Sparkling Wines: Features and Trends from Tradition

CHAPTER

1 Sparkling Wines: Features and Trends from Tradition Susana Buxaderas1 and Elvira Lo´pez-Tamames

Contents

Abstract

I. Historical Background II. Definition and Types of Sparkling Wines and Other Effervescent Wines III. Cultivation and Harvest A. Climate and soil conditions B. Grape varieties C. Cultivation techniques D. Ripening control IV. Elaboration Process A. White vinification B. Second fermentation C. Aging D. Expedition V. Organoleptic Characteristics A. Foam B. Color C. Aroma VI. Data of Production and Consumption Acknowledgments References

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Sparkling wines contain at least three CO2 pressure bars at 20
C. Carbonic gas is required to have an endogenous origin, obtained via a second fermentation, in the following European categories:

Departament de Nutricio´ i Bromatologia, Facultat de Farma`cia, Universitat de Barcelona, Avda Joan XXIII, Barcelona, Spain 1 Corresponding author: Susana Buxaderas E-mail address: [email protected] Advances in Food and Nutrition Research, Volume 66 ISSN 1043-4526, http://dx.doi.org/10.1016/B978-0-12-394597-6.00001-X

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2012 Elsevier Inc. All rights reserved.

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sparkling wines and quality sparkling wines. In these types of sparkling wines, high gas pressure, together with other wine components, enables them to produce effervescence and foam when poured into the glass. The most commonly used grape varieties are Chardonnay and Pinot. Elaboration consists of two phases. In the first phase, the base wine is obtained after applying white vinification. The second phase consists of refermenting the wine, either in the bottle (champenoise or traditional method) or in isobaric tanks (Charmat method). The second fermentation requires the addition of ‘‘liqueur de tirage’’ to the base wine. The sparkling wines have a special biological aging or aging sur lies. As sparkling wines remain in contact with the lees, they develop sensory notes such as toasty, lactic, sweet, and yeasty, which can be attributed to proteolytic processes, components that would serve as the substrate for chemical and enzymatic reactions and to causes related with release– absorption between cell walls and the wine.

I. HISTORICAL BACKGROUND The first signs of the production of sparkling wine in the Champagne region of France occurred in the late seventeenth century. Wine has been produced in this wine-growing region since Roman times (from 50 A.D.), called vinum titillum. However, wine production itself is not documented until the year 800. During the Middle Ages, wines from Champagne were characterized as being lively, light, clear, off-dry, and often coming with a fleeting and gentle effervescence due to the incomplete fermentation of the grape juice (http://www.accua.com/bodega/conten/Historia-de-Champagne-Desde-los-Celtas-hasta-1638-los-inicios. asp; Dı´az de Mendı´vil et al., 1999; Me´heut and Griffe, 1997). About the sixteenth century, the Champagne region was known for white wines from the Marne Valley, red wines from the Reims mountains, and the ‘‘grays,’’ similar to today’s rose´s. The latter were made from a mixture of white and red grapes, and were the forerunners of today’s sparkling wines. The region’s northern climate led to late harvests, and the winter cold could interrupt fermentation of the grape juice. When temperatures rose in spring, secondary fermentation began but the majority of the gas produced escaped from the storage cooperage. With the aim of preserving the natural effervescence, wine was stored in bottles, sealed using wood and canvas. However, the bottles did not withstand the pressure and burst (Dı´az de Mendı´vil et al., 1999). The beginnings of a more methodical and precise process, born out of observation, persistence, and hard work, is attributed to people such as Pierre Pe´rignon. He was an abbot of Hautvilles from 1668 to his death in 1715. He wrote a book entitled: The art of tending vineyards and the wines of

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Champagne, which was published 3 years after his death by Canon Godinot. It is a set of guidelines about how to harvest and obtain the whitest color from the Pinot Noir grape. He describe a way of pruning the vine to produce a smaller crop; the precautions required to ensure the grapes are not damaged during harvest; the need to remove rotten grapes as well as leaves and other plant materials, etc. He even classified vineyards by the quality of their grapes and recommended their independent vinification, a practice that still exists today. Dom Pe´rignon is said to have originated separation of the grape juice through the application of subtle pressure while pressing. The first juice sample, obtained by treading, gave rise to the most delicate and lightest bodied wine, called vin de goutte. The two pressings that followed were called first and second taille. They also produced good wines, but of slightly lower quality. Low quality grape juice came from later pressings, which could not be used to produce high quality wines. There are writers who believe that the abbot of Hautvilles also invented the cork stopper (http://www.accua.com/ bodega/conten/Historia-de-Champagne-Desde-los-Celtas-hasta-1638-losinicios.asp; Dı´az de Mendı´vil et al., 1999). During the seventeenth century, wine from Champagne was consumed at the court of the French King, Louis XIV, the ‘‘Sun King.’’ On being crowned in Reims, he had the opportunity to sample the best wines from the region and became their main supporter having stated: ‘‘Champagne is the only conceivable drink.’’ The wine was introduced into the French and English courts as a wine for the aristocracy. Up until the eighteenth century, sparkling wines of Champagne were transported in barrels to England, where they were bottled in thick, smoked glass bottles that were more resistant to the pressure exerted by the carbon dioxide. In 1640, Sir Kenelm Digby (according to other writers, Eugene Digby) set up the first factory for the manufacture of bottles in bituminous coal furnaces. His patented process was more resistant than any glass made in France or elsewhere. The bottle and cork fixed with wire favored the dispersion of the wine, not only in England, a country that had shown a liking for the bubbles, but also to other European aristocracies. If the appearance of bubbles in the wine in the sixteenth century, caused by an increase in ambient temperature, was considered an inconvenience, in the following millennium, these bubbles came to represent a sign of personality and elegance, despite the presence of flakes and an off-white appearance due to the lees from the secondary fermentation (http:// www.accua.com/bodega/conten/Historia-de-Champagne-Desde-losCeltas-hasta-1638-los-inicios.asp; Dı´az de Mendı´vil et al., 1999). Despite the fact that Louis Pasteur did not clarify the origin of the bubbles until the nineteenth century, the first evidence of refermentation in Champagne wine exists from the middle of the eighteenth century, due to the addition of liqueur de tirage. This was an empirical practice used to

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guarantee the required effervescence. However, the precise amount of sugar necessary to generate a particular gas pressure had not yet been calculated. At the start of the nineteenth century, another significant figure in the development of the sparkling wine appeared on the scene. She was the Veuve Clicquot (Nicole-Barbe Ponsardin). Madame Clicquot wanted to eliminate the off-white cloudiness from her sparkling wine and invented riddling racks with supports that allow bottles to be placed at different angles. The bottles were placed horizontally at first and underwent a gentle one-eighth turn on a daily basis. These turns and an increasingly vertical angle positioned the bottle neck perpendicular to the floor. Progressively, it led to the cloudiness accumulating close to the cork. When the cork was removed, the decompression meant that the lees, which had accumulated near the cork, was expelled from the bottle. The outcome was sparkling wine with a clean aspect and a bright yellow color (Olavarrieta, 1995). The first reference to the consumption of Champagne in Spain goes back to the start of the nineteenth century. There is evidence that four bottles of Champagne were stored in the royal wine cellar during the reign of Fernando VII. It is likely that the French sparkling wines were not to the liking of the Bourbon dynasty. They were not introduced into the Spanish court until the reign of Amadeo I de Saboya, who catered to the taste of the Italian nobility in 1871 (Olavarrieta, 1995). Given that the court dictated the trends and customs of the time, the Spanish nobility wished to consume this elitist product. The proximity to France, demand, and the high prices of Champagne wines most likely encouraged the Catalan wine growers to begin production of sparkling wines, copying French practices. Evidence exists that initial attempts were a failure (Olavarrieta, 1995). The first bottles of Spanish sparkling wine appeared at the Barcelona market in 1879. They were supplied by Josep Ravento´s, the owner of a company with a long tradition of wine growing in the Penede`s region. This is the birthplace of Spanish sparkling wine, Cava. Penede`s is the main area where these sparkling wines are produced today (98%). For the first years of its existence, Catalan sparkling wine was consumed only locally. It did not spread until the distribution of Champagne was halted by the phylloxera epidemic. This disease, which affected the grapevines, arrived in Europe in 1863 through France. It came with grapevines that had been ordered by various French winegrowers in the hope that they would be more resistant to oidium (Uncinula necator) (Olavarrieta, 1995). Daktulosphaira vitifoliae (Phylloxera vastatrix) is an aphid-like parasite that sucks on the sap of the plant until it dies. It was not particularly harmful to American grapevines, but destroyed a major part of French vineyards. Some time afterward, in 1887, the plague traversed the Pyrenees and appeared in Catalonia. In 5 years, phylloxera affected 90% of the vines in the Cava region. The economic disaster for the Champagne

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business, caused by the vine disease, meant that Cava producers benefitted greatly and allowed them to withstand the onslaught of the plague 14 years later. The fight against the phylloxera was won by grafting to American rootstock, which were resistance to the aphid-like creature. The scientific developments of the twentieth century have revolutionized all fields of knowledge, enology being no exception. Our knowledge of the fermentation process and the microorganisms that drive it has expanded greatly. The liqueur de tirage and second in-bottle fermentation were defined as vital stages in the production of sparkling wines. It is necessary to calculate the exact amount of sugar that should be added to reach both the desired alcohol content and carbon dioxide pressure. Also, it is necessary that the yeast strain be able to complete the second fermentation in a 10% v/v hydroalcoholic medium that develops a pressure of around 6 atm. Another equally important point is transferring the lees to the neck, using traditional riddling racks. Riddling is essential for consumers accustomed to clear and bright sparkling wines. In the process of improving the quality of still wines, new proposals appeared to ensure the second fermentation and simplify the riddling process. The most robust alternative was the Charmat method, where the second fermentation took place in pressurized storage tanks. This provided continuous control over the fermentation process, after which the sparkling wine could be filtered and directly bottled under pressure. The economic advantages were obvious. For this reason, it has been used in many countries, including those with the longest tradition, such as France, Spain, and Italy.

