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Food Science 564 Commercial Food & Beverage

White vs Red vs Pink

Christian BUTZKE Professor of Enology Department of Food Science White vs Red vs Pink Winemaking

The U.S. & :

• 8,000 • 30,000 grape growers • 1,000,000 acres of • $ 4 billion crop value () • $ 12 billion value-added products (wine) • $ 162 billion economic impact www.ngwi.org Wine: A Definition

“Wine” signifies the of grapes fermented by and finished into an alcoholic beverage.

Wines made from other be specifically labeled as such, e.g., “apple wine” or “cherry wine”. The Grapevine The Cluster

Vitis vinifera rotundifolia cv. cv. Noble The Scion

The The The “European” Grape

Vitis vinifera Cultivated varieties, vegetatively propagated field selections with specific characteristics, e.g.:

Cabernet Sauvignon + several hundred more grown commercially world-wide

Vitis vinifera Terrific 13

• Cabernet Sauvignon • • Chardonnay • • Gewürztraminer • • Semillon • • Native American Grapes

Vitis labrusca Native to North America - East & Midwest Strong fruity “grape” flavor (Welsh’s) “FOXY” Major varieties: Niagara Catawba Concord

French-American “Hybrids”

Chambourcin sham-bore-san (Marechal) Foch mair-eh-shal foesh Traminette tra-mi-net Chardonel shar-do-nell Vignoles vin-yole(s) Vidal Blanc vee-dal blawn(k) Seyval Blanc say-val blawn(k) Wine Aroma Riesling

Lime Lemon Melon Peach

Green Apple Orange Passionfruit Pineapple

Apricot Grapefruit Mineral Kerosene Varietal Wine Aroma Riesling Composition of Grapes vs. Wine

Component % in Grapes % in Wine Water 75 86 22 0.2 0.0 12 Acids 0.8 0.6 Minerals 0.5 0.2 Phenolics 0.8 0.2 Pectin 0.4 0.2 Glycerol 0.0 0.5 Amino Acids/ 0.5 0.1 Volatile Aromas 0.0 0.04 TOTAL 100 100 Sugar Content

BEVERAGE % Sugar Wine Grape Juice 20 - 25 Cranberry Juice 15 Apple Juice 13 Coca-Cola™ 11 Red Bull™ 11 Ginger 10 Snapple Lemonade™ 9 Alcoholic h u Heat m SUGAR + a n CO2

+ ALCOHOL

h a i r WINE YEAST () (genome size = 12 Mb, 16 chromosomes, 6000 genes) Alcoholic Fermentation

Electron Images by Bill Plunkett @ Clarkson University Microbial Biogeography of wine grapes is conditioned by cultivar, , climate Bokulich, Thorngate, Richardson and Mills, PNAS 2013 Winemaking Styles

Whole cluster Sur lie aging Must fermentation Red Carbonic method Sparkling wines Charmat process Late Dessert wines Port Fortified wines Historic Winemaking Modern Winemaking Wine Quality ?

Grapes 70% 10% 8% Equipment 6% Provenance 5% Bottle Closure 1% White vs Red vs Pink Winemaking

Basic Winemaking:

White Wine: (Destem – Crush) – Press – Ferment JUICE @55°F to 65°F

Red Wine: Destem – Crush - Ferment MUST - Press @80°F to 90°F White vs Red vs Pink Winemaking

Destemming Destemming Crushing Crushing vs Pressing Fermenting Fermenting Pressing Handling

Destemming/Crushing

Destemmer

Crusher Destemmers Destemmer and/or Crusher Crusher Crusher

Basket Press Membrane Press Membrane Press Free-run (Juice) Press Juice ... Fermentation aided integration of fruit aromas and flavors ...

60° to 65° Fahrenheit Stainless Steel Tank Fermentation

White Wines: 55° to 60° Fahrenheit Alcoholic Fermentation

Carbon Dioxide

Must CO2 Gas! Yeast Fermentation

• Esters

– Caprate C10

– Laurate C12

– Pelargonate C9

– Caprylate C8

– Myristate C14

• Higher alcohols – Phenylethanol

www.lallemandwine.com Rehydrating Active Dry Yeast

• Follow the manufacturer's instructions! • Temperature too hot: deadly shock for yeast • Temperature too low: number of viable cells reduced • Stay exactly between 38 and 41°C (100 to 106°F) • Water is the preferable rehydration media • Add slowly to vigorously agitated water • Don't allow longer than 15 to 20 minutes in water • Mix thoroughly with the must or juice ... fresh citrus, apple and tropical fruit flavors with hints of butter ...

