Chemical and Aromatic Characteristics of Brazilian Tropical Wines G.E. Pereira a, A.J.B. Araújo, J. Santos, de O., V. Oliveira, S., R.L. Nascimento and C. Quintino Embrapa Uva e Vinho/ Semi-árido BR 428 Km 152, CP 23. CEP. 56.302-970 Petrolina PE Brazil R. Vanderlinde Universidade de Caxias do Sul, Rua Francisco Getúlio Vargas, 1130 CEP 95070-560 Caxias do Sul RS Brazil L.L.A. Lima Universidade Federal Rural de Pernambuco Universidade Federal Rural de Pernambuco UFRPE, Rua Dom Manoel de Medeiros, s/n Dois Irmãos CEP: 52171-900 Recife Brazil Keywords: Vitis vinifera L., grape, wine, chemical compounds, esters, higher alcohol, PCA Abstract Traditional winegrowing areas are located in temperate climate zones and allow to produce grapes only once per year. Tropical wines have been elaborated in India, Thailand, Venezuela and Brazil and present another kind of viticulture, as compared with countries located in temperate climate zones. Northeast of Brazil started wine production twenty six years ago. This region vines can produce two or three crops per year, depending of the cycle of different cultivars. Harvests can be scaled throughout the year, mainly between May and December, corresponding to the dry season. Red, white, rosé and sparkling wines are being elaborated in the region. The objective of this work was to determine the physico-chemical and aromatic characteristics of some tropical wines elaborated in Northeast of Brazil, with grapes harvested in November 2008. Wines were elaborated using traditional method with control of the alcoholic and malolactic fermentation temperatures, at 25 and 18ºC for red wines, respectively, and at 18ºC for alcoholic fermentation of the white wines. After stabilization and bottling and wines were analyzed to determine physico-chemical characteristics, like alcohol degree, ph, total and volatile acidities, dry extract, sulfur dioxide, total anthocyanin and total phenol index. Aromatic profile was determined by gas chromatography, while 19 esters and 6 superior alcohols were identified. Wines presented different chemical and aromatic characteristics according to different grape cultivars. INTRODUCTION Traditional wines located in temperate climate zones are elaborated in Europe, North and South Americas, South Africa and Oceania, being possible to have one harvest per year, because low temperatures in winter (Reynier, 2003). In Brazil, about 85% of total wines produced are from grapes of Vitis labrusca cultivars, corresponding to 300 million liters per year, and only 15% are from grapes of Vitis vinifera L. cultivars, with about 40 million liters per year. The new Brazilian vitiviniculture zone where tropical wines have been produced is located between 8 o and 9 o latitude of South Hemisphere and it s referred to as the Lowermiddle São Francisco river Valley, in Northeast of Brazil. The activity has been developed since the 1980 s, presenting a semi-arid climate with an intra-annual variability (Tonietto and Teixeira, 2004). Wines are elaborated only using grapes of Vitis vinifera L. cultivars, producing about 7 million wine liters in average per year from two harvests. The main climate characteristics of the region present an annual average temperature of 26.4ºC (21.0ºC for minimum and 31.7ºC for maximum temperatures), it is a gpereira@cpatsa.embrapa.br Proc. II nd IS on Tropical Wines Eds.: G.E. Pereira and J. Tonietto Acta Hort. 910, ISHS 2011 135
