The Art & Chemistry of Wine Ralph Obenauf President, SPEX CertiPrep

Patricia Atkins Applications Specialist, SPEX CertiPrep © SPEX CertiPrep, Inc. 2011

Housekeeping  Everyone in attendance will receive a copy of the slides  The webinar is being recorded and will be available for everyone to view on demand – The recording will be posted about one week after the event

 Questions will be answered at the end of the presentation – Type any questions you may have into the question box and we will answer them during the Q & A portion

 Stay tuned after the Q&A session – we’re giving away a free gift! © SPEX CertiPrep, Inc. 2011

Ralph Obenauf Making wine and making merry…… …..with some chemistry thrown in.

As Ben Franklin said: In wine there is wisdom, In beer there is freedom, In water there is bacteria. © SPEX CertiPrep, Inc. 2011

Viniculture: The science and study of all aspects of wine grape cultivation and production

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Harvesting the Grapes  A grape’s terroir : affects of season, weather, soil, mineral, time of harvest, pruning method and acidity = quality, aroma & flavor

 Harvest time = grape’s level – sugar (ºBrix) usually >15% • Later harvest = more sugar – Acid Levels - Tartaric acid – pH

 Other harvest factors: – Tannin development (seed color & taste)

 De-stemming (removal of stems) depends on winemaking techniques – Stems and seeds = tannins • White wines – stems intact • Red wines – stems removed © SPEX CertiPrep, Inc. 2011

Varietals Original Barrel of Zin #444

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Varietals  Over 10,000 varieties of grapes in world  Vitis vinifera – Most common species of grapes – Almost all the European varieties – Every continent except Antarctica

 Vitis silvestris: ancestor of modern wine  Grape Uses – 71% Wine – 27% Fresh Fruit – 2% Dried fruit

 Top wine production regions: Italy, France, Spain, US & Argentina

 Grafting Root Stocks © SPEX CertiPrep, Inc. 2011

Chemistry of the Grape 70-90% Water 18-25% Glucose & Fructose 0.3-1.5% Tartaric & Malic Acids 0.7% Amino acids

0.15% Potassium

5x Fructose) − At harvest glucose = Fructose  Fructose − Over ripen grapes > Fructose − Twice as sweet as glucose • Important for dessert wines  Sucrose − Minimal in wine, except champagne & sparkling wines © SPEX CertiPrep, Inc. 2011

Alcohol - Ethanol  Alcohol content limited to 18% w/o sucrose addition

 During fermentation, >9% Alcohol needed to prevent bacterial growth – Mother of Vinegar (Acetobacter)

 Target alcohol = 13% Alcohol (24º Brix)  Final Ethanol Content varies by variety

Wine

% Alcohol

Table Wine

8-14%

Claret

6-10%

Shiraz

10-14%

Rose

10%

White, medium

11%

White, dry

11%

Red, medium

12%

White, sparkling

12%

White, sweet

12%

Cabernet, Pinot Noir

11–14%

Dessert Wine

14-20%

Zinfandel

17-22%

Vermouth

17-22%

Syrah

17-23%

Port

20% http://alcoholcontents.com/wine/wine.html © SPEX CertiPrep, Inc. 2011

Pressing the Grape  Pressure removes juice from pulp & skins  Gains 15-30% more juice  Pressed juice has lower acidity (higher pH) than drained juice

 Red wines pressed after fermentation  White wines pressed before fermentation  Pressing releases different compounds from layers of the grape

 pH adjusted (3.0-3.7) – Tartaric or Malic Acid – Prevents bacterial growth – Gives tart flavor or zing

 1º Brix • Stabilized with Potassium Sorbate  Bubbler at top of barrel to release CO2 © SPEX CertiPrep, Inc. 2011

Chemical Anatomy of the Grape Seeds & Stems (Optional Inclusion) • Tannins

Skin • • • • •

Anthocyanins Quercetin Resveratrol Tannins Catechins

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Grape Skin & Seed Compounds: Tannins    

Plant polyphenol Binds and precipitates proteins & other compounds 3 types: hydrolysable, condensed & complex Bad tannins (skins, seeds & stems)

− Don’t polymerize − Produce bitter taste = astringency  Beneficial Tannins (Oak barrels) − Preservative − Wine clarification (Fining agents) • Proteins bind to tannins • Clarify wine: egg whites, gelatin, bentonite − Young Oak barrels = more tannins  Red wines (>tannins) pair with meats = hydrolysable tannins  As tannins age – lose binding − fall to bottom of bottle − wine mellows