Malic Acid

Oenococcus oeni Malolactic Fermentation

Organism: formerly: Malolactic Fermentation

Chemistry: • Diacetyl O O = = 3HC-C-C-CH3 Sensory: • Buttery, nutty, movie popcorn • Desirable in certain wine styles • Spoilage threshold: 5 mg/L Malolactic Fermentation Employed in WHITE & RED Styles

Timing:

• Traditional: spontaneous - when cellar warmed up in the spring

• Modern: inoculated - during or after alcoholic fermentation Red Winemaking

Color pigments, , located in skins! Red Grapes: Destem & Crush Fermentation

manhole

SKINS + CAP

cooling jacket JUICE

manhole SEEDS arm/valve manhole fill valve Cap Management down

Max. Temperature: 85° to 90° Fahrenheit Cap Management

Pump-over

Cap Management Post-Fermentation

racking arm/valve • Bottom Slope • Manhole positions Pink Winemaking

1. Traditional : Juice fermentation with brief skin contact

2. Must fermentation of under-ripe red grapes

3. Must fermentation of lightly colored grapes

4. Must co-fermentation of white and red skins

5. Juice fermentation with bleeding juice from reds

6. White winemaking with red wine added back “Saignée”: Bleeding Juice in Wine

Reduced Oxidized electron -rich neutral electron -poor “... CONTAINS …”

1. Microbial stability

2. Inhibition of browning enzymes

3. Binding of acetaldehyde

4. Antioxidant Regulation of SO2

• In Winemaking

Total SO2 allowed: 350 mg/L Labeling required*: ≥ 10 mg/L

• Naturally produced by yeast: 1 to 14 mg/L *even if naturally produced Microbial Stability and SO2

SO2 sensitivity:

Malolactic bacteria? YES! Saccharomyces? NO! Kloeckera? YES?

Brettanomyces? YES? Microbial Stability, pH and SO2 % Free (mg/L)SO -- 150150

Free SO2 required molecularmolecular 55 -- SO - 75 SO2 2

0 - -- 00

2.9 3.2 3.5 3.8 4.1 pHpH pH and Molecular SO2

molecular 100 % SO2 = pH - 1.83 present 1 + 10

pH - 1.83 Free SO2 = 0.85 • (1 + 10 ) required Decrease pH by 0.1 => use ≈ 20% less Free SO2 Decrease pH by 0.3 => use ≈ 50% less Free SO2 SO2 Chart

www.foodsci.purdue.edu/research/labs/enology/FreeSO2(pH)Pro.pdf Food Science 564 Commercial Food & Beverage Fermentations

and Winemaking

Christian BUTZKE Professor of Enology Department of Food Science Méthode Champenoise

1. Base wine (Blanc de Blanc or Blanc de Noir) + Yeast 2. Blending (Assemblage => Cuvée de tirage) + Sugar 3. 2nd fermentation in bottle (Prise de mousse) 4. Riddling (Rémuage) 5. Disgorging (Dégorgement) 6. Dosage (Dosage) 7. /Wire Cage (Bouchage/Museletage) Sugar Calculations

Pressure Goal: 6 = 90 psi

Theory: 90 g sugar => 46 g + 44 g CO2

Practice: 19.3 g sugar => 8.9 g CO2 (≈94%)

8.9 g/ 750 mL bottle CO2 = 6 bar (atmospheres)

Rule of Thumb: 4.4 g sugar per L per bar

From: Armstrong, Rankine, Linton: Sparkling Wines, 1994 “Champagne Yeast”

Saccharomyces bayanus Active Dry Yeast, e.g. Lallemand EC 1118 3-step adaptation to high EtOH environment + Yeast nutrients, thiamin

Free SO2 ≈10 mg/L Temperature ≈65°F Time ≈3-6 weeks Prise de Mousse En Tirage Riddling Riddling

Yeast deposit Plastic bedule Crown cap Disgorging

Neck Freezer Dosage

Same wine Aged (oaked) wine () Sugar Champagne Dryness

residual sugar (g/L) Extra brut < 6 Brut < 15 Extra dry 12-20 Sec 17-35 Demi-sec 33-50 Doux 50+ Cork/Cage Asti Spumante

Moscato Bianco

Charmat-Martinotti method Dessert Wines

Ice Wine

Late Harvest Wine

Passito Ice Wine

Vidal Blanc Ice Wine

Harvest time Ice Wine

Harvest time Ice Wine

After the first night frost Ice Wine

Frozen cluster BEFORE pressing Ice Wine

What’s “frozen”? Ice Wine

What’s “FROZEN”?