located at 350 m above of sea level, in a flat landscape (Teixeira and Azevedo, 1996; Teixeira, 2001). The rainy season occurs from December to March, with about 567 mm of normal rainfall. The heliotermical availability (about 3000 hours of luminosity.year -1 ) allows a continuous vegetative development, by using drip irrigation with water from the São Francisco river, and grape cropping is done throughout the year. Wineries normally scaled harvests between eight months, corresponding to the dry season (May to December). The soils are primarily classified as Latosols, with variations in depth and in physical and chemical characteristics. Some works were carried out to evaluate different irrigation levels on vine development (Bassoi et al., 2007), physiological behaviour among irrigation strategies (Dantas et al., 2007), rootstock used and harvest date effects on grape and wine composition (Pereira et al., 2007, 2008a,b; Silva Neto et al., 2009; Araújo et al., 2010). Some volatile compounds in wines are higher alcohols, like 1-propanol, 2-methyl- 1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol and the 2-methylethanol (Boulton et al., 1996). The fruity aroma in wines normally are reported to the volatile esters (Ebeler, 2001). Red fruit notes are formed by the 2,3-butanodione, methyl vanilate and β-ionone. The acetate of isoamyle and acetate of 2-phenylethyl are reported to citric and peach aroma. Grape notes are originated from the ethylic esters of the 3-methylbutiric, 2-methyl butyric and 2-methylpropanoic acids, and β-ionone, 3-hydroxi-2-butanone (Aznar et al., 2003). Brazilian tropical wines have been elaborated by using grapes of Syrah, Tempranillo, Cabernet Sauvignon, Ruby Cabernet and Petit Verdot, for reds, and Chenin blanc, Moscato Canelli and Sauvignon blanc for whites. For sparkling wines the cultivars are Muscat Italia (sweet), Chenin blanc and Sauvignon blanc (for white sparkling) and Syrah and Grenache (rosé sparkling wines). The aim of this work was to determine some chemical and aromatic characteristics about white and red tropical wines, elaborated in November of 2008. MATERIAL AND METHODS Grapes of the cultivars Syrah, Tempranillo, Petit Verdot, Chenin Blanc, Sauvignon Blanc, Viognier and Verdejo were harvested in November 2008 at optimal maturity. Wines were elaborated by traditional methods (Peynaud, 1997). Red wines were elaborated at 25ºC during alcoholic fermentation and at 18ºC for malolactic fermentation. White wines were elaborated at 18ºC during the alcoholic fermentation. After stabilization and bottling, wines were analyzed to determine alcohol degree, ph, total and volative acidity, total and free SO 2, total anthocyanins, polyphenols (Harbertson and Spayd, 2006; OIV, 1990; AOAC, 1990), and aroma compounds. Determination of the 25 compounds, while higher alcohols and esters, were carried out by simultaneously gas chromatography with flame ionization detector (GC-FID) (Bertrand, 1981). Principal component analysis was applied to discriminate between wines and to explain the variability (Pereira, 2005; Kemsley, 1998). RESULTS AND DISCUSSION Forty-two chromatograms were obtained of wines elaborated from six grape cultivars, twenty-one of each compound group, alcohols and esters. An example of a chromatogram obtained of a red wine is showed (Fig. 1). Wines were discriminated according to the chemical composition (data not shown) and aromatic profile. PCA was applied on the aromatic compound results, and wine samples were segmented in different groups according to the aroma profile. Higher alcohols allowed to discriminated between red and white wines. PC1 x PC2 plots explained 74.7% of total variability, that separated clearly red from white wines (Fig. 2). In the positive side of PC1 white wines are located and in the negative side there are the red wines. In the positive side of the PC1 and PC2, are located wines elaborated with grapes from Viognier and Verdejo. The compounds responsible to characterize these wines was identified as 3-methyl-1-butanol. In the positive side of PC2 and in the 136
