BIOTECHNOLOGY OF FLAVORED OR SPECIAL WINES
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Monica Butnariu Chemistry & Biochemistry Discipline, Banat’s University of Agricultural Sciences and Veterinary Medicine “King Michael I of Romania” from Timisoara, Timis, Romania
8.1 Aromatized or Special Wines Special wines are prepared by alcoholization of the must during fermentation, which stops the fermentation process and maintains the necessary amount of sugar. The assortment of such wines is rich and varied (e.g., Madera, Portvein, Marsal, Heres, Vermut, and dessert wines). Each one has its original production technology. However, the characteristic for all types of special wines is the grape berry with a high content of sugar (190–200 g/L), aromatic and extractive substances. It is even better if the grapes are harvested at full maturity or even overmaturity. The rectified alcohol used must be of the highest purity. The sulfiting only applies to the production of dessert wines like Muscat, for extracting and protecting the essential oils from oxidation. In the case of caramelized wine production, must concentrate is added to musts or young wine. Aromatized wine vermouths are prepared with the addition of medicinal and aromatic herbs alcoholic extracts. The category of special wines includes strong wines, dessert wines, and aromatized wines. The history of aromatized wines is little known. The beginning of their preparation dates back to very old times. The addition of plants in wine, as such or as infusion, as extract or as active principles, has been known since antiquity. Hippocrates from Kos, the “father of medicine,” created a wine with the addition of wormwood and fern infusion. The Romans prepared a wine called Vinum Ellenicum Absinthiatum, in which they added wormwood and other aromatic herbs, too. In the Middle Ages, aromatized wines have gained importance because they have been used a lot in pharmacopeias as medicinal wines. The best example is the traditional “hippocratic wine.” During the Renaissance, the cities of Turin, Florence, and Venice become the most important centers where Hippocrates wines are produced. The aromatized wines are defined as those wines containing Biotechnological Progress and Beverage Consumption. https://doi.org/10.1016/B978-0-12-816678-9.00008-4 © 2020 Elsevier Inc. All rights reserved.
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addition of a variety of plant species, infusions, and/or plant extracts, which are capable of giving them smells and tastes different from those of the stricto sensu wines. Alcohol, sugar, and caramel may also be added (Dellacassa et al., 2017).
8.2 Overall Characterization A special category of white wines is represented by aromatic wines. Their production must be carefully monitored, requiring a longer production time. The aromatic wines are obtained from special grape varieties. The technology for the production of aromatic wines has a necessary and obligatory stage, the stage where the aromas are extracted from the grape berries peels. Maceration, as it is technologically called, consists in keeping the grape berries peels in contact with the must in order to destroy the cell wall and extract the flavor compounds in the must. By aromatized wine are meant those wines in which plants, infusions, and/or plant extracts of plants are added, which are capable of giving them odors and tastes different from those of the wines themselves. It is understood that all such additions are accepted by the laws of the countries preparing such beverages. The effervescent wines have a high content of CO2, which makes them foam when pouring into glasses or at direct contact with the air (Liger-Belair, 2016). Liqueur wines are made from must or wine with the addition of concentrated must, distilled wine, or alcohol. They have an alcoholic strength between 15% and 22% and a high sugar content of over 80 g/L (de-la-Fuente-Blanco et al., 2016). The well-done Retsina wine is an extremely versatile wine, accompanied by typical Greek cuisine “from the sea to the mountain” but also from other countries. Very often the wines are aggressive, strongly corrected with resin and almost undrinkable. Especially cheap and table specimens found in taverns. The Retsina wines are sometimes lower category wines, and the resin is added to cover their defects and served to the public and to local amateur tourists. That is why, in time, a notso-good image of this type of wine has been created, the quality producers not wanting to produce it, due to this negative image created. At one point, some of them realized that with existing wine varieties, they would not be able to compete globally with Sauvignon Blanc or Chardonnay, and that Retsina is a type of wine that, well done, can be an important asset on foreign markets. After all, it was a brand known to consumers, which only needed a new image and quality improvement. This is the moment when producers started to optimize a new formula. They created a wine with the addition of pine resin (Aleppo Pine) during fermentation, in stainless steel tanks, forming a film over the wine (Lopez Pinar et al., 2017).
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Eventually the film is collected and discarded, the wine remaining impregnated with the specific smell of fir, stronger, or finer depending on the choice and skill of the winemaker. The origins of this type of wine are lost in time, when ancient Greeks used pine resin to seal amphoras with wine or to anoint them on the inside to make them waterproof. Also, the resin has a preservative role, keeping the wine drinkable for a longer period of time. There are also anecdotes about this process that say the Greeks used the resin to “alter” the wine and to keep it from the Romans who did not bear the taste and the smell. As with yeast, there are many resin suppliers, depending on what is desired to be obtained (Lopez Pinar et al., 2017). The “base” wine used is obtained mainly from Roditis and Savatiano, two indigenous varieties that produce generic wines of no particular character. In terms of legislation, Retsina falls into the category of “traditional wine” and can be produced all over Greece and from any grapes, with compulsory use of resin in winemaking. There are around 15 special names of Retsina depending on the area where they are produced, even though only Roditis and Savatiano varieties are used as raw material, and the technology applied is the same. “Base” Retsina, obtained mainly from Roditis, has a fresh taste with floral and roasted hazelnuts impressions accompanied by spice undertones and pine and mint touches subtle in the background. The wine taste behaves on palatine as a normal one, with a medium taste, with citrus notes, fresh, slightly fruity. The aftertaste, however, is shockingly long and complex for a wine of this price category: Creamy with butter, honey, roasted peanuts, and light fir-like impressions that create the feeling of a good wine although the respective wine has had no contact with wood (Garde-Cerdán et al., 2016). Another type of wine in this category is grassy (thyme, rosemary) with citrus and slightly mineral allusions. Spicy aspects of cardanoma, anise, and ginger are blended in the background with butter and vanilla touch. It is a very stylish and extremely well-integrated wine. On the palatin has a complex, structured evolution, concentrated, extracting, excellently balanced by acidity, and grape-specific mineralization. The final taste is crispy, grippy, slightly tanish. Posttaste is incredible, long taking the citrus notes from the end and evolving to a sweet touch, of toasted bread and honey. Flavored wines may also have candied fruit flavors, apricots, peaches accompanied by notes of Asian spices, wax, and honey. On palatine, the fresh acidity of the above leaves the place of integration, the roundness of ripe fruits, honey, and butter, seasoned with nuts and cardamom. The end is still fresh, slightly tonic, and grippy. Others flavored wines may be aromatic, fruity in the first part of evolution and a soft and tonic acidity in the second and final, respectively. Average posttaste is sweet, specific to the variety. Other fragrances are green
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and citrus impressions on the background foundation and complemented by baric touches that come with vanilla, roasted peanuts, ginger, and smoky allusions. Evolution is a successful combination of acidity and body, leading in the first part, “getting tired” along the way and giving way to the mineral and Assyrtiko structure on the final taste. It results in an interesting acidic and mineralized column that well supports fruit extract (Šuklje et al., 2016). Complex red wine combines the red, baked red fruit with balsamic allusions, smoked and spice, and resin-specific clues. On the palatine evolves round, concentrated, extractive as for a rose, with tanned impressions and fresh red fruit (cherries, sour cherries) in the style of red wine. The final blend combines tonic tones with round tannins followed by an average sweetness with the same red fruit blended with mint and pine touches. There is also a herbaceous taste flavored wine, with aroma of red fruit, olives, marzipan, and candied cherries, followed by matured fruits (sour cherries, plums, black cherries) to the foreground. It is interesting that the wine resin acts as a new dimension of taste and smell, without completely dominating it, perfectly integrated and raising and helping virtually the wines to get complexity and flavor (Parr et al., 2017). The technologies for obtaining special wines involve, on the one hand, to prepare the raw material—the base wine, and on the other hand to prepare auxiliary raw materials such as: ethyl alcohol, caramel, citric acid, and plant extracts. The base wine used for the preparation of flavored must be healthy, perfectly clear, well physically, chemically, and microbiologically stabilized and without any foreign taste or smell. The subsequent treatments (sulfitation, bentonization, clarification, demetallization, refrigeration, pasteurization) are generally the same. The number and variety of plants used as ingredients is very high, most of them being cormophyte and only a few are talophite (Agaricus campestris and other edible mushroom species). Most of the plants grow in temperate climates, but there are also some that come from areas with equatorial, sub-sub-tropical, tropical, and subtropical climates (Peng et al., 2015). A list of common botanicals used in flavored or special wines: angelica root, cascarilla, cinchona bark (quinquina/quinine), licorice root, orris root (rhizoma iridis), sweet flag, wormwood, citrus (bergamot orange peel, bitter orange, lemon peel, lime peel, orange peel, pomelo peel), herbs (angelica, coriander, dittany of Crete, gallic rose, ginger, honeysuckle flower, hyssop, juniper, kaffir lime leaves, lavender, marjoram, oregano, orris root, roman chamomile, sage, St. John’s wort), and spices (allspice, cardamom, cinnamon bark, clove, star anise, tonka bean, vanilla). The plants may be used as a whole, or specific