Grapes starting to freeze: <32°F

Grapes frozen solid: <12°F

Optimum ice wine pressing: 16-20°F

Canadian definition: 18°F (-8°C) Ice Wine

Frozen cluster AFTER pressing Ice Wine

After pressing: sugar-less “snow” remaining Ice Wine

Icewinemaker Ice Wine

Whole Cluster Pressing of frozen grapes Ice Wine

Pressed ice wine juice Ice Wine vs. Late Harvest

Concentration of , acids and aromas

IW: Partial freezing of the berry’s water and pressing of frozen berries

LH: Dehydration of berries via perforation of cell walls by Botrytis fungus ” Late Harvest (Botrytised) Wines Examples

TrockenBeerenAuslese Sauterne

Germany & Botrytis cinerea “Noble Rot”

Late-season infections:

• Relative humidity 92+%

• Free moisture on berry surface

• Temperatures up to 82°F Passito

Concentration of sugars, acids, aromas

Dehydration of berries by temperature and humidity-controlled drying Passito Italian Examples

Vin Santo Recioto

Passito Temperature-controlled Drying Purdue Passito @ 100ºF/40% r.H.

Valvin MuscatÔ www.nysaes.cornell.edu/pubs/press/current/images/060707ValvinMuscatL.jpg Purdue Amarone @ 100ºF/40% r.H.

Steuben A Fortified

Harvest red (often interplanted) Crush in Lagares Start fermentation Stop fermentation at about half-way => Drain fermenting juice into (77%)

=> Port wine sweet + fortified (18-20%vol) Barrel/bottle age Lagar Robotic Lagar

Lagar Port Production Food Science 564 Commercial Food & Beverage Fermentations

Brandy

Christian BUTZKE Professor of Enology Department of Food Science Definition (Grape) BRANDY

Alcoholic distillate from the FERMENTED juice, mash, or wine of grapes, or from the residue thereof, produced at less than 190° proof (95% ) in such a manner that the distillate possesses the taste, aroma, and characteristics generally attributed to the product. U.S. Treasury Department 1977

Brandy Pricing

Example Cognac: Designation Age Price VS >2 $ 30 VSOP >4 $ 60 XO >10 Ø20 $ 120 Louis XIII up to 100 $2600 Alambic Brandy Winemaking

• Low sugar => 7 to 9% alcohol • High acid/low pH

• No SO2 ! • Fermentation temperature 68°F - 77°F • Completely dry • No defects • Malolactic fermentation optional Brandy Winemaking

Grape Varieties • Ugni Blanc (99% in Cognac) • Folle Blanche • French • Chardonnay • Pinot noir Component Formation

Fruit, variety

SO2 treatment • Raw material Infections: Botrytis, bacteria Temperature Nutrients addition • Fermentation Yeast strain pH • Wine storage Time Temperature, Preheater • Distilling style Copper still Burner temperature With/without 2-stage/3-stage/rectified Brandy Composition

H2O • 65-72% Ethanol • 27-34% Water EtOH • 0.7-1.0% Congeners (ca. 400 - 500) • Reactions during fermentation/distillation/aging: • Enzymatic Formation of all biological compounds • Chemical Esterification, hydrolysis, Cu-reactions, oxidation, acetalization, re-arrangements, Maillard reactions • Physical Evaporation, wood extraction

Brandy Aroma

Volatile Components: 400 to 500

Distillation Technique mg/L • 100% @ 85%vol 1000-1500 • 100% Pot Still @ 75%vol 1500-2000 • 100% Pot Still @ 75%vol w/lees 2000-3000 Component Formation

During Fermentation During Distillation u Aldehydes u Copper Reaction Products u Ketones u Acetals u Higher Alcohols (‘Fusel Oils’) u Acrolein u Methanol u Isocyanate -> EC u Fatty Acids u Terpenes u Esters u Norisoprenoids u Sulfur Compounds u Volatile Phenols u Volatile Phenols u Furfurals u Lactones u Maillard Products Alcoholic Fermentation

GLUCOSE Glucose-6-P Fructose-6-P

ETHANOL NAD+ Fructose-1,6-P NADH H+

ACETALDEHYDE + CO2 Glyceraldehyde-P DHA-P Pyruvate NAD+ NADH H+ NADH H+ NAD+ P-Enol-Pyruvate 1,3-DiP-Glycerate Glycerol-P

2-P-Glycerate 3-P-Glycerate GLYCEROL Aldehydes

• Acetaldehyde - - CH3CHO + HSO3 CH3CHOHSO3 Acetaldehyde + Bisulfite Hydroxyethane Sulfonic Acid