negative side of PC1, wines of Tempranillo and Syrah were separated, and compounds were identified as 2-methyl-1-butanol. In the negative side of PC1 and PC2, wines of Petit Verdot were separated and compound responsible by this wines were methanol and 1-propanol. Finally, Chenin blanc and Sauvignon blanc wines were placed in the positive side of PC1 and in the negative side of PC2, and the compound characterizing Chenin was 2-methyl-1-propanol, while Sauvignon blanc was marked by ethanal and ethyl acetate. Volatile esters also separated very well red from white wines, but response was different as compared to the higher alcohols, because some white wines were similar. PC1 x PC2 plots explained 81.6% of total variability (Fig. 3). In the positive side of PC1 white wines are located and in the negative side there are the red wines. In the positive side of the PC2 and close to zero in PC1, are located wines elaborated with Sauvignon blanc grapes. The compounds responsible to characterize these wines were hexanol, cis-3- hexen-1-ol, ethyl dodecanoate and trans-3-hexen-1-ol. In the positive side of PC2 and in the negative side of PC1, wines of Petit Verdot were separated, and compound was identified as isovaleric acid. In the negative side of PC1 and PC2, wines of Tempranillo and Syrah were placed together, and compound responsible by this wines were identified as 2-phenylethanol and octanoic acid. Finally, Chenin blanc, Verdejo and Viognier wines were placed in the positive side of PC1 and in the negative side of PC2, and the compounds were identified as ethyl decanoate, lauric, butiric and octanoic acids, hexyl acetate, ethyl octanoate, ethyl hexanoate, acetate of isoamyle and ethyl butyrate. This is the first work characterizing aroma profiles of tropical wines elaborated in Northeast of Brazil. These profiles were obtained from wines elaborated in November. Other works need to be carried out to evaluate the influence of the month of the year on the wine characteristics and aroma profile of these wines. Climate conditions in the region change strongly according to the month, and have an important role on the chemical characteristics of the wines, as well as the genetic influence of each cultivar on wine aroma compounds (Ribereau-Gayon et al., 2004; Reynier, 2003; Pisamitskii, 2001; Schreier, 1979). CONCLUSIONS White and red tropical wines elaborated in Northeast of Brazil in November 2009 presented different aromatic profile. Twenty-five higher alcohols and volatile esters were identified and were very able to discriminate wine types using multivariate statistical analysis. ACKNOWLEDGEMENTS The authors thanks the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Fundação de Amparo à Pesquisa de Pernambuco (Facepe) for their financial support, and the Miolo Wine Group for the grapes. Literature Cited Araújo, A.J. de B., Vanderlinde, R., Lima, L.L. de A. and Pereira, G.E. 2010. Détermination des caractéristiques aromatiques de vins tropicaux Syrah et Tempranillo élaborés au Nord-est du Brésil. In: International Terroir Congress, 8., Soave, Proceedings. 28-33. Aznar, M., López, R., Cacho, J. and Ferreira, V. 2003. Prediction of aged red wine aroma properties from aroma chemical composition. Partial least square regression models. Journal of Agricultural and Food Chemistry 51:2700-2707. Bassoi, L.H., Dantas, B.F., Lima Filho, J.M.P., Lima, M.A.C., Leão, P.C.S., Silva, D.J., Maia, J.L.T., Souza, C.R., Silva, J.A.M. and Ramos, M.M. 2007. Preliminary results of a long term experiment about RDI and PRD irrigation strategies in wine grape in São Francisco Valley, Brazil. Acta Hort. 754:275-282. Boulton, R.B., Singleton, V.L., Bisson, V.F. and Kunkee, R.E. 1996. Principles and practices of winemaking. Chapman and Hall: New York, 604. 137
