The impact of sulphur dioxide and oxygen on the behaviour of 2-furaldehyde in beer: an industrial approach

2‐Furaldehyde is often used as an analytical indicator of beer flavour deterioration. Although 2‐furaldehyde itself has a flavour threshold far above levels generally present in beer, it can be used as a good marker of heat damage of beer. A reversed‐phase liquid chromatographic assay, using ultraviolet‐visible detection, was applied to investigate the behaviour of 2‐furaldehyde throughout the brewing process and during extended storage of beer. The impact of storage temperature, sulphur dioxide and oxygen content on the level of 2‐furaldehyde was studied. It was found that the concentration of 2‐furaldehyde markedly increases during wort boiling and is rapidly reduced by yeast during the first hours of fermentation, emphasising the yeast reducing capacity as a determinant factor for the 2‐furaldehyde content found in the final beer. The results obtained suggest that sulphur dioxide and oxygen content play a key role on the 2‐furaldehyde content in packaged beer. 2‐Furaldehyde increase during ageing is oxygen dependent and sulphur dioxide retards its development by possibly protecting beer against the occurrence of oxidative reactions.     

ESTIMATION AND OCCURRENCE OF ACETALDEHYDE IN BEER

A sensitive routine quantitative method has been developed which determines acetaldehyde in beer. The method is suitable for the measurement of acetaldehyde, its bisulphite addition compound and acetal, with only limited interference from other aldehydes. The examination of a representative selection of beers shows that large differences of acetaldehyde can occur in beers of a similar type. Beers which have been sweetened by the addition of priming sugar vary widely in their acetaldehyde content, many being above the 25 ppm taste threshold. The acetaldehyde content has been shown to vary with both the quantity and point of addition of sulphur dioxide when this is used as a preservative or antioxidant.     

VARIATIONS AMONGST BEERS AND LACTIC ACID BACTERIA RELATING TO BEER SPOILAGE

The ability of lactic acid bacteria to grow in beer has been studied using 31 beers, 13 strains of Lactobacillus and 3 strains of Pediococcus isolated from wort or beer. In 3 beers all the micro-organisms were able to grow, in 5 beers none of them developed and diverse results were obtained with the remaining 23 beers. Resistance of the beers to spoilage was not correlated with values of pH, specific gravity, total or free amino nitrogen, individual or total fermentable sugars, colour or levels of sulphur dioxide. Resistant beers became sensitive after certain filtration treatments and after heating at 80° for 15 minutes, but not after treatment at 60°. Resistance to spoilage is tentatively attributed to the presence of a yeast metabolite which is heat-labile. The lactic acid bacteria varied in their ability to grow in beer but those possessing a broad range of biochemical abilities had the greater propensity to cause spoilage.     

The Role of Malt and Hop Polyphenols in Beer Quality,Flavour and Haze Stability

Pilot‐scale brewing trials of a 12°P pale lager beer were conducted to look at the effect of a modified dose of hop and malt polyphenols on haze, flavour quality, and stability. Results confirmed that malt polyphenols, and particularly hop polyphenols, in the course of wort boiling, improved reducing activity values and the carbonyl content in fresh and stored beers. Hop polyphenols significantly increased reducing activity and decreased the formation of carbonyls (TBA value) in fresh and stored beer. Reduced content of malt polyphenols, combined with the use of hop CO₂ extract, caused an increase in the TBA value in beer. PVPP stabilized beers tended to be lower in reducing activity. Both malt and hop polyphenols affected the intensity of “harsh taste” in fresh beers and a significant influence from PVPP stabilization of beer was not observed. The staling degree of forced‐aged beers depended on the polyphenol content in the brewhouse. Both hop and malt polyphenols had a positive impact on flavour stability. PVPP treatment of beer had a positive effect on the flavour stability of heat‐aged beers. Polyphenols, especially hop polyphenols, slowed down flavour deterioration during the nine month storage period, but the primary effect was seen during the first four months of storage. Storage trials did not show any unambiguous effects for PVPP stabilization on beer flavour stability. Results confirmed the negative impact of malt and hop polyphenols on haze stability, and PVPP stabilization minimized differences in shelf life prediction values between beers prepared with the modified dose of polyphenols.     

Effect of wine barrel ageing or sapa addition on total polyphenol content and antioxidant activities of some Italian craft beers

Beer is a complex mixture of bioactive polyphenols with positive health effects, and its composition is influenced by some technological variables. In this study, the total polyphenol content (TPC) and the antioxidant activity of some Italian craft beers produced by ageing in wood barrel that previously contained red or white wines, and by addition of sapa, a cooked must from wine grapes, were investigated. TPC greatly vary among different beer types. Craft beers stored in wood barrels that contained red wines, such as those added of sapa from red wine grapes, showed a TPC up to 2.5 times higher (1000 GAE mg L^?1) compared with other craft beers, and 3.6 times higher than the industrial beer. The antioxidant activity is remarkably different depending on beer type and strictly correlated with TPC. Results indicate that antioxidant properties of the craft beers could be efficiently improved by the explored technological processes.     

