1. OBJETIVOS, ANTECEDENTES E HIPÓTESIS DE TRABAJO
2.4 ESTUDIOS DEL VINO
2.4.3 CARACTERIZACIÓN AROMÁTICA DEL VINO DETECCIÓN
La Cromatografía de gases acoplada a Olfatometría (GC-O) o “sniffing” es la técnica analítica capaz de correlacionar el análisis sensorial con el instrumental. Los compuestos aromáticos, una vez separados y eludidos en una columna de cromatografía de gases, se huelen (esnifan) a través de un puerto olfatorio. Gracias a esta herramienta, las respuestas humanas y electrónicas se combinan para maximizar las capacidades de detección posibles (Mayol & Acree, 2001). Debido a la mayor parte de los compuestos volatiles se encuentran en concentraciones cercanas o incluso inferiors a los umbrales de detección humana, hace dificil establecer la contribución de cada compuesto al aroma final de un vino. Debida a esta complejidad, es muy adecuado y de gran utilidad para entender el aroma del vino, realizar análisis de GC-O; ayudándonos a establecer cuales son los compuestos volátiles más importantes (Gómez-Míguez et al., 2007), permitiendo establecer el perfil aromático del vino durante las diferentes fases de su elaboración y detectar, en el caso de que sufra alguna alteración organoléptica, cuales son los compuestos alterados responsables del cambio aromático (Aleixandre, 2006). En términos generales, el principal objetivo de los análisis de GC-O es listar y clasificar los compuestos aromáticos presentes en un vino a estudiar de acuerdo a su potencial importancia dentro todo su aroma (Ferreira & Cacho, 2009). El método se optimiza con la introducción del factor de dilución y la evaluación de series de diluciones de la muestra. Las técnicas de dilución más empleadas son el análisis Charm y el AEDA (Aroma Extract Dilution Analysis). (Acree et al., 1984; Schieberle & Grosch, 1987; Ullrich & Grosch, 1987).
La técnica de GC-O ha sido ampliamente utilizada durante los últimos años aportando información sobre el impacto e importancia de muchos compuestos individuales y familias de compuestos volatiles en los diferentes tipos de vinos. Estudios relevantes utilizando esta técnica han sido por ejemplo los publicados por Aznar et al., 2001; Ferreira et al., 2001; Gürbüz et al., 2006; Escudero et al., 2007; Bailly et al., 2009 y Ferreira et al., 2009. Aunque esta técnica tiene una serie de limitaciones como son la falta de sensibilidad para aquellos compuestos cuyo umbral de percepción es menor que el de detección, la discriminación de compuestos durante la extracción y concentración, y la incapacidad de interpreter los efectos
de sinergia y antagonismo que se pueden producir entre diferentes compuestos aromáticos presenets en el vino (Aleixandre, 2006).
2.5 REFERENCIAS
Acree, T.E., Barnard, J. & Cunningham, D.G. (1984). A procedure for the sensory analysis of gas chromatographic effluents. Food Chemistry, 14, 273-286.
Aleixandre, J.L. & Álvarez, I. (2003). Tecnología Enológica. Madrid: Síntesis Ed. 4.5. El sulfitado (pp. 127-137).
Aleixandre, J.L. (2006). La Cultura del Vino. Cata y Degustación. Valencia: Universidad Politécnica de Valencia Ed. 3. Técnicas de Cata de vinos (pp. 45-65).
Atienza J., Esteve, M.D., Aragón, P. & Climent, M.D. (1999). La espectrometría de masas y el aroma del vino. Universidad Politécnica de Valencia, Valencia: L.A.V, S.L. Ed.
Aubry, V., Etievant, P., Sauvageot, F. & Issanchou, S. (2007). Sensory analysis of Burgundy Pinot Noir wines: A comparison of orthonasal and retronasal profiling.
Journal of Sensory Studies, 14, 97-117.
Aznar, M., López, R., Cacho, J.F. & Ferreira, V. (2001). Identification and quantification of impact odorants of aged red wines from Rioja. GC-olfactometry, quantitative GC-MS, and odor evaluation of HPLC fractions. Journal of Agricicultural and Food Chemistry,
49, 2924-2929.