CH3CHO + 2 C2H5OH CH3CH(OC2H5)2 + 2 H2O Acetaldehyde + Ethanol 1,3-Diethoxyethane + Water

• 3-Hydroxypropionaldehyde Acrolein Acroleïn

Precursor Formation by Heterofermentative Lactobacilli

Glycerolhydrolyase GLYCEROL Glyceroldehydrogenase -H O 2 NAD+ 3-HYDROXYPROPANAL NADH H+ Dihydroxyaceton

1,3-Propandiol- NADH H+ ATP T -H O + DHA-Kinase ∆ 2 Dehydrogenese NAD ADP

ACROLEIN 1,3-Propandiol DHA-3-Phosphate Acetals

H H O H I. C O + H O Ö C 2 ALDEHYDE + 2 ALCOHOL ACETAL R R O H

+ H H O H + H O H II. C + B H Ö + B C R O H I. Hydratization (fast) R O H

+ + H H H H O H O H II. Protonization (fast) III. + H O C + C H O H C 2 2 5 Ö O C H R O H R 2 5

+ + H H III. + Ethanol 1 (slow) H H O C H O H 2 5 IV. C + H O C + C H O H 2 2 5 Ö O C H R O C H R 2 5 2 5 IV. + Ethanol 2 (fast) H + H O C H 2 H O C H 5 + 2 5 C V. + B Ö + B H C V. Acetal (fast) R O C H R O C H 2 5 2 5 Acetals

= f(Ethanol concentration)

Ac 20 H Ald 2 Alc Boiling Points: Ac 20 H Acetaldehyde 70°F Ald  Alc Diethoxyethane 219°F

HYDROSELECTION Ketones

- CO - CO • Diacetyl 2 2 NAD+ NADH H+ • LAB: 2 Pyruvate 2-Acetyllactate Acetoin Diacetyl • Yeast: 2 Pyru. 2 Acetald. Acetylald. Acetoin

- 2 CO 2 • Methylketones • 2-Heptanone Fatty Acid • 2-Nonanone . O + Oxidation • 2-Undecanone Methylketone ‘Rancio Charentais•’ 2-Tridecanone Higher Alcohols

Fusel Oils: 240 - 480 mg/L

• 3-Methylbutanol (‘Isoamylalcohol’) C5 • 2-Methylbutanol (‘Active Amylalcohol’) C5 • Isobutanol C 4 Active Amyl • n-Propanol C3 Isobutyl

• 2-Butanol C6 n-Propyl 2-Butyl • n-Hexanol C6 n-Hexyl n-Butyl • n-Butanol C4 Isoamyl • 2-Phenylethanol Higher Alcohols

Metabolic Pathways in Yeast

VALIN GLYCOLYSIS

Deamination - NH3 Pyruvate + Acetaldehyde a- Ketovalerate

Decarboxylation - CO 2 2-Acetyllactate Isobutyraldehyde a- Ketoisovalerate NADH H+ Hydration NAD+ ISOBUTANOL ISOBUTANOL VALIN Higher Alcohols “Fusel Oils”

Ethanol Fusel Oil

Yeast

Kinetics of fusel oil formation, alcoholic fermentation, yeast growth and amino acid consumption Glutamic Acid Castor, 1956 Arginine

t [h] 25 50 75 100 125 150 175 Higher Alcohols “Fusel Oils”

2-Phenylethanol [mg/l]

Gamay Syrah Pinot 60 Cinsault Relationship between amino 40 acid concentration in juice and 20 corresponding alcohol in wine 50 2-Phenylalanine [mg/l] Methanol

O O + CH3OH C - OCH3 H OH C - OH H OH O O H H H H O H OH H O O H OH H O OH O H O H H OH H H O PME O H OH C - OCH3 H OH C - OH O O + CH3OH • Source: fruit PECTIN • Pectin: polymer of carbohydrate 1,4-glycosidic-linked galacturonic acid • Polygalacturonic acid partly methylated Methyl ester • Enzyme pectinmethylesterase (PME) deesterifies METHANOL Distilling House Styles

• distill wine with lees Rémy • heads 1&2 + tails 1&2 back to wine • secondes back into brouillis

• distill wine without lees • separate heads but not tails • 25% of secondes back into wine • distill wine without lees Hennessy • heads 1&2 + tails 1&2 partly back • 30% secondes back into brouillis Fatty Acids