Dantas, B.F., Ribeiro, L.S., Luz, S.R.S., Lima Filho, J.M.P., Lima, M.A.C., Souza, C.R. and Bassoi, L.H. 2007. Foliar Carbohydrate Content and Invertase Activity of Syrah and Moscato Canelli Vines Subjected to Partial Rootzone Drying and Regulated Deficit Irrigation. Acta Hort. 754:301-308. Ebeler, S.E. 2001. Analytical chemistry: unlocking the secrets of wine flavor. Food Reviews International (17)1:45-64. Pereira, G.E., Soares, J.M., Alencar, Y.C.L., Guerra, C.C., Lira, M.M.P., Lima, M.V.D. de and Santos, J. de O. 2007. Rootstock effects on quality of wines produced under tropical climate in Northest Brazil. In Proceedings of the XV International Symposium Gesco, Porec, Croatia, 378-383. Pereira, G.E., Santos, J. de O., Guerra, C.C. and Alves, L.A. 2008a. Evaluation of grape and wine quality according to harvest date, in a tropical region in Northeast Brazil. In Proceedings of the VII Congrès International des Terroirs Viticoles, 19-23/05/, Nyon- Switzerland. Pereira, G.E. and Guerra, C.C. 2008b. Estimation of phenolic compounds in tropical red wines elaborated in Northeast Brazil. In: Proceedings of the 8th International Symposium on Grapevine Physiology and Biotechnology, 23-27/11/, Adelaide- Australia. Peynaud, E. 1997. Connaissance et travail du vin. Ed. Dunod, Paris, 341. Pisamitskii, A.F. 2001. Formation of wine aroma: tones and imperfections caused by minor components (review). Applied Biochemistry and Microbiology 37(6):651-659. Reynier, A. 2003. Manuel de viticulture, Tec & Doc, Lavoisier, 548p. Schreier, P. 1979. Flavor Composition of Wines: A Review. Critical Reviews in Food Science and Nutrition (11) 2:59-111. Silva Neto, H.G. da, Silva, J.B.P. da, Pereira, G.E. and Hallwass, F. 2009. Determination of metabolite profiles in tropical wines by 1H NMR spectroscopy and chemometrics. Magnetic Resonance in Chemistry, Malden, 47(1):127-129. Teixeira, A.H.C. and Azevedo, P.V. 1996. Zoneamento agroclimático para a videira européia (Vitis vinifera L.) no Estado de Pernambuco, Brasil. Revista Brasileira de Agrometeorologia, Santa Maria (4)1:139-145. Teixeira, A.H.C. 2001. Informações agrometeorológicas do Pólo Petrolina-PE/Juazeiro- BA. Petrolina: Embrapa Semi-Árido. 46p. (Embrapa Semi-Árido. Documentos, 168). Tonietto, J. and Teixeira, A.H.C. 2004. Zonage climatique dês périodes viticoles de production dans I année em zonage tropicale: application de la méthodologie du Systéme CCM Géoviticole. In: Joint International Conference on Viticultural Zoning, Cape Town, South Africa [S.I.: s.n.].193-201. 138
Figures Fig. 1. Chromatogram obtained of the esters from Syrah wines elaborated in Northeast of Brazil, in November 2008, by gas chromatography with flame ionization detector (GC-FID). Nineteen compounds were identified: (1) Ethyl butyrate; (2) Acetate of isoamyle; (3) Ethyl hexanoate; (4) Hexyl acetate; (5) Hexanol; (6) Cis-3-hexen-1- ol; (7) Trans-3-hexen-1-ol; (8) Ethyl octanoate; (9) Isobutiric acid; (10) Butiric acid; (11) Ethyl decanoate; (12) Isovaleric acid; (13) Dietil succinate; (14) Fenilethyl acetate; (15) Ethyl dodecanoate; (16) Octanoic acid; (17) Decanoic acid; (18) Lauric acid; (19) 2-feniletanol. 3 2 PC2 25.4 % 1 0-3 -2-1 0 1 2 CB 3 VE -1 SB VI -2 PV SY PC 1 49.3 % -3 Fig. 2. Scores plot of 21 samples of white and red wines from grapes harvested in November 2009, in the Northeast of Brazil, according to the higher alcohol aroma profile. CB: Chenin blanc; VE: Verdejo; SB: Sauvignon blanc; VI: Viognier; PV: Petit Verdot; SY: Syrah; and TE: Tempranillo wines. PC1 x PC2 explained 74.7% of the total variability. TE 139
4 3 CB VE SB PC2 19.8 % 2 1 VI PV SY TE 0-6 -4-2 0 2 4 6 8-1 -2-3 PC1 61.8 % Fig. 3. Scores plot of 21 samples of white and red wines from grapes harvested in November 2009, in the Northeast of Brazil, according to the volatile esters aroma profile. CB: Chenin blanc; VE: Verdejo; SB: Sauvignon blanc; VI: Viognier; PV: Petit Verdot; SY: Syrah; and TE: Tempranillo wines. PC1 x PC2 explained 81.6% of the total variability. 140