Bailly, S., Jerkovic, V., Meurée, A., Timmermans, A. & Collin, S. (2009). Fate of key odorants in Sauternes wines through aging. Journal of Agricultural and Food Chemistry,
57, 8557-8563.
Barril, C., Clark, A. C., Prenzler, P. D., Karuso, P., & Scollary, G. R. (2009). Formation of pigment precursor (+)-1-methylene-6-hydroxy-2H-furan-5-one-catechin isomers from (+)-catechin and a degradation product of ascorbic acid in a model wine system. Journal
of Agricultural and Food Chemistry, 57, 9539–9546.
Boulton, R.B. (2003). A radical view of oxidative reactions in wine. In IX Congreso
latinoamericano de viticultura y enología. Pszczólkowski, P. (Ed.). Pontificia
Bradshaw, M. P., Prenzler, P. D., & Scollary, G. R. (2001). Ascorbic acid induced browning of (+)-catechin in a model wine system. Journal of Agricultural and Food
Chemistry, 49, 934-939.
Bradshaw, M. P., Prenzler, P. D., Scollary, G. R., & Cheynier, V. (2003). Defining the ascorbic acid crossover from anti-oxidant to pro-oxidant in a model wine matrix containing (+)-catechin. Journal of Agricultural and Food Chemistry, 51, 4126–4132. Buck L.B. (1991). A novel multigene family may encode odorant receptors: a molecular
basis for odor recognition. Cell, 65, 175-187.
Buck L.B. (2004). The search for odorant receptors. Cell, 116, 117-119.
Cacho, J. (2004). El reto del análisis del aroma de los vinos. Boletín de la Sociedad
Española de Química Analítica 9, 6-11.
Cacho J. (2006a) El aroma de los vinos: retos y soluciones del análisis sensorial. ACE
Revista de Enología, 66.
Cacho J. (2006b) La percepción de notas aromáticas del vino y el efecto de ciertas moléculas volátiles. ACE Revista de Enología, 66.
Cacho J. (2006c) Estudio comparativo del perfil volátil del vino tinto durante su crianza en barricas de roble. ACE Revista de Enología, 76.
Camara, J.S., Marques, J.C., Alves, M.A., and Ferreira, A.C.S. (2004). 3-hydroxy-4,5- dimethyl-2(5H)-furanone levels in fortified Madeira wines, Relationship to sugar content.
Journal of Agricultural and Food Chemistry, 52, 6765–6769.
Carrascosa, A.V., Muñoz, R. & González, R. (2005). Microbiología del vino. Madrid: AMV Ed. (pp. 19-56).
Casal del Rey, J. (2001). Análisis sensorial y cata de los vinos de España. Unión Española de Catdores. Madrid: Agrícola Española Ed.
Chapman, D.M., Thorngate, J.H., Matthews, M.A., Guinard, J.X. & Ebeler, S.E. (2004). Yield effects on 2-methoxy-3-isobutylpyrazine concentration in Cabernet Sauvignon using a solid phase microextraction gas chromatography/mass spectrometry method.
Journal of Agricultural and Food Chemistry, 52, 5431–5435.
Culleré, L., Cacho, J., & Ferreira, V. (2004). Analysis for wine C5-C8 aldehydes through the determination of their O-(2,3,4,5,6-pentafluorobenzyl)oximes formed directly in the solid phase extraction cartridge. Analytica Chimica Acta, 524, 201-206.
Danilewicz, J. C. (2003). Review of reaction mechanisms of oxygen and proposed intermediate reduction products in wine: Central role of iron and copper. American
Journal of Enology and Viticulture, 54, 73–85.
Danilewicz, J.D. (2007). Interactions of sulfur dioxide, polyphenols and oxygen in a wine-model system: Central role of iron and cooper. American Journal of Enology and Viticulture, 58, 53-60.
Danilewicz, J. C., Seccombe, J. T., & Whelan, J. (2008). Mechanism of interaction of polyphenols, oxygen, and sulfur dioxide in model wine and wine. American Journal of
Enology and Viticulture, 59, 128–136.
