高效液相色谱-四极杆飞行时间质谱测定塑料中短链氯化石蜡

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英文篇名：Determination of Short Chain Chlorinated Paraffins in Plastic by High Performance Liquid Chromatography Coupled with Electron Spray Ionization Quadrupole Time-of-flight Mass Spectrometry 作者：周熙 ; 吴惠勤 ; 黄芳 ; 黄晓兰 ; 林晓珊 ; 侯思润 ; 李荣锡 英文作者：ZHOU Xi;WU Hui-Qin;HUANG Fang;HUANG Xiao-Lan;LIN Xiao-Shan;HOU Si-Run;LI Rong-Xi;Guangdong Provincial Key Laboratory of Emergency Test for Dangerous Chemicals, Guangdong Provincial Public Laboratory of Analysis and Testing Technology, Guangdong Institute of Analysis; 关键词：短链氯化石蜡 ; 塑料制品 ; 高效液相色谱-飞行时间质谱 ; 气相色谱-电子捕获负化学电离源质谱 ; 固相萃取 英文关键词：Short chain chlorinated paraffins;;Plastic products;;High performance liquid chromatography-time-of-flight mass spectrometry;;Gas chromatography-negative chemical ionization mass spectrometry;;Solid phase extraction 中文刊名：FXHX 英文刊名：Chinese Journal of Analytical Chemistry 机构：广东省测试分析研究所广东省化学危害应急检测技术重点实验室广东省分析测试技术公共实验室; 出版日期：2019-02-01 15:55 出版单位：分析化学 年：2019 期：v.47 基金：广东省实施创新驱动发展能力建设专项资金项目(No.2018GDASCX-0919)资助~~ 语种：中文; 页：FXHX201904005 页数：8 CN：04 ISSN：22-1125/O6 分类号：50-57

摘要

建立了固相萃取结合高效液相色谱-电喷雾离子化-四极杆串联飞行时间质谱(HPLC-ESI-QTOF/MS)测定塑料制品中短链氯化石蜡(SCCPs)的方法。在ESI离子源中,无需添加氯代有机溶剂,以[M-H]~-离子检测。选取C_(10～13), Cl_(5～13)共30个SCCPs分子中丰度最高的两个同位素峰为定量与定性离子,通过高分辨质谱的精确质量数排除了相近分子量中链氯化石蜡(MCCPs)的干扰,解决了低分辨质谱对SCCPs检测结果不佳的问题。样品经二氯甲烷超声提取,提取液经硅胶柱净化,用正己烷-二氯甲烷(4∶1,V/V)洗脱。氯含量51.5%～63.0%的SCCPs仪器检出限为0.01～0.05 mg/L,方法检出限与定量限分别为1.4和4.6μg/g。在5、20和50μg/g加标水平下,回收率分别为118.0%±8.2%、81.9%±6.9%、77.8%±6.6%,日内相对标准偏差与日间相对标准偏差分别为5.7%与8.1%。对已知C_(10～13)含量的烷烃原料氯化后SCCPs含量进行测定,结果表明,烷烃中C_(10～13)含量与氯化后SCCPs含量一致,表明本方法的检测结果准确。4类塑料制品中SCCPs的测定结果表明,电缆与跑道中SCCPs含量较高(555～1049μg/g),玩具中SCCPs浓度较低(1.86～6.56μg/g)。
        A method of high performance liquid chromatography coupled with electron spray ionization quadrupole time-of-flight mass spectrometry was established for analysis of short chain chlorinated paraffins(SCCPs) in plastic. No chlorine solvent was added and SCCPs were quantified by their [M-H]~- ions. For each congener group of SCCPs with carbon chain lengths in 10-13 and chlorine substituents in 5-13, the two most abundant m/z signals were extracted from the full-scan mass spectra as the quantitative and qualitative ions. The influence of medium chain chlorinated paraffins(MCCPs) was eliminated efficiently based on the high resolution of the mass spectrometry. Plastic samples were extracted by dichloride methane and purified by silica gel solid phase extraction column. SCCPs were eluted by hexane/dichloride methane(1∶1, V/V). The instrumental detection limits(IDLs) were 0.01-0.05 mg/L for SCCPs with chlorine content from 51.5%-63%. Method detection limit(MDL) and quantitative limit were 1.4 μg/g and 4.6 μg/g, respectively. Recoveries of SCCPs were 118.0%±8.2%, 81.9%±6.9% and 77.8%±6.6%, at spiking concentrations of 5 μg/g, 20 μg/g and 50 μg/g, respectively. The intra-and inter-day variations were 5.7% and 8.1%, respectively. The quantitative results verified that SCCPs concentration in CPs were similar with the short chain alkane in the corresponding paraffin, which demonstrated the accuracy of this method. This method was applied in determination of four kinds of plastic samples. Cable and track presented to have a high concentration of SCCPs within the range of 555-1049 μg/g. Plastic toys had lower concentrations of SCCPs in the range of 1.86-6.56 μg/g.

引文

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