Rapid Determination of Ethyl Carbamate in Chinese Liquor via a Direct Injection Mass Spectrometry with Time-Resolved Flash-Thermal-Vaporization and Acetone-Assisted High-Pressure Photoionization Strategy

Abstract

Ethyl carbamate (EC), a carcinogenic compound, is naturally produced in fermented foods and alcoholic beverages. Rapid and accurate measurement of EC is necessary and important for quality control and safety evaluation of Chinese liquor, a traditionally distilled spirit with the highest consumption in China, but it remains a great challenge. In this work, a direct injection mass spectrometry (DIMS) with time-resolved flash-thermal-vaporization (TRFTV) and acetone-assisted high-pressure photoionization (HPPI) strategy has been developed. EC was rapidly separated from the main matrix components, ethyl acetate (EA) and ethanol, by the TRFTV sampling strategy due to the retention time difference of these three compounds with large boiling point differences on the inner wall of a poly­(tetrafluoroethylene) (PTFE) tube. Therefore, the matrix effect of EA and ethanol was effectively eliminated. The acetone-assisted HPPI source was developed for efficient ionization of EC through a photoionization-induced proton transfer reaction between EC molecules and protonated acetone ions. The accurate quantitative analysis of EC in liquor was achieved by introducing an internal standard method (ISM) using deuterated EC (d 5-EC). As a result, the limit of detection (LOD) for EC was 8.88 μg/L with the analysis time of only 2 min, and the recoveries ranged from 92.3 to 113.1%. Finally, the prominent capability of the developed system was demonstrated by rapid determination of trace EC in Chinese liquors with different flavor types, exhibiting wide potential applications in online quality control and safety evaluation of not only Chinese liquors but also other liquor and alcoholic beverages.