©Copyright 2013 All Rights Reserved 2012-2013 Wine Flavor 101C The Impact of Phenolic Management on...

©Copyright 2013 All Rights Reserved

2012-2013 Wine Flavor 101C

The Impact of Phenolic Management on Wine Style Options

Making the Most of a Partial Extraction:Phenolics Profiling in Real-Time

UC Davis, February 15, 2013

OVERVIEW• Red Wine Phenolic Extractions• What We Measure and How• Repeatability & Reproducibility is Key• Multivariate Analysis & Chemometrics• VESUVVIO© - Our UV-Vis Based Red Wine

Phenolics Profiling Platform• Tasting with Phenolic Profiles Assessment


DOES THIS LOOK FAMILIAR?


RED WINE MACERATIONS


Grape supply and management is the single most important step of

winemaking, both in terms of quality and cost.

Are you getting the most and the best out of your fruit?

THE REALITY


The single most important fact to remember is that red wine macerations

are only PARTIAL extractions.

Anthocyanins: 20% -50% Tannins: 5% - 40%

Total Phenolics: 20% - 50%

IMPORTANT FACTORS

• Incoming Fruit Characteristics & Quality• Movement – Punchdowns / Pumpovers,

Delestage• Fermenter Temperature Profiles• pH, Ethanol Concentration,…• Yeast Strains,…• Maceration Time• Post-Maceration Conditions



Non-flavonoidsbenzoic acids (C6-C1)hydroxycinnamic acids (C6-C3)oak (poly-)phenolics

Flavonoids (C6-C3-C6)

anthocyaninsflavonolsflavanolsproanthocyanidins, Condensed Tannins

p-coumaric acid

WHAT WE DO NOT MEASURE

flavonoidbackbone

anthocyaninsaglycone

flavonolsaglycone

flavan-3-olmonomer

flavan-3-olsoligoner/polymer

WHAT’S THE REASON?• Needs technologically advanced

instrumentation; costly.• Requires highly skilled laboratory personnel.• Time consuming.• Not timely for production environment.• Rather removed from sensory assessments.• Cannot preferentially extract individual

compounds during maceration. • Works best for fundamental research &

development of applied technologies.


WHAT WE DO MEASURE• Pigments – Free and Total Anthocyanins: basis

of color perception and key structural ingredients.

• Bound Anthocyanins: Anthocyanins linked to tannins that form stable color and add textural qualities.

• Tannins: structural building blocks, major sensory effects – very important to wine style and ageability.

• Total (Iron-Reactive) Phenolics: amount of all phenolic compounds in the wine; useful when comparing maceration protocols or blends.


REPRESENTATIVE LEVELS

Total Anthos

FreeAnthos

BoundAnthos

TanninsTotalIRPs

12CS 959 700 231 1026 2386

12ME 634 479 138 806 1968

12PS 1338 1018 290 1716 3524

12ZI 316 254 53 528 1529

12PN 406 334 50 266 1366

Current Vintage, Post-Fermentation


HOW WE MEASURE THEM• Wet Chemistry - We use an extended version

of the Harbertson & Adams Phenolics Assay• New parameters reported – Total Anthocyanins

and Bound Anthocyanins• New extended H&A Assay SOP has resulted in

significant reduction of execution time, and increased repeatability resulting in error standard deviations within 5%

• Execution time - 24 samples in 4 to 5 hours


Harbertson, Adams et al, American Journal of Enology and Viticulture, 2002 & 2003Six Sigma Quality Systems Methodology, Gage Repeatability & Reproducibility

