Surface catalyzed oxidative oligomerization of 17β-estradiol by Fe(3+)-saturated montmorillonite

With widespread detection of endocrine disrupting compounds including hormones in wastewater, there is a need to develop cost-effective remediation technologies for their removal from wastewater. Previous research has shown that Fe(3+)-saturated montmorillonite is effective in quickly transforming phenolic organic compounds such as pentachlorophenol, phenolic acids, and triclosan via surface-catalyzed oligomerization. However, little is known about its effectiveness and reaction mechanisms when reacting with hormones. In this study, the reaction kinetics of Fe(3+)-saturated montmorillonite catalyzed 17β-estradiol (βE2) transformation was investigated. The transformation products were identified using liquid chromatography coupled with mass spectrometry, and their structures were further confirmed using computational approach. Rapid βE2 transformation in the presence of Fe(3+)-saturated montmorillonite in an aqueous system was detected. The disappearance of βE2 follows first-order kinetics, while the overall catalytic reaction follows the second-order kinetics with an estimated reaction rate constant of 200 ± 24 (mmol βE2/g mineral)(−1) h(–1). The half-life of βE2 in this system was estimated to be 0.50 ± 0.06 h. βE2 oligomers were found to be the major products of βE2 transformation when exposed to Fe(3+)-saturated montmorillonite. About 98% of βE2 were transformed into βE2 oligomers which are >10(7) times less water-soluble than βE2 and, therefore, are much less bioavailable and mobile then βE2. The formed oligomers quickly settled from the aqueous phase and were not accumulated on the reaction sites of the interlayer surfaces of Fe(3+)-saturated montmorillonite, the major reason for the observed >84% βE2 removal efficiency even after five consecutive usages of the same of Fe(3+)-saturated montmorillonite. The results from this study clearly demonstrated that Fe(3+)-saturated montmorillonite has a great potential to be used as a cost-effective material for efficient removal of phenolic organic compounds from wastewater.