Role of quantitative mineralogical analysis in the investigation of sites contaminated by chromite ore processing residue

A range of techniques, normally associated with mineralogical studies of soils and sediments, has been used to characterise the solid materials found on sites contaminated with chromite ore processing residue (COPR). The results show that a wide range of minerals are present, many of which are found extensively in high-temperature synthetic systems such as cements and clinkers and their low temperature hydration products. Thus, the minerals in COPR can be divided into three main categories: unreacted feedstock ore (chromite); high temperature phases produced during chromium extraction (brownmillerite, periclase and larnite); and finally, minerals formed under ambient weathering conditions on the disposal sites (brucite, calcite, aragonite, ettringite, hydrocalumite, hydrogarnet). Apart from chromite, chromium occurs in brownmillerite, ettringite, hydrocalumite and hydrogarnet. Detailed study of the chemistry and stoichiometry of chromium-bearing phases in conjunction with phase abundance provides a quantitative description of the solid state speciation of Cr(III) and Cr(VI) in and amongst these minerals and in the COPR as a whole. Of the total chromium present in the samples most, approximately 60–70% is present as Cr(III) in chromite, whilst brownmillerite also represents a significant reservoir of Cr(III) which is approximately 15% of the total. The remaining chromium, between 20 and 25%, is present as Cr(VI) and resides mainly in hydrogarnet, and to a slightly lesser extent in hydrocalumite. In the latter, it is present principally in an exchangeable anionic form. Chromium (VI) is also present in ettringite, but quantitatively ettringite is a much less important reservoir of Cr(VI), accounting for approximately 3% of total chromium in one sample, but less than 1% in the other two. This description provides insight into the processes likely to control the retention and release of Cr(VI) from COPR-contaminated sites. Such information is of particular value in chemical modelling of the system, in risk assessment and in the development of methods of informed remediation.