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Zirconosilicates in the kakortokites of the Ilímaussaq complex, South Greenland: Implications for fluid evolution and high-field-strength and rare-earth element mineralization in agpaitic systems

  • A. M. Borst (a1) (a2), H. Friis (a3), T. Andersen (a4), T. F. D. Nielsen (a1), T. E. Waight (a2) and M. A. Smit (a2) (a5)...

The layered agpaitic nepheline syenites (kakortokites) of the Ilímaussaq complex, South Greenland, host voluminous accumulations of eudialyte-group minerals (EGM). These complex Na-Ca-zirconosilicates contain economically attractive levels of Zr, Nb and rare-earth elements (REE), but have commonly undergone extensive autometasomatic/hydrothermal alteration to a variety of secondary mineral assemblages. Three EGM alteration assemblages are recognized, characterized by the secondary zirconosilicates catapleiite, zircon and gittinsite. Theoretical petrogenetic grid models are constructed to assess mineral stabilities in terms of component activities in the late-stage melts and fluids. Widespread alteration of EGM to catapleiite records an overall increase in water activity, and reflects interaction of EGM with late-magmatic Na-, Cl- and F-rich aqueous fluids at the final stages of kakortokite crystallization. Localized alteration of EGM and catapleiite to the rare Ca-Zr silicate gittinsite, previously unidentified at Ilímaussaq, requires an increase in CaO activity and suggests post-magmatic interaction with Ca-Sr bearing aqueous fluids. The pseudomorphic replacement of EGM in the kakortokites was not found to be associated with significant remobilization of the primary Zr, Nb and REE mineralization, regardless of the high concentrations of potential transporting ligands such as F and Cl. We infer that the immobile behaviour essentially reflects the neutral to basic character of the late-magmatic fluids, in which REE-F compounds are insoluble and remobilization of REE as Cl complexes is inhibited by precipitation of nacareniobsite-(Ce) and various Ca-REE silicates. A subsequent decrease in F– activity would furthermore restrict the mobility of Zr as hydroxyl-fluoride complexes, and promote precipitation of the secondary zirconosilicates within the confines of the replaced EGM domains.

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Andersen, S., Bohsen, H. and Steenfelt, A. (1988) Geological map of Greenland 1: 20 000 the southern part of the Ilímaussaq complex, South Greenland. Grønlands Geologiske Undersøgelse.
Andersen, T., Erambert, M., Larsen, A.O. and Selbekk, R.S. (2010) Petrology of nepheline syenite pegmatites in the Oslo Rift, Norway: Zirconium silicate mineral assemblages as indicators of alkalinity and volatile fugacity in mildly agpaitic magma. Journal of Petrology 51(11) 23032325.
Andersen, T., Erambert, M., Larsen, A.O. and Selbekk, R.S. (2013) Petrology of nepheline syenites pegmatites in the Oslo Rift, Norway: Zr and Ti mineral assemblages in miaskitic and agpaitic pegmatites in the Larvik Plutonic Complex. Mineralogia, 44, 6198.
Ansell, H.G., Roberts, A.C., Plant, A.G. and Stuman, B.D. (1980) Gittinsite, anew calcium zirconium silicate from the Kipawa Agpaitic Syenite Complex, Quebec. The Canadian Mineralogist, 18 201203.
Bailey, J.C., Gwodz, R., Rose-Hansen, J. and Sørensen, H. (2001) Geochemical overview of the Ilímaussaq alkaline complex, South Greenland. Geology of Greenland Survey Bulletin, 190 3553.
Birkett, T.C., Miller, R.R., Roberts, A.C. and Mariano, A.N. (1992) Zirconium-bearing minerals of the Strange Lake intrusive complex, Quebec-Labrador. The Canadian Mineralogist, 30 191205.
Bohse, H. and Andersen, S. (1981) Review of the stratigraphic divisions of the kakortokite and lujavrite in southern Ilímaussaq. Rapport Grønlands Geologisk Undersøgelse, 103 5362.
