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Combustion in an O2/CO2 mixture (oxyfuel) has been recognized as a promising technology for CO2 capture as it produces a high CO2 concentration flue gas. Furthermore, biofuels in general contribute to CO2 reduction in comparison with fossil fuels as they are considered CO2 neutral. Ash formation and deposition (surface fouling) behavior of coal/biomass blends under O2/CO2 combustion conditions is still not extensively studied. Aim of this work is the comparative study of ash formation and deposition of selected coal/biomass blends under oxyfuel and air conditions in a lab scale pulverized coal combustor (drop tube). The fuels used were Russian and South African coals and their blends with Shea meal (cocoa). A horizontal deposition probe, equipped with thermocouples and heat transfer sensors for on line data acquisition, was placed at a fixed distance from the burner in order to simulate the ash deposition on heat transfer surfaces (e.g. water or steam tubes). Furthermore, a cascade impactor (staged filter) was used to obtain size distributed ash samples including the submicron range at the reactor exit. The deposition ratio and propensity measured for the various experimental conditions were higher in all oxyfuel cases. The SEM/EDS and ICP analyses of the deposit and cascade impactor ash samples indicate K interactions with the alumina silicates and to a smaller extend with Cl, which was all released in the gas phase, in both the oxyfuel and air combustion samples.