海产贝类脂溶性贝毒素的高效液相色谱-串联质谱分析方法及其食用安全性评价

Development of A High Performance Liquid Chromatography-Tandem Mass Spectrometry Method for Determination of Lipophilic Toxins in Marine Shellfishes and Edible Safety Evaluation

针对海产贝类存在多种脂溶性贝毒素复合污染的现状,采用高效液相色谱-串联质谱联用技术(HPLC-MS/MS)对海产贝类中的常见脂溶性贝毒素进行同步检测,结合多种毒素复合污染的风险评估方法,用于市售海产贝类的食用安全风险评价。结果表明,在选定的实验条件下,8种典型脂溶性贝毒素加标回收率在63.2%~88.8%之间,方法的精密度(相对标准偏差(RSD)≤14.5%)和灵敏度(检出限为0.5~2.7 ng/g)良好,能满足海产贝类样品的检测要求。在采集的105个市售海产贝类样品中,42.86%的样品中至少检出了一种脂溶性贝毒素,其中鳍藻毒素-1(DTX1)的含量均值最高,为47.6μg/kg,对海产贝类污染最严重。根据每日人均贝类摄入量(TDI)和各种脂溶性贝毒素的急性中毒参考剂量(ARf D),通过计算综合风险指数∑ERI进行市售海产贝类食用安全性评价,结果表明,在所检测的样品中,存在食用安全隐患和高风险的市售海产贝类比率为19.05%,其中扇贝的食用安全风险最大。本研究建立的基于海产贝类中脂溶性贝毒素物质组复合污染的风险评价方法,与欧盟的海产品贝毒素限量标准评价方法(单指标法)相比更加严格,可以使贝类食用者更好地规避中毒风险。

In view of the present situation that edible marine shellfishes are combinedly contaminated by different kinds of lipophilic toxins,common lipophilic shellfish toxins in marine shellfishes were simultaneously detected by liquid chromatography-tandem mass spectrometry,and the safety risk of commercial marine shellfish was evaluated using the risk assessment method based on combined contamination of various toxins.Under the optimum conditions, satisfactory recoveries（ 63. 3%-88. 8%）, precision（ relative standard deviations RSD≤14.5%） and sensitivity（ limit of detection in the range of 0.5-2.7 ng/g） of the method were achieved for all the analytes. Among the 105 commercially available shellfish samples,42.86% of the samples had at least a kind of toxin. The highest average content was 47.6 μg/kg of DTX1,which was the most serious contaminant for marine shellfishes. The total Expose Risk Index（ ΣERI） was calculated based on Tolerable Daily Intake（ TDI） and Acute Reference Dose（ ARf D） of each toxin to evaluate the safety risk of commercial marine shellfish. The results showed that the ratio of commercially available marine shellfish with safety risk was 19.05% and the food safety risk of scallop was the highest. In summary,a new method based on the combined contamination of lipophilic shellfish toxins was successfully developed for risk assessment of the commercial marine shellfish. The proposed method is more harsh compared with the European Food Safety Authority（ EFSA） regulation and can make shellfish consumers better to avoid the risk of poisoning.