微波辅助衍生-气相色谱-质谱法同时测定养殖水体中6种雌激素

建立了微波辅助衍生-气相色谱-质谱法同时测定养殖水体中６种雌激素（雌酮、β-雌二醇、雌三醇、炔雌醇甲醚、乙炔雌二醇和己烯雌酚）。样品经C18固相萃取柱提取净化后，用N-甲基-N-三甲基硅基三氟乙酰胺（MSTFA）在乙酸乙酯存在下进行微波辅助衍生化反应，GC/MS法定性定量检测，以雌二醇-D₂与己烯雌酚-D₈为内标进行定量分析。结果表明，雌激素在1～500 μg/L范围内呈现良好的线性关系，相关系数（R²）均大于0.999 3，方法检出限为0.4～2 ng/L；在0.01、0.05、0.1 μg/L 3个添加水平下，回收率为88.5%～106%，相对标准偏差为0.29%～11.9%，均小于15%。该方法快速、简便、选择性强、灵敏度高，实验设备简单、价格便宜，易于推广。

Simultaneous Determination of Six Estrogens in Water for Aquaculture with Microwave Assisted Derivatization by GC/MS

An endocrine disrupter is defined as “an exogenous substance that causes adverse health effects in an intact organism, or its progeny, consequent to changes in endocrine function”. In the past few years, many papers have highlighted the potentially dangerous consequences to human and wildlife of the presence of endocrine disrupting compounds in aquatic environment. As those compounds have high physiological activity for human and animals at very low concentration, and can be accumulated, assimilated and biomagnified in the tropic web. Thus, the pollution and effect of endocrine disrupters, such as estrogen in aquatic environment should be closely concerned. A method was developed for simultaneous determination of six estrogens (estriol,17-β-estradiol, estrone, diethylstibestrol, mestranol, ethinylestradiol) in water for aquaculture by microwave assisted derivatization and gas chromatography-mass spectrometry (GC/MS). The six estrogens were enriched and purified by C18 solid phase extraction column, and then were derived with microwave, using N-methyl-N-(trimethylsilyl) trifluoro acetamide (MSTFA) as derivatization reagent and ethylene acetate as reaction solvent, then the derivatives were analyzed by GC/MS. The quantification was achieved with estradiol-D₂ and diethylstilbestrol-D₈ as the internal standards. Good linear relationships were obtained in the range of 1-500 μg/L for estrogens with the correlation coefficients (R²) not less than 0.999 3, the limits of detection (LOD, S/N≥3) were 0.4-2 ng/L. The recoveries were 88.5%-106% at the three spiked levels. and the relative standard deviations (RSD) were 0.29%-11.9%, which were below 15%. The method shows high sensitivity, good precision, simple and high analytical speed. It could be applied to the simultaneous detection of the six estrogens in water for aquaculture, and which maked up for the shortcomings of cumbersome and time-consuming for traditional GC/MS method. Furthermore, the derivatization in this method was used microwave oven, which made the procedure more cheaper and easier uses.