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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 were 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

SPEX CertiPrep, Inc. 2011

Harvesting the Grapes


A grapes terroir : affects of season, weather,
soil, mineral, time of harvest, pruning method
and acidity = quality, aroma & flavor

Harvest time = grapes level


sugar (Brix) 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

SPEX CertiPrep, Inc. 2011

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

<0.1% Esters

<0.1% Polyphenols
Trace Amounts
Vitamin A, Vitamin C

2 lbs of Grapes are needed


to create a bottle of wine!
SPEX CertiPrep, Inc. 2011

Flavor & Aroma Chemistry of


Varietals
Compound
Methoxypyrazines

Examples

Odor
Earthy,Grassy,Pepper

Varietals
CabernetSauvignonand
Sauvignonblanc.

2methoxy3isobutylpyrazine(IBMP)

BellPeppers

2methoxy3isopropylpyrazine(IPMP)

Asparagus,Peas,Earth

geraniol,linaloolandnerol

Floral

Gewurtramine,Muscat,Riesling

megastigmatrienone
zingerone
damascenone

Spice
Spice
RoseOil

Chardonnay

vanillin

Vanilla

Monoterpines

Norisoprenoids

Mercaptans

Onion,Garlic

Thiols
4mercapto4methylpentan2one
(4MMP), 4mercapto4methylpentan2
ol,3mercaptohexanol,3mercaptohexyl
acetate
Glycosides

Pinotnoir

CabernetSauvignon,
Gewrztraminer,Merlot,Muscat,
PetitManseng,Pinotblanc,
Pinotgris,Riesling,Scheurebe,
SemillonandSylvaner
Sauvignonblanc

Chocolate,Tobacco

Ports
SPEX CertiPrep, Inc. 2011

Oenology:
The oldest known
the science
wineryand
is located
study ofinall
Armenia
aspectsand
wine
is
over
and6000
wine years
making
old

SPEX CertiPrep, Inc. 2011

Crushing the Grapes


Crushing = start liberation
of juice from grape

The Must = juice, skins,


seeds, pulp

Must contains molds &


native yeasts
Natural is not better

Grape components
crushed = winemaking
method & variety of wine

SPEX CertiPrep, Inc. 2011

Crushing the Grapes


White Wines
Stems can be Intact:
Increases tannins
Reduces exposure to color in skins
Skins directly removed

Rose Wines
Red skinned grapes with minimal skin contact
White & red grapes

Red Wines
Stems usually removed
Contact with skin encouraged to varying degrees

SPEX CertiPrep, Inc. 2011

Potassium metabisulfite & SO2


Added during many stages
Campden tablets = g potassium or sodium
metabisulfite

Levels in wine
Commercial wine = 20 to 40 ppm
Natural wines as low as 6 ppm
Obies wines: no added sulfites; drink within
3-4 years

Produces SO2
Kills native yeast = antimicrobial
Anti-oxidant
Binds w/ acetaldehyde
Binds w/ anthocyanins
red wine = problem
Anthocyanins bind to tannins

SPEX CertiPrep, Inc. 2011

Sulfites

K2S2O5, contributes to sulfites in wine


Contains Sulfites = added sulfite
compounds
Warning labels
1987 US
2005 EU

All wines have sulfites


Sweet & White > Reds
Fermentation process = 6 to 40 ppm
sulfites
US levels allowed = 350 ppm

SPEX CertiPrep, Inc. 2011

Red Wine Headaches


Occurs after drinking red wine
As little as one glass
Usually blamed on sulfites
Only 0.01% population are allergic
to sulfites = asthmatics
Un-metabolized acetaldehyde causes
headaches
Possible other causes:
Histamines
Tannins
Cause release of serotonin
Prostaglandin release
Cause pain and swelling
Strains of yeast or bacteria

SPEX CertiPrep, Inc. 2011

Punching Down the Must


Cap skins, seeds etc. top of juice - CO2
Punching down the must
Juice mix with skins = color & flavor
extraction
introduce O2 to yeast = fermentation
prevent harmful bacterial growth
lower the must temperature
Preserve delicate aroma compounds
Increases production of esters
Keep yeast growing
Red wines: 22 to 25 C
White wines: 15 to 18 C

Cultured, selected yeast added


Beginning of primary fermentation
1-2 weeks
Converts most of sugar to ethanol

SPEX CertiPrep, Inc. 2011

The most Important Chemical


Reaction in Wine Making!

C6H12O6 2 C2H5OH + 2 CO2

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Fermentation Reactions
Bacteria or yeast consumes one compound and
excretes different product(s)

Fruit
(sucrose /
fructose /
glucose)
+
Yeast
=
Alcohol
(Ethanol)

Milk
(lactose)
+
Bacteria
=
Cheese

Flour
(sugars)
+
Yeast
=
Bread

Ethanol
+
Yeast
=
Acetic acid
(Vinegar)

SPEX CertiPrep, Inc. 2011

Sugars
Sugar level in wine = Brix
1.0 Brix = 1% Sugar = 0.55%
EtOH

Sugar level = alcohol content


Sugars = 1 fuel fermentation
Non-fermentable sugars (5 C ring)
Arabinose, Rhamnose & Xylose
Still present after fermentation
No wine is ever completely dry

Chaptalization: Sucrose added to


boost fermentable sugar content
boost alcohol content

17-18% alcohol highest level


w/o added sucrose
SPEX CertiPrep, Inc. 2011

Fermentable Sugars (6 C ring)


Glucose
One of primary sugars of wine
1st sugar metabolized by yeast
Tastes < sweet than Fructose
% Glucose beginning of ripening of
grape (>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 (24 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

1114%

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

<1 Brix before pumping into barrel


Sweet wine >1 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

SPEX CertiPrep, Inc. 2011

Grape Skin & Seed Compounds:


Tannins

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

Dont 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

SPEX CertiPrep, Inc. 2011

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

SPEX CertiPrep, Inc. 2011

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

SPEX CertiPrep, Inc. 2011

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

SPEX CertiPrep, Inc. 2011

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)
Angels Share

3-5 vintages before oak character


absent

Staves sanded to open oak


Oak strips added to impart aroma

SPEX CertiPrep, Inc. 2011

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
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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

SPEX CertiPrep, Inc. 2011

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 Magazines 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)

SPEX CertiPrep, Inc. 2011

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

SPEX CertiPrep, Inc. 2011

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?

SPEX CertiPrep, Inc. 2011

New in 2011

2011-2012 Catalog Now


available on CD!

New Consumer Safety


standards kit for USP 232
(Part# USP-TXM1)

Visit www.spexcertiprep.com for more information!


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Come visit us on your favorite social networking site!

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Thank You!

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