pentene-1-ol 1.8418.924.75 b ± 3.974.6328.4118.61 a ± 9.043.383.783.58 b ± 0.16
cis-3-Hexene-1-ol400 [51]grass, green [51] 29.46678.41102.16 a ± 132.0552.76343.47146.75 a ± 88.3277.12240.48158.80 a ± 66.69
trans-3-Hexene-1-ol1000 [51]grass, resinous, cream [51] 23.69212.6581.96 a ± 56.821.24116.6153.84 a ± 30.4748.9753.1251.05 a ± 1.69
3-Octanol n.d.2.451.26 a ± 0.98n.d.4.972.22 a ± 1.640.102.321.21 a ± 0.91
Isoamyl alcohol30,000 [60]alcohol, nail polish [58]>1163172986223888 b ± 2628250395399139580 a ± 10019202912072420507 b ± 176
Isobutanol40,000 [39]alcohol, nail polish [58] 146752732686 a ± 1013n.d.3042937 b ± 1330240324672435 ab ± 26
Phenylethyl alcohol14,000 [62]floral, rose, honey [58]>12950123479734 ab ± 207753152610715759 a ± 7467734987318040 b ± 564
Volatile phenols
4-Ethylguaiacol33 [39]toasted bread, smoky, clove [51] 2.3723.447.38 b ± 5.365.3556.6026.68 a ± 18.977.9314.4911.21 ab ± 2.68
4-Ethylphenol35 [63]phenol, stable [51] n.d.146.8613.35 a ± 37.64--n.d.0.1188.6844.40 a ± 36.16
4-Vinylguaiacol40 [63]clove, curry [51]>140.57207.87114.75 b ± 40.410.06166.2628.44 c ± 57.37135.81377.52256.67 a ± 98.68
4-Vinylphenol180 [62]phenolic, medicinal [51] n.d.0.420.08 b ± 0.09n.d.0.190.10 b ± 0.11n.d.1.350.68 a ± 0.55
Eugenol6 [54]cinnamon, clove [51] 0.048.131.79 a ± 1.910.030.320.18 a ± 0.140.093.801.95 a ± 1.51
Guaiacol9.5 [55]smoky, hospital [55] 0.075.760.97 a ± 1.32n.d.0.320.20 a ± 0.310.131.030.58 a ± 0.37
Homovanillyl alcohol --n.d.n.d.4.181.69 ± 1.34--n.d.
Vanillin200 [60]vanilla [51] 1.06278.5932.77 a ± 57.533.3871.3316.98 a ± 21.8960.3463.0961.72 a ± 1.12
Tyrosol33 [39]toasted bread, smoky, clove [39] 1.4515.397.50 a ± 4.301.3530.3811.07 a ± 8.823.734.494.11 a ± 0.31
Terpenes
1,8-Terpin 0.229.932.74 a ± 3.010.653.881.68 a ± 15.050.542.521.53 a ± 0.81
6,7-Dihydro-7-hydroxylinalool 0.1180.0224.31 a ± 27.3810.3356.239.41 a ± 250.410.4355.0327.73 a ± 22.29
8-Hidroxylinalool 0.9174.7523.71 a ± 19.551.5420.5211.85 a ± 11.017.3113.4410.38 a ± 2.50
α-Terpineol330 [64]lilac, floral, sweet [51] 6.5251.9321.04 a ± 12.529.3244.3426.05 a ± 165.2024.4152.3638.39 a ± 11.41
β-Farnesen87 [65] 0.078.502.15 a ± 2.78n.d.0.510.27 a ± 0.160.440.590.52 ab ± 0.06
β-Ocimene 0.172.000.87 b ± 0.63n.d.0.760.23 b ± 0.461.171.681.43 a ± 0.21
cis-Linalool oxide, furan6000 [55]flower [55] 0.1020.1310.85 a ± 6.872.2823.1512.04 a ± 38.6217.6930.4424.07 a ± 5.21
Citronelol40 [64]rose [66] 1.8619.154.59 a ± 3.81n.d.5.481.46 a ± 2.136.413.369.88 a ± 2.84
δ-Carene n.d.1.730.58 a ± 0.49n.d.3.542.51 a ± 1.700.352.531.44 a ± 0.89
Dihydroactinidiolide n.d.22.577.69 a ± 5.79n.d.6.912.87 a ± 2.22n.d.n.d.n.d.
