非离子型表面活性剂/涡旋-液液微萃取结合 气相色谱/质谱联用法检测白酒中 邻苯二甲酸酯类塑化剂

Determination of plasticizer of phthalate esters in Chinese liquor by nonionic surfactant/vortex liquid-liquid microextration combined with gas chromato-graphy-mass spectrometry

中文关键词:  非离子型表面活性剂  液液微萃取  气相色谱/质谱联用  邻苯二甲酸酯类塑化剂

英文关键词:nonionic surfactant  liquid-liquid microextration  gas chromatography-mass spectrometry  plasticizer of phthalate esters

中文摘要:

      目的 建立一种高效、简便非离子型表面活性剂/涡旋-液液微萃取结合气相色谱/质谱联用技术检测白酒中6种邻苯二甲酸酯类塑化剂(PAEs)的方法。方法 将酒样稀释至20%, 调节pH至2.0, 取上述样品5 mL至玻璃离心管, 依次加入氯化钠1.4 g, 1倍CMC吐温-20, 混匀, 加入四氯乙烯0.5 mL, 2800 r/min涡旋30 s, 离心10 min, 取下层清液进行GC-MS分析, 选择离子模式检测, 外标法定量。结果 该方法对6种邻苯二甲酸酯类塑化剂的分离效果良好; 检出限(S/N>3)在0.05~5 μg/L之间; 建立了对应标准曲线, 线性关系良好; 日内、日间精密度(RSD)小于6%。应用该方法对6家企业生产的9种浓香型白酒的检测结果显示: 不同企业、相同企业不同品牌酒样中PAEs的种类和含量均存在差异; DMP、DEP、DBP和DEHP在9个酒样中均有检出; DMEP和BBP仅在部分酒样中检出; 从卫计委关注的DBP和DEHP角度出发, S-2-2、S-3-1、S-3-23个酒样中DBP含量虽未超过标准, 但均已接近1 mg/L限量要求, 需要相关企业重点关注。结论 该方法具有高效、简便、灵敏的特点, 适用于白酒中邻苯二甲酸酯类化合物的快速检测和日常筛查。

英文摘要:

      Objective To establish an efficient and easy method for the determination of 6 types of phthalate esters in Chinese liquor by nonionic surfactant/vortex liquid-liquid microextration combined with gas chromatography-mass spectrometry. Methods Aliquots of 5.0 mL liquor samples, which were diluted to 20%, adjusted the pH to 2.0, were placed in a screw cap glass tube with conical bottom. 0.5 mL of Tetrachlorethylene as extraction solvent, 1CMC of Tween 20 as emulsifier and 1.4 g NaCl were added into the sample solution. The mixture was shaken using a vortex agitator at 2800 r/min for 30 s, then centrifuged for 10min. After that, the C2Cl4 phase was directly injected into GC–MS for analysis. External standard method was used in quantification. Results This method showed a good separation on 6 types of phthalate esters; LODs, based on S/N of 3, ranged from 0.05~5 μg/L. The linear relation was excellent under the linear ranges. The intra and inter-day precision were less than 6%. Under the optimum conditions, 6 Luzhou-flavor enterprises and 9 kinds of brand were inspected. The results showed that the type and concentration of PAEs samples existed differences between different enterprises or the same enterprise different brands; DMP, DEP, DBP and DEHP were present in all samples, whereas DMEP and BBP were detected in only parts of the liquor sample. Especially for DBP and DEHP, the concentrations of DBP in S-2-2, S-3-1, and S-3-2 were really high, though it was not exceed standard, it has been closed to 1 mg/L limitation requirement, so the relevant enterprises should pay more attention on this issue. Conclusion This method is suitable for the rapid detection and routine inspection of PAEs in Chinese liquor samples and proved to be simple, rapid, and sensitive.