原位组装TiO_2纳米管阵列固相微萃取-高效液相色谱联用测定环境水样中痕量紫外线吸收剂

In situ fabrication of TiO_2 nanotube arrays-based fibers for solid phase microextraction followed by highperformance liquid chromatography for sensitive determination of UV filters in environmental water

用阳极氧化法在钛丝表面原位组装了TiO2纳米管阵列（TNTs）作为固相微萃取（SPME）纤维头,TNTs的孔径在100～150 nm之间,壁厚为20～30 nm。与高效液相色谱（HPLC）联用,考察了TNTs-SPME纤维头对水样中痕量紫外线吸收剂的吸附效率,优化了实验条件。所建立TNTs-SPME-HPLC法测定紫外线吸收剂的线性范围为0.2～400μg/L,检出限为0.05～0.37μg/L（S/N=3）;对于加标50μg/L的水样平行进行5次测量,同一微萃取头在单日内和隔日间的相对标准偏差（RSD）分别为6.8%～9.2%和10%～13%,重复制作微萃取头的RSD为9.7%～14%。方法用于环境水样分析结果表明,实际水样加标回收率为85.9%~113.2%。所制作微萃取纤维头适用于测定环境水样中的痕量紫外线吸收剂。

In situ fabrication of highly ordered TNTs was performed on a Ti-based wire by anodization for silid- phase mieroextraction （SPME）. The fabricated TNTs-SPME fibers possess wall thickness of 20 -30 nrn and pore diameter of 100 - 150 nm. They were applied to the concentration and determination of UV filters in environmental water samples coupled with HPLC. The main parameters affecting SPME were optimized. Under the optimized conditions, the calibration graphs were linear in the range of 0. 2 - 400μg/L. The limits of detection of the method were 0. 05 - 0. 37 μg/L （ S/N = 3 ）. The intra-day and inter-day repeatability of single fibel were 6.8% - 9. 2% and 10% ~ 13% （ n = 5 ） , respectively and the fiber-to-fiber reproducibilities were 9. 7% - 14% （n = 5）. The current procedure was successfully applied to simultaneous analysis of four UV filters in environmental water samples. The obtained recoveries were between 85.9% and 113.2%. Furthermore the TNTs-SPME fibers have high strength, good stability and long service life. The established method allowed fast and reliable preconcentration and sensitive determination of four UV filters with simple sample pretreatment and was suitable for the analysis of UV filters in real environmental water samples.