超高效液相色谱-四极杆-飞行时间质谱法筛查塑料玩具中邻苯二甲酸酯类增塑剂  

Screening of Phthalates Plasticizers in Plastic Toys by Ultra-performance Liquid Chromatography-Hybrid Quadrupole Time-of-flight Mass Spectrometry

作　　者：孟宪双[1] 连显会 白桦[1] 牛增元[3] 谢堂堂[4] 丁友超 薛宏宇 马强[1] MENG Xian-shuang;LIAN Xian-hui;BAI Hua;NIU Zeng-yuan;XIE Tang-tang;DING You-chao;XUE Hong-yu;MA Qiang(Chinese Academy of Inspection and Quarantine,Beijing 100176,China;School of Life Science and Medicine, Dalian University of Technology,Panjin 124221,China;Inspection and Quarantine Technical Center, Shandong Entry-Exit Inspection and Quarantine Bureau,Qingdao 266002,China;Testing and Technology Center for Industrial Products,Shenzhen Entry-Exit Inspection and Quarantine Bureau,Shenzhen 518067,China;Industrial Products Testing Center,Jiangsu Entry-Exit Inspection and Quarantine Bureau,Nanjing 210019,China)

机构地区：[1]中国检验检疫科学研究院,北京100176 [2]大连理工大学生命与医药学院,辽宁盘锦124221 [3]山东出入境检验检疫局检验检疫技术中心,山东青岛266002 [4]深圳出入境检验检疫局工业品检测技术中心,广东深圳518067 [5]江苏出入境检验检疫局工业产品检测中心,江苏南京210019

出　　处：《分析测试学报》2018年第2期165-173,共9页Journal of Instrumental Analysis

基　　金：国家重点研发计划资助项目(2016YFF0203702);中央级公益性科研院所基本科研业务费专项资金资助项目(2016JK010)

摘　　要：建立了塑料玩具中15种邻苯二甲酸酯类增塑剂的超高效液相色谱-四极杆-飞行时间质谱(UPLC-Q-TOF MS)筛查与定量检测方法。不同基质的塑料玩具样品采用溶剂溶解-超声提取-沉淀分离,经石墨化碳固相萃取柱净化、旋转蒸发和氮吹浓缩后,以C_(18)柱(2.1 mm×50 mm,1.7μm)梯度洗脱分离,在电喷雾正离子及一级全扫描和信息相关二级全扫描模式下检测。以一级精确质量数、同位素分布、保留时间及二级质谱与数据库匹配结果 4种手段准确定性,一级提取离子的峰面积定量。实验结果表明,15种邻苯二甲酸酯的质量偏差均小于3 ppm,在各自线性范围内线性关系良好,相关系数(r2)均大于0.996,检出限和定量下限分别为4.66~11.69μg/kg和13.04~30.71μg/kg,日内和日间精密度分别小于3.8%和6.7%,低、中、高3个加标水平的回收率为80.5%~108.3%,相对标准偏差(n=6)为0.4%~12.3%。在实际样品检测中,1例塑料玩具样品中检出邻苯二甲酸苄基丁基酯,含量为136.9μg/kg。该方法准确、高效、灵敏度高,可用于塑料玩具的实际检测。An analytical method was developed for the rapid screening and quantitative detection of fifteen phthalates(PAEs)plasticizers in plastic toys by ultra-performance liquid chromatography-hybrid quadrupole time-of-flight mass spectrometry(UPLC-Q-TOF MS).Plastic toy samples of different matrixes were extracted by a solvent dissolution-ultrasound extraction-precipitation seperation,cleaned up with a graphite carbon solid phase extraction column and concentrated by rotary evaporation and nitrogen blowing,then separated on a C 18 column(2.1 mm×50 mm,1.7μm)by gradient elution,and detected in positive electrospray ionization(ESI+)and information dependent acquisition(IDA)MS/MS mode.The qualitative analyses for fifteen PAEs were performed by the synergic combination of the accurate m/z of TOF MS,isotopic distribution,retention time and library search results.The quantitative analyses were performed using the peak area of the extracted m/z of TOF MS.Experimental results demonstrated that a favorable mass accuracy less than 3 ppm was obtained for fifteen PAEs,and good linearities(r 2>0.996)were observed in the respective concentration ranges.The limits of detection(LODs)and limits of quantitation(LOQs)were in the ranges of 4.66-11.69μg/kg and 13.04-30.71μg/kg,with intra-day and inter-day(n=7)precision less than 3.8%and 6.7%,respectively.The recoveries at three spiked levels ranged from 80.5%to 108.3%,with relative standard deviations(RSDs,n=6)of 0.4%-12.3%.The present method was practically used to detect butyl benzyl phthalate in a plastic toy.This method was proved to be accurate,efficient and specific,and could be applied for the inspection of commercial plastic toys.

关 键 词：邻苯二甲酸酯 增塑剂 固相萃取 超高效液相色谱-四极杆-飞行时间质谱 塑料玩具 筛查 

分 类 号：O657.7[理学—分析化学] O657.63[理学—化学]