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    气相色谱-质谱法测定食品中17种邻苯二甲酸酯类塑化剂的含量

    Determination of 17 Phthalates Plasticizers in Food by Gas Chromatography-Mass Spectrometry

    • 摘要: 应用气相色谱-质谱法测定了食品中17种危害人体健康的污染物-邻苯二甲酸酯类(PAEs)塑化剂的含量。选择了白酒等12种不同类别的食物作为分析样品,样品的前处理参照国家标准GB 5009.271-2016中所述方法进行。选择正己烷作为溶剂提取样品中的PAEs,在30℃下超声提取30 min。对一些基体效应较明显的样品(如菠菜、芹菜、芒果汁和奶粉等),需经N-丙基乙二胺和硅吸附剂复合填料(PSA/Silica)玻璃固相萃取柱净化处理,洗脱方法参照上述国家标准方法。色谱分离中选择非极性色谱柱(DB-5MS),并适当降低初始温度(60℃)和在60~290℃之间的程序升温速率。在此条件下,17种PAEs可得到很好的分离。质谱测定中采用电子轰击离子源和选择离子监测模式。用外标法定量。结果表明:17种PAEs的质量浓度均在0.05~2.0 mg·L-1内与其对应峰面积呈线性关系,其检出限(3S/N)为0.003~0.020 mg·L-1。按标准加入法进行加标回收试验,一些基质较复杂的样品(如奶粉、蔬菜等)的回收率偏高很多,而一些基质较简单的样品(如白酒、食醋等)的回收率则稍有偏高。其测定值的相对标准偏差(n=6)均小于10%。另根据12种食品样品的分析结果,推测其中测出的PAEs可能来自生产过程中或之后的运输、包装等过程中接触了塑料制品所致。

       

      Abstract: Gas chromatography-mass spectrometry was applied to the determination of 17 phthalates (PAEs), which were proved to be harmful to human health, in 12 kinds of food. Pretreatment of the samples was carried out as described in GB 5009.271-2016. The sample was extractred ultrasonically with n-hexane at 30℃ for 30 min. For some samples (such as spinach, celery, mango juice and milk powder etc.) behaving to show high matrix effects, purification of the n-hexane extract by SPE on PSA/Silica glass column was performed and eluted as described in GB 5009.271-2016. The gas chromatography separation was modified by using the non-polar DB-5MS chromatographic column and selecting a lower initial temperature (60℃) and a lower rate of temperature elevation from 60℃ to 290℃, in order to have a better separation of the 17 PAEs. EI and SIM mode were adopted and the outer standard method for quantification was used in mass spectrometry determination. It was shown that linear relationships between values of mass concentration of the 17 PAEs and the respective peak areas were obtained in the same range of 0.05-2.0 mg·L-1, with their detection limits (3S/N) ranged from 0.003 mg·L-1 to 0.020 mg·L-1. Recovery was tested by the standard addition method, giving values of recovery much higher than for those samples with complex matrixes (such as milk powder, vegetables and etc.) while for those samples with relatively simple matrixes (such as white wine, vinegar and etc.), giving values of recovery a slight extent over 100%. Values of RSDs (n=6) were found all less than 10%. On the base of analytical results of 12 food samples of various categories obtained by this method, the sources of the PAE-contaminators were mainly due to contacts with the plasticizers during their growth, production, transportation, packaging and etc.

       

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