vwt 272 class 11 - napavalley.edu · –wettable –s plus dispersants and surfactants •applied...
TRANSCRIPT
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VWT 272Class 11
Quiz 10
Number of quizzes taken 20
Min 25
Max 30
Mean 29.8
Median 30
Mode 30
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Lecture 11Other (Smelly) Sulfur Compounds
He that lives upon hope will die farting.
Benjamin Franklin (1706-1790)
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Plan of Study• Vineyard Sulfur Additions
– S vs. Bordeaux Mixture
• Amino Acids & Proteins– Structures
• Hydrogen Sulfide– Causes
• Vineyard S, yeast nutrition, or ???
– Prevention
– Removal• CuSO4 vs. wishing
• Thiols & Disulfides
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Where does Sulfur come from?Java, Indonesia
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Where does Sulfur come from?Alberta Oil Sands, Canada
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Vineyard Sulfur
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Vineyard Sulfur• Useful against Powdery Mildew (Uncinula necator)
– Used since 1890’s
– Spray intervals between 7 to 21 days
– Extremely good models of PM growth based upon temperatures between 70° and 85° F
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Vineyard Sulfur
• Mutiple forms
– Dust – S with average particle size of 20 to 45 microns
• applied dry
– Wettable –S plus dispersants and surfactants
• applied wet or dry
– Micronized – S with average particle size of 5 to 25 microns
• applied wet or dry
• Often discontinued when grapes reach 12 °Brix
• Problem if residue in must > 1 to 10 mg/L
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Powdery vs. Downy
• Powdery Mildew on Grapes– Found everywhere in California– Controlled by Sulfur and other
fungicides
• Downy Mildew on Grapes– From Plasmopara viticola– Found in areas with spring & summer
rainfall at temperatures above 50° F– Controlled with “Bordeaux Mixture”
• Copper Sulfate (CuSO4) & Slacked Lime (Ca(OH)2)
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Bordeaux Mixture
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Hydrogen Sulfide (H2S)
AKA: “Reduced”
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Recipe to make something smelly…replace an O with an S
Hydrogen Sulfidefart/rotten egg1 ppb
3-mercaptohexanolPassion fruit60 ppt
1,3-hexanediolodorless
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Where does H2S come from?
• Vineyard based Elemental S residue
– More S leads to more H2S in the wine
– Mechanism not well understood
• S → S2- (sulfide)– Highly yeast strain dependant
– Takes place on cell wall of yeast
– Younger yeast cells produce more S2-
– Higher alcohol produces more S2-
– Amino acid Cysteine may be important
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A Brief Detour into Amino Acids
• A class of compounds that have a specific spine and various side chains
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A Brief Detour into Amino Acids
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A Brief Detour into Amino Acids• Amino acids link together with “Peptide
Bonds” to form Peptides
• Peptides link to form polypeptides
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A Brief Detour into Amino Acids• Polypeptides link to form the “Primary
Structure” of proteins
• The “Primary Structure” folds and packs into complex forms like helices and pleated sheets
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From Amino Acids to Proteins
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From Proteins to the Nobel Prize
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Where does H2S come from?
• “Inappropriate” Yeast nutrition– Yeast “leak” H2S when they make 2 amino acids
• Methionine and Cysteine
• Yeast make all organic S containing compounds from the S containing amino acids
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Where does H2S come from?
• “Inappropriate” Yeast nutrition
– Yeast “release” H2S when they use S containing amino acids to make other necessary building blocks
– Vitamin deficiency
• Biotin deficiency– Yeast need ~ 1 μg/L
• Pantothenate deficiency– Yeast need ~ 50 μg/L
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Where (else) does H2S come from?
• High solids fermentations
• High temperature fermentations
• Lees contact– Release from S containing
compounds in yeast
• Loosely “Bound” to compounds in wine– Poorly understood mechanism
• ???
