气相色谱-质谱法测定玩具中单甲基锡迁移量及其假阳性的确证方法

doi:10.3724/SP.J.1123.2018.06004

色谱 ›› 2018, Vol. 36 ›› Issue (11): 1181-1188.DOI: 10.3724/SP.J.1123.2018.06004

气相色谱-质谱法测定玩具中单甲基锡迁移量及其假阳性的确证方法

李函珂^1,2, 蚁乐洲¹, 谭智贤¹, 丁志勇¹, 黄宁姗¹, 黄理纳¹, 马彤梅²

1. 广东检验检疫技术中心, 广东广州 510623;
2. 华南理工大学化学与化工学院, 广东广州 510640

收稿日期:2018-06-07 出版日期:2018-11-08 发布日期:2014-09-30
通讯作者: 蚁乐洲.Tel:(020)38290540,E-mail:yilz@iqtc.cn;马彤梅.Tel:(020)87113973,E-mail:tongmei@scut.edu.cn.
基金资助:
国家重点研发计划课题（2016YFF0203705）；广东出入境检验检疫局科技计划项目（2017GDK33）.

Determination of monomethyltin migration from toys by gas chromatography-mass spectrometry and confirmation of its false positive

LI Hanke^1,2, YI Lezhou¹, TAN Zhixian¹, DING Zhiyong¹, HUANG Ningshan¹, HUANG Lina¹, MA Tongmei²

1. Guangdong Inspection and Quarantine Technology Center, Guangzhou 510623, China;
2. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China

Received:2018-06-07 Online:2018-11-08 Published:2014-09-30
Supported by:
Planned Project of State Key Research & Development (No. 2016YFF0203705); Planned Technical Project of Guangdong Entry-Exit Inspection and Quarantine Bureau (No. 2017GDK33).

摘要/Abstract

摘要：

基于欧盟玩具安全标准EN 71-3∶2013/A2∶2017中胃液迁移程序，建立了测定玩具中单甲基锡迁移量的气相色谱-质谱法（GC-MS），并首次针对由此引起的单甲基锡假阳性问题建立了确证方法。经优化迁移条件、衍生步骤及色谱条件，单甲基锡在0.02~1.0 mg/L范围内呈现良好线性关系，相关系数（R²）为0.9992，方法检出限和定量限分别为0.11 mg/kg和0.32 mg/kg。单甲基锡在不同加标水平（0.1、0.5和1.5 μg）下的回收率为86.2%~104.2%，相对标准偏差为3.1%~8.2%（n=6）。实际样品测定表明，马口铁（锡铁合金）材质玩具表面涂层中检出了单甲基锡，迁移量为0.44~0.67 mg/kg，并以甲醇和丙酮为迁移溶剂对结果进行确证，经证实其为假阳性结果。

关键词: 单甲基锡迁移, 假阳性, 气相色谱-质谱法, 确证, 玩具

Abstract:

Based on migration procedures using simulated gastric juice specified in the EU toy Safety Standard EN 71-3:2013/A2:2017, a method was developed for the determination of monomethyltin (MMT) migration from toys by gas chromatography-mass spectrometry (GC-MS). Further, a reliable confirmation method for judgement of a false positive for MMT obtained by GC-MS, was established. After optimizing the migration conditions, derivatization steps and chromatographic parameters, the method yielded a linear range from 0.02 to 1.0 mg/L with a correlation coefficient (R²) of 0.9992. The limits of detection and quantification of the method were 0.11 and 0.32 mg/kg, respectively. The recoveries were 86.2%-104.2% under different spiked levels (0.5, 1.0 and 1.5 μg), and the relative standard deviations were 3.1%-8.2% (n=6). MMT migration ranging from 0.44 to 0.67 mg/kg was detected in the surface coating of tin-plating (Sn-Fe alloy) toy materials, which was subsequently confirmed to be false positive. Therefore, a novel confirmative approach using methanol or acetone as the migration solvent was proposed, aiming at verifying the false positive of MMT. The results showed that the previously positive MMT detected by GC-MS could no longer be detected when treated by these migration solvents.Hence, this approach can be used to confirm false positive detected for MMT after GC-MS detection.

Key words: confirmation, false positive, gas chromatography-mass spectrometry (GC-MS), migration, monometyltin (MMT), toys

中图分类号:

O658

李函珂, 蚁乐洲, 谭智贤, 丁志勇, 黄宁姗, 黄理纳, 马彤梅. 气相色谱-质谱法测定玩具中单甲基锡迁移量及其假阳性的确证方法[J]. 色谱, 2018, 36(11): 1181-1188.

