1. 中国检验检疫科学研究院
2. 大连理工大学生命与医药学院
3. 山东出入境检验检疫局检验检疫技术中心
4. 深圳出入境检验检疫局工业品检测技术中心
5. 江苏出入境检验检疫局工业产品检测中心
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孟宪双, 连显会, 白桦, 等. 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[J]. 分析测试学报, 2018,37(2):165-173.
Screening of Phthalates Plasticizers in Plastic Toys by Ultra-performance Liquid Chromatography-Hybrid Quadrupole Time-of-flight Mass Spectrometry[J]. 2018,37(2):165-173.
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C18柱(2.1 mm×50 mm,1.7 μm)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4.66~11.69 μg/kg和13.04~30.71 μg/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136.9 μg/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 C18 column(2.1 mm×50 mm,1.7 μm) 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(r2>0.996) were observed in the respective concentration ranges.The limits of detection(LODs) and limits of quantitation(LOQs) were in the ranges of 4.66-11.69 μg/kg and 13.04-30.71 μg/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.
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
phthalatesplasticizerssolid phase extractionultra performance liquid chromatography-hybrid quadrupole time-of-flight mass spectrometry(UPLC-Q-TOF MS)plastic toysscreening
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