Food irradiation is a common preservation method that is used in many countries. The ability to identify irradiated food is important for assuring compliance with regulatory policies, such as food labeling requirements, and for informed consumer choice. There is thus a significant demand for analytical methods of high sensitivity and selectivity to identify irradiated food, especially for foods subjected to low-dose irradiation and for processed or composite foods that contain small quantities of irradiated ingredients. 2-Alkylcyclobutanones (2-ACBs) are uniquely formed during food irradiation and have been adopted by the European Committee for Standardization as signature biomarkers for the identification of irradiated foods. We now report the development of a novel assay for quantification of 2-ACBs in γ-irradiated food by liquid extraction of fat content followed by precolumn derivatization and liquid chromatography-tandem mass spectrometric (LC-MS/MS) detection. Precolumn derivatization with hydroxylamine introduced a polar functional group into the otherwise nonpolar 2-ACBs, which greatly enhanced ESI-MS response. The method was validated for extraction efficiency, precision, accuracy, and detection limit. In comparison with the current GC-MS based European official method (EN1785:2003) for 2-ACBs determination, our new LC-MS/MS method offers a more efficient sample processing protocol with reduced solvent consumption. More importantly, the combination of chemical derivatization and LC-MS/MS detection significantly enhanced the analytical sensitivity of the method, which allows confident identification of food irradiated with as little as 10 Gy. To the best of our knowledge, this is the first report of 2-ACB determination by LC-MS/MS and the first analytical method allowing confident identification of irradiated food at dosage of down to 10 Gy.

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2-Alkylcyclobutanones (2-ACBs) have long been considered as unique radiolytic products that can be used as indicators for irradiated food identification. A recent report on the natural existence of 2-ACB in non-irradiated nutmeg and cashew nut samples aroused worldwide concern because it contradicts the general belief that 2-ACBs are specific to irradiated food. The goal of this study is to test the natural existence of 2-ACBs in nut samples using our newly developed liquid chromatography-tandem mass spectrometry (LC-MS/MS) method with enhanced analytical sensitivity and selectivity ( Ye , Y. ; Liu , H. ; Horvatovich , P. ; Chan , W. Liquid chromatography-electrospray ionization tandem mass spectrometric analysis of 2-alkylcyclobutanones in irradiated chicken by precolumn derivatization with hydroxylamine . J. Agric. Food Chem. 2013 , 61 , 5758 - 5763 ). The validated method was applied to identify 2-dodecylcyclobutanone (2-DCB) and 2-tetradecylcyclobutanone (2-TCB) in nutmeg, cashew nut, pine nut, and apricot kernel samples (n = 22) of different origins. Our study reveals that 2-DCB and 2-TCB either do not exist naturally or exist at concentrations below the detection limit of the existing method. Thus, 2-DCB and 2-TCB are still valid to be used as biomarkers for identifying irradiated food.