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.
中图分类号 O657.63 DOI 10.11973/lhjy-hx202001008
所属栏目 工作简报
基金项目 浙江省食品药品监管系统科技计划项目(SP201713)
收稿日期 2018/11/6
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备注张国民,工程师,硕士,主要从事食品农产品检测分析工作,272101093@qq.com
引用该论文: ZHANG Guomin,WEN Susu. Determination of 17 Phthalates Plasticizers in Food by Gas Chromatography-Mass Spectrometry[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2020, 56(1): 46~54
张国民,温素素. 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[J]. 理化检验-化学分册, 2020, 56(1): 46~54
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【3】李晓芹,金尉,王莉莉.食品中邻苯二甲酸酯测定方法的优化[J].中国食品添加剂, 2017(1):178-183.
【4】李蕾,宋乃宁,李海山,等.邻苯二甲酸酯类毒理学效应及其机制研究进展[J].中国药理学与毒理学杂志, 2014,28(3):468-474.
【5】蔡艳,赵家青,贺小雨,等.食用油中邻苯二甲酸酯和己二酸酯的GC-MS定量分析与迁移特性研究[J].食品科学, 2014,35(12):191-195.
【6】SUNGUR S, OKUR R, TURGUT F H, et al. Migrated phthalate levels into edible oils[J]. Food Additives and Contaminants: Part B, 2015,8(3):190-194.
【7】韩清,刘正丹,徐立,等.固相萃取-气质联用测定饮用水中16种邻苯二甲酸酯的含量[J].公共卫生与预防医学, 2016,27(5):96-98.
【8】EDJERE O, POLLARD P, MAIER U. Trace determination of phthalates in ground water samples by GC-MS using specific sample concentration techniques[J].Journal of Emerging Trends in Engineering and Applied Sciences, 2016,7(3):128-132.
【9】马荣山,韩营,王凤兰,等.白酒酿造过程中塑化剂来源分析[J].食品科学, 2015,36(20):242-246.
【10】LENG G, CHEN W J, ZHANG M F, et al. Determination of phthalate esters in liquor samples by vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction followed by GC-MS[J]. Journal of Separation Science, 2014,37(6):684-690.
【11】杨春英,刘学铭,徐玉娟.果汁饮料中邻苯二甲酸二(2-乙基己基)酯的测定及其来源分析[J].食品科学, 2013,34(10):259-262.
【12】党富民,孙凤霞,卢春霞,等.奶牛场牛奶中邻苯二甲酸酯残留的来源分析[J].食品工业, 2016,37(6):206-208.
【13】REN R, JIN Q, HE H L, et al. Determination of 17 phthalate esters in infant milk powder and dairy products by GC-MS with 16 internal standards[J]. Chromatographia, 2016,79(13/14):903-910.
【14】郭浩楠,凌云,李玉玉,等.GC-MS法检测谷类、根茎类蔬菜中24种邻苯二甲酸酯[J].食品科学, 2013,34(16):164-168.
【15】易守福,李莎,郑利军,等.分散固相萃取-气相色谱-质谱法测定腐乳中16种邻苯二甲酸酯[J].食品科技, 2017,42(2):289-294.
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