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plant parts may be of interest. Therefore, the following categories of plant parts may be used: − fresh fruits (blueberries, pineapples, strawberries, rosemary), dried fruits (cardamom, fennel, juniper), fresh fruits peels (bergamot, grapefruit, lemons, oranges), unriped fruits (nuts); − inflorescences, flowers, floral buds (isopus, chamomile, sulphin, rose, etc.); − shoots, shoot tips, or buds (eucalyptus, juniper, lavender, pine, etc.); − roots and rhizomes (galanga, calamus, revent, iris, etc.); − straw bark and branches (cascarilla, cedar, cypress, etc.); and − aerial part, as is the case with most grasses (thyme, marjoram, mint, wormwood, etc.). The plants are collected when they contain maximum flavor and taste. For most of them, this moment is during blossoming. When using shoot tips and shoots from shrubs and trees, it is preferable that they are collected at the stage of their intensive formation and growth. Rhizomes and roots are harvested at blossom or immediately after. For most plants, especially grasses, it is recommended to harvest them from dry climate areas drier as they will have a stronger flavor than wet climate areas. The impurities of the vegetal material must not exceed 3%. The plants are allowed to dry, according to their processing technology, in shade, at constant temperature and humidity, in aerated rooms. Annual and biannual plants, known as herbs and the other green parts of shrubs and trees (shoots, buds, leaves, etc.) and their inflorescences and flowers must be well dried so that their moisture does not exceed 14%. From herbs are used only inflorescences, flowers, and leaves, which are separated from the stems by combing technique. Following this combing, the resulting fragments do not exceed 10 cm. Shoots and other parts collected from shrubs and trees can be chopped with mincing machines. The rhizomes and roots are cut into 0.5–2 cm pieces. The dried leaves (cardamom, fennel, juniper, etc.), as well as seeds (almonds, cocoa, nuts) are roasted and then crushed to large particles, without turning them into dust. The use of ingredients in vermouth preparation technology differs from one producer to another, depending on the plant species used. The plant material can be introduced as such directly into dry wine (very rarely and only certain fresh parts), as an infusion or, more often, as an extract. Dry ingredients are used less frequently. The use is simple and consists of placing dried vegetal material in a cloth bag, which is introduces in the wine tank. After a certain time (4–5 days), the cloth bag is removed and squeezed. After another 4–5 days the operation is repeated and continues for 30–35 days, that is, until it is appreciated that flavors and taste have passed almost entirely in wine. After homogenization, the wine is tasted and if it is considered not sufficiently flavored it is
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insert a new bag. When it is too strong flavored, the wine is blended with a known and well-established quantity of non-flavored wine. It is estimated that 1–1.2 kg of dry ingredients are required for the preparation of 1000 L of vermouth. Infusion is obtained by adding hot water over the ingredients. There are some plants or portions of them, such as mint, lime flowers, elderberry flowers, etc., which flavor and taste are better extracted by keeping them in boiling water for a few minutes. When using hard plant parts (bark, stem, young shoots, rhizomes, and roots) the extraction is done by boiling. Boiling takes place in containers made of stainless steel, provided with a mixing system. The extract is prepared from each plant separately, or from a mixture of plant species. The extraction may be done in a 60 vol% alcoholic solution because alcohol is considered as the best extraction solvent for essential oils and flavors (Moreno et al., 2016). By infusion is meant an aqueous solution obtained by maintaining a plant or a mixture of plants in contact with boiling water for a few minutes in order to extract flavors and taste. By extract is meant a solution obtained by maceration of plants in hydroalcoholic solution. The infusion and extract of aromatic plants contain substances that impart a different flavor to wine, a bitter taste, and a certain astringency. The presence of some vitamins and biologically active substances makes them play a tonic and stimulating role (Tanthanuch et al., 2016). Flavored substances are represented by volatile oils, also called essential oils. They are very complex (composed of tens or even hundreds of substances) and very heterogeneous (the components belong to different classes of chemical compounds: hydrocarbons, alcohols, phenols, terpene, ethers, esters, acetals, aldehydes, ketones) as a function of plant species used. Chemical compounds containing bitter principles and whose chemical structure is known can be grouped into isoprenoids, alkaloids, and phenylpropanoids. There are other bitter-tasting substances such as polyosides (gentiobiose, gentianosis, etc.) as well as certain amino acids and oligopeptides. The relationship between the molecular structure of these substances and their effect on taste receptors is not yet known. Astringency of aromatized wines is due to the phenolic compounds of the wines used as raw material, but especially to the extracts from the plants. In the case of wines, it was observed that phenolic monomer substances give more bitter taste than astringency. As the degree of condensation increases with the aging of the wine, astringency is better represented than bitterness. This explains why a young red wine is more bitter than astringent, because after maturation the bitterness decreases or is masked by astringency. It increases due to condensation of phenolic compounds. The contribution of plants to bitterness and astringency of aromatized wines depends on the biological nature of the plants.
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These plants are grouped into bitter aromatic plants and astringent aromatic plants, depending on the dominating substances they contain and release. Substances that have tonic effects can be grouped into: eupeptic appetizer, which stimulates appetite; digestive eupeptic that activate digestion; choleretic and hepatobiliary collagens that stimulate bile secretion and bile discharge into the bile ducts (Pascual et al., 2016). The group of aromatized wines includes absinth wine, retsina, vermouth, and bitter; the absinth wine is considered to be table wine, prepared according to traditional Romanian technology, as well as retsina produced only in Greece. Vermouth and bitter are part of the special wine category, due to the fact that they receive an addition of food-grade alcoholic beverages. Absinth wines are obtained from the long-term maturation of the wine under the influence of a film of yeasts formed on the surface of the liquid, which develops in contact with the air. Absinth wine contains CO2 of exogenous origin, develops a 1.5 bar pressure in the glass at 20°C and alcoholic strength is 7 vol%. The perlantine wine contains total or partial exogenous CO2, develops a pressure in the glass between 1 and 2.5 bar at 20°C and the alcoholic strength is at least 9 vol% alcohol. Absinth wine is a dry or slightly sweet wine with a bitter taste, and pleasant aroma of wormwood (Artemisia absinthium). For the hygienic-food attributes, the wormwood has long been classified as a medicinal wine. In the preparation of absinth wine, inflorescences of wormwood plants from southern, more arid areas are used, where flavoring substances accumulate in a larger quantity. Wormwood inflorescences are harvested in the full blossoming phase. For good preservation of flavors, drying will be done gradually. According to the raw material used, the dry absinth wine may be white, red or rose. The must is supplemented with 150–250 g/h L of wormwood placed in cloth bags. The wormwood inflorescence gives the wine a pleasant bitter taste and a very pleasant flavor. It is advantageous to use a mixture of inflorescences and small proportions of floral stems, because inflorescences contribute to giving the bitter taste and the flower stems imparts aroma. The duration of contact between wormwood and wine should not exceed 5–7 days after the fermentation is completed, to avoid the formation of bitter, harsh taste (the period is determined by repetitive tasting) (Roudnitzky et al., 2015). To improve the olfactory qualities, aromatization can be achieved by adding small amounts of peppermint, milfoil, chamomile, and sulfine. The intensification of the taste and the hygienic-food value is achieved by adding some slices of apple and quince (0.3–0.5 kg/h L) and crushed rosehips (20–100 g/h L). The fermentation rate of the must should be moderate, so that flavorings extracted from plants and fruits are not entrained by carbon dioxide (CO2), which is violently eliminated in the atmosphere (Beyeler, 2011).
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Absinth wine is obtained from fermented must in the presence of wormwood (absinth) or a mixture of plants—including wormwood and possibly fruits. Another possibility is the addition of alcoholic plant extracts. To make the wine more pleasant, together with the wormwood is added a small quantity of sliced quinces, and to harmonize it in taste, it is blended with another wine. If the manufacturer does not yet have the necessary experience, he is advised to do microprobe tests in advance, by adding small amounts of extract at the beginning, which he will gradually increase until the desired taste is obtained. Absinth wines are obtained in several assortments: sweet pea, dry sage, May absinth wine. Sweet absinth wine is made from grape berries that are fermented as such, without pressing. Wormwood, quince and fresh must are added to the pots. After filling, the pot is clogged and allowed to ferment for 3–4 months when the grapes are removed and pressed. The dry absinth wine is made from a dry wine to which is added wormwood macerate, must concentrated by boiling or sugar syrup (up to a concentration of 180–200 g/L determined refractometrically). May absinth wine is prepared from dry wine, concentrated must or sugar syrup (15–20 g/L) and a macerate prepared from the following ingredients (for 1 h L): 200–250 g of wormwood (Artemisia absinthium), 50 g Artemisia austriaca, 20–30 g coriander seed (Coriandrum sativum), 20 g cloves (Caryophylli flos), 30–40 g cinnamon (Cinnamomi cortex), and 25–50 g quince peels (Cydonia vulgaris). The ingredients are macerated in 2 L of 60% alcohol for 8–10 days (Poitou et al., 2017). Vermouth is a special wine, aperitif and tonic wine, made from white or red wine with the addition of refined alcohol, sugar syrup, caramel, plant extracts, and sometimes citric acid. The following conditions are required for the preparation of vermouth: the raw material wine should be 2–3 years old, have an alcoholic strength of at least 12vol%, an extract of 15 g/L and an acidity of 3–3.5 g sulfuric acid/L, be clear, perfectly healthy and free of defects; the sugar should be of a quality, contain not less than 99.8% sucrose, have a maximum moisture content of 0.2%, be white, glossy, impure, not to form conglomerates; refined alcoholic should be 96 vol% alcohol, tasteless, and odorless; crystallized citric acid should be free of impurities, free from foreign smell or taste; plants used for additional flavor should be healthy, have no foreign smell and taste, extraction carried out for 72 h by repeated recirculation; the equipment used for producing vermouth should exhibit chemical inertia in order not to enrich the wines into toxic compounds or compounds with mutagenic action. The production of vermouth is carried out in the following stages: preparation of wine; preparation of auxiliary materials (syrup, macerate, citric acid solution); preparation of macerate; achievement of the technological mix.
