2007-2008年中国谷物中隐蔽型脱氧雪腐镰刀菌烯醇及多组分真菌毒素污染状况

目的 了解我国部分地区谷物中隐蔽型脱氧雪腐镰刀菌烯醇(DON-3-G)及多组分真菌毒素污染状况.方法 2007-2008年在河南、河北、广西、安徽、四川、重庆和江苏7个省(市、自治区)采集玉米、小麦等样品共计446份,用超高效液相色谱-串联质谱(UPLC-MS/MS)方法检测样品中DON-3-G及多组分真菌毒素[包括脱氧雪腐镰刀菌烯醇(DON)、玉米赤霉烯酮(ZEN)、雪腐镰刀菌烯醇(NIV)等]的污染状况.结果 小麦、玉米中污染的主要真菌毒素为DON及其衍生物和ZEN.88%(169/192)的小麦样品中检出DON(1.5～590.7μg/kg;中位数:30.8μg/kg);22.9%(44/192)的小麦样品中ZEN阳性(1.7～3425.0 μg/kg;中位数:8.0μg/kg),其中有6份样品中ZEN含量超过我国规定的限量标准(60μg/kg).50.5%(103/204)的玉米样品中DON阳性(1.6～4374.4 μg/kg;中位数:94.9μg/kg),7份样品中DON含量超过我国规定的限量标准(1000μg/kg);41.7%(85/204)的玉米样品中ZEN阳性(1.6～4808.7 μg/kg;中位数:48.5μg/kg),其中有37份超过我国规定的限量标准(60 μg/kg).首次在国产小麦和玉米中检出DON-3-G,小麦、玉米样品中DON-3-G中位数分别为21.4μg/kg和34.6 μg/kg,小麦中DON-3-G均高于3-乙酰化DON(3-A-DON,中位数:4.1μg/kg)和15-乙酰化DON(15-A-DON,中位数:3.1μg/kg)(t值分别为5.111和5.966,P值均<0.01);玉米中15-A-DON(中位数:48.6μg/kg)高于3-A-DON(中位数:6.8 μg/kg)(t=-3.579,P<0.01).玉米中DON、DON-3-G、3-A-DON、15-A-DON和ZEN的污染水平均高于小麦(Z值分别为-3.492、-1.960、-2.467、-8.711和-6.272,P值均<0.05),而NIV在小麦中水平(中位数:29.0μg/kg)高于玉米(中位数:18.2μg/kg)(Z=-2.086,P<0.05).结论 我国部分地区小麦、玉米被多组分真菌毒素污染,以DON检出率最高;玉米中受DON、DON-3-G、3-A-DON、15-A-DON和ZEN的污染比小麦重.

Abstract：

Objective To elucidate the natural occurrence of masked deoxynivalenol (DON-3-G)and other multi-mycotoxins in cereals from parts of China. Methods A total of 446 corn and wheat samples harvested in 2007 and 2008 collected from Henan, Hebei, Guangxi, Anhui, Sichuan, Chongqing and Jiangsu provinces were analyzed for DON-3-G and other multi-mycotoxins (including deoxynivalenol (DON),zearalenone(ZEN), nivalenol (NIV), et al) by UPLC-MS/MS. Results Corn and wheat samples were mainly contaminated by DON and its derivatives as well as ZEN. 88% (169/192) of wheat samples were positive for DON (range: 1.5-590. 7 μg/kg; median: 30. 8 μg/kg) ;22. 9% (44/192) of wheat samples were contaminated with ZEN (range: 1. 7-3425.0 μg/kg; median: 8.0 μg/kg) and six samples contained ZEN concentration higher than the ZEN tolerance limit of 60 μg/kg. DON was detected in 50. 5% (103/204) corn samples (range: 1.6-4374. 4 μg/kg; median: 94. 9 μg/kg); Seven samples contained DON exceeding the tolerance limit of 1000 μg/kg for DON. Additionally, ZEN was found in 41.7% (85/204) corn samples with the concentration between 1.6 μg/kg and 4808.7 μg/kg (median:48.5 μg/kg)and there were 37 corn samples with ZEN level in the excess of tolerance limit for ZEN (60 μg/kg). DON-3-G was detected in corn and wheat samples for the first time in China with the median level of 21.4 μg/kg and 34. 6 μg/kg for wheat and corn,respectively. Wheat was more heavily contaminated with DON-3-G than both 3-aeetly-DON (3-A-DON,median:4. 1μg/kg) and 15-acetly-DON (15-A-DON,median :3. 1 μg/kg)(t values were 5. 111 and 5. 966, respectively,both P values <0. 01). While,the level of 15-A-DON (median: 48. 6 μg/kg) in corn was higher than 3-A-DON (median: 6. 8 μg/kg) (t =-3. 579,P < 0. 01). The concentration of DON, DON-3-G, 3-A-DON, 15-A-DON and ZEN in corn were higher than that in wheat (Z values were-3. 492,-1. 960,-2. 467,-8. 711 and-6. 272, respectively,all P values < 0. 05). Wheat(median: 29. 0 μ.g/kg) contained higher NIV in comparison with corn(median:18.2 μg/kg,Z=-2.086,P<0.05). Conclusion Wheat and corn samples from parts of China were contaminated with multi-mycotoxins and DON was the predominant;in comparison of wheat,corn was more heavily contaminated with DON, DON-3-G,3-A-DON, 15-A-DON and ZEN.