Alambic Brandy Wine Yeast Distillate 335 mg/L 431 mg/L

Acetic Caproic Butyric/Valeric Caprylic Propionic Propionic Butyric/Valeric Caproic Acetic Caprylic Capric Formic Formic Capric Esters

ALCOHOL + ACID ESTER + WATER

• Ethyllactate ALCOHOLS • EtOH, higher alcohols, MetOH • Ethylacetate ACIDS • Volatile fatty acids • Ethylformiate • Succinate • Diethylsuccinate • Long-chain fatty acids • Laurate • Isoamylacetate • Myristate • 2-Phenylethylacetate • Palmitate • Hexylacetate • Stearate • Ethylcaproate • Oleate • Ethylcaprylate • Linoleate • • Linolenate • Ethylcaprate • Ethyllaurate • Lactate from MLF Esters

Changes in Esters during Distilling Season

Ethyllactate - Ethylacetate - Diethylsuccinate - Ethyllaurate - Ethylcaprate - Ethylcaprylate - Ethylcaproate - Phenylethylacetate - Hexylacetate - [% change/5 months] Isoamylacetate - -100 -50 0 50 100 150 200 250 Copper Reactions

Still copper reacts with:

• Hydrogen Sulfide H2S

• Ethylmercaptan C2H5SH

• Methylmercaptan CH3SH

• Diethylsulfide (C2H5)2S

• Dimethylsulfide (CH3)2S

• Dimethyldisulfide (CH3)2S2 • Fatty Acids http://www.a-holstein.de http://www.a-holstein.de http://www.a-holstein.de

Distillation = Concentration

72%vol

28%vol

9%vol Bubble Cap Plates Bubble Cap Plate Column Still

Energy Out: 21 MJ/L EtOH

Energy In: 11 MJ/L EtOH Column Still

Energy Out: 21 MJ/L EtOH

Energy Inp: 3 MJ/L EtOH Column Still

Copper Reactions

Gas Chromatogram of Sulfides Ethyl Carbamate

O

O N UREA UREA + ETHANOL

Isocyanate ARGININE Ethylisocyanate Carbamic Acid N N

N ETHYLCARBAMATE Ethyl Carbamate

Amygdalin Pathway Oxidation CYANIDE HH CC NN . • Ionized Copper Oxides + O. • Unsaturated Fatty Acids • Benzaldehyde Cyanate H O C N • Diketones (Diacetyl)

Mesomeric Equilibrium Isocyanate O C N H .. + C2 H 5 OH Nucleophilic Addition O- Ethylisocyanate + C2 H 5 OO CC NN HH H Rearrangement O

ETHYLCARBAMATE C2 H 5 O C N H H Terpenes Monoterpenols

Sugar-Bound Free • Linalool CH OH + 2 TERPENE H O • Hotrienol O • a-Terpineol OH DT HO • Nerol • Nerol oxide OH • Geraniol Norisoprenoids

Sugar-Bound Free • Damascenone CH OH + 2 NOR H • ß-Ionone O O • Vitispirane

OH DT • Megastigmanes HO • Oxoedulans OH • Actinidols • TDN Volatile Phenols

Grape Acid Phenol Esters • 4-Ethylphenol • 4-Ethylguaiacol cinnamyl-esterase • 4-Vinylphenol Grape Acid Phenols S. cerevisiae decarboxylase • 4-Vinylguaiacol • 2-Phenylethanol CH OH 2 + • Tyrosol O H O • Vanillin OH DT • Ethylcinnamate HO • Benzaldehyde OH Aroma Descriptors

• Acetaldehyde sherry, Aldehydes • • Benzaldehyde bitter almond • 2-Heptanone fruity,spicy,cinnamon Ketones • • 2-Tridecanone warm, herbaceous Higher Alcohols • • 2-Methylbutanol vegetal, barn • 2-Phenylethanol rose, honey, plastic Fatty Acids • • sweat Esters • • Isoamylacetate fruity, banana, pear

Acetals • • Ethylcaprylate coconut, mouthfeel • Diethoxyethane nutty Terpenes • • Triethoxypropane garlicy Norisoprenoids • • Linalool orange, lemon • a-Terpineol floral, lilac Phenols • • ß-Ionone violet,floral,balsamic • Damascenone fruity, rose, ‘sweet’ • 4-Ethylphenol woody, phenolic • 4-Vinylguiacol medicinal, cloves Alambic Pot Still Distillation Volume Flow

