Cork closures Impact on the quality of bottled wines

Transcription

1 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

2 Impact of closures on wine quality Sustainability Intrinsic wine attributes Impact on aroma, taste, color Extrinsic wine attributes Quality perceived by the consumers

3 How corks can influence wine quality after bottling Gas barrier properties TCA Intrinsic wine attributes Chemical composition

4 Me Cl Cl Cl TCA Current situation and perspectives

5 Main mechanism of TCA formation Molds Lignine rgan chorine products Pesticides, Flame retardants Wood treatment Biodegradation PCP/lindane Sugars Molds H Cl Cl - Cl - Cl H Phenol Cl Cl 2,4,6 trichlorophenol (TCP) Phenol Biomethylation Trichoderma, Fusarium, Penicillium (Alvarez-Rodriguez et al., 2003) CH 3 Cl Cl 2,4,6 trichloroanisole (TCA)

6 Amorim s strategy anti-tca TCA in cork Prevention Cure Quality control Traceability Storage conditions Stringent control of cork Boiling systems Chlorine removal RSA RSA Evolution Vaporisation GC analysis Sensory analysis

7 Prevention Prevent TCA formation during cork stopper manufacture Boiling system that reduces cork storage Cork lots traceability Removal of calços (10 cm) Exclusion of yellow stain cork planks Chlorine exclusion

8 TCA (ng/l) Descontamination Steam distillation treatments RSA Patent nº PT Cork granules -80 to 90% of TCA RSA Evolution Patent nº PT Natural cork stoppers -80% of TCA Vaporization Cork planks -40% of TCA 25 Antes RSA Después RSA % - 69 to 72% - 80% - 75% 5 0 Amorim AWRI CCFRA Geisenheim

9 d5-tca (ng) Mechanism of TCA migration from cork into wine d5-tca 1000 ng Epoxy glue coverage GC-MS wine (GC-MS) GC-MS Control GC-MS Inner cork (bottles) Inner cork (control) Cork surface Wine 10 days 1 month 4 month 8 month 12 month 18 month 24 month Wine contamination occurs by direct contact with cork contaminated surfaces

10 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 > samples per month*

11 ng/l Strategy results Internal 3,0 2,68 Natural corks 3,0 Champagne 3,0 Neutrocork 2,5 2,5 2,5 2,0 2,0 2,0 1,5 1,57 1,32 1,17 1,5 1,2 1,5 1,0 0,94 0,78 0,67 0,56 0,62 1,0 0,9 0,8 1,0 0,88 0,8 0,5 0,5 0,64 0,65 0,58 0,52 0,53 0,5 0,6 0,55 0,52 0,0 0,0 0,0

12 Strategy results External

13 Closures barrier properties Impact on wine quality after bottling

14 L* Measurement of 2 transfer through closures Colorimetry: Indicator of oxidation-reduction (Indigo carmine) Calibration Sodium Dithionite Air oulet y = 176,42e -2,236x R² = 0, Nitrogen 0 0,0 0,5 1,0 1,5 2,0 2,5 2 (ml) Bottling & 2 measurement Sodium dithionite Nitrogen utlet Nitrogen LPES, P.; SAUCIER, C.; GLRIES, Y. Nondestructive colorimetric method to determine the oxygen diffusion rate through closures used in winemaking. J. Agric. Food Chem. 2005, 53,

15 2 (ml) Kinetics of oxygen ingress through different closures 2,8 2,3 Supremecorq Nomacorc classic Natural Cork 1st 1,8 1,3 Natural cork-flor Twin Top 1+1 Agglomerate cork 0,8 0, Horizontal storage (months) Screw cap saran-tin Bottle Ampoule xygen ingresses through closures independently of storage position LPES, P.; SAUCIER, C.; TEISSEDRE, P.L.; GLRIES, Y. Impact of storage position on oxygen ingress through different closures into wine bottles. J. Agric. Food Chem. 2006, 54,

16 2 (ml) 2 (ml) Main routes by which 2 enters into bottles Polyurethane varnish high impermeable to 2 covered different parts of the exposed surface in bottles 2,8 Natural cork 2,8 Nomacorc 2,3 2,3 1,8 1,8 A 1,3 1,3 0,8 0,8 B 0, Horizontal storage (month) 0, Horizontal storage (month) C Cork stoppers releases 2 into wine while synthetic are permeable to atm. 2 LPES, P.; SAUCIER, C.; TEISSEDRE, P.L., GLRIES, Y. Main routes of oxygen ingress through different closures into wine bottles. J. Agric. Food Chem. 2007,55,

17 Total 2 into wine bottle after bottling ) Dissolved oxygen in wine 3 2 2) Gaseous oxygen in the bottle headspace 3) xygen within the closure 4) xygen that enters throughout the closure 1 Wine exposition to oxygen before and during bottling are very important, their effect (cumulative) can be only observed during post-bottling

18 Sealing effectiveness of closures to volatile compounds Storage under contaminated environment d 5 -TCA: 1,75 µg/l air d 4 -E4P: 1,73 mg/l air d 4 -E4G: 0,15 mg/l air Microagglomerate cork Natural cork Nomacorc light Nomacorc premium Screw cap saranex

19 Sealing effectiveness of closures to volatile compounds d 5 -TCA (ng) d 4 -E4P (mg) d 5 -E4G (mg) Cork is an effective barrier!!! TCA does not migrate through cork after bottling PEREIRA, B.; LPES, P.; MARQUES, J.; PIMENTA, M.; ALVES, C.; RSEIRA, I.; MENDES, A.; CABRAL, M. Sealing effectiveness of different type of closures to volatile phenols and hanisoles. American J. Enology and Viticulture. 2011, submitted.

