Ash transformation processes have been studied during co-firing of wheat straw and pine stem wood and softwood bark. Pilot-scale trials in a 150 kW pulverised-fuel-fired burner were performed. Thermodynamic equilibrium calculations were made to support the interpretation of the results. The results show that reactions involving condensed phases are kinetically limited compared to reactions between gaseous ash compounds. Accordingly, the conditions promote gas phase reactions resulting in the formation of chlorides, sulphates and carbonates whereas reactions involving condensed reactants are suppressed. Both the slagging and fouling propensities of all co-firing mixes were reduced compared to that for pure straw. For the wood/straw mixes this was mainly due to a dilution of the ash forming elements of straw whereas for straw/bark, an additional effect from interaction between the fuel ash components was observed to reduce slagging. In general it can be concluded that under powder combustion conditions equilibrium is approached selectively and that the ash matter is strongly fractionated. The general results in this paper are useful for straw-fired power stations looking for alternative co-firing fuels. (C) 2011 Elsevier B.V. All rights reserved.