Nieto Antonio, Borrull Francesc, Pocurull Eva, Marcé Rosa Maria
Department of Analytical Chemistry and Organic Chemistry, University Rovira i Virgili, Sescelades Campus, Marcel.lí Domingo s/n, Tarragona 43007, Spain.
J Chromatogr A. 2008 Dec 12;1213(2):224-30. doi: 10.1016/j.chroma.2008.10.043. Epub 2008 Oct 17.
In this study we present a pressurized liquid extraction/liquid chromatography-tandem mass spectrometry (PLE/LC-MS-MS) method to determine a group of estrogens and conjugated estrogens in sewage sludge. Parameters that affect the extraction step such as extraction solvent, temperature, pressure, static extraction time, number of cycles, purge time and flush volume have been optimized. In the LC-MS-MS system, electrospray ionization and a triple quadrupole analyzer have been used, and the multiple reaction monitoring mode has enabled low levels of target analytes to be detected. All recoveries were higher than 81% except for estrone 3-glucoronide and estradiol 17-glucoronide which were not extracted and consequently, they were not considered in the present study. The repeatability and reproducibility between days expressed as %RSD (n=3), were lower than 6% and 9%, respectively. The method developed allowed the target analytes to be quantified at low levels of microg/kg. The limits of detection were lower than 26 microg/kg of dry weight (d.w.) of sewage sludge, except for 17 alpha-estradiol, 17beta-estradiol, 17 alpha-ethinylestradiol and estradiol 17-acetate whose values were between 150 and 175 microg/kg (d.w.). The method was applied to determine these compounds in sewage sludge from two domestic sewage treatment plants. Estrone 3-sulfate, estradiol 3-sulfate, diethylstilbestrol, estrone and estriol were determined in some samples and estriol showed the highest value (406 microg/kg d.w.).
在本研究中,我们提出了一种加压液体萃取/液相色谱-串联质谱法(PLE/LC-MS-MS)来测定污水污泥中的一组雌激素和共轭雌激素。已对影响萃取步骤的参数进行了优化,如萃取溶剂、温度、压力、静态萃取时间、循环次数、吹扫时间和冲洗体积。在LC-MS-MS系统中,采用了电喷雾电离和三重四极杆分析仪,多反应监测模式能够检测到低水平的目标分析物。除了未被萃取的雌酮3-葡萄糖醛酸苷和雌二醇17-葡萄糖醛酸苷外,所有回收率均高于81%,因此,本研究未考虑它们。以%RSD(n = 3)表示的日间重复性和再现性分别低于6%和9%。所开发的方法能够对低至微克/千克水平的目标分析物进行定量。除了17α-雌二醇、17β-雌二醇、17α-乙炔雌二醇和雌二醇17-醋酸酯(其值在150至175微克/千克(干重)之间)外,检测限低于26微克/千克污水污泥干重。该方法应用于测定两家生活污水处理厂污水污泥中的这些化合物。在一些样品中测定了雌酮3-硫酸盐、雌二醇3-硫酸盐、己烯雌酚、雌酮和雌三醇,其中雌三醇的值最高(406微克/千克干重)。