1. Distillation 2. Distillation

HEADS HEADS 8.5%vol 28%vol 28%vol 70%vol I BRANDY BROUILLIS 185 gal TAILS II

SECONDES

TAILS III

WINE STILLAGE BROUILLIS STILLAGE 660 gal 660 gal Distillate Fractions 1. Distillation • fruity, apple, pear, pineapple, banana • apple, acetaldehyde • cooked fruit HEADS 8.5%vol 28%vol • fruity, soapy • soapy light fruit • vegetal apple BROUILLIS • vegetal pear • almond, furfural plum TAILS • furfural • boiled artichokes • artichokes • artichokes • wet dog • wet dog • wet dog • woody, vegetal WINE STILLAGE • artichokes • artichokes, butyric • artichokes, wet dog 660 gal • horse sweat Distillate Fractions 2. Distillation

• estery, banana, pear, • coconut, fatty, soapy HEADS • fatty, soapy 28%vol 70%vol • fatty, soapy BRANDY • dish water, laundry water • flowery, vegetal, hay 185 gal • soapy, grassy • vegetal , soapy, grassy SECONDES • flowery, soapy • isoamylic, green vegetable TAILS • roselike • neutral • neutral • roselike BROUILLIS STILLAGE • rose, honey, plastic • wet dog • wet dog, artichokes 660 gal • cooked fruit, wet dog, artichokes Brandy Aroma

CATEGORIES • Flowery

• Fruity

• Spicy

• Woody Brandy Aroma

• Petunia • Daisy FLOWERY • Rose • Vine Flower YOUNG • Carnation • Violet • Iris • Potpourri • Jasmine • Lilac • Honeysuckle • Hyacinth • Bluebell OLD • Orange Blossom © Robert Léauté • Narcissus Brandy Aroma

• Plum • Pear FRUITY • Peach • Apricot YOUNG • Hazelnut • Peanut • Almond • Walnut • Orange Peel • Cherry • Jammy • Prune • Marmalade • Lichee • Dried Fruit • • Candied Fruit OLD • Coconut © Robert Léauté • Passion Aroma

• Bell Pepper SPICY • Clove YOUNG • Cinnamon • Pepper • Curry • Ginger • Candied Ginger • Saffron • Nutmeg OLD • Balsamic © Robert Léauté Brandy Aroma

WOODY • Vanilla YOUNG • Tobacco • Leather • Powdered Chocolate • Incense • Cedar • Cigar Box • Eucalyptus OLD • Sandalwood © Robert Léauté Aroma Food Science 564 Commercial Food & Beverage Fermentations

Christian BUTZKE Professor of Food Science Department of Food Science

Definition Vinegar

A wine or wine product not for beverage use produced in accordance with the provisions of this part and having not less than 4.0 grams (4%) of volatile acidity (calculated as acetic acid and exclusive of ) per 100 milliliters of wine. http://www.ttb.gov/forms_tutorials/glossary/glossary-text.html#V_3 Regulations Are commercial vinegar producers regulated by TTB?

YES. Many vinegar production methods include a stage where alcohol has developed but vinegar, with its distinctive taste, has not. TTB regulates commercial vinegar production when there is a potential Federal excise tax liability as beverage alcohol at any stage of production, including on raw materials used to make the vinegar. Finished vinegar is not subject to alcohol beverage excise tax. http://www.ttb.gov/faqs/genalcohol.shtml Raw Materials

• Wine • Sugar cane • Malt wort • Dates • • Sorghum • • Melons • • Coconut • Brandy • Maple syrup • Molasses • Potatoes • Honey • Beets • Rice • Whey Alcoholic Fermentation Saccharomyces cerevisiae

GLUCOSE Glucose-6-P Fructose-6-P

ETHANOL NAD+ Fructose-1,6-P NADH H+ ACETALDEHYDE + CO2 Glyceraldehyde-P DHA-P Pyruvate NAD+ NADH H+ NADH H+ NAD+ P-Enol-Pyruvate 1,3-DiP-Glycerate Glycerol-P

2-P-Glycerate 3-P-Glycerate GLYCEROL Acetic Acid Formation Acetobacter aceti

Alcohol dehydrogenase Aldehyde dehydrogenase H O ETHANOL ACETALDEHYDE + H2O ACETIC ACID + 2 O + 2 + O2

Acetobacter possesses a proton motive force- dependent efflux pump for acetic acid J Bacteriol. 2005 Jul;187(13):4346-52 Acetic Acid Formation Acetic Acid Formation

H O ETHANOL ACETALDEHYDE + H2O ACETIC ACID + 2 + O2 + O2 Fermentation does not necessarily have to be carried out in an anaerobic environment. For example, even in the presence of abundant oxygen, yeast cells greatly prefer fermentation to aerobic respiration, as long as sugars are readily available for consumption (a phenomenon known as the Crabtree effect). en.wikipedia.org/wiki/Fermentation Acetic Acid Formation Acetobacter aceti Acetic Acid Fermentation Process Parameters

