粮食中新兴真菌毒素的污染现状及毒理学研究进展

产毒真菌污染粮食等农产品产生有毒有害的次级代谢产物,称真菌毒素,严重威胁食用和饲用产品的质量安全。较为常见的真菌毒素包括黄曲霉毒素、镰刀菌毒素脱氧雪腐镰刀烯醇、玉米赤霉烯酮等,国内外针对这些主要污染毒素制定了相应的限量标准。近年来,随着真菌毒素研究的发展和检测技术的更新,一些新型真菌毒素不断被发现。将目前尚未被列入常规风险筛查和监管、也尚无相关限量标准的真菌毒素种类,称谓新兴毒素（Emerging toxins）。目前检出频次高、污染较为严重的新兴毒素主要由镰刀菌属（Fusarium spp.）和链格孢属（Alternaria spp.）等产毒真菌产生。这些新兴真菌毒素通常与主要毒素复合污染,本文将依据现有的风险调查报告与数据,综述粮食中常见新兴镰刀菌和链格孢毒素的污染现状和毒理学研究进展,为真菌毒素的全面风险评估和管控技术研发提供依据。     

黄曲霉毒素限量标准对我国居民消费安全和花生产业的影响

2009-2010年对全国产后花生黄曲霉毒素污染进行了普查监测,根据检测结果,利用蒙特卡罗方法,开展了我国与国际食品法典委员会（CAC）、欧盟、日本、澳大利亚和新西兰等国际组织和主要贸易国不同花生黄曲霉毒素限量对我国人群直接食用产后花生的致癌风险和对产业影响的研究。结果表明,不同花生黄曲霉毒素限量标准对我国人群摄入产后花生导致的原发性肝细胞癌年发生率影响差异不显著,但对经济和产业造成的影响差异显著。研究结果为制定我国花生黄曲霉毒素限量标准以及促进花生生产、贸易提供技术参考。     

市售食品黄曲霉毒素污染的监测结果

2014年10月起,从龙湾区超市、菜市场等地区共采集市售样品448份,进行高效液相色谱测定。监测结果显示花生酱中黄曲霉毒素总量的检出率为84.0%,最高为39.392μg/kg,并有12.0%的花生酱黄曲霉毒素B1含量超出限量。玉米粉中黄曲霉毒素总量的检出率为23.33%,最高为17.458μg/kg,且有3.33%的玉米粉黄曲霉毒素B1含量超出限量。花生中黄曲霉毒素总量的检出率为54.0%,最高为5.383μg/kg。其他种类样品污染情况不明显,全部符合国家限量标准。因此得到结论,玉米粉、花生、花生酱是龙湾区受黄曲霉毒素污染的主要食品。监测食品中黄曲霉毒素B1、B2、G1、G2的污染状况,对国家制定食品限量标准及国际相应控制规范具有重要的现实意义。     

养殖对虾T-2毒素蓄积危害研究现状

我国饲料中T-2毒素污染严重,养殖水产动物长期摄入饲料中普遍污染的低剂量T-2毒素,可导致其肌肉残留和生长缓慢,肌肉品质下降,并存在食品安全风险。本文概述了国内外对虾饲料中T-2毒素污染现状,阐明对虾的潜在危害及其评价指标的研究现状,这对进一步开展水产品真菌毒素暴露风险评估和制定膳食接触标准具有重要意义。     

