Jim Harbertson Associate Professor Washington State University Wine Flavor 101: The Impact of High Ethanol, Saignée and Extended Maceration on Wine Phenolic Composition Jim Harbertson Associate Professor Washington State University

INTRODUCTION INTRODUCTION TRENDS IN VITICULTURE/WINEMAKING Color Tannins Polymeric pigments TRENDS IN VITICULTURE/WINEMAKING Saignée Alcohol EXPERIMENTAL DATA ASSESMENT FUTURE DIRECTIONS

Phenolics-why we care Several Classes Contribute Sensory Characteristics of Wine Color- Anthocyanins and co-factors Astringency – Tannins and LPP Bitterness - Catechins Anti-oxidant Capacity- All phenolics especially those with ortho configuration.

Anthocyanins pH Dependent Copigmentation Color Change Ethanol? Water? Self-association Co-Factors Color Change Hyper chromic shift (more color) Bathochromic shift (blue color) Ethanol? Disrupt association Bathochromic shift Partitioning of flavonols? Water? Disruption, dilution

Seed Tannins Very Abundant Decline During Ripening Average Length 3-5 mg/berry Amount per seed does not vary much Decline During Ripening Average Length 10 sub-units Astringent Gallic Acid Ester Alters protein ppt. Winemakers usually avoid seed tannins

Skin Tannins Not so abundant Ripening: No specific pattern 0.5 -0.9 mg/berry Ripening: No specific pattern Average Length 32 sub-units Astringent Unique sub-unit Winemakers want skin tannins

Polymeric Pigments Wine Artifact Mixture Anthocyanins+ (tannins, keto-acids, cinnamates, etc.) More resistant to Sulfur dioxide Less pH sensitive Color: brick-red

Rate of Extraction Graphic This is a graph showing the extraction of color and tannins during a protracted skin and seed experiment. On the Primary Y axis you have Absorbance at 520 nm and on the Secondary Y axis there is tannin on a gram per liter basis. Before methods for measuring anthocyanins became more sophisticated a simple color absorbance was taken at the wavelength where they absorbed maximally was taken. This was used as a simple way of demonstrating the color anthocyanins. This experiment shows that anthocyanins that are represented by red squares are extracted quite more rapidly than the tannins that are represented by the black dots. The anthocyanins are at a maximum at around the sixth day whereas the tannins are at a maximum at around the 40th day of extraction! After the anthocyanins come to a maximum the begin to decline and has been demonstrated that throughout the fermentation process the formation of polymeric pigments is occurring. REDRAWN FROM RIBÉREAU-GAYON 1970

Skin and Seed Tannin Extraction Pinot noir Miniature (3L) Skin Tannin Extraction Fast and Plateaus Seed Tannin Extraction Slow but Linear Increase Demonstrated Redrawn from Calderon and Kennedy 2008

Polymeric Pigment Formation

ENHANCING PHENOLICS: TRENDS VITICULTURE SMALL BERRIES ARE DESIRED CLONAL SELECTION, SITE SELECTION EXTENDED MATURATION SEED MATURATION REMEMBER BERRY SHRINKS! IRRIGATION EARLY STRESS, MORE TANNIC FRUIT LOCATION EXAMPLES AVAILBLE

THE TREND in WA, CA? Cab Family Fruit Resulting Wine Want Brown Seeds, Less green aromas Result: High Brix Result: High pH—more K+, lower Malic Resulting Wine High Ethanol High pH, Low TA Big Extraction Lots of color, plenty of tannins Astringency is muted by ethanol, acidity

How are tannins influenced by ethanol? Higher ethanol extracts more tannins? Consensus says more “bad” seed tannins Bitterness? Catechins are more bitter with more [EtOH] Astringency? Thought that ethanol lowers astringency by making protein-tannin complexes soluble So more tannins but less “tannic?”

Hang Time Fruit Trend-2 Small Berries with 25 Brix and above Increase Skin/Seed: Juice Problem: Water back necessary to avoid stuck ferment How to keep skin/seed: juice from hang time fruit? Answer: Water back and Saignée at the same rate. Sounds simple enough, right?

Complicated Wait overnight for dried fruit to rehydrate Take Brix Measure, Determine total volume of tank Convert all values to metric it is way easier! Calculate % of water to achieve target Brix Bleed that percentage of juice To calculate the amount of water to achieve target Brix you must subtract amount bled off from total first. So the amount you bleed is greater than what you add back.

Math involved M1V1=M2V2 [Brix]V1=[Brix]V2 Brix = g/100 mL Convert Tank volumes to L Or you could convert Brix into pounds of sugar per gallon. Ewww.

Calculate the Run-off X=1060.0 L or 280 gallons Tank #1 Metric 28.4 Brix 284 g/L Target Metric 1569.6 +X 5940.9 +X 24.1 Brix 241 g/L X=1060.0 L or 280 gallons So you bleed off 1060.L or 280 gallons for a total of 4840.9 L or 1289.6 gallons

Now for the water addition Tank #1 Metric 1289.4 gallons 4880.9 L 28.4 Brix 284 g/L Target Metric 1569.6 +X 4940.9 +X 24.1 Brix 241 g/L x=870.9 L or 230 gallons

Experiment: High Ethanol Treatment Juice Removal Water Addition (%) Volume Change (%) Initial Brix Brix at Inoculation Control 18.7 ±0.6 +18.7 28.3 ±0.2 24.3 ±0.9 High Ethanol 4.5 ±0.8 +4.5 28.0 ±0.2 26.8 ±0.6 Low Saignée 18.1 ±1.2 18.1 ±0.2 28.1 ±0.3 24.1 ±0.4 Low Saignée EM 16.8 ±0.4 27.8 ±0.1 24.2 ±0.2 High Saignée 32.7 ±1.7 16.4 ±0.8 -16.4 27.7 ±0.2 24.2 ±0.8 10 ton Scale Duplicates Merlot Columbia Valley pH 3.9 TA 0.33 g/100mL

