Analytical Method Of Androgens And Progestogen And Their Pollution Characteristics In Sewage Treatment Plant

Environmental hormones, also known as endocrine disrupting chemicals (EDs), are classes of environmental contaminants with the potential to elicit negative effects on the endocrine systems of humans and wildlife. Among EDs, steroid hormones one of the most important classes of EDs have attracted considerable attention in recent years, but most of the studies focus on estrogenic steroid hormones. Recently, some studies have documented that exposure of organisms to other steroid hormones, such as androgens and progestagens, could also cause adverse effects. However, the concentration of androgens and progestagens in environment may be several times or hundred times higher than estrogens. In this paper, a sensitive and reliable method based on microwave assisted extraction (MAE)/solid phase extraction (SPE)-derivatization-gas chromatography/mass spectrometry (GC-MS) was developed for the simultaneous analysis of representative androgens and progestogen, such as dihydrotestosterone (DIHYDRO), testosterone(TEST), androstenedione (AND) and progesterone (PROG) in water and sluge samples.Then, the occurrence, elimination and fate of target androgens and progestogen in six full-scale wastewater treatment plants(STPs) were studied.Using N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA)/Trimethy-liodosilane (TMIS)/Dithioerythreitol (DTE)(1000:2:5, v/v/w) as the reagent of silanization, at20℃for5min hydroxyl and ketone groups of target compounds were successfully simultaneous derivatizated. The MAE and SPE procedure were studied and optimized. The optimized conditions were as follows:using ethyl acetate as extraction solvent, sediment samples were extracted by microwave extraction system at120℃for15min; good recoveries of target compounds were obtained when water samples pH value were adjusted to4and Oasis HLB cartridges were used, while ethyl acetate was used as eluting solvent. Reasonable repeatability and reproducibility of the established method were achieved with relative standard deviations<9%for all target chemicals in the both water and sluge samples. The recoveries of spiked water and sediment samples were89.3～101.4%and77.3～92.1%, respectively. The method detection limits for the four analytes in sediment samples and water samples were0.1～0.5ng/L and0.6～0.8ng/L respectively. The limits of quantification were0.4～1.8ng/L and1.9～2.6ng/g dry weight (dw) for water samples and sediment samples, respectively.The occurrence, elimination and fate of target androgens and progestogen in six STPs of the urban area of Kunming City were as fllows. The total concentrations of the target hormones in the influent of the six STPs ranged from284.11to559.21ng/L, in effluent from1.93to76.65ng/L, and in sludge from4.65to54.63ng/g dw. All target hormones received good removal efficiencies ranged from74.40% to100% during the six STPs.3AMBR+ozonation could eliminate the target hormones effectively, while ICEAS+ ultraviolet disinfection processes were inferior to that of the former. The total mass loads of androgens and progestagen in influents of these six STPs were315.01g per day. After treatment processes, the total mass of androgens and progestagen in final effluents were reduced to24.76g per day respectively. The total mass loads of androgens and progestagen in excess sluge of these six STPs were9.73g per day. The effluents and excess sluge containing androgens and progestagen may be risky for the downstream environment.