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通过臭氧氧化和O3/H2O2降解17β-雌二醇和17α-乙炔雌二醇并去除其雌激素活性

Degradation and estrogenic activity removal of 17beta-estradiol and 17alpha-ethinylestradiol by ozonation and O3/H2O2.

作者信息

Maniero Milena Guedes, Bila Daniele Maia, Dezotti Márcia

机构信息

Chemical Engineering Program-COPPE, Federal University of Rio de Janeiro, P.O. Box 68502, 21941-972, Rio de Janeiro, RJ, Brazil.

出版信息

Sci Total Environ. 2008 Dec 15;407(1):105-15. doi: 10.1016/j.scitotenv.2008.08.011. Epub 2008 Sep 20.

Abstract

This work investigated the degradation of a natural (17beta-estradiol) and a synthetic (17alpha-ethinylestradiol) estrogens (pure or in the mixture) and the removal of estrogenic activity by the ozonation and O3/H2O2 process in three different pHs (3, 7 and 11). The effect of oxidation via OH radical was evaluated adding a radical scavenger (t-butanol) in the medium. Estrogenic activity was performed using the YES assay. 17beta-estradiol and 17alpha-ethinylestradiol presented similar estrogenic potential and the association of these estrogens resulted in an addictive effect for estrogenic activity. Ozonation and O3/H2O2 processes were effective in removing the estrogens in aqueous solution. In the mixture at pH 11, removals were higher than 98% and 96% for 17beta-estradiol and 17alpha-ethinylestradiol, respectively. In pH 3, 17beta-estradiol and 17alpha-ethinylestradiol removals were 100% and 99.7%, respectively. When estrogens were treated separately, the removals in pH 11 were superior to 99.7 and 98.8%, while in pH 3 were 100% and 99.5% for 17beta-estradiol and 17alpha-ethinylestradiol, respectively. 17alpha-ethinylestradiol has been always removed at lower rates (pure or in the mixture) for all applied conditions. Estrogenic activity was completely removed in pH 3 for ozonation or O3/H2O2. The samples oxidized in pH 11 presented higher estrogenic activity than those in pH 7. Estrogens removal was lower at pHs 7 and 11, when the scavenger was added to the media. The higher estrogen residual concentrations found in ozonation in presence of tert-butanol are contributing for higher estrogenic activity observed in pHs 7 and 11. By-products with estrogenic activity were formed by oxidation via OH radical. Only a few compounds could be identified in pHs 7 and 11 and they have a phenolic ring, which, probably is contributing to the estrogenic activity observed.

摘要

本研究考察了天然雌激素(17β-雌二醇)和合成雌激素(17α-乙炔基雌二醇)(纯品或混合物)在三种不同pH值(3、7和11)条件下,通过臭氧化和O3/H2O2工艺的降解情况以及雌激素活性的去除情况。通过向介质中添加自由基清除剂(叔丁醇)来评估经羟基自由基氧化的效果。采用酵母雌激素筛查法(YES法)测定雌激素活性。17β-雌二醇和17α-乙炔基雌二醇具有相似的雌激素潜力,这两种雌激素混合后对雌激素活性产生相加效应。臭氧化和O3/H2O2工艺能有效去除水溶液中的雌激素。在pH为11的混合物中,17β-雌二醇和17α-乙炔基雌二醇的去除率分别高于98%和96%。在pH为3时,17β-雌二醇和17α-乙炔基雌二醇的去除率分别为100%和99.7%。当分别处理雌激素时,在pH为11时,17β-雌二醇和17α-乙炔基雌二醇的去除率分别优于99.7%和98.8%,而在pH为3时分别为100%和99.5%。在所有应用条件下,17α-乙炔基雌二醇(纯品或混合物)的去除率始终较低。在pH为3时,臭氧化或O3/H2O2可完全去除雌激素活性。在pH为11时氧化的样品比在pH为7时氧化的样品具有更高的雌激素活性。当向介质中添加清除剂时,在pH为7和11时雌激素的去除率较低。在叔丁醇存在下臭氧化过程中发现的较高雌激素残留浓度导致在pH为7和11时观察到较高的雌激素活性。经羟基自由基氧化会形成具有雌激素活性的副产物。在pH为7和11时仅能鉴定出少数几种化合物,它们具有酚环,这可能是观察到雌激素活性的原因。

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