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Cork closures
Impact on the quality of bottled wines
Paulo Lopes Enologist PhD (Faculté d’Œnologie de Bordeaux)
WineMBA (BEM, UC Davis, UniSA)
Brock University, 12 November 2012
Impact of closures on wine quality
Intrinsic
wine attributes
Impact on aroma, taste, color Sustainability
Extrinsic wine
attributes
Quality perceived by the
consumers
How corks can influence wine quality after bottling
Intrinsic
wine attributes TCA
Gas barrier
properties
Chemical
composition
TCA
Current situation and perspectives
ClCl
Cl
OMe
Main mechanism of TCA formation
Lignine Organ chorine products Pesticides, Flame retardants
Wood treatment
Sugars
O
O
O
O
OO
OH
OH
OH
OOH
OHOHOH
Cl Cl
Cl
OCH
Cl Cl
Cl
3
Molds Molds
Phenol Phenol
Biodegradation
PCP/lindane
ClO- ClO-
2,4,6 – trichlorophenol (TCP)
2,4,6 – trichloroanisole (TCA)
Biomethylation
Trichoderma, Fusarium, Penicillium… (Alvarez-Rodriguez et al., 2003)
Amorim’s strategy anti-TCA
TCA in cork
Prevention Cure Quality control
• Traceability
• Storage conditions
• Stringent control of cork
• Boiling systems
• Chlorine removal
• ROSA®
• ROSA Evolution®
• Vaporisation
• GC analysis
• Sensory analysis
Prevention
Cork lots traceability
Removal of “calços”(10 cm)
Exclusion of yellow stain cork planks
Boiling system that
reduces cork storage
Chlorine exclusion
Prevent TCA formation during cork stopper manufacture
Descontamination
0
5
10
15
20
25
Amorim AWRI CCFRA Geisenheim
TC
A (
ng
/L)
Antes ROSA Después ROSA
- 80.3%
- 69 to 72%
- 80%- 75%
ROSA®
Patent nº PT103910
ROSA Evolution®
Patent nº PT103910
Vaporization
Cork granules
-80 to 90% of TCA
Natural cork stoppers
-80% of TCA
Cork planks
-40% of TCA
Steam distillation treatments
Mechanism of TCA migration from cork into wine
d5-TCA
1000 ng
Epoxy glue
coverage
Control
wine (GC-MS)GC-MS
GC-MS
GC-MS
0
5
10
15
20
25
30
35
40
45
50
10 days 1 month 4 month 8 month 12 month 18 month 24 month
d5-T
CA
(n
g)
Inner cork (bottles)
Inner cork (control)
Cork surface
Wine
Wine contamination occurs by direct contact with cork contaminated surfaces
Quality control
GC and sensory analysis
GC/MS/ECD-SPME (LD = 0,3 ng/L et LQ = 0,5 ng/L)
13 GCs split by the raw material, cork and R&D* Units
> 15000 samples per month*
Strategy results
Internal
0,88 0,8
0,6 0,55 0,52
0,0
0,5
1,0
1,5
2,0
2,5
3,0
ng
/L
2,68
1,57
1,32
1,17
0,94
0,78 0,67
0,56 0,62
0,0
0,5
1,0
1,5
2,0
2,5
3,0Natural corks Champagne
1,2
0,9 0,8
0,64 0,65 0,58
0,52 0,53
0,0
0,5
1,0
1,5
2,0
2,5
3,0Neutrocork
Strategy results
External
Closures barrier properties
Impact on wine quality after bottling
LOPES, P.; SAUCIER, C.; GLORIES, Y. Nondestructive colorimetric method to determine the oxygen
diffusion rate through closures used in winemaking. J. Agric. Food Chem. 2005, 53, 6967-6973.
O2
Sodium
Dithionite
O2 O2
Air oulet
Nitrogen
Nitrogen
Nitrogen
Sodium dithionite
Outlet
y = 176,42e-2,236x
R² = 0,9991
0
10
20
30
40
50
60
70
80
90
100
0,0 0,5 1,0 1,5 2,0 2,5
L*
O2 (mL)
Calibration
Bottling &
O2 measurement
Measurement of O2 transfer through closures
Colorimetry: Indicator of oxidation-reduction (Indigo carmine)
0,3
0,8
1,3
1,8
2,3
2,8
0 6 12 18 24 30 36
O2 (
mL
)
Horizontal storage (months)
Supremecorq
Nomacorc classic
Natural Cork 1st
Natural cork-Flor
Twin Top 1+1
Agglomerate cork
Screw cap saran-tin
Bottle Ampoule
Kinetics of oxygen ingress through different closures
LOPES, P.; SAUCIER, C.; TEISSEDRE, P.L.; GLORIES, Y. Impact of storage position on oxygen ingress
through different closures into wine bottles. J. Agric. Food Chem. 2006, 54, 6741-6746
Oxygen ingresses through closures independently of storage position
Main routes by which O2 enters into bottles
A
B
C
LOPES, P.; SAUCIER, C.; TEISSEDRE, P.L., GLORIES, Y. Main routes of oxygen ingress through
different closures into wine bottles. J. Agric. Food Chem. 2007,55, 5167-5170.