粮油加工副产物中真菌毒素消减技术研究进展

真菌毒素是一些真菌在生长繁殖过程中产生的有毒有害代谢物，其对粮油加工产业、畜牧业和食品工业造成经济损失的同时亦会威胁人类健康。粮油加工副产物中真菌毒素的污染率相对较高，这些污染的副产物用于畜牧业生产，会严重影响畜禽生产性能。对畜禽危害严重的真菌毒素主要有：黄曲霉毒素（aflatoxin，AF）、脱氧雪腐镰刀菌烯醇（又称呕吐毒素，Deoxynivalenol ，DON）、赭曲霉毒素（ochratoxin，OTA）、玉米赤霉烯酮（zenralenone，ZEN）、T-2毒素（属于单端孢霉烯族毒素）、伏马毒素（fumonisin，FB）等。受真菌毒素污染的饲料和谷物颜色、气味及营养成分会发生变化，导致适口性变差，营养价值降低，还会造成畜禽生长缓慢、免疫力降低、生殖障碍甚至死亡。我国《食品卫生标准（GB2761-2017）》对粮油食品中主要真菌毒素的限量有相应的控制标准。《饲料卫生标准（GB13078-2017）》也明确规定粮油加工副产物用作饲料时其中主要六种真菌毒素的限量标准。目前常用的真菌毒素脱毒方法有物理脱毒法、化学脱毒法、脱霉剂脱毒法等。在处理霉变畜禽饲料时，前两种方法都有一定的缺陷，通常采用添加真菌毒素脱霉剂来降低其对畜禽的危害。本文阐述了饲料中常用脱霉剂吸附剂和降解菌/酶以及脱霉剂体外和体内评估方法，总结了现有吸附剂和降解菌/酶对控制粮油副产物中真菌毒素的作用效果以及使用中存在的问题，并对真菌毒素消减技术的发展方向进行了展望，以期为解决资源浪费问题，促进粮油加工副产物的高效利用提供一定的参考价值。     

T-2毒素的危害及脱毒研究进展

T-2毒素是由镰刀属菌产生的一种次级代谢产物,属于单端孢霉烯族常见的A型真菌毒素。T-2毒素具有强毒性,它不仅会污染田间作物和库存谷物造成粮食产后损失,还会对人畜的健康造成巨大损害,是近年来全球范围内粮食行业和畜牧业防治的重点。目前关于T-2毒素生物毒性的研究比较深入,但关于T-2毒素脱毒,尤其是生物脱毒的研究较少。综述了T-2毒素的危害致毒机理及物理、化学、生物等脱毒方法。将获取高效脱毒酶和开发脱毒工艺作为研究重点,利于我国粮食、畜牧、副产物深加工等行业的良性发展。     

乳制品中肉毒杆菌安全事件警示

自恒天然乳粉事件发生后,对我国乳品行业产生了一定的不良影响,由此引发了一系列的问题。本文重点阐述了国际上一些国家在乳制品或食品标准中对肉毒杆菌及其毒素的限量标准现状及检测方法,以期为我国乳制品或食品中肉毒杆菌及其毒素标准的制订提供基础参考,为我国乳品加工行业提供相关技术指导。     

链格孢毒素危害及防控措施的研究进展

链格孢毒素主要是由链格孢霉（Alternaria）产生的次生代谢产物,在世界各地的食品中广泛存在,对人类健康构成严重威胁。因此,解析其毒性和发现危害防控措施已成为目前的研究重点。本文主要概述了食品中常见4种链格孢毒素的毒性、暴露风险、污染控制和毒性干预方法等,旨在为链格孢毒素的风险评估、安全限量标准和防控措施的制定提供参考,对保障食品安全和人类健康具有重要意义。     

贝类毒素检测方法研究进展及其国内外限量要求比较分析

贝类毒素是贝类产品的重要危害因子,其不仅对人类健康造成严重威胁,也影响到海产品加工及出口贸易的健康发展。许多国家和地区制定了相应的贝类毒素检测方法,并规定了贝类产品中毒素的限量要求。本文主要综述了小鼠生物法、酶联免疫吸附法、液相色谱法、液相色谱串联质谱法、生物传感器法等5种常用的贝类毒素检测方法,并分析了其发展趋势;梳理了我国及美国、欧盟、日本、韩国、澳大利亚、新西兰、西班牙等国家和地区的贝类毒素官方检测方法和限量要求,并对我国贝类毒素风险监测工作提出建议,为我国贝类产品质量安全提供数据和资源支持,对保障我国贝类产品养殖业及出口贸易的稳定发展具有重要意义。     

