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采用超高效液相色谱-串联质谱法对河水中 61 种天然和合成孕激素进行痕量分析。

Trace analysis of 61 natural and synthetic progestins in river water and sewage effluents by ultra-high performance liquid chromatography-tandem mass spectrometry.

机构信息

Beijing Key Lab for Source Control Technology of Water Pollution, College of Environmental Sciences & Engineering, Beijing Forestry University, Beijing, 100083, China.

Beijing Key Lab for Source Control Technology of Water Pollution, College of Environmental Sciences & Engineering, Beijing Forestry University, Beijing, 100083, China.

出版信息

Water Res. 2018 Apr 15;133:142-152. doi: 10.1016/j.watres.2018.01.030. Epub 2018 Feb 3.

DOI:10.1016/j.watres.2018.01.030
PMID:29407696
Abstract

A broad number of natural and synthetic progestins are widely used in human and veterinary therapies. Although progestins exhibit adverse effects in aquatic organisms, information about environmental occurrence and fate have been limited to several compounds, hampering the accuracy of risk assessments of the compounds. In this study, a selective and sensitive analytical method was established to simultaneously determine 19 natural and 42 synthetic progestins in environmental waters, and the synthetic progestins included 19-nortestosterone, 17α-hydroxyprogesterone and progesterone derivatives. All of the target compounds were effectively separated using an HSS T3 column, and the recoveries for effluent and river samples were 80-115% and 75-105%, respectively. The detection limits for the 61 analytes were in the range of 0.05-0.60 ng/L and 0.03-0.40 ng/L for the effluent and river samples, respectively. The developed method is applied to analyze the target progestogens in sewage effluent and river water samples from Beijing. The detected concentrations of natural progesterone metabolites (3α-hydroxy-5β-tetrahydroprogesterone) were up to 63 times higher than those of the parent compound. Of the three groups of synthetic progestins, the progesterone derivatives were detected for the first time and had the highest concentrations followed by the 19-nortestosterone and 17α-hydroxyprogesterone derivatives. In contrast to previous studies, the predominant derivative compounds of 19-nortestosterone were found to be 19-nortestosterone, gestodene and mifepristone, and those of 17α-hydroxyprogesterone were 6-epi-medroxy progesterone 17-acetate and melengestrol acetate. The toxicities and environmental risk of these emerging progestins deserves more attention in the future.

摘要

大量天然和合成孕激素被广泛应用于人类和兽医治疗中。尽管孕激素在水生生物中表现出了不良效应,但有关其环境存在和归宿的信息仅限于少数几种化合物,这阻碍了对这些化合物进行准确风险评估。在本研究中,建立了一种选择性和灵敏的分析方法,用于同时测定环境水中的 19 种天然孕激素和 42 种合成孕激素,其中合成孕激素包括 19-去甲睾酮、17α-羟孕酮和孕酮衍生物。所有目标化合物均采用 HSS T3 柱有效分离,废水和河流样品的回收率分别为 80-115%和 75-105%。61 种分析物的检测限范围为废水和河流样品中的 0.05-0.60ng/L 和 0.03-0.40ng/L。所建立的方法应用于分析北京污水厂和河流水样中的目标孕激素。天然孕酮代谢物(3α-羟基-5β-四氢孕酮)的检出浓度比母体化合物高 63 倍。在所研究的三组合成孕激素中,首次检测到孕酮衍生物,且其浓度最高,其次是 19-去甲睾酮和 17α-羟孕酮衍生物。与以往研究不同,19-去甲睾酮的主要衍生化合物被发现为 19-去甲睾酮、孕二烯酮和米非司酮,而 17α-羟孕酮的主要衍生化合物为 6-表-美雄醇 17-醋酸酯和甲地孕酮醋酸酯。未来这些新兴孕激素的毒性和环境风险值得更多关注。

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