气相色谱-质谱检测葡萄酒中氨基甲酸乙酯预处理方法的比较研究

Comparison of different pretreatment methods for determination of ethyl carbamate in wine by gas chromatography-mass spectrometry

目的比较液液萃取法、固相萃取法和分散式固相萃取法作为预处理方法对葡萄酒中的氨基甲酸乙酯的处理效率。方法葡萄酒样品中的氨基甲酸乙酯分别用二氯甲烷进行液液萃取,用氨基甲酸乙酯专用柱进行固相萃取,用乙腈、石墨化炭黑和N-丙基乙二胺进行分散式固相萃取,再以气相色谱-质谱联用仪测定其含量。结果 3种预处理方法的平均回收率均在70%~110%之间,相对标准偏差(n=5)均小于6%。液液萃取法处理单个样品成本小于5元,富集倍数可达5倍,可用于低含量样品的预处理和进出口企业的产品合规性检测;固相萃取法操作简便,每人每工作日可处理40个样品,可用于企业的高通量检测;分散式固相萃取法成本适中、回收率最佳、综合预处理效率高,一次预处理可同时检测葡萄酒中农药残留和氨基甲酸乙酯含量,适用于葡萄酒中多种危害物质的筛查。结论三种方法各具优势,综合考虑处理效率和实验成本,分散式固相萃取法更适合葡萄酒生产企业的日常应用。该方法已用于葡萄酒中氨基甲酸乙酯的含量测定。

Objective To compare the preconditioning efficiencies of ethyl carbamate in wine by liquid-liquid extraction (LLE), solid phase extraction (SPE) and dispersive solid phase extraction (d-SPE). MethodThree methods of LLE with dichloromethane, SPE with Cleanert EC column and d-SPE with acetonitrile, graphitized carbon and primary secondary amine were separately used to extract the ethyl carbamate of the wine samples, which was analyzed by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring mode.Result The spiked recoveries at 3 levels of these methods were in the range of 70%~110% and the relative standard deviations (n=5) were less than 6%, indicating that those methods had a good accuracy and precision. Since it was low-cost and had a high enrichment efficiency, LLE was suitable for pretreatment of samples with trace amount and could meet the requirements of compliance detection in import and export manufacturers. SPE was more appropriate for high through-put determination due to convenience and fast speed. d-SPE could be well applied to various hazard substances screening, because it was mid-cost, best recovery and high comprehensive efficiency.Conclusion In consideration of the pretreatment efficiency and cost, d-SPE was more suitable for the daily quality control inspection in wine manufacturers. d-SPE coupled with GC-MS had been applied to determination of ethyl carbamate in wine.