Bohse, H., Brooks, C.K. and Kunzendorf, H. (1971) Field observations on the kakortokites of the Ilímaussaq intrusion, South Greenland, including mapping and analyses by portable X-ray fluorescence equipment for zirconium and niobium.. Rapport Grønlands Geologiske Undersøgelse, 38 43100.
Boily, M. and Williams-Jones, A.E. (1994) The role of magmatic and hydrothermal processes in the chemical evolution of the Strange Lake plutonic complex, Quebec-Labrador. Contributions to Mineralogy and Petrology, 118 33–7.
Cámara, F., Sokolova, E. and Hawthorne, F.C. (2011) From structural topology to chemical composition. XII. Titanium silicates: the crystal chemistry of rinkite Na2Ca4REETi(Si2O7)2OF3 . Mineralogical Magazine, 75, 27552774.
Chakhmouradian, A.R. andZaitsev, A.N. (2002) Calcite-Amphibole—Clinopyroxene rock from the Afrikanda Complex, Kola Peninsula, Russia: mineralogy and a possible link to carbonatites. III. Silicate minerals. The Canadian Mineralogist, 40 13471374.
Chakhmouradian, A.R. and Zaitsev, A.N. (2012) Rare Earth Mineralization in Igneous Rocks: Sources and Processes. Elements 8(5), 347347.
Chakrabarty, A., Pruseth, K.L. and Sen, A.K. (2012) Compositions and petrogenetic significance of eudialyte group minerals from Sushina, Purulia, West Bengal. Journal of the Geological Society of India, 79, 449–59.
Chakrabarty, A., Mitchell, R.H., Ren, M., Sen, A.K. and Pruseth, K.L. (2013) Rinkite, cerianite-(Ce), and hingganite-(Ce) in syenites gneisses from the Sushina Hill Complex, India: occurrence, compos¬itional data and petrogenetic significance. MineralogicalMagazine, 77 31373153.
Coulson, I.M. (1997) Post-magmatic alteration in eudia¬lyte from the North Qôroq centre, South Greenland. Mineralogical Magazine, 61, 99109.
Currie, K.L. andZaleski, E. (1985) The relative stability of elpidite and vlasovite: a P-T indicator for peralkaline rocks. The Canadian Mineralogist, 23, 577582.
Estrade, G., Salvi, S., Béziat, D. and Williams-Jones, A.E. (2015) The origin of skarn-hosted rare-metal mineral¬ization in the Ambohimirahavavy alkaline complex, Madagascar. Economic Geology v(6), 14851513.
Ferguson, J. (1964) Geology of the Ilímaussaq alkaline intrusion, South Greenland. Part 1. Description of map and structure. Meddelelser om Grønland, 172, 181.
Finch, A.A. (1991) Conversion of nepheline to sodalite during subsolidus processes in alkaline rocks. Mineralogical Magazine, 55, 459–163.
Graser, G. and Markl, G. (2008) Ca-rich ilvaite-epidote-hydrogarnet endoskarns: a record of late-magmatic fluid influx into the persodic Ilímaussaq complex, South Greenland. Journal of Petrology, 49, 239265.
Gysi, A.P. and Williams-Jones, A.E. (2013) Hydrothermal mobilization of pegmatite-hosted REE and Zr at Strange Lake, Canada: A reaction path model. Geochimica et Cosmochimica Acta, 122 324352.
Jarosewich, E. and Boatner, L.A. (1991) Rare earth element reference samples for electron microprobe analyses. Geostandards Newsletter, 15, 397399.
Johnsen, O. and Grice, J.D. (1999) The crystal chemistry of the eudialyte group. The Canadian Mineralogist, 37, 865891.
Johnsen, O., Ferraris, G., Gault, R.A., Grice, J.D., Kampf, A.R. and Pekov, I.V. (2003) The nomenclature of eudialyte-group minerals. The Canadian Mineralogist, 41 785794.