Gage R&R - REPEATABILITY

Op/TechFree

AnthosSPP LPP Tannins

TotalIRPs

GC 3.2 2.2 8.1 3.5 1.5

O/T 2 7.7 6.7 14.8 8.5 12.8

O/T 3 4.5 2.6 6.7 3.6 2.4

O/T 4 2.1 1.9 4.7 4.0 1.0

O/T 5 2.4 5.0 12.8 4.9 2.8

SIX WINES, 4 REPS, AVERAGE PERCENT ERROR


UV-Vis SPECTROSCOPY

Primary Fermentation - One Maceration over Six Days


UV-Vis SPECTROSCOPY

Later During Primary Fermentation-One Maceration Days 8-12


MODEL-BASED H&A ASSAY

24 samples in 1 hour

Total Anthocyanins Free Anthocyanins Bound Anthocyanins©

(p-p) Tannins Total (i-r) Phenolics


MV ANALYSIS & MODELING• Specific Focus – CHEMOMETRICS• Technology Openly Available and Widely

Used in the Process Industries• Applications Include: Laboratory Analyses,

On-line Virtual Sensors, Process Optimization

• Steps: measurements, calibration, internal validation, deployment, field validation.


CALIBRATION & VALIDATION

PC / Notebook

process analytical instrumentation

(at-line or in-line; UV/Vis, IR, …)

standardized measurements

SAMPLERESULTS

SAMPLES

SPECTRA

MEASURED VALUES

laboratory analytical instrumentation

(Wet Chemistry [H&A Assay] or HPLC, GC/MS, …)

model building & deployment(multivariate; PCR, PLS, ANN,…

)

“RMSEC”&

“RMSEV”


DEPLOYMENT

PC / Notebook

process analytical instrumentation

(at-line or in-line; UV/Vis, IR, …)

SAMPLERESULTS

SAMPLES

SPECTRA

model building & deployment(multivariate; PCR, PLS, ANN,…

)

“RMSEP”


PREDICTIVE STATISTICS

Cabernet Sauvignon - During Elevage (Napa)


VESUVVIO©

The UV-Vis Based Red Wine Phenolics Assay,

… no wine sample alterations, fast, precise, and timely.


Harbertson, Adams et al, American Journal of Enology and Viticulture, 2002 & 2003Skogerson, Boulton et al, American Journal of Enology and Viticulture, 2007

PROTOCOL• Obtain Wine Samples To Be Profiled• Centrifuge Wine Samples for 5 Minutes• Prime Flow-Through Cell & Run UV-Vis

Spectrophotometer• Extract (Electronically) Samples Spectra• Run Multivariate Calibration• Report Measured Wine Phenolic Profiles


REQUIRED EQUIPMENT

PC / Notebook / Laptop UV-Vis Spectrophotometer

Micro-Centrifuge

Sipper

Automatic Sample Changer

(OPTIONAL)


KEY ADVANTAGES• Reduced Assay Execution Time compared

to original wet chemistry method - 24 samples per hour per spectrophotometer.

• Very Timely Measurements for Operational Decision-Making.

• Increased Repeatability & Reproducibility – over 95% precision.

• No sample transfer: upload spectra electronically, receive results within minutes.


APPLICATION AREAS• Vineyard Performance and Grower

Feedback: Possible Contractual Element• Maceration and Elevage• Wine Evaluation & Classification• Blending• Fining: Measurable Impact• Bottled Wine and Vintage Comparisons• Vintage Quality Assessment