DeVilliers, A., Alberts, P., Tredoux, A.G.J. & Nieuwoudt, H.H. (2011). Analytical techniques for wine analysis: An African perspective. Analytica Chimica Acta. (Online 21 Diciembre 2011).
Delteil, D. (2003). Enological yeast effect on the SO2 content and management in wines. En: Beverages, Fermentation and Health. San Francisco: Lallemand, (capítulo 4).
Duffy, V.B., Cain, W.S. & Ferris, A.M. (1999). Measurement of sensitivity to olfactory flavor: application in a study of aging and dentures. Chemical Senses, 24, 671-677. Elias, R. J., Andersen, & Waterhouse, A. L. (2010). Controlling the Fenton reaction in
wine. Journal of Agricultural and Food Chemistry, 58, 1699–1707.
Escudero, A., Cacho, J. & Ferreira, V. (2000). Isolation and identification of odorants generated in wine during its oxidation: a gas chromatography-olfactometric study.
Eurpean Food Research and Technology, 211, 105-110.
Escudero, A., Asensio, E., Cacho, J. & Ferreira, V. (2002). Sensory and chemical changes of young white wines stored under oxygen. An assessment of the role played by aldehydes and some other important odorants. Food Chemistry, 77, 325-331.
Escudero, A., Campo, E., Fariña, L., Cacho, J. & Ferreira, V. (2007). Analytical Characterization of the Aroma of five Premium Red Wines. Insights into de Role of Odor Families and the Concept of Fruitiness of Wines. Journal of Agricultural and Food
Chemistry, 55, 4501-4510.
Falcao, L.D., De Revel, G., Perello, M.C., Moutsiou, A., Zanus, M.C., & Bordignon- Luiz, M.T. (2007). A survey of seasonal temperatures and vineyard altitude influences on 2-methoxy-3-isobutylpyrazine, C-13-norisoprenoids, and the sensory profile of Brazilian Cabernet Sauvignon wines. Journal of Agricultural and Food Chemistry, 55, 3605-3612.
Falqué, E., Fernández, E. & Dubourdieu, D. (2001). Differentiation of white wines by their aromatic index. Talanta. 45, 271-281.
Ferreira V., Escudero A., López R. & Cacho J. (1998) Analytical characterization of the flavor of oxygen-spoiled wines through the Gas-Chromatography-Ion-Trap Mass Spectometry of ultratrace odorants: Optimization of conditions. Journal of
Chromatographic Science, 36, 331-339.
Ferreira, V., Aznar, M., López, R. & Cacho, J. (2001). Quantitative gas chromatography- olfactometry carried out at different dilutions of an extract. Key differences in the odor profiles of four high-quality Spanish aged red wines. Journal of Agricultural and Food
Chemistry, 49, 4818-4824.
Ferreira V., López R. & Aznar M. (2002). Molecular methods of plant analysis. Vol. 21. Berlín: Springer Germany.
Ferreira, V., Jarauta, I., López, R., & Cacho, J. (2003). Quantitative determination of sotolon, maltol and free furaneol in wine by solid-phase extraction and gas chromatography-ion-trap mass spectrometry. Journal of Chromatography A., 1010, 95- 103.
Ferreira, V., Ortin, N., & Cacho, J.F. (2007). Optimization of a procedure for the selective isolation of some powerful aroma thiols - Development and validation of a quantitative method for their determination in wine. Journal of Chromatography A, 1143, 190-198.
Ferreira, V. & Cacho, J. (2009). Identification of Impact Odorants of Wines. Capítulo 8E (pp. 393-415) In: Moreno-Arribas, M.V. & Polo, M.C. Ed. Wine Chemistry and
Biochemistry. New York: Springer.
Flanzy, C. (2000). Enología: Fundamentos Científicos y tecnológicos. Madrid: Mundi Prensa Ed.
Fleet, G.H. (2003). Yeast interactions and wine flavour. International Journal of Food
Microbiology, 86, 11–22.
Frivik, S. & Ebeler, S. (2003). Influence of Sulfur Dioxide on the Formation of Aldehydes in White Wine. American Journal of Enology and Viticulture, 54, 31-38. Gil, M., Cabellos, J.M., Arroyo, T. & Prodanov, M. (2006). Characterization of the
volatile fraction of young wines from the Denomination of Origin “Vinos de Madrid” (Spain). Analytica Chimica Acta, 563, 145-153.
