Natural versus conventional production of Spanish white wines: an exploratory study.

BACKGROUND: Natural wine (NW) lacks an official or agreed definition, but it can be generally described as a wine produced with organic or biodynamic grapes with minimal intervention in the cellar, and with minimal or no use of oenological additives. The present study aimed to test the hypotheses that self-defined NWs differ from conventional wines (CW) in their chemical composition and main sensory characteristics. The levels of conventional oenological parameters, turbidity, biogenic amines, ochratoxin A, ethyl carbamate, sulphites, chlorides, some metals, major, trace and Strecker aldehyde volatile compounds were determined in 28 wines, including natural and conventional Spanish commercial white wines. Wines were also sensory described following a labelled free sorting task. RESULTS: NWs presented higher pH, volatile acidity (VA) and turbidity values, and a more intense yellow colour, whereas they have a lower malic acid content compared to theor conventional counterparts. NWs presented lower levels of total sulphur dioxide but significantly higher levels of biogenic amine putrescine, although both compounds are within the legal limits in all cases. None of the dimensions of the similarity space discriminated NWs from CWs. However, 70% of the NWs were grouped on the basis of various aromatic defects related to their higher content in 4-ethylphenols and VA. The remaining 30% were not differentiated from their conventional counterparts. CONCLUSION: It could be confirmed that NW can be globally differentiated from CW with respect to to their chemical and their sensory profiles, whereas the content in toxicants was not significantly different, with the exception of total sulphur dioxide and putrescine levels. © 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Aroma profiling of an aerated fermentation of natural grape must with selected yeast strains at pilot scale.

The use of non-Saccharomyces strains in aerated conditions has proven effective for alcohol content reduction in wine during lab-scale fermentation. The process has been scaled up to 20 L batches, in order to produce lower alcohol wines amenable to sensory analysis. Sequential instead of simultaneous inoculation was chosen to prevent oxygen exposure of Saccharomyces cerevisiae during fermentation, since previous results indicated that this would result in increased acetic acid production. In addition, an adaptation step was included to facilitate non-Saccharomyces implantation in natural must. Wines elaborated with Torulaspora delbrueckii or Metschnikowia pulcherrima in aerated conditions contained less alcohol than control wine (S. cerevisiae, non-aerated). Sensory and aroma analysis revealed that the quality of mixed fermentations was affected by the high levels of some yeast amino acid related byproducts, which suggests that further progress requires a careful selection of non-Saccharomyces strains and the use of specific N-nutrients.

Effect of low molecular weight phenols on the in-mouth sensory perception of high molecular weight phenols by analyzing reconstituted wines.

This research aimed to assess the contribution of monomeric phenols to the perception of bitterness and astringency by means of wine reconstitution experiments. Six wines with distinct total polyphenol indexes were selected and fractioned by preparative liquid chromatography into two fractions. Thirty-one reconstituted wines were prepared by combining distinct low molecular weight fractions (L) with different high molecular weight fractions (H). In-mouth attributes of reconstituted and reference wines were described by a trained sensory panel. Fractions were chemically characterized by UPLC-MS. No significant differences among sensory results were found between reference and reconstituted wines. Bitterness and astringency perception were strongly influenced by total proanthocyanidins content. Flavan-3-ol monomers and dimers were only responsible for astringency in wines with a low content of proanthocyanidins, as was the case in rosé wine. Quercetin-3-O-glucuronide and several anthocyanins presented correlations with bitterness in the reconstituted wines; notwithstanding, several interactions with this attribute were observed.

Attitudes towards natural wines among Spanish winemakers: Relationship with environmental awareness.

