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Nickel-rich metasomatism of the lithospheric mantle by pre-kimberlitic alkali-S–Cl-rich C–O–H fluids

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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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References

  • Alard O, Griffin WL, Lorand JP, Jackson SE, O’Reilly SY (2000) Non-chondritic distribution of the highly siderophile elements in mantle sulphides. Nature 407:891–894

    Article  Google Scholar 

  • Alard O, Lorand J-P, Reisberg L, Bodinier J-L, Dautria J-M, O’Reilly SY (2011) Volatile-rich metasomatism in montferrier xenoliths (Southern France): implications for the abundances of chalcophile and highly siderophile elements in the subcontinental mantle. J Petrol 52:2009–2045

    Article  Google Scholar 

  • Allsopp HL, Barrett DR (1975) Rb-Sr determinations on South African kimberlite pipes. Phys Chem Earth 9:615–617

    Article  Google Scholar 

  • Andersen T, O’Reilly SY, Griffin WL (1984) The trapped fluid phase in upper mantle xenoliths from Victoria, Australia: implications for mantle metasomatism. Contrib Mineral Petrol 88:72–85

    Article  Google Scholar 

  • Aulbach S, Griffin WL, Pearson NJ, O’Reilly SY, Kivi K, Doyle BJ (2004) Mantle formation and evolution, Slave Craton: constraints from HSE abundances and Re-Os isotope systematics of sulfide inclusions in mantle xenocrysts. Chem Geol 208:61–88

    Article  Google Scholar 

  • Ballhaus C, Berry R, Green D (1991) High pressure experimental calibration of the olivine-orthopyroxene-spinel oxygen geobarometer: implications for the oxidation state of the upper mantle. Contrib Mineral Petrol 107:27–40

    Article  Google Scholar 

  • Barnes SJ, Godel BM, Locmelis M, Fiorentini ML, Ryan CG (2011) Extremely Ni-rich Fe-Ni sulfide assemblages in komatiitic dunite at Betheno, Western Australia: results from synchrotron X-ray fluorescence mapping. Austral J Earth Sci 58:691–709

    Article  Google Scholar 

  • Bertrand P, Mercier J-CC (1985) The mutual solubility of coexisting ortho- and clinopyroxene: toward an absolute geothermometer for the natural system? Earth Planet Sci Lett 76:109–122

    Article  Google Scholar 

  • Brey GP, Kohler T (1990) Geothermobarometry in four-phase lherzolites II. New thermobarometers, and practical assessment of existing thermobarometers. J Petrol 31:1353–1378

    Google Scholar 

  • Burgess SR, Harte B (2004) Tracing lithosphere evolution through the analysis of heterogeneous G9–G10 garnets in peridotite xenoliths, II: REE chemistry. J Petrol 45:609–633

    Article  Google Scholar 

  • Carmichael ISE (1991) The redox states of basic and silicic magmas: a reflection of their source regions? Contrib Mineral Petrol 106:129–141

    Article  Google Scholar 

  • Chakraborty S (2010) Diffusion coefficients in olivine, wadsleyite and ringwoodite. Rev Mineral Geochem 72:603–639

    Article  Google Scholar 

  • Dawson JB, Smith JV (1975) Chromite-silicate intergrowths in upper-mantle peridotites. Phys Chem Earth 9:339–350

    Article  Google Scholar 

  • de Waal SA, Calk LC (1973) Nickel minerals from Barberton, South Africa: VI. Liebenbergite, a nickel olivine. Am Mineral 58:733–735

    Google Scholar 

  • Donnelly C, Griffin W, O’Reilly S, Pearson N, Shee S (2011) The Kimberlites and related rocks of the Kuruman Kimberlite Province, Kaapvaal Craton, South Africa. Contrib Mineral Petrol 161:351–371

    Article  Google Scholar 

  • Field SW, Haggerty SE (1994) Symplectites in upper mantle peridotites: development and implications for the growth of subsolidus garnet, pyroxene and spinel. Contrib Mineral Petrol 118:138–156

    Article  Google Scholar 

  • Field M, Stiefenhofer J, Robey J, Kurszlaukis S (2008) Kimberlite-hosted diamond deposits of southern Africa: a review. Ore Geol Rev 34:33–75

    Google Scholar 

  • Fiorentini ML, Beresford SW (2008) Role of volatiles and metasomatized subcontinental lithospheric mantle in the genesis of magmatic Ni–Cu–PGE mineralization: insights from in situ H, Li, B analyses of hydromagmatic phases from the Valmaggia ultramafic pipe, Ivrea-Verbano Zone (NW Italy). Terra Nova 20:333–340

    Article  Google Scholar 

  • Fleet ME (2006) Phase equilibria at high temperatures. Rev Mineral Geochem 61:365–419

    Article  Google Scholar 

  • Fleet ME, Wu T-W (1995) Volatile transport of precious metals at 1000 °C: Speciation, fractionation, and effect of base-metal sulfide. Geochim Cosmochim Acta 59:487–495

