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The Avoidance of Taints and Contaminations During Winemaking1

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    The Australian WineResearch Institute

    The avoidance of taints andcontaminations duringwinemakin

    Geoff CoweySenior Oenologist

    Industry Development and Support

    [email protected]_AWRI

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    Taints in 2005 & 2006

    Tainted batchof yeast hulls

    CCl

    OH

    CH3

    Tainted batchof tartaric acid

    CC

    l

    OH

    Cl

    6 chloro-O-cresol 2, 6 dichlorophenol

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    What happened next…

    AWRI investigations started 2006, resolved 2007

    Legal recourse in 2010, involving: the manufacturer

    supplier

    a contract winery

    number of other wineries

    Court ruled in favour of the supplier in 2011

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    What happened next…

    It was accepted that the ‘contaminated’ tartaric acid provided by

    the supplier was not reasonably fit for use by the winery as anadditive in the making of wines for human consumption foritself or for others, and that the tartaric acid delivered by the

    supplier to the winery was not of merchantable quality

    However the supplier's terms and conditions included clauses whichabsolved the supplier of any responsibility

    T&C signed in a credit application by the winery accountant over fiveyears prior to purchase of this batch of tartaric acid from the supplier

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    Impact of taints & contaminations

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    Flavours, taints and faults

    What is a wine aroma flavour?

    An odour that can be derived from grapes, the winemaking process

    or wine development Consumer preference e.g. Sauvignon blanc

    What is a wine fault/off flavour?

    Fault — internal contamination A characteristic which leads to spoilage, attributed to poor winemaking

    practices or unsound storage conditions.

    e.g. volatile acidity/ VA or vinegar aroma, Brettanomyces flavour

    What is a wine taint?

    Taint — external contamination

    an odour or flavour that is foreign to, and reduces the acceptability of theproduct e.g. cork taint

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    Major faults at wine shows

    2008 winesMicro

    Other

    6 to 7% of wines in the International Wine Challenge in 2006, 2007& 2008 were judged to be faulty

    Data by Sam Harrop, International Wine Challenge

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    The Australian WineResearch InstituteThreshold(ng/L)

    2,4,6-trichloroanisole (TCA) 1.4

    2,4,6-tribromoanisole (TBA) 3.4

    musty, mouldy aroma, bitter metallic taste 

    2-meth lisoborneol 30

    Musty compounds

    geosmin 25

    mouldy, earthy, dirty water 

    1-octen-3-ol 200001-octen-3-one 20

    Fungal must (2-methoxy-3,5-dimethylpyrazine) 2.1

    Chocolate, dirty, dusty, mouldy, mushroom 

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    ‘plastic-like’, ‘chlorine-like’, ‘antiseptic’

    Threshold(ng/L)

    2,4-dichlorophenol (2,4 DCP) 8902,6-dichlorophenol (2,6 DCP) 32

    2,4,6-trichlorophenol (TCP) 2000

    2, 6-dibromophenol (DBP) 502,4,6-tribromophenol (TBP) >890

    plastic, paint-lie, me!icinal or phenolic

    6 chloro-o-cresol 70

    Chemical-like, plastic, chlorine-like and hot, burning aftertaste

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    Aromatic hydrocarbons

    naphthalene

    alkyl naphthalenes

    ‘Mothballs’, ‘chemical’, ‘styrene’

    xylene

    toluene

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    Threshold (µg/L)

    Guaiacol 23

    4 methyl guaiacol 65

    m-cresol 20

    o-cresol 62

    ‘Smoky’, ‘ash’, ‘burnt’, ‘ashtray ’

    p-cresol 64

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    Guided wine taint tasting

    Assess carefully

    Aroma only (taste if you need to)

    6 White wines

    Wine 1 is a control 

    Nothing spiked at ‘harmful to health’ levels

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    Wine 1. Control

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    Wine 2.

    Smell wine 2

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    Wine 2. Chlorine/plastic - Chlorophenol

    (2,6-dichlorophenol at ~ 100 ng/L)

    'plastic', 'paint-like', 'medicinal' or 'phenolic' taint

    2,6-dichlorophenol: 32 ng/L odour threshold in white wine(300 ng/L threshold in water)

    widely used in cleaning products (biocides)

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    Sources of Chloro and bromophenols

    ChlorophenolsTimber floors

    treated with

    Bromophenols

    Bromoanisoles

    Aromatic hydrocarbons

     

    chlorophenols &bromophenol

    preservatives

    Smellbarrelexhibit

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    Contamination in the vineyard

    Australia 2002:2,4-dichlorophenol taint

    − from agrochemical breakdown

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    Wine 3.

