Natural speciation of nickel at the micrometer scale in serpentine (ultramafic) topsoils using microfocused X-ray fluorescence, diffraction, and absorption

Abstract

Serpentine soils and ultramafic laterites develop over ultramafic bedrock and are important geological materials from environmental, geochemical, and industrial standpoints. They have naturally elevated concentrations of trace metals, such as Ni, Cr, and Co, and also high levels of Fe and Mg. Minerals host these trace metals and influence metal mobility. Ni in particular is an important trace metal in these soils, and the objective of this research was to use microscale (μ) techniques to identify naturally occurring minerals that contain Ni and Ni correlations with other trace metals, such as Fe, Mn, and Cr. Synchrotron based μ-XRF, μ-XRD, and μ-XAS were used. Ni was often located in the octahedral layer of serpentine minerals, such as lizardite, and in other layered phyllosilicate minerals with similar octahedral structure, such as chlorite group minerals including clinochlore and chamosite. Ni was also present in goethite, hematite, magnetite, and ferrihydrite. Goethite was present with lizardite and antigorite on the micrometer scale. Lizardite integrated both Ni and Mn simultaneously in its octahedral layer. Enstatite, pargasite, chamosite, phlogopite, and forsterite incorporated various amounts of Ni and Fe over the micrometer spatial scale. Ni content increased six to seven times within the same 500?μm μ-XRD transect on chamosite and phlogopite. Data are shown down to an 8?μm spatial scale. Ni was not associated with chromite or zincochromite particles. Ni often correlated with Fe and Mn, and generally did not correlate with Cr, Zn, Ca, or K in μ-XRF maps. A split shoulder feature in the μ-XAS data at 8400?eV (3.7??^?1 in k-space) is highly correlated (94% of averaged LCF results) to Ni located in the octahedral sheet of layered phyllosilicate minerals, such as serpentine and chlorite-group minerals. A comparison of bulk-XAS LCF to averaged μ-XAS LCF results showed good representation of the bulk soil via the μ-XAS technique for two of the three soils. In the locations analyzed by μ-XAS, average Ni speciation was dominated by layered phyllosilicate and serpentine minerals (76%), iron oxides (18%), and manganese oxides (9%). In the locations analyzed by μ-XRD, average Ni speciation was dominated by layered phyllosilicate, serpentine, and ultramafic-related minerals (71%) and iron oxides (17%), illustrating the complementary nature of these two methods.