Organic Belgian Beers: Legislation and Organic Raw Materials II. Organic Raw Materials II.1. Safety Quality Hop Fungicides and Copper Barley and Malt Mycotoxins II.2. Brewing Quality Barley Malt : EBC analyses Ferulic and coumaric acids II.3. Conclusions
II.1. Safety Quality: Hop Fungicides and Copper On hops, fungicides are used mainly to control mildew and oïdium Example: sample of a conventional hop (Spalter Select 2008, Germany) Pesticide Concentration (mg/kg) Tol rance Allemagne (mg/kg) Utilisation Azoxystrobin 0,85 20 mildiou et l'o dium, spectre large, inhibe les transports dõ lectron, d riv dõun champignon, tr s toxique pour animaux aquatiques Dimethomorph 0,59 50 Folpet 13,1 150 Myclobutanil 0,76 2 Triadimenol 0,18 10 3,7 30 mildiou, syst mique, inhibition des sterols mildiou (affecte la division cellulaire, cancerig ne (souris), tr s toxique sur animaux aquatiques o dium, bloque la synth se de lõergosterol, dangereux pour organismes aquatiques o dium, inhibe la synthese de lõergosterol, toxique pour les champignons entomopathog nes o dium, agit sur les mitochondries du champignon, tr s toxique sur animaux aquatiques Trifloxystrobin Different fungicides targeting the same disease are used all together Levels under tolerated values but pay attention to the accumulation and cocktail effects
II.1. Safety Quality: Hop Fungicides and Copper In organic practices, copper is used in the Bordeaux Mixture to control mildew Copper use has to be limited due to its potential effect on environment (accumulation in soils?) As no synthetic fungicides are used on organic hops, one would expect that much more copper would be found in organic hops, but... Copper concentrations in different samples (organic or conventional) Hop Variety S palter S elec t 2008 (organic ) S palter S elec t 2008 (c onventional) S palter S elec t 2007 (c onventional) K ent 2008 (c onventional) C opper (mg/kg) 318,6 391,1 362,5 266,7 It seems that conventional practices include both copper and synthetic fungicides treatments (to be confirmed on more samples...)
II.1. Safety Quality: Hop Fungicides and Copper Use of copper can also have an important impact on the aroma profile of hops It was shown by Kishimoto et al. (2008) that copper utilization would have a direct impact on odorant polyfunctional thiols such as 4MMP (4-mercapto-4méthylpentan-2-one; grapefruit, blackcurrant, passion fruit aroma present in i.e. Nelson Sauvin variety); this latter being absent if copper was used on the field.
II.1. Safety Quality: Barley and Malt Mycotoxins - Mycotoxins can be produced either on the field (DON,...), during barley storage (OTA,...) or during the malting process (Cytochalasin E,...) - It is said that organic barley might be more sensitive to field infection because of the absence of fungicides (mainly on the field: pyrazolecarboxamide,...) and insecticides (mainly during storage : pyrimiphos méthyl, deltamethrin,...)
II.1. Safety Quality: Barley and Malt Mycotoxins - DON (Deoxynivalenol or Vomitoxin) Similar levels of DON for conventional or organic beers, Anselme et al., 2006 Fungicides used on barley do not always target mycotoxins producing microorganisms: Fusarium versus Helminthosporium, Ramularia,...