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Grape Skin & Seed Compounds: Catechins  Flavanols  Also found in chocolate  React with tannins to make primary flavor components in wine

 Larger flavanol – tannin complexes – mellow

 Smaller flavanol – tannin complexes – bitter  Concentrations in red wine 10 mg/L to 250 mg/L

− Lighter bodied wine > catechin content

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Grape Skin & Seed Compounds: Anthocyanins  Water soluble pigments of red, purple or blue (pH)

    

Flavenoids Antioxidants Odorless and almost flavorless Polymerize with tannins Important in tannin retention and aging of wine

 Five groups of anthocyanins and presence dependent on varietal of grape & wine

− > free hydroxyl groups = blueness − > methyl groups = redness − Malvin group – red grapes © SPEX CertiPrep, Inc. 2011

Other Grape Skin & Seed Compounds  Quercertin − Flavanoid − Antioxidant − Found in skin of grape − Reacts with anthocyanins • deeper vibrant color  Resveratrol (3,5,4'-trihydroxy-transstilbene)

− Phenol produced by plants when under attack by bacteria and fungi

− Found on skin of grape − Antioxidant works in conjunction with Quercertin

− Reported health benefits © SPEX CertiPrep, Inc. 2011

Other Grape Skin & Seed Compounds  Gallic Acid: Phenolic compound − Antifungal & Antiviral compound − Found in seeds & from exposure to new oak − 10 – 100 g/L in wine  Succinic Acid: Dicarboxylic acid − Considered flavor component − Salty bitter flavor in wine elsewhere for sweetness

− Reacts to form esters − Acid + Ethanol = mono-ethyl succinate (fruit aroma)

− In grape & by-product of alcohol and sugar rxn  Caffeic Acid & Caftaric Acid: Cinnamates − Yellow gold color in white wine − Esterifcation rxn: Caffeic Acid + Tartaric Acid = Caftaric Acid

− Oxidation > reaction • Pressed wine have little to no Caftaric Acid © SPEX CertiPrep, Inc. 2011

Chemical Anatomy of the Grape Peripheral Zone Intermediate Zone • Tartaric Acid • Sugars

• • • • • • •

Potassium Sugars Oxidases Acids Astringents Tannins Aroma Compounds

Central Zone • Malic Acid • Sugars © SPEX CertiPrep, Inc. 2011

Grape Flesh Compounds: Acids  Acids are important in winemaking and the finished wine

 Primary Acids in Wine − Malic Acid − Tartaric Acid  Other Acids in Wine − Acetic Acid − Ascorbic Acid − Butyric Acid − Citric Acid − Lactic Acid − Sorbic Acid

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Grape Flesh Compounds: Tartaric Acid    

Most important acid in wine Maintains chemical stability of wine Influences Taste & Color Grape vines -few sources of natural high concentrations

 Majority of acid = potassium acid salt (cream of tartar)

 During fermentation acid binds with pulp debris (lees), tannins, and pigments

 Acid crystals can precipitate out − Wine Diamonds − Cold stabilization precipitates crystals © SPEX CertiPrep, Inc. 2011

Grape Flesh Compounds: Malic Acid

        

One of two Primary Acids in Wine Carboxylic Diacid Bitter, Tart taste Associated with Green Apple Flavor Riesling – high Malic Acid Cooler growing conditions > Malic Acid Decreases as grape ripens Low Malic Acid = flat taste High Malic Acid = sharp bite

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Other Acids Lactic Acid • • • •

Controlled by the winemaker Milder than Tartaric or Malic Acid Creates milky flavor Rxn Lactic acid bacteria (LAB) & Malic Acid • Chardonnays & other white wines • Some LAB -histamines cause RWH Citric Acid • Very small quantities in wine • Supplement for sucrose addition © SPEX CertiPrep, Inc. 2011

Other Acids Acetic Acid • Produced during or after fermentation • Vinegar taste above 300 mg/L • Acetobacter Ascorbic Acid • • • •

Vitamin C Found in young grapes Lost to ripening Added with SO2 as antioxidant (EU limit 150 mg/L)

Butyric Acid • Bacteria Induced wine fault • Smells like rancid butter or blue cheese Sorbic Acid • Used as a preservative © SPEX CertiPrep, Inc. 2011

Sampling Young Wine

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Chemistry in a Glass 70-90% Water