II. DEFINITION AND TYPES OF SPARKLING WINES AND OTHER EFFERVESCENT WINES Generically speaking, sparkling wines are a type of wine that contains carbon dioxide in solution. However, when CO2 is exogenous, added in a continuous manner to wine that has been stabilized and cooled down to  2
C, it is considered fizzy wine. These carbonated wines belong to a lower category, price range, and quality. According to European Union terminology (6.6.2008 Official Journal of the European Union L 148/47), they are called ‘‘aerated sparkling wines.’’ The term ‘‘sparkling wine’’ is reserved for wines whose carbon dioxide is derived exclusively via fermentation (therefore, of endogenous origin). There are two specific subtypes in these European wine categories ‘‘Quality sparkling wines’’ and ‘‘Quality aromatic sparkling wines.’’ The first category is characterized by having carbon dioxide pressures of not less than 3.5 bars at 20
C. The second category includes cuve´e wines, derived from specific wine grape varieties. Other categories, with carbon

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dioxide pressures between 1 and 2.5 bars, occur such as semi-sparkling wines and aerated semi-sparkling wines, with endogenous and exogenous origins of carbon dioxide, respectively. The most prestigious sparkling wines are of European origin, whether through origin, historic tradition, or high production. Champagne ( JORF No. 0273/2010) stands out amongst French sparkling wines, often being considered a symbol of glamor and quality. However, there are also Cre´mants. Those of higher quality are made from designated grapes grown in specific regions (Appellation d’Origine Controˆle´e (AOC) sparkling wines). Another category, cuves close, is so designated because it is made in closed vats. This includes Vins Mousseux Nature (VM) (standard sparkling wines) and Vins Mousseux de Qualite´ (VMQ) (higher quality sparkling wines). The main producing regions for AOC cre´mants are Alsace, Burgundy, and the Loire (Payne et al., 2008). In Spain, Catalonia is the region that stands out in the production of DO Cava sparkling wine. This high quality sparkling wine is produced using the same method as Champagne, but has the distinctive particularity of being made from autochthonous varieties, Macabeo, Xarel lo, and Parellada. Coupled with climate and soil factors, they provide its peculiar and distinctive characteristics (Daban, 2005). With regard to the different German sparkling wines, there are two principal categories: Schaumwein and Qualita¨tsschaumwein (Sekt). Although the term Sekt is almost always used in both cases, it should be used only for the latter category (Woller, 2005). In Germany, Riesling is considered the best variety with which to elaborate a base wine for sparkling wines. This relates to its balanced and stimulating acidity, fruity aroma, and pleasing taste. These characteristics are largely a result of the nature of the soil where the grapes grow. The cretaceous ground of Champagne is equivalent to the shaly ground of the Mosel–Saar–Ruwer, where most German sparkling wines are produced. For a long time, Italian sparkling wines, known as spumanti, have been considered a poor relative of the more noble and renowned French champagne. However, in the past few years, an important revival of the ‘‘national tradition’’ in this sector has been occurring. This relates to the rediscovery of perfumes and aromas typical of its indigenous cultivars and production areas (Zironi and Tat, 2005). In this sense, the Franciacorta DOCG and Trento DOC are of particular note. These wines are certainly sparkling wines, but very different from Asti DOCG, made from Moscato grapes. It is also a full-fledged spumanti produced in Piemonte. Its key characteristics are liveliness, youthfulness, and sweetness. Other sparkling wines of note are Prosecco sparkling wines, derived from the Prosecco variety in the Veneto region, and Lambrusco, produced in Lombardy and especially in Emilia-Romagna. The latter is one of the wines experiencing the largest degree of commercial expansion at the moment.



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III. CULTIVATION AND HARVEST Viticulture, destined to sparkling wine production, combines traditional practices with the newest techniques, to assure the highest grape quality. The most important factors are climatic and soil conditions, grape variety use, training system, and disease and pest control.

A. Climate and soil conditions With regard to European sparkling wines, climatic conditions are extremely varied. For example, the climate of the Champagne region is cool, due to the influence of the Atlantic, coupled with continental influences. The average yearly temperature is 10
C, rainfall exceeds 750 mm, and the average sun exposure is 1750 h/year. This equates to the most northerly limit of grape cultivation. In contrast, grape cultivation in the Cava region spans the area between the Mediterranean coastline and elevated regions, close to 800 m above sea level. The central region, at an altitude of 200–300 m, is where the largest vineyard hectarage is located. It provides a bright, sunny climate, with mild winters and summers that are not excessively hot. Rain fall is spread out throughout the year ( 540 mm/year). Higher quality sparkling wines come from the best vineyards, located in select land plots, with excellent soil and subsoil composition, and optimal microclimates for vine cultivation and grape maturation. In this respect, in Champagne, the quality of the vineyards is classified according to a crus scale (Grand cru, Premie`re cru, and Second cru). It classifies producer municipalities according to location and terrain. The best vineyards are located on slopes, with an altitude between 90 and 150 m, and on soils consisting of limestone deposits. These offer good drainage and enable vine roots to obtain nutrients even under poor climatic conditions. Each region’s moisture regime is one of the most influential affecting grape quality. It can also include thermoregulatory effect of large water bodies, such as the sea. This can attenuate hot summers and cold winters. Evidently, soil type also influences the quality of the vineyard. For example, in the Cava region, the highest areas with the richest terrain are ideal for Parellada, whereas the more calcareous central Penede´s region is more suited to Xarel lo and Macabeo. In northern regions, the best climate conditions are provided by warm summers that are not excessively hot, allowing slow, constant maturation. It is also important to note that pronounced day- and night-time temperature differences improve maturation. Rain fall during maturation is also significant, given that rainy summers considerably increase the risk of fungal diseases. These deteriorate grape quality, causing problems with must clarification and vinification.



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In most regions, irrigation is unnecessary. However, under extended drought and/or excess heat in northern regions, or during the winter in southern regions, irrigation may be necessary to avoid excess vine stress. Irrigation should be applied only before veraison, always keeping in mind that the most important aim is increased grape quality and not quantity.

B. Grape varieties The grape varieties used in making sparkling white wines can be either white or red. When red varieties are used, they are vinified as a white wine, generating wines known as blanc de noir. Evidently, the selection of cultivar should be made while taking into account the soil and climatic conditions mentioned above (Table 1.1), vine productivity, and the desired distinctive character of a wine. Different Designations of Origin have legislated authorized grape varieties. For example, the following sparkling wines primarily use the following cultivars: Champagne (Chardonnay, Pinot noir, and Pinot meunier), Cava (Macabeo, Xarel lo, Parellada, and Chardonnay), Talento (Chardonnay, Pinot nero, and Pinot bianco), Asti spumante (Muscato bianco), Lambrusco (Lambrusco bianco and Lambrusco nero), Pinotage (a cross between Pinot noir and Cinsault), and Sekt (Riesling, Silvaner, Pinot blanc, Pinot noir, and Pinot gris). Different clones can also influence quality of sparkling wines. For example, the Chardonnay clone, VCR10, is recommended for Cava base wine production. It provides high acidity especially suitable for sparkling wines production. Since the phylloxera crisis (late nineteenth and early twentieth centuries), new rootstocks have emerged from a crossing of French and American strains. They were selected for adaptation to European soil conditions and cultivars. For example, 41B is adapted to chalky



TABLE 1.1 Classic)

Most commonly used varieties in the Champenoise method (Traditional or

Cold regions

Temperate regions

Warm regions

Pinot noir (red) Chardonnay (white) Pinot meunier (red) Gamay (red) Pinot blanc (white) Riesling (white)

Chenin blanc (white) Chardonnay (white) Gamay (red) Pinot noir (red) Pinot meunier (red)

Parellada (white) Chardonnay (white) Xarel lo (white) Macabeo (white) Pinot noir (red) Chenin blanc (white) Pinot meunier (red) Semillon (white)

Adapted from Dry and Ewart (1985).



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(Cretaceous) soils and continues to be the most commonly used in Champagne (81% of hectarage). SO4 is adapted to moderately calcareous soils and 3309C is the strain of choice for mildly calcareous soils.

C. Cultivation techniques The training system is also one of the crucial factors in obtaining high quality grapes and sparkling wine. Desirable traits control production, avoid fungal diseases, and permit mechanical harvesting. Although some vineyards still use traditional system, such as the gobelet, use vertical trellis training (VSP) systems, as well as Royat’s spur pruning system, or Guyot’s cane pruning, depending on the variety, terrain, and climate, are becoming increasingly preferred. For example, for Macabeo, used for the elaboration of sparkling Cava wines, Cordon Royat pruning is performed. It is a cordon trained, spur pruned system (two buds/spur), permitting a higher yield. In contrast, for Pinot Noir, Guyot pruning is performed (two canes forming an arch with four or five buds and a renewal spur). It involves the use of an overhead frame. Other varieties can use mixed pruning (Double Guyot, cane and spur). This type of pruning is applicable to Xare lo, used in producing Cava D.O. Besides basic training and pruning methods, suckering (removal of shoots from the trunk), hedging, pinching, basal leaf removal, and inflorescence or cluster thinning may be used as needed. These practices open the vine to air flow and sunlight, reducing disease stress and improving the efficacy of phytosanitary treatments (Hornsey, 2007). Planting density is also regulated for QSWPSR (Quality Sparkling Wines Produced in Special Regions), given that this factor affects quality. For example, in the case of Cava, the density established by the Regulatory Council ranges between 1500 and 3500 vines/ha, the number of buds per hectare depending on the varieties. The established limits are 50,000 fruit buds/ha for Xarel lo and Chardonnay; 30,000 for Parellada; and 40,000 for Macabeo and other varieties. With regards to yield of different varieties, legislation set by different regulatory bodies limits production (no higher than 12,000 grape kg/ha). For Cava, production limits from greater to lower, occur in the order of Macabeo, Parellada, Trepat, Xarel lo, Chardonnay, and Pinot noir. The maximum authorized yield for white varieties is usually 120 quintals (1 quintal ¼ 100 kg)/ha and 80 for red (Nadal Roquet-Jalmar, 2003).







D. Ripening control The most important variables used in assessing grape quality relative to base wines production for sparkling wines are the probable alcohol volume (sugar concentration in g/l), total acidity, pH, gluconic acid content (an index of grape health), and the concentration of assimilable nitrogen.

