气相色谱/电感耦合等离子体质谱联用法测定儿童塑料玩具中多溴联苯醚及有机磷酸酯阻燃剂
Determination of polybrominated diphenyl ethers and organophosphate esters in children's plastic toys using gas chromatography-inductively coupled plasma mass spectrometry
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摘要: 本研究基于气相色谱串联电感耦合等离子体质谱技术（GC-ICP-MS），建立并优化了儿童塑料玩具中常见的3种多溴联苯醚（PBDEs）和3种有机磷酸酯（OPEs）的同时测定新方法，其中包括2，2'，4，4'，5-五溴联苯醚（BDE-99）、2，2'，4，4'，5，5'-六溴联苯醚（BDE-153）、十溴联苯醚（BDE-209）、三（正丁基）磷酸酯（TNBP）、2-乙基己基二苯基磷酸酯（EHDPP）、磷酸三-2-乙基己基酯（TEHP）.采用甲苯超声辅助萃取技术对聚丙烯（PP）、丙烯腈一丁二烯一苯乙烯共聚物（ABS）和聚氯乙烯（PVC）3种塑料材质的玩具样品进行样品前处理.通过优化，所建立的方法在0.20—10.00 μg·mL-1浓度范围内具有良好的线性关系（r2>0.99）.PBDEs的方法检出限和定量限分别为0.15—2.50 ng·g-1和0.40—6.00 ng·g-1，加标回收率为98.5%±5.5%.OPEs的检出限和定量限分别为10.00—38.00 ng·g-1和25.00—85.00 ng·g-1，加标回收率为92.5%±8.5%.应用实际样品对基质效应进行考察，结果表明PP、ABS和PVC基体对PBDEs和OPEs的响应没有明显的影响，所建立方法很好地控制了基质效应.将建立的方法应用于28个玩具样品的分析检测，分别检出了BDE-209、TNBP、EHDPP和TEHP，各化合物检出浓度范围为178.19—60628.77 ng·g-1.其中BDE-209的检出率最高，浓度范围为178.19—1088.59 ng·g-1，通过与欧盟颁布的REACH指令阈值比较，表明当前BDE-209的检出浓度未超过指令的限值.
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关键词:
- 气相色谱/电感耦合等离子联用 /
- 多溴联苯醚 /
- 有机磷酸酯 /
- 塑料玩具
Abstract: An analytical method based on gas chromatography-inductively coupled plasma mass spectrometry (GC-ICP-MS) for simultaneous determination of three polybrominated diphenyl ethers (PBDEs) and three organophosphate esters (OPEs) in plastic toys was developed and optimized. The target analytes were 2,2', 4,4', 5-pentabromobiphenyl ether (BDE-99), 2,2', 4,4', 5,5'-hexabromobiphenyl ether (BDE-153), decabromobiphenyl ether (BDE-209), tri (n-butyl) phosphate (TNBP), 2-ethylhexyl diphenyl phosphate (EHDPP) and tri-2-ethylhexyl phosphate (TEHP). Polypropylene (PP), acrylonitrile-butadiene-styrene copolymer (ABS), and polyvinyl chloride (PVC) materials were obtained as target matrices. Ultrasonic-assisted extraction with toluene was used for sample preparation. The developed method exhibited satisfying linearity in the concentration range of 0.20—10.00 μg·mL-1 (r2> 0.99). The detection limit (LOD) and limit of quantitation (LOQ) for PBDEs were 0.15—2.50 ng·g-1 and 0.40—6.00 ng·g-1. The spiked recovery was 98.5% ±5.5%. The LOD and LOQ for OPEs were 10.00—38.00 ng·g-1 and 25.00—85.00 ng·g-1 and the spiked recovery was 92.5% ±8.5%. The matrix effect was investigated using spiked plastics. No obvious matrix effects were observed for all three plastic materials. To further verify its practicability, the method was applied to the analysis of 28 toy samples. BDE-209, TNBP, EHDPP and TEHP were detected in some samples. The detected concentration of each compound was in the range of 178.19—60628.77 ng·g-1. The detected ratio of BDE-209 was highest with a concentration range of 178.19—1088.59 ng·g-1. The levels of detected BDE-209 were under the threshold value of the REACH regulation published by European Union. -
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