20 Impact of bottling and closure TR 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 H 2 S 4 Volatile acidity 0,29 g/l H 2 S 4 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 S mg/l Free S 2 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 S 2 Total S 2 Ascorbic acid D 420 nm L*a*b* xidation (Sotolon) Reduction (H 2 S) Sensory Analyses after 2, 12 and 24 months

21 Dissolved 2 (mg/l) Impact of bottling and closure TR on the chemical & sensory properties of a Sauvignon blanc Significant variation on 2 dissolved during bottling 3,0 2,5 Microagglomerate 2,0 Nomacorc classic 1,5 1,0 Natural cork Colmated 0,5 0,0 Bottling run (minutes)

22 Ascorbic acid (mg/l) Free S 2 (mg/l) Impact of bottling and closure TR on the chemical & sensory properties of a Sauvignon blanc Ascorbic acid and free S 2 90 Bottling effect 40 Bottling effect Horizontal storage (months) Horizontal storage (months)

23 3 MH (ng/l) 4 MMP(ng/L) Impact of bottling and closure TR on the chemical & sensory properties of a Sauvignon blanc Varietal thiols (3MH & 4MMP) mercaptohexan-1-ol (3MH) Passion fruit, grapefruit 4-mercapto-4-methylpentan-2-one (4MMP) Broom S.T. = 60 ng/l 0 S.T. = 0,8 ng/l 0

24 H 2 S (mg/l) Sotolon (mg/l) Impact of bottling and closure TR on the chemical & sensory properties of a Sauvignon blanc Reductive (H 2 S) and oxidative (Sotolon) characters 40 Hydrogen sulfide (H 2 S) Sewage like odor, rotten egg 2,0 Sotolon Nuts, curry ,6 S.T. = 1,5 ng/l 25 1, , ,4 0 0,0

25 F2 (9,32 %) Impact of bottling and closure TR on the chemical & sensory properties of a Sauvignon blanc Compositional & and sensory at 24 months 4 verall fruit a* Ampoule 2 Natural cork 0-2 Aromatic intensity FS Freshness 2 L* TS 2 D 420 Ascorbic acid b* nm C* H 2 S Closure TR 4MMP 3MH xidised h ab Sotolon 2 Bottling Reductive Colmated cork Agglomerate Neutrocork Nomacorc Sc saran-tin SC saranex F1 (75,92 %) LPES, P.; SILVA, C.; TAKATSHI, T.; LAVIGNE, V.; PNS, A.; SAUCIER, C.; DARRIET, P.; TEISSEDRE, P.L.; DUBURDIEU, 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,

26 Impact of bottling and closure TR on the chemical & sensory properties of a Merlot Vin 100% Merlot 2002, UDP Saint Emilion Composition TAV 12.4% ph 3.5 Total acidity 3.49 g/l H 2 S 4 Volatile acidity 0.37 g/l H 2 S 4 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 S 2 64 mg/l Free S 2 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 S 2 S 2 total Color parameters Tint Anthocyanin Tannins phenolics Polymerized pigments Analyses after 6, 12 and 20 months

27 Factor 2 : 10.34% Impact of bottling and closure TR on the chemical & sensory properties of a Merlot Chemical evolution during 20 months of storage T0 12 months 6 months Tannins A-vinyl-T Flavonols Free S 2 d620% IC' Phenolic acids % Polymerized anthocyanins Pyranoanthocyanins Flavanols 20 months d520% DPm A-ethly-T Free anthocyanins Hue Acetaldehyde d420% TA+ Total S 2 Factor 1 : 53.61%

28 Impact of bottling and closure TR on the chemical & sensory properties of a Merlot Sensory assessment at 36 months 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

29 Metal catalysed wine oxidation mechanism hydroperoxyl radical quinone Hydrogen peroxide semiquinone hydroxyl radical H. CH 3 CH CH 3 CH. Fe 3+ CH 3 CH 2 ethanol sulfuric acid 1-hydroxyethyl radical Fe 2+ Fe 3+ Fe 2+ 2 H. H H H 3 C C H Fe 2+ Fe 3+ + H HS - catechol 3 bisulfite H 2 S 4 S 2 2- HS 3 - bisulfite Flavanol H acetaldehyde CH 3 -Glc Malvidin-3-glucoside Color stabilisation CH RSH Scavenge thiols (nucleophilic compounds) SH Aroma loss