LI Hanke, YI Lezhou, TAN Zhixian, DING Zhiyong, HUANG Ningshan, HUANG Lina, MA Tongmei. Determination of monomethyltin migration from toys by gas chromatography-mass spectrometry and confirmation of its false positive[J]. Chinese Journal of Chromatography, 2018, 36(11): 1181-1188.

参考文献

[1] Moser V C, Barone S, Phillips P M, et al. Neurotoxicology, 2006, 27(3):409
[2] Kruger K, Hiong T, Bensch W, et al. Neurotoxicology, 2007, 28(1):114
[3] European Food Safety Authority (EFSA). EFSA J, 2004, 102:1
[4] EN 71-3:2013
[5] EN 71-3:2013/A2:2017
[6] Cui Z Y, Zhang K G, Zhou Q F, et al. Talanta, 2011, 85(2):1028
[7] Liu J M, Jiang G B, Zhou Q F, et al. Anal Sci, 2001, 17(11):1279
[8] Smitiene V, Semasko I, Vickackaite V. J Sep Sci, 2014, 37(15):1989
[9] Chen B W, Wang T, Yin Y G, et al. Anal Methods, 2012, 4(7):2109
[10] Jitaru P, Infante H G, Adams F C. J Anal At Spectrom, 2004, 19(7):867
[11] Zhai G S, Liu J F, Li L, et al. Talanta, 2009, 77(4):1273
[12] Suyani H, Heitkemper D, Creed J, et al. Appl Spectrosc, 1989, 43(6):962
[13] Li H K, Huang L N, Yi L Z, et al. Chinese Journal of Applied Chemistry, 2016, 33(10):1210 李函珂, 黄理纳, 蚁乐洲, 等. 应用化学, 2016, 33(10):1210
[14] Hobsley M, Whitfield P F. J Physio, 1977, 271(2):57
[15] Van Engelen J G M, Park M V D Z, Janssen P J C M, et al. Chemical in Toys, a General Methodology for Assessment of Chemical Safety of Toys with a Focus on Elements.[2018-03-11]. https://www.rivm.nl/dsresource?objectid=0e8298a9-8490-458d-b9c5-c3be5c5e9a2b&type=org&disposi-tion=inline
[16] Charman W N, Porter C J H, Mithani S, et al. J Pharm Sci, 1997, 86(3):269
[17] Oomen A G, van Twillert K, Hofhuis M F A, et al. Development and Suitability of in Vitro Digestion Models in Accessing Bioaccessibility of Lead from Toy Matrices.[2018-03-11]. https://www.rivm.nl/dsresource?objectid=2590c915-8816-4144-8489-8d9e8fccb8b6
[18] Christensen F N, Davis S S, Hardy J G, et al. J Pharm Pharmacol, 1985, 37(2):91
[19] Degen L P, Phillips S F. Gut, 1996, 39(2):299
[20] GB 6675.4-2014
[21] ISO 8124-3:2010
[22] Oomen A G, Rompelberg C J M, Bruil M A, et al. Arch Environ Contam Toxicol, 2003, 44(3):281
[23] Ruby M V, Davis A, Schoof R, et al. Environ Sci Technol, 1996, 30(2):422
[24] Hamel S C, Buckley B, Lioy P J. Environ Sci Technol, 1998, 32(3):358
[25] Chung S W C, Wu A H T. J Chromatogr A, 2017, 1505(1/2):18
[26] De Smaele T, Moens L, Dams R, et al. J Chromatogr A, 1998, 793(1):99
[27] Leermakers M, Nuyttens J, Baeyens W. Anal Bioanal Chem, 2005, 381(6):1272
[28] Le Gac M, Lespes G, Potin-Gautier M. J Chromatogr A, 2003, 999(1/2):123
[29] Vahcic M, Milacic R, Scancar J. Anal Chim Acta, 2011, 694(1/2):21
[30] Pinel-Raffaitin P, Rodriguez-Gonzalez P, Ponthieu M, et al. J Anal At Spectrom, 2007, 22(3):258
[31] Gu G B, Li P. Inorganic Chemistry. 2nd ed. Beijing:Chemical Industry Press, 2007 古国榜, 李朴. 无机化学. 2版. 北京:化学工业出版社, 2007
[32] Bishop D P, Hare D J, De Grazia A, et al. Anal Methods, 2015, 7(12):5012
[33] Marcic C, Lespes G, Potin-Gautier M. Anal Bioanal Chem, 2005, 382(7):1574
[34] ISO/TS 16179:2012
[35] Kannan K, Tanabe S, Tatsukawa R. Bull Environ Contam Toxicol, 1995, 55(4):510
[36] Lee C C, Wang T, Hsieh C Y. Environ Pollut, 2005, 137(2):198
[37] Wahlen R, Wolff-briche C. Anal Bioanal Chem, 2003, 377(1):140
[38] Xiao Q, Hu B, He M. J Chromatogr A, 2008, 1211(1/2):135

