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Transformation of 17β-estradiol in Humic Acid Solution by ε-MnO2 Nanorods as Probed by High-Resolution Mass Spectrometry Combined With (13)C Labeling

Kai Sun, Shangtao Liang, Fuxing Kang, Yanzheng Gao, Qingguo Huang

Environ Pollut. 2016 Jul;214:211-218.

PMID: 27086077

Abstract:

Steroidal estrogens (SEs), widespread in aquatic systems, have a potential to disrupt the endocrine system of wildlife species and humans. In our experiments, the performance of ε-MnO2 nanorods in transforming 17β-estradiol (E2) was investigated, and the effect of humic acid (HA) on the reaction behaviors was systematically characterized. Reconfiguration of humic molecules was also investigated by high-performance size exclusion chromatography (HPSEC). Results indicated that ε-MnO2 nanomaterials ensured efficient removal of E2 from the aqueous solution. The presence of HA hindered the transformation of E2, while enhanced the cross-coupling between E2 and humic molecules. In particular, we used a mixture of un-labeled E2 and (13)C3-labeled E2 at a 1: 1 set ratio (w/w) to probe the reaction products via high-resolution mass spectrometry (HRMS). The combination of HRMS and (13)C3-labeling revealed the intermediate products including estrone (E1), and hydroxylated, quinone-like, and ring-opened species, as well as E2 dimer and trimer. More importantly, possible cross-coupling products between E2 and HA were also identified. A reaction mechanism including two-electron oxidation and single-electron oxidation was proposed. The applied analytical approach using HRMS along with (13)C3-labeling for reaction-product identification is crucial to understanding the role of HA in the transformation of SEs.

Chemicals Related in the Paper:

Catalog Number Product Name Structure CAS Number Price
AP50282-A 17β-Estradiol solution 17β-Estradiol solution 50-28-2 Price
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