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Additional factors include the weight of 200 berries, given that weight and volume curve are closely related and give an idea of when grapes begin to dehydrate. When berries dehydrate, their relative sugar content (and alcohol potential) increase. Base wines should not possess an alcohol content higher than 10–10.5% v/v, given that the alcohol volume will increase during the second fermentation. It is also important to have adequate acidity to ensure long aging potential. For these reasons, in warm climatic regions, grape harvest tends to occur before the grapes reach a maturation point appropriate for table wine production. The wines would have inappropriately high alcohol values and insufficient acidity. For this, and also increasingly hotter summers, grape harvest is occurring earlier (in the case of Cava, in mid- to late-August). This is a distinguishing feature with respect to other regions producing sparkling wines, where it may be necessary to resort to chaptalization (as is the case of Champagne). In short, the ideal time to harvest is determined by applying the same periodic (every 4–5 days) assessments applied to making all wines (Conde et al., 2007). Regarding grape health, it is especially important to control bunch rot induced by Botrytis cinerea. It not only causes oxidation and browning, generates off-flavors, and produces clarification problems (via b-glucans), but also destroys effervescence at over a 20% infestation rate (due to its protease activity) (Cilindre et al., 2008; Marchal et al., 2001, 2006). The primary indicator of grape botrytization is the gluconic acid content. Of equal importance are the qualities of the must extracted during pressing. Must extracted from the first press fraction is destined for high range products, whereas that obtained from the second fraction is of lower quality. Must quality is also a function of the type of press, with pneumatic presses being preferred. How the grape reach the cellar can also influence quality. Grapes should arrive at the cellar as intact as possible, which is why many companies demand the harvest arrive in 25 kg boxes. If harvesting is mechanical, it is essential that it be performed at night, in order to avoid high daytime temperatures (30–35
C), that may favor unwanted oxidation and fermentation.

IV. ELABORATION PROCESS Regardless of the type of white or red grape used, the elaboration process of white and rose´ sparkling wines encompasses two clearly defined phases. The first stage follows the same vinification practices typical for white or rose´ table wines. By the end of vinification, the so-called base wine used for the second fermentation is ready. The second phase includes a refermentation with added sugar and aging in contact with

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the lees (aging sur lies). This phase is especially delicate as it occurs inside the bottle. It is variously termed the Champenoise method (Champagne, France), the classic method (Talento wines and Spumanti Methodo Classico, Italy), and the traditional method (Cava, Spain). Once the base wine has been bottled with added sugar and inoculated with yeasts, the enologist can no longer intervene in the fermentation or aging progress. The sparkling wine will reach the consumer in the same bottle in which refermentation took place. It is one of the requirements of the respective Certified Brand of Origin that guarantees the wine’s quality. However, this requirement presents the situation where the lees from the second fermentation must be delicately removed once aging is complete. Various alternatives for this separation, other than riddling, have been developed, such as the Charmat (Granvas, bulk) method and the transfer method.

A. White vinification Preventing the oxidation of phenolic compounds is necessary for the production of white table wine. This is even more so when making sparkling wines that undergo a second in-bottle fermentation and sur lies aging for a minimum time of 9–12 months. These procedures begin with the harvest. Grapes are transferred to the cellar in lugs with a capacity of 20–25 kg (Italy and Spain), or 35 kg (France) to avoid crushing (see Section V.B.2). After removing the stems, the grapes are pressed gently to minimize maceration between the skins and juice. The most commonly used presses are those that permit adjusting the pressure from 0.1 kg/cm2 to regulate must quality. Mechanical or pneumatic horizontal or lateral presses are presently replacing old vertical basket presses. The free-run juice produced during press loading and the juice extracted with very gentle pressure are used for making the highestquality sparkling wines. This fraction equates to about 2666 l/4000 kg of grapes. Must obtained by increasing the pressure is used for lower quality sparkling wines or for the elaboration of other wines (table wines) (Buxaderas and Lo´pez-Tamames, 2003; Flanzy et al., 1999). The must is clarified using a static method (sedimentation lasting 12–24 h) or a dynamic method (filtration or centrifuging) and its acid and sugar levels are corrected. Cold climatic conditions promote high acid but low sugar levels, which make chaptalization (addition of sugars or rectified grape must) necessary. Musts obtained in temperate to hot climates have sufficient quantities of sugar to ensure the minimum alcohol content of 9–10% for base wines, but it is often necessary to add tartaric and/or citric acid. In addition, sulfur dioxide is added to avoid uncontrolled fermentation by indigenous yeasts on the grape and to inactivate grape polyphenol oxidase (PPO, EC 1.10.3.1) (Buxaderas and Lo´pez-Tamames, 2003; Flanzy et al., 1999).

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Alcoholic fermentation is initiated by Saccharomyces cerevisiae starters prepared by the winery. It is recommended that fermentation take place in stainless steel tanks possessing a refrigerated double jacket. Keeping the temperature below 20
C limits volatile loss that could affect aroma development. It is also a good idea for the wine to be devatted before fermentation is complete to avoid the accumulation of mercaptans during prolonged contact with the lees. The yeast complete fermentation in a few days, yielding a cloudy, dry wine with a residual sugar not greater than 1.5 g/l. During the wine’s maturation, colloids sediment, making the wine cleaner and brighter. If physical clarification via sedimentation is insufficient, classic fining agents (bentonite, gelatine, caseinates, etc.) or other newer products (vegetable protein, quitine, polyvinilpirrolidone, yeast cell wall, etc.) are employed. To limit oxidation, the head space of the tank is filled with nitrogen. Malolactic fermentation is promoted when the wine’s acidity is too high (15 g/l of malic acid) or to prevent it occurring later in the bottle. The bacterial action would both increase CO2 pressure and could form a viscous lees inside of the bottle. Tartaric stabilization is required. Tartrates are not very soluble in water and even less so in a hydroalcoholic solution. Thus, when storing sparkling wine in a refrigerator, tartrate crystals could form. To prevent this, the temperature of the storage tank is reduced to below 0
C ( 4
C) to favor early precipitation. The precipitate is eliminated by filtering the wines through 0.45 m membranes. Depending on the attributes of the stabilized wines, the enologist prepares an appropriate blending or coupage to obtain the final base wine (Buxaderas and Lo´pez-Tamames, 2003; Flanzy et al., 1999).

B. Second fermentation Refermentation is the key operation in sparkling wine production. It supplies the carbon dioxide and, therefore, the effervescence and foam that produced when the wine is poured into a glass. For this reason, the phase is also called prise de mousse, literally translated as ‘‘catch the foam.’’ Since the grape’s sugars were metabolized during the initial alcoholic fermentation, it is necessary to add sugars to feed the yeast added to the base wine. The yeast must be able to ferment in the presence of 9–10% v/v alcohol, under carbon dioxide pressure, and flocculate with ease when the cells are dead.

1. Champenoise, classic or traditional method The second fermentation takes place in a sealed bottle after a liqueur de tirage has been added to the base wine (Fig. 1.1). This liqueur is composed of 1–2 million yeast cells/ml, 500 g of sucrose/l and 0.1–0.2 g of

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Tirage liqueur White winemaking

Base wine

+ Sugar + Yeasts + Agents

“Tirage”

Racking

≥ Sur lie Aging (Months)

Fermentation Aging Riddling

Disgorging Expedition Liqueur

Dosage & expedition

Corking Wiring Foiling Labeling

Distribution Storage

FIGURE 1.1 Scheme of sparkling wines elaboration using the champenoise or traditional method.

bentonite/l (to ensure the agglutination of the lees during riddling), and/or ammonium phosphate (50 ml/hl) and other compounds to stimulate yeast growth. Because approximately 40–42 ml of liqueur de tirage per 750 ml bottle is added, each bottle receives between 21 and 24 g of sucrose (Flanzy et al., 1999). It is important to adjust the amount of sugar to obtain desired alcohol content as well as sufficient carbon dioxide pressure (5–6 atm at 20
C). Cavazzani (1989) provides details on how to calculate the amount of sugar required. These calculations are based on the presumption that fermentation goes to completion. Thus, the amount of free SO2 should not exceed 25 mg/l and the pH should not be less below 2.8. However, when ‘‘brut nature’’ sparkling wines are produced, the addition

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of sugar with the ‘‘expedition liqueur’’ that is added after disgorging is not permitted (see Section IV.D). Therefore, the ‘‘liqueur de tirage’’ will have to provide an excess of sugar that must coincide with the amount of residual sugar that the winemaker wishes the ‘‘brut nature\pard fs20’’ sparkling wine to have. The bottles are hermetically sealed with a cup-shaped plastic insert known as a bidule and a metal crown cap and are stacked horizontally (Fig. 1.1). The bottle glass is special and is made to resist carbon dioxide pressure. The second fermentation generally lasts 1 month, or, in other words, at 1 month it is possible that 99% of the yeast cells are not longer viable. The speed of this process depends on the yeast strain and on the room temperature of the cellar where the bottles are stacked. Three months after the ‘‘tirage’’ fermentation is completed and 6 months later, there is no fermentation at all and 100% of cells are not viable.

2. Charmat or Granvas method (or bulk method) The second fermentation takes place in a special tank called a Charmat tank. It is isobaric and can withstand pressures up to 13 atm at 20
C (Fig. 1.2). This method was created as an alternative to in-bottle second fermentations to simplify separating the lees when aging is complete. The wine is added to the tank containing the starter, which is prepared with wine in order to adapt the yeast to the presence of alcohol. The composition of the liqueur de tirage is similar to that of the Champenoise or traditional method. The tanks possess agitators and temperature control systems that enable fermentation to occur more rapidly than in-bottle. Another advantage of the Charmat method is that complete fermentation is guaranteed. From both a technical and economic viewpoint, the Charmat method is more advantageous than carrying out the second fermentation in bottles. Pressure and temperature can be regulated, agitation is possible, and there is no need for riddling (remuage) or disgorging (Buxaderas and Lo´pez-Tamames, 2003; Flanzy et al., 1999). The end of fermentation is indicated by the CO2 pressure reached in the tank. In the Charmat method it is not necessary to consider the loss of pressure produced during the bottle disgorging (see Section IV.D). Therefore, when 4 atm of carbon dioxide pressure is reached in the tank, the tank’s temperature is reduced to 8
C to stop fermentation, leaving approximately 10% of residual sugars. The low temperature causes the suspended yeast to sink to the bottom. The next step is to separate the wine from the lees by transferring the partially decanted wine, under pressure, to another tank where it will cold stabilize. When the wine is transferred from one tank to another, it is centrifuged and/or filtered to separate it from the lees. Filtration under pressure implies compensating the empty volume that increases in the first Charmat tank while it is

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15

Charmat method or Bulk process

White winemaking

Base wine

Tirage liqueur + Sugar + Yeasts + Agents

Second fermentation “prise de mouse” Resistant pressure tank

Short Charmat

Long Charmat

Tangential filtration

Counter-pressure filling

FIGURE 1.2

Scheme of sparkling wines elaboration using the Charmat method.

being emptied of the wine under gas pressure (Buxaderas and Lo´pezTamames, 2003). This method also utilizes an expedition liqueur to give the sparkling wine different degrees of sweetness (see Section IV.D and Table 1.3). The expedition liqueur is added to the first or second Charmat tank.

