Over the last decades, several indices based on ash chemistry and ash fusibility have been used to predict the ash behaviour during coal combustion, namely, its tendency for slagging and fouling. However, due to the physical chemical differences between coals and biomass, in this work only the applicability of an ash fusibility index (AFI) to the combustion and co-combustion of three types of biomass (straw pellets, olive cake and wood pellets) with coals was evaluated. The AFI values were compared with the behaviour of ash during combustion in a pilot fluidized bed and a close agreement was observed between them. For a better understanding of the mechanisms associated with bed ash sintering, they were evaluated by SEWEDS and the elements present on the melted ash were identified. Evidences of different sintering mechanisms were found out for the fruit biomass and herbaceous biomass tested, depending on the relative proportions of problematic elements. The particles deposited on a fouling probe inserted in the FBC were analyzed by XRD and the differences between the compounds identified allowed concluding that the studied biomasses present different tendencies for fouling. Identification of KCl and K2SO4 in the deposits confirmed the higher tendency for fouling of fruit biomass tested rather than wood pellets. (C) 2012 Elsevier Ltd. All rights reserved.