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8.3 Vermouth Production Technology Vermouth is defined as an aromatic wine with the addition of alcohol, sucrose, caramel, and plant extracts allowed by sanitary legislation. The proportion of wine in the vermouth composition must be at least 70% of the volume of the finished product. The vermouth’s actual alcoholic strength is at least 15 vol%. In the Lexicon of Vine and Wine, edited by the International Vine and Wine Office (OIV), vermouth is defined as a special, appetizing, sweetened, and alcoholized wine with added extract and/or infusion obtained from various aromatic and bitter plants. The basic ingredient of vermouth is wine, but thanks to the addition it almost can no longer be recognized as a product of the vine. The first vermouth is believed to have been obtained in 1786 in Torino (Italy) by the Benedetto Carpano. Seeking to discover the secret of the ancient Romans about the production of vinum absinthianum, he developed a new product, which has quickly acquired a world reputation. The name of the vermouth comes from German. When this vinum absinthianum was introduced in Bavaria by Piedmontese Alessio, it was translated into the literary form by Wermut Wein. The term Wermut in German means wormwood, which is the main aromatic plant that is added to the beverage preparation. In France, the beverage was named Vermout (Vermouth), and Vermut in Italy. In the city of Torino, considered the capital city of Vermouth, the product is called Vino vermut di Torino, a designation of origin that is still preserved and strictly protected by Italian wine legislation and O.I.V. regulations. Over time, vermouth preparation has expanded. At the beginning of the 20th century, most of the wine- producing countries produced vermouth. In addition to wine, which is considered to be the basic raw material, sugar, alcohol, caramel, sometimes citric acid, and a certain assortment of plants are needed (Panesar et al., 2011). The wine used as raw material in the preparation of vermouth must be healthy, clear, physicochemical, and microbiologically stabilized and free of foreign flavors and odors. It is preferable that the wine is from the same harvest and, if possible, a little older than a year. It may be of the same variety and vineyard or of different varieties and vineyards. Wines obtained from high-yield varieties, even from varieties of mixed character, can be used with good results. The transformations of the wine are profound, so the use a superior wine, which can be consumed as such, would be an unnecessary expense. Wine for vermouth must have an actual alcoholic strength of 10–12 vol% such as that the amount of added alcohol will be between 4 and 8 L of anhydrous alcohol per 1 h L of wine. The nonreducing extract content is 15–16 g/L or even more for red vermouth and the total titratable acidity is relatively low, that is, 3–3.5 g/L
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H2SO4. Technological steps needed for the production of raw material wine for vermouth is similar to that of current consumption wine. Subsequent treatments of the wine are largely the same. A mandatory step, especially for white vermouth, is discoloration. Coal treatment for the discoloration of wine is simple, provided the activated coal conforms to the prescriptions regulated in the International Oenological Codex developed by O.I.V. Once the optimal dose has been established, the quantity of coal required for a certain volume is first mixed with a small volume of wine until a pasta is obtained, which is afterwards thinned and vigorously stirred and mixed with the base wine. When the wine has foreign tastes and smells, the dose can be increased. Typically, 100–300 g/h L is added for discoloration. Sulfurization should be moderate so that the free sulfur dioxide content does not exceed 30 mg/L. Bentonite treatment is especially necessary for its deproteinization effect. Demetalization, when appropriate, is done by potassium ferrocyanide treatment. Casein clarification, in addition to a slightly bleached effect, leads to a decrease in the iron content and especially of the oxidizable or oxidized phenolic compounds, thus diminishing the intensity of the oxidation process. Refrigeration up to +6°C for 10–15 days or other specific treatments to ensure wine stability to tartar precipitations must be guided so that the vermouth can withstand both the tropical heat and the polar cold. Pasteurization, when applicable, is more applicable to inactivating lactic bacteria (Marangon et al., 2012).
8.4 Additives Sugar, made from beet or cane, is used for sweetening. It must have a white color, a high degree of purity (at least 99.7% sucrose), dry (maximum 0.1% water), healthy, and free of impurities. Its presence in vermouth helps to improve the taste, highlighting herbal substances that give vermouth a particular flavor. The sugar is added as a syrup, using wine as solvent. For the dilution to be not too high it is recommended that the sugar and wine be mixed in equal parts when preparing the syrup. From 1 kg of sugar and 1 L of wine results a syrup of 1.6 L. One liter of this syrup contains 616.9 g of sugar at 10°C or 615.9 g of sugar at 15°C. In such a syrup, a more rapid and complete inverting of sucrose is achieved, which is desirable, knowing that the sweetness of invert sugar (125 conventional units) is greater than sucrose (100 conventional units). The sugar solution is made in a vessel equipped with a stirrer, and hence, by pumping, it is introduced into the vessel containing the wine. To facilitate the solubilization of sugar, care should be taken, to be fully homogenized before the alcohol level reaches the maximum.
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The alcohol used in the preparation of vermouth is recommended to be rectified, that is, obtained by redistilling the crude alcohol containing small amounts of acetaldehyde, higher alcohols, etc. The concentration of rectified alcohol is 95.57%. The one used in the preparation of vermouth must contain at least 95 vol% alcohol at 20°C, be colorless, clear, completely volatile, with penetrating odor and burning taste. Wine distillate or similar products are not suitable for the substitution of rectified alcohol as they can alter the typical odor and taste of vermouth. Adding the predetermined quantity of alcohol can be done together with the plant extract, in the base wine or directly in the mixture. In the first case there is a possibility of a high solubilization of the aromatic substances in the plants; the second method is simpler and faster (de-la-Fuente-Blanco et al., 2016). Citric acid is only used when wines are deficient in acidity. When added to increase acidity, it should be remembered that with an addition of 1 g/L citric acid, acidity increases with 1.07 g/L tartaric acid or 0.7 g/L H2SO4. The citric acid used for this purpose has to meet the requirements prescribed in the Codex Oenologique International, that is, to appear as colorless, translucent, brittle, slightly efflorescent crystals, or crystalline powder forms; have a certain degree of solvation in water and alcohol; contain as little foreign substance as possible. The citric acid is introduced into the wine in the form of a preprepared solution, using 1 kg of citric acid for at least 7 L of wine. Caramel, also called burnt sugar, is used for coloring and printing a bitter taste of vermouth. Caramel is obtained by controlled heat action on commercially available sugars (sucrose, glucose, fructose, grape sugar, etc.). Caramel obtained from glucose, although having a color intensity of about four times greater, does not have that fine flavor and taste that is found in the other carbohydrates. The caramelization process can be applied to dry and concentrated glucides. In both situations during the caramelization, small amounts of acids (acetic, citric, phosphoric, sulfuric, sulfurous), hydroxides (ammonium, sodium, potassium), carbonates, phosphates, sulfates, and sulfites (ammonium, sodium) may be added. Caramel is a colloidal substance composed of a complex of compounds, such as caramelans C24H36O18, caramelens C36H48O24, and caramelins C96H102O5. The presence of melanoids (resulting from reactions between carbohydrates and various amines) as well as small amounts of pyrazines, imidazole, and hydroxymethylfurfural has also been reported. Caramel obtained by the ammonia process contains 50% digestible carbohydrates, 25% indigestible carbohydrates, and 25% melanoids. Caramel is found in solid and liquid forms. It is reddish-brown, taste pleasant, slightly bitter, and water soluble. Solid caramel should have a glassy appearance and the liquid should contain at least 50% extract.
