Canned Wine: New Information for Preparing Wines for Canning
George Crochiere, Jasha Karasek, Neil Scrimgeour, and Eric Wilkes
DATE 5/21/20
WEBINAR INFO
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SOME QUESTIONS TO BE ADDRESSED IN THIS WEBINAR
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- What makes a can a unique form of packaging?
- What factors contribute to reduction appearing in canned wines?
- How can winemakers avoid reduction appearing for canned wines?
- What treatments are available to prepare wines for canning?
AGENDA FOR TODAY
George Crochiere – Crochiere & Associates
Packaging perspective
Neil Scrimgeour – Australian Wine Research Institute
Understanding and mitigating the development of reductive characters in canned wines
Eric Wilkes – Australian Wine Research Institute –
Wine in cans? A tale of two metals with various supporting players!
Jasha Karasek – Enartis USA
Analysis and Treatments for Canned Wine
Q&A – 20 - 30 mins
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POLL QUESTION!
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GEORGE CROCHIERE – CROCHIERE & ASSOCIATES
President and Co-Owner of Crochiere and Associates LLC. Since 1977, George has worked polymers, ranging from development of plastics and rubber materials while working for spalding, to working as technical manager of coating & closure systems for W.R. Grace in North America. He has worked most recently with beverage, bottle, closure, and plastics manufacturers providing services and test results that lead to improved shelf-life, performance and consistency in their packaging materials. George is also working currently as the materials development manager for Vibram.
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POLL QUESTION!
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NEIL SCRIMGEOUR – AUSTRALIAN WINE RESEARCH INSTITUTE
Neil works in wine research at the AWRI. He is a Senior Scientist for the commercial services division and manages research for new winemaking technologies, saving the industry money, and improving quality.
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Understanding and mitigating the
development of reductive
characters in canned wines
Neil Scrimgeour
Senior Scientist, Commercial Services
The Australian Wine Research Institute
The evolution of canned wine
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Exp
ort
val
ue
(AU
D F
OB
, mill
ion
s)
Canned wine (250ml) Alternative packaging Linear (Canned wine (250ml))
Canned Wine: Aus vs USA Market Trends
Sources: IRI Worldwide; IRI Market Edge MAT to 30/06/19
Total USA off-trade sales of wine in cansTotal USA off-trade sales of wine in cans by channel breakdown
(year ending June 2019)
Convenience
Drug store
Grocery store
Other
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Sale
s (m
illio
n 9
LE c
ases
)
Australian export value of wines packaged in 250ml can containers and alternative packaging
Project Summary
• Canned wines currently have a short shelf-life and are susceptible to
formation of volatile (stinky) sulfur compounds
• A better understanding of the chemical pathways involved is required to
resolve the issue.
• This will help to identify remediation strategies that can be used to extend
wine shelf-life in cans.
• The study is being supported via an industry consortium, including major
wine producers and suppliers, both in Australia and in the USA.
• Additional funding is provided through a Food Innovation Australia Ltd
(FIAL) grant.
Key Trial Elements
BENCHMARK
• Understand the extent of the reduction issue (and some underlying
trends) through analytical monitoring of commercial canned wines, post-
packaging.
INVESTIGATE
• Identify the key chemical pathways that support the formation of
reductive characters post-packaging and gain a better understanding of
the potential role of the can liner in these processes.
MITIGATE
• Trial the use of remediation methods that can be used to mitigate the risk
of formation of reductive characters post-packaging.
VALIDATE
• Undertake field trials to validate the performance of commercial wines in
achieving extended shelf-life.
Canned wine – risk factors
Attribute Upper limit
Free SO2 <35 mg/L
Copper <0.2 mg/L
Chloride <50 mg/L
pH
CO2
Ullage
Oxygen (TPO)
Al(s) → Al3+ + 3 e-
SO2 + 6 H+ + 6 e-→ H2S + 2 H2O
2 Al(s) + SO2 + 6 H+→ 2 Al3+ + H2S + 2 H2O
Excerpt from Introduction to Corrosion Science [McCafferty, 2010]
Benchmarking commercial canned wines - Aluminium
528
595
1163
252
1171 1150
864
575
1013
1187
1006
611
1031
1250
1006
919
310
406 412
206
538493
430
501
624
869
736
489
1104 1086
471
855
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1600
i j k l m n o p q r s t u v w x
Alu
min
ium
co
nce
ntr
atio
n (
µg/
L)
Canned wine product
5 Months 1 Month
Aluminium transfer in carbonated beverages
0
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400
600
800
1000
1200
Beer 2 Soda Water Soft Drink300mL (Glass)
Soft Drink375mL
Beer 1 Soft Drink200mL
Cider 1 Energy Drink Kombucha 1
Alu
min
ium
co
nce
ntr
atio
n (µ
g/L)
Non-wine canned beverages
1-month 3-months 9-months
Microscopic analysis of canned wines
Benchmarking commercial canned wines - sulfides
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i j k l m n o p q r s t u v w x
Co
nce
ntr
atio
n (
µg/
L)
Hydrogen sulfide
1 Month 3 Months 5 Months
Aroma perception
threshold
Benchmarking commercial canned wines - SO2
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i j k l m n o p q r s t u v w x
Free
SO
2co
nce
ntr
atio
n (m
g/L)
Free sulfur dioxide
5 Months At packaging
Benchmarking commercial canned wines - Ullage
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Ulla
ge (
mL)
TPO
(m
g/L)
Can no.
