Transfer of Fusarium mycotoxins and 'masked' deoxynivalenol (deoxynivalenol-3-glucoside) from field barley through malt to beer

Department of Food Chemistry and Analysis, Institute of Chemical Technology, Prague, Czech Republic.
Food Additives & Contaminants: Part A (Impact Factor: 1.8). 07/2008; 25(6):732-44. DOI: 10.1080/02652030701779625
Source: PubMed

ABSTRACT 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).

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Available from: Pavel Dostálek, Sep 28, 2015
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    • "The natural occurrence of D3G was first reported in contaminated wheat and maize [13]. Since then, D3G has also been detected in barley, oats and cereal-derived products [14] [15] [16]. Due to the toxic potential and high prevalence of DON, the European Commission (EC) established regulatory limits for this mycotoxin in cereal grains and cereal-based products intended for human consumption, by adopting regulation EC No 1881/2006 [17] and amending regulation EC No 1126/2007 [18]. "
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    ABSTRACT: In this study, we compared the performance of conventional sample preparation techniques used in mycotoxin analyses against automated on-line sample clean-up for the determination of deoxynivalenol (DON) and its conjugated derivative, deoxynivalenol-3-β-d-glucoside (D3G), in cereal grains. Blank wheat and barley samples were spiked with DON and D3G, extracted with a mixture of acetonitrile:water (84:16, v/v) and processed by one of the following: extract and shoot, MycoSep(®) 227 clean-up columns, MycoSep 227 with an additional acetonitrile elution step and centrifugal filtration, followed by analysis with liquid chromatography tandem mass spectrometry. Based on method performance characteristics and poor recoveries (<30%) obtained for the polar D3G with some techniques, the extract and shoot approach was chosen for the inter-laboratory method comparison study. Thus, the same spiked samples were analysed in parallel by another laboratory with an in-house validated on-line sample clean-up method, utilising TurboFlow™ chromatography coupled to high resolution mass spectrometry. Method validation was performed by determination of specificity, linearity, recovery, intra-day precision and the limits of detection and quantification. Matrix-matched linearity (R(2)>0.985) was established in the range of 100-1600 and 20-320μg/kg for DON and D3G, respectively. Average recoveries (%RSD) were acceptable with both methods for wheat and barley, ranging between 73% and 102% (3-12%) for DON and 72% and 98% (1-10%) for D3G. The benefit of using automated sample clean-up in comparison to extract and shoot is the ability to inject directly pure extracts into the mass spectrometer, offering faster analyses and improved sensitivity with minimum system maintenance. Copyright © 2014 Elsevier B.V. All rights reserved.
    Journal of Chromatography A 11/2014; 1374. DOI:10.1016/j.chroma.2014.11.046 · 4.17 Impact Factor
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    • "However, the use of barley for food production, as 10 pearled kernels, and for beverage in the malting industry, is increasing, and is 11 generally based on distichous varieties. The use of barley in the food chain can be 12 considered a new economic opportunity, but barley kernels with a high kernel size 13 and test weight (TW) are required (Błażewicz et al., 2007) together with a low 14 occurrence of contaminants (Lancova et al., 2008). Therefore, an improvement of the 15 crop techniques in order to increase grain yield, grain protein content (GPC) and 16 sanitation of this crop, could be a new opportunity to specialize feed and food barley 17 and raise farmer profitability. "
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    • "This masked mycotoxin is formed in plants by enzymatic conjugation of glucose to DON (Poppenberger et al., 2003), thus representing an important defense mechanism of plants against Fusarium related diseases (Lemmens et al., 2005). D3G can be found in different cereal crops (Berthiller et al., 2005; Lancova et al., 2008), as well as in animal feed and foodstuff (De Boevre et al., 2012; Malachova et al., 2011). "
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    ABSTRACT: The metabolism of deoxynivalenol-3-glucoside (D3G) was elucidated in pigs. D3G (oral) was nearly completely hydrolyzed in pigs, but only partially absorbed. Two isomers of deoxynivalenol (DON) glucuronides were detected in pig urine. Two times less urinary metabolites were excreted for D3G compared to DON. D3G (i.v.) was almost exclusively excreted in unmetabolized form via urine. Plants can metabolize the Fusarium mycotoxin deoxynivalenol (DON) by forming the masked mycotoxin deoxynivalenol-3-b-D-glucoside (D3G). D3G might be cleaved during digestion, thus increasing the total DON burden of an individual. Due to a lack of in vivo data, D3G has not been included in the various regulatory limits established for DON so far. The aim of our study was to contribute to the risk assessment of D3G by determination of its metabolism in pigs. Four piglets received water, D3G (116 mg/kg b.w.) and the equimolar amount of DON (75 mg/kg b.w.) by gavage on day 1, 5 and 9 of the experiment, respectively. Additionally, 15.5 mg D3G/kg b.w. were administered intravenously on day 13. Urine and feces were collected for 24 h and analyzed for DON, D3G, deoxynivalenol-3-glucuronide (DON-3-GlcA), LOQ, limit of quantification; MS, mass spectrometry; MS/MS, tandem mass spectrometry; PBS, phosphate buffered saline; R A , apparent recovery; R E , recovery of the extraction step; SSE, signal suppression/ enhancement; UHPLC, ultra high performance liquid chromatography.
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