Karup-Møller, S., Rose-Hansen, J. and Sørensen, H. (2010) Eudialyte decomposition minerals with new hithero undescribed phases from the Ilímaussaq complex, South Greenland. Bulletin of the Geological Society of Denmark, 58, 7588
Karup-Møller, S. and Rose-Hansen, J. (2013) New data on eudialyte decomposition minerals from kakortokites and associated pegmatites of the Ilímaussaq complex, South Greenland. Bulletin of the Geological Society of Denmark, 61, 4770.
Kempe, U., Götze, J., Dandar, S. and Haberman, D. (1999) Magmatic and metasomatic processes during formation of the Nb-Zr-REE deposits Khaldzan Buregte and Tsakhir (Mongolian Altai): Indications from a combined CL-SEM study. Mineralogical Magazine, 63, 165177
Khadem Allah, B., Fontan, F., Kader, M.M., Onchew, P. and Sørensen, H. (1998) Reactions between agpaitic nephelinitic syenitic melts and sedimentary carbonate rocks - exemplified by the Tamazeght complex, Morocco. Geochemistry International, 36, 569581.
Konnerup-Madsen, J. (2001) A review of the composition and evolution of hydrocarbon gases during solidification of the Ilímaussaq alkaline complex, South Greenland. Geology of Greenland Survey Bulletin, 190 159166
Krumrei, T.V., Villa, I.M., Marks, M.A.W. and Markl, G. (2006) A 40Ar/39Ar and U/Pb isotopic study of the Ilímaussaq complex, South Greenland: Implications for the 40K decay sonstant and for the duration of magmatic activity in a peralkaline complex. Chemical Geology, 227, 258273.
Kynicky, J., Chakhmouradian, A.R., Xu, C., Krmicek, L. and Galiova, M. (2011) Distribution and evolution of zirconium mineralization in perkalkaline granites and associated pegmatites of the Khan Bogd complex, southern Mongolia. The Canadian Mineralogist, 49 947965.
Larsen, L.M. (1976) Clinopyroxenes and coexisting mafic minerals from the alkaline Ilímaussaq intrusion, South Greenland. Journal of Petrology, 17, 258290.
Larsen, L.M. and Sørensen, H. (1987) The Ilímaussaq intrusion — progressive crystallization and formation of layering in an agpaitic magma. Pp. 473-488 in: Alkaline Igneous Rocks(J.G. Fitton and B.G. J. Upton, editors). Geological Society of London Special Publication, 30.
Le Maitre, R.W. (2003) Igneous Rocks: A Classification and Glossary of Terms, 2nd edition. Cambridge University Press, Cambridge, UK.
Lindhuber, M.J., Marks, M.A.W.., Bons, P.D., Wenzel, T. and Markl, G. (2015) Crystal mat-formation as an igneous layering forming process: Textural and geochemical evidence from the ‘lower layered’ nepheline syenite sequence of the Ilímaussaq complex, South Greenland. Lithos 224225 and 295-295.
Lorenzen, J. (1884) Untersuchungen einiger Mineralien aus Kangerdluarsuk in Grönland. Zeitschrift für Kristallographie, 9, 243254.
Markl, G. and Baumgartner, L. (2002) pH changes in peralkaline late-magmatic fluids. Contributions to Mineralogy and Petrology, 144 331346
Markl, G., Marks, M.A.W.., Schwinn, G. and Sommer, H. (2001) Phase equilibrium constraints on intensive crystallization parameters of the Ilímaussaq Complex, South Greenland. Journal of Petrology, 42, 22312258.
Markl, G., Marks, M.A.W.. and Frost, B.R. (2010) On the controls of oxygen fugacity in the generation and crystallization of peralkaline melts. Journal of Petrology, 51 18311847.
Marks, M.A.W.. and Markl, G. (2015) The Ilímaussaq Alkaline Complex, South Greenland. Pp. 649-691 in: Layered Intrusions (B. Charlier O. Namur R. Latypov and C. Tegner, editors). Springer Geology, Dordrecht, The Netherlands.
