食品接触塑料中6种金属离子迁移量测定方法研究  

Determination of Migration of Six Metal Ions in Food Contact Plastic

作　　者：凌光耀 熊小婷 刘春生 陈意光 江奋万 仇旭前 李慧勇 黄晓钢 何国山 LING Guang-yao;XIONG Xiao-ting;LIU Chun-sheng;CHEN Yi-guang;JIANG Fen-wan;QIU Xu-qian;LI Hui-yong;HUANG Xiao-gang;HE Guo-shan(Technology Innovation Center of Food Related Product Quality and Safety,State Administration for Market Regulation,Collaborative Innovation Center for NQI-Quality Safety of Guangzhou,National Quality Inspection and Testing Center for Packaging Products(Guangzhou),Guangzhou Quality Supervision and Testing Institute,Guangzhou 511447,China;Guangzhou Institute for Food Inspection,Guangzhou 511410,China)

机构地区：[1]广州质量监督检测研究院,国家包装产品质量检验检测中心(广州),广州市NQI-质量安全科技协同创新中心,国家市场监督管理总局技术创新中心(食品相关产品质量与安全),广东广州511447 [2]广州市食品检验所,广东广州511410

出　　处：《质谱学报》2025年第2期217-223,I0004,共8页Journal of Chinese Mass Spectrometry Society

基　　金：广州市科技计划项目(2023B04J0436,2023B04J0407);广州市院士专家工作站(2024-D012);广东省市场监督局科技项目(2024CZ21,2022CZ05)。

摘　　要：本研究利用金属离子可与乙腈、甲酸形成稳定团簇离子的性质,建立了液相色谱-四极杆-飞行时间质谱(LC-QTOF MS)法测定食品接触塑料中Cd^(2+)、Co^(2+)、Cu^(2+)、Mn^(2+)、Ni^(2+)、Zn^(2+)等6种金属离子迁移量。采用Ultimate Hilic amide色谱柱,以0.02%甲酸溶液-乙腈为流动相进行梯度洗脱,在电喷雾离子源正离子(ESI^(+))模式下,采用多反应监测-高分辨(MRM HR)模式检测。结果表明,本方法的检出限为0.02~0.08 mg/kg,回收率为88.6%~115%,相对标准偏差(RSD)为0.3%~6.1%。采用本方法检测24批次食品接触塑料样品的迁移液,在4批次样品迁移液中检出Cu^(2+)、Mn^(2+)、Zn^(2+)。该方法可直接检测高乙醇比例溶液中金属离子浓度,用于食品接触塑料中钴、铜、锰、锌元素的合规性筛查,对食品接触塑料中未知风险物质的分析有着较好的参考价值。Additives containing metal ions can be added to food contact plastic as stabilizer,catalyzer,colorant,etc.Food safety standards also request specific migration limits(SMLs)for metal elements.The most common methods for determination of multiple metal elements in solutions are inductively coupled plasma-optical emission spectrometry(ICP-OES)and inductively coupled plasma-mass spectrometry(ICP-MS).Metal ions in solution can cluster or coordinate with organic compounds to form new stable complicated ions,which can be detected by electrospray ionization-mass spectrometry(ESI-MS).To apply this nature for determination of metal ions by liquid chromatography-quadrupole time-of-flight mass spectrometry(LC-QTOF MS),further parameter optimization is needed.In this study,five kinds of aqueous mobile phases,including 0.02%(W/W)glycollic acid,0.02%(V/V)formic acid,0.10%(V/V)formic acid,5 mmol/L ammonium formate,and 5 mmol/L ammonium formate-0.02%(V/V)formic acid,were compared for better performance of MS analysis coupled to Ultimate Hilic amide column.Different acids can give rise to form different cluster ions.Higher concentration of formic acid in aqueous mobile phase can produce better peak shape but doesn’t enhance signal to noise ratio apparently.Addition of ammonium ions can weak the signal of cluster ions.With 0.02%formic acid as the mobile phase,Cd^(2+),Co^(2+),Mn^(2+),Ni^(2+),Zn^(2+)form[M(HCOO)+CH_(3)CN]+parent ion,while Cu^(2+)forms[M+2CH_(3)CN]+parent ion.The parent ions of Cd^(2+),Co^(2+),Mn^(2+)and Zn^(2+)are collided to form[M]+,[M(H)]+,[M(H)+CH_(3)CN]+,[M(HCOO)]+,while the parent ion of Ni^(2+)to form[Ni]+,[Ni(H)]+,[Ni+CH_(3)CN]+,[Ni(H)+CH_(3)CN]+,[Ni+CH_(3)CN+N2]+,[NiO+CH_(3)CN]+,[Ni(OH)+CH_(3)CN]+,the parent ion of Cu^(2+)to form[Cu]+,[Cu+CH_(3)CN]+,[Ni+CH_(3)CN+N2]+.Finally,the optimized LC-QTOF MS method was applied to determine the migration of Cd^(2+),Co^(2+),Cu^(2+),Mn^(2+),Ni^(2+),Zn^(2+)in food contact plastic.ESI-QTOF MS analysis was performed under positive ion mode(ESI^(+))and multiple reaction m

关 键 词：液相色谱-四极杆-飞行时间质谱(LC-QTOF MS) 金属离子 食品接触塑料 迁移量 

分 类 号：O657.63[理学—分析化学]