The aim of this study is to demonstrate the potential of coals as a low-cost reactive barrier material for environmental protection applications, with the ability to prevent leaching of toxic Cr(VI) and other transition metals. Depending upon the type of ion and the surface functionalities, the uptake can involve ion sorption, ion exchange, chelation and redox mechanisms with the surface functionalities being considered as partners in electron transfer processes. The capacity for Cr(VI) uptake of low rank coals and oxidized bituminous coals has been found to lie within the range 0.2-0.6 mM g(-1). Air oxidation of bituminous coals can increase their Cr(VI) removal capacities. The effect of air oxidation of coals on uptake capacity was more pronounced for Cr(VI) than Cr(III), but less than for Hg(II) and the other ions (Ca2+, Ba2+, Zn2+, Cd-2) investigated. As previously found for Hg(II), redox mechanisms play an important role in Cr(VI) uptake, with sorption of the resultant Cr(III) being aided by the functionalities arising from oxidation of the coal surface. In acidic media, much of the resultant Cr(III) is exchanged back into solution by hydrogen ions, but some of the sorbed chromium is irreversibly bound to the coal. The reduction of Cr(VI) alone is often considered a satisfactory solution in view of Cr(111) being essentially non-toxic.