Total package oxygen
DO (mg/L) HS O2 (mg/L) Ullage (mL)
Benchmarking commercial canned wines - TPO
Benchmarking commercial canned wines - Copper
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0.05
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0.25
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0.35
0.4
i j k l m n o p q r s t u v w x
Co
pp
er c
on
cen
trat
ion
(mg/
L)
Copper
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i j k l m n o p q r s t u v w x
Ch
lori
de
Co
nce
ntr
atio
n (m
g/L)
Chloride
Benchmarking commercial canned wines - Chlorides
Evaluate impact of wine factors on Al concentration and sulfide formation
2019 CHD
High SO2
Low SO2
Cu + PVI/PVP treated
Control
Low SO2
High SO2
Horizontal storage
Vertical storage
SO2 30-35 mg/L (low)
53-59 mg/L (high)
Ullage 4-6 mL
CO2 1.5-2.2 g/L
TPO 4.5-5.5 mg/L
Small scale canning trial
Small scale canning trial
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inverted upright inverted upright inverted upright inverted upright
low SO2 high SO2 low SO2 high SO2
control treatment
Al c
on
cen
trat
ion
(µg/
L)
Aluminium
Summary
Most commercial canned wines have elevated aluminium levels, due to the corrosive nature of the wine matrix
Most canned wines contain significant concentration levels of hydrogen sulfide (H2S), even after only 1-month post-packaging
The impact of H2S formation can be mitigated by removing residual copper prior to packaging
The degree of risk and potential impact of wine reduction (H2S) is very much wine dependent
ERIC WILKES– AUSTRALIAN WINE RESEARCH INSTITUTE
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Eric Wilkes is the group manager for commercial services at the AWRI. Specialising in technical management, Eric has extensive experience in successfully integrating new technologies and systems into wine production and improving those already in place. He is also a past committee member of the Interwinery Analysis Group, the co-author of a book on wine laboratory analysis and a regular speaker at industry conferences on technical issues around wine analysis and production.
Wine in cans?
A tale of two metals,
with various supporting
players!
Dr Eric Wilkes
A little bit of background
Before we talk about cans
some background on copper
and sulfides we have learned
from wine in bottles.
H2S 1.1-1.6µg/L
MeSH 1.8-3.1µg/L
rotten cabbage, burnt rubber, putrification
rotten egg, sewage like
The 1950s story.
H2S H2S + Cu2+→ CuS
Mercaptans CH3CH2SH + Cu2+→ Cu(CH3CH2S)2
DMDS CH3S-SCH3 + Cu2+→ unreactive
DMS CH3SCH3+ Cu2+→ unreactive
oxidation reduction
Myth 1, the size of copper additions.
All the copper I add drops out as insoluble sulfide!
Sulfide Copper Sulfate
1-2 μg/l0.000002 g/l
0.5ppm0.0005 g/l
It is not unusual to see copper values increase at exactly the same rate as addition.
Myth 2, filtration does not really work.
Clark, A. C., et al. (2015). "Copper(II) addition to white wines containing hydrogen sulfide: residual copper concentration and activity." Australian Journal of
Grape and Wine Research 21(1): 30-39.
So what is this residual copper?
y = 0.943x - 9.6029R² = 0.9758
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No
n-L
abile
Cu
(µ
g/L)
Total Cu (µg/L)
Total Cu vs Non-labile Cu
The majority of copper found in commercial wines is in a tightly bound non-labile form.
A study of 52 commercial wines by Nikolaos Kontoudakis and Andrew Clark, Charles Sturt University.
