Microstructural Analyses of Cr(VI) Speciation in Chromite Ore Processing Residue (COPR)

The speciation and distribution of Cr(VI) in the solid phase was investigated for two types of chromite ore processing residue (COPR) found at two deposition sites in the United States: gray-black (GB) granular and hard brown (HB) cemented COPR. COPR chemistry and mineralogy were investigated using micro-X-ray absorption spectroscopy and micro-X-ray diffraction, complemented by laboratory analyses: GB CON contained 30% of its total Cr(VI) (6000 mg/kg) as large crystals (>20 mu m diameter) of a previously unreported Na-rich analog of calcium aluminum chromate hydrates. These Cr(VI)-rich phases are thought to be vulnerable to reductive and pH treatments. More than 50% of the Cr(VI) was located within nodules, not easily accessible to dissolved reductants, and bound to Fe-rich hydrogarnet, hydrotalcite, and possibly brucite. These phases are stable over a large pH range, thus harder to dissolve. Brownmillerite was also likely associated with physical entrapment of Cr(VI) in the interior of nodules. HB COPR contained no Cr(VI)-rich phases; all Cr(VI) was diffuse within the nodules and absent from the cementing matrix, with hydrogarnet and hydrotalcite being the main Cr(VI) binding phases. Treatment of HB COPR is challenging in terms of dissolving the acidity-resistant, inaccessible Cr(VI) compounds; the same applies to similar to 50% of Cr(VI) in GB COPR.