Use of thiolysis hyphenated to RP-HPLC-ESI(-)-MS/MS for the analysis of flavanoids in fresh lager beers

Proanthocyanidins are well known for their involvement in haze and colour development during beer ageing. New methodologies are needed, however, to understand what happens to them in the bottled beer. For the first time in the brewing field, thiolysis was hyphenated to RP-HPLC-ESI(-)-MS/MS to investigate these flavanoids. Thirty minutes at 40 °C followed by 10 h at room temperature emerged as the best conditions for complete depolymerisation. NP-HPLC-ESI(-)-MS/MS was used to quantify and isolate fractions from monomers to trimers in a Sephadex LH20 acetone/water (70/30, v/v) beer extract. Unsurprisingly, a lower dimer/monomer ratio was evidenced in PVPP-treated beers than in silica gel-filtered beers. Most beer dimers are procyanidins B3 (two catechin units) whilst most trimers are prodelphinidins (catechin in terminal units and gallocatechins or catechins in extension units). Gallocatechin appeared to come mainly from malt. Despite the absence of chromatographic peaks corresponding to oligomers above trimers, an apparent degree of polymerisation close to six was calculated in the total LH20 extract. Still higher mean degrees of polymerisation (mDPs) were calculated for malt and hop, indicating selective extraction or depolymerisation from raw materials to beer. The main part of beer polyphenols is composed of complex undefined structures not degraded by toluene-α-thiol.     

CONTROL OF SULPHURY IMPURITIES IN BEER AROMA

Volatile sulphur compounds, particularly hydrogen sulphide and mercaptans, are normal products of yeast metabolism. Although they tend to be purged out of beer during fermentation and maturation, it is not uncommon for finished beer to retain enough of them—up wards of 0·02 ppm as sulphur—to impair its aroma. The addition of a small amount of copper sulphate to sulphury beer cleanses its aroma by transforming volatile sulphur into non-volatile copper sulphide and mercaptides, but since a considerable proportion of this added copper is liable to be inactivated by complexing with nitrogenous constituents of the beer, the removal of sulphur may necessitate the addition of so much copper as to threaten the shelf life of the beer. It has been found that not only may traces of copper be dosed electrolytically into beer with great precision but that the copper so dosed reacts nearly quantitatively with the volatile sulphur present, thus abolishing the latter with no appreciable increase in the net copper content of the beer. The process has given satisfactory results on an industrial scale, improving the flavour of beers without prejudice to their other characteristics.     

Assessment of endogenous antioxidative compounds and antioxidant activities of lager beers

BACKGROUND: Flavour stability is increasingly becoming the limiting factor in the shelf life of beer. Increasing the antioxidant activity of beer itself could suppress the rate of oxidative reaction and improve the flavour stability of beer. This report describes the levels of phenolic compounds, melanoidins and sulfur dioxide, and antioxidant activities of 40 lager beers. The relationships between antioxidative compounds and antioxidant activity were elucidated by multivariate analysis techniques. RESULTS: The results showed that the total phenolic content and the melanoidins content correlated well (P < 0.05) with antioxidant activity, while there was no significant correlation (P > 0.05) between total sulfur dioxide content and antioxidant activity. Satisfactory discrimination among beer samples with significantly different antioxidant activity was achieved by principal component analysis. Results from stepwise linear regression further demonstrated that different antioxidative components responsible for antioxidant activity were dependent on the assay used. The phenolic compound group is by far the most antioxidative compounds in beer and total phenolic content, melanoidins and sulfur dioxide together made a 22–68% contribution to the antioxidant activities of beers. CONCLUSION: Therefore, it might be an efficient means for brewers to increase total phenolic content during brewing for improvement in flavour stability of the final beer. © 2012 Society of Chemical Industry     

Metabonomics analysis of nonvolatile small molecules of beers during forced ageing

Three kinds of beers with different degrees of ageing were used to examine their nonvolatile small molecules by a metabonomics approach based on ultra performance liquid chromatography coupled with quadrupole time‐of‐flight tandem mass spectrometry (UPLC‐Q‐ToF‐MS/MS). Results showed that a total of 2114 compounds were detected in forced‐aged beers with the positive mode of UPLC‐Q‐ToF‐MS/MS. There was a clear separation among three groups of beers with different degrees of ageing in principal component analysis (PCA) model. Sixteen potential metabolite markers related to beer oxidative stability were identified by orthogonal partial least‐squares discriminate analysis (OPLS‐DA). Results from the changes in the spectrum also indicated that some new compounds formed in beer during forced ageing. Thus, the proposed metabonomics approach is a powerful tool to give a fully understanding the ageing process of beer based on the identification of the markers related to oxidative stability.