• Batch (not continuous) • Alcohol concentration: 11-18%vol • Temperature: 73-86°F • Time: 2+ weeks • Residual alcohol: 0.1-0.3% • (L acetic acid per L ethanol): 92-96% • Acetic acid concentration: 10-17% Vinegar Mother Acetobacter w/Cellulose

Orléans Process Acetic Acid Fermentors Acetic Acid Fermentors

w/Carrier material Submerged culture Acetic Acid Fermentors

Carrier materials: • wood chips/shavings • birch twigs • polyurethane foam • plastic pellets • ceramic shards

Acetic Acid Fermentors Acetic Acid Fermentors Aerators Acetic Acid Fermentors Aeration Acetic Acid Fermentors Vinegar Mold Spoilage

Moniliella acetoabutans

• Yeast-like fungus resistant to AA • Raised white velvety mycelial mat • Later dark brown or black from production of chlamydospores • Sorbic acid will inhibit at < pH 3.3 @ >400 mg/L Volatile Acidity “V.A.” in Wine

Chemistry Acetic acid Sensory Vinegar odor Spoilage threshold: 700 mg/L Legal limits: 1,400/1,200 mg/L (27 CFR Part 4 Subpart C §4.21 a iv) Nailpolish Off-Odor

Chemistry

Alcohol + V.A. = Ethyl acetate Sensory Nailpolish/remover odor

Spoilage threshold: 150 mg/L

vs. Acetic acid: 700 mg/L Vinegar Eels

Turbatrix aceti are free-living nematodes that feed on the microbial culture used to create vinegar, and may be found in unfiltered vinegar. Although they are harmless and non-parasitic, leaving eels in vinegar are considered objectionable in the United States and are not permitted in vinegar destined for American consumers. Manufacturers normally filter and pasteurize their product prior to bottling, destroying the live bacterial culture that these nematodes require for sustenance. They are usually about 1/10” long. Balsamic Vinegar Aceto Balsamico di Modena

1. Boiled-down () juice @ < 194°F (30% of original volume 22 => 73 ) 2. X% 10+year old balsamic vinegar 3. 10+% of volume added as new wine or wine vinegar 4. Contains at least 6% acetic acid Balsamic Vinegar Aceto Balsamico Tradizionale di Modena

Minimum 12 years of aging

$100+ per 100 mL Acetic Acid Fermentors Balsamic Vinegar

• Oak • Juniper • Mulberry • Chestnut • Cherry • Ash • Acacia Balsamic Vinegar Aceto Balsamico di Modena

Minimum 2 months of aging

$0.70 per 100 mL Balsamic Vinegar Aceto Balsamico di Modena

Wine vinegar + grape juice concentrate + 2 months of aging + caramel (+ corn starch + guar gum) + metabisulfite

Balsamic Vinegar Aceto Balsamico di Modena The Future Vinegar Tasting

#1 #2 #3 Food Science 564 Commercial Food & Beverage Fermentations

Christian BUTZKE Professor of Enology Department of Food Science

Cider & Cider & Perry Cider & Perry Cider & Perry

Pomaceous Fruit Berries Tropical Fruit • Apple • Blackberry • Banana • Pear • Raspberry • Mango • Quince • Loganberry • Passion Fruit • Blueberry • Pineapple • Strawberry • Lychee • Cranberry • Pomegranate Vegetables • Red/Black Currants • Watermelon • Rhubarb Stone Fruit • Pumpkin • Cherry • Dandelion • Peach • Onion • Apricot • Tomato • Plum

www.indianaquality.org/ Scott_2013_Cider_Canada.pdf Basics of Fruitwinemaking

• “Ameliorate”: 1. Acidify if pH >3.7 (De-acidify if TA > 12 g/L) 2. Add sugar if <10 Brix

• Add 100 mg/L SO2 at crush • Add yeast nutrients Yeast Rehydration

• Dose: 2 lb/1000 gal • Cell growth: 5m/mL -> 100m/mL • Chlorine-free water • Temperature: 104°F +/-2 • Time: 20 minutes +/-2 • Add 1 volume cold juice over 5 min for every 18°F difference in temperature; let sit for 15 min

Old Cider Mill/Press Crush

Food Science Hammer Mill “New” Cider Press “New” Cider Press

Fruitwine Yields The Claims Increased free run/press yields Increased color extraction Improves color stability Faster clarification Easier Better mouthfeel; “soft ” Enhanced complexity Purity/Side Activities