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After calcination, whatever the state they are found, the ash should account for not more than 3% of the weight of the dry substance. Among its quality recognition tests, its solubility, and its precipitation in acid-rich or tannin-rich solutions, must also be taken into account. The caramel used for the preparation of vermouth is obtained by dehydration of the sugar (sucrose) by heating at a higher temperature (190–200°C). Its melting point is 185°C. Good results are also obtained by using caramel of grape sugar. The presence of potassium in the caramel of grapes may be a limiting criterion, since sugar caramel may contain it when potassium hydroxide or potassium carbonate is used in its preparation. The amount of caramel to be added shall be determined for each wine by multiple testing. Typically, the doses used do not exceed 2–3 g/L of vermouth, depending on the color of the wine from which it is obtained and the one to be reached. On administration, the caramel is solubilized in a smaller volume of wine (a caramel part to 3 or 4 parts of wine) and only after that the solution obtained will be added to the whole quantity of wine. It is recommended that the addition of caramel is carried out after clarifying, in order to avoid a possible reduction of its concentration by flocculation, but prior to filtration, in order to remove any precipitation resulting from precipitation (Smith et al., 2015). The ingredients used to imprint vermouth a special odor, a special flavor, and a special taste, are of vegetal nature. The number of plants used for the preparation of vermouth is high (over 80 plants). However, the wormwood is the basis of the entire complex of flavors. A total of 17 plants are used to obtain the macerate for white vermouth, and 19 for the red vermouth. Their preparation, separation, use and delivery as ingredients for vermouth is done in aromatic wine producing establishments or within specialized companies in this direction. The use of ingredients in vermouth preparation technology varies from one producer to another, depending on the level of planting, the nature of the plants that they uses, the inherited usage, etc. The plant material can be introduced as such into the wine in a dry state (very rarely and only certain fresh parts), in the form of an infusion or, more often, in the form of an extract. Dry ingredients are used less and less (McDougall et al., 2016). Generally, it is considered that 1.0–1.2 kg dry ingredients are required for the preparation of 1000 L of vermouth. In order to intensify and accelerate the extraction process, some producers use different pectolytic enzyme preparations. These, in a proportion of 0.1%–0.3% relative to the mass of dry ingredients, are introduced into a small amount of raw material, heated to 30–45°C, and then everything is added to the macerate. After 2–3 weeks of maceration, the liquid is prepared from the solid. The first fraction combines with the second fraction, acquired by squeezing or by a slight pressing of the solid rest.
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The extract thus obtained is left to rest for several days so that any residual solids and particles will settle down. After settling, coarse (cumulative) filtration is applied if necessary. The extract thus obtained is then added to the raw material wine. The optimum quantity is determined by specialists by tasting several microsamples prepared for this purpose. The second pressing of the macerated plants is no longer carried out because the extracted extract is too rich in less desirable phenolic compounds, as well as in other substances with disagreeable tastes. The alcohol remaining in the solid is recovered by washing it with water, being able to be reused after further distillation. Some producers use both the infusion and the extract to flavor without specifying the quantities or the plants underlying their preparation (Li et al., 2017). In the last 2–3 decades, in addition to traditional methods (the introduction of dried ingredients directly into wine, or as an infusion or extract), modern techniques for the preparation of the extract were developed. The one that uses ultrasound gives very good results. In this case, the crushed plant parts are introduced into a hydroalcoholic solution of variable concentration (50–60vol%). The mixture is placed in containers of a special installation equipped with ultrasonic piezoelectric plates (He et al., 2016). Depending on their flow and distribution, the frequency with which they occur, the operating time, the temperature of the environment as well as other factors, ultrasound destroys cell membranes, reduces the viscosity of colloidal substances in tissues, and even accelerates the activity of some enzymes. Under these conditions, the duration of maceration is considerably reduced, from 20 to 25 days to 25–45 min; the extract obtained is of better quality, being richer in essential oils, active principles, flavor, and taste and poorer in phenolic compounds and other components with odors and unpleasant tastes (Zhu et al., 2017).
8.4.1 Preparation of Vermouth This consists in transferring the preprepared raw material from the storage vessels to the assembly vessel (mandatory provided with a stirrer) and addition of the other ingredients (sugar, caramel, vegetable ingredients, ethyl alcohol, and possibly citric acid) in preestablished quantities by calculation and microsampling. Initially, the sugar syrup is introduced. Its administration is gradually made and continued stirring until good homogenization is achieved. Caramel, previously diluted in a smaller quantity of wine, is added only to white vermouth. The extract, as well as the alcohol, is recommended to reach the bottom of the container. For this purpose, an extension pipe will be attached to the end of the refueling hose which sinks into the wine to the desired
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location. To perform the maceration process, are uses special oak barrels with a capacity of 400–500 L or stainless-steel containers. After a vigorous homogenization for 2–3 h, a sample is taken. This sample will be characterized from physicochemical characteristics (alcohol, sugar, acidity, pH, extract, etc.), and organoleptic will also be done. Possible corrections in terms of the compositional parameters and of the olfacto-taste qualities will be made by a new addition (sugar syrup, extract, alcohol, citric acid, etc.) also determined by calculation or specimens. In the red vermouth, where the color is not always given by the basic wine, one can also use an addition of extract, prepared from cranberries or other fruits with intense red juice.
8.4.2 Maturation and Aging of Vermouth This operation is done in a limited time and more with the purpose of perfecting the “welding” of the components involved in its preparation. Typically, this duration does not exceed 4–5 months. During this period, various processes are applied: cleansing, filtration, and sometimes stabilization treatments. Most vermouths are obtained when aging prolonged for up to 1 year. Most producers and consumers are of the opinion that the organoleptic characteristics of vermouth are changing negatively if their shelf life exceeds 4–5 years. It becomes bitter, loses its freshness, and its own character. Vermouth is marketed only bottled, using specific bottles for this purpose, which generally has a capacity of 1 L. Their sealing is commonly done with Pilferproof thread plugs, rarely with a cork stopper or other closure systems. Among the processing operations for the presentation and sale of the vermouth bottles, the labeling (or the application of the main label, counter labels and possibly flyers) and the application of a cap or capsule are indispensable. Vermouth is presented in a very wide range of variants. For example, regarding the sugar content, it may be dry when the sugar content is approximately 20 g/L to very sweet when it is around 180 g/L. From the point of view of the alcoholic strength, the variation is fairly high, starting from 14.5% to 20%, more frequently 17–18 vol%. The total titratable acidity is generally low (2–3 g/L), rarely exceeding 3.5 g/L H2SO4, and volatile in most cases has values below 0.5 g L H2SO4. The nonreducing extract and the ash have values comparable to those of the raw material wine, that is, 15–20 g/L and 1.5–2.5 g/L, respectively.
8.4.3 Sensory Analysis Organoleptically, vermouth differs greatly from the raw mate rial wine underlying its preparation. It is so different that, by tasting it, you cannot even pronounce on its geographical origin, or on the
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ampelographic one, traits that can be noticed in the case of the wines themselves. In white vermouth, the color may vary from yellow to strawberry to yellow-gold or amber; for the red one, from red to pale to red, from brown to burgundy. The dominating flavor is the one imprinted by the wormwood, but there is no possibility of clearly distinguishing, others plant species favors, due to the variety pf plants used in the production of vermouth. The taste is pleasant, appealing, and a little sour. Vermouth is mainly served as an aperitif (the drink is served before meals to stimulate appetite). It is easy to drink, as such, but it can also be used with gaseous water. Vermouth is used for the preparation of cocktails with other alcoholic beverages, such as gin (a colorless alcoholic beverage obtained by repeated distillation of grain plume, to which juniper berries are added), sparkling wines or fruit syrups, candied fruits, etc. In some countries, especially Russia, vermouth is consumed as a strong and sweet dessert wine and less as an aperitif (Lukić et al., 2017).
8.4.4 Bitter Production Technology The Bitter is an aperitif alcoholic drink with a bitter sweet taste and a specific flavor. The term has a multilanguage etymology in Romanian, coming from French, English, and German, the original etymology being the bitter Dutch word, which means sour. The technology of making bitter is similar to vermouth technology, and the difference between the two products is due to the composition and the organoleptic qualities. Thus, the bitter has an alcoholic strength higher than 23–25 vol% alcohol, a low acidity of 1.5 g/L, a bitter taste, imprinted with the essence of citrus fruits and other plants such as wormwood, centaurea, artichokes, etc. The bitter is obtained from 1-to-2-year-old white or red wine, which is added sugar, alcohol, herbs and fruits extracts, food colorant, and caramel. In other countries, instead of wine, different fruit juices are used as raw material. When preparing the bitter, is added a food color called amaranth, at a rate of 8 g/h L. The use of preservatives, synthetic substances, or mineral acids is prohibited in the preparation of bitter. Few ingredients are used to obtain bitter essence than for vermouth plant extracts. The extraction of flavor and taste is made with alcohol. The essence of bitter is made by mixing the ingredients. Wine raw materials, before being introduced into the manufacturing process, it must be clear and stabilized, as the bitter does not undergo subsequent conditioning treatments. Wine conditioning is used to reduce the protein, pectin, iron, and copper contents. In the process of preparing the bitter, the ingredients are placed in the mixing bowl in the following order: wine, sugar syrup, water,
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g rapefruit juice, alcohol, natural bitter essence, ethylaniline solution, natural dyes, and ascorbic acid. Ascorbic acid acts as an antioxidant and dyes dissolve in the wine used as raw material, and the homogenization is performed perfectly. After homogenization, the bitter is matured for 40 days in containers located in rooms where the temperature is 15°C. After this period, the bitter is filtered, bottled, and marketed. Compared to vermouth, the bitter has a higher degree of alcohol depending on assortment, ranging from 18 to 25 vol%, rarely up to 30%, and a lower titratable acidity, that is, 2–3 g/L H2SO4, which can lower up to 1.5 g/L or even 1 g/L H2SO4. White or red wines used in the preparation of bitter must be of high quality, deproteinized, free of excess salts, and stable clarity, since the various conditioning and stabilizing treatments are less or not at all recommended to be applied after preparation. In addition to wine, other raw materials are needed such as plant extracts (macerated plant materials), alcohol, sugar, and colorants. The extraction of the flavor and taste from the plant species is made with a hydroalcoholic solution prepared on the basis of alcohol of agricultural nature, a solution whose degree varies depending on the nature of the plant material to be macerated. For the herbal part, called herba, an alcoholic solution of 45– 50 vol% is sufficient; for seed and bark a solution of 70–75 vol% alcohol is used. When using citrus fruit peel, successive extractions are used with different alcoholic solutions, so that the whole palette of volatile oils can be extracted. When extracting, it is preferable to use only the outer shell (cedar) that is rich in odor and taste because the white interior (albeda) is bitter and has a bad taste. Among the factors influencing the extraction by maceration with alcohol are: the degree of crushing of the vegetable material, the ratio between dried material and the solvent, the extraction time, the temperature, etc. The degree of maceration has a major influence because, with the reduction of the plant material fragments, the contact surface with the solvent is increased. The ratio between the plant material and the extraction solution should be preestablished by microsampling. Most manufacturers apply the plant/solvent ratio of 1/10 (Dellacassa et al., 2017). The extraction time varies between 10 and 30 days according the nature of the plant material and the extraction methods. The temperature, in the case of traditional maceration, is room temperature, where the process is also known as cold maceration. In addition to classical extracts obtained by maceration in hydroalcoholic solutions, volatile (essential or etheric) oils obtained by water vapor or other processes can also be used in the preparation of the bitter. The color of the bitter is given by that of the wine, to which, to a certain extent, it competes with that of the extract. When a color correction is needed, caramel is added for the white bitter or anthocyanin for the red one (Sengar and Sharma, 2014).
