固相萃取-气相色谱/质谱联用法测定儿童手推车中3种有机磷酸酯阻燃剂

Determination of three organophosphate ester flame retardants in baby carriages by gas chromatography-mass spectrometry combined with solid phase extraction

有机磷酸酯是一类重要的磷系阻燃剂,由于其具有类似持久性有机污染物（persistent organic pollutants,POPs）的性质,欧美等国家已纷纷设立相关法规限制其在儿童用品中的使用。目前国际和国内均未有儿童手推车中有机磷酸酯阻燃剂的检测标准。本文建立了儿童手推车中3种有机磷酸酯阻燃剂的超声萃取-弗罗里硅土固相萃取柱净化-气相色谱/质谱检测方法。该方法的加标回收率为89.5%~107.3%,检出限（3S/N）为0.01 mg/kg,定量限（10S/N）为0.1 mg/kg,能较好地排除基质干扰,适用于儿童手推车软垫材料中3种有机磷酸酯的定性和定量分析。37个样品的分析结果表明,磷酸三（2-氯丙基）酯（TCPP）的检出率为81.1%,含量范围为1.0~15 312.8mg/kg,依据欧盟玩具新指令2014/79/EU,TCPP超标（〉5 mg/kg）率为32.4%;其中2个样品中还检出了磷酸三（2-氯乙基）酯（TCEP）和磷酸三（1,3-二氯-2-丙基）酯（TDCP）,含量范围为6.2~44.1 mg/kg,均已超标。可见,市场上的儿童手推车存在较高的有机磷酸酯阻燃剂暴露风险。

Organophosphate esters（OPEs） are high-production-volume chemicals used as flame retardants. Some western countries（e. g. America and European Union）have imposed restrictions on OPEs in baby products due to their similar persistent-organic-pollutants（POPs）properties. So far,there is no domestic or foreign standard for OPEs flame retardants in baby carriages. Ultrasonic extraction was used to extract three OPEs from baby carriages,and the extracts were purified by a florisil solid phase extraction（SPE）column,and finally detected by gas chromatography-mass spectrometry（GC-MS）. The spiked recoveries of the three OPEs were in the range of 89. 5% to 107. 3%. The limits of detection（3S / N）were 0. 01 mg / kg,and the limits of quantification（10S / N） were 0. 1 mg / kg. This method could eliminate matrix effects and give accurate qualitative analytical results for the three OPE flame retardants in baby carriages. Thirty-seven samples were analyzed and the tris（2-chloro-1-methylethyl）phosphate（TCPP）detection rate was up to 81. 1% with the mass concentration range of 1. 0-15 312. 8mg / kg,and 32. 4% of the samples exceeded the European Union directive（2014 / 79 / EU）for TCPP（ 5 mg / kg）,as well as tris（2-chloroethyl） phosphate（TCEP） and tris[2-chloro-1-（chloromethyl）ethyl]phosphate（TDCP）in two samples,which were in the range of 6. 2-44. 1mg / kg. Thus,relatively high OPEs flame retardants risk was presented in baby carriages.