There is an important movement in the wine industry towards the production of alternative and more sustainable wines. Natural wine (NW) is a controversial category of alternative wines, which needs to be further explored. Given the role of technical experts as opinion leaders, the present work aims to explore the attitudes of Spanish winemakers towards NW and their relationship with their overall environmental awareness. Therefore, 307 Spanish winemakers completed a questionnaire to evaluate: (1) their attitudes towards NW by scoring their agreement with 31 statements, (2) their ecological awareness by evaluating 11 items, (3) their frequency of consumption and interest towards NW, and (4) their sociodemographic profile and general information about wine production. PCA with varimax rotation calculated on 28 of the 31 statements related to their attitudes showed six independent dimensions. Further hierarchical cluster analysis calculated with the six dimensions showed five clusters of wine experts with different attitudes towards NW. Results show that there is a major negative attitude towards the flavour of NW, their ageing capacity and their quality-price ratio, but a positive one in terms of economic impact for the wine industry. Aspects related to the role of NW in tradition, social identity, ecology, health, artisanal production and economic feasibility mark differential attitudes. Interestingly, the dimension related to winemakers attitude towards tradition, social identity, and ecology of NW was positively correlated with their overall ecological awareness and thus their life style. This paper sheds light in the understanding of the behaviour of Spanish winemakers regarding ecological transition and provides tools for policymaking regarding NW certification.

Determination of fungicide pyrimethanil in grapes, must, fermenting must and wine.

BACKGROUND: This study determined the evolution of pyrimethanil, a fungicide commonly used to control Botrytis cinerea, throughout the winemaking process in grapes, must, fermenting must and wine. Tempranillo grapevines were treated with pyrimethanil according to both good Agricultural Practices (GAP) and Critical Agricultural Practices (CAP). Fermentation was carried out in an experimental winery. Grape analysis was based on an ethyl acetate extraction method. Samples from fermentation were analysed by solid phase extraction. The determination was carried out by gas chromatography with nitrogen-phosphorus detection (GC-NPD) and additionally confirmed by gas chromatography/mass spectrometry (GC/MS). RESULTS: Pyrimethanil residues were at least ten times greater in grapes treated 7 days before harvest than in those treated respecting the safety period (21 days). The amount of pyrimethanil in grapes treated under GAP was below the maximum residue limit (5 mg kg(-1)). The level of pyrimethanil decreased during fermentation in both treatments. In the fermentation of grapes treated according to CAP, the pyrimethanil concentration was reduced by over 50% on the first day and then remained constant until the end of the fermentation process. For grapes treated in compliance with GAP, the amount of pyrimethanil decreased to a level below the limit of detection in the bottled wine. CONCLUSION: The described methods for grapes, must, fermenting must and wine gave good recoveries, linearity, precision and accuracy. They were also highly sensitive in avoiding matrix effects. Pyrimethanil residues found in treated grapes were higher in skin than in pulp. The amount of pyrimethanil decreased during fermentation by degradation and/or adsorption. For grapes treated according to GAP, residues disappeared in the final bottled wine. The decrease observed in the final bottled wine may be caused by diverse oenological practices and technologies such us malolactic fermentation, racking and settling.

Insights on the chemical basis of the astringency of Spanish red wines.

The main goal of the present study is to provide an insight on the role played by non-volatile molecules on the different in-mouth attributes, particularly astringency. For achieving such goal, the main in-mouth sensory attributes of 34 oaked Spanish red wines were measured by a trained panel. The wine content in 30 sensory-active molecules was analysed by different HPLC based methodologies together with classical enological parameters and two proanthocyanidin indexes. Fourteen compounds (aconitic acids, polymeric proanthocyanidins, caftaric, caffeic and coutaric acids and seven quercetins) were found to be at concentrations above reported taste thresholds and to have a reasonably high range of occurrence. Two highly statistically significant models for astringency were built with those compounds. Even if the models could not be fully validated by sensory addition experiments, the research has demonstrated that wine astringency is driven by polymeric proanthocyanidins and by certain phenolic acids, the rate trans/cis-aconitic acid and flavonol profiles. The research has highlighted the existence of extremely complex interactions between non-volatile compounds on the in-mouth sensory perception. Particularly remarkable is the lack of additivity and potential antagonism found between the pairs cis/trans-aconitic acids, between aconitic and caffeic acids and between quercetin-3-O-galactoside and quercetin-3-O-glucoside. Also remarkable was the sweetness×astringent interaction and the matrix-dependence of the sensory responses elicited by flavonols. These results suggest the need for new paradigms and experimental procedures for fully decoding the real sensory relevance of individual non-volatile compounds in the overall wine flavour.

