超高效液相色谱-高分辨质谱法快速筛查水产品中邻苯二甲酸酯和酚类环境雌激素

Rapid screening of phathalates and phenolic environmental estrogens in aquatic products by ultra-performance liquid chromatography-quadrupole/ electrostatic field obitrap high-resolution mass spectrometry

中文关键词:  超高效液相色谱法  静电场轨道阱高分辨质谱法  环境雌激素  高通量筛查

英文关键词:Supported by Shandong Entry-Exit Inspection and Quarantine Bureau Research Project (SK201602) and the AQSIQ Project (2015IK202)

中文摘要:

      目的 建立超高效液相色谱-四级杆/静电场轨道阱高分辨质谱法同时快速筛查和分析水产品中14种邻苯二甲酸酯以及3种酚类(壬基酚、辛基酚和双酚A)环境雌激素的分析方法。方法 样品经乙腈提取后, 经Silica/PSA固相萃取小柱净化, 用ACQUITY UPLC@BENC18色谱柱(2.1 mm×50 mm, 1.7 μm)分离, 以甲醇和0.01%氨水为流动相进行梯度洗脱, 采用静电场轨道阱高分辨质谱正负子切换FullMS/ddMS2扫描方式同时测定17种环境雌激素。以保留时间和全扫描获得的化合物的精确质量数, 实现对目标物的快速筛查; 以自动触发采集的二级质谱图进行定性确证。结果 17种化合物的精确质量数相对质量偏差小于5×10-6; 线性良好, 相关系数(r2)大于0.99; 该方法的检出限≤5 μg/kg, 回收率为70.6%~114.3%, 相对标准偏差(relative standard deviations, RSDs)为5.5%~14.3%。结论 该方法适用于水产品中多种环境雌激素的高通量快速筛查和定量分析。

英文摘要:

      Objective To establish a rapid and easy method for screening and analysis of 14 phathalates and 3 phenolic environmental estrogens (nonylphenol, otcylphenol and bisphenol A) in aquatic products by ultra-performance liquid chromatography-quadrupole/electrostatic field obitrap high-resolution mass spectrometry. Methods The samples were extracted with acetonitrile, and purified with Silica/PSA solid phase extraction column. The separation was carried out on an ACQUITY UPLC@BEN C18 column (2.1 mm×50 mm, 1.7 μm) with methanol and 0.01% ammonia aqueous solution as the mobile phase for gradient elution. The 17 environmental estrogens were analyzed by obitrap high-resolution mass spectrometry in switching positive and negative FullMS/ddMS2 scanning modes at the same time. The retention time and accurate mass of analytes obtained in full scan mode were used for rapid screening, while secondary mass spectrum was used for confirmation. Results Under the optimum conditions, the exact mass of all targeted compounds were routinely detected with relative mass deviations below 5×10-6. Good linear relationships were obtained in their respective linear ranges with related coefficients (r2) >0.99. The limits of detection (LODs) of this method were ≤5 μg/kg for all the environmental estrogens. The recoveries were 70.6%~114.3% and the relative standard deviations (RSDs) were 5.5%~14.3%. Conclusion This method is suitable for the rapid screening and confirmation of multiple environmental hormones in aquatic products.