固相萃取-气相色谱-串联质谱法同时测定人体尿液中4种有机磷农药代谢物

引用本文: 黄梦莹, 王娜, 郭欣妍, 邱盼子, 汤卫国, 张尊建. 固相萃取-气相色谱-串联质谱法同时测定人体尿液中4种有机磷农药代谢物[J]. 分析化学, 2016, 44(5): 723-730. doi: 10.11895/j.issn.0253-3820.150932 shu

Citation: HUANG Meng-Ying, WANG Na, GUO Xin-Yan, QIU Pan-Zi, TANG Wei-Guo, ZHANG Zun-Jian. Simultaneous Determination of Four Organophosphate Pesticide Metabolites in Urine Using Solid Phase Extraction Coupled with Gas Chromatography-Tandem Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, 2016, 44(5): 723-730. doi: 10.11895/j.issn.0253-3820.150932 shu

固相萃取-气相色谱-串联质谱法同时测定人体尿液中4种有机磷农药代谢物

1.
中国药科大学药物质量与安全预警教育部重点实验室, 南京 210009;
2.
环境保护部南京环境科学研究所, 南京 210042;
3.
金陵药业股份有限公司, 南京 210009
基金项目:
本文系2014中央级公益性科研院所基本科研业务费资助

摘要: 建立了同时测定尿液中4种有机磷类农药代谢物的气相色谱/串联质谱分析方法。尿液样品以WCX固相萃取柱富集提取,乙酸乙酯-乙腈(70:30,V/V)再萃取,浓缩干燥,甲苯溶解,N-叔丁基二甲基甲硅烷基-N-甲基三氟乙酰胺衍生化。采用HP-5MS色谱柱(30 m×0.25 mm×0.25μm)程序升温分离,串联质谱多反应检测,内标法定量。通过比较尿样中代谢物在不同萃取溶剂、固相萃取柱及pH值洗脱液等条件下的回收率,优化了前处理方法。在0.2~200μg/L范围内,4种代谢物峰面积与内标峰面积的比值与质量浓度的线性关系良好(R² ≥ 0.992),方法检出限为0.083~0.667μg/L,定量限为0.2~2.0μg/L,平均回收率为54.1%~68.6%,相对标准偏差均小于8.5% (n=6)。本方法稳定、可靠,分析时间短,不需要使用大量有机溶剂,可同时处理大批量样品,适用于人群有机磷类农药暴露情况的评估。

关键词:

English

Simultaneous Determination of Four Organophosphate Pesticide Metabolites in Urine Using Solid Phase Extraction Coupled with Gas Chromatography-Tandem Mass Spectrometry

1.
Key Laboratory of Drug Quality Control and Pharmacovigilance, China Pharmaceutical University, Ministry of Education, Nanjing 210009, China;
2.
Nanjing Institute of Environmental Science, Ministry of Environmental Protection, Nanjing 210042, China;
3.
Jinling Pharmaceutical Co., Ltd, Nanjing 210009, China
Received Date: 21 November 2015
Revised Date: 27 January 2016

Abstract: A method for quantifying four urinary metabolites of organophosphorus pesticides using gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed. The metabolites were extracted and enriched from urine samples with WCX solid phase extraction (SPE) cartridges, followed by liquid-liquid extraction with ethyl acetate-acetonitrile (70:30, V/V). The analytes were chemically derivatized with N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide after the derivatives were concentrated by drying and dissolved in phenylmethane. The separation was performed on a HP-5MS capillary column (30 m×0.25 mm×0.25 μm) with temperature programming and the detection was performed in multiple reaction monitoring (MRM) mode using GC-MS/MS. The internal standard method was used for quantification. The extraction solvents, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The result showed that the calibration curves of four metabolites were linear in the range of 0.2-200 μg/L (R² ≥ 0.992). The limits of detection (LODs) and the limits of quantification (LOQs) of the four metabolites were 0.083-0.667 μg/L and 0.2-2.0 μg/L, respectively. The recoveries of four metabolites ranged from 54.1% to 68.6% (RSD<8.5%, n=6). The established method whichs avoid using large amount of organic solvents in liquid-liquid extraction is stable, reliable and efficient, and is suitable for the analysis of large amounts of samples. Therefore, the method can be applied to assess the exposure level of organophosphorus pesticide in general population.