    Article  Google Scholar 

  • Frezzotti ML, Ferrando S, Peccerillo A, Petrelli M, Tecce F, Perucchi A (2010) Chlorine-rich metasomatic H2O-CO2 fluids in amphibole-bearing peridotites from Injibara (Lake Tana region, Ethiopian plateau): nature and evolution of volatiles in the mantle of a region of continental flood basalts. Geochim Cosmochim Acta 74:3023–3039

    Article  Google Scholar 

  • Gaetani GA, Grove TL (1999) Wetting of mantle olivine by sulfide melt: implications for Re/Os ratios in mantle peridotite and late-stage core formation. Earth Planet Sci Lett 169:147–163

    Article  Google Scholar 

  • Garuti G, Oddone M, Torres-Ruiz J (1997) Platinum-group-element distribution in subcontinental mantle: evidence from the Ivrea Zone (Italy) and the Betic—Rifean cordillera (Spain and Morocco). Can J Earth Sci 34:444–463

    Article  Google Scholar 

  • Garuti G, Bea F, Zaccarini F, Montero P (2001) Age, geochemistry and petrogenesis of the ultramafic pipes in the Ivrea Zone, NW Italy. J Petrol 42:433–457

    Article  Google Scholar 

  • Giuliani A, Kamenetsky VS, Phillips D, Kendrick MA, Wyatt BA, Goemann K (2012) Nature of alkali-carbonate fluids in the sub-continental lithospheric mantle. Geology. doi:10.1130/G33221.1

  • Gregoire M, Moine BN, O’Reilly SY, Cottin JY, Giret A (2000) Trace element residence and partitioning in mantle xenoliths metasomatized by highly alkaline, silicate- and carbonate-rich melts (Kerguelen Islands, Indian Ocean). J Petrol 41:477–509

    Article  Google Scholar 

  • Gregoire M, Rabinowicz M, Janse AJA (2006) Mantle mush compaction: a key to understand the mechanisms of concentration of kimberlite melts and initiation of swarms of kimberlite dykes. J Petrol 47:631–646

    Article  Google Scholar 

  • Harte B (1987) Metasomatic events recorded in mantle xenoliths: an overview. In: Nixon PH (ed) Mantle xenoliths. Wiley, New York, pp 625–640

    Google Scholar 

  • Harte B (2012) Mineral associations in diamonds from the lowermost upper mantle and uppermost lower mantle. 10th Internat Kimb conference, Bangalore, India, Ext abstr n.190

  • Ishimaru S, Arai S (2008) Nickel enrichment in mantle olivine beneath a volcanic front. Contrib Mineral Petrol 156:119–131

    Article  Google Scholar 

  • Ishimaru S, Arai S, Shukuno H (2009) Metal-saturated peridotite in the mantle wedge inferred from metal-bearing peridotite xenoliths from Avacha volcano, Kamchatka. Earth Planet Sci Lett 284:352–360

    Article  Google Scholar 

  • Jacob DE, Kronz A, Viljoen KS (2004) Cohenite, native iron and troilite inclusions in garnets from polycrystalline diamond aggregates. Contrib Mineral Petrol 146:566–576

    Article  Google Scholar 

  • Jochum KP, Stoll B (2008) Reference materials for elemental and isotopic analyses by LA–(MC)–ICP–MS: successes and outstanding needs. In: Sylvester P (ed) Laser ablation ICP–MS in the earth sciences: current practices and outstanding issues, Mineral Assoc Canada, pp 147–168

  • Kaneda H, Takenouchi S, Shoji T (1986) Stability of pentlandite in the Fe-Ni-Co-S system. Mineral Depos 21:169–180

    Google Scholar 

  • Karup-Moller S, Makovicky E (1995) The phase system Fe-Ni-S at 725 °C. Neue Jaharb Mineral Mhon 26:1–10

    Google Scholar 

  • Keays RR, Sewell DKB, Mitchell RH (1981) Platinum and palladium minerals in upper mantle-derived lherzolites. Nature 294:646–648

    Article  Google Scholar 

  • Kelemen PB, Hart SR, Bernstein S (1998) Silica enrichment in the continental upper mantle via melt/rock reaction. Earth Planet Sci Lett 164:387–406

    Article  Google Scholar 

  • Kinny PD, Dawson JB (1992) A mantle metasomatic injection event linked to late Cretaceous kimberlite magmatism. Nature 360:726–728

    Article  Google Scholar 

  • Lazarov M, Woodland AB, Brey GP (2009) Thermal state and redox conditions of the Kaapvaal mantle: a study of xenoliths from the Finsch mine, South Africa. Lithos 112S:913–923

    Article  Google Scholar 

  • Litasov KD, Safonov OG, Ohtani E (2010) Origin of Cl-bearing silica-rich melt inclusions in diamonds: experimental evidence for an eclogite connection. Geology 38:1131–1134

    Article  Google Scholar 

  • Lorand J-P, Alard O (2001) Platinum-group element abundances in the upper mantle: new constraints from in situ and whole-rock analyses of Massif Central xenoliths (France). Geochim Cosmochim Acta 65:2789–2806

    Article  Google Scholar 

  • Lorand J-P, Gregoire M (2006) Petrogenesis of base metal sulphide assemblages of some peridotites from the Kaapvaal craton (South Africa). Contrib Mineral Petrol 151:521–538

