The control of soluble metal species in the sub-product leachate generated in electricity production processes is of great concern from an environmental and health point of view. Unlike fly ash, the leaching behaviour of char materials has received little attention. Yet, these solids are captured together with fly ashes in the particle control devices of power plants and are emitted in the same way as by-products. The present study was carried out using two char samples: (i) a raw char and (ii) the same type of char employed in a previous study so that it could serve as a sorbent for mercury species in gas phase. The char samples were by-products (residues) that had been generated during the gasification of plastic and paper waste. The leachates were analyzed for the following elements: Al, Ca, Si, Mg, Ba, Cu, Ni, Pb, Zn, Mo and Hg. In addition, geochemical modelling of the leaching test results was employed to identify the underlying chemical processes that led to the release of toxic elements. The results showed that at alkaline pH values, sorption on the solid surfaces of the char was negligible due to the inorganic complexation of cations in the solution. When the char was used as mercury sorbent slight changes occurred on the reactive surface resulting in the modification of the binding of some elements. As the pH increased, complexation with dissolved organic matter played a more important role in the case of some elements such as Cu because of the greater concentration of dissolved organic matter in solution. (C) 2012 Elsevier B.V. All rights reserved.