Comparative study of an estradiol enzyme-linked immunosorbent assay kit, liquid chromatography-tandem mass spectrometry, and ultra performance liquid chromatography-quadrupole time of flight mass spectrometry for part-per-trillion analysis of estrogens in water samples
Comparative study of an estradiol enzyme-linked immunosorbent assay kit, liquid chromatography-tandem mass spectrometry, and ultra performance liquid chromatography-quadrupole time of flight mass spectrometry for part-per-trillion analysis of estrogens in water samples
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DOI：
10.1016/j.chroma.2007.05.032
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发表时间：
2007-08-10
影响因子：
4.1
通讯作者：
Barcelo, Damia
中科院分区：
文献类型：
--
作者：
Farre, Marinella;Kuster, Marina;Barcelo, Damia
雌激素通常被认为是在环境沃茨中观察到的内分泌干扰活性的主要贡献者。然而，在这些有时非常复杂的基质中分析它们仍然具有挑战性，因为它们的检测限非常低，并且在它们具有生理活性的非常低的浓度下进行可靠测定所需的选择性。本工作建立了17-β-雌二醇的多克隆酶联免疫吸附测定（ELISA）试剂盒，高效液相色谱-串联质谱建立了基于三重四极杆分析器（QqQ）的高效液相色谱-串联质谱（HPLC-MS/MS）联用技术和基于超高效液相色谱-四极杆飞行时间质谱联用技术的新方法（UPLC-Q-TOF-MS）在快速筛选、定量分析和明确鉴定不同水基质（包括城市废水、河水、和地下水。定量和/或鉴定的化合物包括雌激素17-β-雌二醇、雌酮、17-α-乙炔基雌二醇和雌三醇，以及大豆黄酮、染料木黄酮和鹰嘴豆芽素A。除了适度高估使用ELISA试剂盒，特别是在复杂的废水样品的分析，所有的调查技术得到的结果是非常好的，一般协议。仪器灵敏度依次为：UPLC-Q-TOF-MS <多克隆ELISA试剂盒< HPLC-MS/MS（QqQ）。通过使用ELISA试剂盒直接分析水样允许达到2.5纳克L-1的检测限。然而，使用适当的样品预处理方法，所有技术都可以获得纳克至皮克/升水平的检测限，并将基质效应的风险降至最低。在选择性方面，HPLC-MS/MS（QqQ）和UPLC-Q-TOF-MS都表现出出色的性能，但后者允许更短的分析时间（16分钟对45分钟）和非目标未知化合物的鉴定。未知化合物的识别是基于前体和产物离子的准确质量测量，这允许元素组成计算和化学结构被识别，搜索不同的数据库。(c)2007 Elsevier B. V.保留所有权利。
Estrogens have been often identified as the major contributors to the endocrine-disrupting activity observed in environmental waters. However, their analysis in these, sometimes very complex, matrices is still challenging due to the very low detection limits and the selectivity required for their reliable determination at the very low concentrations at which they are physiologically active. In this work, a polyclonal enzyme-linked immunosorbent assay (ELISA) kit for 17-beta-estradiol analysis, high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) based on triple-quadrupole analyzer (QqQ), and a newly developed method based on ultra performance liquid chromatography-quadrupole time of flight mass spectrometry (UPLC-Q-TOF-MS) have been evaluated in terms of performance for the rapid screening, quantitative analysis, and unequivocal identification of some selected, environmentally relevant estrogens in different water matrices, including urban wastewater, river water, and ground water, after solid phase extraction. Compounds quantified and/or identified included the estrogens 17-beta-estradiol, estrone, 17-alpha-ethynyl estradiol and estriol, and the isoflavones daidzein, genistein, and biochanin A. Except for a moderate overestimation using the ELISA kit, especially in the analysis of complex wastewater samples, results obtained by all the investigated techniques were in very good, general agreement. The instrumental sensitivity achieved increased in the order: UPLC-Q-TOF-MS < polyclonal ELISA kit < HPLC-MS/MS (QqQ). Direct analysis of water samples by using the ELISA kit permitted to reach a limit of detection of 2.5 ng L-1. However, using an appropriated sample pretreatment method detection limits at nanogram to picogram per liter levels can be obtained with all techniques and the risk for matrix effects is minimized. In terms of selectivity, both HPLC-MS/MS (QqQ) and UPLC-Q-TOF-MS show outstanding performance, but the latter allows, in addition, shorter analysis times (16 min vs. 45 min) and the identification of non-target, unknown compounds. The identification of unknown compounds is based on the accurate mass measurements for the precursor and product ions, that permit the elemental compositions calculation and the chemical structures to be identified searching against different databases. (c) 2007 Elsevier B.V. All rights reserved.