6-23% Ethanol by Variety

1-3% Pectins, Proteins, Acids

1% Vitamins & Minerals 1% Polyphenols, Flavenoids, Tannins & flavor compounds © SPEX CertiPrep, Inc. 2011

Aging the Wine The average age of a French Oak tree used for wine barrels is 170 years old

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Oak Barrels  Two major origins for Oak barrels – French & American

 Seasoning – French oak traditionally aged or seasoned for two years – American oak kiln dried

 Harvest – French Oak is split – American Oak is sawed • Ruptures xylem cells = release of lactones

 Flavor: American Oak > French Oak – 2-4x > lactones – vanilla © SPEX CertiPrep, Inc. 2011

Oak Barrels      

First widespread use - Roman Empire 400 species of Oak 20 species used for wine barrels One tree = 2 barrels 5% of the trees used for barrels Oak barrels are source for tannins – New barrels = high tannins – Green oak = bad tannins

 Porousness: oxidation & evaporation – 5-6 gal loss (59 gal barrel) – Angel’s Share

 3-5 vintages before oak character absent

– Staves sanded to open oak – Oak strips added to impart aroma

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Other Flavor & Aroma influence of the Barrel  Toasting – exposure of oak barrel to fire & high temperatures – Reduces lactones (fresh oak aromas) – Increases vanilla & caramel aromas Vanillin Furfual 5-methyfurfal – High toast levels = spicy & smoky notes Eugeol & Isoeugenol (spicy) 4-methyl guaiacol (spicy & smoky) Guaiacol (smoky)

 Add oak chips to increase aromas © SPEX CertiPrep, Inc. 2011

Racking the Wine Barking at the moon referred to a process of racking the wine under the clear light of the full moon  Racking: Separate the wine from the solids, “lees”, settled at the bottom of the barrel

 Clearing: Settling of small particulates and matter in wine over time.

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Sampling

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Bottling Process  Bottle Rinsing – Rinsed with Potassium metabisulfate

 Bottles Filling – Wine dispensed into bottles

 Corks are placed in the bottles – Headspace

 Capsules placed on bottles – Heat sealed © SPEX CertiPrep, Inc. 2011

Bottles Volume (liters)

# Standard Bottles

0.1875 0.25 0.375 0.378 0.5 0.62 0.75 0.757 1.5 2.25 3 4.5 6 9 9 12

0.25 0.33 0.5 0.505 0.67 0.83 1 1.01 2 3 4 6 8 12 12 16

15

20

18 20 25 27 30

24 26.66 33.33 36 40

Name Piccolo Chopine Demi Tenth Jennie Clavelin Standard Fifth Magnum Marie Jeanne Jeroboam Rehoboam Methuselah Mordechai Salmanazar Balthazar

 Shape: traditional, cultural or marketing

 Before corks bottles were squat & flat bottomed

 After corks: store on side: long & cylindrical

Nebuchadnezzar Melchior Solomon Sovereign Primat Melchizedek © SPEX CertiPrep, Inc. 2011

Corks  The primary tree for corks is the Cork Oak, Quercus suber

 Trees are 25 years old before cork is stripped from the trunks every ten years

 The trees live for about 200 years

 Cork production − 52.5% Portugal − 29.5% Spain − 5.5% Italy

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Cork Taint  “Corked Wine” − Cork industry claims only 0.7 – 1.2% cork taint

 Trichlorophenol compounds  Found in cork & methylated by fungi  Product is 2,4,6 trichloroanisole, TCA

 Damp moldy odor  Human detection limit of TCA is 1ppt  Eliminate with synthetic corks, screw caps – Also eliminates the “POP” © SPEX CertiPrep, Inc. 2011

Cork Taint Standards Single Component: Part#

Compound

S-133 S-1885 S-1983 S-1985 S-2050 S-2930 S-2950 S-3405 S-3555 S-3586 S-3645 S-4168 S-4183 S-4309 S-5005 S-609

Acetic Acid Ethanol 2-Ethylphenol 4-Ethylphenol 2-Fluorophenol 2,3,4,5,6-Pentachloroanisole Pentachlorophenol 2,3,4,6-Tetrachlorophenol 2,4,6-Tribromophenol 2,4,6-Trichloroanisole 2,4,6-Trichlorophenol Malic Acid 4-Ethyl-2-Methoxyphenol 2,4,6-Tribromoanisole Dextrose 2,3-Butanedione