Farnesol20 [67]floral, clove [46] 0.7714.255.73 a ± 4.650.149.223.06 a ± 2.687.988.088.03 a ± 0.04
γ-Terpinene n.d.90.927.79 b ± 22.990.40240.91131.94 a ± 88.910.320.410.37 b ± 0.04
Geraniol20 [62]citrus, citric fruit [51]>10.3516.522.21 b ± 3.380.58152.6588.33 a ± 52.921.5714.287.93 b ± 5.19
Geranyl acetate9 [68]flowery [68] 0.1117.913.65 a ± 3.84n.d.11.195.97 a ± 18.232.656.584.62 a ± 1.60
Hotrienol110 [52]fresh, floral, fruity [52]>17.69121.1131.94 a ± 28.551.68142.9729.30 a ± 607.88128.35268.59198.47 a ± 57.25
Linalool25 [62]citrus, floral, sweet [51]>10.69103.3811.31 b ± 23.721.3884.845.03 a ± 30.831.3144.9173.11 a ± 58.63
Linalool oxide, pyran3000 [55]flower [51] 2.1813.237.17 a ± 3.370.6219.776.54 a ± 133.0822.6526.4424.55 a ± 1.55
Neric acid 1.87149.8826.84 a ± 40.121.9314.997.42 a ± 4.8832.4440.0536.25 a ± 3.11
Nerol300 [64]rose, fruity, floral [51] 0.126.130.91 b ± 1.230.1760.4133.19 a ± 20.170.773.091.93 b ± 0.95
Nerolidol250 [50]rose, apple, green, waxy, woody [46] 0.113.220.57 a ± 0.640.103.581.28 a ± 1.440.010.670.34 a ± 0.27
Pseudoionon n.d.0.140.06 b ± 0.03n.d.1.490.09 b ± 0.490.081.530.81 a ± 0.59
Terpendiol I n.d.1.890.74 a ± 0.53n.d.0.980.87 a ± 0.800.81.180.99 a ± 0.16
Terpendiol II 2.4040.5011.30 c ± 9.320.8148.8331.69 b ± 39.3053.43114.5984.0 a ± 24.97
Terpinene-4-ol 0.033.972.25 b ± 0.851.7991.436.23 a ± 29.881.733.52.62 b ± 0.72
Tetrahydrolinalool 0.11015183.23 a ± 226.0768.33436.64198.41 a ± 125.281.2653.4227.34 b ± 21.29
trans-Linalool oxide, furan6000 [55]flower [55] 0.25105.3913.87 a ± 21.891.1550.9920.81 a ± 54.3118.2349.2733.75 a ± 12.67
trans-Rose oxide80–160 [69]floral, green [69] 0.110.390.20 a ± 0.120.100.240.24 a ± 0.450.240.480.36 a ± 0.10
Linalyl formate n.d.4.690.81 b ± 1.040.415.992.61 a ± 2.060.270.640.46 b ± 0.15
Ethyl linalyl acetal 0.645.742.62 b ± 1.411.0128.949.90 a ± 8.921.922.452.19 b ± 0.22
2,6-Dimethyl-3,7-octadiene-2,6-diol 0.0712.173.77 b ± 3.290.2014.035.80 b ± 25.3120.230.7825.49 a ± 4.32
2,6-Dimethyl-7-octene-2,6-diol 25.1680.6046.12 a ± 15.098.0640.1916.79 a ± 14.3848.8154.7651.79 a ± 2.43
Menthol 0.9357.069.97 a ± 17.41n.d.1.610.55 a ± 1.672.213.712.96 a ± 0.61
Ocimenol n.d.2.470.95 a ± 0.65n.d.5.593.96 a ± 7.460.591.421.01 a ± 0.34
C13- norisoprenoids
α-Ionol 0.010.780.24 a ± 0.21n.d.0.090.07 b ± 0.130.050.180.12 ab ± 0.05
α-Ionon10.5 [70] floral [70] n.d.0.050.03 b ± 0.010.180.560.37 a ± 0.180.020.060.04 b ± 0.02
β-Damascenone0.05 [60]sweet, fruity, floral, honey [62]>10.059.951.91 a ± 2.950.036.543.68 a ± 2.14n.d.0.280.14 a ± 0.11
TDN2 [71]petrol, kerosene [55]>10.358.862.55 a ± 2.260.17.453.89 a ± 2.720.11.10.55 a ± 0.45
Lactones
cis-Whiskey lactone67 [39]nutty, coconut [61] 0.465.311.59 a ± 1.192.544.642.13 a ± 1.250.740.810.78 a ± 0.03
δ-Nonalactone 5.5113.078.71 a ± 2.04n.d.8.732.86 b ± 2.927.598.117.85 a ± 0.21
γ-Butyrolactone10,000 [58]coconut, caramel [51] n.d.695.54131.27 a ± 208.88n.d.439.2985.94 a ± 227.18--n.d.
γ-Decalactone1000 [58]peach, fruity [51] 0.557.091.93 b ± 1.45n.d.7.345.12 b ± 2.371.93112.4557.19 a ± 45.12
γ-Hexalactone1600 [72]sweet, cake, peach [51] 0.1928.815.80 a ± 5.71n.d.6.223.33 a ± 2.37n.d.13.826.91 a ± 5.64
γ-Nonalacton25 [48]coconut, peach [51]>12.6723.857.58 b ± 5.275.0649.1125.44 a ± 17.367.9514.6611.31 ab ± 2.74
γ-Octalacton7 [48] n.d.8.481.06 a ± 1.78n.d.2.451.77 a ± 0.801.741.851.80 a ± 0.04
γ-Undecalactone60 [48]apricot, peach [46] 0.151.840.54 b ± 0.44n.d.4.662.21 b ± 1.682.0128.5515.28 a ± 10.84
trans-Whiskey lactone790 [39]nutty, coconut [61] 0.1026.932.21 a ± 5.582.372.651.53 a ± 0.860.070.140.11 a ± 0.03
Esters
2-Phenylethyl acetate250 [73]rose, honey, tobacco [58] 7.04115.2223.40 a ± 22.550.1641.7324.05 a ± 14.9710.1447.3128.73 a ± 15.17
Diethyl glutarate n.d.28.0215.39 a ± 8.215.3235.6219.93 a ± 10.195.7318.2912.01 a ± 5.13
Diethyl hydroxysuccinate n.d.5.421.26 b ± 1.960.896960932046 a ± 27325.14n.d.11.815.91 b ± 4.82
Diethyl malonate sweet, fruity, apple [46] 0.9313.037.08 b ± 2.944.0910.958.55 b ± 2.3413.2346.3129.77 a ± 13.50
Diethyl oxalate n.d.1.310.34 a ± 0.35n.d.0.960.48 a ± 0.30--n.d.