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The bitter production technology involves the following steps: dissolving the sugar in the wine, adding macerates, adding alcohol of 96 vol%. There are manufacturers who also use synthetic dyes like tartrazine (E102), azorubine (E123), and ponceau (E124). Sugar that is used must meet the quality requirements of S.R. no. 11-1995. The recipe of a red bitter has the following compositional characteristics: alcoholic strength 23 vol%, sugar 200 g/L, total acidity 5 g/L H2SO4 (due to the addition of concentrated must), volatile acidity maximum 0.5 g/L, higher alcohol expressed in isoamyl alcohol 0.04 g/100 mL anhydrous alcohol, and esters expressed in ethyl acetate 0.165 g/100 mL anhydrous alcohol. For the bitter essence, fewer components are used than vermouth macerate, some of which are listed in Table 8.1 for a volume of 1000 L. After homogenization, the bitter is stored, for twinning and storage un til bottling, in vessels commonly placed in rooms where the temperature is between 15°C and 20°C. Under these conditions it is kept for 30–50 days, after which it can be bottled and delivered to market.
8.4.5 Bottling When transferring the bitter into the bottles, a finishing filtering process is also applied by a filter paper or with medium porosity filters. Table 8.2 lists the main bitter varieties, characterized by color, which are produced at this moment. The bitter is marketed in 750 mL Bordeaux type bottles or in special cylinders with variable capacities
Table 8.1 Bitter Essence Components for 1000 L (Extraction by Maceration) Specification
Quantity (L)
Concentration
Orange extract Lemon extract Grapefruit extract Absinth extract Mint extract Centaurea extract Coriander extract Artichoke extract Clove distilate Cinnamon extract
124.50 87.20 87.20 161.80 124.50 186.80 62.30 124.50 9.97 31.23
450 450 450 450 450 450 450 450 480 480
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Table 8.2 Main Commercial Bitter Varieties by Color Color Yellow-green Red ruby Brown red Red ruby Brown red Red ruby Yellow-green Red ruby Intense red Intense red Red ruby Red ruby Red ruby Red-burgundy Red-burgundy Red-burgundy Red-burgundy Yellow-green Red ruby
Alcohol (vol%) 18 18 18 20 20 20 20 22 22 22 23 23 25 25 25 26 29 32 35
Sugar (g/L) 90 50 250 120 100 140 90 50 50 100 70 80 120 40 70 80 120 100 100
Total Acidity (g/L)
Volatile Acidity (g/L Acetic Acid)
22.6 2.0 4.9 2.5 5.4 4.5 4.4 2.5 2.5 4.0 1.8 1.8 1.8 1.0 3.1 2.5 2.5 3.0 3.0
0.6 0.6 1.0 1.2 1.0 0.6 0.8 0.6 0.6 0.8 0.6 0.6 0.6 0.6 1.5 0.6 0.6 1.0 1.0
according to the production company. Among the trademarks sold around the world, Campari is best known. This appetizing drink, prepared for the first time in 1860 by the Italian Gaspare Campari, which has a very intense red purple color, was originally colored by means of an extract from the dry bodies of female insects from a Coccinella species (living on cactus in Mexico). Bitter wine category is bitter-sweet in nature, which stimulates the production of gastric juices, producing appetite and stimulating appetite. In 1830, the French also offered reward to anyone who invented a good quinine-based wine. An alchemist from Paris, Joseph Dubonnet, developed a drink that was introduced in 1846 against malaria.
8.5 Sparkling Wines Sparkling wines are a category of wines obtained by technologies other than typical wines, so that the CO2, resulting from the fermentation of sugars, remains in the composition of the wine. Bubbly wine is
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a product based on CO2 impregnation. Sparkling wine is the result of a long bottle fermentation process. The difference is that the sparkling wine is the wine that is subject to natural fermentation, and endogenous nature of CO2 is obtained inside the glass, on the other hand the bubbly wine is the wine injected with CO2 (it is obtained artificially, such as carbonated juices). Both beverages are commonly called champagne. Remuting translates to the manual spinning of bottles for several months in some special desks. The “deposit” formed in the neck of the bottle is removed when uncovered. On this occasion, part of the wine is lost and will be replaced with shipping liquid. Bottle sparkling wines, no matter where they are obtained, are inspired by the style of Champagne. The dispensing fluid is sweet, and after the percentages added to the foaming agent, the classifications appear. The absolute dry wine is the crude dry wine or the gross dry wine. Dry and semidry are the most popular sparkling wines, matching most consumers. There is also sweet sparkling wine for desert (Culbert et al., 2017).
8.5.1 Sparkling Wine (Cava, Prosecco, Sekt, Espumante, etc.) Sparkling wines are distinguished from the normal ones by an increased level of CO2, which makes them acidified due to the natural fermentation process. Each type of sparkling wine comes with the story and the characteristics of the area from which it is produced. If the method is almost the same (Champagne fermentation in the glass), we can find the particularities of the producers for each variety. The most famous sparkling wines are: Cava (produced in Spain), Espumante (Portugal), Sekt (Austria and Germany), Pezsgo (Hungary), and Sovetskoye Shampanskoye (Russia, ex-Soviet space). Types of grapes used to make sparkling wine: Macabeo, Parellada and Xarello (cava), Pinot Gris, Aligote, Pinot Blanc, Grolleau, Cabernet Sauvignon, or Chenin Blanc. According to the level of sugar in the wine, the sparkling wines are classified in: natural raw (0–3 g/L sugar), extra gross (3–6 g/L sugar), raw (6–5 g/L sugar), extra dry (15–20 g/L sugar), dry (20–25 g/L sugar), and semi-dry (20–50 g/L sugar). In this case we have Ramon Berenguer I. Cava Brut Nature and Ramon Berenguer I. Cava Brut (Benucci et al., 2016).
8.5.2 Sparkling Wine-Cava Can Paixano Rosat The difference between the production process of sparkling and bubbly wine is that for the latter, the second fermentation is not carried out. Instead, CO2 is added. Types of grapes used to produce sparkling wine:
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− Tempranillo—this grape variety produces a high-alcohol base wine with moderate acidity; − Carignan—this is the grape variety for white wines. It has low acidity and low oxidation, making it ideal for long-term storage; − Trepat—from this variety comes the red color of the sparkling wine CAN PAIXANO. It is ideal for young wines and a basic ingredient for the cava. − When preparing CAN PAIXANO, CO2, sugar, and wine mix all at the same time, resulting in the same taste in each bottle (MartínezLapuente et al., 2016).