Multi-Component: Part# WINE-1

WINE-2

WINE-3

Compound 2,4,6-Tribromoanisole-d5 Pentachloroanisole-d3 2,4,6-Trichloroanisole-d5 2,3,4,5,6-Pentachloroanisole 2,3,4,6-Tetrachloroanisole 2,4,6-Trichloroanisole Carbon Disulfide Ethyl Sulfide Ethanethiol Ethyl Disulfide Ethyl Methyl Sulfide 2-Ethylthiophene Methanethiol Methyl Disulfide Methyl Sulfide 2-Methyl-2-Propanethiol 2-Methylthiophene 1-Pentanethiol 2-Propanethiol Thiophene © SPEX CertiPrep, Inc. 2011

Storage Titanic sits at 12,000 to 13,000 feet below the ocean's surface. Many of the wine bottles in the cellar were intact.

 Most modern wines are consumed within 24 hours after purchase (near term consumption)

 Most important factors: – Light: light rxn with phenolic compounds – Temperature: Chemical rxns 2x every 8 °C increase Ideal: 10 to 15 °C

– Humidity (75%): corks from drying

 Wine refrigerators or Wine cellars keep constant light, temperature & humidity

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Enjoy Breathing the wine: removes hydrogen sulfides from stinky or young reds; rarely helps whites

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Health Benefits Food & Wine Magazine’s 8 Benefits of Drinking Wine (2007) Reduces Heart Attack rate •30% lower risk (Harvard Public Health Study)

Promotes Longevity •34% lower mortality rate (Finnish Study)

Lowers Heart Disease •Queen Mary University, London

Reduces Risk of Type 2 Diabetes •30% lower risk (Amsterdam VU Univ. Medical Center)

Lowers Risk of Stroke •Clot risk drops 50% (Columbia University)

Cuts Risk of Cataracts •32% risk reduction (Nature 2003)

Cuts Risk of Colon Cancer •45% risk reduction (especially red) (Stony Brook)

Slows Brain Decline •Reduced risk (Columbia University)

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Calories in Wine & Alcohol  Recent studies report alcohol is not efficiently metabolized in the body  To calculate the metabolized calories (N): N = T – (7cal/g)*(0.28g/oz%)*P*X = T- 2*P*X N = net calories T = Total calories X = #oz P = % Alcohol

Dry Wine (4oz, 13% abv)

Beer (12oz, 5.5% abv)

Light Beer (12oz, 4% abv)

T=115, N=9 calories

T=150, N=18 calories

T=105, N=9 calories

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Pesticides in Wine  Grapes: one of the ‘Dirty Dozen’ of produce  2008 Pesticide Action Network (PAN) Europe: – 128 pesticide residues in 40 bottles EU wine – Low ppm to ppb range

 Studies being conducted to find out if the pesticide levels are of concern in wine SPEX CertiPrep Pesticide Standards: Part# S-3970 S-5225 S-4622

Pesticide Dimethomorph Pyrimethanil Cyprodinil

Part# S-3984 S-4962 S-4815

Pesticide Azoxystrobin Fenhexamid Boscalid

S-3871 S-2056 S-2272 S-733 S-2061 S-103 S-3450

Procymidone Tebuconazole Iprodione Carbendazim Fludioxonil Bromopropylate Tetradifon

S-2369 S-1997 S-5469 S-4262 S-4267 S-4832

Metalaxyl Fenarimol Spiroxamine Benalaxyl Penconazole Flusilazole © SPEX CertiPrep, Inc. 2011

Heavy Metals in Wine  Studies have found Hazardous levels of metals in wine – Exceed EPA THQ (Target Hazard Quotients) • Vanadium • Copper • Manganese • Zinc • Chromium • Nickel • Lead

 Worst countries for metal levels: – Hungary, Slovakia, France, Austria, Spain, Germany, Portugal, Greece © SPEX CertiPrep, Inc. 2011

Heavy Metals Standards  SPEX CertiPrep carries full line of Inorganic standards

− Heavy Metal Mixes − Heavy Metal Standards  UL and A2LA Stamp of Approval: − Certified by UL-DQS for ISO 9001 − Accredited by A2LA for ISO 17025 and ISO Guide 34

 Inorganic CRMs for: − AA & GFAA − ICP & ICP-MS − IC − XRF − Classical Wet Chemistry Techniques  Single element standards 1,000 mg/L and 10,000 mg/L concentrations

 Custom standards at almost any concentration © SPEX CertiPrep, Inc. 2011

Questions?

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