The aim of this study has been to investigate the chemistry and volatility of the heavy metals As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn on the grate of a MSW fired furnace, using equilibrium calculations. Focus has been on the influence of varying MSW composition and operational parameters such as air/fuel ratio and temperature. Equilibrium distributions at 950-1600 K, under reducing and oxidising conditions on the grate, showed that Cd, Hg and Pb are fully volatilised. However, Cr is found to be stable in solid phase, in the entire temperature range. The volatile behaviour of Cd, Cr, Hg and Pb show no significant influence, while As, Cu, Ni and Zn are strongly influenced by one or more of the parameters; temperature, fuel/air and chlorine/metal ratios. (C) 2003 Elsevier Ltd. All rights reserved.