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Program Book - Master Brewers Association of the Americas

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<strong>the</strong>ir maturation capacity and to save both energy costs and <strong>the</strong><br />

environment by making cold maturation obsolete.<br />

P-199<br />

The influence <strong>of</strong> <strong>the</strong> Fenton- and Haber-Weiss-reaction system<br />

on haze formation in stabilized beer<br />

THOMAS KUNZ (1), Stefanie Karrasch (2), Frank-Juergen Methner<br />

(1)<br />

(1) TU Berlin/VLB Berlin, Berlin, Germany; (2) TU Braunschweig,<br />

Braunschweig, Germany<br />

During <strong>the</strong> last 40 years various working groups have described<br />

generally accepted models for haze formation mechanisms in beer.<br />

The interactions between polyphenols and proteins have been<br />

identified as <strong>the</strong> main reaction system. Based on this cognition <strong>the</strong><br />

brewers utilize PVPP and silica gel to stabilize beer. Never<strong>the</strong>less<br />

chill haze or permanent haze formation can be observed in<br />

beer after a certain storage time. It is also well known that <strong>the</strong><br />

presence <strong>of</strong> oxygen, higher temperatures, light, metallic ions and<br />

mechanical influences accelerate haze formation during storage,<br />

but <strong>the</strong> responsible reaction mechanism could not be determined<br />

satisfactorily up to now. Also <strong>the</strong> described approach according to<br />

an oxidation reaction which activates <strong>the</strong> polyphenols by generating<br />

ortho-chinons, which are able to react with o<strong>the</strong>r beer ingredients, is<br />

not able to explain haze formation in stabilized beer completely. Our<br />

investigations on detached haze by solid measurements using ESR<br />

at 77 K have approved ESR signals in haze, which cannot be found in<br />

filtrate. The different ESR-signals are caused by stabilized organic<br />

radicals and ions like Fe 3+ . These results indicate an interrelation<br />

with <strong>the</strong> Fenton reaction system, resulting in iron-(III)-ions and<br />

hydroxyethyl radicals. The application <strong>of</strong> several analytical methods<br />

(ICP-OES, ESR, gel electrophoresis) helped to characterize <strong>the</strong><br />

composition <strong>of</strong> chill haze and permanent haze during storage.<br />

Based on <strong>the</strong> additional comparison <strong>of</strong> <strong>the</strong> development <strong>of</strong> <strong>the</strong><br />

endogenous antioxidative potential (EAP) and haze formation<br />

during shelf life, an important coherence in <strong>the</strong> haze formation<br />

<strong>of</strong> stabilized beer could be observed. The analytical methods have<br />

clearly demonstrated that oxidative processes are <strong>the</strong> major cause<br />

for colloidal haze formation in stabilized beer. On <strong>the</strong> basis <strong>of</strong> <strong>the</strong><br />

former postulated haze <strong>the</strong>ories, a mechanism was mapped out, in<br />

which <strong>the</strong> reaction products <strong>of</strong> <strong>the</strong> Fenton and Haber-Weiss-reaction<br />

system in beer play a central role in <strong>the</strong> formation <strong>of</strong> haze during<br />

<strong>the</strong> beer aging. After consumption <strong>of</strong> <strong>the</strong> EAP, <strong>the</strong> reactive hydroxyl<br />

radicals and secondary radicals are generated by <strong>the</strong> catalysis <strong>of</strong><br />

iron and copper ions. At <strong>the</strong> same time <strong>the</strong> formation <strong>of</strong> iron-(III)<br />

and copper-(I)-ions, as well as oxidation <strong>of</strong> beer ingredients and<br />

formation <strong>of</strong> stabilized organic radicals occurs. Due to <strong>the</strong> complex<br />

formation among oxidized polyphenol-protein-complexes and iron-<br />

(III) as well as copper-(I)-ions <strong>the</strong> development <strong>of</strong> chill haze can<br />

be observed. During <strong>the</strong> progress <strong>of</strong> beer aging <strong>the</strong> oxidized ironpolyphenol-protein-complexes,<br />

which include <strong>the</strong> stable organic<br />

radicals, react with each o<strong>the</strong>r by attendance <strong>of</strong> radical reactions<br />

and formation <strong>of</strong> covalent bonds. This process describes <strong>the</strong><br />

conversion <strong>of</strong> chill haze to permanent haze. Based on <strong>the</strong> results <strong>the</strong><br />

effectiveness <strong>of</strong> influencing factors on haze formation in stabilized<br />

beer can be better understood, and <strong>the</strong> arrangements to increase<br />

colloidal beer stability can be optimized.<br />

After qualifying as a certified technician in preservation engineering<br />

(1991–1993), Thomas Kunz completed his basic studies in chemistry<br />

at Isny University <strong>of</strong> Applied Sciences (1994–1995) and his basic<br />

studies in food chemistry at Wuppertal University (1995–1998)<br />

before starting to study food technology at Trier University <strong>of</strong> Applied<br />

