Formation of chlorinated estrones via hypochlorous disinfection of wastewater effluent containing estrone

Chlorinated derivatives of estrone (E1) in the effluent of a municipal sewage treatment plant located in Shizuoka prefecture, Japan were detected by gas chromatography/mass spectrometry using electron impact in selected ion monitoring (GC/MS-EI-SIM) analysis. The concentrations of E1, 2-chloroestrone, 4-chloroestrone and 2,4-dichloroestrone in the effluent sample collected in December 2005 were 60.0 ng l−1, 4.0 ng l−1, 14.5 ng l−1, and 9.8 ng l−1, respectively. In the effluent sample taken in June 2005, 2,4-dichloroestrone was detected at 5.6 ng l−1 along with 17.6 ng l−1 of E1. However, only E1 was detected at 5.9 ng l−1 in the sample in May 2005. To elucidate the behavior of E1 during the disinfection process with sodium hypochlorite in the sewage treatment plant, we carried out a reaction of E1 with sodium hypochlorite in buffer solutions at pH 7 and 9. As E1 was consumed rapidly, chlorinated estrones were produced and relatively fast formation of 2-chloroestrone, 4-chloroestrone, and 2,4-dichloroestrone was observed. Furthermore, 1,4-estradiene-3,17-dione derivatives were formed from the reaction between 2,4-dichloroestrone and sodium hypochlorite.