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    Wine 3. Cork-type taint:

    2,4,6-tribromoanisole (TBA) at 5 ng/L

    distinct musty, mouldy aroma

    similar aroma threshold to TCA (3.4 ng/L)

    precursor is 2,4,6-tribromophenol (TBP)

    TBP is both a flame retardant and fungicide, and is widely used totreat wood and wood products

    TBA has been found on winery surfaces: barrels, plastics (includingsynthetic closures), natural corks and wood structures includingwalls, floors and ceilings

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    Wine 4.

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    Wine 4. Cork taint: – 2,4,6-trichloroanisole (TCA) at 5 ng/L

    distinct musty, mouldy aroma

    suppresses fruit intensity

    red wine aroma threshold 1.4 ng/L

    precursor is 2,4,6-trichlorophenol (TCP)

     

    other compounds which impart musty, mouldy, earthy or mushroomaromas to wine include:

    2-methylisoborneol (threshold of 30 ng/L),

    geosmin (threshold of 25 ng/L),

    1-octen-3-ol (threshold of 20 µg/L) and 1-octen-3-one (threshold of 20 ng/L)

    2-methoxy-3,5-dimethylpyrazine (2.1 ng/L in wine)

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    Sources of Chloro and bromoanisoles

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    TCA Vs TBA

    Over last 10 years (1999-2009) AWRI Commercial Services haveanalysed over 2000 wines for a variety of musty taints

    109 positive cases of TBA taint 861 positive cases of TCA taint

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    Wine 5.

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    Wine 5. 6-chloro-o -cresol (6CC) at 100 ng/L

    “Chemical-like”, “plastic”, “chlorine-like” and “hot, burning aftertaste”

    Threshold 16 ng/L

    Contaminant in yeast hulls (> 500 ng/L in one wine)

    ‘disinfectant-type’ taints in chicken meat and biscuits and softdrinks

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    Wine 6.

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    Wine 6. Geosmin — at 20 ng/L

    earthy, musty, muddy, dirty fish tank

    threshold ~25 ng/ L

    metabolites of soil bacteria and algae

    off-flavour in town water supplies/water storage Can contaminate wine when used to push wine through lines, used to

    make up additions to wine

    metabolite of Botrytis cinerea (Kikuchi et al 1983)

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    Guided wine taint tasting

    Tip out your glasses, and pour the next 6 wines

    Assess carefully

     

    6 Red wines

    Wine 1 is a control

    Nothing spiked at ‘harmful to health’ levels

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    Wine 7. Red wine control

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    Wine 8.

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    Wine 8. Guaiacol at 30 µg/L

    threshold 23 µg/L — smoky, phenolic, medicinal

    high toast level in barrels; formed during barrel toasting process/degradation of lignin

    then extracted into wine at typically 10–40 µg/L

    Component of ‘cork taint’? — formed by soil bacteriaand moulds, but at low quantities

    Bushfires and burn-offs

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    Smoke is more than just guaiacol - cresols

    "#aiacol $%D cresols, an! their

    m#ltiple gl#cosi!e congates

    are pro!#ce! !#ring a smoe

    e'ent

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    Contamination in the vineyard

    Australia 2005:2,4-dichlorophenoxyacetic acid− from herbicide spray drift

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    Wine 9.

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    ‘eucalyptus’, ‘fresh’, ‘cool’, ‘medicinal’ and ‘camphoraceous’

    Aroma mentioned in Australian, Californian, South American wines,Cabernet Sauvignon or in wines grown near Eucalypt trees

    Eucalyptol or 1,8-cineole

    Threshold 2.2-3.2 µg/L, consumer rejection threshold 27 µg/L

    Wine 9. Eucalyptus character at 40 µg/L

    Airborne transfer Binds to fatty berry layers

    Extracted from skin duringfermentation

    MOG is the majorcontributor

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    Wines from a vineyard in WA

    Distance of vines from bluegums

    [Eucalyptol] in finishedwine (µg/L)

    First 4 rows running 11-18.5 m 9.5

     econ row runn ng m .

    Seventh row running 27 m 1.1

    Sixteenth row running 50 m 1.6

    Twent-seventh row! 77 m 0.6

    "em#ining rows 2$0-4$0 m 0.4

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    Wine 10.

