Lancova K, Hajslova J, Poustka J, Krplova A, Zachariasova M, Dostalek P, Sachambula L
Department of Food Chemistry and Analysis, Institute of Chemical Technology, Prague, Czech Republic.
Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2008 Jun;25(6):732-44. doi: 10.1080/02652030701779625.
The fate of five Fusarium toxins--deoxynivalenol (DON), sum of 15- and 3-acetyl-deoxynivalenol (ADONs), HT-2 toxin (HT-2) representing the main trichothecenes and zearalenone (ZON) during the malting and brewing processes--was investigated. In addition to these 'free' mycotoxins, the occurrence of deoxynivalenol-3-glucoside (DON-3-Glc) was monitored for the first time in a beer production chain (currently, only DON and ZON are regulated). Two batches of barley, naturally infected and artificially inoculated with Fusarium spp. during the time of flowering, were used as a raw material for processing experiments. A highly sensitive procedure employing high-performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) was validated for the analysis of 'free' Fusarium mycotoxins and DON-conjugate in all types of matrices. The method was also able to detect nivalenol (NIV), fusarenon-X (FUS-X) and T-2 toxin (T-2); nevertheless, none of these toxins was found in any of the samples. While steeping of barley grains (the first step in the malting process) apparently reduced Fusarium mycotoxin levels to below their quantification limits (5-10 microg kg(-1)), their successive accumulation occurred during germination. In malt, the content of monitored mycotoxins was higher compared with the original barley. The most significant increase was found for DON-3-Glc. During the brewing process, significant further increases in levels occurred. Concentrations of this 'masked' DON in final beers exceeded 'free' DON, while in malt grists this trichothecene was the most abundant, with the DON/DON-3-Glc ratio being approximately 5:1 in both sample series. When calculating mass balance, no significant changes were observed during brewing for ADONs. The content of DON and ZON slightly decreased by a maximum of 30%. Only traces of HT-2 were detected in some processing intermediates (wort after trub removal and green beer).
研究了五种镰刀菌毒素——脱氧雪腐镰刀菌烯醇(DON)、15-乙酰脱氧雪腐镰刀菌烯醇与3-乙酰脱氧雪腐镰刀菌烯醇之和(ADONs)、代表主要单端孢霉烯族毒素的HT-2毒素(HT-2)以及玉米赤霉烯酮(ZON)在麦芽制造和酿造过程中的命运。除了这些“游离”霉菌毒素外,首次在啤酒生产链中监测了脱氧雪腐镰刀菌烯醇-3-葡萄糖苷(DON-3-Glc)的存在情况(目前,仅对DON和ZON进行监管)。两批在开花期自然感染和人工接种镰刀菌属的大麦被用作加工实验的原料。采用高效液相色谱-串联质谱联用(LC-MS/MS)的高灵敏度方法经过验证,可用于分析所有类型基质中的“游离”镰刀菌霉菌毒素和DON共轭物。该方法还能够检测雪腐镰刀菌烯醇(NIV)、镰刀菌烯酮-X(FUS-X)和T-2毒素(T-2);然而,在任何样品中均未发现这些毒素。虽然大麦籽粒浸泡(麦芽制造过程的第一步)明显将镰刀菌霉菌毒素水平降低至其定量限(5-10微克/千克)以下,但在发芽过程中它们会相继积累。在麦芽中,监测到的霉菌毒素含量高于原始大麦。DON-3-Glc的增加最为显著。在酿造过程中,含量进一步显著增加。最终啤酒中这种“隐蔽”DON的浓度超过了“游离”DON,而在麦芽粉中这种单端孢霉烯族毒素含量最高,两个样品系列中DON/DON-3-Glc的比例约为5:1。在计算质量平衡时,酿造过程中ADONs未观察到显著变化。DON和ZON的含量最多略有下降30%。在一些加工中间体(除去酒泥后的麦芽汁和生啤酒)中仅检测到痕量的HT-2。