羧基化多壁碳纳米管固相萃取-液相色谱-串联质谱法测定环境水体中四溴双酚A和双酚A

Determination of tetrabromobisphenol A and bisphenol A in environmental water using carboxylated multiwalled carbon nanotubes as sorbent for solid-phase extraction combined with liquid chromatography-tandem mass spectrometry

建立了羧基化碳纳米管固相萃取-液相色谱-串联质谱联用检测环境水体中四溴双酚 A 和双酚 A 的方法。比较了多壁碳纳米管、C60和羧基化多壁碳纳米管作为固相吸附剂对水体中四溴双酚 A 和双酚 A 的吸附效率。固相萃取浓缩后的样品经 Thermo Scientific Hypersil C18色谱柱（150 mm±4.6 mm，3μm）分离，采用串联质谱负离子模式进行检测。结果表明，四溴双酚 A 和双酚 A 在0.02～1.0 mg / L 范围内具有良好的线性关系（ r2≥0.99），空白样品中的检出限（S / N =3）分别为0.04μg / L 和0.2μg / L。将所建立的方法应用于实际环境水体中四溴双酚 A和双酚 A 的检测，添加回收率在82％～99％之间，精密度小于5.0％，该方法可用于复杂环境样品中痕量四溴双酚 A和双酚 A 的检测。

A method for the determination of tetrabromobisphenol A and bisphenol A in environ-mental water using carboxyl-functionalized multiwalled carbon nanotubes as solid-phase extraction sorbent and liquid chromatography-tandem mass spectrometry was established. Com-parison of three nanomaterials including multiwalled carbon nanotubes,C60 and carboxyl-func-tionalized multiwalled carbon nanotubes used as solid-phase extraction sorbents was made. After preconcentration by solid-phase extraction,tetrabromobisphenol A and bisphenol A were separa-ted on a Thermo Scientific Hypersil C18 column（150 mm±4. 6 mm,3 μm）and then detected by tandem mass spectrometry in negative electrospray ionization（ESI）mode. The results showed a good linear response in the concentration range of 0. 02-1. 0 mg / L for tetrabromobisphenol A and bisphenol A,and the limits of detection（S / N = 3）were 0. 04 μg / L and 0. 2 μg / L for tetrabromo-bisphenol A and bisphenol A,respectively. The application of the proposed approach has been carried out for the determination of tetrabromobisphenol A and bisphenol A in spiked lake water and sea water samples. The recoveries varied from 82% to 99% with the relative standard devia-tions below 5. 0%. The proposed method can be used for the determination of tetrabromobisphe-nol A and bisphenol A at trace level in complex environmental samples.