Abstract :
[en] Beer is an extremely popular beverage worldwide, representing the third-most popular drink after water and tea. And barley is the major raw material used for beer production. However, various combinations of pesticides are widely used at several stages of barley culti¬vation and during post-harvest storage to control pest and fungal disease. Hence, traces of these pesticides might remain in the beer produced from the treated ingredients. Hence, monitoring trace levels of pesticide residues during beer brewing and investigated the effects of pesticide residue on the quality of beer is essential.
First, the behavior and fate of 3 pesticides (triadimefon, malathion, and dichlorvos) and the main metabolites (triadimenol and malaoxon) during barley storage or beer processing were assessed using a pilot-plant equipment. The residues of all products were determined using liquid chromatography coupled with tandem mass spectrometry. Field investigation of the dissipation rate kinetics for triadimefon and malathion during storage indicated that their half-life was twice as high when 5 times the recommended dosage was used. Milling had little effect on removing dichlorvos and malathion residues, whereas they were substantially removed when the spent grains were mashed. The calculated processing factors after processing were all <1, indicating that the residual ratios of dichlorvos and malathion were reduced during the entire process. In conclusion, storage and processing extensively reduced pesticide residue levels in barley and beer; however, greater focus needs to be paid to the toxicity of their metabolites in commercial by-products.
Then we selected the triadimefon as the target fungicide to further study its behavior, the dissipation kinetics of TF during fermentation mediated by two different yeast strains, Saccharomyces cerevisiae IAPPST 1401 (Y1) and CICC 1202 (Y2), and found that Y2 promoted the degradation of TF. Response surface methodology was used to optimize fermentation process variables, in order to achieve the maximum removal rate of TF and the minimum production of its corresponding metabolite, triadimenol (TN). Triadimefon is also a widely used triazole fungicide with one chiral carbon center, Stereoselective degradation of triadimefon was found during barley storage, the half-life of S-(+)-triadimefon was 36.5d, 31.5d and 30.1d, while R-(-)-traidmefon was 69.3d, 53.3d and 33d under 4°C, 25°C and 40°C, respectively. During brewing process, both enantiomers of triadimefon were easily degraded. After fermentation, little triadimefon detected in the beer, while RS-(+) and SS-(-)-triadimenol were detectable. This research provides accurate information for evaluating the risk of food safety.
Furthermore, we investigated the effect of triadimefon affect the quality and flavor of the fermented beer, The effect of triadimefon on yeast growth and the sensory quality of beer were studied. There were significant differences in sensory quality between beer samples fermented with and without triadimefon based on data obtained with an electronic tongue and nose. Such an effect was most likely underlain by changes in yeast fermentation activity, including decreased utilization of maltotriose and most amino acids, reduced production of isobutyl and isoamyl alcohols, and increased ethyl acetate content in the fungicide treated samples. Furthermore, yeast metabolic profiling by phenotype microarray and UPLC/TOF-MS showed that triadimefon caused significant changes in the metabolism of glutathione, phenylalanine and sphingolipids, and in sterol biosynthesis. Thus, triadimefon negatively affects beer sensory qualities by influencing the metabolic activity of S. cerevisiae during fermentation, emphasizing the necessity of stricter control over fungicide residues in brewing by the food industry.