Marks, M.W., Hettman, K. and Schilling, J.T. (2011) The mineralogical diversity of alkaline igneous rocks: critical factors for the transition from miaskitic to agpaitic phase assemblages. Journal of Petrology, 52 439455.
Marr, R.A. and Wood, S.A. (1992) Preliminary petrogen-etic grids for sodium and calcium zirconosilicate minerals in felsic peralkaline rocks: The SiO2-Na2ZrO and SiO2—CaZrO, pseudobinary systems. American Mineralogist, 77 810810.
Migdisov, A.A. and Williams-Jones, A.E. (2014) Hydrothermal transport and deposition of the rare earth elements by fluorine-bearing aqueous liquids. Mineralium Deposita, 49, 987997.
Migdisov, A.A., Williams-Jones, A.E. and Wagner, T. (2009) An experimental study of the solubility and speciation of the rare earth elements (III) in fluoride-and chloride-bearing aqueous solutions at tempera¬tures up to 300°C. Geochimica et CosmochimicaActa, 73, 70877109.
Migdisov, A.A., Williams-Jones, A.E., van Hinsberg, V. and Salvi, S. (2011) An experimental study of the solubility of baddelyite (ZrO2) in fluoride-bearing solutions at elevated temperature. Geochimica et Cosmochimica Acta, 75, 74267434.
Mitchell, R.H. and Chakrabarty, A. (2012) Paragenesis and decomposition assemblage of a Mn-rich eudialyte from the Sushina peralkaline nepheline syenite gneiss, Paschim Banga, India. Lithos, 152 218226.
Mitchell, R.H. and Liferovich, R.P. (2006) Subsolidus deuteric/hydrothermal alteration of eudialyte in lujav-rite from the Pilansberg alkaline complex, South Africa. Lithos, 91, 352372.
Morimoto, N. (1988) Nomenclature of pyroxenes. Mineralogy and Petrology, 39, 5576
Olivo, G.R. and Williams-Jones, A.E. (1999) Hydrothermal REE-rich eudialyte from the Pilanesberg complex, South Africa. The Canadian Mineralogist, 37, 653663.
Petersen, O.Y., Ronsbo, J.G. and Leonardsen, E.S. (1989) Nacareniobsite-(Ce), a new mineral species from the Ilímaussaq alkaline complex, South Greenland, and its relation to mosandrite and the rinkite series. Neues Jahrbuch für Mineralogie Monatshefte, 2 8496.
Pfaff, K., Krumrei, T.V., Marks, M.A.W.., Wenzel, T., Rudolf, T and Markl, G. (2008) Chemical and physical evolution of the ‘lower layered series’ from the nepheline syenitic Ilímaussaq intrusion, South Greenland: Implications for the origin of magmatic layering in peralkaline felsic liquids. Lithos, 106 280296.
Pouchou, J.L. and Pichoir, F. (1984) A new model for quantitative X-ray microanalysis. I. Application to the analysis of homogeneous samples. Recherche Aerospatiale, 3, 1338
Ratschbacher, B.C., Marks, M.A.W.., Bons, P.D., Wenzel, T and Markl, G. (2015) Emplacement and geochem-ical evolution of highly evolved syenites investigated by a combined structural and geochemical field study: the lujavrites of the Ilímaussaq complex, SW Greenland. Lithos, 231 6276
Rønsbo, J.G., Sørensen, H., Roda-Robles, E., Fontan, F. and Monchoux, P. (2013) Rinkite-nacareniobsite-(Ce) solid solution series and hainite from the Ilímaussaq alkaline complex: occurrence and compositional variation. Bulletin of the Geological Society Denmark, 62 115
Roskill, (2011) Rare Earths and Yttrium: Market Outlook to 2015. 14th Edition. Roskill Information Services Ltd., London.
Salvi, S. and Williams-Jones, A.E. (1995) Zircono silicate phase relations in the Strange Lake (Lac Brisson) pluton, Quebec-Labrador, Canada. American Mineralogist, 80, 10311040.