8.5.3 Champagne According to specialists’ definition, champagne is a sparkling wine made in the Champagne region of France, according to certain winemaking rules that require the second fermentation to take place in the bottle to promote carbonation. History of champagne dates back 300 years ago. Dom Perignon, a Benedictine monk who managed the cellars in a monastery located in the historic Champagne region of France, has perfected the technique of producing this drink. Hence, the claim that Dom Perignon champagne would be the equivalent of caviar between beverages. In 1743, Claude Moet turned this monastery into a renowned winery. The best champagne produced in its wineries now carries the name of the monk who created it in honor of his memory. As for this drink, there was a brief connection between France and the United States when, in 1787, Moet sent 100 bottles of champagne to America. But 200 years have passed until the French have been involved in setting up a champagne winery in the heart of Napa Valley-Domaine Chandon. Champagne is part of the gourmet food group, falling into the sparkling wine category, being a complex and rich drink with intense effervescence. The grapes from which the champagne is produced are Pinot Noir, Chardonnay, and Pinot Meunier. The main brands are Moët and Chandon champagne (the producers of Dom Perignon), Cristal, Veuve, Clicquot, and Krug. Champagne originated in Champagne, France, has become, over time, a favorite brand all over the world. Unlike other types of wine, champagne is subjected to a second fermentation, responsible for the appreciated bubbles. The two types of champagne grapes are Chardonnay (white grapes) and Pinot noir (black grapes). White champagnes are prepared from Chardonnay, and rose from a mixture of Chardonnay with Pinot Noir or just Pinot Noir. Quality champagne is produced by the so-called traditional method, the second fermentation of wine (which results in bubbles) that takes place in the bottle. The production method is mandatory to be written
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on the label. The name “Champagne” can be used today only by the producers in the Champagne region. All other producers who use this method use the term “sparkling wine produced by the traditional or classic method” or “by the champenoise method.” Most countries prohibit the use of the name Champagne for any other wine not originating in that area, the name itself being regulated and protected by the laws on controlled designations of origin (Banas et al., 2010). There are other methods to produce bubble wine. For example, the wine may be fermenting in tanks, after which the bubble wine is transferred into bottles, but the resulting product is inferior. Chardonnay is a variety of white grapes, while Pinot Noir and Pinot Meunier are red grape varieties. When champagne is obtained exclusively from Chardonnay, it is considered a blanc de blancs, and when it is obtained from one of the other two or a combination of them, it is considered a blanc de noirs. Rosé Champagne is obtained either by similar methods of obtaining normal rosé wine or by the subsequent addition of a small amount of Pinot wine. The main characteristic of champagne grapes is the acidity. The more acidic the variety, the more chances for bubble formation. Most commonly used is the mixture of chardonnay and pinot noir in varying proportions depending on the characteristics of the selected wine. Mixtures of four wines, some old, a year or two, and a single wine can also be used (Liger-Belair, 2016). Once released on the market, the champagne is intended for immediate consumption, during the respective year. If it is not stored in a constant temperature cellar containing specific mold to absorb moisture from the air, the champagne it will not be stored. There are beverages in which the effervescence effect is obtained by the addition of CO2 and that is the difference between a sparkling wine (like champagne) and a bubbly wine, the latter being a product inferior to the first one. They have a transparent color, abundant and persistent flavor; the aroma is endowed with floral shades, but also with peach fragrance. Other assortments have a light silver color; from the glass escapes elegant notes of white flowers, apple, and pear; with savory and fine flavor, discreet but interesting. Others are golden colored; the flavors are of good quality, and they remember pear and pineapple, being somewhat exotic. There are other varieties that are beautiful in color, orange tones; dense, strong, fine bubble pearls; the flavor is subtle and secretive; have a beautiful balance and freshness in full; shades reminiscent of beans and mandarin. Types of champagne are as follows: − “Body” champagne, the basic characteristics of this type of champagne are: strength, structure, and intensity, being so-called “muscular” wines. These champagnes, younger or older, are produced from Pinot Noir or Pinot Meunier, two grape varieties that create special flavors and give the wine depth and vigor.
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− “Heart” champagne, the key features are: generosity, warmth, and finesse. There are wines with a fresh, fine, and always balanced flavor. They are obtained from Pinot, Pinot Noir, and Pinot Meunier, and can be rosé or semi-dry. Their colors range from golden yellow to dark rosé. − “Spirit” champagne, the basic features are: mild, vivacious, delicate. Invariably, there are Brut or Blanc champagne, with a predominance of Chardonnay. This assortment of wine is vibrant, bright, with a golden color, with gray tones. Bubbles are light and delicate. − “Soul” champagne, key features are: maturity, complexity, and wealth. They are the rarest champagnes, the most complex wines. They are mature wines, often coming from an exceptional crop. Extremely fine bubbles and the old, amber-like golden color inspire almost a religious feeling (Roullier-Gall et al., 2016). Unlike the wine, which is different from 1 year to another, champagne, especially the special quality that the French call “grand crue,” must retain the same qualities (aroma, bubble concentration, alcoholic strength) indifferent of the year of manufacture and the composition of the blended wines. The talent of the winemaker consists in choosing the mixture of wine which, although different in terms of the annual harvest, must produce the same result after the second fermentation in the glass, as in the previous years. It takes about 2 years to produce a champagne lot, or 3 years for the very good ones (explains the high price) (Ghabache et al., 2016). One of the greatest qualities of champagne is its versatility. The organoleptic, physicochemical, and microbiological conditions that wine should meet as a raw material of the sparkling wine are summarized in Table 8.3. A really good champagne “goes” in combination with almost any kind of food, but when served as an aperitif, the sparkling wine should be dry, depending on the type of appetizers served. Champagne is a pressure wine (1–5 bar), due to the high CO2 content (2–10 g/L) has a fresh, pungent taste and a fine, reductive, characteristic bouquet. It has an alcoholic strength of 6–13 vol%, pleasant sweetness, 4–100 g/L sugar and relatively high acidity, about 5 g H2SO4/L, depending on the type and range. In champagne, CO2 results from the fermentation of the added sucrose added to the wine, the preparation of the sparkling wine in bottles (champenoise method) or the preparation of the sparkling wine in the tanks (Cuve Close method) or the preparation of the sparkling wine in bottles and the conditioning of the sparkling wine to the tanks (German method). The preparation of sparkling wines comprises two key stages: obtaining basic wine or raw wine for sparkling wine and adding the sparkle to the basic wine. The champenoise method is the best-known method for producing white wines. The preparation of wine for champagne consists of stabilization and conditioning of the wine to obtain homogeneous parts that will be
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Table 8.3 Organoleptic, Physicochemical, and Microbiological Conditions ORGANOLEPTIC CONDITIONS
Characteristics Appearance Color Odor and taste
Admissibility conditions Clear liquid, free of foreign bodies in suspension White-green color for white and red-to-ruby red wine Healthy wine specific to the variety, free of foreign odors, lacking in astringency, bitterness, particular taste
PHYSICAL AND CHEMICAL CONDITIONS
Alcohol in vol% at 15°C minimum Titrable acidity in g H2SO4/L maximum Reduced dry extract g/L maximum Free SO2 in mg/L max SO2 total in mg/L maximum Reducing sugar g/L max Fe in mg/L maximum Air resistance
9.72 4.5 16 25 150 4 15 Appearance and color do not change after 24 h
Microbiological conditions: wine must be healthy without microorganisms; Saccharomyces ellipsoideus cells and lactic bacteria are permitted
transferred to bottles. The next step will be the circulation of the wine that represents the preparation of the draft mixture: the wine + the brewing liquor + the starter yeast + the clarifier and then the preparation of the bottles and the plugs, the mixture transfer into the bottles and their sealing. The second fermentation consists of stacking bottles for fermentation, in horizontal position, in cellars. Now CO2 is formed which is impregnated in wine and it becomes sparkling. Then the bottles are positioned on a storage desk, in a sloping position with the neck down, shake and rotate daily 1/4 of the circumference of the glass so that the deposited sediments descend on the cork. Degorgement consists in translating the bottles into a very cool mixture to form an ice cork with deposits and quickly removing the corks to “throw” the deposits. After the sugar content, the champagne can be natural raw (0–3 g/L sugar), extra raw (3–6 g/L sugar), raw (6–15 g/L sugar), extra dry (15–20 g/L sugar), dry (20–35 g/L sugar), and dessert (35–50 g/L sugar). Classification of champagne styles according to the quantity of sugar, expressed in grams/l, contained by “liqueur de dosage”: Doux, Sweet, 50 g/L sugar, semidry, semiseco 32– 50 g/L sugar, dry, sec, seco 17–32 g/L sugar, extra dry, extra sec, extra seco 12–17 g/L sugar, brut 7–12 g/L sugar, extra brut 1–6 g/L sugar, and
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brut nature (no added sugar) 0 g/L sugar. Other forwarding operations are (plugs + basket), control, bottle toilets, labeling, and storage for shipment (Herrero et al., 2016). The first step in the process of producing champagne and sparkling wine is to obtain the basic wine. After assembling and mixing it to achieve homogeneous batches, it is followed by the liquefaction, the bottling operation of the wine prepared for the second fermentation. The special preparation consists in making a mixture of the basic wine and a draft liqueur, which contains the selected yeast, sugar syrup, and the remuage adjuvants. For fermentation, special bottles are used, which have thick walls and withstand at least 17 atm. Bottles are hermetically sealed with special metal staples or fermentation stoppers attached to the neck of the bottle. After filling, the bottles are taken to the fermentation spaces where they are placed in a horizontal position in stacks. Alcoholic bottle fermentation lasts for 3–6 weeks, during which a 6-atm pressure will be achieved in the glass. After fermentation, the bottles are left for 9 months in stacks in a horizontal position for the autolysis of yeasts, basically a self-destruction process, which results in the release of some aromatic compounds. Remuage is the operation that is performed at the end of the aging period and consists in bringing the yeast deposit on the cork. It is done by placing the bottles on special desks and rotating them daily with one-eighth of the circumference. Gradually, the bottles are brought as close as possible to the vertical position. Remuage usually takes 30 days. The operation is considered complete when the yeast deposit is fully brought to the cork. The yeast deposit from the recipient is discharged under an operation called degorgement. It is carried out by experienced workers so that after removing the clip and throwing the cork, do not leave any residue in the bottle and do not lose too much liquid. The bottles return to homogenize the mixture and are then left to rest. Prior to labeling, the bottles are checked for defects and yeast sediments deposited on the bottles walls (Wolf, 2016). Unlike normal wines, champagne, and sparkling wines do not need grapes with high natural sugar content, and the varieties needed are higher yields. Care is taken to avoid tannins and other phenolic compounds getting into the wine, so premium producers still harvest grapes manually rather than risking a mechanical harvest to hit or crush the grains and cause maceration of the shell. There are essential differences between sparkling wine and champagne, although both are in the category of sparkling wines. However, the champagne is considered essence (the preparation process is very expensive). Since 1935, there is a very strict regulation: the grapes come exclusively from the Champagne region, are hand-picked, the champagne is allowed to mature in cellars from limestone rocks, the minimum storage period is 15 months, and fermentation in bottle is mandatory.
