固相萃取-高效液相色谱检测吸烟人群尿中8 种单羟基多环芳烃

上海大学学报(自然科学版) ›› 2013, Vol. 19 ›› Issue (4): 374-379.

固相萃取-高效液相色谱检测吸烟人群尿中8 种单羟基多环芳烃

李银萍, 李雪

(上海大学环境与化学工程学院, 上海200444)

出版日期:2013-08-27 发布日期:2013-08-27
作者简介:李雪(1981—), 女, 博士, 研究方向为持久性有机污染物环境存在与健康风险评价. E-mail: zlpamylee@gmail.com
基金资助:
国家自然科学青年基金资助项目(21107066); 上海高校青年教师培养资助计划项目; 上海大学创新基金资助项目

Detection of Eight Hydroxylated Metabolites of Polycyclic Aromatic Hydrocarbons Smokers’ Urine Using Solid Phase Extraction Coupled to High Performance Liquid Chromatography

LI Yin-ping, LI Xue

(School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, China)

Online:2013-08-27 Published:2013-08-27

摘要/Abstract

摘要： 采用固相萃取(solid phase extraction, SPE)前处理结合高效液相色谱荧光检测(high performance liquid chromato graphy fluorescence detection, HPLC-FD), 建立了检测吸烟人群尿中8 种羟基多环芳烃(OHpolycyclic aromatic hydrocarbons, OH-PAHs, 环数2~5)的SPE-HPLC-FD 分析方法; 在优化后的SPE 和 HPLC-FD 条件下, 内标法定量检测尿中8 种OH-PAHs. 结果表明, 标准曲线方程的线性范围为0.2~20 μg/L 或 0.5~20 μg/L, 决定系数R²>0.998, 方法定量限(method quantification limit, MQL)为0.03~0.07 μg/L, 回收率R为(70%±4%)~(109%±30%), 日间重现性为5%~28%. 当地吸烟者尿样分析结果显示, 本方法能够检测其尿中不同环数的OH-PAHs, 可用于当地吸烟人群PAHs 暴露健康风险评价.

关键词: 健康风险评价, 尿样, 羟基多环芳烃, 生物标志物, 吸烟人群

Abstract: To assess the exposure to polycyclic aromatic hydrocarbons (PAHs) by smoking, a method to detect 8 types of urinary hydroxylated metabolites of PAHs (OH-PAHs) (containing 2 to 5 rings) was developed by using solid phase extraction (SPE）coupled to high performance liquid chromatography fluorescence detection (HPLC-FD). With optimized SPE and HPLC-FD conditions, 8 standard curve equations were established for individual OH-PAHs with linear ranges of 0.2~20 μg/L or 0.5~20 μg/L (all determination coefficients R²> 0.998). The method quantification limits (MDLs) were 0.03~0.07 μg/L, and recoveries R were (70%±4%)~(109%±30%), while inter-day variations ranged from 5% to 28%. OH-PAHs in urine samples from local smokers were successfully detected, showing that the method is promising in assessing exposure to PAHs for local smokers.

Key words: biomarker, health risk assessment, hydroxylated metabolite of polycyclic aromatic carbons, smoker, urine

中图分类号:

O 614.3

李银萍, 李雪. 固相萃取-高效液相色谱检测吸烟人群尿中8 种单羟基多环芳烃[J]. 上海大学学报(自然科学版), 2013, 19(4): 374-379.

LI Yin-ping, LI Xue. Detection of Eight Hydroxylated Metabolites of Polycyclic Aromatic Hydrocarbons Smokers’ Urine Using Solid Phase Extraction Coupled to High Performance Liquid Chromatography[J]. Journal of Shanghai University（Natural Science Edition）, 2013, 19(4): 374-379.

参考文献

[1] Vijayalakshmi K P, Suresh C H. Theoretical studies

on the carcinogenicity of polycyclic aromatic hydrocarbons

[J]. Journal of Computational Chemistry,

2008, 29: 1808-1817.

[2] 牛红云, 蔡亚岐, 魏复盛, 等. 多环芳烃暴露的生物标

志物——尿中羟基多环芳烃[J]. 化学进展, 2006, 18:

1381-1390.
[3] Campo L, Rossella F, Pavanello S, et al. Urinary

profiles to assess polycyclic aromatic hydrocarbons

exposure in coke-oven workers [J]. Toxicology

Letters, 2010, 192: 72-78.

[4] Kang R H, Wang Y S, Yang H M, et al.

Rapid simultaneous analysis of 1-hydroxypyrene,

2-hydroxyfluorene, 9-hydroxyphenanthrene, 1- and 2-

naphthol in urine by first derivative synchronous fluorescence

spectrometry using Tween-20 as a sensitizer

[J]. Analytica Chimica Acta, 2010, 658: 180-

186.

