Highly acidic and metal-rich runoff from coal storage facilities can have a dramatic impact on local surface and ground water quality. In order to identify important reactions governing metal transport within subsurface environments subject to infiltration of coal pile runoff, samples of uncontaminated subsoil and aquifer materials adjacent to the D-Area coal stockpile runoff containment basin at the Department of Energy's Savannah River Site were collected and subjected to leaching with the acidic, metalliferous coal pile runoff. Columns were packed to bulk densities of 1.5 Mg m³ and subjected to steady, saturated flows of 0.2 and 1.3 cm h⁻¹, Effluent was collected and multicomponent transport through the subsoil and aquifer materials evaluated. Observed transport was then related to soil chemical and mineralogical properties. Mass balance calculations, a sequential dissolution scheme in which column leaching was terminated and elements partitioned to aqueous, <i>M</i> NH₄CI, and ammonium oxalate in the dark (Ox)-extractable phases, and mineralogical and surface chemical analyses were used to identify important chemical processes and mineralogical alterations.Ph. D.