2022年昭通市新收获玉米真菌毒素污染情况分析

目的：调查分析2022年云南省昭通市新收获玉米真菌毒素污染情况。方法：采集2022年昭通市各县区100份玉米样品,分别采用高效液相色谱-柱后衍生法、免疫亲和层析净化高效液相色谱法、液相色谱法测量黄曲霉毒素B₁、脱氧雪腐镰刀菌烯醇、玉米赤霉烯酮。结果：71份玉米样本未检测出真菌毒素,29份样本检测出真菌毒素,所有样本真菌毒素均未超标,脱氧雪腐镰刀菌烯醇总体检出率最高。盐津县有1份检出3种真菌毒素的玉米样本,巧家县有3份检出2种真菌毒素的玉米样本,且脱氧雪腐镰刀菌烯醇与玉米赤霉烯酮检出率最高,巧家县和绥江县所收样本脱氧雪腐镰刀菌烯醇检出率最高,巧家县和水富市所收玉米样本赤霉烯酮检出率最高。结论：昭通市2022年新收获玉米真菌毒素污染情况在合理范围内,盐津县、巧家县新收获玉米易受真菌毒素污染,需加强关注。     

河北省小麦、玉米及其制品中16种真菌毒素污染水平调查与分析

目的调查分析河北省小麦、玉米及其制品中16种常见真菌毒素污染状况。方法收集河北省37份鲜(冻)玉米/玉米粒、74份玉米、玉米面制品以及240份小麦样品。样品经乙腈:水:甲酸(79:20:1, V:V:V)溶液超声离心提取后,通过同位素内标稀释法处理,采用液相色谱-串联质谱法进行检测。结果伏马毒素小麦检出8份,玉米、玉米面制品检出66份,检出范围为ND~3889.9μg/kg;玉米赤霉烯酮检出小麦检出2份,玉米、玉米面制品检出69份,检出范围为ND~323.2μg/kg;脱氧雪腐镰刀菌烯醇小麦检出122份,玉米、玉米面制品检出68份,检出范围为ND~4183.4μg/kg;3-乙酰基-脱氧雪腐镰刀菌烯醇小麦检出5份,玉米、玉米面制品检出18份;15-乙酰基-脱氧雪腐镰刀菌烯醇小麦检出12份,玉米、玉米面制品检出38份;其他毒素均为未检出。鲜(冻)玉米/玉米粒中16种真菌毒素均未检出。结论伏马毒素、玉米赤霉烯酮和脱氧雪腐镰刀菌烯醇为小麦、玉米及其制品的主要污染物,其污染状况应引起关注。     

粮食中脱氧雪腐镰刀菌烯醇风险预警研究进展

脱氧雪腐镰刀菌烯醇是小麦和玉米等粮食中常见的真菌毒素,受污染的粮食会严重影响人和动物健康,控制粮食产前镰刀菌感染和脱氧雪腐镰刀菌烯醇的积累是保障粮油食品安全的重要环节。当前,世界各国都十分重视粮食真菌毒素污染风险预警工作,粮食产前脱氧雪腐镰刀菌烯醇的污染预警研究近年来发展迅速,在脱氧雪腐镰刀菌烯醇积累的田间影响因素研究和建立产前风险预警模型中,都取得了一定进展。本文综述了脱氧雪腐镰刀菌烯醇风险预警的最新研究成果,旨在总结和整合现有的研究方法和成果,为开展我国粮食真菌毒素早期预警提供参考。     

谷物及其制品中脱氧雪腐镰刀菌烯醇及其衍生物的检测及污染规律分析

采用高效液相色谱-质谱联用技术建立测定小麦粉、挂面、玉米糁、大米等谷物及其制品中脱氧雪腐镰刀菌烯醇(deoxynivalenol,DON)、脱氧雪腐镰刀菌烯醇-3-葡萄糖苷(deoxynivalenol-3-glucoside,D3G)、3-乙酰基脱氧雪腐镰刀菌烯醇(3-acetyldeoxynivalenol,3ADON)及15-乙酰基脱氧雪腐镰刀菌烯醇(15-acetyldeoxynivalenol,15ADON)的检测方法,并对各种粮食中的污染情况进行调查。样品采用乙腈提取,正己烷除脂和固相萃取柱净化后,采用高效液相色谱-串联质谱检测,外标法定量。方法均经过优化和验证,满足谷物及其制品的检测要求。分析96份谷物及其制品中4种真菌毒素的污染规律,结果表明,15ADON无检出,只有1个样品检出3ADON,DON和D3G均有不同程度的检出,DON检出率大于D3G,其中在挂面中的含量最高。D3G与DON的含量呈正相关,D3G/DON在30%左右,且不同谷物种类主要污染的毒素种类均以DON为主,其中挂面的污染最为严重。     

