Assessments of Ripeness:

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Assessments of Ripeness: Anita Oberholster in the Foothills: On- the- Road February 27, 2015 Photo s courtesy of Prof. P. Goussard

IntroducBon Physiological changes during ripening Seeds, skins, pulp ComposiBonal changes during ripening Sugars, organic acid, minerals, aroma and phenolic compounds Assessment of ripeness in relabon to wine style

Berry growth phases

Berry growth phases

Grape Berry Ripening During maturabon both physical and chemical changes 1 st growth phase AccumulaBon of minerals, amino acids, micronutrients and aroma compounds (methoxypyrazines) AccumulaBon of compounds with max around véraison Tartaric and malic acid Hydroxycinnamic acids Phenols/Tannins

Phenols in grapes Vi#s vinifera Benzoic acids Gallic acid Non- flavonoids Cinnamic acids Phenols Flavan- 3- ols Monomers Oligomers Ex. catechin Proanthocya- nidins Flavonoids Anthocyanin- gluc Ex. Malv- 3- gluc Flavonols

Grape Berry Ripening During maturabon both physical and chemical changes Veraison Marks beginning of ripening Berry so\ening Cell wall deteriorabon Cellular mulbplicabons and enlargement without proporbonal increases in parietal polyosides (cement) Changes in skin color Start of anthocyanin (red color) accumulabon Translucent skin in white variebes

Veraison Grape Berry Ripening Marks beginning of ripening Sugar accumulabon Rapid increase in glucose and fructose Organic acid decline Rapid decrease in mostly tartaric and malic acid Slower tartaric than malic acid decrease

Biosynthesis of plant phenolics PAL

Biosynthesis of plant phenolics Phenylpropanoid pathway in the grape berry (Koyama et al., 2012)

Biosynthesis of plant phenolics Chalcone synthase

Biosynthesis of plant phenolics From malonic acid pathway HO 8 7 O 8a 1 2 A C From shikimic acid Pathway via phenylalanine 3 2 4 B 5 6 OH 6 4a 3 5 OH 4 The three-carbon bridge

Main Flavonoids Flavonol QuerceBn- glucuronide QuerceBn- glucoside Anthocyanin Malvidin- 3- glucoside Flavan- 3- ol Catechin Epicatechin

Proanthocyanidins Adams (2006), AJEV 57:3

Differences between seed and skin tannins Skin tannin mdp 30 Licle epicatechin- gallate Contains epigallocatechin Seed tannin mdp 10 Contains more epicat- gallate units No epigallo units Prieur et al. (1994) Phytochem. 36, 781-784. Souquet et al. (1996) Phytochem 43, (2), 509-512.

Grape Berry Ripening The study of berry composibonal changes during maturabon is difficult due to extreme berry variability However, in general: Seeds (0 6 % of weight) With maturabon increase in [phenol] and [tannin] Reach maximum before veraison per berry Post- veraison mdp of tannin decrease Post- veraison seed drying and browning Post- veraison tannin covalently bonded to lignified cell layers

Grape Berry Ripening Skins (8-20% of berry weight) Skin phenolics Flavonol synthesize starts at flowering and 1-2 weeks a\er veraison unbl ripe Anthocyanins increase from véraison unbl ripe In overripeness anthocyanins may decrease due to degradabon of the grape skin Skin tannin per berry increase unbl approx. 2 weeks a\er veraison, then constant Skin tannin conc may decrease due to berry growth Post- veraison mdp increase In general in the whole berry: mdp decrease, tannin (mg/berry) decrease

Grape Berry Ripening Skins (8-20% of berry weight) Contains significant amounts of: AromaBc substances» Bound and free monoterpenoids increase from veraison with maturabon» Some decrease with over ripening Monoterpenes (fruity, floral) Muscat, Gewürtztraminer citronellol

Grape Berry Ripening Skins (8-20% of berry weight) Contains significant amounts of: AromaBc substances» Carotenoids in skins decrease with maturabon with increase with carotenoid- derived volables such as norisoprenoids» β- Damascenone (apple, rose, honey)» Vi=spirane (green odor of chrysan- themum, flowery- fruity note)