Diethyl succinate200,000 [39]overripe, aged [55] 1600102725401 a ± 21413141114987430 a ± 2545270051343917 b ± 993
Dimethyl malate 0.1010.033.82 b ± 3.08--n.d.n.d.15.617.81 a ± 6.37
Ethyl benzeneacetate 6.7677.8534.36 a ± 23.910.9771.6011.80 b ± 25.3416.440.0028.20 ab ± 9.63
Ethyl butanoate20 [54]pineapple, apple, peach [58]>1117.13404.93270.94 b ± 82.85204.06580.88417.08 a ± 119.30352.95372.23362.59 ab ± 7.87
Ethyl decanoate200 [63]floral, grape, fruty [61] 0.10150.729.32 b ± 32.790.16239.31136.02 a ± 85.110.180.200.19 b ± 0.01
Ethyl furoate16,000 [54] 6.8581.4343.46 a ± 18.892.51111.9121.80 a ± 34.4232.6646.9739.82 a ± 5.84
Ethyl hexadecanoate>2000 [74] 0.172.500.94 b ± 0.730.3016.276.54 a ± 6.040.241.460.85 b ± 0.50
Ethyl hexanoate14 [62]fruity, green apple, banana [61]>1111.89578.37334.98 b ± 129.46181.96803.90520.55 a ± 190.77423.93447.10435.52 ab ± 9.46
Ethyl hydrogensuccinate 409695466671 a ± 17540.3571602346.13 b ± 314.10269268704781 ab ± 1705
Ethyl lactate154,000 [54]butter [58] 2131148716664 a ± 3755264573254025 b ± 2275831591288721 a ± 331
Ethyl linoleate450 [65] 0.191.910.68 b ± 0.410.543.002.00 a ± 0.790.441.010.73 b ± 0.23
Ethyl octanoate580 [63]sweet, floral, fruity, pear [58]>174.15715.98393.31 b ± 179.89199.76890.39631.90 a ± 230.08365.04499.41432.23 ab ± 54.86
Ethyl vanillate3000 [63]creamy, vanilla [61] 29.10747.97160.67 a ± 178.330.32151.6728.54 a ± 50.9960.33135.8298.08 a ± 30.82
Ethyl-2-hydroxy-3-methylbutanoate 9.07440.2899.98 b ± 88.6067.73653.62431.39 a ± 217.5623.2545.3634.31 b ± 9.03
Ethyl-2-hydroxybutanoate 4.2481.7926.00 a ± 23.450.9833.3214.09 a ± 13.9914.6226.7320.68 a ± 4.94
Ethyl-2-methylbutanoate18 [54]apple, strawberry [61]>12.91106.0630.43 a ± 21.680.1429.069.42 b ± 9.825.5417.8611.70 ab ± 5.03
Ethyl-2-oxopropanoate 38.2253.61126.68 a ± 71.240.14217.1055.96 a ± 96.8964.31116.5990.45 a ± 21.34
Ethyl-3-ethoxypropanoate 0.022.640.54 a ± 0.680.050.140.13 a ± 0.460.020.100.06 a ± 0.03
Ethyl-3-hydroxybutanoate20,000 [66]grape, fruity, caramel, toasted [75] 0.1175.2821.75 a ± 28.470.251.610.93 b ± 10.120.9676.0438.50 a ± 30.65
Ethyl-3-hydroxyhexanoate45 [58]rubber [46] 0.2012.357.19 a ± 3.040.2610.434.99 a ± 2.967.337.917.62 a ± 0.24
Ethyl-3-methylbutanoate3 [54]fruity, pineapple [46]>16.71150.4051.39 a ± 30.1928.9592.3861.76 a ± 20.198.7133.3521.03 a ± 10.06
Ethyl-hydroxyhexanoate 0.15376.69120.86 a ± 92.700.50161.6220.64 b ± 69.5468.6892.9580.82 ab ± 9.91
Ethylmethyl succinate 12.9864.4232.58 a ± 13.000.0240.218.00 b ± 13.8922.0943.4132.75 a ± 8.70
Hexyl acetate670 [57]fruity, green, sweet [61] n.d.183.2951.91 a ± 60.850.13161.5056.90 a ± 7.8849.1583.6966.42 a ± 14.10
Isoamyl acetate30 [62]banana [58]>1117.762825.79436.95 a ± 552.2076.89726.31473.72 a ± 240.34599.36610.28604.82 a ± 4.46
Isoamyl lactate1.6 [60]fruity, apple, banana [46]>10.17602.50144.88 ab ± 158.711.1047.6117.46 b ± 15.35173.59218.43196.01 a ± 18.31
Isobutyl acetate6140 [58]apple, banana [61] 11.3677.8423.30 b ± 15.0910.3838.3321.38 b ± 9.3539.9942.0641.03 a ± 0.85
Isobutyl lactate340,000 [58] 3.3677.5428.01 b ± 21.7027.72346.96112.05 a ± 109.4522.8926.3324.61 b ± 1.40
Methyl hexadecanoate>2000 [74] 0.411.180.78 a ± 0.36n.d.1.610.84 a ± 0.54--n.d.