Modeling grape taste and mouthfeel from chemical composition.

This research aims at predicting sensory properties generated by the phenolic fraction (PF) of grapes from chemical composition. Thirty-one grape extracts of different grape lots were obtained by maceration of grapes in hydroalcoholic solution; afterward they were submitted to solid phase extraction. The recovered PFs were reconstituted in a wine model. Subsequently the wine models, containing the PFs, were sensory (taste, mouthfeel) and chemically characterized. Significant sensory differences among the 31 PFs were identified. Sensory variables were predicted from chemical parameters by PLS-regression. Tannin activity and concentration along with mean degree of polymerization were found to be good predictors of dryness, while the concentration of large polymeric pigments seems to be involved in the "sticky" percept and flavonols in the "bitter" taste. Four fully validated PLS-models predicting sensory properties from chemical variables were obtained. Two out of the three sensory dimensions could be satisfactorily modeled. These results increase knowledge about grape properties and proposes the measurement of chemical variables to infer grape quality.

Role of Grape-Extractable Polyphenols in the Generation of Strecker Aldehydes and in the Instability of Polyfunctional Mercaptans during Model Wine Oxidation.

Polyphenolic fractions from Garnacha, Tempranillo, and Moristel grapes were reconstituted to form model wines of identical pH, ethanol, amino acid, metal, and varietal polyfunctional mercaptan (PFM) contents. Models were subjected to a forced oxidation procedure at 35 °C and to an equivalent treatment under strict anoxia. Polyphenolic profiles significantly determined oxygen consumption rates (5.6-13.6 mg L-1 day-1), Strecker aldehyde (SA) accumulation (ratios max/min around 2.5), and levels of PFMs remaining (ratio max/min between 1.93 and 4.53). By contrast, acetaldehyde accumulated in small amounts and homogeneously (11-15 mg L-1). Tempranillo samples, with highest delphinidin and prodelphinidins and smallest catechin, consume O2 faster but accumulate less SA and retain smallest amounts of PFMs under anoxic conditions. Overall, SA accumulation may be related to polyphenols, producing stable quinones. The ability to protect PFMs as disulfides may be negatively related to the increase in tannin activity, while pigmented tannins could be related to 4-methyl-4-mercaptopentanone decrease.

An assessment of voltammetry on disposable screen printed electrodes to predict wine chemical composition and oxygen consumption rates.

The present work aimed at determining the applicability of linear sweep voltammetry coupled to disposable carbon paste electrodes to predict chemical composition and wine oxygen consumption rates (OCR) by PLS-modeling of the voltammetric signal. Voltammetric signals were acquired in a set of 16 red commercial wines. Samples were extensively characterized including SO2, antioxidant indexes, metals and polyphenols measured by HPLC. Wine OCRs were calculated by measuring oxygen consumption under controlled oxidation conditions. PLS-Regression models were calculated to predict chemical variables and wine OCRs from first order difference voltammogram curves. A significant number of fully validated models predicting chemical variables from voltammetric signals were obtained. Interestingly, monomeric and polymerized anthocyanins can be differently predicted from the first and second wave of the first derivative of voltammograms, respectively. This fast, cheap and easy-to-use approach presents an important potential to be used in wineries for rapid wine chemical characterization.

Sensory variability associated with anthocyanic and tannic fractions isolated from red wines.