Natural occurrence of masked deoxynivalenol and multi-mycotoxins in cereals from China harvested in 2007 and 2008

Objective To elucidate the natural occurrence of masked deoxynivalenol (DON-3-G)and other multi-mycotoxins in cereals from parts of China. Methods A total of 446 corn and wheat samples harvested in 2007 and 2008 collected from Henan, Hebei, Guangxi, Anhui, Sichuan, Chongqing and Jiangsu provinces were analyzed for DON-3-G and other multi-mycotoxins (including deoxynivalenol (DON),zearalenone(ZEN), nivalenol (NIV), et al) by UPLC-MS/MS. Results Corn and wheat samples were mainly contaminated by DON and its derivatives as well as ZEN. 88% (169/192) of wheat samples were positive for DON (range: 1.5-590. 7 μg/kg; median: 30. 8 μg/kg) ;22. 9% (44/192) of wheat samples were contaminated with ZEN (range: 1. 7-3425.0 μg/kg; median: 8.0 μg/kg) and six samples contained ZEN concentration higher than the ZEN tolerance limit of 60 μg/kg. DON was detected in 50. 5% (103/204) corn samples (range: 1.6-4374. 4 μg/kg; median: 94. 9 μg/kg); Seven samples contained DON exceeding the tolerance limit of 1000 μg/kg for DON. Additionally, ZEN was found in 41.7% (85/204) corn samples with the concentration between 1.6 μg/kg and 4808.7 μg/kg (median:48.5 μg/kg)and there were 37 corn samples with ZEN level in the excess of tolerance limit for ZEN (60 μg/kg). DON-3-G was detected in corn and wheat samples for the first time in China with the median level of 21.4 μg/kg and 34. 6 μg/kg for wheat and corn,respectively. Wheat was more heavily contaminated with DON-3-G than both 3-aeetly-DON (3-A-DON,median:4. 1μg/kg) and 15-acetly-DON (15-A-DON,median :3. 1 μg/kg)(t values were 5. 111 and 5. 966, respectively,both P values <0. 01). While,the level of 15-A-DON (median: 48. 6 μg/kg) in corn was higher than 3-A-DON (median: 6. 8 μg/kg) (t =-3. 579,P < 0. 01). The concentration of DON, DON-3-G, 3-A-DON, 15-A-DON and ZEN in corn were higher than that in wheat (Z values were-3. 492,-1. 960,-2. 467,-8. 711 and-6. 272, respectively,all P values < 0. 05). Wheat(median: 29. 0 μ.g/kg) contained higher NIV in comparison with corn(median:18.2 μg/kg,Z=-2.086,P<0.05). Conclusion Wheat and corn samples from parts of China were contaminated with multi-mycotoxins and DON was the predominant;in comparison of wheat,corn was more heavily contaminated with DON, DON-3-G,3-A-DON, 15-A-DON and ZEN.