Gürbüz, O., Rouseff, J.M. & Rouseff, R.L. (2006). Comparison of Aroma Volatiles in Commercial Merlot and Cabernet Sauvignon Wines Using Gas Chromatography- Olfactometry and Gas Chromatography-Mass Spectrometry. Journal of Agricultural and
Food Chemistry, 54, 3990 -3996.
Gómez-Míguez, M.J., Cacho, J., Ferreira, V., Vicario, I.M. & Heredia, F.J. (2007). Volatile components of Zalema white wines. Food Chemistry, 100, 1464-1473.
Halpern, B.P. (2004). Retronasal and orthonasal smelling. Chemosense, 6, 1-7.
Jackson R.S. (1994). Wine Science. Principles and Applications. California: Academic Press, Inc.
Kilmartin, P. A., Zou, H. & Waterhouse, A. L. (2001). A cyclic voltammetry method suitable for characterizing antioxidant properties of wine and wine phenolics. Journal of
Agricultural and Food Chemistry, 49, 1957–1965.
Lambropoulosa, I. & Roussis, I. G. (2007). Inhibition of the decrease of volatile esters and terpenes during storage of a white wine and a model wine medium by caffeic acid and gallic acid. Food Research International, 40, 176–181.
Ledauphin, J., Barillier, D. & Beljean-Leymarie, M. (2006). Gas chromatographic quantification of aliphatic aldehydes in freshly distilled Calvados and Cognac using 3- methylbenzothiazolin-2-one hydrazone as derivative agent. Journal of Chromatography
A, 1115, 225-232.
Li, H., Wang, H., Yuan, C. & Wang, S. (2005). Wine chemistry. Beijing: Scientific Publishing Company. En: Li, H., Guo, A. & Wang, H. (2008). Mechanisms of oxidative browning of wine. Food Chemistry, 108, 1-13.
Li, H., Guo, A. & Wang, H. (2008). Mechanisms of oxidative browning of wine. Food
Chemistry, 108, 1-13.
Leffingwell, J.C. (2002). Olfaction. Leffingwell Reports, 2, 1-34.
López, R., Lapena, A.C., Cacho, J. & Ferreira, V. (2007). Quantitative determination of wine highly volatile sulfur compounds by using automated headspace solid-phase microextraction and gas chromatography-pulsed flame photometric detection – Critical study and optimization of a new procedure. Journal of Chromatography A, 1143, 8-15. Macías, J. (2007). Los sistemas del olfato y del gusto. Temario Ingeniería Neurosensorial
http://insn.die.upm.es/docs/INSN0506-TemaElOlfatoYElGusto-JMG-v29.pdf. Consulta: 10/12/2007).
Makhotkina, O. & Kilmartin, P.A. (2009). Uncovering the influence of antioxidants on polyphenol oxidation in wines using an electrochemical method: Cyclic voltammetry.
Journal of Electroanalytical Chemistry, 633, 165-174.
Malnic, B., Hirono, J., Sato, T. & Buck, L.B. (1999). Combinational receptor codes for odors. Cell, 96, 713-723.
Marchand, S., De Revel, G. & Bertrand, A. (2002). Possible mechanism for involvement of cysteine in aroma production in wine. Journal of Agricultural and Food Chemistry, 50, 6160–6164.
Martínez, J., Bilbao, A., Superviola, J. & Aznárez, J. (1999). Evolución de la Composición Aromática de Tempranillo durante el Proceso de Envejecimiento: IV Congreso Nacional de Enólogos. Nº 2768, 2975-2980.
Mateo-Vivaracho, L., Ferreira, V. & Cacho, J. (2006). Automated analysis of 2-methyl-3- furanthiol and 3-mercaptohexyl acetate at ng L-1 level by headspace solid-phase microextracion with on-fibre derivatisation and gas chromatography-negative chemical ionization mass spectrometric determination. Journal of Chromatography A, 1121, 1-9. Mateo-Vivaracho, L., Cacho, J. & Ferreira, V. (2007). Quantitative determination of wine
polyfunctional mercaptans at nanogram per liter level by gas chromatography-negative ion mass spectrometric analysis of their pentafluorobenzyl derivatives. Journal of
Chromatography A, 1146, 242–250.
