Dry Hopping Mythsversus Reality 1
Major volatile compounds after main fermentation (at start of dry hopping!) 2
Compounds present in beer after main fermentation IR CPSil5 Compounds Flavour Samples YEAST GLYCOSILES PRECURSORS HOP CYSTEINES BY PRODUCTS ACTION ON FATTY ACIDS T 0 Day C (ppm) 730 isobutylacetate banana, fruity 0.037 128 774 ethylbutyrate banana, fruity 0.058 512 812 3-methylbutanoic acid cheese 0.101 512 852 isoamylacetate Banana, apple 0.843 128 921 4-methylpentanoic acid cheese 0.009 <128 957 hexanoic acid Dry leaves, goaty, fatty acids bière FD 0.094 512 974 2-methyl-2-pentanoic acid grassy, acid 0.056 <128 982 β-myrcene lemon, sweet 0.014 <128 1001 hexylacetate + sulfitic grassy, hop 0.002 512 1018 phenylacetaldehyde sweet, hony 0.010 <128 1088 linalool lemon 0.009 <128 1101 β-phenylethanol rose 6.672 512 1226 citronellol lemon 0.037 <128 1260 4-ethylguaiacol spicy 0.011 ND 1294 4-vinylguaiacol cloves 0.70 <128 3BACKGROUND INFORMATIPON
Compounds present in beer after main fermentation IR CPSil5 Compounds Flavour Samples YEAST GLYCOSILES PRECURSORS HOP CYSTEINES BY PRODUCTS ACTION ON FATTY ACIDS T 0J C (ppm) bière FD 808 3-methyl-2-buten-1-thiol (MBT) hop, cheese ND 512 850 3-mercaptopropanol potatoes ND 512 890 2-mercaptoethylacetate grilled meat ND 512 905 4-mercapto-4-methyl-2-pentanone catty ND <128 Analysis performed at the lab of Prof Sonia Collin UCL 1374 beta -damascenone cooked apple ND <128 1432 gamma-decalactone peach ND <128 1465 delta-decalactone coconut ND <128 1441 4-vinylsyringol Cloves ND <128 1578 ethyldodecalactone grassy ND <128 1687 delta-dodecalactone fruity, olive ND <128 4
EBC HOP SYMPOSIUM GDX/JMR/SDK/2009 5
ALCOHOLS ALDEHYDES LACTONES TERPENES Monoterpenes Sesquiterpenes MCF-ACIDS (Medium chain fatty acids) LCF-ACIDS GLUCOSIDE OF TERPENES Monoterpenes Sesquiterpenes GLUCOSIDE OF PHENOLS Phenolic acids Polyphenols 6
ACIDS ALCOHOLS TERPENES Monoterpenes Sesquiterpenes VOLATILE PHENOLS CYSTEINE DERIVATIVES (THIOLS) MCF-ACIDS LACTONES GLUCOSIDE OF TERPENES Monoterpenes Sesquiterpenes GLUCOSIDE OF PHENOLS Phenolic acids Polyphenols 7
Fate of major beer volatiles by dry hopping (maturation) in presence of S.cerevisiae 8
MAJOR BEER VOLATILES MONOTERPENES CITRUS FLAVORS 9
YEAST GLYCOSILES PRECURSORS HOP IR CPSil5 Compounds Flavour Samples TERPENES T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 982 β-myrcene Citrus, sweet 0.014 <128 0.014 <128 0.040 <128 1088 linalool Citrus 0.009 <128 0.05 >128 0.06 >1024 1226 citronellol Citrus, fresh 0.037 <128 0.020 <128 0.118 512 10
CITRUS FLAVORS IR CPSil5 Compounds Flavour Samples TERPENES T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 982 β-myrcene Citrus, sweet 0.014 <128 0.014 <128 0.040 <128 1088 linalool Citrus 0.01 <128 0.05 >128 0.06 >1024 = dil1024x 1226 citronellol Citrus, fresh 0.037 <128 0.020 <128 0.118 512 11
DRY HOPPING: evolution of linalool Influenced by : - Time - Temperature - Hop variety(oil content) - Hop quantity added - Hop dispersion methods (static/dynamic) - Beertype and yeasttype Linalool 12
CITRUS FLAVOURS IR CPSil5 Compounds Flavour Samples TERPENES T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 982 β-myrcene Citrus, sweet 0.014 <128 0.014 <128 0.040 <128 1088 linalool Citrus 0.009 <128 0.034 >128 1.192 >1024 1226 citronellol Citrus, fresh 0.037 <128 0.02 <128 0.12 512 = dil512x 13
DRY HOPPING: evolution of citronellol Influenced by : - Time - Temperature - Hop variety - Hop quantity - Hop dispersion methods (static/dynamic) - Beertype and yeasttype 14
PRESENCE OF CITRONELLOL METABOLISM CASCADE OF MONOTERPENE ALCOHOLS BY LAGER AND ALE YEASTS PROPOSED BY KING AND DICKENSON. THE ASTERIC INDICATES A CHIRAL CENTER. 15
IN LATE HOPPED WORT (10 min beforeend of boiling) Citation: HAPPOSHU 16
G 17
Fateof the othervolatilecompounds as the Acids Esters Alcohols Aldehydes Lactones Thiols Others 18