Clark, A.C. et al., 2016. Measurement of labile copper in wine by medium exchange stripping potentiometry utilising screen printed carbon electrodes. Talanta, 154(C), pp.431–437.
It is the form of copper that is important!
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Free
H2S
(µg/
L)
Electrochemically labile Cu (µg/L)
Free H2S vs Labile Cu (electrochemistry) Levels of electrochemically labile copper above 25 µg/L do limit the formation of free H2S
But most of the copper is in non labile form which does not inhibit the presence of free H2S
Copper in wine can increases the sulfides over time
sulfides
Clare Valley Riesling after
8 months.
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Cu
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g/L
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mg/
L
Cu
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Cu
0.7
5…
Cu
1.5
mg/
L
H2S
After just 2 months this chardonnay was already showing the impact of increased copper.
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H2S
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nc
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pb
Cu Concentration ppm
Relative Amounts of Cu vs H2S
Remember, the threshold for H2S is about 1 for most people!
Important take away!
There are essentially two types of
copper.
Non-labile copperusually bound up with sulfidesthat cannot really remove H2S and may act as a source as the
wine matrix changes
Labile copperwhich can scavenge H2S but also can participate in other
reactions
Wine in cans, the ampoule studies
We need to separate
out all the components
of interactions.
Use glass ampoules
as a substitute for the
low oxygen
environment of a can.
Then add or subtract
each factor
incrementally.
SO2
Contact with Al metal
❖ H2S
❖ MeSH
Pros
Absolutely none, seems inherent in the
current canning systems.
Cons
Massive increases in sulfides, by far the
biggest impact of factors tested.
Note
Aluminium salts do not have the same
impact, only the interaction between the wine
and the metal.
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35
40
45
50
2w
4w
8w
2w
4w
8w
control Al foil
Co
nce
ntr
atio
n (
µg/
L)
Average of Hydrogen sulfide Average of Methanethiol
Contact with Al metal + added Cu salts
❖ H2S
❖ MeSH
Pros
None really, although it does appear to
mitigate the impact of the Al
Cons
Increased in sulfides compared to the control,
i.e. worse than bottled product.
Note-
The added Cu is most likely in the labile form
so it is helping to scavenge out the sulfides
formed in the interaction with the Al. May have
longer term impacts.
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45
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2w
4w
8w
2w
4w
8w
2w
4w
8w
control Al foil Al Foil + Cu
Co
nce
ntr
atio
n (
µg/
L)
Average of Hydrogen sulfide Average of Methanethiol
Increasing pH
❖ H2S
❖ MeSH
Pros
Has a very strong and obvious impact on
stopping sulfide production
Addition of Al at high pH has similar impact
to pH alone
Cons
Very difficult to implement while retaining
wine flavour profile, essentially impossible
in spritz samples0
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45
50
2w
4w
8w
2w
4w
8w
2w
4w
8w
control control pH 3.8 Al foil pH 3.8
Co
nce
ntr
atio
n (
µg/
L)Average of Hydrogen sulfide Average of Methanethiol
Increasing O2 (TPO)
❖ H2S
❖ MeSH
Pros
Has some impact on stopping sulfide
production, particularly H2S
Cons
No indication from this trial on the
impact on wine quality.
Note-no Al in this trial 0
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45
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2w
4w
8w
2w
4w
8w
control high TPO
Co
nce
ntr
atio
n (
µg/
L)Average of Hydrogen sulfide Average of Methanethiol
Contact with Al + reduced SO2 (5-10 mg/L)
❖ H2S
❖ MeSH
Pros
While increased in relation to control,
significantly mitigated compared to Al
alone and absolute increase not massive.
Could be a possible mitigation
process.
Cons
Needs to be put in context with other
production concern around oxidation and
micro activity.
Note- supports the proposed chemistry
around Al and SO2 interactions.
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50
2w
4w
8w
2w
4w
8w
2w
4w
8w
control Al foil peroxide + Al foilC
on
cen
trat
ion
(µ
g/L)
Average of Hydrogen sulfide Average of Methanethiol
Stripping the original Cu
❖ H2S
❖ MeSH
Pros
Has a very strong and obvious impact on
stopping sulfide production
Cons
Only seems to be truly effective in the
absence of Al metal
Note
We are probably stripping non labile Cu, i.e.
Cu bound to sulfides that also act as a
reservoir of sulfides.