多功能净化柱净化-超高液相色谱串联质谱法检测云南所售部分面条及面条制品中的6种真菌毒素

目的 建立多功能净化柱净化-超高液相色谱-串联质谱法检测云南所售部分面条及面条制品中脱氧雪腐镰刀菌烯醇、3-乙酰脱氧雪腐镰刀菌烯醇、15-乙酰脱氧雪腐镰刀菌烯醇、雪腐镰刀菌烯醇、赭曲霉毒素A和玉米赤霉烯酮6种真菌毒素的含量。方法 样品经乙腈-水-甲酸(70: 29: 1, V:V:V)溶液浸泡提取, 通过Pribo Fast?M226多功能净化柱净化, 采用超高液相色谱-串联质谱的多反应监测模式进行分析, 外标法进行定量。结果 6种真菌毒素在0.05~400 μg/L范围内线性关系良好(r>0.994), 加标回收率为87.6%~101.3%, 相对标准偏差为1.09%~3.65%。81份面条样品中, 脱氧雪腐镰刀菌烯醇检出含量为15.2~664 μg/kg, 检出率为98.77%, 检测值均未超过国家食品安全标准规定的参考限量值, 其余5种真菌毒素均为未检出。结论 本检测方法具有快速便捷、准确性好、灵敏度高、特异性强等特点, 适用于面条中6种真菌毒素的同时测定。     

超高效液相色谱串联质谱法检测谷物中8种真菌毒素

建立了液质联用法同时测定脱氧雪腐镰刀菌烯醇、3-乙酰基脱氧雪腐镰刀菌烯醇、15-乙酰基脱氧雪腐镰刀菌烯醇、黄曲霉毒素B_1、B_2、G_1、G_2、玉米赤霉烯酮共8种真菌毒素谷物中的含量。样品经乙腈-水溶液提取,通过多功能净化柱净化、Waters Acquity UPLC? BEH C18色谱柱分离、超高效液相色谱串联质谱系统测定,脱氧雪腐镰刀菌烯醇及其衍生物同位素内标法定量,黄曲霉毒素和玉米赤霉烯酮外标法定量。结果表明,8种真菌毒素在线性范围内线性相关性R~2≥0.999,检出限在0.3~1.0μg/kg之间,加标回收率在72.2%~101.7%之间,相对标准偏差在1.22%~9.69%之间。该方法操作简单、灵敏度高、回收率好,适用于谷物及其制品中多种真菌毒素的同时检测。     

固相萃取柱净化-液相色谱-串联质谱法测定糕点中脱氧雪腐镰刀菌烯醇及其衍生物和玉米赤霉烯酮

建立使用超高效液相色谱-串联质谱仪测定糕点中玉米赤霉烯酮(ZEN)、脱氧雪腐镰刀菌烯醇(DON)及其衍生物3-乙酰基-脱氧雪腐镰刀菌烯醇(3-Ac DON)、15-乙酰基-脱氧雪腐镰刀菌烯醇(15-Ac DON)4种真菌毒素的方法。该方法在4 min内完成4种真菌毒素的分析,线性范围5~1000μg/kg,标准曲线的相关系数均在0.997以上,DON、ZEN的最低检出限为1.0μg/kg,3-Ac DON、15-Ac DON的最低检出限为1.5μg/kg。通过对134份市售预包装糕点样品进行分析发现,4种真菌毒素均有一定检出,其中ZEN、DON、3-Ac DON和15-Ac DON的检出率分别为2.2%、78.4%、3.0%和5.2%,所有样品中4种真菌毒素含量水平均未超过食品安全国家标准限量要求。     

北京地区部分市售食用植物油中玉米赤霉烯酮和脱氧雪腐镰刀菌烯醇的污染状况分析

目的分析北京市售植物油中玉米赤霉烯酮和脱氧雪腐镰刀菌烯醇的污染状况。方法实验采用同位素稀释-超高效液相色谱-串联质谱法,在多反应监测模式下对所采集玉米油、花生油、调和油等食用油样中的玉米赤霉烯酮(ZEN)、脱氧雪腐镰刀菌烯醇(DON)进行了检测,并对其污染现状进行分析。结果 ZEN和DON在3~500 ng/mL浓度范围内线性良好,相关系数为0.999,加标回收率为95.05%~107.10%,ZEN和DON方法的检出限分别为0.03μg/kg和0.9μg/kg;ZEN和DON方法的定量限分别为0.1μg/kg和3μg/kg。对北京市售30个油样检测结果表明,DON为未检出,ZEN检出率为100%,最高含量为333μg/kg,最低含量为1.95μg/kg,平均含量为67.7μg/kg,低于欧盟规定的限量标准400μg/kg。结论通过分析食用油中真菌毒素的含量状况,初步了解了北京市售植物油中玉米赤霉烯酮和脱氧雪腐镰刀碱烯醇的污染状况。     