Methyl hydroxyisovalerate 2.14323.5552.30 a ± 69.630.6757.4918.95 a ± 22.504.9250.5327.73 a ± 18.62
Methyl hexanoate84 [76] n.d.1.420.41 b ± 0.39n.d.0.750.43 b ± 0.241.51.841.67 a ± 0.14
Methyl octadecanoate --n.d.--n.d.n.d.1.040.52 ± 0.42
Methyl-2-furoate 0.051.240.56 b ± 0.360.0924.545.00 a ± 7.360.520.900.71 b ± 0.16
Methyl-3-hydroxyoctanoate 0.060.470.17 b ± 0.100.1029.4010.08 a ± 9.450.110.180.15 b ± 0.03
Methyl geranoate 0.331.841.10 a ± 0.640.462.040.88 a ± 1.030.640.730.69 a ± 0.04
o-Methylbenzyl acetate 2.5991.5930.20 a ± 23.692.70208.2171.44 a ± 74.595.7518.6312.19 a ± 5.26
Phenyl acetate250 [60] 0.25789.1387.35 a ± 226.770.152.031.25 a ± 1.720.110.360.24 a ± 0.10
Fatty acids
2-Methylpropionic acid230 [55]rancid, cheesy [55] 0.929.113.31 b ± 2.064.8216.968.67 a ± 4.223.944.534.24 b ± 0.24
Butanoic acid400 [55]rancid, cheese [51] 0.201.911.08 a ± 0.470.120.970.84 b ± 0.360.961.091.03 a ± 0.05
Decanoic acid1000 [73]rancid, waxy [51]>185156652456 a ± 13240.942100798.88 b ± 1155.30997.1424341715.72 ab ± 586.71
Heptanoic acid3000 [53]rancid, cheesy [51] 0.962.191.39 b ± 0.350.1113.875.65 a ± 4.181.131.851.49 b ± 0.29
Hexanoic acid420 [53]cheese, oily [58]>1137108487006 a ± 254112.62739.12318.30 b ± 250.82195.35303.17249.26 b ± 44.02
Isovaleric acid33 [62]sweat, rancid [51]>10.7843.937.01 ab ± 10.170.324.713.03 b ± 1.5813.9917.1415.57 a ± 1.29
Octanoic acid500 [54]rancid, oily [61]>1209791236207 a ± 19374.8164531252.90 b ± 2500.16570075926646 a ± 772
Propanoic acid8100 [57]rancid, oily [46] 0.0716.584.15 b ± 3.652.3438.3724.27 a ± 14.053.069.126.09 b ± 2.47
Other alcohols
1,4-Butandiol 0.0414.497.37 a ± 5.270.52.952.29 a ± 2.053.4712.077.77 a ± 3.51
2,6-Dimethyl-4-heptanol 57.74657.53246.34 a ± 125.924.55283.8191.41 b ± 110.96119.63163.54141.59 ab ± 17.93
2-Butoxy-ethanol 2.6975.6531.87 a ± 22.620.2020.4310.31 b ± 6.1512.0145.1628.59 ab ± 13.53
2-Ethyl-1-hexanol 8.0134.4616.47 a ± 7.140.4840.5512.17 a ± 19.4126.7128.8427.78 a ± 0.87
3,4-Dimethyl-2-hexanol 9.801579.33169.17 a ± 396.650.5671.5329.10 a ± 25.5798.14135.69116.92 a ± 15.33
3-Ethoxy-1-propanol50,000 [58]overripe, pear [75] 3.60148.1261.84 a ± 44.461.2941.057.87 b ± 12.8823.2590.1156.68 ab ± 27.30
3-Methyl-1-pentanol50,000 [49] 73.67225.57137.92 a ± 38.4155.52113.6989.29 b ± 22.3587.1994.3090.75 b ± 2.90
3-Methyl-3-buten-1-ol 10.5431.2316.35 a ± 5.100.4523.486.30 b ± 4.7016.1118.3417.23 a ± 0.91
4-Ethylcyclohexanol 0.156.61.61 a ± 1.660.173.203.14 a ± 0.112.442.732.59 a ± 0.12
4-Methyl-1-pentanol50,000 [58]almond, toasted [46] 35.03147.7270.08 a ± 28.0625.9360.7238.90 b ± 15.4934.9139.7937.35 b ± 1.99
Benzylalcohol10,000 [64]roasted, toasted, sweet, fruity [51] 1.5219.096.69 a ± 5.132.086.793.64 a ± 1.703.183.713.45 a ± 0.22
Cyclohexanol160,000 [65] 0.034.221.39 a ± 1.400.206.242.30 a ± 2.250.153.351.75 a ± 1.31
Furfuril alkohol15,000 [58]sweet, nutty [61] 0.2945.1013.32 a ± 12.840.2112.006.15 b ± 6.8010.5311.8511.19 ab ± 0.54
2,3-Butanediol668,000 [23] buttery, creamy [58] 0.34564.66158.57 a ± 135.9613.97157.1145.37 b ± 110.71138.48180.36159.42 a ± 17.10
Sulfur compounds
4-(Methylthio)-1-butanol1000 [40]metallic-bitter, garlic, earthy [46] 0.0228.1213.23 b ± 8.578.15932.95548.45 a ± 352.4011.9719.6115.79 b ± 3.12
3-(Methylthio)-1-propanol1000 [62]cooked potato [61] 0.42186.9389.71 a ± 41.91n.d.123.6623.61 b ± 17.6918.2645.9432.10 b ± 11.30