Grape Berry Ripening Skins (8-20% of berry weight) Contains significant amounts of: AromaBc substances» Methoxypyrazines high conc in unripe grapes» Decrease with maturabon (light and temp)» Highest conc found in coldest maturabon condibons Methoxypyrazines (vegeta=ve, herbaceous, bell pepper or earthy aroma)» 2- isobutylmethoxypyrazine (IBMP), 3- butylmethoxy- pyrazine, 3- isopropylmethoxypyraxine

Grape Berry Ripening Pulp (75-85% of berry weight) Contains significant amounts of: Cell walls (<1%) Sugars (fructose and sucrose, 0.9 rabo) Acids (tartaric, malic and citric acid) CaBons (K, Ca, Mg, Na, Fe) Amino acids (proline, arginine, theanine, glutamic acid) 20-25% tot N2 content Aroma compounds (alcohols, aldehydes, esters)

Grape Berry Ripening Pulp: During maturabon Decrease in [organic acids] Synthesized unbl veraison, constant K + increase with sugar during maturabon N 2 increase from berry set unbl mid- maturity

Berry maturabon and opbmal ripeness DefiniBon of maturity varies OpBmal ripeness can be defined as the opbmal berry composibon for your wine style Technological Maturity: Sugars and acidity Phenolic Maturity: Sugar, tartaric acid and phenolic compounds OpBmum phenolic composibon for obtaining a specific wine style AromaBc Maturity: Sugar, TA and aroma profiles - White grapes

DeterminaBon of grape (phenolic) maturity SubjecBve methods InspecBon of skins, connecbon to the pulp TasBng grape skins for specific flavors InvesBgaBng the seed color

RisBc and Iland (2005) Austr. J. Grape Wine Res.(11) 43. Seed color chart

Measurement of phenolic maturity (opbmal phenolic composibon) Extractability assay Color extracted at grape ph and ph 1 (breaks down cell structure). Sudden decrease indicate over ripeness (Ribéreau- Gayon et al., 2000) Color intensity (520 nm) (Iland et al., 2000) CorrelaBon with anthocyanins and quality Winescan good correlabon (r 2 > 0.8) Ribéreau- Gayon et al., (2000) Iland et al,. (2000)

Determine opt ripeness in Cab Sauv grapes~wine quality 4.0 3.5 3.0 mg anth / berry 2.5 2.0 1.5 26 B R 2 = 0.6365 R 2 = 0.7376 1.0 26 B R 2 = 0.6956 0.5 26 B 0.0 Jan 5 Jan 15 Jan 25 Feb 4 Feb 14 Feb 24 Mar 5 Mar 15 Mar 25 Apr 4 Sample date 2003 2004 2005 Strong relabonship between Brix, color and grape and wine quality Seasonal differences result in larger variance then vineyards in different climabc zones Oberholster, Botes, Lambrechts (2010), J. Int. Sci. Vigne Vin. Special issue Macrowine, 33-40.

Importance of 280:520 nm or tannin/anth rabo? RaBo tannin/anth mostly between 1 and 3 for best wines Large variance over years and between farms Kassara and Kennedy found best rated wine had tannin:anth rabo of ±2 Higher rated wines larger contribubon from skin tannins Wine color generally increased with tannin conc Oberholster, Botes, Lambrechts (2010), J. Int. Sci. Vigne Vin. Special issue Macrowine, 33-40. Kassara and Kennedy (2011) J. Agric. Food Chem. 59: 8409-8412.

Phenol extracbon Kennedy, Robinson and Walker, PWV, May/June, 2007

Effect of the climate and environment on berry ripening/content Seasonal differences results in large grape composibon difference sugar ±10% acid content ± 30-40% up to two- fold variability in tannin + anth content In vineyard more skin tannins Reduced vigor and vine water status

Determining opamal ripeness using sugar loading concept Deloire, 2011

Berry AromaAc Sequence Deloire, 2014 ASVO proceedings

Berry AromaAc Sequence Deloire, 2014 ASVO proceedings

Berry maturabon and opbmal ripeness Wine style limited by terroir Sugar/acid balance in pulp Seeds not brown? Skin phenol and aroma concentrabon and composibon opbmal for wine style acainable

No easy answers Conclusion There will be an opbmal Bme to harvest for your specific terroir and wine style However, this may change seasonally Best to build knowledge base of grape composibon and related wine quality Use history to help with future decisions The best grapes make the best wines