0
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10
15
20
25
30
35
40
45
50
2w
4w
8w
2w
4w
8w
2w
4w
8w
control stripped stripped + Al foil
Co
nce
ntr
atio
n (
µg/
L)
Average of Hydrogen sulfide Average of Methanethiol
Stripping the original Cu + adding more Cu
❖ H2S
❖ MeSH
Pros
Has a very strong and obvious impact on stopping sulfide production equivalent to pH increase
Cons
This is without Al contact, but if we can remove or reduce the Al transfer, then it could be a significant mitigation process. Added Cu may have other long term impacts
Note
We are probably stripping non labile Cu, i.e. Cu bound to sulfides that also act as a reservoir of sulfides
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25
30
35
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45
50
2w
4w
8w
2w
4w
8w
2w
4w
8w
control stripped stripped + Cu
Co
nce
ntr
atio
n (
µg/
L)Average of Hydrogen sulfide Average of Methanethiol
Stripping the original Cu + adding more Cu
(with Al contact)
❖ H2S -
❖ MeSH
Pros
Seems to mitigate sulfide generation to
levels similar to control. Promising
mitigation process, especially with
reduced SO2
Cons
Can added Cu have other long term
impacts?
Note
Labile Cu benefits again, combined with
reduced SO2 may be very effective
0
5
10
15
20
25
30
35
40
45
50
2w
4w
8w
2w
4w
8w
2w
4w
8w
control stripped + Cu stripped + Cu + Al foil
Co
nce
ntr
atio
n (
µg/
L)Average of Hydrogen sulfide Average of Methanethiol
What can we do?
Remove the Al source
(not a winery issue)
Reduce the SO2
Add new protective Cu?
(has risks)
Strip the non-labile Cu
Analysis and Treatments for Canned Wine
Jasha Karasek
Winemaking Specialist, Enartis USA
AGENDA
Overview
Analysis and tracking
Removing metals with Claril HM and Stabyl MET
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TRACKING CANNED PRODUCTS
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CANNED PACKAGING PANEL by Vinquiry labs
• ALUMINUM – Initial and tracking, increases over aging indicate migration
of aluminum from the can into the wine
• pH – lower = more chances of reduction appearing. Less than 3.5 is
problematic. Could be related to molecular SO2
• FREE AND TOTAL SO2– Lower Free and Total SO2 will lead to less H2S
formation.
• COPPER - < 0.3 mg/L recommended by liner manufacturers
• IRON - < 1 mg/L recommended by liner manufacturers
• CHLORIDES - < 500 mg/L recommended by liner manufacturers
Triplicate analysis highly recommended! Can be highly variable between cans!
METAL REMOVERS PVI/PVP & CHITOSAN
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PVI/PVPVinylimidizole vinylpyrollidone- Polymer which binds several
different metal types. - Also removes smaller phenolics
like hydroxycinnamates
CHITOSAN- Different forms available and
vary in activities- Processing can improve metal
removal capacity- Also removes smaller phenolics
like catechins
METAL REMOVERS: CLARIL HM & STABYL MET
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METAL CHELATORS CLARIL HM & STABYL MET
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0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
Control 16 g/hL 32 g/hL
Cu
mg
/L
Stabyl Met Dosages
White wine Cu Reduction
PVI/PVPVinylimidizole vinylpyrollidone• Binds Cu, Fe, Al, and Copper-bound
sulfides• Dosage 20-50 g/hL• Trials recommended
CLARIL HM : COMBINING PVI/PVP & CHITOSAN
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PVI/PVP + Chitosan • Binds Cu, Fe, Al, and Copper-
bound sulfides• Settles rapidly• Trials recommended
+
CLARIL HM & STABYL MET COPPER REMOVAL COMPARISON
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0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
PN Control PN Stabyl Met 20 PN Stabyl Met 50 PN Claril HM 20 PN Claril HM 50 CS Control CS Stabyl Met 20 CS Stabyl Met 50 CS Claril HM 20 CS Claril HM 50
Co
pp
er (
mg/
L)
TIPS FOR TRIALS WITH CLARIL HM AND STABYL MET
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• Re-hydration time – 1 hour, 5 - 10% solution recommended• Settling speed – rapid• Pipette tips – wide orifice recommended, clogging otherwise possible• Contact time during trial should be the same as treatment in cellar – 30 mins – 1 hour
T = 0 T = 1 min
CONCLUSIONS
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Analysis via Canning Panel at Vinquiry Labs can be helpful for tracking and monitoring canned wines
Claril HM and Stabyl MET can both benefit canned products for removing copper and copper-bound sulfides.
Trials with Claril HM and Stabyl MET can be tricky, consider the provided guidelines if you decide to try either fining agent
CANNED WINE PART 2. MORE ON THE IMPACT OF SO2
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&
June 18th
@ 1 pm pst