基于GC-MS/MS法检测玩具中的20种可迁移有机锡

Determination of 20 Migratable Organotins in Toys Based on GC-MS/MS Method

为解决第二类玩具材料中有机锡定量限难以达到的问题,同时增加玩具检测的可迁移有机锡化合物(OTCs)种类,以第二类玩具材料为研究对象,通过对实验条件的优化调整,建立了一种能同时测定玩具中20种可迁移OTCs的气相色谱串联质谱(GC-MS/MS)检测方法。在样品中的OTCs经模拟胃液(盐酸)迁移及衍生剂(四乙基硼酸钠)衍生化后,采用多反应监控模式(MRM)进行分析,并对迁移条件、衍生步骤及GC-MS/MS工作参数等进行了优化。实验结果表明:20种OTCs的质量浓度在0.005~0.200 mg/L范围内时线性关系良好,线性相关系数为0.9963~0.9999;样品加标回收率为80.6%~117.2%,相对标准偏差小于5%(n=6);20种OTCs的方法检出限为0.019~3.196μg/kg,定量限为0.065~10.652μg/kg。与日常检测玩具中OTCs最常用的GC-MS测试方法相比,文中方法在20 min内可同时对20种OTCs进行分离和检测,选择性强,定量准确,灵敏度高,降低了检出限和定量限,有效解决了第二类玩具材料中有机锡定量限难以达到的问题,也弥补了目前玩具检测的OTCs种类少等局限性,是一种广泛、高效、灵敏、可靠的检测方法。

In order to solve the problem that the quantification limit of organotin in the second type of toy materials is difficult to reach,and to increase the types of migrating organotin compounds(OTCs)detected in toys,a gas chromatography-tandem mass spectrometry(GC-MS/MS)detection method capable of simultaneously determining 20 migrating OTCs in toys was established,by taking the second type of toy materials as the research object and optimizing the experimental conditions.After migration from simulated gastric juice(HCl)followed by derivatization using the derivatizing agent(sodium tetraethylborate),the OTCs were analyzed by multiple reaciton monitoring mode(MRM),during which,migration conditions,derivatization steps as well as operating parameters of GC-MS/MS were optimized.The experimental result shows that the 20 kinds of OTCs display good linear relationship in the concentration range from 0.005 to 0.200 mg/L with the linear correlation coefficients of 0.9963~0.9999.The spiked recoveries of OTCs in samples are in the range of 80.6%~117.2%with relative standard deviations less than 5%(n=6)and their detection limits are as low as 0.019~3.196μg/kg with the limit of quantifications between 0.065 and 10.652μg/kg.Compared with GC-MS,the most commonly employed method for OTCs detection in toys,the newly established method can separate 20 different kinds of OTCs within 20 min at one time,indicating the advantages of strong selectivity,accurate quantification,high sensitivity with a very low detection limit and quantitation limit,dissolving the problem that the quantitation limit of OTCs for the second type of toy materials was difficult to be achieved.Furthermore,this method also extends the detection limitation of OTCs types in toys to 20 types from the original 11 types given in the EU standard.The developed method was proved to be comprehensive,efficient,reliable and sensitive for fast determination of OTCs in toys.