超高效液相色谱-串联质谱法测定工作场所空气中14种环境激素的含量
Determination of 14 Environmental Hormones in Workplace Air by Ultra- High Performance Liquid Chromatography Tandem Mass Spectrometry
摘 要
用装好玻璃纤维滤膜的采样夹采集某工作场所空气样品,将采样后的玻璃纤维滤膜用5 mL体积比为8∶2的甲醇-水混合液超声洗脱10 min。以Waters Symmetry C18色谱柱为固定相,以不同体积比的乙腈和水的混合液为流动相进行梯度洗脱,采用超高效液相色谱-串联质谱法测定所得溶液中14种环境激素的含量。结果表明:14种环境激素的质量浓度在一定范围内与定量离子的峰面积呈线性关系,雌酮、己烯雌酚、三氯生、三氯卡班、四氯双酚A的检出限(3S/N)为0.1 μg·L-1,17α-雌二醇、17β-雌二醇、17α-炔雌醇、雌三醇、双酚A、四溴双酚A、壬基酚、4-正辛基酚、双酚F的检出限(3S/N)为0.5 μg·L-1。按照标准加入法进行回收试验,回收率为67.6%~119%,重复性和重现性试验所得测定值的相对标准偏差(n=6)分别为1.2%~11%和1.4%~12%。
工作场所空气
超高效液相色谱-串联质谱法
environmental hormone
workplace air
ultra-high performance liquid chromatography tandem mass spectrometry
Abstract
A sampling clip fitted with glass fiber filter membrane was used to collect air sample from a workplace, and the sampled glass fiber filter membrane was eluted ultrasonically with 5 mL of methanol-water mixture at a volume ratio of 8∶2 for 10 min. 14 environmental hormones in the obtained solution were determined by ultra-high performance liquid chromatography tandem mass spectrometry, using Waters Symmetry C18 column as the stationary phase and the mixture of acetonitrile and water at different volume ratios as the mobile phase for gradient elution. As shown by the results, linear relationships between values of peak area of quantitative ions and mass concentrations of 14 environmental hormones were found in definite ranges, with detection limits (3S/N) of 0.1 μg·L-1 for estrone, diethylstilbestrol, triclosan, triclocarban and tetrachlorobisphenol A, and 0.5 μg·L-1 for 17α-estradiol, 17β-estradiol, 17α-ethinylestradiol, estriol, bisphenol A, tetrabromobisphenol A, nonylphenol, 4-n-octylphenol and bisphenol F. Test for recovery was made by standard addition method, giving results in the range of 67.6%-119%, with RSDs (n=6) of the determined values obtained by tests for repeatability and reproducibility in the ranges of 1.2%-11% and 1.4%-12%, respectively.
中图分类号 O657.63 DOI 10.11973/lhjy-hx202212014
所属栏目 工作简报
基金项目
收稿日期 2021/3/2
修改稿日期
网络出版日期
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备注凌云杉,护师,主要从事职业病危害因素检测工作
引用该论文: LING Yunshan,LIU Zhong. Determination of 14 Environmental Hormones in Workplace Air by Ultra- High Performance Liquid Chromatography Tandem Mass Spectrometry[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2022, 58(12): 1449～1456
凌云杉,刘仲. 超高效液相色谱-串联质谱法测定工作场所空气中14种环境激素的含量[J]. 理化检验－化学分册, 2022, 58(12): 1449～1456
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【11】王广军.环境激素检测方法研究进展[J].郑州师范教育, 2012,1(4):10-15.
【12】於明珠,卫伟,刘安然,等.食品中环境激素的检测方法研究进展[J].生物加工过程, 2020,18(4):409-416.
【13】OMAR T F T, AHMAD A, ARIS A Z, et al. Endocrine disrupting compounds (EDCs) in environmental matrices: Review of analytical strategies for pharmaceuticals, estrogenic hormones, and alkylphenol compounds[J]. Trends in Analytical Chemistry, 2016,85:241-259.
【14】冯叙桥,肖琳,李乐,等.环境激素及其检测方法的研究进展[J].食品与生物技术学报, 2013,32(3):232-239.
【15】刘金鹏,仇晓龙,刘新星,等.食品塑料包装中壬基酚检测方法研究现状[J].上海塑料, 2017(1):7-10.
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【18】XIAO Z M, WANG R G, SUO D C, et al. Trace analysis of bisphenol A and its analogues in eggs by ultra-performance liquid chromatography-tandem mass spectrometry[J]. Food Chemistry, 2020,327:126882.
