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    在线固相萃取-液相色谱-串联质谱法同时测定污水中24种滥用药物的含量

    Simultaneous Determination of 24 Abused Drugs in Sewage by Liquid Chromatography-Tandem Mass Spectrometry with Online Solid Phase Extraction

    • 摘要: 取过滤后的污水样品10 mL,加入1 mol·L−1磷酸盐缓冲液(pH 7.2)200 μL和4 μg·L−1混合同位素内标溶液100 μL,混匀,采用在线固相萃取-液相色谱-串联质谱法测定溶液中24种滥用药物的含量。通过Oasis HLB Direct Connect固相萃取柱在线固相萃取,以Poroshell 120 EC C18色谱柱为固定相,以不同体积比的0.1%(体积分数,下同)甲酸溶液-含0.1%甲酸的乙腈溶液混合液为流动相进行梯度洗脱,采用电喷雾离子(ESI)源,在正、负离子扫描模式下进行多反应监测(MRM)模式质谱分析。结果显示:污水样品可于4 ℃储存,并在15 d内检测,同时避免反复冻融;前处理后的样品溶液在24 h内稳定性良好。24种滥用药物的质量浓度均在一定范围内和对应的峰面积与同位素内标峰面积的比值呈线性关系,测定下限(10S/N)为0.2~5.0 ng·L−1。按照标准加入法进行回收试验,回收率为82.8%~110%,测定值的相对标准偏差(n=6)均小于10%。方法用于分析6个实际污水样品,可替宁、甲基苯丙胺、可待因、曲马多、麻黄碱均被检出。

       

      Abstract: The filtered sewage sample (10 mL) was taken, and 200 μL of 1 mol·L−1 phosphate buffer solution (pH 7.2) and 100 μL of 4 μg·L−1 mixed isotope internal standard solution were added. The mixture was homogenized, and 24 abused drugs in the solution were determined by online solid phase extraction-liquid chromatography-tandem mass spectrometry. Online solid phase extraction was performed using Oasis HLB Direct Connect solid phase extraction column. Poroshell 120 EC C18 column was used as the stationary phase and the mixed solution composed of 0.1% (volume fraction, the same below) formic acid solution and acetonitrile solution containing 0.1% formic acid at different volume ratios was used as the mobile phase for gradient elution. Electrospray ion (ESI) source was used for mass spectrometry. The targets were analyzed by multiple reaction monitoring (MRM) mode in positive ion and negative ion scanning mode. As shown by the results, the sewage sample could be stored at 4 ℃ and tested within 15 d, while repeated freeze-thaw cycles were avoided. The pretreated sample solution was demonstrated to have good stability within 24 h. Linear relationships between the ratios of the corresponding peak areas to the isotope internal standard peak areas and mass concentrations of 24 abused drugs were kept in definite ranges, with lower limits of determination (10S/N) in the range of 0.2‒5.0 ng·L−1. Test for recovery was made by the standard addition method, giving results in the range of 82.8%‒110%, with RSDs (n=6) of the determined values less than 10%. This method was applied to the analysis of 6 actual sewage samples, and cotinine, methamphetamine, codeine, tramadol, and ephedrine were all detected.

       

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