MACERATION


MACERATION


MACERATION


MACERATION


ANTHOCYANINS IN TIME


COMPARISON OF PEER GROUP10 CS NAPA

Total Anthos

FreeAnthos

BoundAnthos

TanninsTotalIRPs

Jones 1020 744 228 1135 2448

Bear 655 432 128 1089 2354

CharlieBlock 4

897 568 155 908 2155

Charlie Block 7

745 429 133 844 2033

Seven Oaks

828 608 155 933 2178

Paris 1009 833 188 992 2311

Johnson 644 398 118 1189 2449


* Assayed on 02/2011

Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

12 PN A Sonoma

283 219 44 339 1703

12 PN BCarneros

405 307 69 537 2012

12 CS A Napa

735 589 136 818 1932

12 CS BNapa

482 349 129 1492 2832

11 PS A California

705 590 109 555 1621

12 PS BMendocino

696 510 157 1374 3061

2008 CS“CULT”

526 236 275 956 2137


* Assayed on 02/09/2013

TASTING SESSION WINES

Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

12 PN A Sonoma

283 219 44 339 1703

12 PN BCarneros

405 307 69 537 2012

TASTING SESSION: 2012 PN

* Assayed on 02/09/2013


Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

12 PN A Sonoma

283 219 44 339 1703

12 PN BCarneros

405 307 69 537 2012

- ‘Total Anthocyanins’: ‘B’ 43% higher than ‘A’- ‘Shift’ from ‘Total to Free’ is 23% and 24%, respectively- ‘Tannins’ / ‘Total IRP’s’: 20% and 27%, respectively- ‘Tannins’ very similar to ‘Total Anthocyanins’ for both- Verdict: different grape sources, both wines are balanced

TASTING SESSION: 2012 PN

* Assayed on 02/09/2013


Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

12 CS A Napa

735 589 136 818 1932

12 CS BNapa

482 349 129 1492 2832

TASTING SESSION: 2012 CS

* Assayed on 02/09/2013


- ‘Total Anthocyanins’: ‘A’ 52% higher than ‘B’- Relatively similar ‘Bound Anthocyanins’... Why?- ‘Tannins’ / ‘Total IRPs’: 42% and 53% respectively- ‘Total Anthocyanins’ and ‘Tannins”: ‘A’ ~ ‘B’ ; ‘A’ 32% of ‘B’- Verdict : ‘A’ balanced, ‘B’ over-extracted

TASTING SESSION: 2012 CSTotal

Antho’sFree

Antho’sBound

Antho’sTannins

TotalIRPs

12 CS A Napa

735 589 136 818 1932

12 CS BNapa

482 349 129 1492 2832

* Assayed on 02/09/2013


Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

11 PS A California

705 590 109 555 1621

12 PS BMendocino

696 510 157 1374 3061


TASTING SESSION: 2011 & 2012 PS

* Assayed on 02/09/2013

- ‘Total Anthocyanins’: Higher or lower than ‘Tannins’?- ‘Bound Antho? Driver? Antho or Tannin?- ‘Tannins’ / ‘Total IRP’s’: 34% versus 45%- ‘Total IRP’s’ over 3,000: ‘very extracted’ style- Verdict: ‘A’ possibly under-extracted, ‘B’ over-extracted’


Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

11 PS A California

705 590 109 555 1621

12 PS BMendocino

696 510 157 1374 3061

TASTING SESSION: 2011 & 2012 PS

* Assayed on 02/09/2013

Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

2008 CS ‘CULT’

526 236 275 956 2137



* Assayed on 02/09/2013

Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

2008 CS ‘CULT’

526 236 275 956 2137



* Assayed on 02/09/2013

- So, why is it ‘CULT?’- ‘Tannins’ is 45% of ‘Total IRP’s’ - “Classic”- ‘Total Anthocyanins’: unusually high for its age- ‘Bound Anthocyanins’: “Rare” for the amount of ‘Tannins’- Verdict, depending on preferred style: Balanced. Unusual wine.

Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

2008 CS ‘CULT’

526 236 275 956 2137



* Assayed on 02/09/2013

Total Antho’s

FreeAntho’s

BoundAntho’s

TanninsTotalIRPs

2008 CS ‘CULT’

1071 746 326 1067 2370

* Assayed on 11/24/2008

CONCLUSIONS• Coffee, tea, wine or beer: they are all partial extractions.• Vineyard performance can be measured by phenolic

measurements rapidly and accurately.• Differences in maceration profiles suggest what you do as

a winemaker, greatly affects the final phenolic content of your wines.

• Evaluate maceration protocols: is it time, temperature, alcohol or movement?

• Knowledge of tannins and total phenolics amounts very useful in drain decision.

• Some basic ratios and general knowledge of relative amounts of phenolic materials (per variety and region) offer powerful insights into initial grape and wine quality.



We greatly appreciate the opportunity to share with you our excitement about

Red Wine Functional Phenolics Profiling.

Gianni Colantuoni & Scott McLeod

[email protected]@winexray.com

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