气相色谱-四极杆/飞行时间质谱法快速测定化妆品中全氟和多氟化合物

Rapid Detection of Per-and Polyfluoroalkyl Compounds in Cosmetics Using Gas Chromatography-Quadrupole/Time of Flight Mass Spectrometry

本研究建立了QuEChERS法净化,结合气相色谱-四极杆/飞行时间质谱(GC-Q-TOF MS)法快速检测化妆品中全氟和多氟化合物(PFASs)的含量。样品经乙酸乙酯提取,无水硫酸钠脱水,石墨化炭黑(GCB)和硅胶粉(Si)分散固相萃取净化。目标物经DB-5MS毛细管色谱柱(30 m×0.25 mm×0.25μm)分离,在EI源全扫描模式下采集质谱信号,外标法定量。结果表明:在5.0~1000μg/L范围内,8种化合物呈现良好的线性关系,相关系数(R^(2))均大于0.9976,检出限为20.0、200.0μg/kg,定量限为50.0、500.0μg/kg;在定量限、2倍和10倍定量限3个添加水平下的平均回收率为81.4%~112%,相对标准偏差为1.09%~7.63%(n=6)。该方法快速、准确、灵敏度高,可为化妆品中全氟和多氟化合物的快速检测和质量控制提供依据。

Per-and polyfluoroalkyl substances(PFASs)are a collective term for various artificial fluorinated organic compounds.PFASs not only have hydrophilic functional groups and hydrophobic alkyl side chains,but also have fire resistance,high stability and durability,making them widely used in various industries.PFASs have the characteristics of high toxicity,persistence,bioaccumulation,and long-distance migration of persistent organic pollutants.Different types of PFASs have different harmful effects on biological organisms,and health risks are mostly concentrated in the liver,immune system,and reproductive system.At present,there are many detection methods reported for PFASs in the food and environmental fields,while few methods have been applied for the detection of PFASs in cosmetics.In this work,a method for rapid detection of PFASs in cosmetics was developed by QuEChERS(quick,easy,cheap,effective,rugged,and safe)pretreatment coupled with gas chromatography-quadrupole/time of flight mass spectrometry(GC-Q-TOF MS).Firstly,the extraction solvents,extraction methods,and purification agents were compared,the dosage of purification agents was optimized,and the matrix effect was examined.Eight kinds of volatile PFASs,including two perfluorooctanoic acid esters,four fluoro modified polyacrylates,and two fluoro modified siloxanes in the samples were extracted with 10 mL ethyl acetate,dehydrated by 1 g anhydrous sodium sulfate,and purified by 100 mg graphitized carbon black(GCB)and 50 mg silica gel powder(Si).Target compounds were separated by DB-5MS capillary column(30 m×0.25 mm×0.25μm),and the mass spectrum was acquired under full scan mode of EI ion source with using external standard method for quantification.The result showed that the work curves of the 8 compounds have good linear relationship,and the correlation coefficient(R^(2))is greater than 0.9976 in the range of 5.0-1000μg/L.The limits of detection are 20.0 and 200.0μg/kg,and the limits of quantification are 50.0 and 500.0μg/kg.The average recoveries at three levels range from 81.4%to 112%,and the relative standard deviations are 1.09%-7.63%(n=6).In total,105 cosmetic samples purchased from Guangzhou supermarkets and online e-commerce were tested using this method,8:2FTMAc in 2 samples are detected with 668,1004μg/kg,respectively,indicating that cosmetic samples pose a risk of PFASs contamination,should be taken seriously by regulatory authorities and consumers.This method is high efficiency,sensitive and accuracy,which can provide important basis for the rapid detection and quality control of PFASs compounds in cosmetics.