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The more precious the champagne is, the longer it can be stored. But when the bottles leave a cellar, champagne should already have the optimum age. This means at least 15 months (Moët and Chandon Rosé—3 years). Common champagne should not be stored for more than 2 years. It is important to keep it in a dark place. Champagne must be protected from light (even artificial light!) and agitation. The temperature should be constant ideally at 9–11°C (Chalmers et al., 2016). Presses are often located near vineyards so that grapes are not transported on long distances, and pressed and separated from shells and skin and seeds as quickly as possible. Red grapes, such as Pinot Noir, can be used to produce champagne and white sparkling wines, as their juice is initially very light in color, and becomes reddish only later if red pigments from the skin have been exposed for longer. If such a moderate exposure may be desirable in the case of the production of rosé sparkling wines and some “blanc de noirs,” manufacturers of sparkling wines take many precautions to limit the contact between juice and peels. The first alcoholic fermentation of champagne and sparkling wines is similar to that of quiet wines, although some producers choose to use special yeast cultivated to give predictable and repeatable results in terms of final taste and duration of fermentation. Characteristic of quiet wines, malolactic fermentation, a process that is especially important for red wines, which leads to acidification and “rounding” of taste, can also be part of the process of preparation of champagne. Not a few manufacturers, who wish to obtain a fruitier sparkling and simply wine skip this stage. After fermentation the base wines are then blended to form a “cuvee.” There are plenty of sparkling examples such as “blanc de blancs” (white wines from white grapes) obtained from 100% Chardonnay, but most sparkling wines are obtained from blends of several varieties of grapes, harvests, and vines. Producers who have access to a wide range of grapes use several hundred different wines to create their own blends that reflect the “house style.” If in the first stage, alcoholic and the malolactic lactic fermentation is common to quiet, champagne and sparkling wines, what distinguishes them from the latter is a second stage alcoholic fermentation, which leads to the creation of sparkling carbonation. CO2 also occurs as a result of the first alcoholic fermentation, where it is left to escape. In the case of the second alcoholic fermentation, efforts are made to ensure that the resulting gas is stored and integrated into the wine. This leads to high internal pressure (around 5–6 atm), and producers are forced to bottle these wines in special bottles with special corks and “muzzles.” When the bottle is opened and the wine is poured into the glass, the gas is released and the wine becomes sparkling. The second alcoholic fermentation can be done by several methods, which ultimately lead to the hierarchy of sparkling wines in several different categories.
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The most common method is the traditional method, called “méthode champenoise,” where a cuvée is bottled together with a mixture of sugar and yeast. The introduction of fresh yeast and a source of energy for this yeast triggers fermentation directly inside the bottles in which the wine is finally marketed. By the remuage procedure followed by dégorgement, the yeast residues are removed from the wine, but the gas content is almost intact. In the bottle is added a mixture liqueur de dosage prepared from fresh wine and sugar syrup, to adjust the final level of sweetness. In the “ancestral method,” the dégorgement operation is omitted and the wine is sold with dead yeasts (from wine as sediment). In the “transfer method,” after the wines have undergone the second fermentation, followed by remuage and dégorgement, the bottles are emptied into a large tank where they are bottled in small format bottles for airline, or large format, most often bottles of 3 L, called Jeroboam. Another very common method was developed by Federico Martinotti (1860–1924), director of the Istituto Sperimentale per l’Enologia di Asti, which in 1895 patented the controlled fermentation method in large containers. This method was refined and transposed on an industrial scale by the French Eugène Charmat in 1910. Today the method is called Charmat-Martinotti, but most often just Charmat. The fermentation takes place in pressurized stainless-steel tanks. Fresh yeast and sugar mixture are added, and fermentation takes place in a pressurized system. Finally, the wine is cooled, filtered, and bottled. This method gives champagne and sparkling wines a good quality and is sensibly cheaper than the champenoise method. A third method, which is used for the preparation of champagne and sparkling wines, also used in the manufacture of acidic juices, uses CO2 injected directly into wine. This method produces bigger bubbles of gas that dissipate quickly, and is inherent to the cheapest sparkling wines (Bonhommeau et al., 2014). The European Union stipulates that any wine with a pressure of more than 3 atm may be called sparkling. Semisparkling or sparkling wines are defined as having an internal pressure of 1–2.5 atm. This includes the Spritzig German wines, the Italian ones called “frizzante” and the French called “pétillant.” The bottle pressure is influenced by the amount of sugar added at the beginning of the second alcoholic fermentation. Most sparkling wines are white or rosé. There are also sparkling red wines, much rarer, than white and rosé. Australia, Italy, and Moldova are the only countries with an important production of red sparkling wines. Most currently, consumers prefer very dry sparkling wines. In the 19th century, however, champagne was sweet. Most of the wine lovers liked sweet taste, and that dosage liquor helped producers to cover wine defects or poor grape quality. Champagne producers used the dosage to adjust the final sweetness of the wine according to the market for which it was intended. The Russians were the
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ones who drank the sweetest champagne. The sugar addition reaches 250–330 g/L of sugar. The Scandinavian market required a champagne with an addition of 200 g and French and German about 165–180 g. The United States preferred a quantity of 110–165 g and the English were drinking the finest champagne with an addition of only 22–66 g sugar/L. Meanwhile, tastes have evolved to dry champagne and to better quality wines, as small amounts of sugars cannot mask defects. The earliest sparkling champagne on the market was labeled “demi-dry,” and their success led the producers to try even less sugar, starting to produce extra dry wines. In 1846, the Perrier-Jouët home produced a champagne with zero added sugar. It was badly received by critics, who felt that wine was far too crude. Over time, this “raw” has become the modern champagne style. CO2 is formed at the second alcoholic fermentation and is the main characteristic of champagne and sparkling wines. An initial effervescence occurs when the wine comes into contact with the dry glass. Although the glass looks perfect, and the inner walls appear to be absolutely smooth, they microscopically present thousands of microimperfections. The gas forms bubble nuclei around them, which then diffuse upward through the wine layer, carrying on the surface particles containing compounds that make up the aroma and taste of the beverage. A glass of champagne or sparkling wine loses carbonation in time, much faster than wine in open glass; logical, taking into account that the contact surface between wine and air is much higher when using the glass. The foam as well as the size and consistency of the bubbles may vary depending on the quality of the wine and the glass used (Liger-Belair et al., 2012). A bottle of sparkling wine contains on average enough CO2 to produce 49 million bubbles, the figure that is approximate, other sources indicate 150 million bubbles. Regardless of how many bubbles there would actually be in a bottle of sparkling wine, they initially have diameters of 20 μm and grow in size as it rises to the surface of the liquid, reaching 1 mm in diameter. It appears that gas bubbles can promote alcohol intoxication, as it helps to absorb it faster into the bloodstream. Champagne helps the heart normal functioning and blood circulation. A few glasses of champagne can lower blood pressure and reduce the risk of heart attack and heart disease. Champagne contains antioxidants that protect against free radicals and protect cells, helping to restore cells and tissues.
8.6 Conclusions and recommendations Flavored wines are obtained from musts or wines to which special, authorized treatments are applied during or after processing. The flavored or aromatized wines have specific characteristics, determined by the
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t echnological properties of the raw material and the technology applied to the processing. The aromatized wines are appetizing, tonic, with a pleasant flavor and bitter taste derived from some plants and ingredients, the number and proportions of which are considered manufacturing secrets. By aromatized wines are meant wines with added sugar or must, wine distillate or alcohol, and aromatic extracts obtained from different plants. Aromatized products are obtained by infusing flavor and taste constituents during the fermentation of must, or directly into the wine by the addition of sugar or must, wine distillate or refined alcohol, citric acid, and plant and fruit macerates. In the category of aromatized wines are included: absinth wine, vermouth, bitter, and champagne. Why wines obtained through the champenoise method are more expensive and why is this method generally maintained if Charmat is simpler, cheaper, and gives high-quality wines? The first reason would be that the micro fermentation in bottles combined with the remuage procedure could provide better contact between yeast and wine, resulting in a more complex taste. It is possible that each bottle evolves a bit different from the others, leading to the nonuniformities specific to the traditional products, where the human factor is deeply involved. The Charmat-Martinotti method is much easier to control and the fermentation is done in large quantities, virtually eliminating any irregularities. These small surprises, due to different evolution in each bottle, may have their charm. The second reason is marketing. A traditional method, possibly involving less technology, is more attractive, and some of the buyers may be very sensitive to this type of offer. A traditional method seems to be, in the light of current trends, a very good reason for producers to demand and obtain a higher price. Sparkling wines represent a special universe themselves. Carbonation gives sparkling wines the quality of being extremely versatile and well-fitting with an extremely wide range of dishes. Sparkling wines are, in fact, much more versatile than quiet wines, precisely because of carbonation, which manages to clean the taste buds and refresh them, and also because it can “cut off” the fats present in some preparations, by simply enveloping the oral cavity.
