Temperature programmed combustion of a Chinese brown coal before and after demineralization was carried out in a tubular quartz fixed bed reactor. The evolution of NOx during coal combustion has been investigated with an aim of figuring out the influence of indigenous mineral matter in coal as well as the loaded alkali and alkaline earth metals (Na, Ca). The results show that the mineral matter in the coal suppresses the conversion of fuel-N to NOx, and at the same time, significantly promotes the coal combustion process. The added Na exhibits high catalytic activity for the coal combustion and NOx reduction. In the case of Ca, its effect on the combustion of coal is ignorable but the emission level of NOx increases distinctively due to the presence of Ca. The formation of N-Ca intermediates that preferentially direct the conversion of fuel-N towards NOx during coal combustion is proposed and discussed. (C) 2005 Elsevier Ltd. All rights reserved.