国内外主要粮油产品中真菌毒素限量、检测标准及风险评估现状分析

粮油食品以及动物源食品(奶、蛋、肉)在生产和储藏过程中易被真菌毒素污染,主要涉及毒素为黄曲霉毒素、玉米赤霉烯酮、脱氧雪腐镰刀菌烯醇、赭曲霉毒素A、伏马毒素和T2毒素等,这些毒素经食品流入食物链,会造成人体脏器损伤、生殖异常、免疫抑制、畸变和癌变等不良影响。因此,国内外针对性开展了风险评估工作,并建立了相关限量及检测技术标准。本文对主要粮油产品中常见真菌毒素的毒性进行了综述,比较分析了近年来国内外相关限量及检测标准的制定修订现状与进展,并对世界范围内相关风险评估工作进展进行了总结,以期为粮油产品的质量安全风险评估工作及有效应对国外贸易壁垒提供综合性的参考。     

Measurement of T-2 and HT-2 toxins in eggs by high-performance liquid chromatography with fluorescence detection

T-2 toxin is a mycotoxin produced by several species of common fungi capable of infesting human food and animal feeds. Lower-quality feeds given to chickens may be contaminated with T-2 toxin, which may affect their health. The literature suggests that T-2 toxin is transmitted from the hen to the eggs. This article describes the development of a liquid chromatographic assay for T-2 and the related mycotoxin HT-2 in eggs. T-2 and HT-2 toxins were isolated from spiked eggs with a tandem charcoal-alumina-Florisil column and immunoaffinity column cleanup. The isolated toxins were derivatized with the fluorophore 1-anthroyl nitrile, separated by high-performance liquid chromatography, and quantitated by fluorescence. The limit of detection of the method was 1 ng ml(-1) (parts per billion) of T-2 and HT-2 in whole (with shell removed) eggs. The limit of quantitation for both toxins was 5 ng ml(-1). Recoveries from spiked eggs over the range from 5 to 50 ng ml(-1) averaged 89.2% for T-2 and 100.3% for HT-2, with coefficients of variation of 3.5 and 8.2%, respectively. This method is sensitive enough to be used to check for the presence of T-2 or HT-2 toxins in eggs.     

QuEChERS-高效液相色谱-质谱法检测食品中14 种真菌毒素

建立QuEChERS-高效液相色谱-质谱检测食品中14 种真菌毒素的方法。均质样品用1%乙酸-乙腈提取,经分散固相萃取净化后,采用ACQUITU UPLC BEH C18色谱柱（2.1 mm×50 mm,1.7 μm）分离。采用电喷雾电离、多反应监测方式,可同时对食品中脱氧雪腐镰刀菌烯醇、青霉酸、黄曲霉毒素M1、黄曲霉毒素G2、桔青霉毒素、黄曲霉毒素B1、黄曲霉毒素B2、黄曲霉毒素G1、玉米赤霉烯酮、赭曲霉毒素A、杂色曲霉毒素、HT-2毒素、T-2毒素、鬼臼毒素14 种真菌毒素进行定性和定量分析。最低检出限为0.5～1 μg/kg。该方法简便快速、选择性佳、灵敏度高,适用于食品安全事件分析中真菌毒素的分析。     

Mycotoxin contamination of cereal grain commodities in relation to climate in North West Europe

This study aimed to investigate mycotoxin contamination of cereal grain commodities for feed and food production in North Western Europe during the last two decades, including trends over time and co-occurrence between toxins, and to assess possible effects of climate on the presence of mycotoxins. For these aims, analytical results related to mycotoxin contamination of cereal grain commodities, collected in the course of national monitoring programmes in Finland, Sweden, Norway and the Netherlands during a 20-year period, were gathered. Historical observational weather data, including daily relative humidity, rainfall and temperature, were obtained from each of these four countries. In total 6382 records, referring to individual sample results for mycotoxin concentrations (one or more toxins) in cereal grains were available. Most records referred to wheat, barley, maize and oats. The most frequently analysed mycotoxins were deoxynivalenol, 3-acetyl-deoxynivalenol, nivalenol, T-2 toxin, HT-2 toxin and zearalenone. Deoxynivalenol had the highest overall incidence of 46%, and was mainly found in wheat, maize and oats. Mycotoxins that showed co-occurrence were: deoxynivalenol and 3-acetyl-deoxynivalenol in oats; deoxynivalenol and zearalenone in maize and wheat; and T-2 toxin and HT-2 toxin in oats. The presence of both deoxynivalenol and zearalenone in wheat increased with higher temperatures, relative humidity and rainfall during cultivation, but the presence of nivalenol was negatively associated with most of these climatic factors. The same holds for both nivalenol and deoxynivalenol in oats. This implies that climatic conditions that are conducive for one toxin may have a decreasing effect on the other. The presence of HT-2 toxin in oats showed a slight decreasing trends over time, but significant trends for other toxins showed an increasing presence during the last two decades. It is therefore useful to continue monitoring of mycotoxins. Obtained results can be used for development of predictive models for presence of mycotoxins in cereal grains.     

