固相萃取-衍生化气相色谱/质谱法测定制药厂污水中的环境雌激素

采用固相萃取-衍生化气相色谱/质谱法(GC/MS)测定某制药厂污水中的雌酮(E1)、雌二醇(E2)、雌三醇(E3)和乙炔基雌二醇(EE2)4种雌激素化合物。样品经固相萃取柱萃取富集及双(三甲基硅烷基)三氟乙酰胺(1%三甲基氯硅烷)（BSTFA(1%TMCS)）衍生化后进行GC/MS分析。该法对4种目标物的检出限为1.8～4.7 ng/L,相对标准偏差为2.3%～9.1%(n=8)。目标化合物的加标回收率为（94.0±2.9）%～（101±3.8）%,说明该方法能较好地应用于污水中雌激素化合物的定量检测。通过对某制药厂污水中的雌激素进行定量分析,发现污水中乙炔基雌二醇和雌酮质量浓度分别达396.6 和39.9 ng/L；经过传统的厌氧兼氧好氧生物处理后,污水中的环境雌激素的去除率仅为35%～40%,说明传统的污水处理工艺对去除污水中雌激素效果并不明显，需要改进。

Determination of environmental estrogens in pharmacy wastewater using solid-phase extraction-gas chromatography/mass spectrometry with derivatization

A method for the determination of estrone (E1), estradiol (E2), ethinylestradiol (EE2) and estriol (E3) in pharmacy wastewater was developed using solid-phase extraction-gas chromatography/mass spectrometry （SPE-GC/MS） with derivatization. The sample was extracted by an SPE column, derivatized by bis(trimethylsilyl) rifluoroacetamide （BSTFA）, and analyzed by GC/MS. The detection limits were 1.8-4.7 ng/L, and the relative standard deviations were 2.3%-9.1% (n=8). The recoveries of above four environmental estrogen compounds were (94.0±2.9)% to (101±3.8)%. The method can be applied in the determination of the estrogenic compounds in wastewater samples successfully. The concentrations of EE2 and E1 in wastewater were 396.6 ng/L and 39.9 ng/L, respectively, and the removal rates of EE2 and E1 were 35%-40% after traditional biological treatment. The results demonstrated that the removal efficiency was not satisfactory and the traditional treatment process of wastewater containing estrogen compounds from pharmaceaticals factory should be improved.