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Susana Buxaderas and Elvira Lo´pez-Tamames

Depending on the amount of time the wine is left in contact with the lees, two Charmat methods can be described: short and long. The short method usually lasts between 1 and 3 months, and the sparkling wines obtained possess a young, fresh, and fruity aroma. Contact with the lees does not last long enough to produce a more evolved aroma (see Section IV.C). In order to produce sparkling wines, using the Charmat method, that are more similar to wines produced using the Champenoise or traditional method, the wine’s contact with the lees in the tank is extended to 6 months (long Charmat). In spite of this longer lees contact, an aromatic difference still is detectable between sparkling wines produced using the Charmat method and those fermented in-bottle for prolonged periods (24 months). This is due to the slow process of yeast autolysis, involving the interaction between components released by dead yeast cells and the wine. These influence the aromatic aspects tasters perceive. To offset this difference, heat was used to accelerate the yeast autolysis, a process called thermal lysis. Different temperatures and heating times have been tested: 65–70
C for 5 days and 33–45
C for 2 or 3 days (Flanzy et al., 1999). Thermal treatment causes the carbon dioxide pressure increase in the tank. Because the increase depends on the temperature used, it is a factor that needs to be taken into account when applying thermal lysis. It is difficult to compare thermal lysis with the autolysis that occurs during bottle aging. Heating enriches the wine with amino acids, such as glutamic acid, lysine, and arginine; causes a decrease of colloids of high molecular weight; and results in an increase of glucidic compounds of low molecular weight (Flanzy et al., 1999). Amino acids can originate from the surplus synthesized by the yeasts during fermentation, whereas the heat can favor colloidal precipitation (afford greater stability to the sparkling wine), while the increase of simple glucids may be due to the hydrolysis of glucosides. However, even at low temperatures (40/45
C) and a short 2-day treatment, inactivation of protease enzymes has been confirmed. It is also true that there are still many unknowns to be resolved regarding the biological aging of sparkling wines fermented in-bottle. The problem lies in reproducing under laboratory conditions the autolytic conditions of yeasts under carbon dioxide pressure. There is a third alternative to the Champenoise and Charmat methods. This is the transfer method developed in Italy. In this procedure, the second fermentation takes place in a bottle, and instead of applying the riddling and disgorging steps (see Section IV.D), the content of the bottle is emptied out in a Charmat tank. The wine remains in the bottle in contact with the lees over a minimum period of 9 months and is afterward transferred under pressure with the lees to the Charmat tank. From this moment onward, the process follows the steps of the Charmat method. This method has not been very warmly welcomed by wineries, probably because it does not present any clear advantages over the Charmat

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17

method. This method has been abandoned in Italy but is still used in a limited fashion by some German, Austrian, Greek, Hungarian, American, and Argentinean companies (Buxaderas and Lo´pez-Tamames, 2003).

C. Aging Sur lies aging is an enologic practice that has gained prominence with still winemaking over the last few years. It is required in producing sparkling wines via traditional methods, where it is mandated by law. It must last for several months to years in the case of Champagne ( JORF No. 0273/ 2010) and Cava (BOE No. 50 8487-8491/2007; Order APA/415/2007). Its duration is conditioned by the way in which the second fermentation is conducted and the type of sparkling wine (Colagrande et al., 1994). In the traditional method, long aging is associated with higher organoleptic quality. In the Charmat method, sur lies aging is reduced or even skipped, given that the method seeks to produce fresh and youthful attributes. Hence, the main reasons justifying longer or shorter aging in contact with the lees are of a sensory nature. Wines with better structure, body, and aromatic complexity are achieved using sur lies aging (Alexandre and Guilloux-Benatier, 2006). Although the base wine, yeast lysis, and duration of aging are considered the primary factors regulating the wine’s organoleptic characteristics, there are still significant gaps regarding our understanding of the physical–chemical interactions between lees and wine (Moreno-Arribas and Polo, 2009; Pozo-Bayo´n et al., 2009a,b,c). Wine lees (DOUE L208 16/07/1982 Commission Regulation No. 337/79) consists mostly yeast cells, within a size range of about 5 mm (Fig. 1.3), tartaric acid crystals, cell remnants, and clarifying agents (primarily bentonite). When wine is in contact with lees, autolysis results in a leaching of cellular constituents into the wine. These can impact on the wine’s stability and organoleptic characteristics (Martı´nez-Rodrı´guez et al., 2001a). Aging in contact with lees tends to produce more aromatic, balanced wines that also have a longer aging potential. This is associated with a higher antioxidant capacity and color stability (Caridi, 2007; Escot et al., 2001; Pe´rez-Serradilla and Luque de Castro, 2008). Yeast autolysis represents an enzymatic self-degradation of cell components that begins at the end of the stationary growth phase of alcoholic fermentation and is associated with cell death. The modified organization and structure of the cells during accelerated aging in contact with wine has been studied by Piton et al. (1988) and Martı´nez-Rodrı´guez et al. (2001b). The changes appear to be the result of proteolysis and cell wall degradation (Charpentier, 2010). Lees contain a wide array of hydrolytic enzymes, proteases being the most studied (Arevalo Villena et al., 2007; Charpentier, 2010; Loscos et al., 2009; Pati et al., 2010; Perrot et al., 2002; Rowe et al., 2010; Tirelli et al., 2010). Protease A is an endopeptidase

18

Susana Buxaderas and Elvira Lo´pez-Tamames

A

B

FIGURE 1.3 MET image of the vinic lee provided by Freixenet S.A. (A) and close-up image of cell wall (B).

responsible for the release of 85% of the nitrogen and the majority of peptides (Alexandre et al., 2001). Degradation begins with an enzymatic hydrolysis of glucans in mannoproteins. Afterward, the glucanes are released by residual glucanase activity in the cell wall or solubilized cytoplasmic glucanases. Finally, the protein fraction of the mannoproteins is degraded by proteases released by the yeasts. The release of polysaccharides varies depending on the yeast strain (Caridi, 2007), their physiological state (Guilloux-Benatiere and Chassagne, 2003), as well as the temperature and duration of sur lies aging. Autolysis could also play an important role in the release of aromatic compounds during the second fermentation and the aging of sparkling wines (Cebollero and Reggiori, 2009; Cebollero et al., 2005). Autolysis (autophagy) is a ubiquitous process that occurs in eukaryote cells and involves the massive degradation of cytoplasm and organelles in vacuoles or lysosomes. It is favored by adverse conditions (presence of alcohol and CO2 pressure) and can be considered an adaptive response

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19

executed by the cell due to the recycling of the elements, resulting from its own digestion (Cebollero et al., 2008). Autolysis results in the release of cellular components into the wine (Burattini et al., 2008; Cavagna et al., 2010; Tudela et al., 2011) and their interaction with wine constituents (Gallardo-Chaco´n et al., 2010). The mouth feel of sparkling wines is a result of the degradation of yeast cell walls during aging. It is a long process in which cell wall constituents provide roundness. In addition, the release of ribonucleotides may be important in increasing flavor in the mouth (Charpentier et al., 2005; Courtis et al., 1998; Leroy et al., 1990; Zhao and Fleet, 2005). Yeast cell wall can also act as absorptive surface agents and improve wine’s safety and quality (Caridi, 2007). This property has also been studied relative to sparkling wine lees (Gallardo-Chaco´n et al., 2009, 2010) and their changes during aging (Vichi et al., 2010). The absorptive properties of lees as wine additives are directing new research on Inactive Dry Yeast (IDY), commercial preparations of inactive dry yeasts (Andu´jar-Ortiz et al., 2010; Pe´rez-Serradilla and Luque de Castro, 2011; Pozo-Bayo´n, et al., 2009a,b, 2010), as well as the selection of more actively autolytic yeasts with a greater flocculation capacity (Divies et al., 1994).

D. Expedition Generically speaking, expedition is the stage prior to the finished product’s launch into the market. This stage is mandatory not only to perform the final corking and labeling but also to remove lees from the second fermentation and aging, equalize wine volume and supply enough sulfur dioxide to ensure conservation during the product’s shelf-life. For bulk and transfer processed sparkling wine, lees removal is performed via filtration and bottling performed under isobaric conditions (to retain the carbon dioxide in solution). For traditionally produced sparkling wine, lees removal requires prior riddling (remuage, Fr. or aclarado, Sp.) to assist flocculation and accumulation of the lees at the bottle neck. Historically, riddling was performed manually by placing the bottles in racks, called pupitres, at an angle of 25–30
to the ground. Bottles are progressively given a 1/8th of a twist and their inclination increased. This slowly moves the sediment toward the bottle neck. At the end of the process (1 or 2 months) the bottle is inverted with the lees next to the cork. Removal is a tedious and arduous process. Several systems have been developed that are far more efficient. Most wineries have replaced the racks with automatic riddlers, such as the Gyropallet. In it, bottles are placed in a cage (500-bottle bins) and shaken in a way which simulates the action of a remueur, but with motors and automatic controls. The Champagel system is another riddler with recliners especially designed

20

Susana Buxaderas and Elvira Lo´pez-Tamames

to rapidly prepare 500-bottle cages for disgorging (Bujan, 2003). These robotic units decrease the time required from weeks to a few days or hours. Riddling is not homogeneous process, as it depends on the lees’ variable surface area and flocculation characteristics (Vichi et al., 2010). The addition of clarifying agents, mainly bentonite, together with the liqueur of tirage, aims to normalize sedimentation (Martı´nez-Rodrı´guez and Polo, 2003). However, bentonite absorbs volatile components from the wine (Lubbers et al., 1994; Voilley et al., 1990) as well as proteins (Vanrell et al., 2007). Thus, it can affect the wine’s sensory attributes. In this regard, yeast immobilization in alginate (alginate bead ‘‘billes’’) (Divies et al., 1994; Fumi et al., 1987; Godia et al., 1991; Hornsey, 2007; Martynenko and Gracheva, 2003; Martynenko et al., 2004) and the Millipore Company’s Millispark system have been tested. In the latter, yeasts are contained inside a cartridge which is attached to the cap, where they remain during the prise de mousse. The cartridge contains a series of membranes and filters permeable to wine but retains yeast of cells and their residue. When disgorged, the cap is ejected with the yeasts and the wine stays crystal clear. The cost and reduced contact between encapsulated yeasts and the wine (restricted release of autolytic byproducts)are the primary drawbacks. This relates especially to higher quality sparkling wines and those aged for longer periods. Disgorging (lees removal) is carried out together with dosage. The necks of the bottles, pointed downward, are submerged into a freezing bath of ethylene glycol (45%). This freezes the sediments into an ice plug. When the bottle is inverted and opened, the ice plug pops out together with the cap. Immediately after, the dosage (expedition liqueur) is added. Each producer has a slightly different formula for the dosage, and some add no dosage in certain products. The dosage may consist of wine, sugar, brandy, sulfur dioxide, ascorbic acid, citric acid, or copper sulfate, amongst other substances. In the case of quality aromatic sparkling wines, the addition of expedition liqueur is prohibited (Official Journal of the European Union L 193/35, Commission Regulation (EC) No 606/ 2009). According to this European regulation, expedition liqueur refers to a product added to sparkling wines to give them special taste attributes. This liqueur may contain sucrose, grape must, grape must in fermentation, concentrated grape juice, rectified concentrated grape juice, wine, or a mixture thereof, with the possible addition of wine distillate. The dosage must not increase the alcoholic strength of the sparkling wine by more than 0.5% by vol. Based on the amount of sugar added, different indications that may be mentioned on the label (Table 1.2) (Official Journal of the European Union L0 6/391, Commission Regulation (EC) No 607/2009; implementation of Council Regulation (EC) No 479/2008). Currently, dosage is automated and 0–45 ml is added by means of a piston system. These machines also add sparkling wine from another

