Determination of 16 types of phthalic acid esters in commercial liquors by magnetic nanoparticles solid-phase extraction combined with gas chromatography-tandem mass spectrometry
WANG Fang1, YANG Fenghua1, SHAO Guojian2, HU Mingyou2, WANG Ye2
1. Department of Education and Quality Management, Huzhou Center for Disease Control and Prevention, Zhejiang, Huzhou 313000, China; 2. Huzhou Center for Disease Control and Prevention, Zhejiang, Huzhou 313000, China
Abstract：Objective To develop a magnetic solid-phase extraction combined with gas chromatography-tandem mass spectrometry (GC-MS/MS) based on pyrrole-modified magnetic nanoparticles to determine 16 types of phthalic acid esters (PAEs) in commercial liquors. Methods Fe3O4 magnetic nuclei were prepared by hydrothermal synthesis, and the polypyrrole-modified magnetic nanomaterials were prepared with the chemical oxidation method. Magnetic solid-phase extraction of beer, grape wine, rice wine and Chinese spirits was performed at 10% alcohol by volume, extraction duration of 20 min and ethyl acetate elution of 10 min, followed by addition of 1 g NaCl for reduction of emulsification effect. The 16 types of PAEs were determined using GC-MS/MS with DB-5MS capillary column (30 m×250 μm, 0.25 μm) under the mode of electron impact ionization (EI) and dynamic multiple reaction monitoring (dMRM), with quantitative analysis using the external standard method. The standard curve, detection limit, spike recovery rate and precision of GC-MS/MS for determination of 16 types of PAEs were evaluated. Results Pyrrole was successfully embedded onto the surface of magnetic nanoparticles in the form of polymer, and the magnetic nanoparticles modified by polypyrrole were well characterized, showing unapparent matrix and emulsification effects. There was a good linear relationship for the 16 types of PAEs at 50 to 5 000 ng/mL (r=0.999 5-0.999 9), and the spike recovery rate of 16 types of PAEs ranged from 71.61% to 110.50% at 100, 500 and 1 000 μg/kg, with relative standard deviations of 3.78% to 7.41%, detection limits of 0.02 to 1.47 μg/kg. PAEs were detected in 20 out of 50 liquor samples, with 30.00%, 60.00%, 40.00% and 70.00% detection rates in beer, grape wine, rice wine and Chinese spirits, respectively. Conclusions This method is sensitive to determine 16 types of PAEs in liquor samples, with unapparent matrix and emulsification effects, and the polypyrrole-modified magnetic composite nanoparticles present high adsorption of PAEs in liquor samples, which is feasible for monitoring of PAEs in multiple types of liquor samples.
王芳, 杨凤华, 邵国健, 胡明友, 王晔. 磁性固相萃取-气相色谱-串联质谱法测定市售酒中16种邻苯二甲酸酯[J]. 预防医学, 2022, 34(8): 855-860.
WANG Fang, YANG Fenghua, SHAO Guojian, HU Mingyou, WANG Ye. Determination of 16 types of phthalic acid esters in commercial liquors by magnetic nanoparticles solid-phase extraction combined with gas chromatography-tandem mass spectrometry. Preventive Medicine, 2022, 34(8): 855-860.
