cork closures · paulo lopes enologist phd (faculté d’Œnologie de bordeaux) winemba (bem, uc...

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



0

10

20

30

40

50

60

70

80

90

0 4 8 12 16 20 24

Asco

rbic

acid

(m

g/L

)


0

10

20

30

40

0 4 8 12 16 20 24

Fre

e S

O2 (

mg

/L)


Bottling effect Bottling effect



Ascorbic acid and free SO2



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 &


Reductive (H2S) and oxidative (Sotolon) characters

Hydrogen sulfide (H2S)

Sewage like odor, rotten egg

S.T. = 1,5 ng/L



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


sensory properties of a Merlot

Analyses after 6, 12 and 20 months



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



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


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


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


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

cork closures · paulo lopes enologist phd (faculté d’Œnologie de bordeaux) winemba (bem, uc...

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