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21

TABLE 1.2 List of terms to be used for sparkling wine, aerated sparkling wine, quality sparkling wine or quality aromatic sparkling wine (Official Journal of the European Union L0 6/391, Commission Regulation (EC) No 607/2009; implementation of Council Regulation (EC) No 479/2008) Terms

Conditions of use

brut nature, naturherb, bruto natural, pas dose´, dosage ze´ro, natu¯ralusis briutas, ¯ısts bruts, prˇ´ırodneˇ tvrde´, popolnoma suho, dosaggio zero, брют натюр, brut natur extra brut, extra herb, ekstra briutas, ekstra brut, ekstra bruts, zvla´sˇteˇ tvrde´, extra bruto, izredno suho, ekstra wytrawne, екстра брют brut, herb, briutas, bruts, tvrde´, bruto, zelo suho, bardzo wytrawne, брют extra dry, extra trocken, extra seco, labai sausas, ekstra kuiv, ekstra sausais, ku¨lo¨nlegesen sza´raz, wytrawne, suho, zvla´sˇteˇ suche´, extra suche´, екстра сухо, extra sec, ekstra tør sec, trocken, secco, asciutto, dry, tør, xZro´B, seco, torr, kuiva, sausas, kuiv, sausais, sza´raz, po´łwytrawne, polsuho, suche´, сухо demi-sec, halbtrocken, abboccato, medium dry, halvtør, ZmίxZrοB, semi seco, meio seco, halvtorr, puolikuiva, pusiau sausas, poolkuiv, pussausais, fe´lsza´raz, po´łsłodkie, polsladko, polosuche´, polosladke´, полусухо doux, mild, dolce, sweet, sød, gluko´B, dulce, doce, so¨t, makea, saldus, magus, e´des, ħelu, słodkie, sladko, sladke´, сладко, dulce, saldais

If its sugar content is > 3 g/l; these terms may be used only for products to which no sugar has been added after the secondary fermentation. If its sugar content is between 0 and 6 g/l.

If its sugar content is > 12 g/l.

If its sugar content is between 12 and 17 g/l.

If its sugar content is between 17 and 32 g/l.

If its sugar content is between 32 and 50 g/l.

If its sugar content is < 50 g/l.

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bottle to adjust the volume to the proper fill level. Gushing, a phenomenon that is not well understood but very problematic, occasionally occurs. Particulate matter derived from case or cork dust, fibers or particles from packaging materials, and possibly particles from the wine or dosage itself, occlude very small air bubbles. These act as nuclei into which carbon dioxide can diffuse, releasing the pressure in the wine. The final phase of expedition includes the final corking, placement of the capsule, wire, and labeling. In spite of the risk of 2,4,6 trichloroanisole (TCA; musty off-flavors) absorption, the most commonly used bottle closures are made from conglomerate cork. One or more discs of high quality cork are attached to the end in contact with the wine. Other closures, for example, agglomerate corks, plastic (polyethylene) corks, crown caps, do not offer the proper physical–chemical properties to retain the effervescence and aroma attributes desired (Mas et al., 2001). Only with agglomerate corks is there evidence that the bottle should be stored horizontally. In this case, an upright positioning showed somewhat faster carbon dioxide loss and higher oxidation levels. After corking, the bottle is wired (muselet) to prevent the cork ejecting spontaneously. Finally, the bottle is ‘‘dressed’’ with foil and labeled. Subsequently, the bottles are stored in cases depending on their dimensions. The most common being those that contain 6 or 12 standard 750-ml bottles (Table 1.3). Some producers impose an empilage period while the wine and dosage marry prior to release. During this period, frequently lasting up to 6 months, undesirable mercaptan off-flavors dissipate, possibly due to interaction with oxygen absorbed from, or that permeates through, the cork.

TABLE 1.3

Name and volume of various types of bottles

Bottle name

Volume

Equivalent in Standard Bottles

1. Quarter or Piccolo 2. Half-Bottle 3. Standard Bottle 4. Magnum 5. Jeroboam 6. Rehoboam 7. Methuselah 8. Salmanazar 9. Balthazar 10. Nebuchadnezzar

187 ml 375 ml 750 ml 1.5 l 3l 4.5 l 6l 9l 12 l 15 l

1 bottle 2 bottles 4 bottles 6 bottles 8 bottles 12 bottles 16 bottles 20 bottles

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V. ORGANOLEPTIC CHARACTERISTICS The sensory attributes of wine are the reason for its consumption. Wines, including sparkling wines, are enjoyable food products that provide pleasure to the consumer. Although they possess some nutritional value due to their caloric content and/or healthy bioactive compounds, from a nutritional standpoint they are easily replaced by other foods. All winemaking strategies, from grape to bottling, are secondary to its sensory characteristics. There are three principal attributes that should be considered relative to sparkling wines: effervescence, color, and aroma. Although these are different properties, they are chemically related, especially color, flavor, and effervescence. An attempt to accentuate any of these could end up being harmful to the others. It is essential that the enologist find the best balance between the wine’s components to enhance all of the wine’s sensory properties.

A. Foam The foam (mousse) observed when sparkling wine is poured into a glass is an agglomerate of bubbles that have risen through the liquid and remain temporarily on the surface. Hence, the bubble is the unitary component of the mousse. Comelles et al. (1991) proposed a definition of this development: it is a group of small bubbles, composed of a sphere-like shaped liquid film that surrounds endogenous carbonic gas produced during a second fermentation. It is well known that effervescence is produced when a drink, containing an over saturated solution of carbon dioxide, is opened. This results due to the decompression that occurs when the cap is removed. However, even if there is effervescence, not all produce a foam. In a soft drink, for example, when decompression occurs, the rising gas bubbles break as soon as they reach the surface. Based on this it is evident that something more is needed for the bubbles to remain on the surface. In sparkling wines, bubbles consist of gas surrounded by a film of wine constituents. These tensioactive components and other substances afford viscosity to the film, giving texture to the bubble (Fig. 1.4). In soft drinks, there are insufficient tensioactive components and viscosifying substances that provide firmness to the bubbles

1. Bubbles The presence of tensioactive molecules in the wine is imperative for the formation of small, practically spherical, bubbles. These molecules also reduce the wine’s surface tension, enabling the bubbles to overcome the force that pulls them down into the wine, permitting them to accumulate on the wine’s surface, creating a small mound of foam.

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Carbon dioxide/liquid interphase of the bubble’s film Tensioactive compound Bicapa film

Liquid/air interphase of the wine’s surface

FIGURE 1.4 Outline of the bubble and its interface representation.

Tensioactive molecules are characterized by having a hydrophilic group that dissolves in the aqueous phase of both the wine and the film that surrounds the bubble, and a hydrophobic group insoluble in water that needs to be in the air or gaseous phase (Fig. 1.4). These compounds entrap the gas within a gas/film interface. Decreased surface tension in both interfaces is conducive. Both stabilize the foam and facilitate gas entry into the bubble’s interior. These bubble nuclei to increase in size (Jordan and Napper, 1988). Wine possesses several tensioactive molecules, such as ethanol, glycerol, and tartaric acid, present in g/l concentrations. Others, such as fatty acids occur in mg/l amounts. Ethanol is the most abundant. Tests performed with water, containing increasing amounts of ethanol, show that the surface tension decreases from 72 to 47.3 mN/m at a concentration of about 12% v/v ethanol. Once this concentration is reached the surface tension remains constant (Fig. 1.5). The concentration at which a tensioactive molecule can no longer reduce surface tension is known as its critical micelle concentration (Fig. 1.5). A tensioactive molecule remains in the liquid, forming a micelle structure, except in the case of ethanol. The limited distance between the hydrophilic hydrophobic groups prevents it from forming micelles and acts as a dissolvent of scarcely hydrophilic groups (Comelles et al., 1991). Some authors have determined that a wine’s foam capacity increases with the level of alcohol up to a concentration of 12% v/v, while foamability decreases at higher concentrations (Lo´pez-Barajas et al., 1997). The combination of the three main

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25

Superficial tension

mN/m

mN/m = Constant

cmc

Tensioactive concentration

Air

Wine

Absortion of tensioactives in wine/air interfase

Micellar structure of tensioactives at cmc

FIGURE 1.5 Relationship between tensioactive compounds and surface tension. mN/m, millinewtons per meter; cmc, quantity of tensoactive compound that saturates the liquid’s surface.

tensioactives constituents has a synergic action. The surface tension falls to 42.7 mN/m values when present as follows: 12% v/v ethanol and 0.4% p/v glycerol and tartaric acid. According to Andre´s-Lacueva et al. (1997) the surface tension of 96 sparkling wines ranged from 48.8 and 50.2 mN/m. Other wine components that participate in foam production donate viscosity to the bubble film, including proteins, polysaccharides, and polyphenols (Bramforth, 1985). These compounds generate the film’s elastic properties and enable it to serve as a barrier. This maintains the individuality of each bubble, strengthening their resistance to rupture (Casey, 1995). However, their durability is limited. Bubbles located on the surface gradually lose liquid due to gravity-related drainage, atmospheric pressure, and/or evaporation (Maujean, 1989). Consequently, the film’s thickness decreases and the bubbles become more fragile and break, or they collapse when compressed by neighboring bubbles. Foam stability depends on the average life span of the bubbles of which it is comprises. This depends on the film’s viscosity or colloidal composition (Dickinson, 1994; Jordan and Napper, 1988). Some authors have demonstrated that the viscosity of a bubble’s film is directly related to the wine’s viscosity (Bourne, 1982; Maeda et al., 1991). The speed of drainage and the destructive effects of bubble interaction decrease as viscosity increases (Brissonnet and Maujean, 1991; Kinsella, 1981; Marchal et al., 1996; Robillard et al., 1993).

