Ozonation of a mixture of estrogens and progestins in aqueous solution: Interpretation of experimental results by computational methods

The degradation of the mixture of steroid hormones including seven estrogens (17α-estradiol, 17β-estradiol, 17α-dihydroequilin, 17α-ethinyl estradiol, estriol, estrone and equilin) and five progestins (levonorgestrel, gestodene, trimegestrone, medrogestone and progesterone) by ozonation in aqueous solution is investigated. The ozonation process provides high removal (up to 100%) of hormones and estrogenicity in the treated water. Computational methods such as quantum chemistry calculations (QCCs) are applied to interpret the observed results. Quantum chemistry descriptors computed for steroid hormones explain the nature of the reactions and differences in reactivities between estrogen and progestin hormones within the framework of the Density Functional Theory (DFT). Computed molecular descriptors were combined with physical properties to develop qualitative structure activity relationship (QSAR) models (using multiple linear regression algorithm). The developed models have correlation coefficients (R2) of 0.994 for estrogens and 0.997 for progestins, and could be used to predict the removal efficiencies for similar compounds. The frontier molecular orbitals (the HOMO and the LUMO) have a major impact on the reactivity of steroid hormones. The susceptibility of certain functional groups to ozone and possible reactive sites for all steroids was discussed by Frontier Molecular Orbital approach.

► The ozonation of steroid hormones (estrogens and progestins) from water was studied.
► Low doses of ozone resulted in high degradation with loss of estrogenicity.
► Detailed DFT study of steroids allowed to explain reactivity of steroids with ozone.
► DFT QSAR models were developed to correlate degradation efficiency of steroids hormones.