Comparison Of Analysis Methods For Bisphenol Diglycidyl Ethers In Food And Their Contact Packaging Materials

Bisphenol diglycidyl ethers are raw materials of food contact packaging materials, especially for the inner coatings of cans. In addition, bisphenol diglycidyl ethers are usually used as additive, crosslinker and epoxy stabilizer in the food industry. These compounds are easily dissolved in edible oil and food liped, and may migrate into the oily food, which make bisphenol diglycidyl ether residues in food possible. That bisphenol diglycidyl ethers accumulated in human body have toxicity side effect, which caused endocrine, immunologic and nervous systems of human and animals abnormal. These compounds could also interrupt the reproductive and hereditary capabilities of human and animals, which would endanger human health. It is very necessary to explore the satisfied analytical methods of bisphenol diglycidyl ethers in food and their contact packaging materials, which will improve monitoring of bisphenol diglycidyl ether residues in food and their contact packaging materials and ensure food-safety. Two analytical methods of bisphenol diglycidyl ethers were developed and compared in this paper. The extraction solvent, extracting way and clean-up method were studied in the experiment. Two extraction solvents were compared for the extraction of bisphenol diglycidyl ethers in food contact packaging materials. Four extraction solvents, three extracting ways and three clean-up methods were compared for the extraction and purification effects of bisphenol diglycidyl ethers in food. The extraction rate of acetonitrile and n-hexane/acetone (50/30, v/v) solutions were highest for extraction of target analytes in food cans and food respectively, the extraction effect of microwave-assisted extraction was best and the clean-up method of SPE was more effective. Varian-PS-DVB was selected as SPE cartridge. SPE cartridge was conditioned with 4 mL methanol and 4 mL purified water. The cartridge was washed with 4 mL 20% methanol aqueous solution and eluted with 5 mL acetonitrile.In this paper, a high performance liquid chromatography (HPLC-FLD) method for determination of bisphenol diglycidyl ethers in food and their contact packaging materials has been explored. Several parameters of HPLC were optimized for the determination of bisphenol diglycidyl ethers. The linear range was 12.5～500.0 ng/g for four bisphenol diglycidyl ethers (1.25～375.0 ng/g for BADGE·H2O,5.0～375.0 ng/g for BADGE·HCl,5.0～500.0 ng/mL for BADGE-2HCl and BADGE·HClH2O,12.5～375.0 ng/g for BFDGE, 12.5～625.0 ng/g for 3R-NOGE) with the good linear relation, and the correlation coefficients R2 was 0.9990～0.9999. LOD and LOQ were 0.79～3.77 ng/g and 2.75～10.92 ng/g for 10 analytes respectively. The recoveries of blank samples spiked at three levels of bisphenol diglycidyl ethers were 70.46%～103.44%, whose inter and intra RSD were 0.50～9.04% and 0.27%～6.56% respectively. Various bisphenol diglycidyl ethers could be determined by HPLC because of high sensitivity and simple operation.Ultra performance liquid chromatography-tandem mass spectrometric (UPLC-MS/MS) could reduce the analysis time and improve the analytical categories of bisphenol diglycidyl ethers as compared to HPLC. UPLC-MS/MS was established for determination of ten bisphenol diglycidyl ethers in food and their contact packaging materials. Several parameters of UPLC and MS/MS were optimized for the determination of target analytes. The interference of matrix was reduced by the matrix-matched calibration standards curve. The calibration curve of six concentrations for ten bisphenol diglycidyl ethers showed good linearity and good correlation coefficients R2 (0.9927～0.9996). LOQ was 0.0340 ng/g～0.6573 ng/g. The recovery range of bisphenol diglycidyl ethers was 65.7%～99.1%,0.5%～7.2%, respectively, with RSD. The accuracy and sensitivity of the method was good for simultaneous determination of 10 bisphenol diglycidyl ethers. Therefore, it is suitable to analyze targets by UPLC-MS/MS in food and their contact packaging materials.Compared with HPLC-FLD, UPLC represented the quick analytical speed and good separation efficiency. Multiple reaction monitoring (MRM) of MS detector could achieve multi-residue analysis of bisphenol diglycidyl ethers in one time, even if multicomponent bisphenol diglycidyl ethers could not be separated absolutely by HPLC. Ten bisphenol diglycidyl ethers were analyzed in the study and analytical methods will be developed for more bisphenol diglycidyl ethers in future. HPLC-FLD is cheaper than that of UPLC-MS/MS, and the stability is better than that of UPLC-MS/MS. HPLC-FLD and UPLC-MS/MS are simple, accurate and sensitive for simultaneous determination of various bisphenol diglycidyl ethers. The limits of quantitation of were far below MRLs regulated by EU. Therefore, HPLC-FLD and UPLC-MS/MS were fit to analyze residues of bisphenol diglycidyl ethers in food and their contact packaging materials.