固相萃取-高效液相色谱-串联质谱法测定大气细颗粒物中全氟/多氟化合物  

Determination of per-and polyfluoroalkyl substances in PM_(2.5)by high performance liquid chromatography-tandem mass spectrometry combined with solid phase extraction

作　　者：李孝通 王媛 史亚利[3] 崔建升[1,2] 蔡亚岐[3] LI Xiaotong;WANG Yuan;SHI Yali;CUI Jiansheng;CAI Yaqi(College of Environmental Science and Engineering,Hebei University of Science and Technology,Shijiazhuang,050018,China;Pollution Prevention Biotechnology Laboratory of Hebei Province,Shijiazhuang,050018,China;State Key Laboratory of Environmental Chemistry and Ecotoxicology,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences,Beijing,100085,China)

机构地区：[1]河北科技大学环境科学与工程学院,石家庄050018 [2]河北省污染防治生物技术实验室,石家庄050018 [3]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,北京100085

出　　处：《环境化学》2023年第2期399-408,共10页Environmental Chemistry

基　　金：国家自然科学基金(21777182,41907321);河北省自然科学基金(B2019208273);环境化学与生态毒理学国家重点实验室(KF2018-17)资助。

摘　　要：大气细颗粒物(PM_(2.5))中全氟/多氟化合物(PFASs)浓度的测定对于了解大气环境中PFASs的赋存水平和远距离传输具有重要意义.本研究通过比较采样膜对PM_(2.5)以及PFASs的富集效率差异,选取了效果最佳的石英纤维滤膜(QFF)为采样膜.利用基质提取液添加法对基质效应进行评估,发现样品基质对短链PFASs存在一定的信号抑制,通过采用相对应的内标可消除部分影响.最终优化建立了固相萃取-高效液相色谱-串联质谱(SPE-HPLC-MS/MS)同时测定PM_(2.5)中包括氯代多氟醚磺酸(Cl-PFESAs)在内的16种PFASs的方法.PM_(2.5)样品经甲醇超声-振荡萃取后,选用弱阴离子交换(WAX)固相萃取柱富集净化,使用Acclaim 120 C18色谱柱,以甲醇和50 mmol·L^(-1)乙酸铵水溶液为流动相对目标PFASs进行梯度洗脱和分离,经电喷雾离子源离子化后在负离子多重反应监测模式(MRM)下进行检测.在优化的分析条件下,16种PFASs的方法检出限(MDLs)为0.09—1.53 pg·m-3,加标回收率为76.6%—122.3%,相对标准偏差为0.5%—13.1%.该方法灵敏度好,准确度高,适用于实际环境PM_(2.5)中PFASs的分析检测.对北京市采暖期前后PM_(2.5)中PFASs进行测定,结果表明∑PFASs浓度在8.9—101.3pg·m^(-3)之间,以PFOA和PFBA为代表的全氟烷基羧酸(PFCAs)为主,冬季采暖期PM_(2.5)中PFASs污染水平有一定升高,其原因有待进一步研究.Determination of per-and polyfluoroalkyl substances(PFASs)in PM_(2.5)(particulate matter with an aerodynamic diameter less than 2.5 micrometres)is important for understanding their occurrence and long-range transportation in the atmospheric environment.In this study,quartz fiber filter(QFF)was selected as the appropriate filter based on comparable findings of enrichment efficiency of PM_(2.5)and PFASs.The matrix effects of PFASs in PM_(2.5)were evaluated by postextraction spiking method.The results indicated that matrix suppression was found for the measurement of short-chain PFASs,but it could be eliminated by using their corresponding mass labeled standards.The method was developed successfully for simultaneous determination of 16PFASs,including chlorinated polyfluoroalkyl ether sulfonic acids(Cl-PFESAs),in PM_(2.5)by using solid phase extraction(SPE)and high performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS).Target PFASs in PM_(2.5)samples were extracted with methanol using ultrasonic and shaking,and then purified using weak anion exchange(WAX)cartridges.An Acclaim 120 C18 column was applied to separate all compounds.The mobile phase was the mixture of methanol and 50 mmol·L^(-1)ammonium acetate,which were run in a gradient program.The PFASs were detected using electrospray ionization tandem mass spectrometry(ESI-MS/MS)operated in negative and multiple reactive monitoring(MRM)mode.Under the optimized analysis condition,the method detection limits(MDLs)for 16 PFASs ranged from 0.09 pg·m-3to 1.53 pg·m-3.Average recoveries of 16 PFASs in PM_(2.5)ranged from 76.6%to 122.3%,with relative standard deviations(RSDs)of 0.5%—13.1%.Hence,this method is accurate,sensitive and suitable for analysis of PFASs in PM_(2.5)from real environment.Moreover,the method was used to determine PFASs in PM_(2.5)around heating period in Beijing.It was found that the concentrations of∑PFASs in PM_(2.5)ranged from 8.9 pg·m^(-3)to101.3 pg·m^(-3).Perfluorooctanoic acid(PFOA)and perfluorobutanoic acid(PFBA)were th

关 键 词：高效液相色谱-串联质谱 PFASs PM_(2.5) 基质效应 富集效率 

分 类 号：X831[环境科学与工程—环境工程] O657.63[理学—分析化学]