An automotive diesel engine was tested in three representative modes of soot accumulation, active regeneration and spontaneous regeneration of its catalyzed diesel particulate filter (DPF), among the typical driving operation modes. During the engine tests, pressure and temperature along the DPF were measured, and soot samples were taken from the exhaust manifold upstream of the DPF for their thermal, structural and morphological characterization. The collected soot samples were subjected to: Transmission Electron Microscopy (TEM) for morphological analysis, thermal heating under oxidant atmosphere for studying the oxidation kinetics, Raman spectroscopy for describing their nanostructure and X-ray diffraction spectroscopy (XRD) for studying their internal lattice parameters. When the engine was operated in a typical accumulation mode, the pressure drop across the DPF increased up to 80 hPa with diesel fuel, while pressure drop stopped increasing after 4000 s of engine testing with biodiesel. In the regeneration mode, the DPF regenerated more slowly in the biodiesel case as a consequence of lower post-injected fuel energy and thus lower exhaust temperature. In the self-regenerating mode, the DPF was charged more slowly with biodiesel than with diesel fuel and its break even temperature was 40 degrees C lower with biodiesel fuel. These results provide further evidence that biodiesel soot is more reactive to oxidation. Although thermogravimetric results confirmed this tendency based on the differences on the pre-exponential factor, Raman spectra showed that biodiesel soot reached more ordered graphite-like structures and lower amorphous carbon concentration and XRD analysis showed that biodiesel soot displayed a higher degree of graphitization. The TEM analysis of the agglomerates showed that soot primary particles obtained with biodiesel fuel were significantly smaller and had higher specific active surface than those of diesel soot. From these results, an interpretation of the differences in soot oxidation between both soot samples was made based on the different length scales, from the carbon fringes to the particulate filter. (C) 2011 The Combustion Institute. Published by Elsevier Inc. All rights reserved.