果蔬制品中链格孢霉毒素检测与控制研究进展

链格孢霉属(Alternaria species)是链格孢霉毒素这种次级代谢产物的已知生产者。链格孢霉毒素具有明显的毒理学潜力,食用被其污染的果蔬和粮食产品会对消费者的健康造成威胁。果蔬营养丰富、含水量高,更易于被链格孢霉毒素感染,因此建立高效、简单、快速的检测技术和实现该毒素的高效控制一直是当今果蔬领域研究的热点。本文总结和分析了链格孢霉毒素常见的检测技术和控制方法,以期为链格孢霉毒素的快速检测和果蔬类食品安全控制与风险评估等提供参考。     

真菌毒素检测与限量标准的现状与问题分析

真菌毒素是一类由丝状真菌在适宜条件下产生的有毒次级代谢产物, 极易污染粮谷类食品、食用油及乳制品等, 具有肝毒性、肾毒性、致畸性、致癌性、免疫抑制及破坏生殖系统等毒性, 对人体危害极大, 是继农药残留、兽药残留、重金属污染后, 影响农产品质量安全的又一类关键风险因子, 极大的制约了我国农产品的出口贸易, 同时也造成了我国食品安全的又一问题。本文重点介绍了农产品中真菌毒素的类型品种、毒性特点以及不同检验方法的适用范围、限量及检出限, 阐述了真菌毒素限量标准的研究进展和标准内容, 通过比对国内外真菌毒素的研究种类和进展, 分析目前真菌毒素污染现状及存在的问题, 提出应对策略, 对真菌毒素污染检测的发展进行了展望, 对今后保障饮食安全提供科学依据。     

Use of cyclodextrins as modifiers of fluorescence in the detection of mycotoxins

Cyclodextrins, cyclic oligosaccharides composed of amylose subunits, are known to interact with mycotoxins. The interactions may be useful to analytical chemists by altering the properties of the mycotoxin of interest, namely the chromatographic properties, electrophoretic properties, fluorescence, or absorption of these fungal metabolites. Practical applications of these effects have been the incorporation of cyclodextrins into high-performance liquid chromatography and capillary electrophoresis methods for mycotoxin detection. Specific mycotoxins include those with a native fluorescence such as the aflatoxins, ochratoxin A (OTA) and zearalenone (ZEN) as well as those that can be rendered fluorescent through derivatization, such as T-2 toxin. The literature describing the applications of cyclodextrins in mycotoxin analysis is reviewed and an attempt to extend the use of cyclodextrins to the detection of labelled T-2 toxin is presented. Twenty cyclodextrins were evaluated for their ability to enhance the fluorescence emission of T-2 toxin derivatized with pyrene-1-carbonyl cyanide (T2-Pyr). This evaluation revealed that heptakis (2,6-di-O-methyl)-β-cyclodextrin (DIMEB), in particular, enhanced T2-Pyr fluorescence. DIMEB was used as a buffer modifier in a capillary electrophoresis-laser-induced fluorescence (CE-LIF) method for detecting T-2 in maize. Because of the effects that certain cyclodextrins have, especially under aqueous conditions, they may make useful additives for a variety of mycotoxin analytical methods.     

