固相萃取-衍生化-气相色谱/质谱测定水中类固醇类环境内分泌干扰物  

Simultaneous Determination of Steroid Endocrine Disrupting Chemicals in Water by Solid Phase Extraction-Derivatization Gas Chromatography-Mass Spectrometry

作　　者：黄斌[1] 潘学军[1] 万幸[1] 刘晶靓[1] 赵世民[1,2] 胡平[2] 李发荣[2] 

机构地区：[1]昆明理工大学环境科学与工程学院,昆明650093 [2]昆明市环境监测中心,昆明650228

出　　处：《分析化学》2011年第4期449-454,共6页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金(No.20767002);国家环保公益性行业科研专项基金(No.200809136);教育部留学回国人员科研启动基金(教外司留[2008]890号);云南省自然科学基金(No.2007B035M)资助项目

摘　　要：建立了固相萃取-衍生化-气相色谱/质谱联用同时测定水中4种类固醇类环境内分泌干扰物雌酮（E1）、17β-雌二醇（E2）、17α-乙炔基雌二醇（EE2）、雌三醇（E3）的分析方法。通过对比衍生化试剂N,O-双三甲基硅基三氟乙酰胺（BSTFA）和N-甲基-N-三甲基硅基三氟乙酰胺（MSTFA）的衍生化条件及效果,解释了文献报道中使用BSTFA和MSTFA需要加热和催化剂的原因,并在不加热、不加催化剂的条件下（常温反应10 min）将BSTFA应用于环境水样的测定。以Oasis HLB为固相萃取柱,调节水样至pH 4.5,采用10 mL丙酮为洗脱溶剂。本方法对E1,E2,EE2和E3的线性范围分别为1~500 ng/L和5~500 ng/L;相关系数R2〉0.98;检出限和定量限分别为0.1~1.3 ng/L和0.3~4.2 ng/L;滇池水样3个不同浓度水平（5,50和300ng/L）的加标平均回收率为83.8%~94.7%,相对标准偏差为3.2%~9.1%（n=6）。应用此方法对环境水样进行了检测。An analytical method for the simultaneous determination of steroid endocrine disrupting chemicals,such as estrone（E1）,17β-estradiol（E2）,estriol（E3） and 17α-ethynylestradoil（EE2）,in water was developed by solid phase extraction,derivatization and gas chromatography-mass spectrometry.To explain the necessity of heating and catalyst in previous papers when N,O-bis（trimethylsilyl）trifluoroacetamide（BSTFA） or N-methyl-N-（trimethylsilyl）trifluoroacetamide（MSTFA） was used as derivatization reagent,the derivatization condition and effect of BSTFA and MSTFA were studied.BSTFA was applied to determine steroids in waters under the condition of without heating and catalyst.By optimizing SPE parameters,the best recoveries of steroids were obtained when water pH value was adjusted to 4.5 and Oasis HLB cartridge was used,while 10 mL acetone was efficient in eluting steroids from SPE cartridges.Under the optimal conditions,linear range was 1-500 ng/L for E1 and E2,while 5-500 ng/L for EE2 and E3.The correlation coefficient（R2） was above 0.98 for all the analytes,with the limit of detection（LOD） and the limit of quantification（LOQ） of 0.1-1.3 ng/L and 0.3-4.2 ng/L,respectively.The proposed method was further verified by performing spiking experiments in Dianchi Lake water at three spiked levels（5,50 and 300 ng/L）,with good recoveries（83.8%-94.7%） and RSD（n=6）（3.2%-9.1%） for all the target compounds.The established method was successfully applied to determine steroids in water samples of Dianchi Lake,Green Lake and effluent of Kunming fifth sewage treatment plant.

关 键 词：类固醇 内分泌干扰物 固相萃取 衍生化 气相色谱-质谱联用 

分 类 号：X832[环境科学与工程—环境工程]