References Banas, D., Marin, B., Skraber, S., Chopin, E.I., Zanella, A., 2010. Copper mobilization affected by weather conditions in a stormwater detention system receiving runoff waters from vineyard soils (Champagne, France). Environ. Pollut. 158 (2), 476–482. Benucci, I., Liburdi, K., Cerreti, M., Esti, M., 2016. Characterization of active dry wine yeast during starter culture (Pied de Cuve) preparation for sparkling wine production. J. Food Sci. 81 (8), M2015–M2020.
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Beyeler, Y., 2011. Wine, whiskey, absinthe, etc. Rev. Med. Suisse. 7 (279), 187–188. Bonhommeau, D.A., Perret, A., Nuzillard, J.M., Cilindre, C., Cours, T., Alijah, A., LigerBelair, G., 2014. Unveiling the interplay between diffusing CO2 and ethanol molecules in champagne wines by classical molecular dynamics and (13)C NMR spectroscopy. J. Phys. Chem. Lett. 5 (24), 4232–4237. Chalmers, P.N., Cvetanovich, G.L., Kupfer, N., Wimmer, M.A., Verma, N.N., Cole, B.J., Romeo, A.A., Nicholson, G.P., 2016. The champagne toast position isolates the supraspinatus better than the Jobe test: an electromyographic study of shoulder physical examination tests. J. Shoulder Elb. Surg. 25 (2), 322–329. Culbert, J.A., McRae, J.M., Condé, B.C., Schmidtke, L.M., Nicholson, E.L., Smith, P.A., Howell, K.S., Boss, P.K., Wilkinson, K.L., 2017. Influence of production method on the chemical composition, foaming properties, and quality of australian carbonated and sparkling white wines. J. Agric. Food Chem. 65 (7), 1378–1386. de-la-Fuente-Blanco, A., Sáenz-Navajas, M.P., Ferreira, V., 2016. On the effects of higher alcohols on red wine aroma. Food Chem. 210, 107–114. Dellacassa, E., Trenchs, O., Fariña, L., Debernardis, F., Perez, G., Boido, E., Carrau, F., 2017. Pineapple (Ananas comosus L. Merr.) wine production in Angola: characterisation of volatile aroma compounds and yeast native flora. Int. J. Food Microbiol. 241, 161–167. Garde-Cerdán, T., Portu, J., López, R., Santamaría, P., 2016. Effect of methyl jasmonate application to grapevine leaves on grape amino acid content. Food Chem. 203, 536–539. Ghabache, E., Liger-Belair, G., Antkowiak, A., Séon, T., 2016. Evaporation of droplets in a Champagne wine aerosol. Sci. Rep. 6, 25148. He, B., Zhang, L.L., Yue, X.Y., Liang, J., Jiang, J., Gao, X.L., Yue, P.X., 2016. Optimization of ultrasound-assisted extraction of phenolic compounds and anthocyanins from blueberry (Vaccinium ashei) wine pomace. Food Chem. 204, 70–76. Herrero, P., Sáenz-Navajas, P., Culleré, L., Ferreira, V., Chatin, A., Chaperon, V., LitouxDesrues, F., Escudero, A., 2016. Chemosensory characterization of chardonnay and pinot noir base wines of champagne. Two very different varieties for a common product. Food Chem. 207, 239–250. Li, X., Xing, Y., Cao, L., Xu, Q., Li, S., Wang, R., Jiang, Z., Che, Z., Lin, H., 2017. Effects of six commercial Saccharomyces cerevisiae strains on phenolic attributes, antioxidant activity, and aroma of kiwifruit (Actinidia deliciosa cv.) wine. Biomed. Res. Int. 2017, 2934743. Liger-Belair, G., 2016. Modeling the losses of dissolved CO2 from laser–etched champagne glasses. J. Phys. Chem. B. 120 (15), 3724–3734. Liger-Belair, G., Bourget, M., Pron, H., Polidori, G., Cilindre, C., 2012. Monitoring gaseous CO2 and ethanol above champagne glasses: flute versus coupe, and the role of temperature. PLoS ONE 7 (2), e30628. Lopez Pinar, A., Rauhut, D., Ruehl, E., Buettner, A., 2017. Effects of bunch rot (Botrytis cinerea) and powdery mildew (Erysiphe necator) fungal diseases on wine aroma. Front. Chem. 5, 20. Lukić, I., Budić-Leto, I., Bubola, M., Damijanić, K., Staver, M., 2017. Pre-fermentative cold maceration, saignée, and various thermal treatments as options for modulating volatile aroma and phenol profiles of red wine. Food Chem. 224, 251–261. Marangon, M., Van Sluyter, S.C., Robinson, E.M., Muhlack, R.A., Holt, H.E., Haynes, P.A., Godden, P.W., Smith, P.A., Waters, E.J., 2012. Degradation of white wine haze proteins by Aspergillopepsin I and II during juice flash pasteurization. Food Chem. 135 (3), 1157–1165. Martínez-Lapuente, L., Apolinar-Valiente, R., Guadalupe, Z., Ayestarán, B., PérezMagariño, S., Williams, P., Doco, T., 2016. Influence of grape maturity on complex carbohydrate composition of red sparkling wines. J. Agric. Food Chem. 64 (24), 5020–5030.
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McDougall, G.J., Austin, C., Van Schayk, E., Martin, P., 2016. Salal (Gaultheria shallon) and aronia (Aronia melanocarpa) fruits from Orkney: phenolic content, composition and effect of wine–making. Food Chem. 205, 239–247. Moreno, J., Moreno-García, J., López-Muñoz, B., Mauricio, J.C., García-Martínez, T., 2016. Use of a flor velum yeast for modulating colour, ethanol and major aroma compound contents in red wine. Food Chem. 213, 90–97. Panesar, P.S., Joshi, V.K., Panesar, R., Abrol, G.S., 2011. Vermouth: technology of production and quality characteristics. Adv. Food Nutr. Res. 63, 251–283. Parr, W.V., Valentin, D., Reedman, P., Grose, C., Green, J.A., 2017. Expectation or sensorial reality? An empirical investigation of the biodynamic calendar for wine drinkers. PLoS ONE 12 (1), e0169257. Pascual, O., González-Royo, E., Gil, M., Gómez-Alonso, S., García-Romero, E., Canals, J.M., Hermosín-Gutíerrez, I., Zamora, F., 2016. Influence of grape seeds and stems on wine composition and astringency. J. Agric. Food Chem. 64 (34), 6555–6566. Peng, B., Li, F., Cui, L., Guo, Y., 2015. Effects of fermentation temperature on key aroma compounds and sensory properties of apple wine. J. Food Sci. 80 (12), S2937–S2943. Poitou, X., Thibon, C., Darriet, P., 2017. 1,8-Cineole in french red wines: evidence for a contribution related to its various origins. J. Agric. Food Chem. 65 (2), 383–393. Roudnitzky, N., Behrens, M., Engel, A., Kohl, S., Thalmann, S., Hübner, S., Lossow, K., Wooding, S.P., Meyerhof, W., 2015. Receptor polymorphism and genomic structure interact to shape bitter taste perception. PLoS Genet. 11 (9), e1005530. Roullier-Gall, C., Witting, M., Moritz, F., Gil, R.B., Goffette, D., Valade, M., SchmittKopplin, P., Gougeon, R.D., 2016. Natural oxygenation of Champagne wine during ageing on lees: a metabolomics picture of hormesis. Food Chem. 203, 207–215. Sengar, G., Sharma, H.K., 2014. Food caramels: a review. J. Food Sci. Technol. 51 (9), 1686–1696. Smith, T.J., Wolfson, J.A., Jiao, D., Crupain, M.J., Rangan, U., Sapkota, A., Bleich, S.N., Nachman, K.E., 2015. Caramel color in soft drinks and exposure to 4-methylimidazole: a quantitative risk assessment. PLoS ONE 10 (2), e0118138. Šuklje, K., Zhang, X., Antalick, G., Clark, A.C., Deloire, A., Schmidtke, L.M., 2016. Berry shriveling significantly alters shiraz (Vitis vinifera L.) grape and wine chemical composition. J. Agric. Food Chem. 64 (4), 870–880. Tanthanuch, S., Kukiattrakoon, B., Peerasukprasert, T., Chanmanee, N., Chaisomboonphun, P., Rodklai, A., 2016. The effect of red and white wine on color changes of nanofilled and nanohybrid resin composites. Restor. Dent. Endod. 41 (2), 130–136. Wolf, B., 2016. Biotinidase deficiency and our champagne legacy. Gene. 589 (2), 142–150. Zhu, L.X., Wang, G.Q., Xue, J.L., Gou, D.Q., Duan, C.Q., 2017. Direct stamp of technology or origin on the genotypic and phenotypic variation of indigenous Saccharomyces cerevisiae population in a natural model of boiled grape juice fermentation into traditional Msalais wine in China. FEMS Yeast Res. https://doi.org/10.1093/femsyr/ fow108.