Abstract
Metasomatism of the lithospheric mantle sometimes produces unusual assemblages containing native metals and alloys, which provide important insight into metasomatic processes in the mantle. In this study, we describe the metasomatic enrichment of a refractory harzburgite xenolith in Ni, Fe and, to a lesser extent, Cu, Co, As and Sb. The xenolith (XM1/422) derives from the Bultfontein kimberlite (Kimberley, South Africa) and hosts Ni mineralisation that includes native nickel (Ni84.5-98.0), heazlewoodite (Ni3S2) and Ni-rich silicates (e.g. up to 37.5 wt % NiO in olivine, and 22.4 wt % NiO in phlogopite). The presence of several mineral phases enriched in alkali and volatile species (e.g. phlogopite, phosphates, carbonates, chlorides, djerfisherite) indicates that the transition metal cations were likely introduced during metasomatism by alkali-rich C–O–H fluids or alkali-carbonate melts. It is postulated that sulphide breakdown and fluid reaction with refractory mantle rocks contributed to the fluid’s enrichment in Ni and other metallic cations. The Ni-rich assemblages of xenolith XM1/422 show local chemical disequilibrium, and modelling of the Ni diffusion profiles adjacent to olivine-native nickel and olivine-heazlewoodite grain boundaries, suggests a close temporal relationship between Ni-rich metasomatism and subsequent entrainment by the kimberlite magma. However, metal-rich metasomatism has also been observed in other lithospheric mantle domains, including orogenic peridotitic massifs and the suboceanic mantle; regions unaffected by kimberlite magmatsim. As micro-scale occurrences of metallic phases are easily overlooked, it is possible that metal-rich metasomatism is more widespread in the Earth’s mantle than previously recognised.
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Acknowledgments
We thank Chris Ballhaus for constructive discussions at the early stage of this study and for editorial handling; Fanus Viljoen, Michel Gregoire and Jean-Pierre Lorand for constructive reviews; Reid Keays, Sonja Aulbach and Antje Wildau for useful discussions during manuscript preparation; Alan Greig for help with LA-ICP-MS analyses, and Graham Hutchinson for support with the SEM imaging and EMP analyses at the University of Melbourne. Finally, we acknowledge De Beers Consolidated Mines Ltd. for providing DP with the sample for this study. AG’s PhD research is supported by an International Australian Postgraduate Award, the 2011 John Hodgson Scholarship and the 2012 AusIMM Bicentennial Gold Endowment.
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Appendix: Model of diffusion duration of Ni into olivine
Appendix: Model of diffusion duration of Ni into olivine
The Ni diffusion profiles in porphyroblastic olivine can be modelled by applying Fick’s second law to estimate the duration of the diffusion process. The diffusion coefficient for Ni in olivine has been determined at different values of temperature, pressure and oxygen fugacity using the formulation of Chakraborty (2010). Note that in the olivine lattice, diffusion operates 6 times faster along the c axis than along the other two crystallographic axes (Chakraborty 2010, and references therein). For this calculation, we have assumed temperatures equivalent to, or higher than, the equilibration temperature of the xenolith minerals (664–727 °C). Pressure has a negligible effect on the value of the diffusion coefficient. The oxygen fugacity is assumed to have been intermediate between the QFM buffer (which is the maximum value previously calculated for the shallow spinel facies mantle beneath the Kaapvaal craton; Woodland and Koch 2003), and the Ni–NiO buffer (which is indicated by the crystallisation of nearly pure native nickel; Carmichael 1991). The Ni chemical profiles in olivine adjacent to heazlewoodite show Ni diffusion at distances between 73 and 85 μm; consequently we have modelled Ni diffusion into olivine up to a length scale of 80 μm. Based on the above input parameters, and considering diffusion along the ‘fastest’ axis c, Ni could diffuse 80 μm into olivine over a minimum period of ca. 100 year at 1,000 °C, or over a maximum period of 0.7–1.7 Myr at 700 °C (see Online Resource Table 6EA).
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Giuliani, A., Kamenetsky, V.S., Kendrick, M.A. et al. Nickel-rich metasomatism of the lithospheric mantle by pre-kimberlitic alkali-S–Cl-rich C–O–H fluids. Contrib Mineral Petrol 165, 155–171 (2013). https://doi.org/10.1007/s00410-012-0801-1
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DOI: https://doi.org/10.1007/s00410-012-0801-1