Formation of estrogenic products from environmental phthalate esters under light exposure

• Published in: Chemosphere (Oxford) 2006-09, Vol.64 (10), p.1785-1792
• Main Authors: Okamoto, Yoshinori, Hayashi, Tomohiro, Toda, Chitose, Ueda, Koji, Hashizume, Kiyomatsu, Itoh, Kazuo, Nishikawa, Jun-ichi, Nishihara, Tsutomu, Kojima, Nakao
• Format: Article
• Language: English
• Subjects: Animal, plant and microbial ecology; Applied ecology; Biological and medical sciences; Chromatography, High Pressure Liquid; Ecotoxicology, biological effects of pollution; Endocrine disrupting chemicals; Environmental Pollutants; Esters - chemistry; Estrogenic activity; Estrogens - chemical synthesis; Fundamental and applied biological sciences. Psychology; General aspects; Hydrogen Peroxide - analysis; Hydroxyl radical; Hydroxylation; Light; Mass Spectrometry; Photochemistry; Photodegradation; Phthalic Acids - chemistry; Ring hydroxylation; Risk assessment
• ISSN: 0045-6535; 1879-1298
• DOI: 10.1016/j.chemosphere.2005.12.046

Phthalate esters (PEs) have been suspected to be environmental endocrine disruptors and the detailed mechanism remains unclear. The activities of these chemicals can be enhanced through chemical modification under the environmental conditions. We demonstrate that PEs acquire unequivocal estrogenic activity by light exposure. Through UV exposure of an aqueous PE solution, one active photoproduct, identified as 4-hydroxyPE (PE-4OH) based on its characteristic UV and mass spectra, was detected in an estrogen receptor α-dependent transactivation assay. PE-4OH was effectively generated by UV 290 nm. The PE-4OH production accompanied H 2O 2 generation in a UV dose-dependent manner. Both PE and UV irradiation were indispensable in the generation of H 2O 2. Addition of H 2O 2 to the PE solution increased PE-4OH production under UV irradiation. The PE-4OH production was also observed in the PE reaction with the Fenton reagent generating hydroxyl radical without UV irradiation. The proposed mechanism for PE-4OH production based on these results is such that by PE-mediated photosensitization H 2O 2 is generated from O 2 and H + and decomposed to hydroxyl radical, thus oxidizing the PE benzene ring. The PEs-4OH are remarkably active estrogenic products of PEs and would be involved in ER-mediated endocrine disruption.