[1] 刘静,徐沛维,陈志健,等.人群邻苯二甲酸酯暴露水平研究综述[J].预防医学,2021,33(9):906-909,912. LIU J,XU P W,CHEN Z J,et al.The exposure levels of phthalic acid esters in population:a review[J].Prev Med,2021,33(9):906-909,912. [2] TAO Y,LI Z,YANG Y,et al.Effects of common environmental endocrine-disrupting chemicals on zebrafish behavior[J].Water Res,2022,35(6):208-212. [3] SHEN C,WU T,ZANG X.Hollow fiber stir bar sorptive extraction combined with GC-MS for the determination of phthalate esters from children's food[J].Chromatographia,2019,82:683-693. [4] NET S,SEMPÉRÉ R,DELMONT A,et al.Occurrence,fate,behavior and ecotoxicological state of phthalates in different environmental matrices[J].Environ Sci Technol,2015,49(7):4019-4035. [5] 中华人民共和国卫生部办公厅.通报食品及食品添加剂中邻苯二甲酸酯类物质最大残留量[EB/OL].(2011-06-22)[2022-06-29].https://www.sc.gov.cn/10462/10464/10727/10735/2011/6/24/10166814.shtml. [6] 熊思琦,范淑雯,牛溪滢.酒中痕量邻苯二甲酸酯类塑化剂的检测研究进展[C]//中国食品科学技术学会第十八届年会摘要集.北京:中国学术期刊电子出版社,2022:100-101. XIONG S Q,FAN S W,NIU X Y.Advance of the methods in determining the trace phthalic acid ester plasitcizers in liquor[C]//Abstracts of the 18th Anunual Meeting of CIFST.Beijing:China Academic Journal Electronic Publishing House,2022:100-101. [7] 黄河,黄婷,王媚,等.白酒中邻苯二甲酸酯塑化剂问题研究进展[J].酿酒科技,2022,10(1):97-103. HUANG H,HUANG T,WANG M,et al.Research progress in phthalic acid esters in Baijiu[J].Liquor-Mak Sci Technol,2022,10(1):97-103. [8] 陈雅萍,唐海尧.网售白酒中邻苯二甲酸酯的测评与分析[J].广东化工,2021,48(13):213-214. CHEN Y P,TANG H Y.Evaluation and analysis of phthalates in Baijiu selling online[J].Guangdong Chem Ind,2021,48(13):213-214. [9] DONG W,GUO R,XIAOTAO S,et al.Assessment of phthalate ester residues and distribution patterns in Baijiu raw materials and Baijiu[J].Food Chem,2019,283:508-516. [10] 张洁,王谢,马青青,等.QuEChERS结合磁性纳米材料前处理GC-MS/MS法同时检测蔬菜水果中28种农药残留[J].预防医学,2021,33(9):963-967. ZHANG J,WANG X,MA Q Q,et al.Detection of 28 pesticide residues in fruits and vegetables by GC-MS/MS and QuEChERS combined with magnetic nanoparticles[J].Prev Med,2021,33(9):963-967. [11] 中华人民共和国国家卫生和计划生育委员会,国家食品药品监督管理总局.食品安全国家标准食品中邻苯二甲酸酯的测定:GB 5009.271—2016[S].北京:中国标准出版社,2017. National Health and Family Planning Commission of the People's Republic of China,China Food and Drug Administration.National food safety standard-determination of phthalates in food:GB 5009.271-2016[S].Beijing:Standards Press of China,2017. [12] 蒲彦利,宋寅生,和佳鸳,等.气相色谱-质谱联用法快速检测黄酒和醋中17种邻苯二甲酸酯[J].中国卫生检验杂志,2015,25(22):3842-3845. PU Y L,SONG Y S,HE J Y,et al.Rapid determination of 17 phthalic acid esters in rice wine and vinegar by GC-MS[J].Chin J Health Lab Technol,2015,25(22):3842-3845. [13] 秦德萍,杨小珊,黄思瑜,等.重庆市售白酒中18种邻苯二甲酸酯类物质的含量调查及健康风险评估[J].现代食品,2021(13):164-168,171. QIN D P,YANG X S,HUANG S Y,et al.A survey of 18 types phthalates plasticizer concentrations in Chinese Baijiu of Chongqing and risk assessment[J].Mod Food,2021(13):164-168,171. [14] 江萍,杨旖旎,胡顶峰,等.碳布/聚吡咯储能包装膜材料的制备及表征[J].包装工程,2019,40(7):60-65. JIANG P,YANG Y N,HU D F,et al.Fabrication and characterization of carbon cloth/polypyrrole film for energy storage packaging[J]. Packag Eng,2019,40(7):60-65. [15] 吕慧威,耿迪,解慧,等.啤酒中邻苯二甲酸酯检测方法优化及迁移量研究[J].中国酿造,2021,40(8):157-162. LÜ H W,GENG D,XIE H,et al.Optimization of detection method and migration amount for phthalate acid esters in beer[J].China Brew,2021,40(8):157-162. [16] 毕荣宇,卢君,唐平,等.GC-MS/MS法测定不同香型白酒中邻苯二甲酸酯类的含量分析[J].中国酿造,2021,40(4):159-163. BI R Y,LU J,TANG P,et al.Determination of phthalate esters in different flavor Baijiu by GC-MS/MS[J].China Brew,2021,40(4):159-163.
