1.中国科学院生态环境研究中心,环境化学与生态毒理学国家重点实验室,北京 100083
2.国科大杭州高等 研究院 环境学院,浙江 杭州 310024
3.中国科学院大学,北京 100049
史亚利,博士,研究员,研究方向:环境污染物的色谱-质谱分析方法及其环境存在、迁移转化、归趋以及人体暴露研究,E-mail:shiyali@rcees.ac.cn
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侯敏敏,史亚利,蔡亚岐.超高效液相色谱-串联质谱法测定医用口罩中有机磷酸酯[J].分析测试学报,2021,40(10):1439-1445.
HOU Min-min,SHI Ya-li,CAI Ya-qi.Determination of Organophosphate Esters in Medical Masks by Ultra-high Performance Liquid Chromatography-Tandem Mass Spectrometry[J].Journal of Instrumental Analysis,2021,40(10):1439-1445.
侯敏敏,史亚利,蔡亚岐.超高效液相色谱-串联质谱法测定医用口罩中有机磷酸酯[J].分析测试学报,2021,40(10):1439-1445. DOI: 10.19969/j.fxcsxb.21032202.
HOU Min-min,SHI Ya-li,CAI Ya-qi.Determination of Organophosphate Esters in Medical Masks by Ultra-high Performance Liquid Chromatography-Tandem Mass Spectrometry[J].Journal of Instrumental Analysis,2021,40(10):1439-1445. DOI: 10.19969/j.fxcsxb.21032202.
该研究优化了医用口罩样本中16种有机磷酸酯(OPEs)的萃取和净化前处理过程,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)测定方法。样本经甲醇超声萃取后,采用ENVI-18固相萃取小柱净化,最终使用Acquity UPLC BEH C,18,色谱柱以5 mmol/L乙酸铵缓冲溶液-甲醇为流动相进行分离,采用UPLC-MS/MS测定,内标法定量。结果表明,16种OPEs在0.1~50 µg/L质量浓度范围内呈良好的线性关系(,r ,>, 0.995),方法检出限为0.004 60~1.03 ng/dm,2,,定量下限为0.015 2~3.43 ng/dm,2,,加标回收率为68.8%~140%,相对标准偏差为0.70%~18%。采用所建立的方法对42个医用口罩中16种OPEs进行测定,其总浓度为6.60~2 387 ng/dm,2,,其中12种OPEs的检出率高于50%,表明这些OPEs在医用口罩中普遍存在。磷酸三苯酯(TPHP)和磷酸三(1-氯-2-丙基)酯(TCIPP)为主要的OPEs,浓度分别为0.131~2 274 ng/dm,2,和0.370~79.8 ng/dm,2,。整体上OPEs的浓度均较低,推测口罩样本中的OPEs可能是生产和包装过程中受空气或塑料包装污染所致。
In this study,a method was developed for simultaneous determination of 16 organophosphate esters(OPEs) in medical masks by ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).In addition,the extraction and purification process for 16 OPEs was optimized.Specifically,three different extracting solvents including dichloromethane-,n,-hexane(1∶1),dichloromethane-acetonitrile(1∶1) and methanol,coupled with two purification processes,were compared. Meanwhile,the mask samples were ultrasonically extracted three times with methanol,then purified with ENVI-18 cartridges using 6 mL acetonitrile containing 25% dichloromethane as the eluent.The analytes were separated on a Acquity UPLC BEH C,18, column by gradient elution using 5 mmol/L ammonium acetate and methanol as the mobile phases,then analyzed in electrospray ionization positive(ESI+) mode under the multiple reaction monitoring(MRM) mode,and finally quantified by internal standard method.Results indicated that the limits of detection(LOD,,S/N, = 3) for 16 OPEs in mask were in the range of 0.004 60-1.03 ng/dm,2,,while the limits of quantitation(LOQ,,S/N, = 10) were 0.015 2-3.43 ng/dm,2,.The average recoveries for 16 OPEs in medical mask at three spiked levels of 5, 20 and 40 ng ranged from 68.8% to 140%,with relative standard deviations(RSD) of 0.70%-18%.These results indicated that the established method was suitable for the determination of OPEs in medical mask samples.The method was applied to the quantitation of 16 OPEs in forty-two medical mask samples.The total concentrations of 16 OPEs were in the range of 6.60-2 387 ng/dm,2,,with a median concentration of 34.2 ng/dm,2,.The detection frequencies for twelve OPEs were higher than 50%.Tri-phenyl phosphate(TPHP) and tri(1-chloro-2-propyl) phosphate(TCIPP) were the most abundant OPEs,with concentrations of 0.131-2 274 ng/dm,2, and 0.370-79.8 ng/dm,2,,respectively.Considering that the concentration of each analyte was relatively low,it is speculated that the OPEs in medical mask may be adsorbed from the air or transferred from plastic packaging during the manufacturing or packaging process.
有机磷酸酯超高效液相色谱-串联质谱医用口罩纺织品阻燃剂
organophosphate esterultra-high performance liquid chromatography-tandem mass spectrometrymedical masktextileflame retardant
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