The purpose of this investigation was (i) to test the effectiveness of a barrier engineered to remove Cr(VI) from leachates of higher pH and salinity typical of coal burning ashes and (ii) to determine which geochemical processes control Cr immobilization. Laboratory column and batch desorption experiments show that a barrier composed of sand, Fe(0), and bentonite irreversibly immobilizes Cr. Concentrations fall from 25 mg Cr L-1 in the leachate to below detection limits (0.0025 mg Cr L-1) and solution pH increases by about two units. Solid-phase analytical techniques such as SEM, EDS, XPS, and TOFSIMS were used to characterize the barrier material prior to and after exposure to the Cr leachate. In the barrier material, Cr(III) was found associated with Fe(III)-oxides, as separate Cr oxides and as a Ca,Cr phase, probably Cachromite, CaCr2O4. The attenuating barrier can be an alternative to traditional liners and leachate collection systems at coal ash storage and disposal sites.