Other compounds
2,5-Hexadione 0.384.532.89 a ± 1.15n.d.1.070.97 b ± 0.762.452.692.57 a ± 0.10
2,7-Octanedione 0.1181.6111.43 a ± 16.45n.d.42.7622.16 a ± 16.45n.d.3.481.74 a ± 1.42
2 H-Pyran-2,6(3H)-dione 0.1948.7624.08 a ± 18.89n.d.70.5810.39 a ± 24.300.490.500.50 a ± 0.00
2-Pentylfuran2000 [65] 3.789.736.63 b ± 1.803.8714.259.81 a ± 2.788.488.948.71 ab ± 0.19
3-Penten-2-on 0.521021.2679.69 a ± 215.90n.d.3.893.81 a ± 1.711.193.992.59 a ± 1.14
4-Hydroxy-4-methyl-2-pentanone n.d.14.525.85 a ± 2.79n.d.5.331.64 b ± 1.322.633.843.24 ab ± 0.49
4-Methyl-2-penten-2-one n.d.4.140.93 b ± 1.251.3654.5130.18 a ± 20.50n.d.0.320.16 b ± 0.13
5-Ethyl-4-methyl-3-heptanone 0.2689.8916.29 a ± 22.790.1155.8912.56 a ± 16.900.601.441.02 a ± 0.34
Acetoin150,000 [54]buttery, creamy [58] 17.302904.72310.34 a ± 729.870.96131.2634.45 a ± 50.24176.86247.6212.23 a ± 28.88
Acetylfurane 3.8131.3615.60 a ± 6.090.1317.5314.33 a ± 7.1412.4119.1215.77 a ± 2.74
Benzofurane350 [50] 2.60178.3434.30 a ± 38.710.3122.685.32 b ± 7.138.6420.4614.55 ab ± 4.83
Dihydro-2-methyl-3(2H)-furanone n.d.8.482.55 a ± 1.950.219.793.75 a ± 2.811.121.501.31 a ± 0.16
N-(2-phenylethyl)acetamide 0.402.911.53 b ± 0.511.1425.638.59 a ± 8.630.981.361.17 b ± 0.16
N-Ethylacetamide 15.3356.9031.59 a ± 11.282.4152.0019.32 a ± 17.6930.2440.3835.31 a ± 4.14
ODT- odour detection treshold, OAV-odour active value, MIN-minimum value, MAX-maximum value, SD-standard deviation; Means mean± S.D. are calculated only from samples in which analytes were quantified; Means with different superscript letters in the same row differ significantly (p ≤ 0.05).
Table
Table 4. Summary of the variables selection and ranking in Discriminant analysis using forward stepwise model for discrimination among sparkling wines samples from three vine growing region.
Table 4. Summary of the variables selection and ranking in Discriminant analysis using forward stepwise model for discrimination among sparkling wines samples from three vine growing region.
RankVariable Included Partial R²FpWilks’ Lambda ap
1Methyl hexanoate0.8688.5<0.1 × 10−41.45 × 10−1<0.1 × 10−4
2Hexanoic acid0.8160.0<0.1 × 10−42.82 × 10−2<0.1 × 10−4
34-Hydroxy-4-methyl-2-pentanone0.4813.01.02 × 10−41.46 × 10−2<0.1 × 10−4
4Heptanal0.5717.9<0.1 × 10−46.29 × 10−3<0.1 × 10−4
5Octanoic acid0.5817.7<0.1 × 10−42.66 × 10−3<0.1 × 10−4
63-Penten-2-on0.428.91.21 × 10−31.55 × 10−3<0.1 × 10−4
7Isobutyl acetate0.407.82.41 × 10−39.41 × 10−4<0.1 × 10−4
82-Methylpropionic acid0.438.81.47 × 10−35.34 × 10−4<0.1 × 10−4
91,4-Butandiol0.407.43.40 × 10−33.18 × 10−4<0.1 × 10−4
10Acetylfurane0.427.53.43 × 10−31.85 × 10−4<0.1 × 10−4
11Isobutyl lactate0.416.85.54 × 10−31.10 × 10−4<0.1 × 10−4
12Ethyl linoleate0.5813.02.78 × 10−44.66 × 10−5<0.1 × 10−4
13Propanoic acid0.467.83.63 × 10−32.50 × 10−5<0.1 × 10−4
142H-Pyran-2,6(3H)-dione0.539.41.79 × 10−31.19 × 10−5<0.1 × 10−4
15TDN0.528.62.86 × 10−35.70 × 10−6<0.1 × 10−4
16Ethyl linalyl acetal0.487.07.30 × 10−32.96 × 10−6<0.1 × 10−4
17Ethyl-2-oxopropanoate0.6010.71.53 × 10−31.17 × 10−6<0.1 × 10−4
18Benzaacetaldehyde0.516.79.94 × 10−35.76 × 10−7<0.1 × 10−4
19Hexanal0.516.21.42 × 10−32.84 × 10−7<0.1 × 10−4
20β-Farnesen0.424.04.91 × 10−21.64 × 10−7<0.1 × 10−4
21Benzaldehyde0.586.91.33 × 10−26.92 × 10−8<0.1 × 10−4
a Wilks’ Lambda test of the assumption of equality of the mean vectors of classes.
