超高效液相色谱-四极杆/静电场轨道阱高分辨质谱非靶向筛查生物消化液浸滤作用下塑料制品中添加剂的释放  

Non-target Screening of Plastic Additives Leaching under Artificial Biodigestive Condition Using Ultra-High Performance Liquid Chromatography Coupled with Quadrupole-Orbitrap Mass Spectrometry

作　　者：郭上 陈光仕 周静 梁文耀 谭建华 彭先芝[1,3] GUO Shang;CHEN Guang-Shi;ZHOU Jing;LIANG Wen-Yao;TAN Jian-Hua;PENG Xian-Zhi(Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,Guangzhou 510603,China;University of Chinese Academy of Sciences,Beijing 100049,China;CAS Center for Excellence in Deep Earth Science,Chinese Academy of Sciences,Guangzhou 510603,China;Guangzhou Quality Supervision and Testing Institute,Guangzhou 511447,China)

机构地区：[1]中国科学院广州地球化学研究所,广州510603 [2]中国科学院大学,北京100049 [3]中国科学院深地科学卓越创新中心,广州510603 [4]广州质量监督检测研究院,广州510110

出　　处：《分析化学》2022年第9期1373-1383,共11页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(Nos.4207070014,41877365)资助。

摘　　要：采用超高效液相色谱串联四极杆/静电场轨道阱高分辨质谱(UHPLC-Q-Orbitrap HRMS)建立了塑料制品中添加剂的非靶向筛查方法,并将其应用于筛查人工生物胃液浸滤作用下塑料制品中释放的添加剂。以Hypersil GOLD C_(18)色谱柱进行色谱分离,采用电喷雾离子源(HESI),MS/dd-MS^(2)全扫描模式,分别在正离子模式和负离子模式下进行数据采集。自建了31种塑料添加剂的标准品质谱库和6028种塑料添加剂可疑库,优化了包括UHPLC-HRMS仪器方法、质谱数据分析及物质鉴定的非靶向筛查流程。依据母离子(MS)、二级碎片(MS2)以及保留时间(RT)与数据库匹配程度及碎片计算模拟,将鉴定级别分为4级置信度(L1~L4)。从电线聚氯乙烯(PVC)绝缘层萃取液中筛查出L1置信度的化合物有4种(邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二(2-乙基己)酯(DEHP)、磷酸三(2-氯乙基)酯(TCEP)和双酚A(BPA)),L2和L3置信度的化合物分别为88和50种(含邻苯二甲酸酯类、酰胺、烯酸等),L4及以上化合物共1944种。电线PVC绝缘层在人工鸟胃液浸滤作用下释放出添加剂132种,L1置信度包括DEHP、BPA、2-(2-羟基-5-苯甲基)苯并三唑(UVP)和磷酸三乙酯(TEP),浸出量分别达到4.6 mg/g、38.1μg/g、47.8 ng/g和158.2 ng/g。A non-target screening method based on ultra-high performance liquid chromatography-quadrupole-orbitrap high resolution mass spectrometry(UHPLC-Q-Orbitrap HRMS)was established for screening and identification of plastic additives in plastic products.Chromatographic separation was performed on a Hypersil GOLD C_(18) chromatographic column.The MS data were obtained under MS/dd-MS^(2) scan mode with electrospray ionization source(HESI)in both positive and negative ion modes.A MS data base including 31 kinds of plastic additives and a suspect list including more than 6028 kinds of plastic additives were established.The non-target screen workflow including UHPLC-HRMS method,MS data analysis and compound identification were optimized.According to the matching level of precursor ion(MS),fragment ions(MS2)and retention time(RT)with data bases and/or silico fragment,the compounds screened here could be categorized based on confidence levels from L1 to L4.A total of 1944 compounds in the extract of PVC sheath of cords were screened and identified by the developed non-target screening method,among which 4 compounds including diethyl phthalate(DEP),bis(2-ethylhexyl)phthalate(DEHP),tris(2-chloroethyl)phosphate(TCEP)and bisphenol A(BPA)were identified as L1 confidence,88 and 50 compounds were identified as L2 and L3 confidence(phthalates,amides,alkenoic acids,etc.).This method was further applied to primary investigation of plastic additives released from typical plastic products under the artificial biodigestive system.A total of 132 kinds of additives were identified.L1 compounds included DEHP,BPA,drometrizole(UVP)and triethyl phosphate(TEP),with release amount of 4.6 mg/g,38.1μg/g,47.8 ng/g and 158.2 ng/g,respectively.

关 键 词：塑料添加剂 人工生物消化液 超高效液相色谱-四极杆/静电场轨道阱高分辨质谱 非靶向筛查 

分 类 号：O657.63[理学—分析化学] TQ320.77[理学—化学]