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Given the bubble’s dependence on wine composition, many authors have investigated this relationship (Buxaderas and Lo´pez-Tamames, 2010). However, the large number of potential interactions among polysaccharides, proteins, phenols, fatty acids, and organics complicate the interpretation. The appearance of more or less stable bubbles probably depends on a balance between these constituents (Buxaderas and Lo´pezTamames, 2010). Employing a flow of carbon dioxide gas has been used to separate bubbles to determine film composition. The critical issue is to be able to separate the bubbles without being diluted by simultaneously drawing up wine. Correspondingly the film’s components may occur in considerably higher amounts than those found in the wine (Brissonnet and Maujean, 1991, 1993; Gallart et al., 2002). Brissonnet and Maujean (1991) suggest that the film contains more proteins with greater hydrophobic properties than those in the wine. Other authors believe that the positive charge on proteins at wine pH levels is what enables them to migrate to the wine/air interface, stabilizing the foam (Robillard et al., 1993). Contradictory results have been published on the influence of fatty acids (Dussaud et al., 1994; Maujean et al., 1990; Pueyo et al., 1995). Gallart et al. (2002) found increased amounts of free fatty acids (C6, C8, C10, and C16) and ethyl esters in the film. According to these authors, esterified forms promote foamability, demonstrating that the higher the coefficient between esterified and free fatty acids, the higher the foaming capacity. Other studied compounds have been polysaccharides. Again there is no unanimity of opinion (Andre´s-Lacueva et al., 1996, 1997; Lao et al., 1999; Lo´pez-Barajas et al., 2001). The work conducted by Sene´e et al. (1999) noted that proteoglycans (polymers between polysaccharides and proteins) have tensioactive properties. They easily dissolve in the gas/liquid interface, decreasing the rate at which liquid drains from the film. A review conducted by Buxaderas and Lo´pez-Tamames (2010) suggests that many compounds influence foamability, either directly, as is the case of the aforementioned compounds, or indirectly, by modifying the solubility of colloids, the wine’s pH, compound concentration, and interactions between various components. In addition, enologic practices that modify the chemistry of sparkling wine composition can influence foaming capacity.

2. Effervescence The chains of bubbles (rosaries) that rise through the wine generate its effervescence. In sparkling wine, there are two types of effervescence: one tumultuous and the other slower, calmer, and continuous. Tumultuous effervescence is generated when wine is poured into the glass immediately after opening, initiating instantaneous decompression. This effervescence is caused primarily by microbubbles that have formed in the wine during its handling and transport (Bidan et al., 1986; Jordan and

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Napper, 1988; Maujean, 1989). When the bottle is opened and pressure drastically drops, these microbubbles can grow and explode (Maujean, 1989). The process is known as induced homogeneous nucleation. Tumultuous foam rises a few centimeters in the glass, but the foam height rapidly collapses back to a few millimeters. It is maintained by bubble rosaries that rise more slowly. This is the foam that remains on the surface, whose duration winemakers wish to prolong. The incessant generation of bubbles that rise to the surface is believed to originate primarily in microcavities. These contain gas protected by a lipophilic layer (Casey, 1988; Liger-Belair et al., 2008; Sene´e et al., 1999). Particles of cork dust, yeast cell residues, cloth fibers (from drying cloths), or macromolecules such as bentonite or potassium bitartrate microcrystals may serve as microcavities. Carbon dioxide enters these microcavities due to capillarity. When it reaches a certain volume the bubble breaks off and rises to the surface. These microcavities produce continuously produce successive bubbles, creating a rosary. This is known as induced heterogeneous nucleation (Casey, 1988; Jordan and Napper, 1988). It is responsible for the appearance of a stable foam on the surface of the wine. When the bubbles reach the surface, they overcome surface tension, forming a layer initially covering the entire surface (Fig. 1.6). Depending on the number of chains that develop, there will be one, two, or more bubble layers. However, as the wine rises to room temperature, bubbles moves toward the sides of the glass. Here, they occupy the circumference

Initial foam Total

Categories

Scores

Abundant Normal Poor

3 2 1

Partial

Non

Foam area 3 2

1

3 2

1

Foam collar

Buble size

FIGURE 1.6

Small

Medium Large

Sensory descriptors of foam according to Gallart et al. (2004).

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Susana Buxaderas and Elvira Lo´pez-Tamames

and create what is known as a foam crown (Fig. 1.6). It is likely that room temperature favors alcohol evaporation, more so in the center than at the circumference, causing surface tension to be higher at the center. This makes it is easier for bubbles to reach the surface in contact with the walls, leading to crown formation (Tuinier et al., 1996). Tasting cards used in the sensory assessment of sparkling wines primarily use visual appreciation to measure foam quality, based on a hedonic scale (much/little foam, small/large bubbles) (Hardy, 1991). Some authors have tried to reach a consensus with enologists in terms of the sensory descriptors appropriate for assessing foam quality (Gallart et al., 2004; Obiols et al., 1998). These authors propose four main descriptors: initial foam, foam area, foam collar, and bubble size. Depending on the assessment of these features, they ask the taster to give a measure of overall impression, on a scale of 1–4 (Fig. 1.6). The initial foam refers to the height present in the glass after tumultuous foaming has subsided. The foam area assesses whether bubbles manage to cover the entire surface area of the wine, whereas foam collar measures the appearance of a complete or partial foam crown. Bubble size, large, average, or fine, is an attribute that is indirectly related with the prior properties. It is preferable for bubbles emanating from microcavities are fine, given that they grow during their rise to the surface. Carbon dioxide continues to diffuse into the bubble during its assent. When they reach the surface, the film coating loses liquid, due to drainage. This makes them increasingly prone to rupture due to poor resistance to atmospheric pressure and coalescence with other bubbles. The larger the bubbles that reach the surface, the shorter their duration and the more ephemeral the foam. Although a wine’s capacity to produce foam depends on its composition and on the viticulture and enologic practices applied in its elaboration (Andre´s-Lacueva et al., 1996, 1997; Girbau-Sola` et al., 2002a,b; Lo´pezBarajas et al., 1997, 1998; Maujean et al., 1990; Moreno-Arribas et al., 2000; Poinsaut, 1991; Robillard et al., 1993; Vanrell et al., 2007), foam development in the glass also depends on factors independent the producer. An important factor is the wine’s temperature: the colder the wine, the greater the amount of carbon dioxide gas can remain dissolved in the wine, the slower the rate of release on opening and the longer the effervescence and foam will last. On the other hand, the way in which the bottle is opened, how the wine is poured, the type of cleaning, and drying of the glass, as well as its shape can all influence the foam and effervescence the taster will observe. According to Casey (1995), the correct type of glass for drinking sparkling wine is a flute shaped glass. It offers a small surface for gas escapes and reduces ethanol evaporation. Aroma loss is reduced, while effervescence and foam are prolonged. These factors affect foam assessment, requiring standardization of the service protocol before tasting to obtain objective and consistent results (Obiols et al., 1998).

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There are specially designed wine glasses that guarantee sufficient effervescence and foam over the time it takes to consume the sparkling wine. These glasses are manufactured with small scratches in the bottom of the glass. These act as microcavities for induced heterogeneous nucleation (Liger-Belair et al., 2001, 2008). This glass offers the winemaker the certainty that the care taken in producing sparkling wine will be expressed in the glass.

B. Color The color of a sparkling wine largely depends on the grape varieties used in its production. Golden yellow is typical for wines made from white grapes (blanc de blanc). This is also true for sparkling wines made from red grapes (blanc de noir) by eliminating must maceration and intensified clarification. Rose´ sparkling wines acquire their hue from the red grapes used. They contain natural pigments, such as carotenoids and phenolics, the content of which depends on grape variety, climatic conditions, stage of maturity, soil characteristics, and viticulture practices. However, in sparkling wines color seems to depend primarily on phenolic compounds and the oxidation reactions in which they are involved. Most wine cellars traditionally use a simple measure of color, the color index (CI: sum of the absorbance at 420 and 520 nm), or just the value of absorbance at 420 nm. In base wines, it ranges between 80 and 140 a.u., depending on whether it is a blanc de blanc or a blanc de noir, while in rose´ sparkling wines values are located around 200 a.u (Buxaderas and Lo´pez-Tamames, 2010).

1. Compounds related with color

Grape skin contains 2–3 times more carotenoids than the pulp, b-carotene and lutein being the most abundant, the remaining 15% consisting of xanthophylls, such as neochrome, neoxanthin, violaxanecesthin, luteoxanthin, flavoxanthin, lutein-5,6-epoxide, and zeaxanthin (Guedes de Pinho et al., 2001; Mendes-Pinto et al., 2004). The biosynthesis of these compounds takes place until veraison and is enhanced by direct sun exposure. However, sunlight also facilitates their degradation from veraison to maturity. This explains why lower levels are found in the mature grapes of warmer areas than in colder climates (Crupi et al., 2010; MendesPinto et al., 2005). After veraison, the grape carotenoid content decreases drastically, being metabolized to norisoprenoids. These often contribute to a cultivar’s varietal aroma (Baumes et al., 2002; Crupi et al., 2010; Lee et al., 2007; Mendes-Pinto, 2009). Different carotenoid degradation routes to norisoprenoids have been described, including enzymatic, autoxidation, and thermal decomposition. The latter is more significant in food preparation than enology (Kanasawud and Crouzet, 1990; Mendes-Pinto, 2009; Mendes-Pinto et al., 2005). Carotenoid levels in must and white and

