建立气相色谱-串联质谱法(gas chromatography-series mass spectrometry, GC-MS/MS)同时测定食用油中6种增塑剂(plasticizer, PAEs)和14种多环芳烃(polycyclic aromatic hyolrocarbon, PAHs)的准确定性定量方法。样品经V(二氯甲烷)∶V(丙酮)=1∶1混合溶剂萃取,旋涡提取(2 000 r/min)30 s,再超声萃取8 min,10 000 r/min离心5 min,使溶液充分分层后,置于-20 ℃冷冻除脂60 min,低温氮气吹干以及2 mL二氯甲烷复溶后上机检测。采用多反应监测模式,以保留时间和特征离子对比较定性定量,同时测定20种持久性污染物,采用外标法定量。结果显示,20种目标物在5~200 μg/L范围内呈良好线性,线性相关系数均＞0.995。3个水平加标回收率为51.34%~116.2%,相对标准偏差为0.9%~12.1%。对实际样品检测均有不同程度的PAEs和PAHs检出,对照国内限量苯并(a)芘(BaP)超标率12.5%。该方法前处理简便,快速准确,干扰少,适用于食用油中增塑剂和多环芳烃的检测。
A deterministic quantitative method for the determination of 6 plasticizers(PAEs) and 14 polycyclic aromatic hydrocarbons(PAHs) in edible oils by gas chromatography-series mass spectrometry(GCMS/MS) was established. The sample was preperaed by methylene chloride-acetone (V∶V, 1∶1), vortex extraction(2 000 r/min) 30 s, and ultrasonic extraction for 8 min, 10 000 r/min centrifugation 5 min. When the liquid solution is fully separate, the sample is placed at -20 ℃ for 60 min to remove fat, spray dry with low-temperature nitrogen gas, and dissolve in 2 mL dichloromethane. 20 persistent pollutants were simultaneously detected by qualitative and quantitative analysis of keeping time and specific ion under MRM mode and external standard method. The results show that the 20 targets are well linear in the 5-200 μg/L range, and the linear correlation coefficients are all greater than 0.995. The recovery rate of standard addition at three levels are 51.34%-116.2%, and the relative standard deviation is 0.9%-12.1%. Both PAEs and PAHs were detected to different degrees, compared with the 12.5% excess rate of benzopyrene(a) pyrene(BaP) in China. The method is simple, rapid, accurate and has less interference. It is suitable for the detection of edible oil plasticizer and polycyclic aromatic hydrocarbons.
[1] 张延平,沈丹玉,陈振超,等.分散固相萃取-气相色谱/串联质谱法测定竹笋中38种持久性有机污染物[J].分析试验室, 2018,37(6): 671-676.
[2] 马燕玲,陈令新,丁养军,等.超声辅助分散液液微萃取-高效液相色谱测定水样中的4种邻苯二甲酸酯类增塑剂[J].色谱, 2013,31(2): 155-161.
[3] 艾连峰,李玮,王敬,等.气相色谱-串联质谱法测定牛奶中多氯联苯及多环芳烃[J].分析测试学报, 2015,34(5):570-575.
[4] 王颖,边照阳,李中皓,等.气相色谱-质谱法测定烟用接装纸中的邻苯二甲酸酯、磷酸三丁酯和多氯联苯[J].理化检验(化学分册), 2018,54(9): 1 092-1 100.
[5] 刘妙芬,刘佳,邱佩丽,等.气质联用内标法同时测定白酒中16种邻苯二甲酸酯类化合物[J].食品与机械, 2015,31(4):51-54;83.
[6] 朱金红. 气相色谱-质谱联用测定油墨中17种邻苯二甲酸酯 [J].广州化工, 2013,41(4):119-121.
[7] CHEN S J, TIAN M, ZHENG J, et al. Elevated levels of polychlorinated biphenyls in plants,air, and soils at an E-waste site in southern China and enantioselective biotransformation of Chiral PCBs in Plants[J].Environmental Science & Technology,2014,48(7): 3 847-3 855.
[8] 苏丽敏,袁星.持久性有机污染物 (POPs)及其生态毒性的研究现状与展望[J].重庆环境科学,2003,25(9): 62-64;78.
[9] KIM L,JEON J W,SON J Y,et al. Monitoring and risk assessment of polychlorinated biphenyls(PCBs) in agricultural soil from two industrialized areas[J].Environmental Geochemistry and Health,2017,39(2): 279-291.
[10] 殷雪琰,王洁琼,堵燕钰,等.在线凝胶渗透色谱-气相色谱串联质谱法分析土壤和茶叶中的多氯联苯[J].化学分析计量, 2018,27(2): 22-26.
[11] WANG Z, NA G, MA X. et al. Occurrence and gas/particle parti-tioning of PAHs in the atmosphere from the North Pacific to the Arctic Ocean [J].Atmospheric Environment, 2013,77: 640-646.
[12] 陈园园,李胜生.串联质谱法测定土壤中多环芳烃和多氯联苯的分析[J].西部资源,2018,(4):164-166.
[13] 王国庆,王宗义,程明捷,等.冷冻除脂-气相色谱-串联质谱法检测食用植物油中30种多环芳烃[J].食品科学2018,39(8):282-287.
[14] 乌日娜.多环芳烃在食用植物油加工工艺中的污染特征研究 [D].北京:中国农业科学院, 2016: 9-19.
[15] WU S M, YU W J. Liquid-liquid extraction of polycyclic aromatic hydrocarbons in four different edible oils from China[J]. Food Chemistry, 2012, 134(1): 597-601.
[16] PETTER O,IOANNIS S,JAN H,et al. Class separation of lipids and polycyclic aromatic hydrocarbons in normal phase high performance liquid chromatography-a prospect for analysis of aromativs in edible vegetable oils and biodiesel exhaust particulates[J]. Journal of Chromatography A, 2014,1 360:39-46.
[17] 张东东,刘玉兰,马宇翔,等. SPE净化-同位素稀释-GC-MS法检测食用油脂中16 种多环芳烃[J]. 粮食与油脂, 2016, 29(1): 53-59.
[18] HUERTAS-PÉREZ J F, BORDAJANDI L R, SEJERØE-OISEN B, et al. PAHs in baby food: assessment of three different processing techniques for the preparation of reference materials[J]. Analytical & Bioanalytical Chemistry, 2015, 407(11): 3 069-3 081.
[19] WANG J H, GUO C. Ultrasonication extraction and gel permeation chromatography clean-up for the determination of polycyclic aromatic hydrocarbons in edible oil by an isotope dilution gas chromatography mass spectrometry[J]. Journal of Chromatography A, 2010,1 217(28): 4 732-4 737.
[20] GB 5009.265—2016食品中多环芳烃的测定[S]. 北京: 中国标准出版社, 2016: 1-8.
[21] LUDIVINE F, NATHALIE D, DOUGLAS N R, et al. Optimizing separation conditions of 19 polycyclic aromatic hydrocarbons by cyclodextrin modified capillary electrophoresis and application to edible oils[J]. Talanta, 2014,119: 572-581.
[22] 曹梦思, 王君, 张立实,等. 我国食用油脂中欧盟优控15+1 种多环芳烃的污染状况分析[J]. 中国食品学报, 2016, 16(12): 198-205.
[23] 李国文, 吉正元, 杨春涛,等. 加速溶剂萃取-气相色谱质谱法测定土壤中16种多环芳烃研究[J]. 安全与环境学报, 2019, 19(2): 591-599.