气相色谱-质谱法测定玩具中单甲基锡迁移量及其假阳性的确证方法

Determination of monomethyltin migration from toys by gas chromatography-mass spectrometry and confirmation of its false positive

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	王亚婷, 杨阳, 孙秀兰, 纪剑. 基于气相色谱-质谱法的广泛靶向代谢组学方法开发[J]. 色谱, 2023, 41(6): 520-526.
[2]	章璐幸, 黄朝辉, 罗淑青, 曹琳, 谢莹, 钱江. 应用超高效液相色谱-四极杆-飞行时间质谱法建立谷物中18种真菌毒素非靶向筛查数据库及确证方法[J]. 色谱, 2023, 41(1): 66-75.
[3]	胡国绅, 王红, 余可垚, 沈伟健, 侯燕, 季美泉, 朱一鸣, 田雯, 李锡东. 气相色谱-负化学源质谱法测定船舶压载水中4种三卤甲烷[J]. 色谱, 2022, 40(6): 584-589.
[4]	王雪婷, 李静静, 姜珊, 沈伟健, 王毅谦, 顾强. 酸性酯交换-气相色谱-质谱法同时测定植物油中氯丙二醇酯和缩水甘油酯[J]. 色谱, 2022, 40(2): 198-205.
[5]	曹琦, 张亚珍, 朱正伟, 吴婉琴, 江丰, 余婷婷. 气相色谱-四极杆/飞行时间质谱筛查确证辣椒中244种农药残留及其代谢物[J]. 色谱, 2021, 39(5): 494-509.
[6]	吕稳, 李红英, 刘杰, 韩玮, 黄伟. 气相色谱-质谱法测定化妆品中13种防晒剂[J]. 色谱, 2021, 39(5): 552-557.
[7]	谢瑜杰, 陈辉, 盖丽娟, 霍思宇, 范春林, 吕美玲. 液相色谱-四极杆-飞行时间质谱法快速筛查与确证紫甘蓝中415种农药残留[J]. 色谱, 2021, 39(3): 301-315.
[8]	乔勇升, 王俊虎, 仇雅静, 钱忠义, 胡慧, 陈伟, 王萍. 应用超高效液相色谱-四极杆-飞行时间质谱建立茶叶中农药残留的筛查与确证方法[J]. 色谱, 2020, 38(12): 1402-1412.
[9]	胡巧茹, 曹鹏, 丛中笑, 梁君妮, 沙美兰, 李晓玉, 尹大路, 鲁闽. 超高效液相色谱-四极杆/静电场轨道阱高分辨质谱对粮谷产品中20种真菌毒素的快速筛查和确证[J]. 色谱, 2019, 37(11): 1241-1248.
[10]	魏敏芝, 万建春, 张富生, 潘华. 高效液相色谱-串联质谱法检测猪肉中3-甲基喹喔啉-2-羧酸残留[J]. 色谱, 2019, 37(10): 1059-1063.
[11]	唐涛, 杨三东, 赵海青, 谈义萌, 封娇, 夏明珠, 李彤. 基于双定性原则的高效液相色谱-二极管阵列检测法分析中药组分[J]. 色谱, 2018, 36(8): 766-771.
[12]	徐仿敏, 李海波, 魏万里, 刘凌云, 李强. 基于可变亲水性溶剂的液液微萃取-气相色谱-质谱法分析尿中的2'-氯地西泮[J]. 色谱, 2018, 36(10): 1067-1072.
[13]	胡明珠, 连显会, 刘晗, 郭项雨, 吕悦广, 白桦, 薛宏宇, 马强. 中空纤维液相微萃取-超高效液相色谱-串联质谱法测定儿童玩具中6种致敏香豆素类化合物[J]. 色谱, 2017, 35(11): 1145-1151.
[14]	黄会秋, 黄莉来, 夏坪. 水相衍生-气相色谱-质谱法同时测定水产品中甲基汞和无机砷[J]. 色谱, 2016, 34(9): 918-924.
[15]	霍巨垣, 欧阳钢锋, 陈丽琼, 王欣. 顶空固相微萃取-气相色谱-质谱法测定玩具中可迁移有机锡化合物[J]. 色谱, 2016, 34(6): 615-620.