纺织品中9种有机磷酸酯类阻燃剂的超高效液相色谱-串联质谱快速测定方法

Rapid Determination of 9 Organophosphorous Flame Retardants in Textiles by Ultra High Performance Liquid Chromatography Tandem Mass Spectrometry

建立了纺织品中9种有机磷酸酯类阻燃剂的超高效液相色谱-串联质谱（UHPLC-MS/MS）测定方法。样品在密闭萃取瓶中于50℃用甲醇超声萃取30 min,萃取液过滤后直接进样;采用C18色谱柱分离、甲醇/水（含5.0 mmol/L甲酸铵）为流动相,进行梯度洗脱,电喷雾正离子模式电离,多重反应监测模式测定,外标法定量。实验优化了纺织样品的超声萃取条件及色谱分离、质谱测定条件,对不同类型纺织样品的基质效应进行详细研究并拟定了基质效应消除/补偿技术。优化实验条件下,方法的精密度（RSD,n=5）分别为棉布5.2%（TOCP）~12.5%（TRIS）、聚酯纤维6.4%（TBEP）~13.8%（TRIS）、羊毛6.9%（TDCP）~14.5%（TEPA）;在上述类型纺织品添加低、中、高3个浓度水平时,加标回收率在52.5%（TEPA）~116.4%（TPP）之间;方法定量限（LOQ,S/N=10）为1.0（TBP）~10.0（TRIS）μg/kg。方法具有样品前处理简单,分析速度快、选择性好的特点,适用于纺织品中多种有机磷酸酯类阻燃剂的准确测定。

A rapid method was developed for the determination of 9 organophosphorous flame retardants （OPFRs） in textiles by ultra high performance liquid chromatography tandem electrospray ionization mass spectrometry （UHPLC-MS/MS）. Analytes in textile samples were extracted in a closed bottle at 50℃ with methanol by ultrasonic extraction for 30 min. And then, the extracted solution was injected after filtration and determined by UHPLC-MS/MS. Target analytes were separated by Cls column and methanol/water containing 5.0 mmol/L NH4COOH. The positive electrospray ionization and multiple reaction monitoring mode （MRM） was utilized. The matrix effect （ME） could be compensated by adjusting the concentration of NH4COOH and the composition of the mobile phase after careful investigation with blank samples. An external standard calibration method was chosen to the quantitative analysis. Under the optimized conditions, method precision represent with relative standard deviations （RSDs） was 5.2% （TOCP） -12.5% （TRIS） for cotton, 6.4% （TBEP）-13.8% （TRIS）for polyester, and 6.9% （TDCP）-14.5% （TEPA）for wool samples. The recoveries for standard addition were in the range of 52.5% （TEPA） -116.4% （TPP）. The limits of quantification （ LOQ, S/N= 10） were between 1.0 （TBP） and 10.0 （TRIS） μg/kg.