A Salting-out Liquid-Liquid extraction (SALLE) for the analysis of caprolactam and 2,4-di-tert butyl phenol in water and food simulants. Study of the salinity effect to specific migration from food contact materials
JOURNAL OF CHROMATOGRAPHY B-ANALYTICAL TECHNOLOGIES IN THE BIOMEDICAL AND LIFE SCIENCES
Authors: Tsochatzis, Emmanouil D.; Mieth, Anja; Lopes, Joao Alberto; Simoneau, Catherine
Abstract
Caprolactam and 2,4-di-tert-butyl phenol (2,4-DTBP) are substances typically found in some food contact materials (FCMs). They are known to often migrate into food, and are difficult to analyse in liquid food simulants using GC. In this work a simple salting-out Liquid-Liquid Extraction (SALLE) for the analysis of both substances in water and the official food simulant A (10 % v/v ethanol, Regulation (EU) No. 10/2011) is presented. The method, which included analytical determination by GC-MS, was optimized and validated to ensure sufficient analytical quality. The method's LOQs allowed the proper quantification of caprolactam at its EU legislative limit (15 mg kg(-1)). For 2,4-DTBP the method also revealed good sensitivity, although no official limits have been established yet. Linear regression coefficients (R-2) were in all cases higher than 0.999, and recoveries ranged from 87 % and 95% for caprolactam and 2,4-DTBP, respectively. Precision was also acceptable, with the RSDs (%) below 12 %. The method proved to be adequate to be used for routine analysis. The presence of salt during migration of caprolactam and 2,4-DTBP was also investigated in this work. Polyamide/polyethylene FCM multilayer films have been tested with water and simulant A, containing different amounts of NaCl (up to 15 % m/v), and applying different migration conditions (temperature and time). The results indicated that salinity plays an important effect on the migration of caprolactam, with the presence of salt reducing its migration in case of water and increasing it in case of simulant A. These preliminary results seem to indicate that migration testing should consider not only the well-known fatty content of a food, but also its salinity content, as it may end up affecting drastically the migration of polar substances.
Detection and identification of ethanal-derived spin-trapped free radicals using headspace thermal desorption gas chromatography-mass spectrometry (TD-GC-MS)
FREE RADICAL RESEARCH
Authors: Manzoor, Kamran; Mishra, Sanat K.; Podmore, Ian D.
Abstract
In this study, we demonstrate a novel approach to the detection and identification of the products of spin-trapped free radicals. Hydroxyl free radicals were generated by Fenton-based chemistry in the presence of ethanal and the spin-trapping agent N-tert-butyl-alpha-phenylnitrone (PBN). The resulting volatile compounds present in the reaction vial headspace were collected using thermal desorption (TD) and analysed by gas chromatography-mass spectrometry (GC-MS). Eleven compounds were detected in the headspace, and their identification was aided by using either a fluorinated or deuterated analogue of PBN as an alternative spin trap and/or deuterated ethanal (CD3CHO) as the secondary source of free radicals. The electron-ionisation (EI) mass spectra clearly demonstrate the "capture" of methyl radicals; two of the compounds detected were identified as containing one methyl group derived from ethanal, and four were shown to contain two methyl groups. This study demonstrates that sampling the reaction headspace using TD-GC-MS is a viable method for analysing products of free radical trapping, and potentially may be applied to a wide range of free radical systems.