[5] 沈惠麒, 顾祖维, 吴宜群. 生物监测和生物标志物——

理论基础及应用[M]. 2 版. 北京: 北京大学医学出版

社, 2006: 3-17.

[6] Chetiyanukornkul T, Toriba A, Kizu R, et al.

Urinary 2-hydroxyfluorene and 1-hydroxypyrene levels

in smokers and nonsmokers in Japan and Thailand

[J]. Polycyclic Aromatic Compounds, 2003, 24:

467-474.

[7] Benowitz N L, Jacob P, Bernert J T, et al. Carcinogen

exposure during short-term switching from

regular to “Light” cigarettes [J]. Cancer Epidemiology

Biomarkers & Prevention, 2005, 14: 1376-1383.

[8] Peuss R, Drexler H, Bottcher M, et al. Current

external and internal exposure to naphthaleneof workers occupationally exposed to polycyclic aromatic

hydrocarbons in different industries [J]. International

Archives of Occupational and Environmental

Health, 2005, 78(5): 355-362.

[9] Jacob P, Wilson M, Benowitz N L. Determination

of phenolic metabolites of polycyclic

aromatic hydrocarbons in human urine as their

pentafluorobenzyl ether derivatives using liquid

chromatography-tandem mass spectrometry [J]. Analytical

Chemistry, 2007, 79(2): 587-598.

[10] Hagedorn H W, Scherer G, Engl J, et al. Urinary

excretion of phenolic polycyclic aromatic hydrocarbons

(OH-PAH) in nonsmokers and in smokers of

cigarettes with different ISO tar yields [J]. Journal of

Analytical Toxicology, 2009, 33(6): 301-309.

[11] Ramsauer B, Sterz K, Hagedorn H W, et al.

A liquid chromatography/tandem mass spectrometry

(LC-MS/MS) method for the determination of phenolic

polycyclic aromatic hydrocarbons (OH-PAH) in

urine of non-smokers and smokers [J]. Analytical and

Bioanalytical Chemistry, 2011, 39(2): 877-889.

[12] Sthelen G, Goniewicz M L, Demosey D, et al.

Exposure and kinetics of polycyclic aromatic hydrocarbons

(PAHs) in cigarette smokers [J]. Chemical

Research in Toxicology, 2012, 25(4): 952-964.

[13] Scherer G, Frank S, Riedel K, et al. Biomonitoring

of exposure to polycyclic aromatic hydrocarbons

of nonoccupationally exposed persons [J]. Cancer

Epidemiology Biomarkers & Prevention, 2000, 9:

373-380.

[14] Hecht S S, Carmella S G, Le K A, et al.

Effects of reduced cigarette smoking on levels of1-hydroxypyrene in urine [J]. Cancer Epidemiology

Biomarkers & Prevention, 2004, 13: 834-842.

[15] Lafontaine M, Champmartin C, Simon P, et al.

3-hydroxybenzo a pyrene in the urine of smokers and

non-smokers [J]. Toxicology Letters, 2006, 162: 181-

185.

[16] Chetiyanukornkul T, Toriba A, Kameda T, et

al. Simultaneous determination of urinary hydroxylated

metabolites of naphthalene, fluorene, phenanthrene,

fluoranthene and pyrene as multiple biomarkers

of exposure to polycyclic aromatic hydrocarbons

[J]. Analytical and Bioanalytical Chemistry,

2006, 386: 712-718.

[17] Elovaara E, Mikkola J, M¨akel¨a M, et al. Assessment

of soil remediation workers’ exposure to polycyclic

aromatic hydrocarbons (PAHs): biomonitoring

of naphthols, phenanthrols, and 1-hydroxypyrene in

urine [J]. Toxicology Letters, 2006, 162: 158-163.

[18] Buratti M, Campo L, Fustinoni S, et al. Urinary

hydroxylated metabolites of polycyclic aromatic

hydrocarbons as biomarkers of exposure in asphalt

workers [J]. Biomarkers, 2007, 12(3): 221-239.

[19] Kuusimaki L, Peltonen Y, Mutanen P, et al.

Urinary-metabolites of naphthalene, phenanthrene

and pyrene as biomarkers of exposure to diesel exhaust

[J]. International Archives of Occupational and

Environmental Health, 2004, 77: 23-30.

[20] Liu A L, Lu W Q, Wang Z Z, et al. Elevated levels

of urinary 8-hydroxy-2’-deoxyguanosine, lymphocytic

micronuclei, and serum glutathione s-transferase in

workers exposed to cokeoven emissions [J]. Environmental

Health Perspectives, 2006, 114: 673-677.