固相萃取-液相色谱-串联质谱法同时测定尿液中9种多环芳烃代谢物

建立了固相萃取-液相色谱-串联质谱同时测定尿中2-羟基萘、1-羟基萘、2-羟基芴、3-羟基菲、1-羟基芘等9种多环芳烃代谢物的液相色谱-串联质谱测定方法。尿样中结合态的多环芳烃代谢物在β-葡萄糖苷酸酶-芳基硫酸酯酶缓冲液(pH 5.0)作用下,于37℃水浴中避光水解4 h后,以C18固相萃取小柱富集、净化,以甲醇洗脱,采用Waters Symmetry C18色谱柱,流动相为乙腈-0.2%氨水(72∶27,V/V)等度淋洗分离后进入质谱测定。在喷雾电压4 kV,毛细管温度300℃下,以3-羟基菲13C为内标,采用SRM模式负离子扫描方式测定,内标法定量。9种多环芳烃代谢物在尿中的线性范围为0.90～100μg/L;相关系数为0.9970～0.9990;回收率为79.0%～119.8%;相对标准偏差为4.3%～12.4%;检出限为0.04～0.90μg/L;结果表明,本方法可用于尿中9种多环芳烃代谢物的测定。

Simultaneous Determination of Nine Phenolic Metabolites of Polycyclic Aromatic Hydrocarbons in Human Urine by Liquid Chromatography Tandem Mass Spectrometry

A method was developed for the simultaneous determination of nine phenolic metabolites of polycyclic aromatic hydrocarbons(OH-PAHs) in human urine,i.e.2-hydroxynaphthalene,1-hydroxynaphthalene,2-hydroxyfluorene,3-hydroxyphenanthrene,1-hydroxypyrene,3-hydroxychrysene,6-hydroxychrysene,1-hydroxybenza] anthracen,9-hydroxybenzoa] pyrene by solid-phase extraction-liquid chromatography tandem mass spectrometry(LC-MS/MS).After adding the internal standard(13C3-Hydroxyphenanthrene),the urine samples were hydrolyzed by enzyme(pH 5.0) at 37 ℃ for 4 h,then cleaned up and concentrated on C18 SPE column,and then the targeted compounds were analyzed by LC-MS/MS under negative ion mode using Waters symmetry C18 column as analyzed column.The mobile phase was CH3CN ∶ NH3·H2O(0.2%)=72 ∶ 27(volume ratio).The spray voltage was 4 KV.The capillary temperature was 300 ℃.The linear ranges were 0.90-100 μg/L.The correlation coefficients were 0.9970-0.9990.The detection limits were 0.04-0.90 μg/L.The recoveries were 79.0%-119.8%.The relative standard deviations were 4.3%-12.5%(n=6).The method has been used for the simultaneous determination of nine phenolic metabolites of polycyclic aromatic hydrocarbons(OH-PAHs) in human urine.