Mateo-Vivaracho, L., Cacho, J. & Ferreira, V. (2009). Selective preconcentration of volatile mercaptans in small SPE cartridges: quantitative determination of trace odor- active polyfunctional mercaptans in wine. Journal of Separation Sciences, 32, 3845-53. Mayol, A.R. & Acree, T.E. (2001). Advances in gas chromatography-olfactometry. En
Leland, J.V., Schieberle, P., Buettner, A., Acree, T.E. (Eds.). Gas chromatography- olfactometry. The state of the art. ACS Symposium series, 782 (pp. 1-10). Washington D.C.
Mestres, M., Busto, O. & Guasch, J. (2000). Analysis of organic sulfur compounds in wine aroma. Journal of Chromatography A, 881, 569-581.
Mestres, M., Busto, O. & Guasch, J. (2002). Application of headspace solid-phase microextraction to the determination of sulphur compounds with low volatility in wines.
Journal of Chromatography A, 945, 211-219.
Moreno, J.A., Zea, L., Moyano, L., and Medina, M. (2005). Aroma compounds as markers of the changes in sherry wines subjected to biological ageing. Food Control, 16, 333–338.
Noble, A.C., Arnold, R.A., Buechsenstein, J., Leach, E.J., Schmidt, J.O. & Stern, P.M. (1987). Modification of a standardized system of wine aroma terminology. American
Journal of Enology and Viticulture, 38, 143-146.
Oliveira, C.M., Silva Ferreira, A.C., De Freitas, V. & Silva, A.M.S. (2011). Oxidation mechanisms occurring in wines. Food Research International, 44, 1115-1126.
Oliveira e Silva, H., Guedes de Pinho, P., Machado, B.P., Hogg, T, Marques, J.C., Câmara, J.S., Albuquerque, F. & Silva Ferreira, A.C. (2008). Journal of Agricultural and
Food Chemistry, 56, 11989-11996.
Peinado, R.A., Moreno, J., Bueno, J.E., Moreno, J.A., Mauricio, J.C. (2004). Comparative study of aromatic compounds in two young white wines subjected to pre- fermentative cryomaceration. Food Chemistry, 84, 585-590.
Perestrelo, R., Fernandes, A., Albuquerque, F.F., Marques, J.C. & Câmara, J.S. (2006). Analytical characterization of the aroma of Tinta Negra Mole red wine: Identification of the main odorants compounds. Analytica Chimica Acta 563, 154-164.
Pomar García, M. (1997). Tesis Doctoral: Envejecimiento de vino tinto de la D.O. Tacoronte-Acentejo: Influencia de la madera de roble y de las condiciones de vinificación em la evolución de parâmetros fisicoquímicos de interés enológico y su impacto organoléptico. Departamento de Ingeniería Química y Tecnología Farmacéutica de la Universidad de la Laguna.
Pripis-Nicolau, L., De Revel, G., Bertrand A. & Maujean, A. (2000). Formation of Flavor Components by the Reaction of Amino Acid and Carbonyl Compounds in Mild Conditions. Journal of Agricultural and Food Chemistry, 48, 3761-3766.
Prouteau, C., Schneider, R., Lucchese, Y., Nepveu, F., Renard, R. & Vaca-Garcia, C. (2004). Improving headspace-solid-phase microextraction of 3-isobutyl-2- methoxypyrazine by experimental design with regard to stable isotope dilution gas
chromatography-mass spectrometric analysis of wine. Analytica Chimica Acta, 513, 223- 227.
Rapp, A. (1998). Volatile flavour of wine: correlation between instrumental analysis and sensory perception. Nahrung, 42, 351-363.
Ribéreau-Gayon, P., Dubourdieu, D., Donèche & B., Lonvaud, A., (2006). The Microbiology of wine and vinifications. En: Handbook of Enology, vol 1, (pp. 1-51). West Sussex (Inglaterra): John Wiley and Sons.
