张荧，魏立菲，刘胜玉，刘威，刘昕宇，李逸

珠江水资源保护科学研究所，珠江流域水环境监测中心，广州 510611

自动化前处理-气相色谱串联质谱法测定淡水鱼体中的有机磷阻燃剂

张荧*，魏立菲，刘胜玉，刘威，刘昕宇，李逸

珠江水资源保护科学研究所，珠江流域水环境监测中心，广州 510611

应用自动化前处理设备和气相色谱串联四级杆质谱仪建立了淡水鱼体中10种有机磷阻燃剂的检测方法。该方法先采用自动索氏提取仪进行样品的提取，再应用凝胶渗透色谱净化仪和florisil柱对提取液进行两级净化，最后用气相色谱串联四级杆质谱法(多反应监测模式)对样品中的有机磷阻燃剂(OPFRs)定性定量。实验表明，凝胶渗透色谱净化系统在以乙酸乙酯∶环己烷(1∶1，V/V)为流动相，流速为5.0 mL·min-1的条件下，收集OPFRs的最佳时间为900～1 680 s；方法的检出限为0.002～0.192 ng·g-1湿重，加标水平为5.000 ng·g-1湿重时，平均加标回收率为48.7%～122%，相对偏差除磷酸三乙酯(TEP)(17.7%)和磷酸三(1,3-二氯异丙基)酯(TDCP)(11.9%)外均小于10%。应用该方法测定采集于东江某污水处理厂入河排污口的鱼类样品时，回收率指示物(d27-TBP)的回收率为82.4%～114%，鱼类样品中∑OPFRs的浓度范围为nd～6.41 ng·g-1湿重。

有机磷阻燃剂；自动化；串联质谱；淡水鱼体

Received14 January 2017accepted20 March 2017

Abstract: An analytical method for the determination of 10 organophosphorus flame retardants (OPFRs) in freshwater fish samples was developed using automated equipment for pretreatment and gas chromatography-tandem mass spectrometry (GC-MS/MS) for quantification. In the present method, the samples were extracted using automatic soxhlet extraction system, and then a two-step clean-up (including automatic gel permeation chromatography (GPC) and florisil) was used to purify the extract. Finally, the GC-MS/MS was used for qualitation and quantitation by multi-reaction monitoring (MRM) mode. Experimental results showed that the best collection time of the automatic GPC system was from 900 to 1 680 seconds using ethyl acetate and hexane mixture (1:1, V/V) as mobile phase at a flow rate of 5.0 mL·min-1. The method detection limits ranged from 0.002 ng·g-1to 0.192 ng·g-1wet weight, and the recoveries were in the range of 48.7%-122%, with relative standard deviations (RSDs) of less than 10% except for triethylphosphate (TEP) (17.7%) and tris(1,3-dichloropropyl) phosphate (TDCP) (11.9%). The developed method was applied to determine the OPFRs in freshwater fish collected from an outlet of a sewage treatment plant in the East River. The recoveries of d27-TBP spiked in the samples ranged from 82.4% to 114%, and the total concentrations of OPFRs in the samples ranged from not detected to 6.41 ng·g-1wet weight.

Keywords: organophosphorus flame retardants; automation; tandem mass spectrometry; freshwater fish

近30年来，阻燃剂在减少火灾引起的生命财产损失方面发挥了重要的作用。然而，部分阻燃剂由于具有持久性、生物富集性和环境毒性等，进入环境后，可能对生物体和人类产生危害。随着各国对溴代阻燃剂(brominated flame retardants, BFRs)环境效应的关注以及BFRs的禁用，有机磷阻燃剂(organophosphorus flame retardants, OPFRs)的产量快速提高，据欧洲阻燃剂协会的统计，2006年西欧OPFRs的产量大约为91 000 t·a-1，比2005年提高了7.1%，比2001年提高了9.6%[1]。……