Androgens, oestrogens, and progesterone concentrations in wastewater purification processes measured with capillary electrophoresis.

A novel analytical-scale concept to improve reliability of detection and analysis of natural and processed wastewater samples from a purification plant was developed. A sequential sample clean-up system of polymer-based octadecyl and silane-based quaternary amine sorbents were used for concentrating human based steroid hormones and their metabolites and detecting them by UV absorption with capillary electrophoresis (CE). The water samples were collected from influent and effluent processes of the water purification plant in Helsinki, Finland.The CE methods were partial-filling micellar electrokinetic chromatography and capillary zone electrophoresis. The analysis times and method concentration levels were optimized with eight steroids at the range of 0.5-10 mg/L. Since in CE the detectable quantities were higher than the existing amounts in the process waters, the real samples needed matrix removal combined with steroid enrichment. After 20,000-fold concentration testosterone-glucoside, androstenedione, progesterone, and estradiol-glucoside could be determined in the process water samples. The amounts of individual steroids in influent and effluent waters were 0-429 and 0-207 ng/L, respectively. Correspondently, their total amounts were 735 and 212 ng/L with excellent in day and inter-day repeatability. The RSD values were less than 1, 9.7, and 19% in repeated analyses, calculated from 60 analyses during 24 h, and from 130 analyses during 15 months, respectively. The steroid removal in purification process was 65% on average. The solid particles separated in three steps during the water clean-up concept contained 9.8-45 ng/g steroids in combined dry precipitates.