Tannins and anthocyanins are important modulators of the intrinsic quality of red wines, playing a major role in consumer preference and appreciation. Tannins are chiefly responsible for the astringency in wines although their role in eliciting different astringent subqualities is still relatively unknown. On the other hand, the sensory contribution of anthocyanic fractions is even less clear. The main aim of the present study was to assess whether anthocyanic fractions from red wine elicit specific mouthfeel and taste attributes that differ from their tannin counterparts, and to evaluate the contribution of anthocyanic and tannic fractions to taste and mouthfeel of red wines. Isolation of tannin (Ftannin) and anthocyanin (Fantho) fractions from 20 wines involved reversed-phase semipreparative liquid chromatography followed by solid phase extraction. The 40 derived fractions subsequently underwent sensory characterisation using a labelled sorting task and a rate-K attributes method. Bitterness and dryness were the salient attributes differing among the sensory spaces of both Fantho and Ftannin. Likewise, other independent and non-correlated mouthfeel dimensions differed for both Fantho ("grainy" and mouthcoating") and Ftannin ("gummy"). A significant linear model predicting wine dryness from the "dry" intensity of Fantho and Ftannin was obtained, with tannic fractions presenting a higher contribution than anthocyanic fractions. These results not only confirmed that tannins have a major implication in red wine dryness but also unequivocally demonstrated a relevant implication of certain anthocyanins in this attribute. In contrast, bitterness of the original wines could not be directly related to the bitterness perceived in any of the two groups of fractions. The addition of an extremely bitter anthocyanic fraction to wines only increased bitterness in certain wines, suggesting that bitterness in wines may result from perceptual interactions and that some wines contain strong bitterness suppressors.

Effect of aroma perception on taste and mouthfeel dimensions of red wines: Correlation of sensory and chemical measurements.

The present study was aimed at increasing the understanding of red wine mouthfeel by investigating the potential cross-modal effect of aroma and establishing relationships between sensory dimensions and chemical measurements. Investigations involved a set of 42 non-wooded red wines that were described with a novel application of a variant of the rate-all-that-apply sensory methodology ("rate-K attributes") by a group of Spanish wine experts under two conditions: (1) with no aroma perception (using nose clips) and (2) with aroma perception. In parallel, ethanol content, pH, titratable acidity, tannin activity, concentration of tannins, and spectroscopic measures of wines were determined. Results suggest that aroma does not play a main effect on taste or mouthfeel perception of red wines, except for oily mouthfeel, which was hypothesised to be masked by earthy aromas and enhanced by alcoholic nuances attributed to cognitive interactions. Independent and non-correlated mouthfeel dimensions such as dry/silky and sticky, grainy, prickly or oily were also identified. Tannin activity was shown to be highly positively correlated to dry on the palate, and tannin concentration with both overall dry and dry on the palate. A significant partial least squares regression model showed that tannin concentration and activity (positive contribution) as well as pH values (negative) were good predictors of the mouthfeel dimension mainly related to dry and sticky terms.

Some clues about the changes in wine aroma composition associated to the maturation of "neutral" grapes.

This paper presents a study of the influence of the harvesting date on concentrations of odorants in Moristel wines of two vintages. The wine made from grapes harvested early facilitated the accumulation of acetaldehyde (associated with low polyphenols concentrations) and higher concentrations of branched acids. A reason for these greater levels could be the lack of reduction factors (NADH or NADPH). Other changes with potential sensory consequences are the decrease of the branched acid/branched alcohol, branched ester/branched acid and branched ester/branched alcohol ratios that occurs as the grapes ripen. Besides, the variations of varietal or typical maturation markers did not have sensory importance. These results suggest that the characteristics of wines associated to the degree of maturity of grapes are mostly related to the changes in the profiles of fermentative compounds (especially acetaldehyde) induced by changes in the polyphenolic content and in the medium in which the yeast develops.

Formation and Accumulation of Acetaldehyde and Strecker Aldehydes during Red Wine Oxidation.

