The devolatilization behavior of a bituminous coal and different biomass fuels currently applied in the Dutch power sector for co-firing was experimentally investigated. The volatile composition during single fuel pyrolysis as well as during co-pyrolysis was studied using TG-FTIR characterization with the focus on the release patterns and quantitative analysis of the gaseous bound nitrogen species. It was shown that all investigated biomass fuels present more or less similar pyrolysis behavior, with a maximum weight loss between 300 and 380 degrees C. Woody and agricultural biomass materials show higher devolatilization rates than animal waste. When comparing different fuels, the percentage of fuel-bound nitrogen converted to volatile bound-N species (NH3, HCN, HNCO) does not correlate with the initial fuel-N content. Biomass pyrolysis resulted in higher volatile-N yields than coal, which potentially indicates that NOx control during co-firing might be favored. No significant interactions occurred during the pyrolysis of coai/biomass blends at conditions typical of TG analysis (slow heating rate). Evolved gas analysis of volatile species confirmed the absence of mutual interactions during woody biomass co-pyrolysis. However, non-additive behavior of selected gas species was found during slaughter and poultry litter co-pyrolysis. Higher CH4 yields between 450 and 750 degrees C and higher ammonia and CO yields between 550 and 900 degrees C were measured. Such a result is likely to be attributed to catalytic effects of alkali and alkaline earth metals present in high quantity in animal waste ash. The fact that the co-pyrolysis of woody and agricultural biomass is well modeled by simple addition of the individual behavior of its components permits to predict the mixture's behavior based on experimental data available for single fuels. On the other hand, animal waste co-pyrolysis presented in some cases synergistic effects in gas products although additive behavior occurred for the solid phase. (C) 2009 Elsevier B.V. All rights reserved.