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基于放射分析的方法研究农业土壤中共轭雌激素和游离雌激素的归宿与转化

Radioassay-Based Approach to Investigate Fate and Transformation of Conjugated and Free Estrogens in an Agricultural Soil.

作者信息

Shrestha Suman L, Casey Francis X M, Hakk Heldur, Padmanabhan G

机构信息

Department of Soil Science, North Dakota State University , Fargo, North Dakota.

出版信息

Environ Eng Sci. 2013 Feb;30(2):89-96. doi: 10.1089/ees.2012.0206.

Abstract

Estrogens, a potent group of endocrine disruptors toward aquatic species, are primarily excreted as conjugates from humans and animals. Radioassay-based approaches with detailed speciation have been frequently conducted for environmental-fate studies for pesticides; however, such techniques have not been exploited for reproductive hormones, and especially for hormone conjugates. This article describes a simple, robust, and high-mass-recovery approach to investigate the fate and transformation of a prototype estrogen conjugate, that is, 17β-estradiol-3-glucuronide (E2-3G), and its metabolites (free estrogens) in a laboratory soil and water matrix without the need for enzymatic cleavage and/or fluorescent derivatization. E2-3G and its metabolites were baseline resolved in a single run using high-performance liquid chromatography (HPLC) and quantified by liquid scintillation counting of the HPLC effluents. Transformation of E2-3G and the disposition of its metabolites--the free estrogens 17β-estradiol and estrone--into aqueous, sorbed, and gaseous phases, were adequately accounted for in a soil-water batch system. High mass balances ranging from 99.0% to 114.1% were obtained. Although the method gave lower sensitivity (parts per billion) than tandem mass spectrometer (parts per trillion), it offered sufficient chromatographic resolution and sensitivity to study the fate of labile estrogens in environmental matrices, using the concentration range of this study. An additional advantage of the approach was the relatively low cost of the instrumentation employed. The presented approach can be successfully applied to study the fate of conjugated hormones and their metabolites in the environment allowing simultaneous discernment of complex fate and transformation processes in soil, water, and gas.

摘要

雌激素是一类对水生物种具有强大内分泌干扰作用的物质,主要以结合物形式从人类和动物体内排出。基于放射性测定且具有详细形态分析的方法已频繁用于农药的环境归趋研究;然而,此类技术尚未用于生殖激素,尤其是激素结合物的研究。本文描述了一种简单、可靠且回收率高的方法,用于研究原型雌激素结合物即17β-雌二醇-3-葡萄糖醛酸苷(E2-3G)及其代谢物(游离雌激素)在实验室土壤和水基质中的归趋与转化,无需酶解和/或荧光衍生化。使用高效液相色谱(HPLC)在一次运行中对E2-3G及其代谢物进行基线分离,并通过对HPLC流出物进行液体闪烁计数来定量。在土壤-水批次系统中充分考虑了E2-3G的转化及其代谢物——游离雌激素17β-雌二醇和雌酮——在水相、吸附相和气态相中的分布情况。获得了99.0%至114.1%的高物质平衡率。尽管该方法的灵敏度(十亿分之一)低于串联质谱仪(万亿分之一),但在本研究的浓度范围内,它提供了足够的色谱分辨率和灵敏度来研究环境基质中不稳定雌激素的归趋。该方法的另一个优点是所使用仪器的成本相对较低。所提出的方法可成功应用于研究结合激素及其代谢物在环境中的归趋,能够同时识别土壤、水和气体中复杂的归趋和转化过程。

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本文引用的文献

1
Effects of liquid swine manure on dissipation of 17β-estradiol in soil.液体猪粪对土壤中 17β-雌二醇消解的影响。
J Hazard Mater. 2011 Feb 28;186(2-3):1111-7. doi: 10.1016/j.jhazmat.2010.11.112. Epub 2010 Dec 3.
4
Occurrence, fate, and biodegradation of estrogens in sewage and manure.雌激素在污水和粪便中的存在、归宿和生物降解。
Appl Microbiol Biotechnol. 2010 May;86(6):1671-92. doi: 10.1007/s00253-010-2547-x. Epub 2010 Mar 31.
8
Abiotic oxidation of 17beta-estradiol by soil manganese oxides.土壤锰氧化物对 17β-雌二醇的非生物氧化作用。
Environ Pollut. 2009 Oct;157(10):2710-5. doi: 10.1016/j.envpol.2009.04.030. Epub 2009 May 24.

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