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

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

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1.8～4.7ng/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39.9ng/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。

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）trifluoroacetamide（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.