固相萃取-分散液液微萃取-柱前衍生法测定水样中痕量雌激素  

Combination of Solid Phase Extraction-Dispersive Liquid Liquid Microextraction and Pre-column Derivatization Method for Determination of Trace Level Estrogens in Water Sample

作　　者：李鱼[1,2] 刘建林[1] 张琛[1,2] 王夏娇[1] 

机构地区：[1]华北电力大学能源与环境研究院,北京102206 [2]华北电力大学区域能源系统优化教育部重点实验室,北京102206

出　　处：《分析化学》2012年第1期107-112,共6页Chinese Journal of Analytical Chemistry

基　　金：国家重点基础研究发展规划“973”项目(No.2004CB418501)资助

摘　　要：建立了碳纳米管的固相萃取-分散液液微萃取-柱前荧光衍生化(SPE-DLLME-PFD)测定水体中痕量雌三醇(E3)、双酚A(BPA)、17α-乙炔基雌二醇(EE2)及17β-雌二醇(E2)的高效液相色谱方法。采用中心复合设计和响应曲面法分析并优化SPE、DLLME及PLD条件,最佳条件为210 mL水样以2.0 mL/min的流速过固相萃取柱(碳纳米管量30 mg),甲醇洗脱,氮气浓缩并定容至0.6 mL(分散剂),将100μL C6MIM[PF6]与分散剂的混合液注入到NaCl含量为25%的2.0 mL去离子水中,离心,移取20μL下层有机相于样品瓶中,与4.0 mg衍生剂混合,在40℃水浴中衍生25 min;用0.1 mL甲醇溶解过量的衍生剂颗粒,取20μL进样分析。在优化条件下。4种雌激素的线性范围为0.05～5.00μg/L,相关系数R2=0.9966～0.9999;检出限介于0.13～6.33 ng/L(S/N=3)之间。不同加标浓度条件下,雌激素的加标回收率在83.1%～122.4%范围内(RSD=1.7%～9.6%)。在实际水样中E3和BPA检出率较高。与其它方法相比,本方法虽然萃取时间长、水样量大、步骤多,但具有检出限低、操作简便、环境友好等优点。A method,carbon nanotubes assisted solid phase extraction combined with dispersive liquid-liquid microextration and pre-column derivatization（SPE-DLLME-PFD）,was developed for the determination of estriol（E3）,bisphenol A（BPA）,17α-ethinyl estradiol（EE2） and 17β-estradiol（E2） in water samples.SPE,DLLME and PFD process was studied and optimized using central composite design and response surface plot.The optimized conditions were as follows： target estrogens were adsorbed from 210 mL aqueous samples into 30 mg carbon nanotubes at 2.0 mL/min;methanol used as elution solution was concentrated to a volume of 0.6 mL,which was mixed with 100 μL of C6MIM and the blend was added to 2.0 mL of deionized water（25.0% NaCl,g/L）.After centrifugation,20 μL of the settled organic phase was mixed with 4.0 mg derivating agent,and the reaction was occurred for 25 min at 40 ℃.Finally,0.1 mL of methanol was used to dissolve the particles of derivating agent,and 20 μL of that sample was analyzed.Under the chosen conditions,linearity range of the established method was 0.05-5.00 μg/L with R2 of 0.9966-0.9999 for the target estrogens,and the LODs were in the range of 0.13-6.33 ng/L.The recoveries of estrogens under different spiked levels for four estrogens were 83.13%-122.39%（RSD was 1.7%-9.6%）.E3 and BPA could be detected in the most of the real water samples.Compared with some other methods,the present method needed long extraction time,large volume sample and multi-steps,while it also had many advantages such as low LOD,simplicity of operation,and environmental friendly.

关 键 词：固相萃取 分散液液微萃取 柱前荧光衍生 高效液相色谱 碳纳米管 

分 类 号：O657.3[理学—分析化学] X832[理学—化学]