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    Wine 10. Reduction - Methyl mercaptan

    at 40 µg/L methyl mercaptan (methane thiol) threshold: 3.1 µg/L

    rotten cabbage, onion, rubbery 

    Other reduction or ‘sulfide’ compounds:

    Hydrogen sulfide (rotten egg)

    Disulfides (rotten onions)

      Dimethyl sulfide (canned corn, tomato sauce)

    Chemical & biological formation – often

    wines that have experienced fermentation problems

    Elemental Sulfur agrochemical residues

    Often confused with Brett spoilage

    Wi 11

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    Wine 11.

    Wi h l h l h l i l

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    4-eth%&heno%

    HO

    medicinal bandaid ® 

    phenolic metallic taste 'ntrinsic sensor #ttri(utes

    Wine 11. 4-ethylphenol: 4-ethylguaiacol

    at 400: 45 µg/L

    Dekkera (Brettanomyces) bruxellensis

    4-eth%gu#i#co%

    HO

    H3CO

    4-eth%c#techo%

    HO

    HO

    smoky 

    spicy 

    clove-like 

    medicinal 

    horsy 

    smoky smoky-bacon 

    antiseptic 

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    30:1

    40:1

     

    survey data

    4-EP & 4-EG

    are always present together

    “Brett” Compounds

    0

    10:1

    20:1

    50% = 9:1

    2.5% = 3:1

    .

    Frequency

       R  a   t   i  o  o   f   4  -   E   P  :   4  -

       E

    Cabernet, Nebbiolo

    Pinot Noir

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    Aroma thresholds for ‘Brett’ compounds in three base wines

    1200

    1400

    1600

    1800

     

       h  o   l   d   (   g   /

       L   )

    1131

    1528

    Variable threshold, depending on the wine

    0

    200400

    600

    800

    1000

    4-EP

       A  r  o  m  a   t   h

      r  e

     

    368425

    569

    4-EG

    158 209

    373

    Neutral Green Oaky Neutral Green Oaky

    4-EC

    774

    Neutral Green Oaky

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    The ‘Brett’ zone - prevention

    8

    Alcoholic fermentation 

     

       )

    Maturation and bottling 

    The ‘Brett’ zone  Healthy ferments Healthy ferments

     Minimise residual sugar  Minimise residual sugar 

    >0.8 mg/L Molecular>0.8 mg/L Molecular SO pH control pH control

    SanitationSanitation

    0

    2

    4

    Vinification time

    Saccharomyces cerevisiae 

    Non-Saccharomyces yeasts

    O.oeni (post-ferment)

    Dekkera bruxellensis 

    Indigenous bacteria

       C  e   l   l   g

      r  o

      w   t

       (   l  o  g  c  e   l   l  s

       /  m

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    Wine 12 Sorbic acid metabolism

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    Wine 12. Sorbic acid metabolism

    (Geranium off-odour) odour reminiscent of crushed geranium leaves

    result of metabolism of sorbic acid by LAB (mainly only

    Oenococcus oeni – not Pediococcus and Lactobacillus spp.)

    pathway: hydrogenation of sorbic acid to sorbinol which rearranges, - - -

    3,5-hexadien-2-ol then reacts with ethanol to form 2-ethoxyhexa-3,5-diene (geranium tone)

    If use sorbic acid, must sterile filter to remove LAB

    M i t i t

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    Main contaminants

    Hydraulic oil

    Hydrocarbons

    (aliphatic and aromatic)

    Refrigerant ‘brines’

    Alcohol solutions containing

    ethanol/methanol

    rhodamine dye

    ethylene glycol solutions

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    !pac" epo#y paint taint“plastic”, “PVC”, “styrene”, “solvent/chemical/oily”

    in harvested grapes in grape bin

     

    Truck and trailer had just been painted with anon-food grade paint which was not fully

    cured for 2 weeks

     pac epoxy pa n s:• Not contain phenols• Not contain solvent• Suitable for potable water• Tested by approved water authority• 7-12 days curing before use

    $ i t f t t

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    The Australian WineResearch Institute$aint from pump stator

    Red wine had a “petroleum/grease-like” taint

    Taint observed after simple wine transfer

    Winemaker suspected that the mono pump

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    Oils aint always oils!

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    Oils aint always oils!

    Grapeseed oil

    Fluorescent green

    Unique acrid smell

    Heavily pressed wines

    The basic steps in managing quality

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    The basic steps in managing quality

    Specify the quality requirements

    (no taints)

    Control the processes

    Monitor the processes

    Corrective action system

    Continuous review

    Th A li WiWinemaking flowchart

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    1. Harvest &

    Transport

    Yeast & DAP

    2. Crushing

    3. Must holding& Settling

    4. Inoculation

    & fermentation

    Acid adjustment

    g – critical control points?