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Susana Buxaderas and Elvira Lo´pez-Tamames

red wines are negligible, except in port must and wine (Mendes-Pinto, 2009; Mendes-Pinto et al., 2005). This is probably due to the way Porto fortified wines are made (Guedes de Pinho et al., 2001). In this type of sweet wines, fermentation is incomplete and occurs in the presence of grape skins. Fermentation is terminated 3 or 4 days later when brandy is added to reach about 20% alcohol (v/v). The high alcohol content facilitates the dissolution of carotenoids into the wine. Although red table wines also involve fermentation in the presence of seeds and skins, it is likely that maceration accelerates enzymatic oxidation generating norisoprenoids. In addition, the alcohol content does not dissolve detectable carotenoid levels. Nonetheless, carotenoids are important in red wines as aromatic precursors. In the case of white wines, which are fermented in the absence of grape skins and possess equivalent amounts of alcohol, that residual carotenoids are not detected is expected. Their significance is only in terms of aroma precursors from grapes. Phenolic compounds are secondary metabolites synthesized by the plant, occasionally in response to stress, such as fungal attack, drought, ultraviolet radiation, and temperature extremes (Deloire et al., 1998). Phenolics may not only influence color but also astringency, bitterness, clarity, and even aroma. Some are precursors of volatile phenol off-odors (Chatonnet et al., 1992). Phenolic compounds are subdivided into two large groups, nonflavonoids, found in grape skins and pulp, and flavonoids, located in grape skins, seeds, and the pedicel. Nonflavonoids include acidic and nonacidic derivates, such as tyrosol and tryptophol, hydroxybenzoic acid derivatives (gallic, protocatechuic, p-hydroxybenzoic, vanillic, and syringic), hydroxycinnamic acids (trans-caffeic, trans-p-coumaric, and cis-p-coumaric), esterified hydroxycinnamates (cis-caftaric, trans-caftaric, cis-coutaric, trans-coutaric, trans-fertaric, and 2-S-glutathionylcaftaric), and stilbenes (trans-resveratrol glucoside, cis-resveratrol glucoside, cis-resveratrol, and trans-resveratrol) (Chamkha et al., 2003; Ibern-Go´mez et al., 2000; Pozo-Bayo´n et al., 2003a). The most abundant forms in white wines are hydroxycinnamic acids (50–60%). These are colorless compounds that can intervene in redox reactions, generating yellow-brownish compounds (Baderschneider and Winterhalter, 2001; Chamkha et al., 2003; Gonzalez Cartagena et al., 1994; Salacha et al., 2008). Flavonoids are a large group of compounds, the basic structure of which consists of two benzene rings (rings A and B) connected by an oxygenated heterocycle. Depending on the heterocycle structure, several subgroups are distinguished: flavonols, anthocyanins, catechins, and procyanidins. Anthocyanins possess a red color at wines pH levels. They are absent in white wines. Other flavonoids are yellow and found in grape skins of both white and red grapes. The minimal maceration between the must and grape skins involved in the production of white wines explain the residual quantities of free and glycosylated flavonols in white wines,

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for example 0.05–0.21 mg/l of quercetin. Catechins, also known as flavan3-ols, are the primary flavonoids, occurring in the range of 0.22–3.93 mg/l for (þ)-catechin and 0.28–1.98 mg/l for ()-epicatechin (Chamkha et al., 2003; Ibern-Go´mez et al., 2000). The yellow color of white wines (expressed as absorbance at 420 nm) is mainly a result of oxidized phenolic compounds. During the interim between grape crushing and sulfur dioxide addition to the must, enzymic oxidation by polyphenol oxidase (PPO, EC 1.10.3.1) is possible (Nagel and Graber, 1988). After fermentation (during wine maturation and aging), phenolic oxidation in sparkling wine is nonenzymatic (Cilliers and Singleton, 1990). Oxidation initially intensifies the yellow color, but when extensive, it produces a brownish color. This process is considered desirable for dessert wines, but is unacceptable in young white and sparkling wines. Until recently, flavonols were believed to be the primary cause of the oxidative browning of white wines (Cheynier et al., 1989). Today, the role of hydroxycinnamates, the most abundant phenolic compounds in white wine, is recognized in oxidative browning. In particular, the polymerization of caffeic and other hydroxycinnamic acids with ortho-quinones, derived from oxidized ortho-dihydroxyphenolic compounds such as (þ)catechin, ()-epicatechin, leads to the formation of yellow or brown byproducts (Guyot et al., 1996). Data from Oszmianski et al. (1996) confirm their potential as browning agents. Quinones are themselves yellow in color, potentially generating a brown or brickish color. Quinones, being unstable, oxidant and strongly electrophilic (lacking in electrons) play a role in reactions with nucleophilic molecules (an excess of electrons) and in oxide reduction reactions. Caffeoyl tartaric o-quinone is abundant in white wines. Caftaric acid is not only the most abundant cinnamic derivative in grapes but also the main PPO substrate. Caffeoyl tartaric o-quinone can be used to piggyback nucleophilic molecules, such as glutathione (a tripeptide abundant in grapes). This generates 2-S-glutathionylcaftaric acid (2-SGC) or Grape Reaction Product (GRP), a colorless compound. Thus, glutathione can help avoid nonenzymatic browning, blocking caffeoyl tartaric o-quinone production by preventing its action with other substrates. This occurs if there is more glutathione than caftaric acid, and that it can bind with all the caffeoyl tartaric o-quinone. Nonetheless, 2-SGC can itself become oxidized via a coupled oxidation reaction with caffeoyl tartaric o-quinone, giving rise to 2-SGC-derived o-quinone. Caffeoyl tartaric o-quinone can also trigger this type of reactions with flavonoids. On the one hand, the reaction allows the caftaric acid-derived quinone to attach to carbon 6 or 8 of the A nucleophilic ring of flavonoids, or alternatively a coupled oxidation, leading to the formation of quinine and regeneration of the caftaric acid (Cheynier and Van Hulst, 1988; Cilliers and Singleton, 1990; Singleton, 1988). Both products, derived from the coupling reaction

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Susana Buxaderas and Elvira Lo´pez-Tamames

between caffeoyl tartaric o-quinone and flavonoids or 2-SGC-derived quinone, give rise to polymers with a brownish color. In addition to polyphenols, other compounds such as carbohydrates can affect color alterations. Furfural and its derivatives have long been considered indicators of deterioration in processed foods, including fruit juices. Heat treatment favors the formation of furfural compounds and their accumulation during storage (Lee and Nagy, 1988; Lo Coco et al., 1994). Although most wines are not intentionally heated, furanes can form nonenzymatically from sugar degradation in white wines (Caˆmara et al., 2006; Lavigne et al., 2008; Pereira et al., 2010). These compounds can interact with anthocyanins (Daravingas and Cain, 1968) and, in model solutions, furfural and 5-hydroxymethyl furfural (HMF) influence the degradation of cyanidin 3-O-glucoside (Debicki-Pospisˇil et al., 1983). In a recent work, (þ)-catechin was separately incubated with furfural or HMF, leading to the formation of oligomeric bridged compounds having flavanol units linked by furfuryl or 5-hydroxymethilfurfuryl (Es-Safi et al., 2000). The presence of furfural derivatives in white wines, associated with the prolonged aging of sparkling wines, could play a role in the flavanol-induced polymerization processes and contribute to color generation and browning.

2. Influence of vinification on color development As soon grapes are crushed, phenolic compounds begin to oxidize in the presence of polyphenol oxidase as well undergo autoxidation. For this reason, white grapes should arrive uncrushed to the cellar, at least those destined to sparkling wine production. In France, Italy, and Spain grapes, as noted, grapes arrive at the winery uncrushed. Juice is extracted by soft pressing and is immediately sulfited to block the action of PPO. Another precaution, to reduce autooxidation, is flushing the head space of wine storage containers with nitrogen. During vinification, approximately 20% of phenolic content is lost, most of this involving hydroxycinnamic acids. Some authors (Bete´s-Saura et al., 1996) have demonstrated that all assessed phenolic compounds varied significantly (p < 0.001) during vinification, except for gallic acid, syringic acid, trans-ferulic acid, and procyanidin B2. These losses occur during must settling, racking, wine clarification, tartaric stabilization, and filtration. When clarification involves chemical additives, their properties affect the phenolics remained and the wine’s browning potential (Cosme et al., 2008; PuigDeu et al., 1999). Under laboratory conditions, casein primarily reduces the flavonoid content, while isinglass and potassium caseinate are more effective at reducing the nonflavonoid content. Gelatin slowly eliminates all phenolic compounds (Cosme et al., 2008; Sims et al., 1995). Few studies have studied the phenolic composition of sparkling wine and their evolution during aging (Chamkha et al., 2003; Ibern-Go´mez

Sparkling Wines

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et al., 2000; Pozo-Bayo´n et al., 2003a). There is no consensus between researchers on whether sur lies aging enhances browning. According to Ibern-Go´mez et al. (2000), absorbance at 420 nm increases relative to the phenolic content of the base wine used for sparkling wine production. However, other authors believe that aging in contact with yeast lees protects the wine from oxidation. During aging, the color is stabilized due to bonding between phenolic compounds and polysaccharides or mannoproteins, through absorption to yeast cell walls (Escot et al., 2001; Fornairon-Bonnefond et al., 2002; Vidal et al., 2003). These processes could explain the reduction in absorbance at 420 nm found by Girbau-Sola` et al. (2002b). They found that in 12 Cavas (two blanc de blanc, five blanc de noir, and five rose´), color intensity (absorbance at 420 and 520 nm) did not vary in 5, decreased about 22% in the rest, and between 19% and 36% in the rose´s. The tendency to brown during aging may depend on the phenolic content or oxidative state of the base wine initially used (Girbau-Sola` et al., 2002b; Ibern-Go´mez et al., 2000). However, it contact with yeast cell walls and bentonite (added to the tirage liquor to assist flocculation) may absorb phenolic compounds (Fornairon-Bonnefond et al., 2002; Vidal et al., 2003).

C. Aroma The volatile compounds that donate the aroma to sparkling wines largely depend on the grape varieties used and the manner of second fermentation completing (in-bottle or tank). For example, Italian spumanti wines derive their fruity, floral, and perfumed notes from the use of Muscat. It possesses a terpenic profile due to the presence of linalool, hotrienol, diols, geraniol, nerol, linalool oxides, etc. In contrast, Sekt wines, produced from Riesling, boast a citrus, fresh, floral, mineral, and honeyed fragrance. The influence of varietal aromas is especially important when using the Charmat method. Whereas aging occurs in the bottle, as is the case of Cava or Champagne, the most influential factor is yeast autolysis. Sur lies aging involves an enrichment with components provided by the lees (nucleotides, amino acids, oligosaccharides, fatty acids, aromas, and vitamins) (Alexandre and Guilloux-Benatier, 2006). In addition, poorly understood chemical and biochemical processes involving yeast/wine interaction, dependent on the age and physical–chemical characteristics of the base wine, are also involved (Torrens et al., 2010a). These phenomena are essential to the wine acquiring its aromatic profile (Comuzzo et al., 2006; De la Presa-Owens et al., 1998; Noble and Ebeler, 2002). Of the sur lie aroma components that increase during aging, compounds of a varietal origin, such as norisoprenoids, furanic, and thiol compounds, should be noted (Bosch-Fuste´ et al., 2007). Sulfur components especially have a double and controversial participation in the wine’s