0,3
0,8
1,3
1,8
2,3
2,8
0 6 12 18 24 30 36
O2 (
mL
)
Horizontal storage (month)
Cork stoppers releases O2 into wine … while synthetic are permeable to atm. O2
0,3
0,8
1,3
1,8
2,3
2,8
0 6 12 18 24 30 36
O2 (
mL
)
Horizontal storage (month)
Natural cork Nomacorc
Polyurethane varnish high
impermeable to O2 covered
different parts of the
exposed surface in bottles
1) Dissolved oxygen in wine
2) Gaseous oxygen in the bottle headspace
3) Oxygen within the closure
4) Oxygen that enters throughout the closure
Wine exposition to oxygen before and during bottling are
very important, their effect (cumulative) can be only
observed during post-bottling
•1
•2
•3
O2 O2 •4
Total O2 into wine bottle after bottling
• Microagglomerate cork
• Natural cork
• Nomacorc light
• Nomacorc premium
• Screw cap saranex
Storage under contaminated environment
Sealing effectiveness of closures to volatile compounds
d5-TCA: 1,75 µg/Lair
d4-E4P: 1,73 mg/Lair
d4-E4G: 0,15 mg/Lair
0
5
10
15
20
25
30
35
40
45
0
10
20
30
40
50
60
70
0
1
2
3
4
5
6
7
8
9
10d5-TCA
(ng)
d5-E4G
(mg)
d4-E4P
(mg)
PEREIRA, B.; LOPES, P.; MARQUES, J.; PIMENTA, M.; ALVES, C.; ROSEIRA, I.; MENDES, A.; CABRAL, M. Sealing effectiveness
of different type of closures to volatile phenols and hanisoles. American J. Enology and Viticulture. 2011, submitted.
Sealing effectiveness of closures to volatile compounds
Cork is an effective barrier!!! TCA does not migrate through cork after bottling
Impact of bottling and closure OTR on the chemical &
sensory properties of a Sauvignon blanc
Vin 100% Sauvignon blanc; Côte du Duras 2005
Composition TAV
12,2%
pH
3,25
Total acidity
4,27 g/l H2SO4
Volatile acidity
0,29 g/l H2SO4
Malic acid
3,02 g/L
Tartaric acid
1,40 g/L
Sugars (frutose + glucose)
0,40 g/L
Iron
3,5 mg/L
Copper
0,4 mg/L
Total SO2
132 mg/L
Free SO2
41 mg/L
Ascorbic
acid 79
mg/L
Bottles
Bordelaise Tradition
CETIE
Bordelaise BVS
30H60
Ampole
Closures
Natural
cork
Colmated
cork
Agglomerate
Micro
agglomerate
Nomacorc
classic
SC
saran-tin
SC
saranex
Analyses Free SO2 Total SO2 Ascorbic acid OD 420 nm L*a*b* Oxidation
(Sotolon)
Reduction
(H2S)
Sensory
Analyses after 2, 12 and 24 months
0,0
0,5
1,0
1,5
2,0
2,5
3,0
Dis
so
lve
d O
2 (
mg
/L)
Bottling run (minutes)
Natural cork
Colmated
Microagglomerate
Nomacorc
classic
Significant variation on O2 dissolved during bottling
Impact of bottling and closure OTR on the chemical &
sensory properties of a Sauvignon blanc
0
10
20
30
40
50
60
70
80
90
0 4 8 12 16 20 24
Asco
rbic
acid
(m
g/L
)
Horizontal storage (months)
0
10
20
30
40
0 4 8 12 16 20 24
Fre
e S
O2 (
mg
/L)
Horizontal storage (months)
Bottling effect Bottling effect
Impact of bottling and closure OTR on the chemical &
sensory properties of a Sauvignon blanc
Ascorbic acid and free SO2
Impact of bottling and closure OTR on the chemical &
sensory properties of a Sauvignon blanc
