全蒸发顶空-气相色谱-质谱法快速测定塑料玩具中的致敏性芳香剂

Determination of Fragrance Allergens in Plastic Toys by Full Evaporation Headspace with Gas Chromatography-Mass Spectrometry

建立了全蒸发顶空-气相色谱-质谱技术(FEHS-GC-MS)快速检测ABS塑料玩具中54种致敏性芳香剂的方法。玩具样品经粉碎后采用丙酮溶解-甲醇沉淀的方式进行提取,以将芳香剂完全提取至溶液中,取上清液40μL加入顶空瓶,在优化的顶空条件下(平衡温度200℃,平衡时间6 min,辅助气压力80 kPa),芳香剂及溶剂全部蒸发转移至气态,并在6 min内形成动态平衡,然后将定量环中1 mL气体引入至GC-MS检测。通过DB-35MS色谱柱分离,外标法定量。结果表明,塑料基质由于沉积在瓶底,未对检测结果产生明显干扰。本方法对于不同物质的定量限(LOQ)为0.5~15 mg/kg,在线性范围0.5~750 mg/kg内相关系数大于0.9987。3个浓度添加水平的回收率在81.0%~135.7%之间,相对标准偏差(RSD,n=6)为1.7%~16.8%。采用本方法对20个玩具实际样品进行了检测。本方法操作简便、快速、准确、成本低,可为塑料样品中挥发物及半挥发物的快速检测提供参考。

A rapid method based on a full evaporation headspace gas chromatography-mass spectrometry（ FEHS-GC-MS） for determination of 54 fragrance allergens in ABS plastic toys was developed. The samples were extracted by dissolution-precipitation approach. In this way,a complete extraction of fragrances could be obtained from plastic samples. Then 40 μL of supernatant was transferred into a headspace vial. Under the optimized headspace conditions（ equilibration temperature = 200℃; equilibration time = 6 min; pressing pressure = 80 k Pa）,the fragrances and solvent were evaporated to gaseous state quickly and reached dynamic equilibrium within 6 min,then 1 mL of gas in the quantitative loop was introduced to GC-MS. The separations were performed on a DB-35 MS column and then quantified by external standard method. As the plastic matrix was deposited at the bottom of the vial,the results showed that the interference caused by different sample matrices was negligible. The proposed method exhibited sufficient sensitivity with LOQ of 0.5-15 mg/kg for all fragrances. The calibration curves showed good linearity in the range of 0. 5-750 mg/kg with the correlation coefficients greater than 0.9987. The average recoveries ranged from 81.0% to 135.7%,and the RSD（ n = 6）varied from 1.7% to 16.8%. Finally,the method was applied to monitor the fragrances in 20 commercial toys.This study provides a good reference for rapidly determining the volatile organic compounds and semi-volatile organic compounds in plastic samples.