2019年中国四省小麦中12种真菌毒素污染情况调查

目的 调查分析2019年中国4个小麦主产省生产的小麦中12种真菌毒素的污染情况。方法 从河南、河北、安徽和山东4省采集2019年产小麦样品289份,采用高效液相色谱-串联质谱法测定8种镰刀菌毒素和4种黄曲霉毒素共计12种真菌毒素含量,并对其进行分析。结果 脱氧雪腐镰刀菌烯醇(DON)是小麦样品中污染的主要真菌毒素,其污染率与平均污染水平分别为95.5% (276/289)和135.9 μg/kg;DON 的乙酰化衍生物15-乙酰基-脱氧雪腐镰刀菌烯醇(15-Ac-DON)和3-乙酰基-脱氧雪腐镰刀菌烯醇(3-Ac-DON)的污染率和平均污染水平分别为37.4% (108/289)、4.4 μg/kg和36.7% (106/289)、5.2 μg/kg;4种黄曲霉毒素和其他5种镰刀菌毒素污染率和平均污染水平均较低。4省小麦中12种真菌毒素污染情况差异不显著。289份小麦样品中,59.9%(173/289)的样品被2种或2种以上真菌毒素协同污染,其中DON及其衍生物15-Ac-DON和/或3-Ac-DON为常见协同污染毒素组合。结论 DON是我国小麦中污染的主要真菌毒素,且存在与其衍生物3-Ac-DON 和/或15-Ac-DON的协同污染,黄曲霉毒素及其他镰刀菌毒素污染水平较低。建议对我国小麦中以DON及其衍生物为主的镰刀菌毒素污染水平进行持续监测。     

QuEChERS-超高效液相色谱串联质谱法测定谷物中的8种真菌毒素

建立了谷物中黄曲霉毒素B_1、B_2、G_1、G_2、玉米赤霉烯酮、脱氧雪腐镰刀菌烯醇、3–乙酰基脱氧雪腐镰刀菌烯醇、15–乙酰基脱氧雪腐镰刀菌烯醇共8种真菌毒素的测定方法。样品采用改良的Qu ECh ERS方法进行提取,用超高效液相色谱串联质谱仪进行测定。8种毒素的线性相关系数(R2)均不小于0.998,检出限为0.3~1.0μg/kg,加标回收率为76.5%~113.4%,相对标准偏差为0.78%~5.03%。该方法简单快速、准确、灵敏度高,可适用于谷物及其制品中多种真菌素的同时分析。     

2020年饲料原料霉菌毒素污染状况调查

目的 为更好的指导饲料生产企业对原料质量的把控、采购及配方设计,汇总分析了2020年饲料原料霉菌毒素污染状况。方法 采用胶体金免疫层析法或上转发光免疫分析法（up-conversion immunoassays, UPT）对安佑集团各分子公司在2020年度所收集（含退货）的28519份大宗饲料原料中的呕吐毒素、玉米赤霉烯酮和黄曲霉毒素B1含量进行快速检测。结果 对比安佑集团企业标准,2020年饲料原料霉菌毒素污染总超标率为0.92%,污染整体情况较轻,其中上半年污染较重,主要由玉米副产物和次粉霉菌毒素污染超标所致,下半年霉菌毒素污染程度整体较轻,但第4季度玉米的玉米赤霉烯酮和黄曲霉毒素B1污染情况加重,玉米的霉菌毒素整体达中度污染;从产地来源看,2020年山东、湖北产地的麸皮和次粉呕吐毒素中度污染,四川、陕西产地的次粉重度污染;四川产地的米糠黄曲霉毒素B1达中度污染,山东产地的玉米呕吐毒素和江苏产地的玉米黄曲霉毒素B1达重度污染;且饲料原料中的霉菌毒素并非单一存在,多数情况下是多种毒素共存。结论 与2019年饲料原料霉菌毒素污染调查数据相比,2020年原料的霉菌毒素污染程度较轻。     

