溶剂诱导相变萃取-超高效液相色谱-串联质谱法测定人尿中14种有机磷酸酯代谢物OA

A method based on solvent induced phase transition extraction(SIPSE)coupled with ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)was established for simultaneous quantification of 14 kinds of organophosphate ester metabolites(OPEMs)in human urine.Briefly,1.0 mL of urine samples were treated with ammonium acetate solution and β-glucuronidase,followed by 16 h of enzymatic digestion.Then,acetonitrile was added and the target analytes were extracted using a mixture of n-hexane and methyl tert-butyl ether.After nitrogen evaporation and reconstitution,the extracts were separated on a Zorbax Eclipse Plus C18 column.Detection was conducted via electrospray ionization with multiple reaction monitoring,and quantification was achieved using the internal standard calibration.All 14 kinds of OPEMs showed good linearity with correlation coefficients greater than 0.990.The method detection limits(MDLs)and method quantification limits(MQLs)ranged from 0.01 to 0.39 μg/L and from 0.04 to 1.30 μg/L,respectively.At spiked concentrations of 1.0,2.0 and 10.0 μg/L,the recoveries were 70.4%-114.2%,with relative standard deviations of 0.5%-9.1%.This method was applied to 100 urine specimens collected from primary school students in City X,Guangdong Province.The detection rates of DNBP,DPHP,BCEP,BCIPP and DEP all exceeded 50%.Relatively high concentrations were observed for BCEP,DPHP,BCIPP,DEP,DNBP and BBOEP,with geometric mean concentrations of 9.75,0.47,0.45,0.26,0.25 and 0.23 μg/L,respectively.The proposed method was characterized by low consumption of both sample and organic solvent,operational simplicity,and high extraction efficiency,which collectively facilitated its application in high-throughput sample analysis.It could be reliably applied to the routine monitoring of OPEMs in human urine.