Winemaking Details Mechanical harvest-Yield 170 gallon/ton 30 ppm SO2 at destemming YAN adjusted to 225 ppm with DAP Yeast Strain “Premier Cuvee”-S. cerevisiae bayanus Mix after water/SO2 1 minute per ton Pump-overs 1 minute per ton 3 times a day Until drain and press (~ 8.5 minutes) Drained to Tank- Press Fractions Recombined-finish primary in tank Sent to Barrel to undergo ML Sensory on wines 1 year after crush

Columbia Basin Vineyard Merlot BIG CANOPY CLONE 3 9 year old 5 TON/ACRE Read Veggie to the point nobody likes it! VINEYARD SIZE 20 acre~8 hectare 16 REPLICATES SAMPLE SIZE 15 clusters per rep Evenly spaced across vineyard Fruit from alternate sides of canopy 15 Clusters dissected into berries 30 Berries per replicate for tannins Harvest date Oct 12-13 Harvest Data 28 Brix 0.33 g/100mL TA pH 3.9 Tannin by protein ppt Row 73-74 Row 81-82 Row 89-90 Row 97-98 Row 105-106 Row 113-114 Row 121-122 Row 129-130 Sampled Rows Row 9-10 Row 17-18 Row 25-26 Row 33-34 Row 41-42 Row 49-50 Row 57-58 Row 65-66

Data AVE Treatments STDEV STD ERROR RANGE N Berry weight (g) 1.18 0.073 0.018~1.5% 1.06-1.26 16 Seed number per berry 1.68 0.115 0.029~1.7% 1.53-1.87 Skin Tannin mg per berry 0.78 0.094 0.024~3.0% 0.53-0.91 Seed Tannin 3.30 0.223 0.056~1.7% 2.89-3.65 3.45 mg/g FW ~ 3450 mg/L wine potential 19 % Skin Tannin 81% Seed Tannin Berry Weight Variability less than fruit tannin Overall variability similar

Basic Wine Chem pH Treatments TA EtOH % Control High Alcohol 3.81 ±0.02 0.50 ±0.05 14.0 ±0.31 High Alcohol 3.89 ±0.04 0.52 ±0.03 15.9 ±0.16 Low Saignée 3.86 ±0.03 13.8±0.23 High Saignée 3.81 ±0.04 0.51 ±0.03 13.8±0.13 Extended Maceration 3.84 ±0.04 0.50 ±0.02 14.2 ±0.33

Anthocyanins-

Anthocyanins-Low Saignée

Anthocyanins-High Saignée

Anthocyanins-High Ethanol

Anthocyanins-Low Saignée Ex Mac.

Anthocyanins-All Muddled

Tannin Extraction

Anthocyanin, tannin and iron reactive phenolics at press and 185 days Anthocyanins (mg/L) Tannins (mg/L) Fe Phenolics (mg/L) TREATMENT PRESS 185 Days Control 468 C 418 C 469 B 399 D 1145 D 1338 D High Ethanol 656 B 401 C 577 B 512 C 1338 C 1578 C Low Saignée 687 B 461 B 549 B 500 C 1300 CD 1291 D Low Saignée-EM 528 B 352 D 985 A 980 A 2026 A 2353 A High Saignée 750 A 558 A 686 B 658 B 1690 B 1783 B Letters within a column indicate significant differences at p<0.05 Error bars excluded for space.

% Skin Tannins Extracted % Seed Tannins Extracted Treatment mg skin tannins per g FW mg seed tannins per g FW % Skin Tannins Extracted % Seed Tannins Extracted Wine Proportion Skin Wine Proportion Seed Harvest Fruit 0.66 A 3.29 A NA Control 0.36 B 2.77 B 46% 16% 42% 58% High Ethanol 0.40 B 2.45 B 40% 25% 26% 74% Low Saignée 0.36 B 2.74 B 45% 17% 60% Low Saignée-EM 0.31 B 1.83 C 53% 44% 21% 79% High Saignée 0.44 B 2.54 B 33% 22% 27% 73%

Polymeric Pigments

Polymeric Pigments Treatment Effect

Sensory Courtesy of Dr. Carolyn Ross WSU PULLMAN

Principle Components Analysis

Assessment Saignée at the same rate as water back No effect on phenolics No effect on sensory Complicated Time Consuming Potentially Wasteful

Assessment Want more Color or More Tannins? High Saignée More anthocyanins, tannins, more SPP Extended Maceration More tannins, more LPP Sensory: Can be more drying

Assessment Higher Ethanol Wine More Tannins Not less astringent than control with large increase in EtOH More Seed Tannin Extraction Some Color enhancement Hot Description Less Fruit Flavor! Solubility of aromas in alcohol found in other work Trending towards less smooth, more dry but more dynamic ~ stats indicate not significant Is it worth it? Dilution is the solution? Greater Volume, lower taxes

Acknowledgments Linda Bisson UC Davis Chateau Ste. Michelle Winemaking: Josh Maloney, Bob Bertheau Sensory: Carolyn Ross, Karen Weller Family: Eileen and Andrew Harbertson

Vineyard Data By Row Based on variation across vineyard the winemaking reps should be consistent. No ability to separate rows because of mechanized harvest.

Vineyard Data By Row Based on variation across vineyard the winemaking reps should be consistent. No ability to separate rows because of mechanized harvest.

Tannin/seed vs. seeds per berry Shows that berries with fewer seeds seem to compensate. No relationship between seed tannin/berry and seeds per berry. Good relationship (r=0.81) seed weight and berry weight