固相支撑液液萃取-液相色谱-串联质谱测定尿液中10种双酚类化合物和5种对羟基苯甲酸酯OA北大核心CSTPCDMEDLINE

Bisphenols(BPs)and parabens(PBs)are of great concern for environmental pollu-tion and human health because of their endocrine-disrupting effects and potential health haz-ards.Urinary biomonitoring of BPs and PBs can provide basic data for human internal exposure evaluation,which is a prerequisite for accurately assessing their health risks.In this study,we developed a new pretreatment procedure based on solid supported liquid-liquid extraction(SLE)for the simultaneous separation of ten BPs and five PBs in human urine,followed by high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS)analysis.In the instrumental analysis,the HPLC conditions and MS/MS parameters were comprehensive-ly optimized.Accurate qualitative and quantitative determination of ten BPs and five PBs was achieved by introducing a ternary gradient elution system of water,methanol,and acetonitrile for LC separation.During sample pretreatment,the extraction solvent and elution volume were optimized.Specifically,urine samples were held at room temperature and centrifuged at 3 000 r/min for 10 min.The supernatant(2 mL)was then transferred to a glass tube,and the pH was adjusted to 5.0 using HCl(0.5 mL;0.1 mol/L)and NaAc-HAc buffer(1.5 mL).Thereafter,β-glucuronidase-arylsulfatase(20 μL)and surrogate standard solutions(10 ng;13 C12-BPS,13 C12-BPAF,13 C6-MeP,and 13 C6-BuP)were added,and the mixture was incubated in a shaker bath in the dark at 37℃for 16 h.After incubation,the hydrolyzed sample(4 mL)was loaded onto an SLE cartridge and equilibrated for a minimum of 5 min to ensure the solution was completely absorbed by the packing material.Subsequently,the target chemicals were eluted with a mixed ethyl acetate/n-hexanesolution(3∶7,v/v;15mL).Separationofthetargetswasperformedon a ZORBAX SB-C18 reversed-phase column(250 mm×4.6 mm,5 μm)using an acetonitrile-methanol-water system as the mobile phase.The method was verified by spiking mixed urine samples at three levels(1,5,and 50 μg/L),with the recoveries ranging from 84.3%to 119.8%.Except for bisphenols(BPS),whose matrix effect was calculated as-21.8%,the ma-trix effects of other analytes were lower than 20%,indicating low matrix interference.The line-ar ranges of the analytes varied from 0.1-500 μg/L to 1-500 μg/L,with correlation coefficients higher than 0.995.The method limits of quantification for target chemicals ranged from 0.03 to 0.30 μg/L,and the relative standard deviations of intra-and inter-day experiments were 1.4%-8.4%and 5.7%-14.6%,respectively,suggesting high stability and reproducibility.The method was successfully applied to the determination of ten BPs and five PBs in 10 urine samples from a general population.The concentrations of target chemicals in the human urine samples varied.Methylparaben(MeP),ethylparaben(EtP),propylparaben(PrP),and bisphenol A(BPA)were detected in all samples,with median mass concentrations of 1.10,0.60,0.21,and 0.55 μg/L,respectively.The detection rates of the other chemicals were less than 50%,which may be related to the production and use of specific chemicals,their bioavailability,and biological metabolism in humans.