The main aim of the present work is to study the accumulation of acetaldehyde and Strecker aldehydes (isobutyraldehyde, 2-methylbutanal, isovaleraldehyde, methional, phenylacetaldehyde) during the oxidation of red wines, and to relate the patterns of accumulation to the wine chemical composition. For that, eight different wines, extensively chemically characterized, were subjected at 25°C to three different controlled O2 exposure conditions: low (10 mg L-1) and medium or high (the stoichiometrically required amount to oxidize all wine total SO2 plus 18 or 32 mg L-1, respectively). Levels of volatile aldehydes and carbonyls were then determined and processed by different statistical techniques. Results showed that young wines (<2 years-old bottled wines) hardly accumulate any acetaldehyde regardless of the O2 consumed. In contrast, aged wines (>3 years-old bottled wines) accumulated acetaldehyde while their content in SO2 was not null, and the aged wine containing lowest polyphenols accumulated it throughout the whole process. Models suggest that the ability of a wine to accumulate acetaldehyde is positively related to its content in combined SO2, in epigallocatechin and to the mean degree of polymerization, and negatively to its content in Aldehyde Reactive Polyphenols (ARPs) which, attending to our models, are anthocyanins and small tannins. The accumulation of Strecker aldehydes is directly proportional to the wine content in the amino acid precursor, being the proportionality factor much higher for aged wines, except for phenylacetaldehyde, for which the opposite pattern was observed. Models suggest that non-aromatic Strecker aldehydes share with acetaldehyde a strong affinity toward ARPs and that the specific pattern of phenylacetaldehyde is likely due to a much reduced reactivity toward ARPs, to the possibility that diacetyl induces Strecker degradation of phenyl alanine and to the potential higher reactivity of this amino acid to some quinones derived from catechin. All this makes that this aldehyde accumulates with intensity, particularly in young wines, shortly after wine SO2 is depleted.

Chemo-sensory approach for the identification of chemical compounds driving green character in red wines.

The present work seeks to define the "green character" of red wines and characterise the groups of molecules potentially involved in that perception. Fifty-four wines were screened by wine experts for different levels of green character. Six different phenolic fractions were obtained by liquid chromatography (LC) and further submitted to sensory and chemical characterisation. The volatile fraction was screened by semipreparative LC, Gas Chromatography-Olfactometry (GC-O) and quantitative analysis. The green character was linked to vegetal aroma, astringency, green and dry tannins according to experts of the Somontano region. Non-volatile fractions containing tannins with mean degree of polymerisation of ten and smaller anthocyanin-derivative pigments (

The kinetics of oxygen and SO2 consumption by red wines. What do they tell about oxidation mechanisms and about changes in wine composition?

This work seeks to understand the kinetics of O2 and SO2 consumption of air-saturated red wine as a function of its chemical composition, and to describe the chemical changes suffered during the process in relation to the kinetics. Oxygen Consumption Rates (OCRs) are faster with higher copper and epigallocatechin contents and with higher absorbance at 620nm and slower with higher levels of gallic acid and catechin terminal units in tannins. Acetaldehyde Reactive Polyphenols (ARPs) may be key elements determining OCRs. It is confirmed that SO2 is poorly consumed in the first saturation. Phenylalanine, methionine and maybe, cysteine, seem to be consumed instead. A low SO2 consumption is favoured by low levels of SO2, by a low availability of free SO2 caused by a high anthocyanin/tannin ratio, and by a polyphenolic profile poor in epigallocatechin and rich in catechin-rich tannins. Wines consuming SO2 efficiently consume more epigallocatechin, prodelphinidins and procyanidins.

Oxygen and SO2 Consumption Rates in White and Rosé Wines: Relationship with and Effects on Wine Chemical Composition.

This Article addresses the study of O2 and SO2 consumption rates of white and rosé wines, their relationship to the initial chemical composition, and their effects on the chemical changes experienced by wine during oxidation. Eight wines were subjected to five consecutive air-saturation cycles. O2 was monitored periodically; SO2, color, and antioxidant indexes were determined after each cycle, and the initial and final compositions of the wines were thoroughly determined. Wines consumed oxygen at progressively decreasing rates. In the last cycles, after a strong decrease, consistent increases of oxygen levels were seen. Oxygen consumption rates were satisfactorily modeled, being proportional to wine copper, quercetin, and kaempherol contents and negatively proportional to cinnamic acids. SO2 consumption rates were highly diverse between wines and were positively related to free SO2, Mn, and pH, among others. In the last saturations, SO2 consumption took place regardless of O2 consumption, implying that SO2 should reduce chemical species oxidized in previous saturations. Some volatile phenols seem to be the end point of radical-mediated oxidation of polyphenols taking place preferably in the first saturation.