CHEESY FLAVOURS HOP YEAST IR CPSil5 812 921 Compounds Flavour Samples SHORT CHAIN FATTY ACIDS 3-methylbutanoic acid 4-methylpentanoic acid cheesy cheesy T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 0.101 512 0.102 512 0.179 >1024 0.009 <128 0.003 <128 0.018 512 957 hexanoic acid mild cheesy 0.094 512 0.102 512 0.179 >1024 974 2-methyl-2- pentanoic acid grassy, acid 0.056 <128 0.037 <128 0.160 512 19
HOP CONDITIONNING AND STORAGE CONDITIONS CHEESY: linked to bad storage of hop bales and/or pellets and to the use of aged hop (presence of degradation products as 2-methylpropionic acid/ isobutyric acid and of 2-methylbutyricacid/ isovalericacid) 20
FRUITY, FLORAL FLAVOURS YEAST HOP IR CPSil5 Compounds Flavour Samples ESTERS T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 730 isobutylacetate banana, fruity 0.037 128 0.065 512 0.096 >1024 774 ethylbutyrate 852 isoamylacetate banana, fruity, flowery banana, sweet 0.058 512 0.113 >1024 0.156 >1024 0.843 128 1.086 128 1.821 >1024 1001 hexylacetate grassy, hop 0.002 512 0.002 512 0.011 512 21
FRUITY, FLORAL FLAVOURS YEAST HOP GLYCOSILES PRECURSORS CYSTEINES BY PRODUCTS ACTION ON FATTY ACIDS IR CPSil5 Compouds Flavour Samples HIGHER ALCOHOLS T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 1101 β-phenylethanol rose 6.672 512 6.532 512 11.685 >1024 IR CPSil5 Compouds Flavour Samples ALDEHYDES T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 1018 phenylacetaldehyde sweetened, honey 0.010 <128 0.015 <128 0.022 512 22
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YEAST HOP GLYCOSILES PRECURSORS CYSTEINES BY PRODUCTS ACTION ON FATTY ACIDS FRUITY, FLORAL FLAVOURS IR CPSil5 Compounds Flavour Samples 1432 1465 1578 1687 LACTONES gammadecalactone deltadecalactone Ethyldodecalactone deltadodecalactone T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD peach ND <128 ND <128 ND 512 coconut ND <128 ND <128 ND 512 grassy ND <128 ND <128 ND 512 fruity, olive ND <128 ND <128 ND 512 24
WHY LACTONES? FRUITY FLAVORS 25
FRUITY FLAVORS BIOSYNTHESIS YEAST PEROXISOME 26
FRUITY FLAVORS YEAST PEROXISOME BIOSYNTHESIS 27
SULFITIC FLAVOURS CYSTEINES BY PRODUCTS YEAST IR CPSil5 Compounds Flavour Samples T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 808 3-methyl-2-buten-1-thiol (MBT) hop, cheese ND 512 ND >1024 ND >1024 850 3-mercapto-propanol potatoes ND 512 ND >1024 ND >1024 890 2-mercapto-ethylacetate 905 4-mercapto-4-methyl- 2-pentanone grilled meat ND 512 ND >1024 ND >1024 catty ND <128 ND <128 ND 512 28
Concentration of major non-volatile compounds after maturation in presence of raw hops Polyphenols Glucosides 29
Non volatile compounds extracted POLYPHENOLS Year 2008 30
POLYPHENOLS MOST INTERESTING PHENOLIC COMPOUNDS Phenolic acids Flavonoids Flavanoids Proanthocyanidin = anthocyanogen Resveratrol 31
POLYPHENOLS PHENOLIC ACIDS HOP YEAST ACTION ON PHENOLIC ACIDS ONLY IF PRESENCE OF BRETTANOMYCES sp (Vinyl reductase activity) CLOVES AND SPICY FLAVORS PRESENCE OF POF or PAD YEASTS (Phenolic acid decarboxylase activity) Several TOP fermenting yeasts FERULIC ACID = Phenolic acid (Barley, Hops) IR CPSil5 Compounds Flavour Samples PHENOLS T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 1260 4-ethylguaiacol spicy 0.011 ND 0.000 ND 0.067 >1024 1294 4-vinylguaiacol Cloves, dentist 0.70 <128 1.32 <128 3.36 >1024 32
Formation of vinylguaiacol vinylphenol and styrene from phenylalanine by S. cerevisiae! 33
POLYPHENOLS FLAVANOIDS WHY ARE FRESH FLAVANOIDS INTERESTING! BECAUSE. 34
Non volatile compounds extracted - POLYPHENOLS - GLUCOSIDES 35
NON VOLATILE COMPOUNDS EXTRACTED POLYPHENOLS PHENOLIC ACIDS FLAVANOIDS GLUCOSIDES GLYCOSIDES IMPORTANCE OF THE HOPS INFLUENCE OF THE YEAST STRAINS CULTURE YEASTS WILD YEASTS Brettanomyces sp 36
- GLUCOSIDES A few theory Glucosidic bound can be hydrolysed by : - High temperature - Enzymatic activity - endogenouspresence(yeastby maturation, bottle refermentation) - (addition of exogenous betaglucosidase during the process) Non volatile compounds extracted 37
