顶空固相微萃取/气相色谱-质谱联用测定尿液中8种苯系物和17种挥发性卤代烃

引用本文: 展学旺, 李彭辉, 徐琳. 顶空固相微萃取/气相色谱-质谱联用测定尿液中8种苯系物和17种挥发性卤代烃[J]. 分析化学, 2023, 51(6): 1033-1041. doi: 10.19756/j.issn.0253-3820.221372 shu

Citation: ZHAN Xue-Wang, LI Peng-Hui, XU Lin. Determination of 8 Kinds of Benzenes and 17 Kinds of Volatile Halogenated Hydrocarbons in Urine by Headspace-Solid Phase Microextraction/Gas Chromatography-Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, 2023, 51(6): 1033-1041. doi: 10.19756/j.issn.0253-3820.221372 shu

顶空固相微萃取/气相色谱-质谱联用测定尿液中8种苯系物和17种挥发性卤代烃

展学旺 ^1,2, ,
李彭辉 ^{1,
,} ,
徐琳 ^{2,
,}

1.
天津理工大学环境科学与安全工程学院, 天津 300382;
2.
中国科学院生态环境研究中心, 环境化学与生态毒理学国家重点实验室, 北京 100085

通讯作者: 李彭辉,E-mail:lipenghui406@163.com; 徐琳,E-mail:linxu@rcees.ac.cn

基金项目:
国家自然科学基金项目(Nos.22036007,21876189)和中国科学院青年创新促进会项目(No.2018059)资助。

摘要: 建立了尿液样品中8种苯系物（BTEX）和17种挥发性卤代烃（VHC）的顶空固相微萃取/气相色谱-质谱分析方法（GC-MS）。通过单因素实验考察了萃取纤维、萃取温度、萃取时间、尿液pH值、搅拌速度和盐效应等因素对实验结果的影响，然后根据Box-Behnken试验设计原理，以25种目标化合物色谱图总峰面积为响应值进行因素之间交互作用的分析。优化后的条件为：将2 mL调至pH=4的尿样、40 μL内标（氟苯和氯苯-d5，500 μg/L）和0.55 g NaCl加入40 mL顶空瓶中，选用75 μm羧基/聚二甲基硅氧烷（Carboxen/PDMS）纤维于51℃、搅拌速度为400 r/min条件下顶空萃取35 min。25种目标物在0.05~50 μg/L范围内具有良好的线性关系（R² > 0.990），方法检出限为0.008~5.780 ng/L，定量限为0.027~19.268 ng/L； 25种目标物的回收率为78.9%~115.2%，相对标准偏差为0.7%~16.2%。将本方法应用于山东省莱阳地区健康人群尿液的测定，结果表明，在15个人体尿液样本中共检出20种目标化合物，总浓度范围为3.13~43.17 μg/L，中位浓度为5.78 μg/L。1,2,4三甲基苯（1,2,4-TMB）是BTEX中位数含量最高的化合物，1,3二氯苯（1,3-DCB）是VHC中位数含量最高的化合物。本方法灵敏度高、重现性好，适用于尿液样品中BTEX和VHC的同时检测，可为这两类化合物的人体暴露研究提供重要的方法学基础。

关键词:

English

Determination of 8 Kinds of Benzenes and 17 Kinds of Volatile Halogenated Hydrocarbons in Urine by Headspace-Solid Phase Microextraction/Gas Chromatography-Mass Spectrometry

ZHAN Xue-Wang ^1,2, ,
LI Peng-Hui ^{1,
,} ,
XU Lin ^{2,
,}

1.
School of Environmental Science and Safety Engineering, Tianjin University of Technology, Tianjin 300382, China;
2.
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China

Corresponding author: LI Peng-Hui, ; XU Lin,

Received Date: 24 July 2022
Revised Date: 07 February 2023
Fund Project:
Supported by the National Natural Science Foundation of China (Nos. 22036007, 21876189) and the Youth Innovation Promotion Association, CAS (No. 2018059).