Sensory and chemical drivers of wine minerality aroma: An application to Chablis wines.

The goal of this work was to evaluate the effect of vineyard position on the minerality of wines and to establish relationships between minerality scores, sensory descriptors and chemical composition. Sensory analyses included minerality rating and free description performed by wine professionals under two conditions: orthonasal olfaction alone and global tasting. Chemical characterization included analysis of major and minor volatile compounds, volatile sulphur compounds, mercaptans, metals, anions and cations. Results showed a significant effect of the river bank on wine minerality scores only in the orthonasal olfaction condition, samples from the left being more mineral than those from the right bank. Methanethiol, involved in shellfish aroma, was significantly higher in wines from the left (more mineral) than from the right bank. Contrary, copper levels, related to lower levels of free MeSH, and norisoprenoids, responsible for white fruit and floral aromas, were higher in wines from the right bank (less mineral).

Evaluation of the impact of initial red wine composition on changes in color and anthocyanin content during bottle storage.

Sixteen commercial red wines, selected to cover a different range of color and total polyphenols index (TPI), were stored at 25°C during 6months under controlled and different oxygen additions (0, 1.1, 3.1, 10.6 and 30.4mgL(-1)) during the bottling process. Changes in color and the anthocyanic composition were evaluated using transmittance spectra and UPLC-MS-UV/Vis respectively. Results reveal a general pattern in the evolution of wines. However, different patterns of evolution related to initial wine composition, especially to TPI, were observed. Wines with higher TPI had a lower evolution, whereas wines with lower TPI showed a higher evolution and greater variability in behavior. In general, oxygen seemed to accelerate all changes observed during aging although the oxygen effect was more limited than the effect of the storage time. These results are relevant for wine experts and help explain the evolution of wine at the bottling stage.

Sensory interactions between six common aroma vectors explain four main red wine aroma nuances.

This work aims at assessing the aromatic sensory dimensions linked to 6 common wine aroma vectors (N, norisoprenoids; A, branched acids; F, enolones; E, branched ethyl esters; L, fusel alcohols, M, wood compounds) varying in their natural range of occurrence. Wine models were built by adding the vectors at two levels (fractional factorial design 2(VI)) to a de-aromatised aged red wine. Twenty other different models were evaluated by descriptive analysis. Red, black and dried fruits and woody notes were satisfactorily reproduced. Individual vectors explained just 15% of the sensory space, mostly dependent on perceptual interactions. N influences dried and black fruits and suppresses red fruits. A suppresses black fruits and enhances red and dried fruits. F exerts a major role on red fruits. E suppresses dried fruits and modulates black fruits. L is revealed as a strong suppressor of red fruits and particularly of woody notes.

Oxygen Consumption by Red Wines. Part II: Differential Effects on Color and Chemical Composition Caused by Oxygen Taken in Different Sulfur Dioxide-Related Oxidation Contexts.

Chemical changes caused by oxidation of red wines during 5 consecutive air-saturation cycles have been assessed. In order to investigate the existing relationship between the effects caused by O2 and the levels and consumption rates of wine SO2, the total oxygen consumed by the wines (16-25 mg/L) was subdivided into different nonmutually exclusive categories. The ones found most influential on chemical changes were the O2 consumed in the first saturation without equivalent SO2 consumption (O2preSO2) and the O2 consumed when levels of free SO2 were below 5 mg/L (radical forming O2). Chromatic changes were strongly related to both O2 categories, even though anthocyanidin degradation was not related to any O2 category. Radical forming O2 prevented both formation of red pigments and reduction of epigallocatechin and other proanthocyanidins, induced accumulation of phenolic acids, and caused losses of ß-damascenone and whiskylactone without evidence of acetaldehyde formation. O2preSO2 seemed to play a key role in the formation of blue pigments and in the decrease of Folin index and of many important aroma compounds.