高效液相色谱-串联质谱法同时测定水体和沉积物中12种有机磷酸酯类化合物

Simultaneous Determination of 12 Kinds of Organophosphates in Water and Sediment by High Performance Liquid Chromatography-Tandem Mass Spectrometry

建立了高效液相色谱-质谱联用技术结合固相萃取和液液萃取方法检测水体和沉积物中12种磷酸酯类(OPEs)化合物残留的方法。水样样品经HLB固相萃取柱富集,乙酸乙酯洗脱两次,沉积物样品以乙腈超声萃取,旋转蒸发至干,用超纯水稀释后重复水样处理步骤,采用ZORBAX Eclipse Plus C_(18)色谱柱(150 mm×2.1 mm,3.5μm)进行分离,以0.2%甲酸-甲醇作为流动相进行梯度洗脱,采用正离子MRM监测模式,外标法定量分析。水样中,12种OPEs在0.05、0.10和0.50μg/L加标水平下,除TMP(28.5%~47.8%)和TEHP(22.4%~73.8%)外,其余目标化合物的平均回收率为66.4%~115.0%,相对标准偏差为0.5%~9.1%,方法定量限(MOQ)为0.001~0.050μg/L;沉积物中,在5、10和50μg/kg加标水平下,除TMP(35.7%~44.9%)、TCEP(31.2%~48.9%)外,其余目标化合物的平均回收率为65.9%~120.0%,相对标准偏差为0.01%~9.5%,方法定量限(MOQ)为0.02~2.0μg/kg(dw)。基于上述方法对太湖水样和沉积物样品中目标化合物定量检测分析,∑OPEs含量分别为0.1~1.7μg/L和8.1~420μg/kg dw。

A method was developed for determination of 12 kinds of phosphate compounds in water and sediment by high performance liquid chromatography-tandem mass spectrometry( HPLC-MS/MS) coupled with solid phase extraction( SPE) and ultrasonic extraction. The water samples were concentrated by HLB solid-phase extraction( SPE) column and eluted twice with ethyl acetate,ultrasonic solvent extraction for sediment samples and then repeated the operation of water samples after diluted with deionized water. The sample were separated on a ZORBAX Eclipse Plus C_(18)( 150 mm × 2.1 mm,3.5 μm) column by a gradient elution with 0.2% formic acid aqueous solution and methanol as the mobile phase. Ion mode analysis was monitored by high performance liquid chromatography mass spectrometer( MRM). The target compounds were quantified by external standard method. At the spiked levels( 0. 05,0. 1 and 0. 5 μg/L),the average recoveries of 12 kinds of OPEs in water samples ranged from 66.4% to 115%,except for TMP( 28.5%-47.8%) and TEHP( 22.4%-73.8%). The relative standard deviation RSD( n = 3) was 0.5%-9.09%,and the method quantification( MOQ) was 0.001-0.05 μg/L,However at the spiked levels of 5,10 and 50 μg/kg,the average recoveries of 12 kinds of OPEs in sediment samples ranged from 65. 4% to 120. 0%,except for TMP( 35.7%-44. 9%) and TCEP( 31. 2%-48. 9%). The relative standard deviation RSD( n = 3) was0.01%-9.54%,and the MOQ for sediment was 0. 02-2. 0 μg/kg dw. Based on the above methods,the detection and analysis of the targets in the water and sediments samples of Taihu Lake were carried out. The results showed that the concentrations of ΣOPEs were 0.1-1.7 μg/L and 8.1-420 μg/( kg dw),respectively.