大气压气相色谱串联质谱法测定牛奶中的9种新型溴代阻燃剂

Determination of nine novel brominated flame retardants in milk by atmospheric pressure gas chromatography-triple quadrupole mass spectrometry

目的建立了一种基于大气压气相色谱串联质谱(APGC-MS/MS)同时测定牛奶中9种新型溴代阻燃剂(NBFRs)的方法,并对提取溶剂和净化方法进行了优化。方法冻干牛奶样品经正己烷/二氯甲烷(1∶1,V/V)提取后,采用GPC净化,浓硫酸进一步除脂后,采用多反应监测模式进行分析。结果目标化合物在一定浓度范围内线性关系良好,R2均>0.99,检测限(LOD)和定量限(LOQ)分别为0.0002~0.0984μg/L(fw)和0.0005~0.2952μg/L(fw)。采用空白牛奶进行加标回收实验,加标回收率为73.94%~116.98%,精密度不大于19.30%。该方法已成功地应用于22份牛奶样品。其中,五溴甲苯、五溴乙苯、2-乙基己基-四溴苯甲酸、1,2-双(2,4,6-三溴苯氧基)乙烷和十溴二苯乙烷是主要的污染物,检出率分别为86.36%、100.00%、54.55%、50.00%和54.55%,浓度分别为0.001~0.20μg/L(fw)、<LOQ~0.06μg/L(fw)、<LOQ~0.11μg/L(fw)和<LOQ~0.85μg/L(fw)。结论本方法灵敏度高,精密度和准确度好,可用于牛奶中9种NBFRs的同时测定。

Objective A method was developed for the simultaneous determination of nine novel brominated fire retardants(NBFRs)in milk by atmospheric pressure gas chromatography-tandem mass spectrometry(APGC-MS/MS),and the extraction solvent and clean-up method were optimized.Methods The freeze-dried milk samples were extracted by hexane/dichloromethane(1∶1,V/V),cleaned up by GPC and further degreased by sulfuric acid,and then analyzed by Multi-selected reaction monitoring(MRM)mode.Results The result showed that there were good linear relationships for the target compounds in a certain concentration range,with their correlation coefficients(R2)no less than 0.99.The limits of detection and the limits of quantification(LOQs)were 0.0002-0.0984μg/L(fw)and 0.0005-0.2952μg/L(fw),respectively.The spiked recoveries were 73.94%-116.98%with RSD not more than 19.30%using blank milk.The method has been successfully applied to 22 milk samples.Among them,PBT,PBEB,EH-TBB,BTBPE and DBDPE were the major contaminants with the detection rates of 86.36%,100.00%,54.55%,50.00%and 54.55%,respectively.The concentrations were 0.001-0.20μg/L(fw),<LOQ-0.06μg/L(fw),<LOQ-0.11μg/L(fw)and<LOQ-0.85μg/L(fw),respectively.Conclusion The method was sensitive,precise and accurate,and can be used for the simultaneous determination of 9 NBFRs in milk.