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Removing H2S – The Smart Way
• Copper Sulfate (CuSO4) additionCuSO4 → Cu2+ + SO4
2-
Cu2+ + SO42- + H2S → CuS (s) + 2H+ + SO4
2-
– What matters is the Cu2+
• CuSO4 available as:– CuSO4 (anhydrus)
• white powder
– CuSO4●5(H2O) copper sulfate pentahydrate• blue power
• 10% & 1% (as ? (usually CuSO4))
• Confirm with supplier
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Removing H2S – The Smart Way
• According to the TTB (27 CFR Ch 1 24.246)
– “The quantity of copper sulfate added (calculated as copper) (Cu2+) must not exceed 6 parts copper per million parts of wine (6.0 mg/L). The residual level of copper in the finished wine must not exceed 0.5 parts per million (0.5 mg/L).”
• Atomic Mass of Cu2+ = 63.5
• Molar Mass of CuSO4●5(H2O) = 249.7– So 25.4% of CuSO4●5(H2O) is Cu2+
– 100 mg CuSO4●5(H2O) / 25.4 mg Cu2+
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Removing H2S – The Smart Way
• The “secret” about Cu2+
– If there any yeast present, especially live yeast, they will capture large amounts of any remaining Cu2+ left in the wine after addition
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Calculation with Cu2+
• 1500 gal of Grenache with a serious H2S problem. Bench trials suggest that you need to add 0.5 mg/L Cu2+. How much CuSO4●5(H2O) do you add?
1500 gal x 3.785 L/1 gal x 0.5 mg Cu2+ /L x 100 mg CuSO4●5(H2O) / 25.4 mg Cu2+ x 1 g CuSO4●5(H2O)/ 1000 mg CuSO4●5(H2O) =
11.2 g CuSO4●5(H2O)
225 L of Chenin Blanc with slight “reduction”. Bench trials suggest that you need to add 0.2 mg/L Cu2+.
How much 1% Cu2+ solution do you add? – First confirm that the 1% is as 1% Cu2+ (not 1%
CuSO4●5(H2O) 225L x 0.2 mg Cu2+ /L x 100 ml Cu2+ solution / 1 g Cu2+ x 1 g Cu2+ / 1000 mg Cu2+ =
4.5 ml Cu2+ solution
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Removing H2S – The Dumb Way
• Splash or run Oxygen through the wine
– Splashing will force the volatile H2S out of the wine
– O2 will displace the S in the H2S
2H2S + O2 2H2O + 2 S
• Run the risk of forming thiols/mercaptans from the H2S reacting with acetaldehyde.
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Acetaldehyde Formation
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Removing H2S – The Dumb Way
2H2S + CH3CHO → HSCH2CH2SH + H2O
• Ethanedithiol
– Highly reactive
• Degrades into other thiols
– Smells like durian
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Your New BSF - Durian
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Removing H2S – The Dumb Way
• Ethanedithiol can degrade into:
• None of the above compounds are easily removed from wine– SOME react with Cu2+ slowly (months)
Compound Chemical Formula
Aroma Description Concentration in Wine (µg/L)
Odor Threshold (µg/L)
Methanethiol (Methyl mercaptan) CH3SH
Cooked cabbage, rotten eggs
0 to 16 2
Ethanethiol (Ethyl mercaptan)
CH3CH2SHOnion, rubber,
natural gas, fecal0 to 12 1.1
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Removing H2S – The Dumb Way
• Thiols can form an equilibrium with disulfides
• Disulfides do not react with Cu2+
Compound Chemical Formula
Aroma Description Concentration in Wine (µg/L)
Odor Threshold
(µg/L)Dimethyldisulfide
CH3SSCH3 Cooked vegetable, strong onion
Cabbage
0 to 22 29
Diethyl disulfide CH3CH2SSCH2CH3 Strong onion, burnt rubber
0 to 80 4.3
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Next Week
• Spring Break!?!
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Next Next Week
• Heat Stability
• Cold Stability