超声萃取-超高效液相色谱-静电场轨道阱高分辨质谱法测定涂布纸中邻苯二甲酸酯类增塑剂

Determination of Phthalate Plasticizers in Coated Papers by Ultra-high Performance Liquid Chromatography/OrbitrapHigh Resolution Mass Spectrometry Coupled with Ultrasonic Extraction

建立了超高效液相色谱-静电场轨道阱高分辨质谱(UPLC/OrbitrapHRMS)同时测定涂布纸中多种邻苯二甲酸酯类增塑剂的方法,该方法以三氯甲烷为萃取溶剂,超声萃取涂布纸中的邻苯二甲酸酯类增塑剂,提取液经处理后进行UPLC/OrbitrapHRMS分析,外标法定量。样品用Hypersil GOLD色谱柱(100mm×2.1mm×1.9μm)进行分离,以5mmol/L乙酸铵水溶液(含0.1%甲酸)/甲醇为流动相,电喷雾正离子(ESI+)模式进行电离,以保留时间和准分子峰的精确质量数定性,以提取色谱峰的面积定量。23种邻苯二甲酸酯类增塑剂的质量准确度小于3mg/kg,在各自线性范围内,各组分线性良好,线性相关系数均大于0.997,检出限为0.1μg/kg^2.0μg/kg。在3个不同浓度的加标水平下,方法的加标平均回收率为80.2%~93.1%,相对标准偏差(RSD,n=9)为3.3%~9.9%。该方法定性可靠,定量准确,灵敏度高。采用该方法对市售涂布纸进行测定,在部分样品中检出不同含量水平的多种邻苯二甲酸酯类增塑剂。

An effective method was established for the determination of phthalate plasticizers in coated paper.Phthalate plasticizers in coated paper were ultrasonically extracted using trichloromethane as the extraction solvent,then the extract was treated and analyzed by ultra-high performance liquid chromatography/Orbitrap high resolution mass spectrometry（UPLC/OrbitrapHRMS） technique. The concentration of each analyte was calibrated bythe external standard method. The analysis was carried out on a Hypersil GOLD column（100 mm × 2. 1mm ×1. 9μm） with a gradient elution of methanol and 5mmol/L ammonium acetate solution consisting of 0. 1% aqueous formic acid,and then detected by orbitrapHRMS in ESI positive ion mode. The screening and qualitative analysis were carried out by the retention time and the accurate mass of quasimolecur ion. The quantitative analysis was carried out by the peak area in extracted chromatogram with accurate mass. Under the optimal conditions,23 phthalate plasticizers were routinely detected with mass accuracy below 3mg/kg,and good linearity was provided in their respective linear ranges with correlation coefficients higher than 0. 997. The limits of detection（LODs） varied from0. 1μg/kg to 2. 0μg/kg. The blank samples were spiked at three levels and the spiked average recoveries changed from 80. 2% to 93. 1% while the relative standard deviation（RSD） changed from 3. 3% to 9. 9%. The proposed method was simple,accurate and sensitive. The proposed method was applied in the determination of phthalate plasticizers in coated papers available commercially and phthalate plasticizers at different content levels were detected in some samples.