Impacts of Copper, Iron, and Manganese Metal Ions on the EPR Assessment of Beer Oxidative Stability

ABSTRACT Beer flavor stability is a key quality parameter as brewers seek to maintain the quality of their product throughout the supply chain. The electron paramagnetic resonance (EPR) oxidative stability assay is one method that brewers are utilizing to optimize their process with regard to flavor stability without the time requirements of stored aging and sensory testing of beer. There are still gaps in our knowledge relating to the EPR measurement and the factors within the assay that affect the measured results. This investigation aimed to understand the influence that transition metal ions have on the measurement in four different beers (three lagers and one stout). The detrimental impact of copper and iron on the lag time (an indication of when staling may begin) of trial beers is demonstrated, while the influence of manganese is shown to differ between beers. The T450 value (an indication of how much staling may occur in a particular beer) is shown to increase with iron and manganese addition in most beers. However, copper reduces the T450 or maximum spin adduct concentration achieved and the potential reasons for this are discussed. Crucially for brewers, it has been shown that as little as a 10 ppb transition metal ion addition can make a detectable difference to the measured oxidative stability.

[1]  M. Broadley,et al.  The influence of style and origin on mineral composition of beers retailing in the UK , 2017, European Food Research and Technology.

[2]  J. Danilewicz Chemistry of Manganese and Interaction with Iron and Copper in Wine , 2016, American Journal of Enology and Viticulture.

[3]  C. Bamforth,et al.  Manganese in Brewing Raw Materials, Disposition during the Brewing Process, and Impact on the Flavor Instability of Beer1 , 2016 .

[4]  M. Andersen,et al.  Antioxidative Mechanisms of Sulfite and Protein-Derived Thiols during Early Stages of Metal Induced Oxidative Reactions in Beer. , 2015, Journal of agricultural and food chemistry.

[5]  J. Danilewicz Reactions Involving Iron in Mediating Catechol Oxidation in Model Wine , 2013, American Journal of Enology and Viticulture.

[6]  T. Kunz,et al.  Influence of Intermediate Maillard Reaction Products with Enediol Structure on the Oxidative Stability of Beverages1 , 2013 .

[7]  R. Lametsch,et al.  Effect of pasteurization on the protein composition and oxidative stability of beer during storage. , 2012, Journal of agricultural and food chemistry.

[8]  F. Clarke,et al.  125th Anniversary Review: The role of proteins in beer redox stability , 2012 .

[9]  T. Shellhammer,et al.  Chelating Properties and Hydroxyl-Scavenging Activities of Hop α- and Iso-α-Acids , 2011 .

[10]  C. Blanco,et al.  Free iron in pale, dark and alcohol-free commercial lager beers. , 2011, Journal of the science of food and agriculture.

[11]  P. Pohl,et al.  Chemical fractionation of Cu, Fe and Mn in canned Polish beers , 2010 .

[12]  David R. Jones,et al.  Bioavailability and catalytic properties of copper and iron for Fenton chemistry in human cerebrospinal fluid , 2010, Redox report : communications in free radical research.

[13]  L. Skibsted,et al.  Key Factors Affecting Radical Formation in Wine Studied by Spin Trapping and EPR Spectroscopy , 2009, American Journal of Enology and Viticulture.

[14]  Barr Standard Method for Measurement of Oxidative Resistance of Beer by Electron Paramagnetic Resonance , 2008 .

[15]  P. Pohl Determination and fractionation of metals in beer: A review , 2008, Food additives & contaminants. Part A, Chemistry, analysis, control, exposure & risk assessment.

[16]  P. Pohl,et al.  Fractionation analysis of manganese and zinc in beers by means of two sorbent column system and flame atomic absorption spectrometry. , 2007, Talanta.

[17]  J. Danilewicz Interaction of Sulfur Dioxide, Polyphenols, and Oxygen in a Wine-Model System: Central Role of Iron and Copper , 2007, American Journal of Enology and Viticulture.

[18]  Guy Derdelinckx,et al.  The chemistry of beer aging – a critical review , 2006 .

[19]  A. Smirnov,et al.  Antioxidant pool in beer and kinetics of EPR spin-trapping. , 2005, Journal of agricultural and food chemistry.

[20]  L. Skibsted,et al.  Potential antioxidants in beer assessed by ESR spin trapping. , 2000, Journal of agricultural and food chemistry.

[21]  M. P. Hernández-Artiga,et al.  Differentiation and classification of beers with flame atomic spectrometry and molecular absorption spectrometry and sample preparation assisted by microwaves , 2000 .

[22]  M. Ono,et al.  Technological Approach to Improve Beer Flavor Stability: Analysis of the Effect of Brewing Processes on Beer Flavor Stability by the Electron Spin Resonance Method , 2000 .

[23]  L. Skibsted,et al.  Electron spin resonance spin trapping identification of radicals formed during aerobic forced aging of beer , 1998 .

[24]  M. Ono,et al.  Improvement for oxidative flavor stability of beer : Rapid prediction method for beer flavor stability by electron spin resonance spectroscopy , 1996 .

[25]  M. Ono,et al.  Improvement for oxidative flavor stability of beer: role of OH-radical in beer oxidation , 1996 .

[26]  H. Kaneda,et al.  Behavior and role of iron ions in beer deterioration , 1992 .

[27]  R P Mason,et al.  Direct evidence for inhibition of free radical formation from Cu(I) and hydrogen peroxide by glutathione and other potential ligands using the EPR spin-trapping technique. , 1992, Archives of biochemistry and biophysics.

[28]  A. J. Irwin,et al.  The role of copper, oxygen, and polyphenols in beer flavor instability , 1991 .

[29]  T. Osawa,et al.  Detection of Free Radicals in Beer Oxidation , 1988 .

[30]  C. Bamforth,et al.  New procedures to improve the flavor stability of beer , 1985 .

[31]  L. Chapon,et al.  Peroxidatic Step in Oxidation of Beers , 1979 .

[32]  H. Filik,et al.  Cloud point extraction for speciation of iron in beer samples by spectrophotometry , 2012 .

[33]  E. Samp,et al.  Electron Paramagnetic Resonance [EPR] profiling for potential flavor stability improvements in beer , 2001 .

[34]  W. Lund,et al.  Speciation of Cu, Fe and Mn in beer using ion exchange separation and size-exclusion chromatography in combination with electrothermal atomic absorption spectrometry , 2000 .

[35]  R. Mason,et al.  Hydroxyl radical formation from cuprous ion and hydrogen peroxide: a spin-trapping study. , 1995, Archives of biochemistry and biophysics.