人体尿液中有机磷阻燃剂代谢物的液液萃取-超高效液相色谱-串联三重四级杆质谱测定法

Determination of 10 metabolites of organophosphate flame retardants in human urine by liquidliquid extraction coupled with UPLC-MS-MS

目的利用液液萃取的前处理方法和超高效液相色谱-串联三重四级杆质谱检测方法,建立对人体尿液中常见的10种有机磷阻燃剂代谢物(metabolites of organophosphate flame retardants,mOPFRs)的分析方法。方法尿液样本经酶解后调节溶液酸碱度,采用氯化钠盐析,乙腈及乙酸乙酯作为萃取剂,提取样本中目标化合物。样本经超高效液相色谱进行梯度洗脱分离,在经优化后的质谱条件下实现对mOPFRs的定量分析。结果在0.20~10.0μg/L的线性范围内,所得回归方程均呈良好的线性关系,r>0.999。该方法的检出限为0.004~0.066μg/L,定量下限为0.014~0.221μg/L;加标回收率在74.6%~127.2%之间,RSD为1.1%~28.1%。结论该方法无需进行固相萃取,线性范围良好、准确可靠、灵敏度高,适用于同时测定人体尿液样本中多种有机磷阻燃剂代谢物。

Objective To establish an analytical method for the detection of 10 common metabolites oforganophosphate flame retardants(mOPFRs)in human urine by using liquid-liquid extraction and ultra-high-performance liquid chromatography tandem with mass spectrometry(UPLC-MS/MS).Methods Urine samples were enzymatically digested,and the solution pH was adjusted.Sodium chloride salting-out was employed,with acetonitrile and ethyl acetate as extractants to isolate the target compounds.The gradient elution mode was applied in chromatographic separation and the samples were detected by UPLCMS/MS.Quantitative analysis of target compounds was achieved under optimized mass spectrometry conditions.Results The linear range of the instrumental method was 0.2 to 10μg/L,with regression coefficients ranging from 0.994 to 0.999.The method detection limits were determined to be in the range of 0.004 to 0.066μg/L,and the quantification limits were in the range of 0.014 to 0.221μg/L.The spiked recovery rates ranged from 74.6%to 127.2%.Bio-monitoring of urine samples from the Zengcheng district,Guangzhou,revealed the presence of all 10 mOPFRs.However,four mOPFRs exhibited relatively low detection rates,while the detection rates of the remaining six metabolites were all above 60%.Stratified analysis by gender indicated a significantly higher concentration of BCEP in male urine compared to female urine,while there was no statistically significant difference in the concentration of total mOPFRs results between genders.Conclusion The method was reliable,sensitive and suitable for the determination of different mOPFRs in human urine samples.