粮食加工品中玉米赤霉烯酮和呕吐毒素污染 情况调查

目的初步了解粮食加工品中玉米赤霉烯酮和呕吐毒素的污染情况。方法对北京地区和网购的200批次样品进行随机抽检,分别采用液相色谱法、免疫亲和层析净化高效液相色谱法对粮食加工品中的玉米赤霉烯酮和呕吐毒素进行了检测。结果初步调查发现玉米碾磨加工品中的玉米赤霉烯酮和小麦粉中的呕吐毒素检出率较高,分别达34%和74%;散装样品中玉米赤霉烯酮含量不合格率和检出率明显高于预包装样品。结论建议监管部门加强对散装玉米碾磨加工品和小麦粉等粮食加工品中毒素指标的监控力度和监测频次,同时针对我国特殊敏感人群加快设定合理限值。     

基于能力验证活动对玉米真菌毒素快检技术的评价

玉米原粮贸易过程中,真菌毒素快检是主要的卫生指标检测技术之一,但由于真菌毒素在原粮中的污染通常分布极不均匀,造成了检测数据差异大,准确性难于评估等问题。本研究通过广泛筛查玉米原粮天然真菌毒素污染物,研制满足均匀性、稳定性要求的玉米中脱氧雪腐镰刀菌烯醇（DON）、玉米赤霉烯酮（ZEN）质量控制样品。通过组织行业内企业参加原粮检测化验室能力验证活动,评价粮食中真菌毒素快检技术的应用情况。本研究报名参加毒素快检能力验证共153家企业,其中仓储粮库占36%、饲料养殖企业占64%。实验室遍布17个省、市、自治区,均采用食品快速检验技术检测并报送数据。DON及ZEN能力验证稳健CV分别为26%及29%,一定程度上反应了原粮毒素快检的实际使用情况,为提升快检技术及实验室原粮检测能力,提供行业数据支持。     

Mycotoxins in infant cereal foods from the Canadian retail market

Three hundred and sixty-three samples of cereal-based infant foods were collected from the Canadian retail marketplace over 3 years. The samples included oat-, barley-, soy-, and rice-based infant cereals, mixed-grain infant cereals, teething biscuits, creamed corn, and soy-based formulas. Samples were analysed for targeted mycotoxins (deoxynivalenol, nivalenol, HT-2 toxin, zearalenone, ochratoxin A, fumonisins B₁ and B₂, and five ergot alkaloids). Soy-based cereals (which usually contain corn) exhibited the highest incidences of deoxynivalenol (100%), zearalenone (46%) and fumonisins (75%). Overall, deoxynivalenol was the most frequently detected mycotoxin -- it was detected in 63% of samples analysed. Survey results demonstrated the regular occurrence of multiple mycotoxins in cereal-based infant foods.     

Stability of mycotoxins during food processing

The mycotoxins that commonly occur in cereal grains and other products are not completely destroyed during food processing operations and can contaminate finished processed foods. The mycotoxins most commonly associated with cereal grains are aflatoxins, ochratoxin A, fumonisins, deoxynivalenol and zearalenone. The various food processes that may have effects on mycotoxins include sorting, trimming, cleaning, milling, brewing, cooking, baking, frying, roasting, canning, flaking, alkaline cooking, nixtamalization, and extrusion. Most of the food processes have variable effects on mycotoxins, with those that utilize the highest temperatures having greatest effects. In general the processes reduce mycotoxin concentrations significantly, but do not eliminate them completely. However, roasting and extrusion processing show promise for lowering mycotoxin concentrations, though very high temperatures are needed to bring about much of a reduction in mycotoxin concentrations. Extrusion processing at temperatures greater than 150 degrees C are needed to give good reduction of zearalenone, moderate reduction of alfatoxins, variable to low reduction of deoxynivalenol and good reduction of fumonisins. The greatest reductions of fumonisins occur at extrusion temperatures of 160 degrees C or higher and in the presence of glucose. Extrusion of fumonisin contaminated corn grits with 10% added glucose resulted in 75-85% reduction in Fumonisin B(1) levels. Some fumonisin degredation products are formed during extrusion, including small amounts of hydrolyzed Fumonisin B(1) and N-(Carboxymethyl) - Fumonisin B(1) and somewhat higher amounts of N-(1-deoxy-d-fructos-1-yl) Fumonisin B(1) in extruded grits containing added glucose. Feeding trial toxicity tests in rats with extruded fumonisin contaminated corn grits show some reduction in toxicity of grits extruded with glucose.     