Table
Table 5. Fisher distance among samples of sparkling wines from three vine-growing regions based on 3 volatile compounds.
Table 5. Fisher distance among samples of sparkling wines from three vine-growing regions based on 3 volatile compounds.
KrašićPlešivicaZelina
Krašić026.3 ***14.0 ***
Plešivica 57.3 ***
Zelina 0
p-values for Fisher distances: *** p < 0.001.
Table
Table 6. Odour activity values (OAV) and relative odour contribution (ROC) in sparkling wines.
Table 6. Odour activity values (OAV) and relative odour contribution (ROC) in sparkling wines.
ParametersVine-Growing Regions
Plašivica (n = 19)Zelina (n = 8)Krašić (n = 3)
OAVROC(%)OAVROC(%)OAVROC(%)
Aldehydes
2,4-Nonadienal18.885.17.772.25216.08
2-Heptenal46.7614.253.711.1533.139.61
Decanal12.853.527.618.28133.76
Hexanal40.7311.0686.7426.3827.337.92
Nonanal10.042.73.651.1117.475.06
∑ 36.61 39.17 32.43
Higher alcohols
1-Hexanol0.740.20.640.191.180.34
Isoamyl alcohol0.790.211.320.40.680.19
Phenyethyl alcohol0.690.181.120.340.570.16
∑ 0.59 0.93 0.69
Volatile phenols
4-Vinylguaicol2.850.770.710.216.41.85
Terpenes
Geraniol0.110.024.41.340.390.11
Hotrienol0.280.070.260.071.80.52
Linalool0.450.121.80.552.920.84
∑ 0.21 1.96 1.47
C13-norisoprenoides
β-Damascenone38.210.473.622.572.80.81
TDN1.270.31.940.590.270.07
∑ 10.7 23.16 0.88
Lactones
γ-Nonalacton0.30.0810.310.450.13
Esters
Ethyl butanoate13.53.420.856.3918.15.24
Ethyl hexanoate23.856.3937.1411.5431.079.16
Ethyl octanoate0.670.181.080.330.740.21
Ethyl-2-methylbutanoate1.690.460.520.150.650.18
Ethyl-3-methylbutanoate17.134.6620.336.436.671.93
Isoamyl aceatet14.532.9515.764.8320.135.83
Isoamyl lactate9024.5210.93.34122.535.36
∑ 42.56 33.01 57.91
Fatty acids
Decanoic acid2.40.620.790.241.70.49
Hexanoic acid16.664.430.750.230.590.17
Isovaleric acid0.210.050.090.020.450.13
Octanoic acid12.413.382.50.7613.293.85
∑ 8.48 1.25 4.64
Table
Table 7. Identification and quantification parameters for GC-MS analysis.
Table 7. Identification and quantification parameters for GC-MS analysis.
Parameters RT/minLRIQionIDChemical Standard
Aldehydes
2,4-Decadienal67.87183781S, MS, RISigma
2,4-Heptadienal (E,E)49,36151881S, MS, RISigma
2,4-Heptadienal (Z,Z)47.49148881S, MS, RISigma
2,4-Nonadienal61.83172881S, MS, RISigma
2-Heptenal38.01134441S, MS, RISigma
5-Hydroxymethylfurfural100.53252597S, MS, RISigma
5-Methyl-furfural54.471601110S, MS, RISigma
Benzeneacetaldehyde58.90167691S, MS, RISigma
Benzaldehyde51.541553106S, MS, RISigma
Decanal49.32151843S, MS, RISigma
Furfural47.70149296S, MS, RISigma
Heptanal28.29120144S, MS, RISigma
Hexanal21.27109744S, MS, RISigma
Nonanal42.53141257S, MS, RISigma
Higher alcohols
1-Butanol25.20155556S, MS, RISigma
1-Decanol64.67177955S, MS, RISigma
1-Heptanol46.33147170S, MS, RISigma
1-Hexanol39.61136841S, MS, RISigma
1-Methoxy-2-propanol24.03113845S, MS, RISigma
1-Octadecanol104.93260483S, MS, RISigma
1-Octanol52.77157356S, MS, RISigma
1-Pentanol32.50126342S, MS, RISigma
2-Heptanol37.20133245S, MS, RISigma
trans-2-Hexene-1-ol43.28142357S, MS, RISigma
cis-2-Hexene-1-ol41.76144657S, MS, RISigma
2-Methyl-1-butanol29.55122057S, MS, RISigma
2-Pentadecanol75.47198345S, MS, RISigma
2-Pentene-1-ol37.40133557S, MS, RISigma
cis-3-Hexene-1-ol41.76140541S, MS, RISigma
trans-3-Hexene-1-ol40.42138041S, MS, RISigma
3-Octanol42.19140759S, MS, RISigma
Isoamyl alcohol29.80122355S, MS, RISigma
Isobutanol21.66110243S, MS, RISigma
Phenylethyl alcohol71.53190791S, MS, RISigma
Volatile phenols
4-Ethylguaiacol79.53206685S, MS, RISigma
4-Ethylphenol86.582216107S, MS, RISigma
4-Vinylguaiacol87.462236150S, MS, RISigma