Roussis, I. G. & Sergianitis, S. (2008). Protection of some aroma volatiles in a model wine medium by sulfur dioxide and mixtures of glutathione with caffeic acid or gallic acid. Flavour and Fragrance Journal, 23, 35-39.
Schieberle, P. & Grosch, W. (1987). Evaluation of the flavour of wheat and rey bread crusts by aroma extract dilution analysis. European Food Research and Technology /
Zeitschrift für Lebensmittel-Untersuchung und -Forschung A, 185, 111–113.
Schneider, R., Kotseridis, Y., Ray, J.L., Augier, C. & Baumes, R. (2003). Quantitative determination of sulfur-containing wine odorants at sub parts per billion levels. 2. Development and application of a stable isotope dilution assay. Journal of Agricultural
and Food Chemistry, 51, 3243–3248.
Silva Ferreira A., Guedes de Pinho P., Rodrigues P. & Hogg T. (2002) Kinetics of oxidative degradation of white wines and how they are affected by selected technological parameters. Journal of Agricultural and Food Chemistry, 50, 5919-5924.
Silva Ferreira, A., Hogg, T. & Guedes de Pinho, P. (2003). Identification of key odorants related to the typical aroma of oxidation-spoiled white wines. Journal of Agricultural and
Food Chemistry, 51, 1377-1381.
Singleton, V.L. (1987). Oxygen with phenols and related reactions in musts, wines, and model systems: Observations and practical implications. Americal Journal of Enology
and Viticulture, 38, 69-77.
Sun, B.C. & Halpern, B.P. (2005). Identification of Air Phase Retronasal and Orthonasal Odorant Pairs. Chemical Senses, 30, 693-706.
Tello, J., Cordero-Bueso, G., Aporta, I., Cabellos J.M. & Arroyo, T. (2012). Genetic diversity in commercial wineries: effect of the farming system and vinification management on wine yeasts. Journal of Applied Microbiology, 112, 302-315.
Thuret, S., Moon L.D.F. & Gage, F.H. (2006). Therapeutic interventions after spinal cord injury. Nature Reviews Neuroscience, 7, 628-643.
Tominaga, T. & Dubourdieu, D. (2006). A novel method for quantification of 2-methyl- 3-furanthiol and 2-furanmethanethiol in wines made from Vitis vinifera grape varieties.
Journal of Agricultural and Food Chemistry, 54, 29-33.
Ugliano, M. & Henschke, P.A. (2009). Yeast and Wine Flavour. Capítulo 8D (pp. 313- 393) In: Moreno-Arribas, M.V. & Polo, M.C. Ed. Wine Chemistry and Biochemistry. New York: Springer.
Ullrich, F., & Grosch, W. (1987). Identification of the most intense volatile flavour compounds formed during autoxidation of linoleic acid. European Food Research and
Technology / Zeitschrift für Lebensmittel-Untersuchung und -Forschung A, 184, 277–
282.
Usseglio-Tomasset, L. (1998). Química Enológica. Capítulo 21: El anhídrido sulfuroso en enología. Madrid: Mundi-Prensa Eds. (pp. 337-353).
Warner, C. R., Diachenko, G. W. & Bailey, C. J. (2000). Sulfites: An important food safety issue. Food Testing and Analysis, 6, 1-4.
Waterhouse, A. L., & Laurie, V. F. (2006). Oxidation of wine phenolics: A critical evaluation and hypotheses. American Journal of Enology and Viticulture, 57, 306–313. Zhou, D., Zhang, S., & Xin, S. (2004). Review on the function and application of sulphite
in food processing. Food Science in China, 25(12), 198–201.
Zoecklein, B.W., Fugelsang, K.C., Gump, B.H. & Nury, F.S (2001). Análisis y
producción de vino. Zaragoza: Acribia SA. Ed. (pp. XVII)
Nota: Aunque el reglamento (CE) 479/2008 está derogado, por el Reglamento (CE) 491/2009 (DOUE L 154 de 17/06/2009, Pág. 1), su contenido se mantiene vigente, al haber quedado incluido en el Reglamento (CE) 1234/2008 (DOUE L 334 de 12/12/2008, Pág. 7). Éste, regula la OCM única para todo el sector agrícola, donde queda integrada la vitivinícola.