    CCP1 - Pesticides

    CCP3 - MOG

    CCP4 Oil leaks CCP5 - taints

    CCP2 – Hydraulic oil, brine leaks

    5. Protein

    Stabilisation

    7. Fining

    Bentonite

    6. Tartrate

    Stabilisation

    Casein, PVPP & Copper

    8. Wine adjustments RS & Acid adjustment

    9. Sterile Filtration

    10. Bottling

    Filtration

    CCP7 – Removal of microorganisms

    CCP6 taints

    The Australian Wine

    Example - Taints from agrochemicals

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    Example - Taints from agrochemicals

    Risk – illegal additives, taints from pesticide breakdown,contaminated pesticide or non-adherence withwithholding period

    Control – ‘AWRI Registered Agrochemicals booklet” &spray diary

     

    Frequency – check each batch of incoming fruit

    Corrective action - reject grapes

    Responsible person – winemaker

     

    The Australian Wine

    Refrigerant brine

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    Risk – leaks from Brine refrigeration

    Control – engineer out risk no interior tank dimple plating

    no brine lines over open tanks

    Frequency – monitor brine reservoir level weekly

     – annual R&M of hoses, clamps etc

    Corrective action – analyse for rhodamine

     – quarantine batch, dispose of as waste

     – recover through insurance

    Responsible person – winemaker

    The Australian WineAdditives and processing aids

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    Additives and processing aids

    An additive or rocessin aid has the

    potential to taint juice or wine if thatadditive or aid is tainted!

    The Australian Wine

    Aerial contamination of

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    Directly from the air during production

    Aerial contamination of

    additives & processingaids

    From containers during transport

    Through packaging materials

    The Australian WineScreening techniques - Distributors

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    Research InstituteScreening techniques Distributors

    http://news.reseau-concept.net/images/oiv/Client/Codex_2006_FR.pdf

    The Australian Wine

    Example Taints from additives

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    Research InstituteExample - Taints from additives

    Risk – taints from contaminated additives

    Control – foil barriers during transport

     – assess additives before use

    Frequency – check each batch

    Corrective action – reject batch

     – inform supplier

    Responsible person – lab staff

    The Australian WineR h I i

    L-Tartaric acid

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    Research InstituteL Tartaric acid

    Procedure: (SolubilityTest)

    Dissolve 1 g of tartaric acid in 1 mL of water or 4 mL of

    95% v/v ethanol.

    Interpretation:

      Tartaric acid should be soluble in its own weight of waterand in four times its weight of ethanol, i.e. no residueshould be apparent). (2006 OIV Oenological Codex)

    A B

    Pass – L-Tartaric acidFail – D/L Tartaric acid

    The Australian WineR h I tit t

    Bentonite

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    Research Institute

    “Bentonite should not have any undesirable odour (e.g.mould), and should not change the taste of wine.”

    International Oenological Codex, 2006 Procedure:

     u u y . -

    hydrate using warm clean water). Important that thewater is the same water used when performing benchfining trial.

    Safety note: Take care when handling. Wear appropriatebreathing protection, due to fine dust hazard.

    Simply place some of this bentonite in a glass andassess the aroma for any mouldy odour and any taints.

    Capitol Reef National Park, Utah, USA

    The Australian WineResearch Institute

    Bentonite

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    Research Institute

    Interpretation:

    If the bentonite is tainted or exhibits mouldy odour, then

    the bentonite is unsuitable for use. (2006 OIVOenological Codex)

    The Australian WineResearch Institute

    Diatomataceous earth filter aid (DE)

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    Research Institute

    Procedure:

    Place 2.5 g of DE into 1L of wine. Mix and leave for 24hours. **Safety note. Take care when handling. Wearappropriate breathing protection, due to fine dust hazard.

    Compare the taste to wine not containing any DE.

    Interpretation:

    The DE should not impart any odour or foreign taste to thewine. (2006 OIV Oenological Codex)

    The Australian WineResearch Institute

    Copper sulfate (CuSO4.5H2O)

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    Research Institute

    Procedure:

    Dissolve 10g in 50 mL of clean water. Swirl

    and assess aroma of solution.

    Inter ret tion:

    The solution should be clear and free fromturbidity and taint aromas. (2006 OIV OenologicalCodex)

    The Australian WineResearch Institute

    Yeast hulls

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    Procedure:

    Add ~5 g of yeast hulls to 50 mL of 95% ethanol and place on amagnetic stirrer for approximately 24hrs. Next, dilute this solution

    down to ~30% v/v ethanol (16mL of yeast hull solution and make upto 50mL with water).

    Interpretation: Yeast hulls should not impart any odour or foreign taste tothe wine.

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    Paint and other surface coatings

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    Procedure:

    Paint 2 microscope slides or stainless steel (approx 25mm x

    70mm) with the article to be tested. Place in a schott bottle and immerse in 3% NaOH for

    approximately 10 minutes. Thoroughly rinse off NaOH with water.

    Transfer slides into 2 separate schott bottles and add 100 mL ofwine simulant (~14% ethanol and water solution) to each and soakfor 5-7 days.

    After 5-7 days, mix thoroughly, divide into 2 equal portions and

    place in schott bottles. Chlorinate one of the samples by adding approximately 50 mg/L of

    chlorine (sodium hypochlorite), mix and allow to stand for 24hrs.

    The Australian WineResearch Institute

    Paint and other surface coatings

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    Interpretation:

    Assess aroma of both samples as well as noting any

    discolouration of the sample and the colour and turbidityof the extraction medium.

    The Australian WineResearch Institute

    Hoses

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    Procedure:

    Use approximately 300mm of hose. Attach a stainless steel plug toone end of the hose and secure with a clamp to make an effective

    seal.

    Carefully fill with 3% NaOH and soak for approximately 10 minutes.Thorou hl rinse off NaOH with water. 

    Using the following table as a guide, fill the hose with wine simulant(~14% ethanol and water solution), seal with a stainless steel plugor alfoil and soak for 5-7 days.

    Hose Diameter

    Volume of wine

    simulant

    38mm 200 mL

    75mm 200 mL

    100mm 400 mL

    The Australian WineResearch Institute

    Hoses

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    After 5-7 days, mix thoroughly, divide into 2 equal portions andplace in schott bottles.

    Chlorinate one of the samples by adding approximately 50 mg/L ofchlorine (sodium hypochlorite), mix and allow to stand for 24hrs.

    Interpretation:

    Assess aroma of both samples as well as noting any discolourationof the sample and the colour and turbidity of the extractionmedium.

    The Australian WineResearch Institute

    Screening techniques

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    All products should be sampled when entering and leaving yourpremises.

    (Irrespective of where you are in the supply chain)

    Check approved materialCheck approved materialQuality assuranceprogram

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    Obtain product information

    QC Assessment of material

    Purchase of material

    Evaluate & select supplier

    Ordering system

    (Traceability)

    Obtain product information

    QC Assessment of material

    Purchase of material

    Evaluate & select supplier

    Ordering system

    (Traceability)

    program

    Receive material

    Quarantine material

    Release to production Return to supplier

    Transfer to generaluse or storage

    QC Assessment of material

    Pass   Fail

    Receive material

    Quarantine material

    Release to production Return to supplier

    Transfer to generaluse or storage

    QC Assessment of material

    Pass   Fail

    The Australian WineResearch Institute

    Approved supplier system

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    Contracts – liability

    Legal compliance for purity

    Legal additives Food grade

    Absence of GMOs 

    Non tainting

    The Australian WineResearch Institute

    Spray Diary

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    The Australian WineResearch Institute

    Traceability

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    How do you keep records for:

    Fruit, juice and wine:

    R07COWEYSHZBLKA

    Tank 1004

     

    Additives11:56 L7103 RL Batch #: 14314DE

    The Australian WineResearch Institute

    Corrective action

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    Quarantine wine batch/additive

    Prevent cross contamination

    Product Recall System

    Reassess controls to prevent reoccurrence

    The Australian WineResearch Institute

    Take home messages

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    Taints =

    potential health risks to consumers

    serious economic & brand loss

    unsaleable wine

      –

    safety program

    Implement a screening program to prevent accidental introductionof taints from winemaking additives and processing aids

    Recognise and be aware of your own sensitivities to taints

    The Australian WineResearch Institute

    Acknowledgements

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    Institute of Masters of Wine

    Staff & students of The AWRI

    Con Simos, Adrian Coulter, Matt Holdstock

    Wine Australia

    The AWRI’s research is financially supported by Australia's

    grapegrowers and winemakers through their investment body

    the Grape and Wine Research and Development Corporation 

    with matching funds from the Australian Government 

     

    Australian wine industry partners

    Australian Grapegrowers and winemakersdiscussed in this presentation


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