    Article  Google Scholar 

  • Lorand J-P, Keays RR, Bodinier JL (1993) Copper and noble metal enrichments across the lithosphere-asthenosphere boundary of mantle diapirs: evidence from the Lanzo Lherzolite Massif. J Petrol 34:1111–1140

    Article  Google Scholar 

  • Lorand J-P, Delpech G, Gregoire M, Moine B, O’Reilly SY, Cottin J-Y (2004) Platinum-group elements and the multistage metasomatic history of Kerguelen lithospheric mantle (South Indian Ocean). Chem Geol 208:195–215

    Article  Google Scholar 

  • Lorand J-P, Alard O, Luguet A (2010) Platinum-group element micronuggets and refertilization process in Lherz orogenic peridotite (northeastern Pyrenees, France). Earth Planet Sci Lett 289:298–310

    Article  Google Scholar 

  • Luguet A, Shirey SB, Lorand J-P, Horan MF, Carlson RW (2007) Residual platinum-group minerals from highly depleted harzburgites of the Lherz massif (France) and their role in HSE fractionation of the mantle. Geochim Cosmochim Acta 71:3082–3097

    Article  Google Scholar 

  • Mitchell RH (1986) Kimberlites: mineralogy, geochemistry and petrology. Plenum, New York

    Google Scholar 

  • Mungall JE, Su S (2005) Interfacial tension between magmatic sulfide and silicate liquids: constraints on kinetics of sulfide liquation and sulfide migration through silicate rocks. Earth Planet Sci Lett 234:135–149

    Article  Google Scholar 

  • Navon O, Stolper E (1987) Geochemical consequences of melt percolation: the Upper Mantle as a chromatographic column. J Geol 95:285–307

    Article  Google Scholar 

  • Pearson DG, Canil D, Shirey SB (2003) Mantle samples included in volcanic rocks: xenoliths and diamonds. In: Carlson R (ed) Treatise on geochemistry. The Mantle and Core, vol 2. Pergamon, Oxford, pp 171–275

    Chapter  Google Scholar 

  • Peregoedova A, Barnes S-J, Baker DR (2004) The formation of Pt-Ir alloys and Cu-Pd-rich sulfide melts by partial desulfurization of Fe-Ni-Cu sulfides: results of experiments and implications for natural systems. Chem Geol 208:247–264

    Article  Google Scholar 

  • Philippot P, Selverstone J (1991) Trace-element-rich brines in eclogitic veins: implications for fluid composition and transport during subduction. Contrib Mineral Petrol 106:417–430

    Article  Google Scholar 

  • Rose LA, Brenan JM (2001) Wetting properties of Fe-Ni-Co-Cu-O-S melts against olivine: implications for sulfide melt mobility. Econ Geol 96:145–157

    Google Scholar 

  • Sharygin VV, Golovin AV, Pokhilenko NP, Kamenetsky VS (2007) Djerfisherite in the Udachnaya-East pipe kimberlites (Sakha-Yakutia, Russia): paragenesis, composition and origin. Eu J Mineral 19:51–63

    Article  Google Scholar 

  • Smith CB (1983) Pb, Sr and Nd isotopic evidence for sources of southern African Cretaceous kimberlites. Nature 304:51–54

    Article  Google Scholar 

  • Spandler C, Pettke T, Rubatto D (2011) Internal and external fluid sources for eclogite-facies veins in the Monviso Meta-ophiolite, Western Alps: implications for fluid flow in subduction zones. J Petrol 52:1207–1236

    Article  Google Scholar 

  • Wallace ME, Green DH (1988) An experimental determination of primary carbonatite magma composition. Nature 335:343–346

    Article  Google Scholar 

  • Wood SA, Crerar DA, Borcsik MP (1987) Solubility of the assemblage pyrite-pyrrhotite-magnetite-sphalerite-galena-gold-stibnite-bismuthinite-argentite-molybdenite in H2O-NaCl-CO2 solutions from 200 to 350 °C. Econ Geol 82:1864–1887

    Article  Google Scholar 

  • Woodhead JD, Hellstrom J, Hergt JM, Greig A, Maas R (2007) Isotopic and elemental imaging of geological materials by laser ablation inductively coupled plasma-mass spectrometry. Geostand Geoanal Res 31:331–343

    Google Scholar 

  • Woodland AB, Koch M (2003) Variation in oxygen fugacity with depth in the upper mantle beneath the Kaapvaal craton, Southern Africa. Earth Planet Sci Lett 214:295–310

    Article  Google Scholar 

  • Wyllie PJ, Huang W-L (1975) Peridotite, kimberlite, and carbonatite explained in the system CaO-MgO-SiO2-CO2. Geology 3:621–624

    Article  Google Scholar 

  • Yaxley GM, Green DH, Kamenetsky VS (1998) Carbonatite metasomatism in the Southeastern Australian lithosphere. J Petrol 39:1917–1930

    Article  Google Scholar 

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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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Correspondence to Andrea Giuliani.

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Communicated by C. Ballhaus.

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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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