Markus Grafe

Nickel distribution and speciation in rapidly dehydroxylated goethite in oxide-type lateritic nickel ores: XAS and TEM spectroscopic (EELS and EFTEM) investigation

The distribution of Ni in four lateritic Ni-goethites that were rapidly dehydroxylated to form hematite by shock heating at 340/400°C and 800°C for 30 min was investigated using synchrotron X-ray diffraction (SXRD), TEM spectroscopy (EELS and EFTEM) and synchrotron X-ray absorption spectroscopy (XAS). The Ni K-edge EXAFS results for non-heated samples showed three distinct Ni–Fe shells, including two edge-sharing (R Ni–Fe ∼ 3.01 and R Ni–Fe ∼ 3.22 Å) and a double corner-sharing (R Ni–Fe ∼ 3.52 Å) complex for most of the samples. These interatomic distances are indicative of Ni substituting for Fe in goethite, which has resulted in an expansion in the goethite structure along the a-axis direction and a contraction along the b-axis direction. Ravensthorpe Ni goethite was considerably different from the other goethites, with two Ni–O interatomic lengths (R Ni–O ∼ 2.04 and 2.46 Å), an edge-sharing (R Ni–Fe ∼3.04 Å) and a corner-sharing (R Ni–Fe ∼ 3.56 Å) complex. The R Ni–O ∼ 2.46 Å bond length is not indicative of Ni substituting for Fe in goethite, nor is it associated with single or multiple scattering events in NiO, Ni(OH)2 or Ni substituting for Fe in Fe oxides. The corresponding Ni K-edge EXAFS results for 340/400°C and 800°C heated samples (i.e. hematite) were very similar. Four distinct metal neighbours correspond to Fe/Ni in face-sharing (R Ni–Fe ∼ 2.87–2.91 Å) and three different corner-sharing complexes (R Ni–Fe ∼ 3.37– 3.41 Å, R Ni–Fe ∼ 3.62– 3.64 Å and R Ni–Fe ∼ 3.92– 4.09 Å) represent Ni substituting for Fe in hematite. The fourth shell is indicative of an inner sphere surface complex. EFTEM maps for Ni in goethite are consistent with the formation of a surface complex as they provide evidence for clustering of Ni on the surface of neoformed hematite crystals. There was no evidence from EXAFS or SXRD supporting the formation of discrete Ni phases (e.g. NiO) as a result of shock heating. Therefore, for Ni-goethites subjected to shock heating at 800°C (i.e. high-temperature dehydroxylation to hematite), most of the Ni is retained in the structures of the neoformed hematites, whereas some of the Ni migrates to the surface of the neoformed hematite where it forms a surface complex. During acid dissolution (e.g. heap leaching) of oxide-type lateritic Ni ores, Ni on the hematite surface is more accessible to acid solutions; therefore, these results may provide a basis for more efficient extraction methods for Ni in oxide-type lateritic Ni ores, as well as providing information on the possible redistribution of Ni in heated goethite-rich soils.

Combined application of QEM-SEM and hard X-ray microscopy to determine mineralogical associations and chemical speciation of trace metals.

We describe the application of quantitative evaluation of mineralogy by scanning electron microscopy in combination with techniques commonly available at hard X-ray microprobes to define the mineralogical environment of a bauxite residue core segment with the more specific aim of determining the speciation of trace metals (e.g., Ti, V, Cr, and Mn) within the mineral matrix. Successful trace metal speciation in heterogeneous matrices, such as those encountered in soils or mineral residues, relies on a combination of techniques including spectroscopy, microscopy, diffraction, and wet chemical and physical experiments. Of substantial interest is the ability to define the mineralogy of a sample to infer redox behavior, pH buffering, and mineral-water interfaces that are likely to interact with trace metals through adsorption, coprecipitation, dissolution, or electron transfer reactions. Quantitative evaluation of mineralogy by scanning electron microscopy coupled with micro-focused X-ray diffraction, micro-X-ray fluorescence, and micro-X-ray absorption near edge structure (mXANES) spectroscopy provided detailed insights into the composition of mineral assemblages and their effect on trace metal speciation during this investigation. In the sample investigated, titanium occurs as poorly ordered ilmenite, as rutile, and is substituted in iron oxides. Manganeses spatial correlation to Ti is closely linked to ilmenite, where it appears to substitute for Fe and Ti in the ilmenite structure based on its mXANES signature. Vanadium is associated with ilmenite and goethite but always assumes the +4 oxidation state, whereas chromium is predominantly in the +3 oxidation state and solely associated with iron oxides (goethite and hematite) and appears to substitute for Fe in the goethite structure.