Degradation and estrogenic activity removal of 17β-estradiol and 17α-ethinylestradiol by ozonation and O3/H2O2

This work investigated the degradation of a natural (17β-estradiol) and a synthetic (17α-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. 17β-estradiol and 17α-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 17β-estradiol and 17α-ethinylestradiol, respectively. In pH 3, 17β-estradiol and 17α-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 17β-estradiol and 17α-ethinylestradiol, respectively. 17α-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.