超高效液相色谱-质谱法测定鸡蛋中全氟烷酸和全氟磺酸前体物质

Determination of perfluorosulfonate and perfluorocarboxylate precursors in eggs by ultra-highperformance liquid chromatography-mass spectrometry

目的建立超高效液相色谱．串联三重四级杆质谱（UPLC．MS／MS）测定鸡蛋中11种全氟烷酸与全氟磺酸前体物质的方法。方法鸡蛋中的目标化合物用100mmol／LNaOH-乙腈，水（90：10，V／V）超声提取后，经固相萃取柱（WatersOasis。WAX6cc）净化，体积分数9％氨水．甲醇溶液洗脱。经WatersACQUITYTM BEH 18C色谱柱（50mm×2．1mm，1．7μm）分离后，在电喷雾负离子源（ESI一）和多反应监测模式（MRM）T进行测定，采用内标法进行定量分析。并对方法的检出限、定量限、精密度和准确度进行评价。用确定的方法对7份市售鸡蛋样品中目标化合物进行检测。结果11种目标化合物加标回收率为74．09％～116．82％；相对标准偏差为2．37％-13．62％；检测限为0．06～1．50pg／g（湿重）；定量限为0．15—3．00Pg／g（湿重）。7份市售鸡蛋样品中检出5种全氟烷酸和全氟磺酸前体物质，其中1H，1H，2H，2H．全氟辛基磺酸在7份样品中均有检出，含量为1．67～3．11pg／g，6份样品中检出2H．全氟．2．辛烯酸，含量为〈LOD-5．11pg/g，6份样品中检测出1H，1H，2H，2H-全氟辛基-2-磷酸盐，含量为3．78～9．16pg／g，在同1份样品中检出1H，1H，2H，2H-全氟壬基磺酸和N-甲基全氟-1-辛基磺酰胺乙酸，含量分别为105．78、4．95pg／g。其余化合物均未检出。结论本方法简单、快速，准确度和灵敏度高，适用于鸡蛋中全氟烷酸与全氟磺酸前体物质的检测，并可满足人体膳食暴露研究的需要。

Objective To develop a method for the determination of 11 perfluorosulfonate and perfluorocarboxylate precursors in eggs using ultra-high performance liquid chromatography-tandem quadruple mass spectrometry （UPLC-MS/MS）. Methods The target compounds of egg were extracted with 100 mmol/L NaOH-acetonitrile/water（90： 10, V/V） by ultrasonic. Then the extract was purified by solid phase extraction （Waters Oasis WAX 6ec） and then eluted with 9% NH4OH in methanol. The target compounds were separated on a Waters ACQUITYTM BEH 18C column （50 mm × 2.1 mm, 1.7 μm） and detected by negative electrospray ionization （ESI-） mass spectrometry in multiple reaction monitoring mode （MRM）. All compounds were quantified with internal standards. The accuracy, precision and the limits of detection and quantification of the method were evaluated. Then we detected 7 different egg samples from the market. Results The average recoveries for the eleven precursors at 3 levels were 74.09%-116.82% and the relative standard deviations were 2.37%-13.62%. The limits of detection （LOD） of the method were in the range of 0.06-1.50 pg/g （wet weight） and the limits of quantification （LOQ） were in the range of 0.15- 3.00 pg/g （wet weight）. And 5 target compounds were detected in the 7 market samples. 6：2 fluorotelomer sulfonate （6：2 FTS） was detected in all of samples with the concentrations of 1.67-3.11 pg/g. 6：2 fluorotelomer unsaturated acid （FHUEA） and 6：2 disubstituted polyfluoroalkyl phosphate ester （ 6：2 diPAP） were detected in 6 samples and the concentrations were〈LOD-5.11 pg/g and 3.78-9.16 pg/g, respectively. And the concentrations of 8：2 fluorotelomer sulfonate （8：2 FTS） and N-methyl perfluorooctane sulfonamidoacetic acid （N-Me FOSAA） founded in the same sample were 105.78, and 4.95 pg/g, respectively. Conclusion This method was simple, rapid, and suitable for determination of perfluorosulfonate and perfluorocarboxylate precursors in eggs with high accuracy and sensitivity. It could also be applied to human burden studies of these precursors.