II.1. Safety Quality: Barley and Malt Mycotoxins - OTA (Ochratoxin A) Anselme et al., 2006 In 2003-2004, levels of OTA higher in organic beers, and sometimes higher than the recommended level of 200ng/l
II.1. Safety Quality: Barley and Malt Mycotoxins - OTA (Ochratoxin A) A second survey was conducted in 2005 on the same brands leading to much better results, Anselme et al., 2006
II.1. Safety Quality: Barley and Malt Mycotoxins OTA issue is not specifically related to organic malt; levels above 3000 ng/l have been reported in some surveys dealing with conventional beers (Gumus et al., 2004) Safety in organic practices : a general review Mycotoxins: both systems are comparable provided that good agricultural and manufacturing practices are respected (Pussemier et al., 2006) Less nitrates in organic (especially for broad leaf vegetables in winter time) Pesticides: essentially in conventional, only traces of synthetic pesticides in organic (Pussemier et al., 2006)
II.2. Brewing Quality: EBC Analyses Comparison of data from the same brewery for organic (n=11) and conventional malts (n=13) Extract % Colour EBC Total N% Kolbach I Viscosity (cp) ph Friability (%) D. P. (WK) FAN (mg/l) Organic Malts Mean Min 81,97 80,6 3,57 3 8,58 7,2 42,45 36 1,51 1,43 5,96 5,86 92,28 86,2 306,36 250 128,33 100 Sizing Organic Barley Conventional malts Max Mean Min Max 83,6 82,20 80,9 84 4,5 3,15 2,9 3,3 9,97 10,32 9,4 11,15 49 41,04 37 44,8 1,57 1,54 1,51 1,57 6,08 5,78 5,65 6,02 99,4 89,48 86 91,1 330 304,20 282 330 145 159,54 142 170 > 2,8 mm > 2,5 mm > 2,2 mm < 2,2 mm 76,06 17,51 4,25 1,43 93,57 Conventionnal Barley 84,28 11,65 95,93 5,68 2,58 1,05 3,63
II.2. Brewing Quality: EBC Analyses Comparison of data from the same brewery for organic (n=11) and conventional malts (n=13) Same yield extract Similar modification (Kolbach - Friability) and enzymatic power Colour : more difficult to manage in organic malts Smaller batches, less blending possibilities Lower nitrogen (1,7%) and FAN levels in organic malts: effect on foam, yeast growth, colloidal stability,... No chemical fertilizers Higher ph No correction possible? Same Yield, lower nitrogen : 1,7% ---> higher husk proportion? Sizing: less > 2,8 mmm; more < 2,5 mm, higher variability
II.2. Brewing Quality: ferulic and coumaric acids Fruit (blanc, jaune, ) 5 4 Levure Fruit vert 3 2 1 Phénolique Agrumes Conventional Organic 0 Malt-Caramel Floral Soufré Epicé Consistently more phenolic/clove like flavours perceived in the organic version (all data from Consalim Project)
II.2. Brewing Quality: ferulic and coumaric acids Higher concentrations of 4-vinylguaïacol coming from ferulic acid Similar concentrations of 4-vinylphenol coming from coumaric acid
II.2. Brewing Quality: ferulic and coumaric acids Organic Malts Mix 2RP (?) 2008 Danemarker (DK) 2008 Prestige (FR) 2008 Prestige (FR) 2008 Wetsminster (UK) 2008 Henley (FR) 2008 Prestige (FR) 2009 Prestige (FR) 2009 Westminster (UK) 2009 Scarlet (FR) 2009 Decase Power (NOP) 2009 Mean (n=11) Conventional Malts Prestige (FR) 2008 Sebastan/Tipple 2008 Tipple 2008 Sebastian 2008 Sebastian 2008 Sebastian Tipple 2008 6RH 2008 Tipple 2008 Mix 2RP (FR) (2008) Scarlet (FR) 2009 Prestige (FR) 2009 Mean (n=11) Coumaric Acid (mg/l) Ferulic Acid (mg/l) 0,21 0,9 0,87 0,66 1,09 2,16 0,7 0,6 3,4 3 0,6 1,29 0,86 1 1,05 0,9 0,88 1,17 1,37 1,19 0,21 2,6 0,5 1,07 0,59 4,01 4,02 3,58 2,8 2,81 4,6 6,1 9,4 13,3 4,3 5,05 1,55 1,79 1,77 1,42 1,7 1,78 1,42 1,54 0,78 6,5 2,9 2,10 Higher concentrations of ferulic acid --> 4 VG Similar concentrations of coumaric acid --> 4 VP
II.2. Brewing Quality: ferulic and coumaric acids 4,5 4 3,5 3 2,5 2 1,5 1 0,5 0 35 37 39 41 43 45 47 49 51 53 55 Kolbach Index No link with protein modification In wheat, ferulic acids are located in the outer layers of the grain and in the cell walls In barley, the higher concentrations are located in the husks Link with husks proportion should be checked, sizing better in conventional barleys
II.3. Conclusions Brewing Safety : Hops : Presence of copper and pesticides in conventional hops Only presence of copper in organic hops Copper can have big influence on the thiols profile of hops Barley Malt : Similar levels of DON in Belgian beers, organic or conventional Higher levels of OTA in organic Belgian beers 2003-2004 Similar levels of OTA in organic and conventional beers in 2005 No true problem but growers and malsters have to stay vigilant
II.3. Conclusions Brewing Quality: Colour is currently difficult to manage Nitrogen levels are lower Sizing is more variable and less qualitative Ferulic acid levels are higher leading to higher concentrations of 4vinylguaïacol Husk influence on the amount of 4VG precursors should be checked
Acknowledgments Consalim Project supported by the Region Wallone Prof Collin and UCL Dupont Brewery Beloeil Malting Plant