Permeable-reactive redox walls, placed below the ground surface in the path of flowing groundwater, provide an alternative remediation approach for removing electroactive chemicals from contaminated groundwater. Four types of Fe-bearing solids, siderite [FeCO 3 ], pyrite [FeS 2 ], coarsegrained elemental iron [Fe 0 ], and fine-grained Fe 0 , were assessed for their ability to remove dissolved Cr(VI) from solution at flow rates typical of those encountered at sites of remediation. Batch studies show that the rate of Cr-(VI) removal by fine-grained Fe 0 is greater than that for pyrite and coarse-grained Fe 0 . Results from column studies suggest that partial removal of Cr(VI) by pyrite and coarsegrained Fe 0 and quantitative removal of Cr(VI) by fine-grained Fe 0 occur at rapid groundwater flow velocities. The removal mechanism for Cr(VI) by fine-grained Fe 0 and coarse-grained Fe 0 is through the reduction of Cr(VI) to Cr(III), coupled with the oxidation of Fe 0 to Fe(II) and Fe(III), and the subsequent precipitation of a sparingly soluble Fe-(III)-Cr(III) (oxy)hydroxide phase. Mineralogical analysis of the reactive material used in the batch tests indicates that Cr is associated with goethite (R-FeOOH). These results suggest that Cr(III) is removed either through the formation of a solid solution or by adsorption of Cr(III) onto the goethite surface. The effective removal of Cr(VI) by Fe 0 under dynamic flow conditions suggests porous-reactive walls containing Fe 0 may be a viable alternative for treating groundwater contaminated by Cr(VI).
Extremely acidic mine waters with pH values as low as -3.6, total dissolved metal concentrations as high as 200 g/L, and sulfate concentrations as high as 760 g/L, have been encountered underground in the Richmond Mine at Iron Mountain, CA. These are the most acidic waters known. The pH measurements were obtained by using the Pitzer method to define pH for calibration of glass membrane electrodes. The calibration of pH below 0.5 with glass membrane electrodes becomes strongly nonlinear but is reproducible to a pH as low as -4. Numerous efflorescent minerals were found forming from these acid waters. These extreme acid waters were formed primarily by pyrite oxidation and concentration by evaporation with minor effects from aqueous ferrous iron oxidation and efflorescent mineral formation.
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