Varietal thiols (3MH & 4MMP)
0
200
400
600
800
1000
3 M
H (
ng
/L)
3-mercaptohexan-1-ol (3MH)
Passion fruit, grapefruit
0
5
10
15
20
25
30
4 M
MP
(ng
/L)
4-mercapto-4-methylpentan-2-one (4MMP)
Broom
S.T. = 60 ng/L S.T. = 0,8 ng/L
Sotolon
Nuts, curry
0,0
0,4
0,8
1,2
1,6
2,0
So
tolo
n (m
g/L
)
0
5
10
15
20
25
30
35
40
H2S
(m
g/L
) Impact of bottling and closure OTR on the chemical &
sensory properties of a Sauvignon blanc
Reductive (H2S) and oxidative (Sotolon) characters
Hydrogen sulfide (H2S)
Sewage like odor, rotten egg
S.T. = 1,5 ng/L
Impact of bottling and closure OTR on the chemical &
sensory properties of a Sauvignon blanc
Compositional & and sensory at 24 months
Ascorbic acid FSO2 TSO2 L*
a*
b*
hab
C* OD 420 nm
H2S 3MH 4MMP
Sotolon O2 Bottling
Closure OTR
Aromatic intensity
Overall fruit
Freshness
Oxidised Reductive
-4
-2
0
2
4
-30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30
F2
(9
,32
%)
F1 (75,92 %)
Neutrocork
Colmated cork
Ampoule
Natural cork
Agglomerate
Nomacorc
Sc saran-tin
SC saranex
LOPES, P.; SILVA, C.; TAKATOSHI, T.; LAVIGNE, V.; PONS, A.; SAUCIER, C.; DARRIET, P.; TEISSEDRE, P.L.;
DUBOURDIEU, D. Impact of dissolved oxygen at bottling and transmitted through closures on the composition and
sensory properties of Sauvignon blanc during bottle storage. J. Agric. Food Chem. 2009, 57, 10261-10270.
Vin 100% Merlot 2002, UDP Saint Emilion
Composition TAV
12.4%
pH
3.5
Total acidity
3.49 g/l H2SO4
Volatile acidity
0.37 g/l H2SO4
Lactic acid
0.98 g/L
Tartaric acid
1.80 g/L
ITP 56.5
Tannins 3.4 g/L
IC’ 10.1; tint 0.71
Iron
3.5 mg/L
Copper
0.15 mg/L
Total SO2
64 mg/L
Free SO2
21 mg/L
Sugars
0,22 g/L
Bottles
Bordelaise Tradition
CETIE
Bordelaise BVS
30H60
Ampoule
Closures
Natural
cork
Colmated
cork
Agglomerate
Micro
agglomerate
Nomacorc
classic
Screw cap
saran-tin
Screw cap
saranex
Analyses Free
SO2 SO2 total
Color
parameters Tint
Anthocyanin
Tannins
phenolics
Polymerized
pigments
Impact of bottling and closure OTR on the chemical &
sensory properties of a Merlot
Analyses after 6, 12 and 20 months
Impact of bottling and closure OTR on the chemical &
sensory properties of a Merlot
Factor 1 : 53.61%
Facto
r 2 :
10.3
4%
Free anthocyanins
TA+
A-vinyl-T
Pyranoanthocyanins% Polymerized anthocyaninsPhenolic acids
Flavanols
Flavonols
Tannins
DPm
Total SO2
Free SO2
Acetaldehyde
IC'
d420%
d520%
d620%
A-ethly-T
Hue
T0
6 months
12 months
20 months
Chemical evolution during 20 months of storage
Lopes, P. (2005). L’Etude des phénomènes
oxydatifs pendant le vieillissement des vins en
bouteille. Role de l’obturateur. Thèse de doctorat.
Faculté d’oenologie de Bordeaux
Impact of bottling and closure OTR on the chemical &
sensory properties of a Merlot
Sensory assessment at 36 months
Metal catalysed wine oxidation mechanism
O2HOO. HOOH
HO. CH3CHOH CH3CHO
Fe2+ Fe3+
Fe2+ Fe3+CH3CH2OH
Fe2+
Fe3+
.