High activity of - Polygalacturonase (EC 3.2.1.15) - Pectin lyase (EC 4.2.2.10)

Low activity of - Pectin esterase (EC 3.1.1.11) Purity/Side Activities

High activity of - Hemicellulase - Exocellulase - Endocellulase

Low activity of - Cinnamyl esterase => volatile phenols (4-EP) Questions What activity at crush temperature? Why increased color extraction? Color in cellar vs. on table? More Brett substrate? More N from skins => more lees? Modified colloidal content/stability Pectins needed for mouthfeel? Enzyme Activity = f (Temperature and pH) 2005

T (°F) ./mar. jan

São Paulo São

n.1

v.36

. ? 86 104 122 140 158 176 194 Braz. J. Microbiol Braz. Ellagic Acid

• Ellagic acid is a natural polyphenol found in numerous fruits and vegetables, e.g. • Blackberry • Raspberry • Loganberry • Strawberry • Pomegranate • Cranberry • Muscadine grapes Tannins Fruit Wine Styles

Fruit wine is VERY versatile. Can make many types of wines for almost any application. 1. Low alcohol “cider style” (2-7% alcohol) 2. Dry or “off-dry” fruit wine (8.5-13.5% alcohol) 3. Sweet fruit wine (usually done with berry wines) 4. Cryo-extracted fruit wines 5. Fortified or “Port-style” fruit wines (up to 24% alc)

6. Sparkling fruit wine – CO2 injected, Charmat or Champenoise style Slide courtesy of Dominic Rivard - WinePlanet Consulting Low Alcohol Style

• 2 to 7% alcohol • Usually made with an apple base and blended with fruit. • High dilution ratio • Geared for the larger volume • Lower price due to lower taxes • VERY popular now in Europe

Slide courtesy of Dominic Rivard - WinePlanet Consulting Off-Dry Style

• Usually between 8.5-13.5% alcohol • Under 30g/L RS • Has the highest appeal for the casual wine drinker. • Should be made “food friendly” • Having a good balance is key. A little less forgiving if the balance is wrong (acid, flavor concentration, sugar)

Slide courtesy of Dominic Rivard - WinePlanet Consulting Sweet Fruit Wine

• Well suited for higher acid fruit such as raspberry or currants • Easier to balance the wine • Less dilution, more intensity can be achieved • Aim for an RS of higher than 40g/L • TA levels of higher than 7 to 8g/L • Can be “cloying” if not done right.

Slide courtesy of Dominic Rivard - WinePlanet Consulting Cryo-Extracted Style

• Geared for the premium and export markets. • Made my freezing juice. Start at about 36 Brix • Gaining in popularity very fast • High intrinsic value – good profit • Aim for an RS of >140g/L and TA of 9g/L depending on fruit. • Should use tree fruits for this or blend berry wine with tree fruit base.

Slide courtesy of Dominic Rivard - WinePlanet Consulting Fortified Style

• Depending of state laws, can be fortified to 24% alcohol. • RS levels of >80g/L • Excellent for raspberry, blackberry or currants (Cassis). • To pair with desserts, chocolates • Use high acid fruit, no dilution needed as alcohol dilutes it. • Can ferment a few % then fortify for Port style • Age in neutral oak for higher complexity. • Just add alcohol to juice for style, usually sweeter. Slide courtesy of Dominic Rivard - WinePlanet Consulting Sparkling Style

• Can be made by CO2 injection, Charmat or Traditional • Can easily be made dry to sweet with the same wine base • Made “frizzante” or “Sparkling” • Sold to weddings, celebrations • Champagne corks or caps.

Slide courtesy of Dominic Rivard - WinePlanet Consulting Wine Carbonation Calculations

Pressure Goal: 6 bar = 90 psi @ 45°F

Theory: 90 g sugar => 46 g Ethanol + 44 g CO2

Practice: 19.3 g sugar => 8.9 g CO2 (@≈94%

8.9 g/ 750 mL bottle CO2 = 6 bar (atmospheres)

Rule of Thumb: 4.4 g sugar per L per bar

From: Armstrong, Rankine, Linton: Sparkling Wines, 1994 Beer Carbonation Calculations

Pressure Goal: 1.75 bar = 26 psi @ 68°F

Theory: 90 g sugar => 46 g Ethanol + 44 g

CO2

Practice: 2 g sugar => 0.9 g CO2 (@≈94%) per 355 mL = 12 oz bottle

Rule of Thumb: 4.4 g sugar per L per bar