4-Vinylphenol96.412439120S, MS, RI.Sigma
Eugenol86.072205164S, MS, RISigma
Guaiacol70.931895124S, MS, RISigma
Homovanillyl alcohol116.112817137- S, MS, RISigma
Vanillin103.412577151S, MS, RISigma
Tyrosol97.962473107S, MS, RISigma
Terpenes
1,8-Terpin82.19212281S, MS, RISigma
6,7-Dihydro-7-hydroxylinalool75.92199271S, MS, RIBoc Science
8-Hidroxylinalool92.01233943S, MS, RIAurora Fine Chemicals
α-Terpineol61.39172059S, MS, RIExtrasynthese
β-Farnesen59.30168369S, MS, RIExtrasynthese
β-Ocimene62.74174493S, MS, RIExtrasynthese
cis-Linalool oxide, furan47.54148959S, MS, RIExtrasynthese
Citronelol65.03178569S, MS, RIExtrasynthese
δ-Carene37.71134093S, MS, RIExtrasynthese
Dihydroactinidiolide94.542398111S, MS, RIBoc Science
Farnesol93.73238069S, MS, RIExtrasynthese
γ-Terpinene32.29126093S, MS, RIExtrasynthese
Geraniol69.49186869S, MS, RIExtrasynthese
Geranyl acetate91.81233469S, MS, RIBoc Science
Hotrienol56.14162971S, MS, RIBoc Science
Linalool52.17156371S, MS, RIExtrasynthese
Linalool oxide, pyran63.76176268S, MS, RIBoc Science
Neric acid93.83238169S, MS, RIExtrasynthese
Nerol67.04182269S, MS, RIExtrasynthese
Nerolidol79.20205969S, MS, RIBoc Science
Pseudoionon83.10214158S, MS, RIBoc Science
Terpendiol I62.31173682MS
Terpendiol II74.54196567MS
Terpinene-4-ol55.87162471S, MS, RIExtrasynthese
Tetrahydrolinalool44.62144473S, MS, RIBoc Science
trans-Linalool oxide, furan45.67146059S, MS, RIExtrasynthese
trans-Rose oxide39.641368139S, MS, RISigma
Linalyl formate47.38148769S, MS, RIBoc Science
Ethyl linalyl acetal46.95148073S, MS, RIBoc Science
2,6-Dimethyl-3,7-octadiene-2,6-diol61.25171882S, MS, RIBoc Science
2,6-Dimethyl-7-octene-2,6-diol76.07199571S, MS, RIBoc Science
Menthol57.94166071S, MS, RISigma
Ocimenol58.50166993S, MS, RIExtrasynthese
C13- norisoprenoids
α-Ionol72.23192095S, MS, RISigma
α-Ionon70.001877121S, MS, RISigma
β-Damascenone68.46184869S, MS, RISigma
TDN64.431774157S, MS, RIBoc Science
Lactones
cis-Whiskey lactone75.95199391S, MS, RISigma
δ-Nonalactone87.43223599S, MS, RISigma
γ-Butyrolactone58.30166642S, MS, RISigma
γ-Decalactone85.06218385S, MS, RISigma
γ-Hexalactone62.40173885S, MS, RISigma
γ-Nonalacton79.55206785S, MS, RISigma
γ-Octalacton73.94195385S, MS, RISigma
γ-Undecalactone90.28229985S, MS, RISigma
trans-Whiskey lactone72.28192199S, MS, RISigma
Esters
2-Phenylethyl acetate68.281845105S, MS, RISigma
Diethyl glutarate65.931801143S, MS, RISigma
Methyl hydroxyisovalerate70.101879131S, MS, RISigma
Diethyl hydroxysuccinate97.002454101S, MS, RIBoc Science
Diethyl malonate54.351598115S, MS, RIBoc Science
Diethyl oxalate43.67142959S, MS, RISigma
Diethyl succinate60.091697101S, MS, RISigma
Dimethyl malate78.272040103S, MS, RISigma
Ethyl benzeneacetate66.64181491S, MS, RISigma
Ethyl butanoate18.32105371S, MS, RISigma
Ethyl decanoate57.48165288S, MS, RISigma
Ethyl furoate57.28164895S, MS, RISigma
Ethyl hexadecanoate88.91226888S, MS, RISigma
Ethyl hexanoate31.40124788S, MS, RISigma
Ethyl hydrogensuccinate96.702445101S, MS, RISigma
Ethyl lactate39.28136345S, MS, RISigma
Ethyl linoleate101.66264567S, MS, RISigma
Ethyl octanoate45.05144788S, MS, RISigma
Ethyl vanillate107.171425151S, MS, RISigma
Ethyl-2-hydroxy-3-methylbutanoate44.82106773S, MS, RISigma
Ethyl-2-hydroxybutanoate43.41129059S, MS, RIBoc Science
Ethyl-2-methylbutanoate19.29135057S, MS, RIBoc Science
Ethyl-2-oxopropanoate34.34154143S, MS, RISigma
Ethyl-3-ethoxypropanoate38.39135059S, MS, RIBoc Science
Ethyl-3-hydroxybutanoate50.79154143S, MS, RIBoc Science
Ethyl-3-hydroxyhexanoate72.001915117S, MS, RIBoc Science
