色谱2023，Vol.41Issue(12)：1095-1105,11.DOI:10.3724/SP.J.1123.2023.07017
快速滤过型净化结合超高效液相色谱-串联质谱法测定中华绒螯蟹中14种全氟烷基化合物
Determination of 14 perfluoroalkyl substances in Chinese mitten crab by multi-plug filtration cleanup coupled with ultra-performance liquid chromatography-tandem mass spectrometry
摘要
Abstract
Perfluoroalkyl substances(PFASs)have become a new food-safety problem.Dietary intake is a major pathway of human exposure to PFASs.Chinese mitten crab(Eriocheir sinen-sis)is a high-end aquaculture product popular among consumers in China.Conventional extrac-tion methods for PFASs are cumbersome and time consuming,and result in incomplete purifi-cation;thus,this technique does not meet the requirements for PFAS detection.Herein,an an-alytical strategy was established for the rapid detection of 14 PFASs in Chinese mitten crab based on multi-plug filtration cleanup(m-PFC)and ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS).The carbon-chain length of the 14 PFASs analyzed in this study ranged from 4 to 14,and they are perfluorobutanoic acid(PFBA),perfluoro-n-pentanoic acid(PFPeA),perfluorohexanoic acid(PFHxA),perfluoroheptanoic acid(PFH-pA),perfluorooctanoic acid(PFOA),perfluorononanoic acid(PFNA),perfluorodecanoic acid(PFDA),perfluoroundecanoic acid(PFUnDA),perfluorododecanoic acid(PFDoDA),perflu-orotetradecanoic acid(PFTeDA),perfluoro-1-butane sulfonic acid(PFBS),perfluoro-1-hex-ane sulfonic acid(PFHxS),perfluoro-1-octane sulfonic acid(PFOS),and perfluoro-1-decane-sulfonate(PFDS).The m-PFC column was prepared using carboxy-based multiwalled carbon nanotubes,and used to reduce the interference of sample impurities.The samples were extrac-ted with 5 mL of 0.1%formic acid aqueous solution,15 mL of acetonitrile and extraction salt(2 g Na2SO4 and 2 g NaCl).The supernatant(10 mL)was purified using the m-PFC column,concentrated to near dryness under nitrogen,and then redissolved in 1 mL of methanol.Final-ly,the sample solution was filtered through a 0.22 μm polypropylene syringe filter for UPLC-MS/MS analysis.The target analytes were separated using a Shimadzu Shim-pack G1ST-C18 chromatographic column(100 mm×2.1 mm,2 μm)using methanol(A)and 5 mmol/L ammo-nium acetate aqueous solution(B)as the mobile phases via gradient elution.The linear gradi-ent program were as follows:0-0.5 min,10%A-35%A;0.5-3 min,35%A-60%A;3-5 min,60%A-100%A;5-6.5 min,100%A;6.5-7 min,100%A-10%A.The target analytes were ana-lyzed using negative electrospray ionization in multiple-reaction monitoring mode,and quantita-tive analysis was performed using the internal standard method. In this study,we optimized the mobile-phase system as well as the extraction solvent,time,volume,and salt.The 14 PFASs exhibited good peak shapes and sensitivities when the 5 mmol/L ammonium acetate solution-methanol system was used as the mobile phase.Compared with acetonitrile or methanol alone,the extraction efficiencies of the 14 PFASs were significant-ly improved when 5 mL of 0.1%formic acid aqueous solution was added,followed by 15 mL of acetonitrile.The extraction efficiencies of the 14 PFASs did not differ significantly when the ex-traction time was within 3-15 min.The extraction salt(MgSO4,Na2SO4,NaCl,(NH4)2 SO4,and Na2SO4+NaCl)significantly affected the extraction efficiencies of the 14 PFASs.The high-est extraction efficiencies of the 14 PFASs,which ranged from 47.9%to 121.9%,were ob-tained when Na2SO4+NaCl was used as the extraction salt.Under the optimal experimental con-ditions,good linearities(R2=0.998-0.999)were obtained for seven PFASs(PFBS,PFHxA,PFHpA,PFHxS,PFDA,PFDoDA,PFTeDA)at 0.10-100 μg/L,and seven PFASs(PFBA,PF-PeA,PFOA,PFOS,PFNA,PFUnDA,PFDS)at 0.50-100 μg/L.The average spiked recoveries for the 14 PFASs in Chinese mitten crabs at three levels ranged from 73.1%to 120%,with rela-tive standard deviations(RSDs)in the range of 1.68%-19.5%(n=6).The limits of detection(LODs)and quantification(LOQs)of the 14 PFASs were in the range of 0.03-0.15 and 0.10-0.50 μg/kg,respectively.The developed method was applied to the analysis of crab samples collected from three farms in Shanghai,and PFASs with total concentrations of 3.52-37.77 μg/kg were detected in all samples.The detection frequencies for PFDA,PFUnDA,PFDoDA,PFTeDA,and PFOS were 100%.PFDA,PFUnDA,PFOS,and PFDoDA were the most abundant congeners,accounting for 31.2%,30.6%,15.0%,and 10.9%,respectively,of the 14 PFASs detected.The proposed method is simple,efficient,accurate,and suitable for the rapid analy-sis of 14 PFASs in Chinese mitten crabs.关键词
快速滤过型净化/超高效液相色谱-串联质谱/全氟烷基化合物/中华绒螯蟹Key words
multi-plug filtration cleanup(m-PFC)/ultra-performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)/perfluoroalkyl substances(PFASs)/Chinese mit-ten crab分类
化学化工引用本文复制引用
王献礼,饶钦雄,张其才,杜鹏辉,宋卫国..快速滤过型净化结合超高效液相色谱-串联质谱法测定中华绒螯蟹中14种全氟烷基化合物[J].色谱,2023,41(12):1095-1105,11.基金项目
上海市科委启明星(扬帆专项)项目(22YF1440700) （扬帆专项）
上海市农业科学院卓越团队项目(沪农科卓(2022)010) （沪农科卓(2022）
上海市农业科学院助跑计划. Shanghai Sailing Program(No.22YF1440700) （No.22YF1440700）
Outstanding Team of Shanghai Academy of Agricultural Sci-ences(No.2022(010)) （No.2022(010）
Shanghai Academy of Agricultural Sciences"Zhu Pao"Project. （）
