National Science Foundation - Water and Environmental Technology Center, Temple University, Philadelphia, PA 19122, USA.
Environ Monit Assess. 2012 Mar;184(3):1657-69. doi: 10.1007/s10661-011-2068-9. Epub 2011 May 5.
Simultaneous analysis of 11 free estrogen hormones and five conjugated estrogens in water and municipal wastewater was studied. The analytical method was developed and tested for different types of solid-phase extraction adsorbents, eluents, sample containers and storage conditions, derivatization, and matrix effects. Varian Bond Elut C-18 solid-phase extraction adsorbent cartridge was selected based on its high recoveries for both free and conjugated estrogens. Sample storage conditions, as well as selection and pretreatment of sample container materials, can affect the trace level analysis of estrogens. Silanization of glassware is observed to provide low relative standard deviation (RSD) in the analysis and less percentage loss due to contacting with sample container materials. Light exposure during the test can significantly impact the results. The derivatized samples stored at -20°C for at least 6 days showed less than 10.5% average RSD in the analysis. The recovery efficiency in clean water varies from 72% to 101% for free estrogens and 78% to 82% for conjugated estrogens. The method detection limits (MDL) for most of the compounds range from 30 to 870 ng/L using a sample volume of 200 mL. With a sample volume of 3 L, the most sensitive compound produces a MDL of 0.03 ng/L. Dilute methanol is used to wash the loaded cartridge as a cleanup step in order to remove interfering species during analysis of wastewater samples. Using the optimized analytical methods, the concentration level of free estrogens in the influent and effluent municipal wastewaters is tested.
研究了同时分析水中和城市废水中 11 种游离雌激素和 5 种结合雌激素的方法。开发并测试了不同类型的固相萃取吸附剂、洗脱液、样品容器和储存条件、衍生化和基质效应。基于对游离和结合雌激素均具有较高回收率，选择了 Varian Bond Elut C-18 固相萃取吸附剂柱。样品储存条件以及样品容器材料的选择和预处理会影响雌激素的痕量分析。硅烷化玻璃器皿可提供分析中较低的相对标准偏差（RSD）和因与样品容器材料接触而导致的较低百分比损失。测试过程中的光照会显著影响结果。在-20°C 下储存衍生化样品至少 6 天，分析中平均 RSD 小于 10.5%。在清洁水中，游离雌激素的回收率效率在 72%至 101%之间变化，结合雌激素的回收率效率在 78%至 82%之间变化。使用 200mL 样品体积，大多数化合物的方法检测限（MDL）范围为 30 至 870ng/L。使用 3L 样品体积，最敏感的化合物产生的 MDL 为 0.03ng/L。在分析废水样品时，用稀甲醇作为加载柱的清洗步骤，以去除分析过程中的干扰物质。使用优化的分析方法，测试了城市废水中进水和出水的游离雌激素浓度水平。