- GLyCOSIDES In beer, the aglycon part is liberated by two different types of activities -by β-1-3-glucanase activity in case of S. cerevisiae strains -by β -glucosidase activity in case of Brettanomyces sp. strains Non volatile compounds extracted 38
Glycosidic bounds hydrolysed by endogenous presence (by yeast during maturation and/or during bottle fermentation) Preferential links detected in hops Terpenes TERPENIC SUB UNIT + SUGAR : FLAVOUR PRECURSOR linalool- β-d- glucoside α terpineol β D -glucoside 1-octen-3-ol- β D glucoside 3 hydroxy β damascenone D glucoside PHENOLIC SUB UNIT + SUGAR : SHELF LIFE PROTECTOR PRECURSOR Flavonoids Kaempferoland Quercetin 3 glycosides glycosidic sub-unit : mono or di- glycosides glucose, galactose, rhamnose Flavanoids As yet, flavanol dimers or multimers glucoside aren t detected nor described Non volatile compounds extracted 39
Glucosidic bound hydrolyses by endogenous presence (yeast by maturation, bottle refermentation) Importance of the yeaststrainand yeast species Non volatile compounds extracted 40
Influence of hop quantity and of yeast strain TYPICAL YEASTS β-glucanase and βglucosidase activities of different yeast strains and yeast species LEGEND : SC: S.CEREVISIAE(ALE YEAST) BB: BRETTANOMYCES BRUXELLENSIS BC: BRETTANOMYCES CUSTERSII *SC+ D : S. CEREVISIAE+ CARBOHYDRATE SOURCE(GLUCOSE) AR: AR 2000 GLYCOSIDASIC CONCENTRATE OF ASPERGILLUS NIGER(COMMERCIALLY AVAILABLE) 41
Glucosidic bound hydrolyses by endogenous presence (yeast by maturation, bottle refermentation) Importance of the aglycon moiety (glucoside of higher alcohols) 1-octen-3-ol cis-3-hexen-1-ol Non volatile compounds extracted 42
HOP GLYCOSILES PRECURSORS YEAST FRUITY, FLORAL FLAVOURS IR CPSil5 Compounds Flavour Samples OTHERS T 0J T 14J T 21J C (ppm) bière FD C (ppm) bière FD C (ppm) bière FD 1374 beta - damascenone cooked apple, rose ND <128 ND <128 ND >1024 43
BEER DRY HOPPING IS A CONFLICTUAL ART WHEN RAW HOP EXTRACTION TAKES PLACE IN PRESENCE OF ACTIVE YEAST ACTIVE YEAST BY DRY HOPPINGIMPROVES THE BEER VALUE BY : - PROTECTING BEER FROM OXIDATION BY CAPTURING MOLECULAR OXYGEN - PROTECTING BEER BY EXERTING A REFRESHING EFFECT - IMPROVING (IN A FIRST STEP) THE BEER FLAVOUR BY : increasing the content of citronellol synthesizing nice flavours as lactones liberating aglycons from glucosides: - Linalool, Geraniol, 44
BEER DRY HOPPING IS A CONFLICTUAL ART WHEN RAW HOP EXTRACTION TAKES PLACE IN PRESENCE OF ACTIVE YEAST ACTIVE YEAST by dry hopping DECREASES THE BEER VALUE BY : - LIBERATING ESTERASES THAT DECREASE THE AROMA - METABOLIZING H + ACCEPTORS AS SOME ALDEHYDES AND OTHER POTENT SUBTILE FLAVOURS AS LACTONES 45
BEER DRY HOPPING IS A CONFLICTUAL ART WHEN BOTTLING TAKES PLACE IN PRESENCE OF ACTIVE YEASTs 46
Orval A B C TRADITIONNAL EUROPEAN METHODS Methods by batch dry hopping D A : Parts of 4 KG of dried hop cones are compacted under inert gas (N2) in onion bags that are sealed in aluminium packets by the hop supplier. of 4 KG. These are stored in the fridge of the brewery at + 2 /+ 4 C. B : Just before use, the aluminium packets are opened and the onion bags containing the hop cones are decompressed. C : Before introduction in the empty tank, E the hop cones are decompacted too D : In order to improve the contact between the beer and the hop bells, the hop bag can be attached to the tank. E : Hop plugs of 5 Oz ( 140 Gr) are also available by hop suppliers and can be added to beer casks directly. Sierra Nevada 47
Methods by continuous extraction in separated vessels 1.1. by hop cones Sierra Nevada Brewery NEW AMERICAN METHODS 1.2. by hop pellets Stone Brewery (designed plant) New Belgium Brewery Pneumatic Method = dry method Out-Indoorhop cellar canoon Lagunitas Brewery 48 With authorization of Steven Pauwels, CBC Dry hopping subcommittee
HOP and BEER 49