30 Possible post-bottling reduction mechanism Sulfur contanining aminoacids Sulfate S 2 Pesticides Sulfites Inorganic sulfur catechol?? Metal Catalyzed quinone semiquinone H 2 S Ethanol CH 3 CH 2 Rotten egg, sewage like aroma Ethanethiol CH 3 CH 2 SH nion, rubbery, burnt match aroma

31 Chemical composition of cork Structural fraction 45% suberin 27% lignin 12% polysaccharides Extractible fraction 6% Triterpenes 6% phenolic compounds 1% minerals

32 Chemical composition of cork Phenolic compounds H H Me C H C m/z 151 (vanilin) CH C m/z 179 (Caffeic acid) m/z 301 (Ellagic acid) Phenolic acids and aldehydes H H H C C m/z 169 (Gallic acid) m/z 137 (Protocatechuic aldehyde) HC H m/z 469 (Valoneic acid dilactone) Me H C H C m/z 153 (Protocatechuic acid) H C CH C m/z 177 (Conyferaldehyde) Gallic and Ellagic acid derivates HC C m/z 505 (Valoneic acid) H H H C H H H H H C H C C C H H C C H C C C Vescalagin m/z / 933 Castalagin (21) (Vescalagin/castalagin) H m/z 937 Trigalloyl-glucose (23) (Trigalloyl-HHDP-glucose) H H H C H Ellagictannins H H H H H H H C H C H C C H C C C Pentagalloyl-glucose (24) C H H C H H m/z 935 di-hhdp-galloyl-glucose (m/z 935) (di-hhdp-galloyl-glucose) m/z 939 (Pentagalloyl-glucose) H H H H H H H H C C C C H C C H C C H C di-hhdp-glucose (m/z 783) H Mongolicain A / B (25) m/z 783 (di-hhdp-glucose) m/z 1135 (Mongolicain) H FERNANDES, A., MATEUS, N., CABRAL, M.; FREITAS, V Analysis of phenolic compounds in cork from Quercus suber L. by HPLC-DAD/ESI-MS. Food Chemistry 125,

33 Concentration of phneolic compounds (mg/l) eq. gallic acid Chemical composition of cork Migration of phenolic compounds from cork into bottled solutions Natural cork "Flor" Natural cork grade 3 Natural cork "Flor" treated Natural cork grade 3 treated n going study for 36 months (30ºC) Natural cork Flor grade with and without surface treatment Natural cork grade 3 with and without surface treatment Storage time(months) Very small amounts of phenolic compounds migrate into wine

34 Concentration (mg/l) eq. gallic acid Chemical composition of cork Migration of phenolic compounds from cork into bottled solutions 5,0 Natural cork "Flor" Natural cork "Flor" treated 4,5 Natural cork grade 3 Natural cork grade 3 treated 4,0 3,5 3,0 2,5 2,0 1,5 1,0 0,5 0,0 The amounts observed phenolic do not impact the wine sensory properties but do they can contribute to the modulation of oxidative reductive reactions???

35 Metal catalysed wine oxidation mechanism Phenolic compounds have a key role on wine bottle ageing hydroperoxyl radical quinone Hydrogen peroxide semiquinone hydroxyl radical H. CH 3 CH CH 3 CH. Fe 3+ CH 3 CH 2 ethanol sulfuric acid 1-hydroxyethyl radical Fe 2+ Fe 3+ Fe 2+ 2 H. H H H 3 C C H Fe 2+ Fe 3+ + H HS - catechol 3 bisulfite H 2 S 4 S 2 2- HS 3 - bisulfite Flavanol H acetaldehyde CH 3 -Glc Malvidin-3-glucoside Color stabilisation CH RSH Scavenge thiols (nucleophilic compounds) SH Aroma loss

36 Sustainability Intrinsic wine attributes Impact on aroma, taste, color Extrinsic wine attributes Quality perceived by the consumers

37 Importance of extrinsic wine attributes on the consumer 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

38 Importance of extrinsic wine attributes for Canadians purchase Attributes ANVA p=0.05 n-line survey 597 wine consumers ntario; n= 298; Québec, n = 299 Price n.s. Label information n.s. Alcohol level n.s. Country of origin n.s. Grape variety n.s. Region of origin n.s. Brand name n.s. Type of closure n.s. Eco-label logo n.s. Capsule material n.s. Label pictures n.s. Bottle weight n.s. Label material n.s. Bottle shape n.s. 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

39 Consumers attitudes towards wine closures Canada n-line survey 597 wine consumers (ntario; 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) LPES. 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., 22 nd ctober 2011.

40 Relative utility and marginnal WTP Consumers attitudes towards wine closures Canada 1,20 $1.11 $0.99 0,80 0,40 0,00-0, $ $ Relative utility Marginal WTP $0.30 PI= 78% P= CAD$ ,80 -$0.70-1,20 -$1.10 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

41 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

42 Thanks very much!!!! Questions, critics, comments LinkedIn: Paulo Lopes