超声提取-分散液液微萃取-气相色谱串联质谱法测定大气PM_(10)中的7种有机磷酸酯阻燃剂

Determination of seven organophosphate flame retardants in atmospheric particulate matter(PM;) by ultrasonic extraction-dispersed liquid-liquid microextraction combined with gas chromatography tandem mass spectrometry

建立了超声提取-分散液液微萃取联合气相色谱串联三重四极杆质谱测定大气中7种有机磷酸酯阻燃剂(磷酸三丙酯(TPrP)、磷酸三异丁酯(TiBP)、磷酸三正丁酯(TnBP)、磷酸三(1-氯-2-丙基)酯(TCIPP)、磷酸三(1,3-二氯-2-丙基)酯(TDCPP)、磷酸三苯酯(TPP)、磷酸三甲苯酯(TCP))的方法.本实验采用单因素优化法结合BBD实验设计法对超声波提取以及分散液-液微萃取的工艺参数进行优化后确定实验的最佳条件.样品以乙酸乙酯和丙酮(3∶2,V/V)混合溶液为提取剂进行超声提取,再采用分散液-液微萃取技术(纯水为纯化基质,四氯化碳为萃取剂,无水乙醇为分散剂)进一步提纯浓缩. 7种OPFRs的检出限为0.0049-0.3310 pg·m^(-3),定量下限为0.0158-1.0835 pg·m^(-3),加标回收率为70.0%-119.7%,相对标准偏差为0.2%-9.4%.将此方法用于苏州地区实际样品大气PM_(10)的检测,检测显示当地大气PM_(10)中存在大部分有机磷酸酯阻燃剂.

A method of ultrasonic extraction-dispersive liquid-liquid microextraction combined with gas chromatography-triple quadrupole tandem mass spectrometry(GC-MS/MS) was established for the determination of 7 organophosphate flame retardants(OPFRs)tripropyl phosphate(TPrP),triisobutyl phosphate(TiBP),tri-n-butyl phosphate(TnBP),tris(1-chloro-2-propyl) phosphate(TCIPP),tris(1,3-dichloro-2) ester(TDCPP),triphenyl phosphate(TPP),tricresyl phosphate(TCP).In this experiment,the single factor optimization method combined with BBD experimental design method was adopted to optimize the technological parameters of ultrasonic extraction and dispersed liquid-liquid microextraction.Finally,the optimal conditions for the experiment were determined.The samples were ultrasonic extracted with ethyl acetate and acetone(3:2,V/V) as the extraction agent,and then further purified and concentrated with the dispersive liquid-liquid microextraction technology(pure water as the purification matrix,carbon tetrachloride as the extraction agent,anhydrous ethanol as the dispersant).The results showed that the limits of detection(LOD) ranged from 0.0049 pg·m^(-3) to 0.3310 pg·m^(-3),and the limits of quantitative(LOQ) ranged from 0.0158 pg·m^(-3)to1.0835 pg·m^(-3).The spiked recoveries ranged from 70.0% to 119.7%,and the RSDs ranged from 0.2%to 9.4%.The method was applied to the actual atmospheric PM_(10)samples in Suzhou area,the results showed that most of the organophosphate flame retardants existed in the local atmospheric PM_(10).