A method combining liquid chromatography with a dual-probe ultraspray electrospray ionization (ESI) source and time-of-flight high-resolution mass spectrometry (LC-ESI-TOF/MS) was developed for the simultaneous determination of four steroidal sex hormones, estrone (E1), 17β-estradiol (E2), 17α-ethinyl estradiol (EE2), and estriol (E3), as well as five of their hydroxylated metabolites, 2-hydroxyestrone (2-OHE1), 4-hydroxyestrone (4-OHE1), 16α-hydroxyestrone (16-OHE1), 2-hydroxyestradiol (2-OHE2), and 4-hydroxyestradiol (4-OHE2), in water samples in a short chromatographic run of 10 min. Derivatization of the analytes was optimized using dansyl chloride as the derivatizing agent. Under optimal positive ionization conditions, the following signals, which had not been previously reported, were observed (with theoretical values of m/z 377.1373 for 2- and 4-OHE1 and 378.1452 for 2- and 4-OHE2), corresponding to doubly derivatized catechol estrogens in the form of [M+2H]²⁺. These mass spectrometric signals were more abundant than those reported previously for the [M+H]⁺ forms of these hydroxylated metabolites. Solid-phase extraction (SPE) with an octadecyl-endcapped sorbent was used to pretreat tap water and effluent from a wastewater treatment plant (WWTP) in Santiago, Chile. The method achieved the simple, fast, and sensitive measurement of nine estrogens with quantitative recoveries (higher than 85.4%). Detection and quantification limits were between 1 and 17 ng L^–1 and between 3 and 58 ng L^–1, respectively, for all compounds in water. The estrogens E1 and E2 were found in WWTP effluent at concentrations of 7 ± 1 and 41 ± 1 ng L^–1, respectively, and EE2 was detected at a concentration below the limit of quantitation. This study shows that the proposed method is suitable for the accurate, rapid, and selective determination of all these analytes at trace levels.

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建立了一种将液相色谱与双探针超喷雾电喷雾电离（ESI）源和飞行时间高分辨率质谱（LC-ESI-TOF / MS）相结合的方法，用于同时测定四种甾体性激素雌酮（E1），17β-雌二醇（E2），17α-乙炔基雌二醇（EE2）和雌三醇（E3）以及它们的五个羟基化代谢产物，2-羟基雌酮（2-OHE1），4-羟基雌酮（4-OHE1 ），水样中的16α-羟基雌酮（16-OHE1），2-羟基雌二醇（2-OHE2）和4-羟基雌二醇（4-OHE2）的色谱图仅需10分钟。使用丹磺酰氯作为衍生剂优化了分析物的衍生。在最佳正电离条件下，观察到以下以前未报道的信号（理论值为2- / 4-OHE1的m / z 377.1373，2-和4-OHE2的m / z 378.1452），对应于[M + 2H] ²⁺形式的双衍生邻苯二酚雌激素。这些质谱信号比以前报道的这些羟基化代谢物的[M + H] ⁺形式更丰富。带有十八烷基封端吸附剂的固相萃取（SPE）用于预处理智利圣地亚哥污水处理厂（WWTP）的自来水和废水。该方法实现了对九种雌激素的简单，快速和灵敏的测定，定量回收率（高于85.4％）。检测和定量限在1到17 ng L ^–1之间和3到58 ng L ^–1之间分别用于水中的所有化合物。在污水处理厂废水中发现雌激素E1和E2的浓度分别为7±1和41±1 ng L ^–1，在低于定量极限的浓度下检测到EE2。这项研究表明，所提出的方法适用于痕量水平上所有这些分析物的准确，快速和选择性测定。

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