In this work, the impact of moisture on the volatility of heavy metals present in municipal solid wastes (MSW) in a laboratory scale simulated incinerator was studied, using synthetic waste consisting of 5.4 g of wood powder, 2.6 g lava, 1.9 polythene, 0.19 g polyvinyl chloride, and a given quantity of water and heavy metals represented by lead, zinc and copper in forms of metallic, chlorides and oxides. It is found that the presence of high moisture in MSW will greatly reduce the volatilization of heavy metals in MSW in the incineration process. The volatilization behavior of chlorides, oxides and the metallic species with respect to the effect of moistures is quite different. For copper, the presence of moisture in MSW depresses the volatilization of oxides, and increases that of chloride and the metallic species, while in contrast, the volatilization of both lead and zinc is always depressed by the presence of moisture in MSW, regardless of the chemical forms used. The chemical mechanisms, which govern the volatilization behaviors of different chemical forms in the incineration process, are proposed. Hydrolysis, dewatering of hydrolyzed species, sublimation, chemical transformation of less volatiles to more volatiles or reverse, may participate in and affect the volatilization of heavy metals in MSW. (C) 2004 Elsevier Ltd. All rights reserved.