OLD WINES IN NEW BOTTLES? A MODERN APPROACH TO THE WINE STABILITY. Michele Bogianchini, Enar0s ITALY

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1 OLD WINES IN NEW BOTTLES? A MODERN APPROACH TO THE WINE STABILITY Michele Bogianchini, Enar0s ITALY

2 OXIDATION IN WINES: REACTIONS Effect on tannins (mouthfeel, color) and aromas 1- Formation of quinones Loss of aromas Binds with Mercaptans Browning Loss of polyphenols (structure and color) 2- Fenton: oxida0on of alcohols and acids Aldehydes Loss of color Loss of aromas Browning Loss of other compounds Andrew L. Waterhouse, 2011

3 ACTIVATION OF O 2 METALS = CATALYZERS OF OXIDATION 1 2

4 THE EQUATION OF DECLINE Wine parameters Cu+ > 0,5 mg/l Fe 2+ > 5 mg/l Catechin > 20 mg/l Acetaldehyde > 10 mg/l Microbial developement High Redox poten0al matured aromas Color oxida0on Pinking Loss of freshness

5 HOW TO PROTECT? Metals removing PVP/PVI PVPP fining Other factors: - ph<3.4 - Light exposure - Temperature < 15 C. SO 2 Ascorbic acid Dissolved O 2 <0.5-1 mg/l SO 2 Oak tannin GSH Tannin

6 MANAGE DO2 Inert gas Top wine Low rh (lees ageing) check pumps, closures, etc

7 MANAGE DO2 IN WINE Pumping Racking Cold stabiliza0on Topping Centrifuga0on Filtra0on Transport (full tank) Bo]ling Dissolved O2 (mg/l)

8 REMOVE SUBSTRATES PVPP based product Plant protein, K casein..

9 PVPP AND YEAST LEES: EFFECT ON CATECHINS AND O2 CONSUMPTION % catechins removal / Control g/hl STAB SLI g/hl STAB SLI mg/g O2 CONSUMPTION CAPACITY Yeast hulls A Stab SLI

10 10 PVI/PVP: Cu 2+ > Au 2+ = Ag 2+ > Fe 3+ > Mn 2+ > Al 3+ > Zn 2+ Chitosan: Fe 3+ > Cu 2+ > Au 2+ = Ag 2+ > Mn 2+ > Al 3+ > Zn 2+ AFFINITY Other effects: Remove hydroxycinnamic acids Remove LMW catechins Other effects: Remove hydroxycinnamic acids An0microbial

11 EFFECT ON METALS CONCENTRATION REDUCTION OF METALS IN WINE - CLARIL HM AND STABYL MET 100% 80% Cu Fe 77% 86% 89% 94% 67% 60% Al 57% 40% 20% 20% 26% 15% 6% 7% 7% 0% Claril Claril HM 10 g/hl g/hl Claril HM g/hl g/hl PVI/PVP Stabyl Met 10 g/hl PVI/PVP Stabyl Met g/hl

12 Cu CHELATION BY TANNINS 100 % Cu RESIDUAL CONTROL ELLAGIC GALLIC CONDENSED 0 Rielaborato da Vivas, Revue Oen.

13 EFFECT OF PVI/PVP ON JUICE Composition: PVI-PVP + yeast mannoproteins + GSH Addition at beginning of AF Dosage: 50 g/hl

14 RADICAL SCAVENGER SO 2 Tannins

15 ANTIRADICALIC EFFECT OF DIFFERENT TANNINS % DO 420nm increasing (radicalic oxidation) no SO2, Iron 5 ppm. 120,0 100,0 80,0 60,0 40,0 20,0 0,0 tes0mone Gallic tannin Ellagic Tannin light toast small Procyanidins galloylate SLI big Procyanidins monocatechins French hight toast American untoasted oak tannin

16 OAK TANNINS: REDOX POTENTIAL Source Seasoning ToasOng ExtracOon Drying EmV Control Gallic Tannin Tan SLI Toasted Oak Tannin Ellagic Tannin WINE REDOX POTENTIAL

17 ELLAGIC TANNIN ROLE? DOUBLE «OPENING» WINE AROMA Ellagic tannin increases wine redox potenoal E (mv) Control 50 g/hl ELLAGIC TANNIN 50 g/hl GALLIC TANNIN 50 g/hl SEEDS TANNIN CONDENSED (Vivas, 1997)

18 BOTTLING. LAST CHANCE! 18

19 PINKING ALWAYS INVOLVED.REDOX POTENTIAL CORRECTIVE AGENTS PVPP CARBON PREVENTIVE AGENTS ASCORBIC ACID SO 2 GALLIC TANNIN REDOX POTENTIAL

20 SOLUTION CITROSTAB RH THE SINERGY Ascorbic Acid (AA) 44 ppm of AA to eliminate 8 ppm of O 2 Will consume 16 mg/l of SO 2 Citric Acid Prevent Fe haze Makes complex with Fe and balance redox poten0al Gallic tannin Chelate copper An0oxidant Free radical scavenger SO 2 Neutralize H 2 O 2 produced by AA +O 2

21 TRIPLE EFFECT Reducing AA, SO 2, gallic tannin Chela0ng Gallic tannin Complexing Citric Acid

22 CALCULATION... Informations we need to remember 10 g/hl of Citrostab rh provide about 5.5 mg/l of SO 2 6 g/hl of Citrostab rh blocks about 1 ppm dissolved O 2 Add citrostab rh only in presence of free SO2!