Abstract: A headspace solid-phase microextraction coupled with gas chromatography-mass spectrometric (GCMS) method was developed for analysis of 8 kinds of benzenes (BTEX) and 17 kinds of volatile halogenated hydrocarbons (VHC) in urine samples. The effects of extraction fiber, extraction temperature, extraction time, urine pH, stirring speed and salt effect on the experimental results were investigated by single-factor experiments, followed by the interaction analysis between factors based on the Box-Behnken experimental design principle with the total peak areas of the chromatograms of 25 kinds of target compounds as the response values. The optimized conditions were as follows: 2 mL of urine sample adjusted to pH=4, 40 μL of internal standard (fluorobenzene and chlorobenzene-d5, 500 μg/L) and 0.55 g NaCl were added to a 40-mL headspace vial; 75 μm Carboxen/ polydimethylsiloxane (Carboxen/PDMS) fiber was selected for headspace extraction at 51℃ with stirring speed of 400 r/min for 35 min. The calibration curves showed good linearity (R² > 0.990) in the range of 0.05-50 μg/L for the 25 kinds of targets, with the detection limits of 0.008-5.780 ng/L and the lower limits of quantification of 0.027-19.268 ng/L. The recoveries of the 25 kinds of stargets ranged from 78.9% to 115.2% and the relative standard deviations were 0.7%-16.2%. The method was applied to determination of urine samples from the healthy population in Lai Yang, Shandong Province. The results showed that 20 kinds of target compounds were detected in 15 human urine samples, with total concentrations ranging from 3.13 to 43.17 μg/L and a median content of 5.78 μg/L. 1,2,4-Trimethylbenzene (1,2,4-TMB) was the compound with the highest median content of BTEX and 1,3-dichlorobenzene (1,3-DCB) was the compound with the highest median content of VHC. The method was sensitive and reproducible for simultaneous determination of BTEX and VHC in urine samples and might provide an important methodological basis for human exposure studies of these two compounds.

Key words:

