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Methyl esters obtained from the most interesting Spanish oleaginous crops for energy use -sunflower and cynara cardunculus- were both used as diesel fuels in this work, pure and in 25% blends with a reference commercial fuel which was also used pure. A stationary engine test bed, together with the appropriate instrumentation for chemical and morphological analysis, allowed to evaluate the effect of these fuels on the engine emissions, particularly in the main particulate matter characteristics, such as soluble organic fraction, origin of adsorbed hydrocarbons, sulphate content, particle number per unit filter surface, and mean particle diameter. Both the consideration of the main thermochemical properties of the tested fuels and the computations of a chemical equilibrium model were helpful for the analysis of the experimental results.