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©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
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DOES THIS LOOK FAMILIAR?
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RED WINE MACERATIONS
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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
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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
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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.
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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.
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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
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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
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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
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UV-Vis SPECTROSCOPY
Primary Fermentation - One Maceration over Six Days
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UV-Vis SPECTROSCOPY
Later During Primary Fermentation-One Maceration Days 8-12
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MODEL-BASED H&A ASSAY
24 samples in 1 hour
Total Anthocyanins Free Anthocyanins Bound Anthocyanins©
(p-p) Tannins Total (i-r) Phenolics
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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.
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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”
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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”
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PREDICTIVE STATISTICS
Cabernet Sauvignon - During Elevage (Napa)
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VESUVVIO©
The UV-Vis Based Red Wine Phenolics Assay,
… no wine sample alterations, fast, precise, and timely.
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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
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REQUIRED EQUIPMENT
PC / Notebook / Laptop UV-Vis Spectrophotometer
Micro-Centrifuge
Sipper
Automatic Sample Changer
(OPTIONAL)
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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.
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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
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MACERATION
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MACERATION
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MACERATION
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MACERATION
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ANTHOCYANINS IN TIME
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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
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* 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
©Copyright 2013 All Rights Reserved
* 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
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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
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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
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- ‘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
©Copyright 2013 All Rights Reserved
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
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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’
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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
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TASTING SESSION: 2008 CS
* Assayed on 02/09/2013
Total Antho’s
FreeAntho’s
BoundAntho’s
TanninsTotalIRPs
2008 CS ‘CULT’
526 236 275 956 2137
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TASTING SESSION: 2008 CS
* 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
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TASTING SESSION: 2008 CS
* 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.
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We greatly appreciate the opportunity to share with you our excitement about
Red Wine Functional Phenolics Profiling.
Gianni Colantuoni & Scott McLeod
Gianni@winexray.comScott@winexray.com