HSO3-
H2SO4catechol
quinone
semiquinone
hydroperoxyl
radical
Hydrogen
peroxide
bisulfite
sulfuric acid
acetaldehyde1-hydroxyethyl
radicalhydroxyl
radical
ethanol
Scavenge thiols
(nucleophilic compounds)
Aroma loss
RSH
OH
SH
OH
O
O
OH
OH
O
O O+
OH
OH
OH
O-Glc
O
O
C HCH3
OH
OHO
OH
OH
OH
CH3
CH3
Malvidin-3-glucoside
Flavanol
Color stabilisation
HSO3-
bisulfite
SO22-
Possible post-bottling reduction mechanism
SulfitesPesticides
Sulfate
Sulfur contaniningaminoacids
SO2
Inorganicsulfur
H2S
Rotten egg, sewage like aroma
CH3CH2OH
Ethanol
CH3CH2SH
Ethanethiol
Onion, rubbery, burnt match aroma
OH
OH
O
O
O
O
catechol
quinone semiquinone
?? Metal Catalyzed
Structural fraction
• 45% suberin
• 27% lignin
• 12% polysaccharides
Extractible fraction
• 6% Triterpenes
• 6% phenolic compounds
• 1% minerals
Chemical composition of cork
Chemical composition of cork
FERNANDES, A., MATEUS, N., CABRAL, M.; FREITAS, V. 2011. Analysis of phenolic compounds in cork from
Quercus suber L. by HPLC-DAD/ESI-MS. Food Chemistry 125, 1398-1405
OH
OH
OH
COOH
OH
OH
COOH
OH
COOH
OHOH
OH
CH
CH COOH
OH
CH
CH
MeO
COH
m/z 169 (Gallic acid)
m/z 153 (Protocatechuic acid)
m/z 137 (Protocatechuic
aldehyde)
m/z 177 (Conyferaldehyde) m/z 179
(Caffeic acid)
OH
COH
MeO
m/z 151 (vanilin)
O
O
O
O
OH
OH
OH
OH
m/z 301
OH
OH
OH
OH
COOH
COOH
OH O
OH
OH
OHHOOC
m/z 505
O
OO
OOH
OH
OH
OOH
OH
OHHOOC
m/z 469
(Ellagic acid) (Valoneic acid)
Mongolicain A / B (25)
OH
OHOH
CO
O
O O
OC
OHOH
OH
OHOH
OH
CO
O
OH
OH
OH
CO OC
O
O
OH
O
OH
H
OHOH
OH
O
(Valoneic acid dilactone)
OH
OH
CO OO
OO
O
CO
OH
OH
OH
CO
OH
OH OH
O
OH
OH
CO
HO
HO
Trigalloyl-glucose (23)
OH
OHOH
CO
HO
HO
OO
OO
O
CO
OH
OH
OH
CO
OH
OH OH
O
OH
OH
CO
OH
OHOH
CO
OH
OH
CO
Pentagalloyl-glucose (24)
OH
OHOH
CO
O
O OHO
OC
OHOH
OH
OHOH
OH
CO
O
OH
OH
OHOC
O
OH
OH
OH
CO
Vescalagin / Castalagin (21)
OH
OH
CO
OO
OOO
OH
CO
OH
OH OH
HO
di-HHDP-glucose (m/z 783)
OH
OHOH
CO CO
OH
OH
OH
OH
OH
CO
OO
OOO
O
CO
OH
OH OH
OH
OH
CO
HO
HO
di-HHDP-galloyl-glucose (m/z 935)
OH
OHOH
CO CO
OH
OH
OH
m/z 933 (Vescalagin/castalagin)
m/z 939 (Pentagalloyl-glucose)
m/z 937 (Trigalloyl-HHDP-glucose)
m/z 783 (di-HHDP-glucose)
m/z 935 (di-HHDP-galloyl-glucose)
m/z 1135 (Mongolicain)
Gallic and Ellagic acid derivates
Ellagictannins Phenolic acids and aldehydes
Phenolic compounds
On going study for 36 months (30ºC)
Natural cork “Flor” grade with and without surface treatment
Chemical composition of cork
Migration of phenolic compounds from cork into bottled solutions
Natural cork grade 3 with and without surface treatment
0
2
4
6
8
10
12
14
0 5 10 15 20 25
Co
nc
en
tra
tio
n o
f p
hn
eo
lic
co
mp
ou
nd
s
(mg
/L)
eq
. g
all
ic a
cid
Storage time(months)
Natural cork "Flor" Natural cork "Flor" treated
Natural cork grade 3 Natural cork grade 3 treated
Very small amounts of phenolic compounds migrate into wine
Chemical composition of cork
Migration of phenolic compounds from cork into bottled solutions
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
Co
nc
en
tra
tio
n (
mg
/L)
eq
. g
all
ic a
cid
Natural cork "Flor" Natural cork "Flor" treated
Natural cork grade 3 Natural cork grade 3 treated
The amounts observed phenolic do not impact the wine sensory properties…but do they
can contribute to the modulation of oxidative reductive reactions???