Salvi, S. and Williams-Jones, A.E. (1996) The role of hydrothermal processes in concentrating high-field strength elements in the Strange Lake peralkaline complex, northeastern Canada. Geochimica et Cosmochimica Acta, 60, 19171932.
Salvi, S. and Williams-Jones, A.E. (2005) Alkaline Granite-Syenite Deposits. Pp. 315-341 in: Rare-Element Geochemistry and Mineral Deposits (R.L. Linnen and I.M. Samson, editors). GAC Short Course Notes 17. Geological Association of Canada, St. John's, Canada.
Salvi, S. and Williams-Jones, A.E. (2006) Alteration, HFSE mineralisation and hydrocarbon formation in peralkaline igneous systems: Insights from the Strange Lake Pluton, Canada. Lithos, 91, 1934.
Salvi, S., Fontan, F., Monchoux, P., Williams-Jones, A.E. and Moine, B. (2000) Hydrothermal mobilization of high field strength elements in Alkaline Igneous Systems: Evidence from the Tamazeght complex (Morocco). Economic Geology, 95, 559576.
Schilling, J., Wu, F.Y., McCammon, C., Wenzel, T., Marks, M.A.W.., Pfaff, K., Jacob, D.E. and Markl, G. (2011) The compositional variability of eudialyte-group minerals. Mineralogical Magazine, 75, 87115
Sheard, E.R., Williams-Jones, A.E., Heiligmann, M., Pederson, C. and Trueman, D.L. (2012) Controls on the concentration of zirconium, niobium and the rare earth elements in the Thor Lake rare metal deposit, Northwest Territories, Canada. Economic Geology, 107 81104.
Shmulovich, K.I. and Churakov, S.V. (1998) Natural fluid phases at high temperature and low pressures. Journal of Geochemical Exploration, 62, 183191.
Sokolova, E. and Hawthorne, F.C. (2008) From structural topology to chemical composition. Y Titanium silicates: crystal chemistry of nacareniobsite-Ce. The Canadian Mineralogist, 46, 13231342
Stromeyer, F. (1819) Summary of meeting 16 December 1819. Göttingische gelehrte Anzeigen, 3, 19932000.
Sørensen, H. (1992) Agpaitic nepheline syenites: a potential source of rare elements. Applied Geochemistry, 7 417417.
Sørensen, H. (1997) The agpaitic rocks — an overview. Mineralogical Magazine, 61 485–98.
Sørensen, H. (2001) Brief introduction to the Geology of the Ilímaussaq alkaline complex, South Greenland, and its exploration history. Geology of Greenland Survey Bulletin, 190 724.
Sørensen, H., Bohse, H. and Bailey, J.C. (2006) The origin and mode of emplacement of lujavrites in the Ilímaussaq alkaline complex, South Greenland. Lithos, 91 286300.
Timofeev, A., Migdisov, A.A. and Williams-Jones, A.E. (2015) An experimental study of the solubility and speciation of niobium in fluoride-bearing aqueous solutions at elevated temperature. Geochimica et Cosmochimica Acta, 158 103111.
Upton, B.G.J.. (2013) Tectono-magmatic evolution of the younger Gardar southern rift, South Greenland. Geological Survey of Denmark and Greenland Bulletin, 29, 1128.
Ussing, N.V.. (1912) Geology of the country around Julianehaab, Greenland. Meddelelser om Grønland, 38, 426.
Waight, T., Baker, J. and Willigers, B. (2002) Rb isotope dilution analyses by MC-ICPMS using Zr to correct for mass fractionation: towards improved Rb-Sr geochronology. Chemical Geology, 186 99116.
Zakharov, V.I., Maiorov, D.V., Alishkin, A.R. andMatveev, V.A. (2011) Causes of insufficient recovery of zirco¬nium during acidic processing of lovozero eudialyte concentrate. Russian Journal of Non-Ferrous Metals, 52, 423–2.
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