Distribution of Fusarium mycotoxins in UK wheat mill fractions

The EU has set maximum limits for the Fusarium mycotoxins, deoxynivalenol (DON) and zearalenone (ZON). The maximum permitted level decreases from unprocessed wheat, through intermediary products, e.g. flour, to finished products such as bakery goods and breakfast cereals. It is, therefore, important to understand the effects of processing on the mycotoxin distribution in mill fractions. Between 2004 and 2007, samples were taken at commercial flour mills at various points in the milling process and analysed for trichothecenes and ZON. Samples with a range of mycotoxin concentrations harvested in 2004 and 2005 were processed in a pilot mill and the mycotoxins in the different mill fractions quantified. In the commercial samples, DON was the predominant mycotoxin with highest levels detected in the bran fraction. Analysis of the pilot mill fractions identified a significant difference between the two years and between mycotoxins. The proportion of DON and nivalenol in the mill fractions varied between years. DON and nivalenol were higher in flour fractions and lower in bran and offal in samples from 2004 compared to samples from 2005. This may be a consequence of high rainfall pre-harvest in 2004 resulting in movement of these mycotoxins within grains before harvest. There was no significant difference in the distribution of ZON within mill fractions between the two years. For DON, higher concentrations in the grain resulted in a greater proportion of DON within the flour fractions. Understanding the factors that impact on the fractionation of mycotoxins during milling will help cereal processors to manufacture products within legislative limits.     

Occurrence and dietary exposure assessment of multiple mycotoxins in corn-based food products from Shandong,China

This study was designed to investigate the occurrence and exposure assessment of multiple mycotoxins in corn-based food products from Shandong Province, China. Results demonstrated that the mean level of total mycotoxins in test samples was 197.2 µg/kg. The most frequently found mycotoxins were deoxynivalenol (96.7%) and fumonisin B₁ (94.4%), with mean contamination levels of 65.24 and 128.2, respectively. Among these corn-based food products, thin corn pancake had the highest mean contamination (886.7 µg/kg), followed by wotou (143.7 µg/kg), corn cake (135.4 µg/kg) and mantou (63.73 µg/kg). The average exposure values to total fumonisins and deoxynivalenol were 0.05 and 0.02 µg/kg bw/day, which were lower than the provisional maximum tolerable daily intake values of 2 and 1 µg/kg bw/day, respectively, as established by the Joint FAO/WHO Expert Committee on Food Additives. In the future strict control and systematic monitoring are needed to secure food safety and human health.     

Detection of masked mycotoxins derived from type A trichothecenes in corn by high-resolution LC-Orbitrap mass spectrometer

Masked mycotoxins (mycotoxin glucosides) derived from type A trichothecenes were detected in commercially available corn powder reference material. These new glucosides were identified as neosolaniol-glucoside (NESGlc) and diacetoxyscirpenol-glucoside (DASGlc) on the basis of accurate mass measurements of characteristic ions and fragmentation patterns using high-resolution liquid chromatography–Orbitrap mass spectrometric (LC-Orbitrap MS) analysis. Although the absolute structure was not clarified, 3-OH glucosylation appeared to be the most probable when considering the structures of neosolaniol and diacetoxyscirpenol and the fragmentation profiles of these masked mycotoxins. Concomitant detection of deoxynivalenol-3-glucoside, the most well-known masked mycotoxin derived from the type B trichothecene, deoxynivalenol, in the identical material further supports this probability.     

河北地区面制品中脱氧雪腐镰刀菌烯醇及其衍生物和玉米赤霉烯酮污染水平调查与分析

目的了解河北地区面制品中脱氧雪腐镰刀菌烯醇(deoxynivalenol,DON)及其衍生物3-ADON、15-ADON和玉米赤霉烯酮(zearalenone,ZEN)污染状况。方法对河北地区79份烘烤食品(饼干、面包)、87份生面制品和89份馒头样品进行调查分析。样品经乙腈:水(84:16, V:V)溶液超声离心提取后,通过多功能固相萃取柱进行净化处理,采用高效液相色谱-串联质谱法进行检测。结果 255份样品中,3A-DON、15A-DON和ZEN检出率均不高;DON检出率较高,共检出阳性样品252份,检出率为98.8%,超标样品10份,超标率为3.9%。4种真菌毒素污染较为严重的样品为饼干样品,其检出率和超标率明显高于其他面制品。结论在面制品中,主要的污染物为DON,污染最严重的样品类别为饼干样品,其污染状况应引起关注。