PII: $0963-9969(98)00029-5 Food Research Internationa, Vol. 30, No. 9, pp. 699-108, 199 “© 1998 Canadian Institute of Food Science and Technology Published by Elsevier Science Lu. All igs reserved Printed in Great Britain (963.9969,97 S19.00-+0.00, Evolution of the CIELAB and other spectrophotometric parameters during wine fermentation. Influence of some pre and postfermentative factors R. |-Mufioz,* E. Gomez-Plaza,** A. Martinez* & J. M. Lopez-Roca® Centro de Investigacién y Desarrollo Agroalimentario, Ctra. La Alberca s\n 30150, Murcia, Spain Unidad Docente de Tecnologia de los Alimentos, Facultad de Veterinaria, Universidad de Murcia, Campus de Espinardo, 30071 Murcia, Spain The evolution of CIELAB and other color parameters has been studied during wine fermentation, as well 3s the influence of grape teraperature on color extrac tion. In the postférmentative phase, two dillerent fining treatments have been tested to check their influence on color parameters. Grape temperature affected colar during the first days but at the end of alcoholic fermentation color char= fcteristics of both wines were almost the same and they evolved similarly, Fining ‘treatments influenced color slightly, while cold stabilization had more of an effect «due to the precipitation of color pigments. Some correlations were found within the CIELAB parameters and between them and other color parameters. ©) 1998 Canadian Institute of Food Science and Technology. Published by Elsevier Science Ltd. All rights reserved Keywords: color, wine, fermentation, grape temperature, fining treatments, CIE LAB parameters, INTRODUCTION Color contributes to the organoleptic attributes of a wine. Color depends on some parameters such as the grape composition, vinification techniques and the numerous reactions that take place during wine storage (Auw et al., 1996). The composition of red wine color changes continuously during vinification and storage, with associated changes in sensory characteristics. Progressive changes are inevitable because of the reactivities of the phenolic compounds extracted during alcoholic fermentation but the role and course of phenolic interactions and degradations may be subject (o many influences. Most rapid changes in color composition occur during the first year (Somers and Evans, 1986), *To whom correspondence should be addressed: Fax: (34) 68 £84480 2; e-mail: encarna.gomer@uccesosises 699 ‘The accepted color analysis for red wines is that made by measurements at three wavelengths, 420, 520 and 620nm, and the calculations of color density (sum of these absorbances as defined by Glories, 1984) and tint (defined by Sudraud, 1958 as the ratio of absorbance at 420 to $20nm) provide a useful way to describe wine color. Most recently, the CIELAB space has been used by several authors in publications on wine color (Her- edia and Guzmin, 1986; Bakker e¢ ai., 1986; Negueruela and Echevarri, 1990; Timberlake, 1981), The CIELAB space is a uniform three dimensional space defined by the colorimetric coordinates L*, a* and b* (C.LE., 1986). The vertical axis L* is a measure of lightness, from completely opaque (0) to completely transparent (100), while on the hue-circle, a* is a measure of redness (or —a* of greenness) and 6* of yellowness (or —b* of blueness. Hue angle (#*) and chroma (C*) values are obtained from L*, a* and b* coordinates.700 R, GileMurtoz et al. The main objective of this paper is to learn the evo- lution of the wine color from must to wine and how this evolution is affected by factors such as the temperature Of the grapes at the time of crushing and the use of some fining agents during postfermentation. MATERIALS AND METHODS Grapes from Vitis vinifera variety Monastrll, cultivated in the Jumilla area (Southeast of Spain) were harvested at optimum maturity (12° Baumé) in 20kg boxes and carried to the winery. Two different lots were prepared from these grapes. One lot was processed immediately (inifcation at normal temperature, VT) and the other lot of grapes was cooled to reach a temperature of 10°C before being processed in the same manner as the fist Jot (vinification at low temperature, VLT). The vinifications were carried out in a