Studies on the Impact of Malting and Mashing on the Free, Soluble Ester-Bound, and Insoluble Ester-Bound Forms of Desired and Undesired Phenolic Acids Aiming at Styrene Mitigation during Wheat Beer Brewing

Mitigation studies on styrene in wheat beer found no correlation between the free phenolic acid contents in the processing steps and the final concentrations of the toxicologically relevant styrene and the desired aroma-active vinyl aromatics in beer, which can be explained by the presence of phenolic acid releasing enzymes that are still active after kiln-drying and by the yeast's own feruloyl esterase activity. The present study contributed to a better understanding of the coherence between the free, soluble ester-bound, and insoluble ester-bound forms of cinnamic, p-coumaric, and ferulic acid during malting and mashing of barley and wheat varieties. Concentration differences in malt by factors of up to 1700 were found between the total cinnamic acid contents (an undesired precursor of the toxicologically relevant styrene) and the total contents of p-coumaric and ferulic acid (both desired precursors of the aroma-active compounds 4-vinylphenol and 2-methoxy-4-vinylphenol). In grain and malt, cinnamic acid occurred predominantly in a soluble form, whereas the desired precursors were mainly insoluble ester-bound. This had a direct effect on the transfer rates from malt into wort, which were found to be >100% for cinnamic acid, revealing that a complete transfer was accompanied by an additional biosynthesis, but only <8% for the desired phenolic acids. Interestingly, in the wort, cinnamic and p-coumaric acid contents were dominated by the free form, while ferulic acid was mostly still soluble ester-bound. Overall, the use of barley malts led to an introduction of cinnamic, p-coumaric, and ferulic acid into the wort in a ratio of 2:14:84, and the use of wheat malt in a ratio of 1:2:97.