Sciences (1998–2002). After graduating, he worked as an engineer<br />

(Dipl.-Ing. FH) in <strong>the</strong> area <strong>of</strong> ESR spectroscopy at <strong>the</strong> Institute <strong>of</strong><br />

164<br />

Biophysics at Saarland University (2002–2004). Since January<br />

2005, he has been employed as a Ph.D. student at <strong>the</strong> Research<br />

Institute for <strong>the</strong> Technology <strong>of</strong> Brewing and Malting at VLB/<br />

Technical University <strong>of</strong> Berlin under <strong>the</strong> supervision <strong>of</strong> Pr<strong>of</strong>essor<br />

Methner. His main research focus is analysis <strong>of</strong> radical reaction<br />

mechanisms in beer and o<strong>the</strong>r beverages using ESR spectroscopy.<br />

P-200<br />

Colloidal stability—The effect <strong>of</strong> excess stabilization<br />

MORITZ PÖSCHL (1)<br />

(1) TU Munich, Lehrstuhl für Technologie der Brauerei II, Germany<br />

Preservation <strong>of</strong> colloidal stability in bottom fermented and<br />

filtered beers can be regarded as one <strong>of</strong> <strong>the</strong> biggest challenges<br />

breweries have to meet in <strong>the</strong> current beer markets, which exhibit<br />

an ever increasing tendency toward globalization combined<br />

with rising consumer-expectancy <strong>of</strong> <strong>the</strong> clarity and quality <strong>of</strong><br />

beer. One focal point <strong>of</strong> <strong>the</strong> current research is <strong>the</strong> improvement<br />

<strong>of</strong> <strong>the</strong> predictability <strong>of</strong> haze formation before filtration and<br />

stabilization to enable more specific beer stabilization and prevent<br />

excess stabilization. This in turn would lead to reduced costs<br />

for stabilization agents and <strong>the</strong> preservation <strong>of</strong> health-relevant<br />

substances such as polyphenols. The aim <strong>of</strong> this study is to highlight<br />

<strong>the</strong> effect <strong>of</strong> excess stabilization on <strong>the</strong> composition and quality<br />

<strong>of</strong> <strong>the</strong> resulting beers. In this context unstabilized beer has been<br />

compared to PVPP-stabilized (50 g/hl) beer and to double stabilized<br />

beer (PVPP 50 g/hl, Xerogel 100 g/hl), each beer deriving from<br />

<strong>the</strong> same batch (Pilsner type). Analyses included monitoring <strong>of</strong> <strong>the</strong><br />

phenolic spectrum and protein fractions as well as measurement<br />

<strong>of</strong> <strong>the</strong> reducing power, foam stability and colloidal stability. PVPP<br />

stabilization resulted in an obvious decrease in total polyphenols,<br />

flavanoids and haze relevant flavan-3-ols (measured by HPLC) but<br />

did not influence <strong>the</strong> concentrations <strong>of</strong> phenolic acids. Stabilization<br />

with silica gel induced a significant decrease in tannin-precipitable<br />

proteins; <strong>the</strong> reduction <strong>of</strong> total nitrogen was quite low. The<br />

measurement <strong>of</strong> <strong>the</strong> reducing power, using two electrochemical<br />

methods, brought out a significant deterioration <strong>of</strong> antioxidative<br />

capacity stabilizing with PVPP compared to <strong>the</strong> unstabilized beer.<br />

Foam stability was slightly worse after stabilizing with silica gel. The<br />

force test (0°C/40°C) in <strong>the</strong> unstabilized beer showed an increase<br />

in haze <strong>of</strong> 2 EBC already after 2 warm days; <strong>the</strong> stabilized samples<br />

can be regarded as excessive stabilized, showing an increase in haze<br />

lower than 0.2 EBC even after 16 warm days. It has been shown that<br />

stabilization should be done in a more specific and selective way to<br />

produce higher quality beer combined with lower costs.<br />

Moritz Pöschl was born in Munich in 1978. After studying brewing<br />

and beverage technology at <strong>the</strong> Technical University Munich, he<br />

is now (since 2004) a scientific assistant at <strong>the</strong> Chair for Brewing<br />

Technology II. The focal points <strong>of</strong> his research are <strong>the</strong> enhancement <strong>of</strong><br />

stabilization in a technological/natural way and <strong>the</strong> improvement <strong>of</strong><br />

<strong>the</strong> predictability <strong>of</strong> colloidal stability.

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