废水中类固醇物质的LCMSMS检测方法优化及其在养殖废水检测中的应用

以固相萃取为预处理手段，用高效液相色谱 串联四极杆质谱联用技术，针对澳大利亚南威尔士州畜牧业废水中的丙酸睾酮等13种类固醇化合物含量建立了分析方法.采用大气压化学电离源，在正离子模式下，对色谱条件和质谱条件进行优化，其中，丙酸睾酮等7种化合物以质子化的准分子离子峰［M+H］⁺、另6种化合物以产生了脱去水的离子峰［M+H-H₂O］⁺为母离子进行二级质谱扫描，以最大丰度确定定量离子对.结果表明：该方法所建立的13种化合物的9点标准曲线的线性相关范围为1～1000 ng·ml^-1，在该范围内，相关系数均>0.9990；各化合物的平均回收率在83.75%～111.50%，相对标准差2.02%～14.21%；除美雌醇和雌三醇的灵敏度相对较低，检测限高于15 ng·ml^-1外，其余物质的检测限均低于5 ng·ml^-1；实际样品测定时，不同处理流程中各化合物的浓度均能得到较好体现，该方法能满足检测要求.

Optimization of LCMSMS determination method for steroid compounds in wastewater and its application in feedlot wastewater

Taking Solid-Phase Extraction (SPE) as pre-treatment process, a laboratory experiment was conducted by adopting the technology of High Performance Liquid Chromatography-Tandem Mass Spectrometry (HPLC-MSMS) to develop a method to determine the concentrations of 13 steroids in feedlot wastewater. Atmospheric Press Chemical ionization (APCI) source was applied and operated in negative ion model, with the parameters of Chromatography and Spectrometry being optimized. Quasi-molecular ion peak M + H ] ~+ appeared in the full scan of the first quadrupole of mass spectrometer ( Q1 ) of Testosterone propionate and other 6 steroid compounds, while quasi-molecular ion peak M + H-H_2O] ~+ appeared in the full scan of Q1 of rest 6 steroid compounds. The linear range of the 9 points calibration curve for the 13 target compounds was determined to be from 1 to 1000 ng· ml~(-1) , and the calibration curve regression correlation coefficients (R) were always above 0. 9990 for all sample batches. The average recovery rate of all target compounds was 83. 75%-111.50%, and the methodological stability was determined to be acceptable, with the relative standard deviations between 2. 02%- 14. 21% ( n = 6 ). Except that the limit of detection (LOD) of Mestradiol and Oestriol was higher than 15 ng · ml~(-1), all the other target compounds had a LOD lower than 5 ng · ml~(-1). In the determination of real samples from feedlot wastewater, the developed method represented a good profile to all target compounds at different concentrations in each stage of treatment.ss; APCI ; determination.