Integrated management of the risks of stored grain spoilage by seedborne fungi and contamination by storage mould mycotoxins – An update

Fungal spoilage of stored grains may occur when activity of water (aw) in cereal grain exceeds a critical limit enabling mould growth. Because it is not feasible to maintain all parts of large grain bulks below this critical moisture limit during prolonged storage time, an infection by seed-borne fungi is not rare in cereal grain stored under humid temperate or hot climates, inducing irreversible qualitative losses. Additionally, some fungal species produce harmful mycotoxins. The most harmful toxigenic species belong to the group of xerophilic species (genera Aspergillus and Penicillium). Because mycotoxin contamination of cereal grain is a worldwide issue for public health and a permanent concern for cereal-food industries facing the challenge of a permanent monitoring mycotoxin content in their primary matters, tolerable levels of mycotoxins are severely regulated worldwide. Mycotoxin-producing species growth is closely dependent of grain moisture levels enabling biological activity in grain ecosystem. Consequently, mould growth in stored grain bulks can be anticipated through early detection of grain and mould respiration. The prevention of mycotoxigenic fungi spoilage of stored grain can be managed by a preventive strategy. The main objective of the review was to describe the different methods, material and practices combined in such an integrated preventive approach. Some solutions potentially acceptable for the decontamination of moderately contaminated grain are also discussed.Integrated management of mould spoilage risks in stored grain is based on five pillars: i/Prevention of mould development by keeping grain moisture below the critical limit of fungal growth; ii/Accurate monitoring of grain aw and temperature changes during the storage period, associated to the monitoring of early indicators of respiration activity of storage fungi; iii/Reduction of grain bulk moistening trends by physical intervention means; iv/Use of physical treatments (ozone, grain peeling or abrasion) to limit mycotoxin contamination transfer to processed cereal products; v/Possible use of bio-competitive strains of fungi or bacteria to prevent the development of mycotoxigenic fungi in grain bulks. The future research needs on this topic are also evocated.     

Occurrence of mycotoxins in spelt and common wheat grain and their products

Organic farming does not allow the use of conventional mineral fertilizers and crop protection products. As a result, in our experiments we chose to grow different species of cereals and to see how cereal species affect mycotoxin accumulation. This study describes the occurrence of deoxynivalenol (DON), zearalenone (ZEA) and T-2/HT-2 toxin in a survey of spelt and common wheat and their bran as well as flour. The analysis was conducted using an enzyme-linked immunosorbent assay (ELISA) method. The concentrations of DON, ZEA and T-2/HT-2 in Triticum spelta and T. aestivum were influenced by species, cereal type and year interaction. The highest concentrations of these mycotoxins were found in spelt grain with glumes, in spelt glumes and in spring wheat. These results show significantly higher concentrations of Fusarium toxins in glumes than in dehulled grain, which indicates the possible protective effect of spelt wheat glumes. The lowest DON, ZEA and T-2/HT-2 concentrations were determined in spelt grain without glumes. The research shows that it is potentially risky to produce bran from grain in which mycotoxin concentrations are below limits by European Union Regulation No. 1881/2006, since the concentration of mycotoxins in bran can be several times higher than that in grain. As a result, although bran is a dietary product characterised by good digestive properties, it can become a harmful product that can cause unpredictable health damage.     

河南省粮食及其制品中真菌毒素污染情况调查

目的了解河南省市售粮食及其制品中真菌毒素污染的种类和程度。方法 2018—2019年采集河南省市售粮食及其制品,采用同位素稀释超高效液相色谱-串联质谱(UPLC-MS/MS)法测定16种真菌毒素含量,检测结果按照GB 2761—2017《食品安全国家标准食品中真菌毒素限量》进行评价分析。结果 100份玉米面、玉米渣及玉米粒中伏马菌素、玉米赤霉烯酮、黄曲霉毒素、脱氧雪腐镰刀菌烯醇是主要污染真菌毒素,检出率范围为0.0%～95.7%;220份小麦粉、面条和馒头中脱氧雪腐镰刀菌烯醇检出率分别为78.0%(124/159)、64.3%(18/28)和87.9%(29/33);其他真菌毒素含量较低或未检出。结论河南省粮食及其制品中存在不同程度的真菌毒素污染问题,尤其是玉米及其制品中伏马菌素有较高的检出率,应及时开展溯源调查,尽快采取相应控制措施。