Spin trapping EPR spectroscopy and DFT methods were used to investigate the structure of antioxidants present in bioglycerols [glycerol fractions (GF) derived from biodiesel production]. For this purpose the reactions of GF components and their pure reference chemicals with PBN and H2O2 were examined via EPR measurements. The EPR parameters of formed PBN spin adducts indicated the alpha-tocopherol origin of the trapped radicals. The comparative analysis of experimental and theoretically calculated hyperfine constants for the spin adducts strongly suggests the carbon-centered nature of the radicals generated and trapped by PBN in the bioglycerol systems. (C) 2010 Elsevier B.V. All rights reserved.