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Susana Buxaderas and Elvira Lo´pez-Tamames

aroma (Howell et al., 2004). Milder thiols, such as methane and ethanethiols provide fecal and putrid notes, whereas components such as 3-mercaptohexanol and 2-furfurylthiol donate tropical fruit and coffeelike notes (Blanchard et al., 2001; Tominaga and Dubourdieu, 2006). Modern enologic practice attempts to eliminate mercaptans but promote the retention of sulfur compounds. Yeast autolysis not only affects morphological changes in cell structure (Martı´nez-Rodrı´guez et al., 2001a) but also affects the volatile fraction of sparkling wines more than the grape variety used (Pozo-Bayo´n et al., 2003b). In contrast, the nitrogenous fraction relates to both sur lies aging and yeast strain used (Martı´nez-Rodrı´guez et al., 2001b). Volatile compounds can act as indicators of the duration of lees contact in Cava wines (Bosch-Fuste´ et al., 2007; Campo et al., 2008; Francioli et al., 2003; Riu-Aumatell et al., 2006). These lead to detectable sensory influences, such as a loss of fruity aromas (decline in acetate content and changes in mono- and dicarboxylic acids esters), while other more complex sensations increase. The perceptions of dry fruit, nuts, toasted aromas, and ripe fruit may come from the breakdown of nonvolatile glycosides. This can release volatile lactones and norisoprenoid, and the favor the formation furanic compounds from carotenoids and sugars (Francioli et al., 2003; Riu-Aumatell et al., 2006; Torrens et al., 2010a). The latter are probably involved in generating notes of eucalyptus, kerosene, tobacco, and ripe fruits, associated with increased concentrations of vitispiranes, 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN), b-damascenone, and teaspirane (Rapp, 1998; Winterhalter, 1991). In Champagnes, heptenal (biscuit/cookie like); 5-nonanolide, acetal (nutty); undecalactone, diacetyl (bread and yeast notes); phenylacetic acid, phenylethyl acetate, ethyl cinnamate, 2-phenylethanol (honey elements); sotolon, guaiacol, isoeugenol (toasted aromas); undecalactone, 4-methylthiazole, 2-acetylthiazole, diacetyl (hazelnut); 2-furanmethanethiol (coffee); 2,6-dimethylpirazine (chocolate); acetoin, furfural (marzipan) have been detected (Escudero et al., 2000; Vannier et al., 1999). Lees play an interactive sensory role (Charlier et al., 2007; Torrens et al., 2010b), notably in reference to esters. Long chain esters are especially likely to be absorbed by yeast cell walls (Pozo-Bayo´n et al., 2003b) and be subsequently released as cell hydrophobicity increases during aging (Gallardo-Chaco´n et al., 2009, 2010). In addition, these esters could be degraded by yeast enzymes released during autolysis. Because the absorption of volatile compounds is reversible, a function of hydrophobicity, and changes during aging, it could have a significant effect on the wine’s sensory attributes at disgorging. This has recently been demonstrated for several potential impact compounds (Gallardo-Chaco´n et al., 2010). Such changes could clearly affect the perceived quality and, therefore, the wine’s commercial value.

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VI. DATA OF PRODUCTION AND CONSUMPTION According to data from the International Wine and Spirit Research (IWSR), provided by Freixenet S.A., the total production of sparkling wines worldwide was 2079 million bottles. Figure 1.7 shows that since 2007, production has been decreasing, possibly as a result of the economic crisis that has unfolded in developed countries. However, with the recovery and economies of emerging countries, the outlook for market growth is optimistic (Fig. 1.8). The leading producers of sparkling wines are the EU countries, such as France, Germany, Spain, and Italy. Their production accounts for 65% of world production (Payne et al., 2008). However, even though Europe continues to dominate consumption, other consumer countries have appeared, including many from the Commonwealth of Independent States (CIS) (former USSR) and the USA (Fig. 1.8). In the same regard, it is forecast that as a result of increasing consumption, the top five growth markets for sparkling wines in 2015 will be Russia, the United States, Australia, the United Kingdom, and the Ukraine. Regarding the types of sparkling wines, Champagne sales decreased between 2007 and 2009 in the United States and the United Kingdom. In 2009, for the first time, Cava overtook Champagne as the most consumed sparkling wine (Cava Regulatory Board, http://www.crcava.es; Martı´nez Carrio´n and MedinaAlbaladejo, 2010). World production of sparkling wine per year (volume in thousands 9 -l cases) 180,000 175,000 170,000 165,000 160,000 155,000 150,000 145,000 2005

2006

2007

2008

2009

FIGURE 1.7 Evolution of sparkling wine production since 2005. Data provided by Freixenet S.A.

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Susana Buxaderas and Elvira Lo´pez-Tamames

50,000 45,744

45,000

Others

42,672 40,024

40,000

40,242

35,000

34,405 30,536

41,101

40,933

31,933

Germany

40,845

32,363

32,448

France

30,000 25,666

25,000

26,458

Russia

23,103

20,000 15,000 10,000

14,272 13,287 11,515

15,535

11,694

11,605

8883

9979

7184 8685

7993

4362

4337

4465

2009

2012

8426

5000 0

14,713

2004

16,596

12,022 10,371 8575 6980 5777 4452

USA italy UK Spain Australia Ukraine Poland

2015

FIGURE 1.8 Forecast consumption for the top 10 sparkling wine markets (volumes in thousands of 9-l cases).

In terms of exportation, Italy is the leading country in exportation, followed by Spain and France. Chile and Australia are the producers with the highest exportation growth rate in the last 5 years (Smith, 2011). Traditionally, consumption of sparkling wines had been linked to aperitifs and celebrations and/or luxury. However, increasing sales in the CIS, Asia-Pacific, and the Americas, combined with improved quality–price relationships and diversification, make increased consumption ‘‘on a more regular basis’’ and not just as a celebratory drink (Fischer and Gil-Alana (2009); Herna´ndez, 2009).

ACKNOWLEDGMENTS This study was supported by Ministerio de Ciencia y Tecnologı´a (MCYT, Spain), project AGL and AGL2011-23872/AGL, and by the Generalitat de Catalunya, project 2009SGR606 (Spain). Special thanks to Jordi Torrens from Freixenet S.A.

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Andre´s-Lacueva, C., Lo´pez-Tamames, E., Lamuela-Ravento´s, R. M., Buxaderas, S., and Torre-Boronat, M. C. (1996). Characteristics of sparkling base wines affecting foam behavior. J. Agric. Food Chem. 44, 989–995. Andre´s-Lacueva, C., Lamuela-Ravento´s, R. M., Buxaderas, S., and Torre-Boronat, M. C. (1997). Influence of variety and aging on foaming properties of sparkling wine (Cava) 2. J. Agric. Food Chem. 47, 2520–2525. Andu´jar-Ortiz, I., Pozo-Bayo´n, M. A., Garcı´a-Ruiz, A., and Moreno-Arribas, M. V. (2010). Role of specific components from commercial inactive dry yeast winemaking. Preparations on the Growth of lactic acid bacteria. J. Agric. Food Chem. 58, 8392–8399. Arevalo Villena, M., Ubeda Iranzo, J. F., and Briones Perez, A. I. (2007). b-Glucosidase activity in wine yeasts: Application in enology. Enzyme Microb. Technol. 40, 420–425. Baderschneider, B. and Winterhalter, P. (2001). Isolation and characterization of novel benzoates, cinnamates, flavonoids, and lignans from Riesling wines and screening for antioxidant activity. J. Agric. Food Chem. 49, 2788–2798. Baumes, R., Wirth, J., Bureau, S., Gunata, Y., and Razungles, A. (2002). Biogeneration of C13-norisoprenoid compounds: Experiments supportive for an apo-carotenoid pathway in grapevines. Anal. Chim. Acta 458, 3–14. Bete´s-Saura, C., Andre´s-Lacueva, C., and Lamuela-Ravento´s, R. M. (1996). Phenolics in white free run juices and wines from Penede`s by high-performance liquid chromatography. Changes during vinification. J. Agric. Food Chem. 44, 3040–3046. Bidan, P., Feuillat, M., and Moulin, P. J. (1986). Vins mousseux, rapport de France. Bull. Off. Int. Vigne Vin 59, 563–626. Blanchard, L., Tominaga, T. Y., and Dubordieu, D. (2001). Formation of furfurylthiol exhibiting a strong coffee aroma during oak barrel fermentation from furfural released by toasted staves. J. Agric. Food Chem. 49, 4833–4835. BOE No. 50 February 2007. ORDEN APA/415/2007, de 23 de febrero, por la que se modifica el Reglamento de la Denominacio´n «Cava» y de su Consejo Regulador. 50, pp. 8487–8491. Bosch-Fuste´, J., Guadayol, J. M., Caixach, J., Lo´pez-Tamames, E., and Buxaderas, S. (2007). Volatile profile of sparkling wines obtained by three extraction methods and gas chromatography-mass spectrometry (GC-MS) analysis. Food Chem. 105(1), 428–435. Bourne, M. C. (1982). Food Texture and Viscosity: Concept and Measurement. Academic Press Inc., New York. Bramforth, C. W. (1985). The foaming properties of beer. J. Inst. Brew. 91, 370–383. Brissonnet, F. and Maujean, A. (1991). Identification of some foam-active compounds in Champagne base wines. Am. J. Enol. Vitic. 42, 150–152. Brissonnet, F. and Maujean, A. (1993). Characterization of foaming proteins in Champagne base wines. Am. J. Enol. Vitic. 44, 297–301. Bujan, J. (2003). Robotizacio´n de una cava de gran produccio´n: una solucio´n particular. ACE Rev. Enol. 1697–4123 No. 29. Burattini, E., Cavagna, M., Dell’Anna, R., Malvezzi Campeggi, F., Monti, F., Rossi, F., and Torriani, S. (2008). A FTIR microspectroscopy study of autolysis in cells of the wine yeast Saccharomyces cerevisiae. Vibrat. Spectr. 47(2), 139–147. Buxaderas, S. and Lo´pez-Tamames, E. (2003). Wines production of sparkling wines. In ‘‘Encyclopedia of Food Sciences and Nutrition’’, (B. Caballero, L. Trugo, and P. Finglas, Eds), Vol. 10, pp. 6203–6209. Elsevier Science Ltd., London. Buxaderas, S. and Lo´pez-Tamames, E. (2010). Managing the quality of sparkling wines. In ‘‘Managing Wine Quality: Oenology and Wine Quality’’, (A. G. Reynolds, Ed.), Vol. 2, pp. 553–588. Woodhead Publishing Ltd., Cambridge, U K. Caˆmara, J. S., Alves, M. A., and Marques, J. C. (2006). Changes in volatile composition of Madeira wines during their oxidative aging. Anal. Chim. Acta 563, 188–197.

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