【19】DONG H, ZENG X F, BAI W D. Solid phase extraction with high polarity Carb/PSA as composite fillers prior to UPLC-MS/MS to determine six bisphenols and alkylphenols in trace level hotpot seasoning[J]. Food Chemistry, 2018,258:206-213.
【20】ZHU C, LI L S, WANG Z J, et al. Recent advances of aptasensors for exosomes detection[J]. Biosensors & Bioelectronics, 2020,160:112213.
【21】ZHANG M C, HONG W, WU X, et al. A highly sensitive and direct competitive enzyme-linked immunosorbent assay for the detection of di-(2-ethylhexyl)phthalate (DEHP) in infant supplies[J]. Analytical Methods, 2015,7(13):5441-5446.
【22】梁静,高宏峰.一种新的分子识别元件:核酸适配子[J].化学教育(中英文), 2018,39(6):1-6.
【23】HE M Q, WANG K, WANG J, et al. A sensitive aptasensor based on molybdenum carbide nanotubes and label-free aptamer for detection of bisphenol A[J]. Analytical and Bioanalytical Chemistry, 2017,409(7):1797-1803.
【24】MIRZAJANI H, CHENG C, WU J, et al. A highly sensitive and specific capacitive aptasensor for rapid and label-free trace analysis of bisphenol A (BPA) in canned foods[J]. Biosensors & Bioelectronics, 2017,89(2):1059-1067.
【25】LI S H, LI J P, LUO J H, et al. A microfluidic chip containing a molecularly imprinted polymer and a DNA aptamer for voltammetric determination of carbofuran[J]. Microchimica Acta, 2018,185(6):1-8.
【26】AN J, LI L, DING Y, et al. A novel molecularly imprinted electrochemical sensor based on Prussian blue analogue generated by iron metal organic frameworks for highly sensitive detection of melamine[J]. Electrochimica Acta, 2019,326:134946.
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【28】BIE Z J, CHEN Y, YE J, et al. Boronate-affinity glycan-oriented surface imprinting: A new strategy to mimic lectins for the recognition of an intact glycoprotein and its characteristic fragments[J]. Angewandte Chemie, 2015,127(35):10211-10215.
【29】GUHA A, AHMAD O S, GUERREIRO A, et al. Direct detection of small molecules using a nano-molecular imprinted polymer receptor and a quartz crystal resonator driven at a fixed frequency and amplitude[J]. Biosensors & Bioelectronics, 2020,158:112176.
【30】MA Y, PAN G Q, ZHANG Y, et al. Narrowly dispersed hydrophilic molecularly imprinted polymer nanoparticles for efficient molecular recognition in real aqueous samples including river water,milk,and bovine serum[J]. Angewandte Chemie, 2013,52(5):1511-1514.
【31】SHINDE S, EL-SCHICH Z, MALAKPOUR A, et al. Sialic acid-imprinted fluorescent core-shell particles for selective labeling of cell surface glycans[J]. Journal of the American Chemical Society, 2015,137(43):13908-13912.
【32】LI Y, LIU Y, YANG Y, et al. Novel electrochemical sensing platform based on a molecularly imprinted polymer decorated 3D nanoporous nickel skeleton for ultrasensitive and selective determination of metronidazole[J]. ACS Applied Materials & Interfaces, 2015,7(28):15474-15480.
【33】DES AZEVEDO S, LAKSHMI D, CHIANELLA I, et al. Molecularly imprinted polymer-hybrid electrochemical sensor for the detection of β-estradiol[J]. Industrial & Engineering Chemistry Research, 2013,52(39):13917-13923.
【34】YU M, WU L, MIAO J, et al. Titanium dioxide and polypyrrole molecularly imprinted polymer nanocomposites based electrochemical sensor for highly selective detection of p-nonylphenol[J]. Analytica Chimica Acta, 2019,1080:84-94.
【35】XU S F, LU H Z. One-pot synthesis of mesoporous structured ratiometric fluorescence molecularly imprinted sensor for highly sensitive detection of melamine from milk samples[J]. Biosensors & Bioelectronics, 2015,73:160-166.
【36】WANG L, CAO H X, PAN C G, et al. A fluorometric aptasensor for bisphenol a based on the inner filter effect of gold nanoparticles on the fluorescence of nitrogen-doped carbon dots[J]. Microchimica Acta, 2018,186(1):1-9.
【37】SHENG W, DUAN W, SHI Y, et al. Sensitive detection of bisphenol A in drinking water and river water using an upconversion nanoparticles-based fluorescence immunoassay in combination with magnetic separation[J]. Analytical Methods, 2018,10:5313-5320.
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