large scale experimental winery. Triplicate samples of each wine were taken on day I (initial must), day 3, day 7 (end of skin contact period), day 13 (end of alcoholic fermenta- tion), day 50 (end of malolactic fermentation), day 86, day 211 Gust before the finning treatments), day 227 (aller the finning treatments) and day 260 just afier cold stabilization and bottling). SO. was added after crushing the grapes. No selected yeasts were used. First racking was done one week after aleoholie fermentation was fine ished and then every 7 days for @ period of 3 weeks. For the clarification treatments two different fining agents were used: PYPP (polyvinylpirrolidone, Polycar VT, Gaf, USA) at a concentration of 459/1001 and a combination of Bentonite (Volelay, American Colloid Company, USA) at 2g/1001+Gelatin (Diamainte, J Laffort y Cia, Spain) at 45 g/1001. After the fining treat- ments, wines were cold stabilized at ~4°C for I month. Table | shows the analytical composition of both musts and the final wine before the fining treatments ‘Spectrophotometric determinations Absorbance measurements were done on a Hitachi 2000 spectrophotometer (Tokyo, Japan) with 0.2em_ path length glass cells, on a range between 420 and 630m. ‘The samples were clean and contained no COs. Color definition was made using the CIELAB space, using the C illuminant and a 2° observer. Hue angle (H*) was calculated as [arctan(b"/a*)] and chroma (C*) as [(ar)+ 6)" Color density was calculated as the sum at $20 and 420 nm (Sudraud, 1958), Wine color (WO), total color of pigments (WCA) and polymeric pigment color (PPC) were calculated accord- ing to Mayén (1993), WC was determined by adding 20yl of acetaldehyde to 2ml of wine and measuring absorbance at 520nm alter 45mins, WCA was deter mined by adding 9ml of HC10.1N to ml of wine to and wines before finning treatments VI _VLT Must Temperature 20 10 Density 1091.08 “Baume 1221 179 Acidity (g/I“! tartaric acid) 435, 3.60 pH 3.68 3.68 Wine % alcohol 18. Density 0.99 Total acidity (g/!~! tartaric acid) 4.49 Volatile acidity (g™’ tartaric acid) oT pur 378 ‘VT: Vinification at normal temperature YLT: Vinitication at low temperature, obtain a pH lower than 1 and measuring the absor- bance, at $20nm after 4-Shs. PPC was determined by adding 15mg of NaHSO, to Sml of wine, and measur- ing absorbance at $20nm after 1 min. Data processing was performed with the Statgraphies statistical analysis software (Statistical Graphies Cor poration, USA). “@ > ue i i 2 Fig. I. Evolution of color density in the different vinifeations (r=3). VT, vinification at normal temperature; VLT, vinifica- tion at low temperature; VI-PVPP, vinification at normal temperature, PYPP used as fining agent; VI-B~G, vinifica- tion at normal temperature, Bentonite + Gelatin used as fining agents; VLT-PYPP, vinification at low temperatue. PVPP used as fining agent, VLT-B+G, vinification at low temperature. Bentonite + Gelatin used as fining agents,CIELAB and other color parameters in wine 701 RESULTS AND DISCUSSION Color density Figure 1 shows the evolution of color density during vinification, The color density at the beginning of fer- mentation was greatly influenced by temperature. On day 3 the color density of VT was more than twice the color density of VLT. The lower temperature of the grapes in VLT resulted in the maximum color density being reached on day 7, but at this point it was higher than VT Color density values are the same at the end of alco- holic fermentation and there is a decrease of the color density until the end of malolactic fermentation. Large losses of wine color have been also observed by other, author (Somers, 1980), and they have been attributed to the precipitation of condensed pigments, anthocyanin condensation with proteins and pigment fixation on yeast cells (Mayén, 1993). Also, from the end of aleo- holic fermentation to the end of malolactic fermentation there is an increase of pH due to the transformation of malic acid to lactic acid and this increase of pH can affect color density substantially, Some investigations (Almela er al., 1995) have demonstrated that there is @ strong correlation with the ionized forms of anthocya: ins and colon density and the former are strongly dependent on pH. After malolactic fermentation there is another increase in color density. This increase cannot be attributed to an increase in anthocyanins (since the skins were separated on day 7), and must be related to the contribution of new chemical compounds formed, Fig. 2. Evolution of £* (lightness) during the different Vinifications. (23). See Fig. I for abbreviations. In this way, the color due to free anthocyanins (absor- bance at 520nm) is substituted for the color resulting from the polymerization pigments, with an hypso- chromic change towards 420m, with an extinction coefficient that gave higher values of absorbance (Almela et al, 1993). In this way, reactions among malvidin 3 glucoside and acetaldehyde and catechin give increase in color density, and in the level of poly- meric pigments (Somers and Evans, 1986) PVPP typically binds and removes smaller molecular weight phenolics while gelatin reportedly removes larger molecular weight phenolics (Sims et al., 1995). Bento- nite is a volcanic aluminum silicate clay with exchange- able cationic components and is used to reduce protein content (Main and Morris, 1991). Bentonite absorbs polyphenol oxidase, phenols and other positively charged molecules (Danilatos, 1979; Main and Mortis, 1991). With the fining agents treatments there is a decrease in the color density when bentonite+ gelatin is used. PVPP did not affect the color density of the wines. Afler cold stabilization a decrease in color density was observed, due to the precipitation of pigments formed. CIELAB parameters Lightness (L*) is also affected by the grapes temperature (Fig. 2) but at the end of the skin contact period the values were very similar and both wines followed the same evolution. As we have reported regarding color density of wines, the effect of the temperature of the grapes only can be observed in the very first stages of, the vinification, Z* increases slightly (the wine clears a little) with the fining treatments due to the elimination Fig. 3. Evolution of C* (chroma) during the different Vinifications, (n=3). See Fig. | for abbreviations702 R, GileMurtoz et al. » : ® + 8 7 8 © 6 on mr ao :_. = = © » © Fig. 5. Cartesian diagrams obtained for L* versus 5" Fig. 4, Evolution of #7* (hue) during the different vinifications, (n= 3), See Fig. | for abbreviations. of pigments and almost no difference could be found ‘between the effect of both fining agents. The evolution sin agreement with the one found by Almela etal. (1995). C* (chroma) is a parameter that indicates the con- tribution of a* (redness) and 6* (yellowness). Values of C* close to or higher than 50 correspond to vivid colors. C* showed very small differences between both vinitfi- cations (Fig. 3). From day 3 to day 13, C* values were almost constant and higher than 70. After a small decrease due to malolactic fermentation, values started increasing again, The fining agents promoted only a slight increase in C* values and a decrease after cold stabilization was found, H* (hue) value is higher in VT than VLT at the beginning of the vinification and after that values remained very close (Fig. 4). Again, the effect of fining, Table 2. Pearson correlation coefficients matrix Fig. 6. Cartesian diagrams obtained for L* versus 1* the chromatic parameters considered we PPC WEA o - co oD we PPC 1 Wea o.679e* 0.253 i Lt 0810" mot -0.746r Ie a 0.323 0.204 0.082 0.474 id a 40s 0635" = 08k 0.414 i Cc osiT* 0.409 O77s — ogsst oglate se im 0.768" oot = 0928 0332 o.9Ngre orate te cD 0570 osdit* — 0.901" 0280 «0.907 0.699 o.9a3F 1 Significance level (p=0.05). **Significance level (0.01), WC: Wine color; WCA: Total color of pigments; PPC: Polymeric pigments; CD: Color densityCIELAB and other color parameters in wine 703 agents did not show substantial differences and a litte docrease was observed after cold stabilization. High values of H* are due to yellow pigments that absorb at 420nm and some of them precipitated during cold sta bilization. Table 2 shows the Pearson correlation coefficients (*) ‘This matrix revealed the relationship between the dif- ferent parameters studied. L* versus b* and H* showed a high linear correlation (p<0.01), as also shown in their cartesian diagrams (Figs 5 and 6). Therefore, 6* and L* values gave an accurate definition of the color characteristics ofthese wines. A similar study performed with white wines showed an analogous relationship (Chiralt et al, 1987), whereas Almela er al. (1995) found a similar relationship but between L* and a*, The diagram of L* versus a* in this study shows @ high second degree correlation (Fig. 7) and the same rela tionship was found for red wines by Negueruela et al (1995). Other spectrophotometric parameters WC measures wine color, including those anthocyanins that were bound to SO» (acetaldehyde binds more strongly to SO; than anthocyanins) so this parameter is related to the anthocyanin composition of the wine. The highest values were found in the first days of the vinification (Fig. 8) as also observed by Bourzteix et al. (1970), We found that the contribution of anthocyanins was very low in VLT at the beginning of the vinification due to the low temperature of the grapes. The tempera- ture of grapes during skin contact greatly affected the polyphenol transfer. Similarly to color density, an important decrease was found from the end of alcoholic fermentation to the end of malolactic fermentation. ‘The increase of pH can promote a displacement of Fig, 7. Cartesian diagrams obtained for a® versus L*. ig. 8. Evolution of WC (wine color) during the different ‘inifcations, (n=3). Soe Fig, | for abbreviations. the anthocyanin equilibrium towards the uncolored forms (Mazza, 1995). After malolactic fermentation, several rackings were done, The aeration produced by racking can allow a recovery of color (Ribereau-Gayén, 1977). WCA measures the color due to ionized anthocya- nins, The color of young wines is closely associated with the ionized form of anthocyanin (Somers and Evans, 1986). Figure 9 shows that a decrease in WCA occurred Fig. 9. Evolution of WCA during the different vinifieations (3). See Fig, I for abbreviations708 R, GileMurtoz et al. pe Fig. 10. Evolution of PPC (polymeric pigment color) during, the different viniications. (n= 3). See Fig. for abbreviations afler alcoholic fermentation because there was @ decrease in monomeric anthocyanins and the formation ‘of compounds with lower absorbance at 520 nm and less sensitive to pH (Bakker ef al, 1986). WCA was not affected by PVPP but a decrease was observed when bentonite + gelatin were used. PPC measures color of polymeric pigments (those compounds that do not bleach in presence of $O2) and Color density ° 2 4 6 3 0 we Fig. 11, Cartesian diagrams for color density versus WC. its evolution is shown in Fig. 10. The pigments are formed by condensation reactions between anthocyanins and other phenolic compounds. They are artifacts of the wine making process (Somers, 1980). Their formation begins very early in the fermentation, These polymeriza- tion reactions are normal reactions in Vitis vinifera wines and help wine stabilization. During postfermentation, there was an increase in PPC levels and they did not decrease when PVPP was used because this agent affects mainly low molecular weight pigments. There was decrease in the levels of PPC with the use of bentoni- te gelatin because gelatin has the ability to eliminate high molecular weight compounds (Sims et al., 1995) L* showed high correlation (p<0.01) with color density (Table 2) as also found by Bakker er al. (1986) and Almela ef al. (1995) and also with 6* and H* as already seen previously. The negative correlation of L* with color density would indicate that an increase in color density leads to a darker color and the positive correlation with #* indicates that wines brown (H1*) and clear (L*) simultaneously. WC correlated (P<0.01) with the CIELAB parameters h* and H1* and had a very low correlation with a* (0.2197); WC also showed a good correlation with color density as also can be observed in the cartesian diagram (Fig. 11). The coeli- cients of correlation for WCA were not very high, being the highest for color density (0.81). For PPC, the high- est correlation coefficients were found with 17* and 6°. CONCLUSIONS This study has shown that the temperature of the grapes at the time of crushing greatly affected the evolution of color parameters the first days of vinification. When the alcoholic fermentation is finished, these differences have disappeared and the evolution of both wines was almost the same. Both fining treatments had little effect ‘on wine color, The largest differences were found in the spectrophotometric measurements WC, WCA and PPC, where some differences between the use of PVPP and bentonite + gelatin could be observed. In this way, bentonite+ gelatin promoted larger losses of ionized anthocyanins and polymeric pigments than PVPP. ‘The Pearson correlation matrix has shown that some relationships within the CIELAB parameters and between CIELAB parameters and other color determi- nations can be found, REFERENCES Almela, L., Javaloy, S., Fernéndez-Lépee, J. A. and Lépez- Roca, J. M. (1993) Color de los vinos varictales producidos en la Regién de Murcia. In Quimica Agricola y Alimentaria, feds European Federation of Chemical Engineering, Vol. 101, pp. 205-212.CIELAB and other color parameters in wine 705 Almela, L., Javaloy, S., Fernindez-Lépez, J. A. and Lépez- Roca, J. M. (1995) ‘Comparison between the tristimulus measurements Yay and L* a* B* to evaluate the colour of young red wines. Food Chem. 83, 321-327. ‘Aiww, JM, Blaneo, V., O'Keefe, S, F, and Sims, C. A. (1996) Effect of processing on the phenolics and color of Cabernet Sauvignon, Chamboureia and Noble wines and juices. dm. J. Enol. Vite. 81, 279-286. Bakker, J, Bridle, P. and Timberlake, C. F. (1986) Tristimulus measurements (CIELAB 76) of port wine color. Vitis 28, 61-78, Bourztcix, M,, Mourges, J. and Aubert, 8. (1970) Influence de la “dure do maceration sur la constitution en polyphenols et sur la degustation des vins rouges. Conn. Vigne Vin 4, 487 460. Chiralt, A., Macstud, P., Fito, P, and Giner, 1, (1987) Estudio. del color de vinos biancos varietales j6venes de la D.O. Rueda. Adv. Food Technol. 3, 1677-1680, GLE, (1986) Colorimetry 2nd edn. Publication C.LE. No. 152, Central Bureau of the Commission Internationale de L'Belairage, Vienna Danilatos, N. (1979) Donnés récentes sur lemploi des bento- nites Aspect chimique. Bull O.1.V. 580, 456-481 Glories, Y. (1984) La colour des ving rouges. 2° Partie. Conn Vigne Vin 18, 253-271 Heredia, G. and Guzman, M. (1986) Evolucién del analisis ‘eromatico en vinos, La Semana Vitinicola 2104-2105, 4959 4963. Main, G. and Morris, J. (191) Color of Riesling and Vidal wines as affected by bentonite, cufex and sulfur dioxide juice treatments, Am. J. Enol Viti. 42, 354-3357. Mayén, M. (1993) Comportamiento de la fraccién de polite roles durante la vinificacion de variedades tintas de V. vin! {fora Cabernet Sauvignon y Tempranillo y de la vaiedad ‘blanca. Pedro Ximénez culticadas en el marco de D.O. Montilla-Moriles, Ph.D. dissertation, Univ, Cordoba Spain. ‘Mazza, G. (1995) Anthocyanins in grapes and grape products CAR. Food Sei. Nut, 38, 341-371 Negueruela, A- and Echevarsi, J. F. (1990) Study of color of quaternafy mixtures of wines by means of the Schelle Design. Am. J. Enol. Viti. 41, 232-240 Negueruela, A., Echevarri J, P. and Pérez, M. (1995) A study correlation between enological colorimetric indexes and CTE colorimetcic parameters in red wines. Am, J. Enal, Vitic. 6, 353-356, Ribereau-Gayén, P. (1977) Problemas y_soluciones, en a ‘evollucién del color en los vinos tintos, Presented at Jorna- dlas Internacionales del vino, Jérez, Spa, Sims, C., Eastridge, I. and Bates, R. (1995) Changes in phe- ‘ols, color and sensory characteristics of Muscadine wines by pre: and post-fermentation additions of PVPP, casein and gelatin. Am. J. Bnol. Vite. 46, 155-158. Somers, T. C. und Evans, M. E. (1986) Evolution of red wines. Ambient influences on color composition during early maturation, Vitis 25, 31-39, Somers, T. C. (1980) Pigment phenomena. From grapes to wine. Presented at Centenial Grape Symposium, University of California, Davis, pp. 254-257, Sudraucl, P. (1958) Interpretation des courbes dabsortion des vins rouges. dn. Techrol. Agric. 7, 203-208, Timberlake, C. T. (1981) Parameters of red wine quality. Food Technol, 33, 139-144 (Received 28 October 1997; accepted 8 March 1998)