Metal catalysed wine oxidation mechanism
O2HOO. HOOH
HO. CH3CHOH CH3CHO
Fe2+ Fe3+
Fe2+ Fe3+CH3CH2OH
Fe2+
Fe3+
.
HSO3-
H2SO4catechol
quinone
semiquinone
hydroperoxyl
radical
Hydrogen
peroxide
bisulfite
sulfuric acid
acetaldehyde1-hydroxyethyl
radicalhydroxyl
radical
ethanol
Scavenge thiols
(nucleophilic compounds)
Aroma loss
RSH
OH
SH
OH
O
O
OH
OH
O
O O+
OH
OH
OH
O-Glc
O
O
C HCH3
OH
OHO
OH
OH
OH
CH3
CH3
Malvidin-3-glucoside
Flavanol
Color stabilisation
HSO3-
bisulfite
SO22-
Phenolic compounds have a key role on wine bottle ageing
Intrinsic
wine attributes
Impact on aroma, taste, color Sustainability
Extrinsic wine
attributes
Quality perceived by the
consumers
Wine (red, white, rosé)
Wine variety
Promotion
Brand
Country
Region
Price
Alcohol level
Year
Medals
Green credentials: logo
Packaging:
Type of closure
Type of capsule
Bottle: volume, type, color
Label: style, type, color
…
Importance of extrinsic wine attributes on the consumer
Values represent mean values based upon 7 likert scale with 7 = very important, 4 = neutral ,1 = unimportant
Same color within the each column indicates homogenous statistical groups at 95% confidence level
Attributes ANOVA
p=0.05
Price 5.5 5.2 n.s.
Label information 4.7 4.4 n.s.
Alcohol level 4.4 4.3 n.s.
Country of origin 4.2 4.5 n.s.
Grape variety 4.3 4.4 n.s.
Region of origin 4.3 4.3 n.s.
Brand name 4.2 4.3 n.s.
Type of closure 3.8 3.8 n.s.
Eco-label logo 3.8 3.7 n.s.
Capsule material 3.5 3.5 n.s.
Label pictures 3.5 3.3 n.s.
Bottle weight 3.4 3.3 n.s.
Label material 3.2 3.4 n.s.
Bottle shape 3.3 3.1 n.s.
Importance of extrinsic wine attributes for Canadians purchase
On-line survey
597 wine consumers
Ontario; n= 298;
Québec, n = 299
Canada
On-line survey
597 wine consumers
(Ontario; n= 298; Québec, n = 299)
Technique: Traditional Conjoint Analysis
12 graphical representations with the following
scenario: « Purchase in retail of an eco-labeled wine to drink by
themselves or with other people at home
Questions:
- Likelihood of buying this bottle (juster scale)
- price
- Realistically intention of purchase (yes/no)
LOPES. P., 2011, “Importance of closure type on consumer expectations, price perception and willingness to
purchase eco-labeled wines. Wine MBA Thesis, BEM Bordeaux Management School., 22nd October 2011.
Consumers attitudes towards wine closures
0.73
-0.18 -0.19
0.14
0.61
-0.09 -0.09
-$1.10
-$0.04
$0.03
$1.11 $0.99
-$0.30
-$0.70
-1,20
-0,80
-0,40
0,00
0,40
0,80
1,20
Re
lati
ve
uti
lity
an
d m
arg
inn
al W
TP
Relative utility
Marginal WTP
Canada
PI= 78%
OP= CAD$ 15.53
Wine sealed with natural corks enjoys a pricing advantage of CAD$1.69 and
CAD$1.39 per bottle when compared with screw caps and synthetic
Consumers attitudes towards wine closures
Key findings
TCA is under control; however, there is some room to improvement
Gas barrier properties of cork closures are unique, providing an effective
barrier against exogenous compounds and releasing low amounts of oxygen
that provide a well-balanced wine development
Wine development after bottling seems to be rather reductive than oxidative;
operations and closures that provide a high and continuous oxygenation are
detrimental to wine quality!
Phenolic compounds migrate from cork into wine; can they participate on the
wine oxidative-reductive reactions ???
Natural cork ingrains itself in the minds of consumers as the status quo,
while screw caps and synthetic introduce a cognitive dissonance, create
poor brand image and thus negative influence the purchase and price
Thanks very much!!!!
Questions, critics, comments
LinkedIn: Paulo Lopes