1. [1]
  JIANG Yang, FANG Li-Ping, YANG Gang, WANG Wei, CHEN Yong-Mei, TIAN Wen. Environ. Chem., 2015, 34(9):1611-1618. 姜洋, 房丽萍, 杨刚, 王伟, 陈咏梅, 田文. 环境化学, 2015, 34(9):1611-1618.
2. [2]
  LIN X, XU C, ZHOU Y, LIU S, LIU W. Sci. Total Environ., 2020, 703:134646.LIN X, XU C, ZHOU Y, LIU S, LIU W. Sci. Total Environ., 2020, 703:134646.
3. [3]
  YANG S, ZHOU M, WANG B, MU G, WANG X, YUAN J, CHEN W. J. Hazard. Mater., 2020, 389:121889.YANG S, ZHOU M, WANG B, MU G, WANG X, YUAN J, CHEN W. J. Hazard. Mater., 2020, 389:121889.
4. [4]
  PAN Y, LIU Q, LIU F F, QIAN G R, XU Z P. Sci. Total Environ., 2011, 409(20):4289-4296.PAN Y, LIU Q, LIU F F, QIAN G R, XU Z P. Sci. Total Environ., 2011, 409(20):4289-4296.
5. [5]
  YU B, YUAN Z, YU Z, XUE-SONG F. Chem. Eng. J., 2022, 435:134825.YU B, YUAN Z, YU Z, XUE-SONG F. Chem. Eng. J., 2022, 435:134825.
6. [6]
  CHAMBERS D M, EDWARDS K C, SANCHEZ E, REESE C M, FERNANDEZ A T, BLOUNT B C, DE JESÚS V R. ACS Omega, 2021, 6(19):12684-12690.CHAMBERS D M, EDWARDS K C, SANCHEZ E, REESE C M, FERNANDEZ A T, BLOUNT B C, DE JESÚS V R. ACS Omega, 2021, 6(19):12684-12690.
7. [7]
  AGGARWAL P, BAKER J, BOYD M T, COYLE S, PROBERT C, CHAPMAN E A. Metabolites, 2020, 10(12):482.AGGARWAL P, BAKER J, BOYD M T, COYLE S, PROBERT C, CHAPMAN E A. Metabolites, 2020, 10(12):482.
8. [8]
  MESQUITA A D S, ZAMORA-OBANDO H R, DOS SANTOS F N, SCHMIDT-FILHO J, DE LIMA V C, COSTA F D A, DE ANDRADE V P, EBERLIN M N, COLNAGHI SIMIONATO A V. Microchem. J., 2020, 159:105679.MESQUITA A D S, ZAMORA-OBANDO H R, DOS SANTOS F N, SCHMIDT-FILHO J, DE LIMA V C, COSTA F D A, DE ANDRADE V P, EBERLIN M N, COLNAGHI SIMIONATO A V. Microchem. J., 2020, 159:105679.
9. [9]
  CALEJO I, MOREIRA N, ARAÚJO A M, CARVALHO M, BASTOS M L, DE PINHO P G. Talanta, 2016, 148:486-493.CALEJO I, MOREIRA N, ARAÚJO A M, CARVALHO M, BASTOS M L, DE PINHO P G. Talanta, 2016, 148:486-493.
10. [10]
  RAFIEE A, DELGADO-SABORIT J M, SLY P D, AMIRI H, HOSEINI M. Sci. Total Environ., 2019, 656:540-546.RAFIEE A, DELGADO-SABORIT J M, SLY P D, AMIRI H, HOSEINI M. Sci. Total Environ., 2019, 656:540-546.
11. [11]
  TSANGARI X, ANDRIANOU X D, AGAPIOU A, MOCHALSKI P, MAKRIS K C. Chemosphere, 2017, 173:261-266.TSANGARI X, ANDRIANOU X D, AGAPIOU A, MOCHALSKI P, MAKRIS K C. Chemosphere, 2017, 173:261-266.
12. [12]
  QIN N, ZHU Y, ZHONG Y, TIAN J, LI J, CHEN L, FAN R, WEI F. Int. J. Environ. Res. Public Health, 2022, 19(2):847.QIN N, ZHU Y, ZHONG Y, TIAN J, LI J, CHEN L, FAN R, WEI F. Int. J. Environ. Res. Public Health, 2022, 19(2):847.
13. [13]
  POLI D, MANINI P, ANDREOLI R, FRANCHINI I, MUTTI A. J. Chromatogr. B, 2005, 820(1):95-102.POLI D, MANINI P, ANDREOLI R, FRANCHINI I, MUTTI A. J. Chromatogr. B, 2005, 820(1):95-102.
14. [14]
  FURUKI K, UKAI H, OKAMOTO S, TAKADA S, KAWAI T, MIYAMA Y, MITSUYOSHI K, ZHANG Z W, HIGASHIKAWA K, IKEDA M. Int. Arch. Occup. Environ. Health, 2000, 73(4):221-227.FURUKI K, UKAI H, OKAMOTO S, TAKADA S, KAWAI T, MIYAMA Y, MITSUYOSHI K, ZHANG Z W, HIGASHIKAWA K, IKEDA M. Int. Arch. Occup. Environ. Health, 2000, 73(4):221-227.
15. [15]
  SAKAI T, MORITA Y, WAKUI C. J. Chromatogr. B, 2002, 778(1-2):245-250.SAKAI T, MORITA Y, WAKUI C. J. Chromatogr. B, 2002, 778(1-2):245-250.
16. [16]
  LIN Qiang, ZHOU Zhi-Rong, HU Xiao-Jian, LIN Shao-Bin. J. Environ. Hyg., 2017, 7(3):243-247, 254. 林强, 周志荣, 胡小键, 林少彬. 环境卫生学杂志, 2017, 7(3):243-247, 254.
17. [17]
  ERB A, MARSAN P, BURGART M, REMY A, LAMBERT-XOLIN A M, JEANDEL F, HANSER O, ROBERT A. J. Chromatogr. B, 2019, 1125:121724.ERB A, MARSAN P, BURGART M, REMY A, LAMBERT-XOLIN A M, JEANDEL F, HANSER O, ROBERT A. J. Chromatogr. B, 2019, 1125:121724.
