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The Australian Wine

Research Institute

The avoidance of taints and


contaminations during
winemaking

Geoff Cowey
Senior Oenologist
Industry Development and Support
geoff.cowey@awri.com.au
The_AWRI

Taints in 2005 & 2006

Tainted batch
of yeast hulls

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Tainted batch
of tartaric acid

OH
Cl

OH
C 3
CH

6 chloro-O-cresol

Cl

C
Cl

2, 6 dichlorophenol

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

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It was accepted that the contaminated tartaric acid provided by


the supplier was not reasonably fit for use by the winery as an
additive in the making of wines for human consumption for
itself 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 which


absolved the supplier of any responsibility
T&C signed in a credit application by the winery accountant over five
years prior to purchase of this batch of tartaric acid from the supplier

Impact of taints & contaminations

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Flavours, taints and faults

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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 the
product e.g. cork taint

Major faults at wine shows

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Other
Micro

2008 wines

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

Musty compounds
2,4,6-trichloroanisole (TCA)
2,4,6-tribromoanisole (TBA)

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Threshold
(ng/L)
1.4
3.4

musty, mouldy aroma, bitter metallic taste

2-methylisoborneol
geosmin

30
25

mouldy, earthy, dirty water

1-octen-3-ol
1-octen-3-one
Fungal must (2-methoxy-3,5-dimethylpyrazine)
Chocolate, dirty, dusty, mouldy, mushroom

20000
20
2.1

plastic-like, chlorine-like, antiseptic

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Threshold
(ng/L)

2,4-dichlorophenol (2,4 DCP)


2,6-dichlorophenol (2,6 DCP)
2,4,6-trichlorophenol (TCP)

890
32
2000

2, 6-dibromophenol (DBP)

50

2,4,6-tribromophenol (TBP)

>890

plastic, paint-like, medicinal or phenolic

6 chloro-o-cresol
Chemical-like, plastic, chlorine-like and hot, burning aftertaste

70

Mothballs, chemical, styrene

Aromatic hydrocarbons
naphthalene
alkyl naphthalenes
styrene
xylene
toluene

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Smoky, ash, burnt, ashtray


Threshold (g/L)
Guaiacol

23

4 methyl guaiacol

65

m-cresol

20

o-cresol

62

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)

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'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)

Sources of Chloro and bromophenols

Timber floors
Chlorophenols
treated with
Chloroanisoles
chlorophenols &
Bromophenols
bromophenol

Bromoanisoles
preservatives
Aromatic hydrocarbons

Smell
barrel
exhibit

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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

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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 to
treat wood and wood products
TBA has been found on winery surfaces: barrels, plastics (including
synthetic closures), natural corks and wood structures including
walls, floors and ceilings

Wine 4.

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Wine 4. Cork taint:


2,4,6-trichloroanisole (TCA) at 5 ng/L

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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 mushroom
aromas to wine include:
2-methylisoborneol (threshold of 30 ng/L),
geosmin (threshold of 25 ng/L),
1-octen-3-ol (threshold of 20 g/L) and 1-octen-3-one (threshold of 20 ng/L)
2-methoxy-3,5-dimethylpyrazine (2.1 ng/L in wine)

Sources of Chloro and bromoanisoles

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TCA Vs TBA

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Over last 10 years (1999-2009) AWRI Commercial Services have


analysed over 2000 wines for a variety of musty taints
109 positive cases of TBA taint
861 positive cases of TCA taint

Wine 5.

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

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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

Wine 6.

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Wine 6. Geosmin at 20 ng/L

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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)

Guided wine taint tasting


Tip out your glasses, and pour the next 6 wines
Assess carefully
Aroma only (taste if you need to)
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 g/L

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threshold 23 g/L smoky, phenolic, medicinal


high toast level in barrels;
formed during barrel toasting process/degradation of lignin
then extracted into wine at typically 1040 g/L

Component of cork taint? formed by soil bacteria


and moulds, but at low quantities
Bushfires and burn-offs

Smoke is more than just guaiacol - cresols

Guaiacol AND cresols, and their


multiple glucoside conjugates
are produced during a smoke
event

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Aerial contamination in the vineyard

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Switzerland
m-cresol and p-cresol taints
pollution of vineyards from nearby factories
Italy
ethylphenol taints
vineyards contaminated from industrial air pollution
Australia
creosote-crudded posts
burn-offs

Contamination in the vineyard


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

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Wine 9.

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Wine 9. Eucalyptus character at 40 g/L

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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 g/L, consumer rejection threshold 27 g/L

Airborne transfer
Binds to fatty berry layers
Extracted from skin during
fermentation
MOG is the major
contributor

Wines from a vineyard in WA

Distance of vines from blue


gums

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[Eucalyptol] in finished
wine (g/L)

First 4 rows running 11-18.5 m

9.5

Second row running 15 m

6.4

Seventh row running 27 m

1.1

Sixteenth row running 50 m

1.6

Twenty-seventh row, 77 m

0.6

Remaining rows 230-430 m

0.4

Wine 10.

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Wine 10. Reduction - Methyl mercaptan


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

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Wine 11.

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Wine 11. 4-ethylphenol: 4-ethylguaiacol


at 400: 45 g/L
bandaid

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4-ethylphenol

medicinal
HO

metallic taste

phenolic

Intrinsic sensory attributes

4-ethylguaiacol

spicy
HO

clove-like

H3CO

medicinal
smoky

4-ethylcatechol

horsy
HO
HO

smoky
Dekkera (Brettanomyces) bruxellensis

antiseptic
smoky-bacon

Brett Compounds
40:1

survey data

4-EP & 4-EG


are always present together

30:1
Ratio of 4-EP:4-EG
EG

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97.5% = 23:1

Shiraz

20:1

10:1

50% = 9:1
2.5% = 3:1

0
Frequency

Cabernet, Nebbiolo
Pinot Noir

Variable threshold, depending on the wine

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Aroma threshold ((g/L)

Aroma thresholds for Brett compounds in three base wines


1800
1528

1600
1400
1131

1200
1000
774

800
569

600
373

400
200

158

368

425

209

0
Neutral Green Oaky Neutral Green Oaky Neutral Green Oaky
4-EG

4-EP

4-EC

The Brett zone - prevention


The Brett zone
Alcoholic fermentation

Maturation and bottling

Cell growth
(log cells/mL)

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Healthy ferments
Minimise residual sugar
>0.8 mg/L Molecular SO2
pH control
Sanitation
Filtration

4
Saccharomyces cerevisiae
Non-Saccharomyces yeasts

O.oeni (post-ferment)
Dekkera bruxellensis
Indigenous bacteria

0
Vinification time

Wine 12.

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Wine 12. Sorbic acid metabolism


(Geranium off-odour)

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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
in the presence of acid to 3,5-hexadien-2-ol
3,5-hexadien-2-ol then reacts with ethanol to form 2-ethoxyhexa3,5-diene (geranium tone)
If use sorbic acid, must sterile filter to remove LAB

Main contaminants
Hydraulic oil
Hydrocarbons
(aliphatic and aromatic)

Refrigerant brines
Alcohol solutions containing
ethanol/methanol
rhodamine dye
ethylene glycol solutions

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2-pack epoxy paint taint

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plastic, PVC, styrene, solvent/chemical/oily


in harvested grapes in grape bin

2 pack epoxy paints:

Not contain phenols


Not contain solvent
Suitable for potable water
Tested by approved water authority
7-12 days curing before use

Truck and trailer had just been painted with a


non-food grade paint which was not fully
cured for 2 weeks

Taint from pump stator

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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!

Grapeseed oil
Fluorescent green
Unique acrid smell
Heavily pressed wines

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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

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Winemaking flowchart
critical control points?
1. Harvest &
Transport
2. Crushing

CCP3 - MOG
CCP4 Oil leaks

CCP1 - Pesticides
CCP2 Hydraulic oil, brine leaks

3. Must holding
& Settling

Acid adjustment

4. Inoculation
& fermentation

Yeast & DAP

5. Protein
Stabilisation

Bentonite

CCP5 - taints

6. Tartrate
Stabilisation
7. Fining

Casein, PVPP & Copper

CCP6 taints

Filtration
8. Wine adjustments

RS & Acid adjustment

9. Sterile Filtration
10. Bottling

CCP7 Removal of microorganisms

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Example - Taints from agrochemicals

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Risk illegal additives, taints from pesticide breakdown,


contaminated pesticide or non-adherence with
withholding period
Control AWRI Registered Agrochemicals booklet &
spray diary

Spray Diary
Frequency check each batch of incoming fruit
Responsible person winemaker
Corrective action - reject grapes

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
Responsible person winemaker
Corrective action analyse for rhodamine
quarantine batch, dispose of as waste
recover through insurance

Additives and processing aids

Any additive or processing aid has the


potential to taint juice or wine if that
additive or aid is tainted!

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Aerial contamination of
additives & processing
aids

Directly from the air during production


From containers during transport
Through packaging materials

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Screening techniques - Distributors

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

Example - 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

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L-Tartaric acid
Procedure:

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(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 water
and in four times its weight of ethanol, i.e. no residue
should be apparent). (2006 OIV Oenological Codex)

A
Fail D/L Tartaric acid

B
Pass L-Tartaric acid

Bentonite

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Bentonite should not have any undesirable odour (e.g.


mould), and should not change the taste of wine.
International Oenological Codex, 2006
Procedure:
Make up a 10% slurry of bentonite as per normal. (rehydrate using warm clean water). Important that the
water is the same water used when performing bench
fining trial.
Safety note: Take care when handling. Wear appropriate
breathing protection, due to fine dust hazard.

Simply place some of this bentonite in a glass and


assess the aroma for any mouldy odour and any taints.
Capitol Reef National Park, Utah, USA

Bentonite

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Interpretation:
If the bentonite is tainted or exhibits mouldy odour, then
the bentonite is unsuitable for use. (2006 OIV
Oenological Codex)

Diatomataceous earth filter aid (DE)


Procedure:
Place 2.5 g of DE into 1L of wine. Mix and leave for 24
hours. **Safety note. Take care when handling. Wear
appropriate 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 the
wine. (2006 OIV Oenological Codex)

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Copper sulfate (CuSO4.5H2O)


Procedure:
Dissolve 10g in 50 mL of clean water. Swirl
and assess aroma of solution.
Interpretation:
The solution should be clear and free from
turbidity and taint aromas. (2006 OIV Oenological
Codex)

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Yeast hulls

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Procedure:
Add ~5 g of yeast hulls to 50 mL of 95% ethanol and place on a
magnetic stirrer for approximately 24hrs. Next, dilute this solution
down to ~30% v/v ethanol (16mL of yeast hull solution and make up
to 50mL with water).
Interpretation: Yeast hulls should not impart any odour or foreign taste to
the wine.

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 of
wine simulant (~14% ethanol and water solution) to each and soak
for 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.

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 turbidity
of the extraction medium.

Hoses

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Procedure:
Use approximately 300mm of hose. Attach a stainless steel plug to
one 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.
Thoroughly 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 plug
or alfoil and soak for 5-7 days.
Hose Diameter

Volume of wine
simulant

38mm

200 mL

75mm

200 mL

100mm

400 mL

Hoses

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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.

Interpretation:
Assess aroma of both samples as well as noting any discolouration
of the sample and the colour and turbidity of the extraction
medium.

Screening techniques

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All products should be sampled when entering and leaving your


premises.
(Irrespective of where you are in the supply chain)

Quality assurance
program

Check approved material


Obtain product information
Evaluate & select supplier
QC Assessment of material

Ordering system
(Traceability)

Purchase of material
Receive material
Quarantine material
QC Assessment of material
Pass

Release to production

Transfer to general
use or storage

Fail
Return to supplier

Approved supplier system

Contracts liability
Legal compliance for purity
Legal additives
Food grade
Absence of GMOs
Non tainting

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Spray Diary

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Traceability

Traceability
How do you keep records for:
Fruit, juice and wine:
R07COWEYSHZBLKA
Tank 1004
11:56 L7103 RL

Additives
11:56 L7103 RL
Batch #: 14314DE

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Corrective action

Quarantine wine batch/additive


Prevent cross contamination
Product Recall System
Reassess controls to prevent reoccurrence

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Take home messages

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Taints =
potential health risks to consumers
serious economic & brand loss
unsaleable wine
Prevention is better than cure avoid taints with a QC/QA/food
safety program
Implement a screening program to prevent accidental introduction
of taints from winemaking additives and processing aids
Recognise and be aware of your own sensitivities to taints

Acknowledgements

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Institute of Masters of Wine


Staff & students of The AWRI
Con Simos, Adrian Coulter, Matt Holdstock
Wine Australia
Australian wine industry partners
Australian Grapegrowers and winemakers
discussed in this presentation
The AWRIs 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

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