23 APPLICATIONS Pre-bo]ling Prevent premature ageing During ageing Prevent pinking Prevent browning

24 PROPOSAL FOR WHITE/ROSE Eliminate metals PVP/PVI based product Enartis Pro FT Claril HM Stabyl Met Prevent dissolved O2 during stabilisation CMC Control oxidation at bottling Citrostab RH Tannins (Cellogum LV20) Prevent dissolved O2 during racking OAK TANNIN (Enartis Tan SLI) Wine Storage Yeast lees + PVPP Glutathion

25 RED WINES COLOR STABILITY

26 HOW AND WHEN CAN WE STABILIZE COLOR? WHEN? HOW? WHY? IN GRAPES - Adding sacrificial tannins - Adding an0oxidants with a wide-spectrum ac0vity Anthocyanin are dissolved in aqueous media and easily oxidized BEGINNING AF DURING AF BETWEEN AF and MLF - Adding enzymes with pectoli0c and proteoly0c ac0vi0es - proanthocyanidin tannins (condensa0on) - Monocatechins tannins (copigmenta0ons) - Adding reac0ve tannins - Macro-OX Proteins have to be hydrolized because they precipitate tannins during the extrac0on Unbalanced Tannins/ anthocyanins ra0o - No SO2 - High reac0vity - Acetaldehyde is present

27 GRAPES

28 TAN ROUGE E TAN FERM COLOR Good grapes + scavenging ac0vity Gallic Digallic An0oxidant Ac0on against oxida0ve enzymes Strong an0radicalic proper0es Ellagic Condensed Tan Rouge Tan Ferm color - _ Time

29 BEGINNING OF AF

30 HOW PROTEINS REACT WITH THE TANNINS? Beginning of AF

31 BEGINNING OF AF How much tannins did we save? It is equivalent to add 50 ppm of grape-derived tannin. Control Enzyme 1 Enzyme 2 Tannins (mg/l) t = 8h Tannins (mg/l) t = 48h tannins extracoon (mg/l) ,4 g/hl +3 g/hl 50 ppm more in the first 48 hours of maceration!!!

32 FERMENTATION

33 2000 Tannins Anthocyanins mg/l High Ratio A/T Alcohol> 4º Alcohol> 12º Alcohol> 12º days Macera0on 0me

34 How to improve the color stability during fermentation?

35 CONDENSATION During AF 2. Reac0on with ethanal: (red-purple pigments) Tannins-ethanal-Anthocyanins (T-et-A) è Ethanal formed from ethanol, reacts with tannins and anthocyanins and stable compounds are formed è COLOR STABILITY! Tannins-ethanal-Tannins (T-et-T) è it happens in parallel with T-et-A. It leads to polymers with variable structuresè less astringent but suscep0ble of precipita0on if they are excessively polimerized.)

36 HOW THE CONDENSATION WORKS? Tannins with low MW (dimeric-tetrameric form), Very reacove acetaldehyde anthocyanins condensa0on STABLE COLOR! CH C3 H

37 WHEN DO WE ADD TANNINS TO PROMOTE THE CONDENSATION? 2000 mg/l E Alcohol> 4º Tannins Anthocyanins Alcohol> 12º days Macera0on 0me

38 COPIGMENTATION During AF è Interac0on with cofactors like tannins, mannoproteins, polysaccharides. è H bonds and hydrophobic interac0ons (low-energy bonds) è Batocromic effect (color-ship towards redmauve (λ increases) è Hypercromic effect (color intensity increases)

39 WHEN DO WE ADD TANNINS FOR COPIGMENTATION? g/hl during AF Tannins Alcohol> 4º anthocyanins Alcohol> 12º mg/l days FML

40 STABILISATION BETWEEN AF AND MLF

41 HOW DO WE STABILIZE COLOR? Adding LMW grape seed tannins Using oxigen (macro-ox) Adding ellagic tannins that promote the acetaldehyde formaoon from ethanol and work as anooxidant compounds. Tannin Quinon Available for condensa0on!! Ethanol Acetaldehyde

42 POLYMERIZE THE RIGHT WAY!!!! AF and MLF Mannoproteins are very important for a correct polymerizaoon Key point between AF and MLF for color stabilizaoon

43 THANK YOU FOR YOUR ATTENTION