Ethyl-3-methylbutanoate20.30108288S, MS, RISigma
Ethyl-hydroxyhexanoate52.19156369S, MS, RISigma
Ethylmethyl succinate57.801657115S, MS, RIMol Port
Hexyl acetate34.16128743S, MS, RISigma
Isoamyl acetate23.81113543S, MS, RISigma
Isoamyl lactate53.70158845S, MS, RISigma
Isobutyl acetate16.97103243S, MS, RISigma
Isobutyl lactate46.90147945S, MS, RISigma
Methyl hexadecanoate87.32223374S, MS, RISigma
Methyl hexanoate28.33120274S, MS, RISigma
Methyl octadecanoate96.36243874S, MS, RISigma
Methyl-2-furoate54.67160395S, MS, RISigma
Methyl-3-hydroxyoctanoate77.702029103S, MS, RIBoc Science
Methyl geranoate61.25171869S, MS, RIBoc Science
o-Methylbenzyl acetate92.952361104S, MS, RISigma
Phenyl acetate57.31164994S, MS, RISigma
Fatty acids
2-Methylpropionic acid54.73160443S, MS, RIMolPort
Butanoic acid58,56167160S, MS, RISigma
Decanoic acid90.90231360S, MS, RISigma
Heptanoic acid76.17199760S, MS, RISigma
Hexanoic acid70.25188260S, MS, RISigma
Isovaleric acid60.88171160S, MS, RISigma
Octanoic acid81.05209760S, MS, RISigma
Propanoic acid53.16157974S, MS, RISigma
Other alcohols
1,4-Butandiol73.70194942S, MS, RISigma
2,6-Dimethyl-4-heptanol52.26156569S, MS, RISigma
2-Butoxy-ethanol41.34139457S, MS, RISigma
2-Ethyl-1-hexanol48.54150557S, MS, RISigma
3,4-Dimethyl-2-hexanol35.48130645S, MS, RISigma
3-Ethoxy-1-propanol41.34139459S, MS, RISigma
3-Methyl-1-pentanol37.86134256S, MS, RISigma
3-Methyl-3-buten-1-ol32.63126541S, MS, RISigma
4-Ethylcyclohexanol49.37151881S, MS, RISigma
4-Methyl-1-pentanol37.00132956S, MS, RISigma
Benzylalcohol71.50190678S, MS, RISigma
Cyclohexanol41.95140343S, MS, RISigma
Furfuril alkohol59.56168898S, MS, RISigma
2,3-Butanediol51.90155945S, MS, RISigma
Sulfur compounds
4-(Methylthio)-1-butanol69.56186961S, MS, RISigma
3-(Methylthio)-1-propanol62.801745106S, MS, RISigma
Other compounds
2,5-Hexadione50.09153043S, MS, RISigma
2,7-Octanedione41.95140343S, MS, RIAurora Fine Chemicals
2H-Pyran-2,6(3H)-dione78.282040112S, MS, RIMolPort
2-Pentylfuran31.40124781S, MS, RISigma
3-Penten-2-on24.21114169S, MS, RISigma
4-Hydroxy-4-methyl-2-pentanone40.46138143S, MS, RISigma
4-Methyl-2-penten-2-one24.65114755S, MS, RISigma
5-Ethyl-4-methyl-3-heptanone26.19117057S, MS, RIAurora Fine Chemicals
Acetoin35.55130745S, MS, RISigma
Acetylfurane50.27153395S, MS, RISigma
Benzofurane66.161805118S, MS, RISigma
Dihydro-2-methyl-3(2H)-furanone63.07175043S, MS, RISigma
N-(2-phenylethyl)acetamide106.272629104S, MS, RISigma
N-Ethylacetamide57.77165743S, MS, RISigma
RT-retention time; LRI-linear retention indices; Qion-ion qualifier; ID: S-retention time and mass spectrum consistent with standard, RI—retention index consistent with those find in the literature, MS—mass spectra consistent with those find in NIST02 electronic library.

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Jagatić Korenika, A.-M.; Preiner, D.; Tomaz, I.; Jeromel, A. Volatile Profile Characterization of Croatian Commercial Sparkling Wines. Molecules 2020, 25, 4349. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25184349

AMA Style

Jagatić Korenika A-M, Preiner D, Tomaz I, Jeromel A. Volatile Profile Characterization of Croatian Commercial Sparkling Wines. Molecules. 2020; 25(18):4349. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25184349

Chicago/Turabian Style

Jagatić Korenika, Ana-Marija, Darko Preiner, Ivana Tomaz, and Ana Jeromel. 2020. "Volatile Profile Characterization of Croatian Commercial Sparkling Wines" Molecules 25, no. 18: 4349. https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25184349

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