Key words:

Solid phase extraction
/ Gas chromatography-tandem mass spectrometry
/ Organophosphorus pesticides metabolites
/ Urine

1. [1]
  ZHU Xiao-Lan, CAI Ji-Bao, YANG Jun, SU Qing-De. Chinese J. Anal. Chem., 2005,33(6):821-824 朱晓兰, 蔡继宝, 杨俊, 苏庆德.分析化学,2005,33(6):821-824
2. [2]
  WU Yan, KANG Qing-He, GAO Kai-Yang, LI Zhi-Bin. Chinese J. Anal. Chem., 2009,37(5):753-757 吴岩, 康庆贺, 高凯扬, 李志斌.分析化学,2009,37(5):753-757
3. [3]
  Koureas M, Tsakalof A, Tsatsakis A. Hadjichristodoulou. Toxicol Lett., 2012,210:155-168
4. [4]
  LIU Yong, TANG Ying-Fei, SONG Jin-Feng, HU Zhi-Wei. Chinese Journal of Chromatography, 2014,32(2):139-144 刘永, 唐英斐, 宋金凤, 胡志伟.色谱,2014,32(2):139-144
5. [5]
  YANG Yu-Lin, RUI Zheng-Rong, WANG Hong, WANG Guo-Quan, CHEN Jia, ZHOU Zhi-Jun. Chinese J. Health Lab. Technol., 2003,13(1):24-26 杨玉林, 芮振荣, 王宏, 汪国权, 陈嘉, 周志俊.中国卫生检验杂志,2003,13(1):24-26
6. [6]
  Engel S M, Wetmur J, Chen J, Zhu C B, Barr D B, Canfield R L, Wolff M S. Environ. Health Perspect., 2011,119(8):1182-1188
7. [7]
  CHEN Chao, CHEN Guo-Qing, GAO Shu-Mei, KONG Fan-Biao, LI Run, HUANG Qi-Feng. Spectroscopy and Spectral Analysis, 2012,32(6):718-722 陈超, 陈国庆, 高淑梅, 孔凡标, 李润, 黄奇峰.光谱学与光谱分析,2012,32(6):718-722
8. [8]
  Rauh V, Arunajadai S, Horton M, Perera F, Hoepner L, Barr D B, Whyatt R. Environ. Health Perspect., 2011,119(8):1196-1201
9. [9]
  Ding G D, Shi R, Gao Y, Zhang Y, Kamijima M, Sakai K, Wang G Q, Feng C, Tian Y. Environ. Sci. Technol., 2012,46:13480-13487
10. [10]
  Prapamontol T, Sutan K, Laoyang S, Hongsibsong S, Lee G, Yano Y, Hunter R E, Ryan P B, Barr D B, Panuwet P. Int. J. Hyg. Environ. Health, 2014,217(4-5):554-566
11. [11]
  Ueyama J, Kamijima M, Kondo T, Takagi K, Shibata E, Hasegawa T, Wakusawa S, Taki T, Gotoh M, Saito I. J. Chromatogr. B, 2010,878:1257-1263
12. [12]
  Ueyama J, Saito I, Kamijima M, Nakajima T, Gotoh M, Suzuki T, Shibata E, Kondo T, Takagi K, Miyamoto K, Takamatsu J, Hasegawa T, Takagi K. J. Chromatogr. B, 2006,832:58-66
13. [13]
  Alwis G K H D, Needham L L, Barr D B. J. Chromatogr. B, 2006,843:34-41
14. [14]
  Bravo R, Caltabiano L M, Weerasekera G, Whitehead R D, Fernandez C, Needham L L, Bradman A, Barr D B. J. Expo. Anal. Environ. Epidemiol., 2004,14:249-259
15. [15]
  Hill Jr. R H, Shealy D B, Head S L, Williams C C, Bailey S L, Gregg M, Baker S E, Needham L L. J. Anal. Toxicol., 1995,19:323-329
16. [16]
  Dulaurent S, Saint-Marcoux F, Marquet P, Lachatre G. J. Chromatogr. B, 2006,831:223-229
17. [17]
  Bicker W, Lammerhofer M, Lindner W. J. Chromatogr. B, 2005,822:160-169
18. [18]
  WANG Na, SUN Juan, SHI Li-Li, JI Gui-Xiang, CHEN Guo-Song. Chinese Journal of Chromatography, 2013,31(9):903-907 王娜, 孙娟, 石利利, 吉贵祥, 陈国松.色谱,2013,31(9):903-907
19. [19]
  Odetokun M S, Montesano M A, Weerasekera G, Whitehead Jr. R D, Needham L L, Barr D B. J. Chromatogr. B, 2010,878:2567-2574
20. [20]
  Alwis G K H D, Needham L L, Barr D B. Talanta, 2009,77:1063-1067
21. [21]
  WU Chun-Hua, ZHENG Li-Xing, ZHOU Zhi-Jun. Fudan Univ. J. Med. Sci., 2006,33(4):552-555 邬春华, 郑力行, 周志俊.复旦学报医学版,2006,33(4):552-555

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沈阳化工大学材料科学与工程学院沈阳 110142

固相萃取-气相色谱-串联质谱法同时测定人体尿液中4种有机磷农药代谢物

English

Simultaneous Determination of Four Organophosphate Pesticide Metabolites in Urine Using Solid Phase Extraction Coupled with Gas Chromatography-Tandem Mass Spectrometry

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

固相萃取-气相色谱-串联质谱法同时测定人体尿液中4种有机磷农药代谢物

English

Simultaneous Determination of Four Organophosphate Pesticide Metabolites in Urine Using Solid Phase Extraction Coupled with Gas Chromatography-Tandem Mass Spectrometry

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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