18. [18]
  MESQUITA A D, ZAMORA-OBANDO H R, DOS SANTOS F N, SCHMIDT-FILHO J, DE LIMA V C, COSTA F D, DE ANDRADE V P, EBERLIN M N, SIMIONATO A V. Microchem. J., 2020, 159:105479.MESQUITA A D, ZAMORA-OBANDO H R, DOS SANTOS F N, SCHMIDT-FILHO J, DE LIMA V C, COSTA F D, DE ANDRADE V P, EBERLIN M N, SIMIONATO A V. Microchem. J., 2020, 159:105479.
19. [19]
  DRABINSKA N, STAROWICZ M, KRUPA-KOZAK U. J. Anal. Chem., 2020, 75(6):792-801.DRABINSKA N, STAROWICZ M, KRUPA-KOZAK U. J. Anal. Chem., 2020, 75(6):792-801.
20. [20]
  WANG D, WANG C, PI X, GUO L, WANG Y, LI M, FENG Y, LIN Z, HOU W, LI E. Biomed. Rep., 2016, 5(1):68-72.WANG D, WANG C, PI X, GUO L, WANG Y, LI M, FENG Y, LIN Z, HOU W, LI E. Biomed. Rep., 2016, 5(1):68-72.
21. [21]
  TAUNK K, TAWARE R, MORE T H, PORTO-FIGUEIRA P, PEREIRA J A M, MOHAPATRA R, SONEJI D, CÂMARA J S, NAGARAJARAM H A, RAPOLE S. RSC Adv., 2018, 8(44):25040-25050.TAUNK K, TAWARE R, MORE T H, PORTO-FIGUEIRA P, PEREIRA J A M, MOHAPATRA R, SONEJI D, CÂMARA J S, NAGARAJARAM H A, RAPOLE S. RSC Adv., 2018, 8(44):25040-25050.
22. [22]
  WANG Zi-Yi, DU Xin-Zhen, ZHANG Xing-Hui, SHI Hai-Xiong, WU Xiao-Jia. Chem. Res. Appl., 2022, 34(12):2793- 2800. 王子宜, 杜新贞, 张兴辉, 师海雄, 邬小佳. 化学研究与应用, 2022, 34(12):2793-2800.
23. [23]
  MONTEIRO M, CARVALHO M, HENRIQUE R, JERÓNIMO C, MOREIRA N, BASTOS M D, DE PINHO P G. Eur. J. Cancer, 2014, 50(11):1993-2002.MONTEIRO M, CARVALHO M, HENRIQUE R, JERÓNIMO C, MOREIRA N, BASTOS M D, DE PINHO P G. Eur. J. Cancer, 2014, 50(11):1993-2002.
24. [24]
  SHUAI Jia-Qi, LYU Chang-Ping, YANG Zheng-Min, SHI Yang, MAO Mi, JIANG Li-Na, KANG Min. China Oils Fats, 2023, 48(4):57-62. 帅佳琪, 吕长平, 秧拯民, 石杨, 毛咪, 江莉娜, 康敏. 中国油脂, 2023, 48(4):57-62.
25. [25]
  YU Ming-Yue, YANG Xiao-Qiu, FAN Rong, ZHENG Yu-Kang, SHI Jian-Bo, ZHENG Qi. Chin. J. Anal. Chem., 2020, 48(9):1228-1235. 余明月, 杨小秋, 樊蓉, 郑禹康, 史建波, 郑琦. 分析化学, 2020, 48(9):1228-1235.
26. [26]
  WANG M, ZHONG Y, QIN J, ZHANG Z, LI S, YANG B. Food Chem., 2017, 227:329-334.WANG M, ZHONG Y, QIN J, ZHANG Z, LI S, YANG B. Food Chem., 2017, 227:329-334.
27. [27]
  XU Lin, SHI Ya-Li, CAI Ya-Qi. J. Instrum. Anal., 2012, 31(9):1115-1119. 徐琳, 史亚利, 蔡亚岐. 分析测试学报, 2012, 31(9):1115-1119.
28. [28]
  FUSTINONI S, ROSSELLA F, CAMPO L, MERCADANTE R, BERTAZZI P A. Sci. Total Environ., 2010, 408(14):2840- 2849.FUSTINONI S, ROSSELLA F, CAMPO L, MERCADANTE R, BERTAZZI P A. Sci. Total Environ., 2010, 408(14):2840- 2849.

扫一扫看文章

计量

PDF下载量: 11
文章访问数: 1145
HTML全文浏览量: 49

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

顶空固相微萃取/气相色谱-质谱联用测定尿液中8种苯系物和17种挥发性卤代烃

通讯作者: 李彭辉,E-mail:lipenghui406@163.com; 徐琳,E-mail:linxu@rcees.ac.cn

English

Determination of 8 Kinds of Benzenes and 17 Kinds of Volatile Halogenated Hydrocarbons in Urine by Headspace-Solid Phase Microextraction/Gas Chromatography-Mass Spectrometry

Corresponding author: LI Peng-Hui, ; XU Lin,

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？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

顶空固相微萃取/气相色谱-质谱联用测定尿液中8种苯系物和17种挥发性卤代烃

通讯作者: 李彭辉,E-mail:lipenghui406@163.com; 徐琳,E-mail:linxu@rcees.ac.cn

English

Determination of 8 Kinds of Benzenes and 17 Kinds of Volatile Halogenated Hydrocarbons in Urine by Headspace-Solid Phase Microextraction/Gas Chromatography-Mass Spectrometry

Corresponding author: LI Peng-Hui, ; XU Lin,

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？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs