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The Sheahan Diamond Literature Reference Compilation - Scientific and Media Articles based on Major Keyword - Carbonatite
The Sheahan Diamond Literature Reference Compilation is compiled by Patricia Sheahan who publishes on a monthly basis a list of new scientific articles related to diamonds as well as media coverage and corporate announcements called the Sheahan Diamond Literature Service that is distributed as a free pdf to a list of followers. Pat has kindly agreed to allow her work to be made available as an online digital resource at Kaiser Research Online so that a broader community interested in diamonds and related geology can benefit. The references are for personal use information purposes only; when available a link is provided to an online location where the full article can be accessed or purchased directly. Reproduction of this compilation in part or in whole without permission from the Sheahan Diamond Literature Service is strictly prohibited. Return to Diamond Keyword Index
Sheahan Diamond Literature Reference Compilation - Scientific Articles by Author for all years
Each article reference in the SDLRC is tagged with one or more key words assigned by Pat Sheahan to highlight the main topics of the article. In an effort to make it easier for users to track down articles related to a specific topic, KRO has extracted these key words and developed a list of major key words presented in this Key Word Index to which individual key words used in the article reference have been assigned. In most of the individual Key Word Reports the references are in crhonological order, though in some such as Deposits the order is first by key word and then chronological. Only articles classified as "technical" (mainly scientific journal articles) and "media" (independent media articles) are included in the Key Word Index. References that were added in the most recent monthly update are highlighted in yellow.
Carbonatite is a sub-class of alkaline rocks which is dominated by Carbonate Minerals, namely minerals with the CO3 carbonate ion. Normally when we hear about "carbonates" we think of sedimentary rocks such as limestone and dolomite which are host to skarn and replacement style mineralization containing metals such as gold, silver, zinc, lead or copper. In the case of a carbonatite we are dealing with an igneous intrusion which may be enriched in rare earths and other critical metals, but never contains diamonds in the manner of a kimberlite. Articles about carbonatites are far more important for rare earths than diamonds.
Iugs Subcommision on the Systematics of Igneous Rocks; Classification and Nomenclature of Volcanic Rocks, Lamprophyres, carbonatites and Melilitic Rocks; Recommendations and Suggestions.
Neues Jahr. Min., Vol. 134, No. 1, PP. 1-14.
Global
Melilite, Lamprophyre, Carbonatite, Rock Classification
Rare Earth Element and Fluorine Contents of Apatite As Reflecting Formation Conditions, Alteration and Potential Mineralization for Rocks of the Foscorite Carbonatite.
Geochemistry International (Geokhimiya), Vol. 21, No. 1, PP. 93-107.
Compositional variation of some rare earth minerals from the Fen Complex (Telemark, southeast Norway)- implications for the mobilityof rare earths in a carbonatite syste
Mineralogical Magazine, Vol. 50, Sept. pp. 503-509
Compositional variation of some rare earth minerals from the Fen complex(telemark, southeast Norway): implications for the mobility of rare earths in a carbonatite system
Mineralogical Magazine, Vol. 50, No. 357, September pp. 503-509
The Mount Grace carbonatite- an niobium and light rare earth element enriched marble of probable pyroclastic origin in the Shuswapcomplex, southeastern British Columbi
Economic Geology, Vol. 81, No. 6, Sept-Oct. pp. 1374-1386
lead, Strontium, neodymium isotope studies of the 100-2700 Ma old alkalic rocks-carbonatite complexes in the Canadian Shield: inferences on the geochemical and structural evolution
Ph.D. Thesis, University of of California Santa Barbara,
Trace element charactertistics of the Strange Lake Zirconium, Yttrium, Niobium,and Berylium rare earth elements (REE) mineralization and the host peralkaline granite
Geological Association of Canada (GAC) Annual Meeting, Vol. 11, p. 102. (abstract.)
Quebec, Labrador
Rare earth, Zirconium, Berylium, REE, yttrium, Carbonatite, Alkaline rock
Mantle and crustal components in a carbonatite complex and the evolution of carbonatite magma: rare earth elements (REE) and isotopic evidence from the Fen complex, southeast Norway
Chemical Geology, Vol. 65, No. 2, May 15, pp. 147-166
The early Proterozoic Mt. Weld carbonatite: implications for mantle Strontium, neodymium, and lead isotopic evolution of subcontinental lithosphere beneath the Yilgarnblock, Western
Road log from Las Vegas Nevada to Mountain Pass, California.Rare earth mineral deposits ,San Bernardino County-geochemistry of shonkinites, syenite sand granites wit
Seg Guidebook Series, Proterozoic Ore Deposits Of The Southwestern U.s., No. 1, pp. 1-56
Preliminary characterization of the supergene evolution of the carbonatite rocks of the Juquia (sp) Alkaline carbonatite complex with phosphateenrichment
Xiii International Geochemical Exploration Symposium, Rio 89 Brazilian, p. 219. Abstract
Partioning of rare earth elements (REE)'s Berylium, Barium, Calsium and Strontium between clino-pyroxene, olivine and carbonate melt at mantle conditions
Geological Society of America (GSA) Annual Meeting Abstracts, Vol. 21, No. 6, p. A105. Abstract
Investigation for apatite and other associated minerals in the Tamar-Porapahar shear zone in Perulia district and the petrological studies of Association carbonatites
Records of the Geological Survey of India, extended abstracts of progress, Vol. 122, pt. 3, p. 45
Study of the carbonatite complex in Ampavalli area near Sunki, Koraputdistrict, and Khariar area in Kalahandidistrict, Orissa with special ref. toR.E.E.
Records of the Geological Survey of India, extended abstracts of progress, Vol. 122, pt. 3, p. 47
Field and petrographic textural evidence for the epigenetic hydrothermalmetasomatic origin of the Bayan Obo rare earth ore deposit of inner Mongolia, China
International Mineralogical Association Meeting Held June, 1990 Beijing China, Vol. 2, extended abstract p. 930-931
Migration of elements from carbonatites into dolostone at Carillon Dam, southeastern Ontario
Geological Association of Canada (GAC)/Mineralogical Association of Canada (MAC) Vancouver 90 Program with Abstracts, Held May 16-18, Vol. 15, p. A59. Abstract
Mineralogy and geochemistry of perovskite- rich pyroxenites
Geological Association of Canada (GAC)/Mineralogical Association of Canada (MAC) Vancouver 90 Program with Abstracts, Held May 16-18, Vol. 15, p. A83. Abstract
Alkaline and carbonatitic magmatism of the earth and related ore deposits.International Geological Correlation Programme (IGCP)Proposal Project 314. 1991-1995
Marker, A., Friedrich, G., Carvalho, A., Melfi, A.
Control of the distribution of Manganese, Cobalt, Zinc, Zrirconium, Titanium and REEs during the evolution of lateritic covers above ultramafic complexes
Journal of Geochemical Exploration, Special Publications Geochemical, Vol. 40, No. 1-3, pp. 361-384
Short lived decay series disequilibration temperatures in the natrocarbonatite lavas of Oldoinyo Lengai, Tanzania: constraints on the timing of magma genesis
Earth and Planetary Science Letters, Vol. 105, pp. 378-396
Chao, E.C.T., Back, J.M., Minkin, J.A., en Yinchen
Host rock controlled epigenetic, hydrothermal metasomatic origin of the Bayan Obo rare earth elements (REE)-iron-Nb ore deposit, Inner Mongolia, P.R.C.
Titaniam clinohumite in the carbonatites of the Jacupiranga Complex, Brasil: mineral chemistry and comparison with titanian clinohumite fromenvironments
American Mineralogist, Vol. 77, No. 1-2, January-February pp. 168-178
neodymium, lead, and Strontium isotopic dat a Napak carbonatite -nephelinite centre, eastern Uganda: implications for crustal assimilation and fractional crystalization
Eos Transactions, Vol. 73, No. 14, April 7, supplement abstracts p.329
Mangas, J., Perez-Torrado, F.J., Reguilon, R., Martin-Izard, A.
Geological characteristics of alkaline rocks and carbonatites of Fuerteventura (Canary Islands, Spain) and their rare earth elements (REE) ore potential.
Terra Abstracts, IAGOD International Symposium on mineralization related to mafic, Vol. 5, No. 3, abstract supplement p. 32.
The rare earth elements (REE) content in the laterites developed on the alkaline complexes of Araxa and Catalao (States Minas Gerais and Goias, Brasil).
Rare earth Minerals: chemistry, origin and ore deposits, International Geological Correlation Programme (IGCP) Project, pp. 114-116. abstract
Cogenetic silica rich and carbonate rich melts trapped in mantle minerals in Kerguelen ultramafic xenoliths -implications for metasomatism in the oceanic upper mantl
Earth Planet. Sci. Letters, Vol. 123, No. 1-2, May pp. 167-178.
Paragenetic sequence of pyrrhotite alterations to marcasite, pyrite, magnetite, hematite and goethite in pyroxene and pegmatitic carbonatites and fluorite ores.
11th. Quadrennial Iagod Symposium And Geocongress 2002 Held Windhoek, Abstract p. 26.
Oxygen isotope contamination of carbonates, silicates and oxides in selected carbonatites: constraints on crystallization temperatures of carbonatitic magmas.
Magmatic evolution of the differentiated ultramafic, alkaline and carbonatite intrusion of Vuoriyarvi, Kola Peninsula, Russia, A LA ICP MS study of apatite.
Geochemistry and mineralogy of HFSE in intracratonic carbonatites: implications for their economic potential (on the example of Kola alkaline province).
GAC Annual Meeting Halifax May 15-19, Abstract 1p.
Continuous gradations among primary carbonatitic, kimberlitic, melilititic, basaltic, picritic and komatiitic melts in equilibrium with garnet lherzolite at 3-8 GPa.
Kovdor apatite francolite deposit as an example of explosive and phreatomagmatic endogeneous activity in the ultramafic alkaline and carbonatite complex Kola.
Plumes and problems of deep sources of alkaline magmatism, pp. 155-170.
Solubility of niobium in the system CaCO 3-CaF 2-NaNbo 3 at 0.1 GPa pressure: implications for the crystallization of pyrochlore from carbonatite magma.
Contributions to Mineralogy and Petrology, Vol. 148, 3, pp. 281-287.
Ventura Santos, R., Souza de Alvarenga, C.J., Babinski, M., Ramos, M.L.S., Cukrov, N., Fonsec, M.A., Da Norbrega
Carbon isotopes of Mesoproterozoic Neoproterozoic sequences from southern Sao Francisco craton and Aracuai Belt, Brazil: paleogeorgraphic implications.
Journal of South American Earth Sciences, Vol. 18, 1, Dec. 30, pp. 27-39.
Zirconolite and Zr Th U minerals in chromities of the Finero complex, western Alps, Italy: evidence for carbonatite type metasomatism in a subcontinental ... mantle plume.
Sr Na REE titanates of the crichtonite group from a fenitized megaxenolith, Khibin a alkaline complex, Kola Peninsula, Russia: first occurrence and implications.
European Journal of Mineralogy, Vol. 18, 4, August pp. 493-502.
Immiscible transition from carbonate rich to silicate rich melts in the 3 GPa melting interval of eclogite + CO2 and genesis of silica undersaturated Oceanic lavas.
Journal of Petrology, Vol. 47, 4, April pp. 647-671.
Petrochemical interpretation of carbonatite-like rocks from the Chagatai Complex of the Tien Shan with appllication to the problem of diamond potential.
The Ilmeny Vishnevorgorsky complex of alkaline rocks and carbonatites.
IUGS/UNESCO IGG RAS The eroded Uralian Paleozoic ocean to continent transition zone: Ed. Seltmann, R., et al., Excursion Guidebook Project 373, pp. 48-57.
Genesis of ultramafic lamprophyres and carbonatites at Aillik Bay, Labrador: a consequence of incipient lithospheric thinning beneath the North Atlantic Craton
Tichomirowa, M., Grosche, G., Gotze, J., Belyatsky, B.V., Savva, E.V., Keller, J., Todt, W.
The mineral isotope composition of two Precambrian carbonatite complexes from the Kola Alkaline Province - alteration versus primary magmatic signatures.
Crystallization of mela-aillikites of the Narsaq region, Gardar alkaline province, south Greenland and relationships to other aillikitic carbonatitic assoc.
New evidence from a calcite dolomite carbonatite dyke for the magmatic origin of the massive Bayan Obo ore bearing dolomite marble, Inner Mongolia China.
Crystallisation of mela-allikites of the Narsaq region, Gardar alkaline province, south Greenland and relationships to other allikitic carbonatitic associate
Wall, F., Niku-Paavola, V.N., Storey, C., Muller, A.,Jeffries, T.
Xenotime from carbonatite dykes at Lofdal Namibia - an extension of carbonatite REE mineralization, first dating of xenotime overgrowths on zircon.LA-ICP-MS-U-Pb
Frontiers in Mineral Sciences 2007, Joint Meeting of Mineralogical societies Held June 26-28, Cambridge, Abstract Volume p. 89-90.
Wall, F., Niku-Paavola, V.N., Storey, C., Muller, A.,Jeffries, T.
Xenotime from carbonatite dykes at Lofdal Namibia - an extension of carbonatite REE mineralization, first dating of xenotime overgrowths on zircon.LA-ICP-MS-U-Pb
Frontiers in Mineral Sciences 2007, Joint Meeting of Mineralogical societies Held June 26-28, Cambridge, Abstract Volume p. 89-90.
Guzmics, T., Zajacz, Z., Kodoenyi, J., Halter, W., Szabo, C.
LA ICP MS study of apatite and K feldspar hosted primary carbonatite melt inclusions in clinopyroxenite xenoliths from lamprophyres, Hungary: implications
Geochimica et Cosmochimica Acta, Vol. 72, 7, pp. 1864-1886.
Le Bas, M.J., Xueming, Y., Taylor, R.N., Spiro, B., Milton, J.A., Peishan, Z.
New evidence from a calcite dolomite carbonatite dyke for the magmatic origin of the massive Bayan Obo ore bearing dolomite marble, Inner Mongolia, China.
Mineralogy and Petrology, Vol. 90, 3-4, pp. 223-248.
The 24th September 2007 ash eruption of the carbonatite volcano Oldoinyo Lengai: mineralogy of the ash and implications for formation of a new hybrid magma type.
Mineralogical Magazine, Vol. 71, 5, Oct, pp. 483-492.
Experimental studies of the system Na2Ca(COs)2 NaCl KCL at 0.1 GPa: implications for the differentiation and low temperature crystallization of natrocarbonatite.
The Majuagaa kimberlite dike, Maniitsoq region, West Greenland: constraints for an Mg rich silico carbonatite melt composition from groundmass mineralogy and bulk compositions.
Wall, F., Niku-Paavola, V.N., Storey, C., Muller, A., Jeffries, T.
Xenotime - (Y) from carbonatite dykes at Lofdal, Namibia: unusually low LREE:HREE ratio in carbonatite, and the first dating of xenotime overgrowths on zircon.
Zhang, Y., Bi, H., Yu, L., Sun, S., Qui, J., Xu, C., Wang, H., Wang, R.
Evidence for metasomatic mantle carbonatitic magma extrusion in Mesoproterozoic ore hosting dolomite rocks in the middle Kunyang rift, central Yunnan China.
Progress in Natural Science, Vol. 18, 8, pp. 965-974.
Carbonatite melts and electrical conductivity in the athenosphere: the electrical conductivity of molten carbonates is higher than that of silicate minerals;
Science, Vol. 322, no. 5906, Nov. 28, pp. 1363-1364.
Marks, M.A.W., Neukirchen, F., Vennemann, T., Markl, G.
Textural, chemical and isotopic effects of late magmatic carbonatitic fluids in the carbonatite syenite Tamazeght complex, High Atlas Mountains, Morocco.
Trace elements and volatile components in silicate and silicate salt magmas of the Mushugai Khuduk carbonatite bearing alkaline complex, southern Mongolia.
International Mineralogical Association meeting August Budapest, abstract p. 564.
The influence of carbonatite during petrogenesis of nepheline syenites at the Pocos de Caldas Complex, Brazil: evidence from geochemistry and fluid inclusions
International Mineralogical Association meeting August Budapest, abstract p. 567.
Guzmics, T., Mitchell, R.H., Szabo, C., Berkesi, M., Milke, R., Abart, R.
Carbonatite melt inclusions in coexisting magnetite, apatite and monticellite in Kerimasi calciocarbonatite, Tanzania: melt evolution and petrogenesis.
Contributions to Mineralogy and Petrology, Vol. 161, 2, pp. 177-196.
Gwalani, L.G., Rogers, K.A., Demeny, A., Groves, D.L., Ramsay, R., Beard, A., Downes, P.J., Eves, A.
The Yungul carbonatite dykes associated with the epithermal fluorite deposit at Speewah, Kimberley, Australia: carbon and oxygen isotope constraints origin
Mineralogy and Petrology, Vol. 98, 1-4, pp. 123-141.
Neoproterozoic inheritance during Cainozoic rifting in the western and southwestern branches of the East African Rift system: evidence from carbonatite alkaline
Tanzanian Journal of Earth Science, Vol. 1, Dec. pp. 29-37.
Pinto, L.G.R.,Banik de Padua, M., Ussami, N., Vitorello, I., Padilha, A.L., Braitenberg, C.
Magnetotelluric deep soundings, gravity and geoid in the south Sao Francisco craton: geophysical indicators of cratonic lithosphere rejuvenation and underplating.
Earth and Planetary Science Letters, Vol. 297, pp. 423-434.
Yoshikawa, M., Kawamoto, T., Shibata, T., Yamamoto, J.
Geochemical and Sr Nd isotopic characteristics and pressure temperature estimates of mantle xenoliths from French Massif Central: metasomatism and carbonatites..
Geological Society of London Special Publication, No. 337, pp. 153-175.
Silicate carbonate liquid immiscibility and phase relations in the system SiO2-Na2O-Al2O3-CaO-CO2 at 0.1-2.5 GPa with application to carbonatite genesis.
Journal of Petrology, Vol. 52, 7-8, pp. 1281-1305.
Casillas, R., Demeny, A., Nagy, G., Ahijado, A., Fernandez, C.
Metacarbonatites in the Basal Complex of Fuerteventura ( Canary Islands). The role of fluid/rock interactions during contact metamorphism and anatexis.
Enigmatic association of the carbonatite and alkali pyroxenite along the Northern Shear Zone, Purulia, West Bengal: a saga of primary magmatic carbonatite.
Journal of Geological Society of India, Vol. 76, 5, pp.399-402.
De Oliveire Cordeiro, P.F., Brod, J.A., Ventura Santos, R., Dantas, E.L., Gouveia de Oliveira, C., Soares Rochas Barbosa, E.
Stable (C,O) and radiogenic (Sr,Nd) isotopes of carbonates as indicators of magmatic and post-magmatic processes of phoscorite series rocks and carbonatites from Catalao 1, central Brazil.
Contributions to Mineralogy and Petrology, Vol. 161, 3, pp. 451-464.
Tian, W., Chen, B., Ireland, T.R., Green, D.H., Suzuki, K., Chu, Z.
Petrology and geochemistry of dunites, chromitites and mineral inclusions from the Gaositai Alaskan type complex, North Chin a craton: mantle source characters
Formation and transformation of zircon grains from the Archean carbonatite Siilinjarvi - evidence from cathodluminescence, rare earth elements and U/Pb geochr
Peralk-Carb 2011, workshop held Tubingen Germany June 16-18, Poster
Yang, K-F, Fan, H-R., Santosh, M., Hu, F-F., Wang, K-Y.
Mesoproterozoic carbonatitic magmatism in the Bayan Obo deposit, Inner Mongolia, North China: constraints for the mechanism of super accumulation of rare earth elements.
Yang, K-F., Fan, H-R., Santosh, M., Hu, F-F., Wang, K-Y.
Mesoproterozoic mafic and carbonatitic dykes from the northern margin of the North Chin a craton: implications for the fin al breakup of Columbia supercontinent.
Comparative in-situ U-Th-Pb geochronology and trace element composition of baddeleyite and low U zircon from carbonatites of the Paleozoic Kovdor, Kola Pen.
Flourine , yttrium and lanthaide rich cerianite (Ce) from carbonatitic rocks of the Kerimasi volcano and surrounding explosive craters Gregory Rift Tanzania.
Mineralogical Magazine, Vol. 75, 6, pp. 2813-2822.
Guzmics, T., Mitchell, R.H., Szabo, C., Berkesi, M., Milke, R., Ratter, K.
Liquid immiscibility between silicate, carbonate and sulfide melts in melt inclusions hosted in co-precipitated minerals from Kerimasi volcano (Tanzania): evolution of carbonated nephelinitic magma.
Contributions to Mineralogy and Petrology, Vol. 164, pp. 101-122.
Experimental study in the Na2OCaOMgOAl203Si02CO2 system at 3 Gpa: the effect of sodium on mantle melting to carbonate -rich liquids and implications for the petrogenesis of silicocarbonatites.
Mourao, C., Mata, J., Doucekance, R., Madeira, J., Millet, M-A., Moreira, M.
Geochemical temporal evolution of Brava Island magmatism: constraints on the variability of Cape Verde mantle sources and on carbonatite-silicate magma link.
Mourao, C., Moreira, M., Mata, J., Raquin, A., Madeira, J.
Primary and secondary processes constraining the noble gas isotopic signatures of carbonatites and silicate rocks from Brava Island: evidence for a lower mantle origin of the Cape Verde Plume.
Contributions to Mineralogy and Petrology, Vol. 163, 6, pp. 995-1009.
Origin and evolution of the Ilmeny-Visnevogorsky carbonatites (Urals, Russia): insights from trace element compositions, and Rb-Sr, Sm-Nd, U-Pb, Lu-Hf isotope data.
Origin and evolution of the Ilmeny Vishnevogorsky carbonatites ( Urals, Russia): insights from trace element compositions and Rb Sr, Sm Nd, U Pb, Lu Hf isotope data.
Carbonatites out of a subducted altered oceanic crust? New experimental evidences for "low temperature" carbonatitic melts in COH bearing gabbros at 3.8-4.2 Gpa.
Comparative in-situ U-Th-Pb geochronology and trace element composition of baddeleyite and low U-zircon from carbonatites of the Paleozoic Kovdor alkaline ultramafic complex Kola Peninsula, Russia.
Soares Rocha Barbosa, E., Brod, J.A., Junqueira-Brod, T.C., Dantas, E.L., De Oliveira Cordeiro, P.F., Siqueira Gomide, C.
Bebdourite from its type area Sailtre 1 complex: a key petrogenetic series in the Late-Cretaceous Alto Paranaiba kamafugite carbonatite phoscorite association, central Brazil.
Tichomirowa, M., Whitehouse, M., Gerdes, A., Gotze, J.
Carbonatite metasomatism: evidence from geochemistry and isotope composition ( U-Pb, Hf, O) on zircons from two Precambrian carbonatites of the Kola alkaline province.
Genesis of magmas of carbonate- bearing ijolites and carbonatites from the Belaya Zima carbonatite complex ( eastern Sayan Russia) dat a from melt inclusion study.
Vladykin, N.V. ed. Deep seated magmatism, its sources and plumes, Russian Academy of Sciences, pp. 133-163.
Azzone, R.G., Enrich, G.E.R., De Barros Goes, C., Ruberti, E.
Trace element composition of parental magmas from mafic-ultramafic cumulates by in situ mineral analyses: the Juquia mafic-ultramafic alkaline carbonatite massif, SE Brazil.
Journal of South American Earth Sciences, Vol. 41, pp. 5-21.
A cathodluminescence study of calcite dolomite microstructures and Cal-Dol geothermometry in highly metamorphosed carbonatites: an example from the Fir carbonatites, east central British Columbia, Canada.
GAC-MAC 2013: GS2: Igneous and Metamorphic Petrology and Volcanology, abstract only
Isotopic and trace element geochemistry of alkalic mafic ultramafic carbonatitic complexes and flood basalts in NE India: origin in a heterogeneous Kerguelen plume.
Geochimica et Cosmochimica Acta, Vol. 115, pp. 46-72.
The effect of amphibolite facies metamorphism on the U-Th-Pb geochronology of accessory minerals from meta-carbonatites and associated meta-alkaline rocks.
Moteani, G., Kostitsyn, Y.A., Gilg, H.A., Preinfalk, C., Razakamanana, T.
Geochemistry of phlogopite, diopside, calcite, anhydrite and apatite pegmatites and syenites of southern Madagascar: evidence for crustal silicocarbonatitic (CSC) melt formatio in a Panafrican collisional tectonic setting.
International Journal of Earth Sciences, Vol. 102, 3, pp. 627-645.
Origin and evolution of the Ilmeny-Vishnevogorsky carbonatites ( Urals, Russia): insights from trace element compositions, and Rb Sr Sm Nd, U Pb, Lu Hf isotope data.
Mineralogy and Petrology, Vol. 107, 1, pp. 101-123.
Tichomirowa, M., Whitehouse, M.J., Gerdes, A., Gotze, J., Schulz, B., Belyatsky, B.V.
Different zircon recrystallization types in carbonatites caused by magma mixing: evidence from U-Pb dating, trace element and isotope composition ( Hf and O) of zircons from two Precambrian carbonatites from Fennoscandia.
Geochemical and Sr-Nd-Hf-O-C isotopic constraints on the origin of the Neoproterozoic Qieganbulake ultramafic carbonatite complex from the Tarim block, northwest China.
Campbell, L.S., Compston, W., Sircombe, K.N., Wilkinson, C.C.
Zircon from the East orebody of the Bayan Obo Fe Nb REE deposit, China, and SHRIMP ages for carbonatite related magmatism and REE mineralization events.
Contributions to Mineralogy and Petrology, Vol. 168, pp. 1041-
Downes, P.J., Demeny, A., Czuppon, G., Jacques, A.L., Verrall, M., Sweetapple, M., Adams, D., McNaughton, N.J., Gwalani, L.G., Griffin, B.J.
Stable H-C-O isotope and trace element geochemistry of the Cummins Range carbonatite complex, Kimberley region Western Australia: implications for hydrothermal REE mineralization, carbonatite evolution and mantle source regions.
Downes, P.J., Demeny, A., Czuppon, G., Jaques, A.L., Verrall, M., Sweetapple, M., Adams, D., McNaughton, N.J., Gwalani, L.G., Griffin, B.J.
Stable H-C-O isotope and trace element geochemistry of the Cummins Range carbonatite complex, Kimberley region western Australia: implications for hydrothermal REE mineralization, carbonatite evolution and mantle source regions.
Mangler, M.F., Marks, M.A.W., Zaitsev, A.N., Eby, G.N., Markl, G.
Halogens (F, Cl and Br) at Oldoinyo Lengai volcano ( Tanzania): effects of magmatic differentiation, silicate, natrocarbonatite melt seperation and surface alteration of natrocarbonatite.
Midende, G., Boulais, P., Tack, L., Melcher, F., Gerdes,A., Dewaele, S., Demaiffe, D., Decree, S.
Petrography, geochemistry and U Pb zircon age of the Matongo carbonatite Massif ( Burundi): implication for the Neoproterozoic geodynamic evolution of Central Africa.
Journal of African Earth Sciences, Vol. 100, pp. 656-674.
Trace element and isotopes Hf as a signature of zircon genesis during evolution of alkaline carbonatite magmatic system ( Ilmeny Vishnevogorsky complex, urals, Russia.)
30th. International Conference on Ore Potential of alkaline, kimberlite and carbonatite magmatism. Sept. 29-, http://alkaline2014.com
Simandl, G.J., Paradis, S., Stone, R.S., Fajber, R., Kressall, R.D., Grattan, K., Crozier, J., Simandl, L.J.
Applicablity of handheld X-ray fluroescence spectrometry in the exploration and development of carbonatite related niobium deposits: a case study of the Aley carbonatite, British Columbia, Canada.
Geochemistry: Exploration, Environment, Analysis, Vol. 14, 3, pp. 211-221.
Rare earth elements in phoscorites and carbonatites of the Devonian Kola alkaline province, Russia: examples from Kovdor, Khibina, Vuoriyarvi and Turiy Mys complexes.
Rare earth elements in phoscorites and carbonatites of the Devonian Kola alkaline province, Russia: examples from Kovdor, Khibina, Vuoriyarvi and Turiy Mys complexes.
Rare earth elements in phoscorites and carbonatites of the Devonian Kola alkaline province, Russia: examples from Kovdor, Khibina, Vuoriyarvi and Turiy Mys complexes.
Midende, G., Boulvais, P., Tack, L., Melcher, F., Gerdes, A., Dewaele, S., Demaiffe, D., Decree, S.
Petrography, geochemistry and U-Pb zircon age of the Matongo carbonatite Massif ( Burundi): implication for the Neoproterozoic geodynamic evolution of Central Africa.
Journal of African Earth Sciences, Vol. 100, pp. 656-674.
Contributions to Mineralogy and Petrology, Vol. 169, 18p.
Africa, Tanzania
Carbonatite
Abstract: We have reconstructed the compositional evolution of the silicate and carbonate melt, and various crystalline phases in the subvolcanic reservoir of Kerimasi Volcano in the East African Rift. Trace element concentrations of silicate and carbonate melt inclusions trapped in nepheline, apatite and magnetite from plutonic afrikandite (clinopyroxene-nepheline-perovskite-magnetite-melilite rock) and calciocarbonatite (calcite-apatite-magnetite-perovskite-monticellite-phlogopite rock) show that liquid immiscibility occurred during the generation of carbonatite magmas from a CO2-rich melilite-nephelinite magma formed at relatively high temperatures (1,100 °C). This carbonatite magma is notably more calcic and less alkaline than that occurring at Oldoinyo Lengai. The CaO-rich (32-41 wt%) nature and alkali-"poor" (at least 7-10 wt% Na2O + K2O) nature of these high-temperature (>1,000 °C) carbonate melts result from strong partitioning of Ca (relative to Mg, Fe and Mn) in the immiscible carbonate and the CaO-rich nature (12-17 wt%) of its silicate parent (e.g., melilite-nephelinite). Evolution of the Kerimasi carbonate magma can result in the formation of natrocarbonatite melts with similar composition to those of Oldoinyo Lengai, but with pronounced depletion in REE and HFSE elements. We suggest that this compositional difference results from the different initial parental magmas, e.g., melilite-nephelinite at Kerimasi and a nephelinite at Oldoinyo Lengai. The difference in parental magma composition led to a significant difference in the fractionating mineral phase assemblage and the element partitioning systematics upon silicate-carbonate melt immiscibility. LA-ICP-MS analysis of coeval silicate and carbonate melt inclusions provides an opportunity to infer carbonate melt/silicate melt partition coefficients for a wide range of elements. These data show that Li, Na, Pb, Ca, Sr, Ba, B, all REE (except Sc), U, V, Nb, Ta, P, Mo, W and S are partitioned into the carbonate melt, whereas Mg, Mn, Fe, Co, Cu, Zn, Al, Sc, Ti, Hf and Zr are partitioned into the silicate melt. Potassium and Rb show no preferential partitioning. Kerimasi melt inclusions show that the immiscible calcic carbonate melt is strongly enriched in Sr, Ba, Pb, LREE, P, W, Mo and S relative to other trace elements. Comparison of our data with experimental results indicates that preferential partitioning of oxidized sulfur (as SO4 2?), Ca and P (as PO4 3?) into the carbonate melt may promote the partitioning of Nb, Ta, Pb and all REE, excluding Sc, into this phase. Therefore, it is suggested that P and S enrichment in calcic carbonate magmas promotes the genesis of REE-rich carbonatites by liquid immiscibility. Our study shows that changes in the partition coefficients of elements between minerals and the coexisting melts along the liquid line of descent are rather significant at Kerimasi. This is why, in addition to the REE, Nb, Ta and Zr are also enriched in Kerimasi calciocarbonatites. We consider significant amounts of apatite and perovskite precipitated from melilite-nephelinite-derived carbonate melt as igneous minerals can have high LREE, Nb and Zr contents relative to other carbonatite minerals.
Intracontinental anorogenic alkaline magmatism and carbonatites, associated mineral systems and the mantle plume connection. Brandberg, Erongo, Parana-Etendeka, Kruidfontein, Goudini
Gondwana Research, Vol. 27, 3, pp. 1181-1216.
Africa, East Africa, Namibia, South Africa, China, Australia
Abstract: Galena from four REE-rich (Khibina, Sallanlatvi, Seblyavr, Vuoriyarvi) and REE-poor (Kovdor) carbonatites, as well as hydrothermal veins (Khibina) all from the Devonian Kola Alkaline Province of northwestern Russia was analysed for trace elements and Pb and S isotope compositions. Microprobe analyses show that the only detectable elements in galena are Bi and Ag and these vary from not detectable to 2.23 and not detectable to 0.43 wt.% respectively. Three distinct galena groups can be recognized using Bi and Ag contents, which differ from groupings based on Pb isotope data. The Pb isotope ratios show significant spread with 206Pb/204Pb ratios (16.79 to 18.99), 207Pb/204Pb (15.22 to 15.58) and 208Pb/204Pb ratios (36.75 to 38.62). A near-linear array in a 207Pb/204Pb vs. 206Pb/204Pb ratio diagram is consistent with mixing between distinct mantle sources, one of which formed during a major differentiation event in the late Archaean or earlier. The S isotopic composition (?34S) of galena from carbonatites is significantly lighter (–-6.7 to -–10.3% Canyon Diablo Troilite (CDT) from REE-rich Khibina, Seblyavr and Vuoriyarvi carbonatites, and - 3.2% CDT from REE-poor Kovdor carbonatites) than the mantle value of 0%. Although there is no correlation between S and any of the Pb isotope ratios, Bi and Ag abundances correlate negatively with ?34S values. The variations in the isotopic composition of Pb are attributed to partial melting of an isotopically heterogeneous mantle source, while those of ?34S (together with Bi and Ag abundances) are considered to be process driven. Although variation in Pb isotope values between complexes might reflect different degrees of interaction between carbonatitic melts and continental crust or metasomatized lithosphere, the published noble gas and C, O, Sr, Nd and Hf isotopic data suggest that the variable Pb isotope ratios are best attributed to isotopic differences preserved within a sub-lithospheric mantle source. Different Pb isotopic compositions of galena from the same complex are consistent with a model of magma replenishment by carbonatitic melts/fluids each marked by quite different Pb isotopic compositions.
Hf isotopes and trace elements as indicators of zircon genesis in the evolution of the alkaline-carbonatite magmatic system ( Il'meno-Visnevogorskii complex, Urals, Russia.)
Abstract: The composition of calcite and dolomite from several carbonatite complexes (including a large set of petrographically diverse samples from the Aley complex in Canada) was studied by electron-microprobe analysis and laser-ablation inductively-coupled-plasma mass-spectrometry to identify the extent of substitution of rare-earth and other trace elements in these minerals and the effects of different igneous and postmagmatic processes on their composition. Analysis of the newly acquired and published data shows that the contents of rare-earth elements (REE) and certain REE ratios in magmatic calcite and dolomite are controlled by crystal fractionation of fluorapatite, monazite and, possibly, other minerals. Enrichment in REE observed in some samples (up to ~2000 ppm in calcite) cannot be accounted for by coupled substitutions involving Na, P or As. At Aley, the REE abundances and chondrite-normalized (La/Yb)cn ratios in carbonates decrease with progressive fractionation. Sequestration of heavy REE from carbonatitic magma by calcic garnet may be responsible for a steeply sloping "exponential" pattern and lowered Ce/Ce* ratios of calcite from Magnet Cove (USA) and other localities. Alternatively, the low levels of Ce and Mn in these samples could result from preferential removal of these elements by Ce4+- and Mn3+-bearing minerals (such as cerianite and spinels) at increasing f(O2) in the magma. The distribution of large-ion lithophile elements (LILE = Sr, Ba and Pb) in rock-forming carbonates also shows trends indicative of crystal fractionation effects (e.g., concomitant depletion in Ba + Pb at Aley, or Sr + Ba at Kerimasi), although the phases responsible for these variations cannot be identified unambiguously at present. Overall, element ratios sensitive to the redox state of the magma and its complexing characteristics (Eu/Eu*, Ce/Ce* and Y/Ho) are least variable and in both primary calcite and dolomite, approach the average chondritic values. In consanguineous rocks, calcite invariably has higher REE and LILE levels than dolomite. Hydrothermal reworking of carbonatites does not produce a unique geochemical fingerprint, leading instead to a variety of evolutionary trends that range from light-REE and LILE enrichment (Turiy Mys, Russia) to heavy-REE enrichment and LILE depletion (Bear Lodge, USA). These differences clearly attest to variations in the chemistry of carbonatitic fluids and, consequently, their ability to mobilize specific trace elements from earlier-crystallized minerals. An important telltale indicator of hydrothermal reworking is deviation from the primary, chondrite-like REE ratios (in particular, Y/Ho and Eu/Eu*), accompanied by a variety of other compositional changes depending on the redox state of the fluid (e.g., depletion of carbonates in Mn owing to its oxidation and sequestration by secondary oxides). The effect of supergene processes was studied on a single sample from Bear Lodge, which shows extreme depletion in Mn and Ce (both due to oxidation), coupled with enrichment in Pb and U, possibly reflecting an increased availability of Pb2+ and (UO2)2+ species in the system. On the basis of these findings, several avenues for future research can be outlined: (1) structural mechanisms of REE uptake by carbonates; (2) partitioning of REE and LILE between cogenetic calcite and dolomite; (3) the effects of fluorapatite, phlogopite and pyrochlore fractionation on the LILE budget of magmatic carbonates; (4) the cause(s) of coupled Mn-Ce depletion in some primary calcite; and (5) relations between fluid chemistry and compositional changes in hydrothermal carbonates.
Abstract: Carbonatites are nominally igneous rocks, whose evolution commonly involves also a variety of postmagmatic processes, including exsolution, subsolidus re-equilibration of igneous mineral assemblages with fluids of different provenance, hydrothermal crystallization, recrystallization and tectonic mobilization. Petrogenetic interpretation of carbonatites and assessment of their mineral potential are impossible without understanding the textural and compositional effects of both magmatic and postmagmatic processes on the principal constituents of these rocks. In the present work, we describe the major (micro)textural characteristics of carbonatitic calcite and dolomite in the context of magma evolution, fluid-rock interaction, or deformation, and provide information on the compositional variation of these minerals and its relation to specific evolutionary processes.
Abstract: A set of small volcanic edifices with tuff ring and maar morphologies occur in the Catanda area, which is the only locality with extrusive carbonatites reported in Angola. Four outcrops of carbonatite lavas have been identified in this region and considering the mineralogical, textural and compositional features, we classify them as: silicocarbonatites (1), calciocarbonatites (2) and secondary calciocarbonatites produced by the alteration of primary natrocarbonatites (3). Even with their differences, we interpret these lava types as having been a single carbonatite suite related to the same parental magma. We have also estimated the composition of the parental magma from a study of melt inclusions hosted in magnetite microphenocrysts from all of these lavas. Melt inclusions revealed the presence of 13 different alkali-rich phases (e.g., nyerereite, shortite, halite and sylvite) that argues for an alkaline composition of the Catanda parental melts. Mineralogical, textural, compositional and isotopic features of some Catanda lavas are also similar to those described in altered natrocarbonatite localities worldwide such as Tinderet or Kerimasi, leading to our conclusion that the formation of some Catanda calciocarbonatite lavas was related to the occurrence of natrocarbonatite volcanism in this area. On the other hand, silicocarbonatite lavas, which are enriched in periclase, present very different mineralogical, compositional and isotopic features in comparison to the rest of Catanda lavas. We conclude that its formation was probably related to the decarbonation of primary dolomite bearing carbonatites.
Abstract: Mantle-derived carbonatites are igneous rocks dominated by carbonate minerals. Intrusive carbonatites typically contain calcite and, less commonly, dolomite and siderite as the only carbonate minerals. In contrast, lavas erupted by the only active carbonatite volcano on Earth, Oldoinyo Lengai, Tanzania, are enriched in Na-rich carbonate phenocrysts (nyerereite and gregoryite) and Na-K halides in the groundmass. The apparent paradox between the compositions of intrusive and extrusive carbonatites has not been satisfactorily resolved. This study records the fortuitous preservation of halite in the intrusive dolomitic carbonatite of the St.-Honoré carbonatite complex (Québec, Canada), more than 490 m below the present surface. Halite occurs intergrown with, and included in, magmatic minerals typical of intrusive carbonatites; i.e., dolomite, calcite, apatite, rare earth element fluorocarbonates, pyrochlore, fluorite, and phlogopite. Halite is also a major daughter phase of melt inclusions hosted in early magmatic minerals, apatite and pyrochlore. The carbon isotope composition of dolomite (?13C = –5.2‰) and Sr-Nd isotope compositions of individual minerals (87Sr/86Sri = 0.70287 in apatite, to 0.70443 in halite; ?Nd = +3.2 to +4.0) indicate a mantle origin for the St.-Honoré carbonatite parental melt. More radiogenic Sr compositions of dolomite and dolomite-hosted halite and heavy oxygen isotope composition of dolomite (?18O = +23‰) suggest their formation at some time after magma emplacement by recrystallization of original magmatic components in the presence of ambient fluids. Our observations indicate that water-soluble chloride minerals, common in the modern natrocarbonatite lavas, can be significant but ephemeral components of intrusive carbonatite complexes. We therefore infer that the parental magmas that produce primary carbonatite melts might be enriched in Na and Cl. This conclusion affects existing models for mantle source compositions, melting scenarios, temperature, rheological properties, and crystallization path of carbonatite melts.
Abstract: More than half a gigaton of CO2 is subducted into Earth’s interior each year1. At least 40% of this CO2 is returned to the atmosphere by arc volcanism2, 3, 4. Processes that are known to release carbon from subducting slabs—decarbonation or carbonate dissolution in fluids—can account for only a portion of the CO2 released at arc volcanoes5. Carbonatitic liquids may form from the subducting crust, but are thought to form only at very high temperatures. Melting of carbonated rocks could restrict the subduction of carbon into the deeper Earth. However, the behaviour of such rock types in subduction zones is unclear. Here I use laboratory experiments to show that calcium-rich hydrous carbonatitic liquids can form at temperatures as low as 870 to 900 °C, which corresponds to shallow depths of just 120 km beneath subduction zone arcs, in warm thermal regimes. I find that water strongly depresses the solidus for hydrous carbonate gabbro and limestone rocks, creating carbonatitic liquids that efficiently scavenge volatile elements, calcium and silicon, from the slab. These extremely mobile and reactive liquids are expected to percolate into the mantle wedge, and create a CO2 source for subduction zone magmatism. Carbonatitic liquids thus provide a potentially significant pathway for carbon recycling at shallow depths beneath arcs.
Abstract: The article focuses on the study of composition of garnets of the lherzolitic and harzburgitic parageneses and the conditions of peridotite. As per the study, reconstruction of the conditions of metasomatism of peridotitic sources of kimberlite is possible in the evolution of garnet. It mentions the importance of dry and hydrous carbonatitic melt upon alteration of peridotitic sources of kimberlite as it acted as an another heat source.
Deep-seated magmatism, its sources and plumes, Proceedings of XIII International Workshop held 2014., Vol. 2014, pp. 124-147.
Baltic Shield, Fennoscandia
Carbonatite, alkaline rocks
Abstract: The paper presents the results of a study of the large Paleozoic ore-magmatic system in the northeastern Fennoscandian Shield comprising the Khibiny and Lovozero plutons, the Kurga intrusion, volcanic rocks, and numerous alkaline dike swarms. As follows from the results of deep drilling and 3D geophysical simulation, large bodies of rocks pertaining to the ultramafic alkaline complex occur at the lower level of the ore-magmatic system. Peridotite, pyroxenite, melilitolite, melteigite, and ijolite occupy more than 50 vol % of the volcanic-plutonic complex within the upper 15 km accessible to gravity exploration. The proposed model represents the ore-magmatic system as a conjugate network of mantle magmatic sources localized at different depth levels and periodically supplying the melts belonging to the two autonomous groups: (1) ultramafic alkaline rocks with carbonatites and (2) alkali syenites-peralkaline syenites, which were formed synchronously having a common system of outlet conduits. With allowance for the available isotopic datings and new geochronological evidence, the duration of complex formation beginning from supply of the first batches of melt into calderas and up to postmagmatic events, expressed in formation of late pegmatoids, was no less than 25 Ma.
Abstract: Carbon emission at volcanic centers requires a constant balance between output (mostly by volcanism, either at plate boundaries or intraplate) and input (mostly at trench settings) of carbon from and to the Earth's mantle. The form of carbon that resides in the mantle is controlled by depth (pressure) and oxygen fugacity, the latter in turn depending on the depth and the concentration of iron in the mantle. In the shallow, lithospheric mantle, carbon is likely to be present in the oxidized form of CO2 (except under cratons where carbon is reduced to graphite or diamond). Below approximately 90 km, in the asthenosphere, the oxidized form of carbon is carbonate, either mineral or melt, depending on the thermal regime. At depths greater than approximately 150 km, the asthenospheric mantle is too reducing for carbon to stay in its oxidized form and only diamond is present, unless there is sufficient hydrogen to form reduced C-H fluids. Hence, the region located in the depth range of 90 to 150 km deep is where carbonatitic melts can most likely be produced and impregnate the surrounding mantle through metasomatism. The upper bound of this region is called the carbonate ledge. This limit prevents carbonate (either solid or molten) from ascending because of degassing and CO2 liberation. The lower bound is a redox front where redox melting (that is, melting caused by oxidation) may take place in an ascending portion of carbon-containing mantle. Carbonatite eruptions and presence of carbonate mineral inclusions in deep-seated diamonds provide evidence that these boundaries can be trespassed in some cases.
An analysis of the experimental data that has bearing on silicate melting in the presence of carbon further shows that the carbonate ledge is a melting curve with a negative or flat Clapeyron (dP/dT) slope. In the carbonated ultrabasic (peridotite) systems, the carbonate ledge is located between ~ 2-3 GPa. The ledge divides the pressure-temperature space into a region of low-pressure silicate melt production, and a high-pressure region where carbonatites can be produced. Carbonatitic melts in equilibrium with mantle peridotite have compositions close to dolomitic (approximately equal amounts of Ca and Mg) with a general trend of becoming markedly more magnesian with increasing pressure. Calcic carbonatites may be stable at pressures < 2 GPa if clinopyroxene is absent. At mantle transition zone pressure range, there seems to be a melting temperature decrease (negative fusion slope), which may be caused by the stabilization of majoritic garnet.
The carbonated basic (broadly eclogitic) system is more complex than the peridotitic one, because of the strong control of bulk silicate composition on melting temperatures, and hence, on melt composition. In carbonated eclogite systems, we propose that the effect of bulk composition upon all observed features can perhaps be related to silica super-saturation, or lack thereof. In some cases, high calcium (> 80 mol% CaCO3) melts can be produced, making the melting of carbonated eclogites an appealing scenario for the genesis of calcio-carbonatites in the Earth's mantle. Comparison with modeled pressure-temperature paths of subducted oceanic lithosphere shows that fusion of carbonated eclogite at depths shallower than 200 km should be expected for hot (Cascadian-type) subduction thermal regimes. On the other hand, in the case of cooler thermal regimes (Honshu-type, for instance), subducted carbonates may be stable to greater depths in Earth at trench settings, depending on the bulk composition of the system.
Furthermore, high-pressure experiments show evidence of a continuum among carbonatitic, kimberlitic, melilititic, and basaltic liquids, for increasing melting degree of carbonated peridotite. This continuum has not been documented in the case of fusion of carbonated eclogite. It may be present, however, when certain sediments are fused, although the silicate melts are granitic to rhyodacitic instead of being kimberlitic in composition. Additional high-pressure work on phase relations in the simple binary system CaCO3-MgCO3 and specific focus on oxide solubility in the vapor phase have the potential to further clarify phase relations on complex silicate-carbonate systems at mantle conditions.
GSA Annual Meeting, Paper 131-14, 1p. Abstract only
Africa, South Africa
Carbonatite
Abstract: Petrologic and geochemical data for carbonatites and associated alkaline igneous rocks are presented for the Zandkopsdrift Carbonatite Complex, Namaqualand. The samples included in this study are relatively fresh, collected by coring at depths of >70 m below the weathered cap zone. The Zandkopsdrift complex is the only locality in the province known to contain significant carbonatite. The carbonatites studied are calico-, ferro- and silico- carbonatites, based on mineralogy, texture, and major element composition. They have low to moderate Mg-numbers (35-65), variable MgO contents (1.2-8.50 wt.%) and high atomic Ca/Ca+Mg (0.73-0.97), indicating that they are not likely simple mantle melts. The carbonatites contain significant apatite, magnetite, pyrochlore and phlogopite. Zandkopsdrift also contains significant amounts of aillikite and olivine melilitite. These rocks have relatively low SiO2 (25-31 wt.%) and Al2O3 (5.3- 6.1 wt.%), high K2O (6-6.3 wt.%) and TiO2 (5.6-9.5 wt.%) and moderate Mg numbers (51-58). ?18O and ?13C isotopes were measured for carbonatites and aillikites. ?13CPDB values are close to those expected for mantle-derived carbonatites (-3.9 to -8.83), while the ?18OSMOW values are significantly higher (+13. 25 to 21.84‰). The high ?18O value observed in carbonatites and aillikites is most likely attributable to secondary alteration by hydrous/hydrothermal fluids. This supports the inference that the Zandkopsdrift carbonatite is magmatic in origin but was later affected by secondary alteration which resulted in the elevated O stable isotopes. The ‘mantle-like’ ?13C is inconsistent with significant assimilation of C-bearing crustal rocks. Chondrite-normalised REE contents in the carbonatites are 2400 to 10,600 for La and 36 to 170 for Lu. The high REE contents of the carbonatites are most likely due to a combination of a source metasomatised by a highly LREE-enriched agent, as well as significant magmatic differentiation. The relatively fractionated composition of the Zandkopsdrift aillikites and melilitites is also consistent with this hypothesis. We propose that the Zandkopsdrift carbonatites were most likely formed by either immiscible liquid separation from or fractional crystallization of a moderately fractionated, carbonate-rich silicate parental magma.
Session No. 131--Booth# 338
Abstract: The petrochemistry of carbonatites of three formation types were studied: (1) ultrahigh-pressure garnet-containing carbonatites (UHPC) of the Caledonian sheet (Tromsö, Norway); (2) rocks of the carbonatite-lkaline-ultrabasic Kovdor massif (the Kola Peninsula); and (3) rocks of the carbonatite-alkaline-gabbroid Tikshozero massif (north of Karelia). The samples of carbonatites were examined and tested with a microprobe; the microelements were determined using the ICP-MS technique at the Institute of Microelectronics Technology and High Purity Materials (Chernogolovka). The carbonatites of the Kovdor and Tikshozero massifs are characterized by similar negative REE trends, with a degree of REE enrichment of the Tikshozero carbonatites. The UHPC from Tromsö are different from those of the Kovdor and Tikshozero massifs in the negative trend along with lower concentrations of light REEs. The Tromsö UHPC are similar to the carbonatites of the Kovdor and Tikshozero massifs in the trend and concentrations of heavy REEs. The carbonatites of the Fennoscandian shield of various formation times and types are characterized by the geochemical similarity to those in different regions of the world with the sources associated to mantle plumes. This similarity might be caused by the formation of the mantle carbonated magmas of carbonatite-containing igneous complexes from a mantle source enriched under either mantle metasomatism or plume-lithosphere interaction, with similar mechanisms of formation. The appearance of the formations as such within a wide time interval points to the long-term occurrence of a superplume at the Fennoscandian shield and to permanent activation of the related processes of magma formation.
Abstract: The Matongo carbonatite intrusive body in the Neoproterozoic Upper Ruvubu alkaline plutonic complex (URAPC) in Burundi is overlain by an economic phosphate ore deposit that is present as breccia lenses. The ore exhibits evidence of supergene enrichment but also preserves textures related to the concentration of fluorapatite in the carbonatitic system. Magmatic fluorapatite is abundant in the ore and commonly occurs as millimeter-sized aggregates. It is enriched in light rare earth elements (LREE), which is especially apparent in the final generation of magmatic fluorapatite (up to 1.32 wt% LREE2O3). After an episode of metasomatism (fenitization), which led to the formation of K-feldspar and albite, the fluorapatite-rich rocks were partly brecciated. Oxygen and carbon isotope compositions obtained on the calcite forming the breccia matrix (?18O?=?22.1?- and ?13C?=??1.5?‰) are consistent with the involvement of a fluid resulting from the mixing of magmatic-derived fluids with a metamorphic fluid originating from the country rocks. In a subsequent postmagmatic event, the carbonates hosting fluorapatite were dissolved, leading to intense brecciation of the fluorapatite-rich rocks. Secondary carbonate-fluorapatite (less enriched in LREE with 0.07-0.24 wt% LREE2O3 but locally associated with monazite) and coeval siderite constitute the matrix of these breccias. Siderite has ?18O values between 25.4 and 27.7?- and very low ?13C values (from ?12.4 to ?9.2?, which are consistent with the contribution of organic-derived low ?13C carbon from groundwater. These signatures emphasize supergene alteration. Finally, the remaining voids were filled with a LREE-poor fibrous fluorapatite (0.01 wt% LREE2O3), forming hardened phosphorite, still under supergene conditions. Pyrochlore and vanadiferous magnetite are other minerals accumulated in the eluvial horizons. As a consequence of the supergene processes and fluorapatite accumulation, the phosphate ore, which contains 0.72 to 38.01 wt% P2O5, is also enriched in LREE (LaN/YbN from 47.1 to 83.5; ?REE between 165 and 5486 ppm), Nb (up to 656 ppm), and V (up to 1232 ppm). In the case of phosphate exploitation at Matongo, REE could prove to have a subeconomic potential to be exploited as by-products of phosphates.
Abstract: This study presents compositional data for a statistically significant number (n=180) of heated and quenched (recreated) carbonate melt inclusions trapped in magnetite and clinopyroxene in jacupirangite from Kerimasi volcano (Tanzania). On the basis of homogenization experiments for clinopyroxene-hosted melt inclusions and forsterite-monticellite-calcite phase relations, a range of 1000 to 900 °C is estimated for their crystallization temperatures. Petrographic observations and geochemical data show that during jacupirangite crystallization, a CaO-rich and alkali-"poor" carbonate melt (relative to Oldoinyo Lengai natrocarbonatite) existed and was entrapped in the precipitating magnetite, forming primary melt inclusions, and was also enclosed in previously crystallized clinopyroxene as secondary melt inclusions. The composition of the trapped carbonate melts in magnetite and clinopyroxene are very similar to the parental melt of Kerimasi calciocarbonatite; i.e., enriched in Na2O, K2O, F, Cl and S, but depleted in SiO2 and P2O5 relative to carbonate melts entrapped at an earlier stage and higher temperature (1050-1100 °C) during the formation of Kerimasi afrikandite. Significant compositional variation is shown by the major minerals of Kerimasi plutonic rocks (afrikandite, jacupirangite and calciocarbonatite). Magnetite and clinopyroxene in the jacupirangite are typically transitional in composition between those of afrikandite and calciocarbonatite. These data suggest that the jacupirangite represents an intermediate stage between the formation of afrikandite and calciocarbonatite. Jacupirangite most probably formed when immiscible silicate and carbonate melts separated from the afrikandite body, although the carbonate melt was not separated completely from the silicate melt fraction. In general, during the evolution of the carbonate melt at Kerimasi, concentrations of P2O5 and SiO2 decreased, whereas volatile content (alkalis, S, F, Cl and H2O) increased. Volatiles were incorporated principally in nyerereite, shortite, burbankite, nahcolite and sulfohalite as identified by Raman spectrometry. These extremely unstable minerals cannot be found in the bulk rock, because of alteration by secondary processes. On the basis of these data, an evolutionary model is developed for Kerimasi plutonic rocks.
Abstract: Magmatic volatiles are critically important in the petrogenesis of igneous rocks but their inherent transience hampers the identification of their role in magmatic and mineralization processes. We present evidence that magmatic volatiles played a critical role in the formation of the 1894 Ma Paleoproterozoic Montviel alkaline-carbonatite complex, Canada, and the related carbonatite-hosted REE-Nb deposit. Field and drill core relationships indicate that lithological units of the complex were emplaced in the following order: clinopyroxenites, melteigites, ijolites, melanosyenites, leucosyenites, granites, lamprophyric silicocarbonatites, rare magnesiocarbonatites, calciocarbonatites, ferrocarbonatites, late mixed carbonatites, kimberlitic silicocarbonatites and polygenic breccias. Magmatic minerals within these units were systematically metasomatized. In undersaturated silicate rocks, augite recrystallized to aegirine–augite and aegirine, plagioclase recrystallized to albite, and nepheline recrystallized with analcime, cancrinite and albite. Primary biotite was replaced by secondary, REE-rich metasomatic biotite, particularly along fractures and alteration pockets. In carbonatites, liquidus phases consisted of calcite and dolomite and were recrystallized to ferroan dolomite, ankerite, siderite, barytocalcite, witherite and strontianite, which are intimately related to the REE-bearing carbonates and fluorocarbonates. Biotite is common to all lithologies, ranges in REE concentrations from 1.5 to 230 ppm and yielded subsolidus crystallization temperatures ranging from 770 °C to 370 °C. Sm-Nd isotope analyses from biotite and aegirine-augite yield a range of ?Nd values (+ 3.4 to ? 3.0) that suggests mixing of fluids from three sources during the crystallization of the Montviel magmas. The clinopyroxenites to melteigite, ijolites and melanosyenites crystallized augite and biotite with initial ?Nd value ? 3.4 and these minerals were metasomatized by a 1st fluid, lowering their ?Nd to values comprised between 0.8 and 3.4. Silicocarbonatites and carbonatites subsequently crystallized aegirine-augite and biotite with initial ?Nd value ? 2.6 and a 2nd fluid metasomatized the minerals to lower ? values. Both the 1st and the 2nd fluids eventually mixed with a 3rd recrystallizing aegirine-augite and biotite and lower their ?Nd values down to ? 3.0. The results presented herein suggest that the mantle magmas evolved through 4 distinct mantle pulses by fractional crystallization, mixing of depleted mantle fluids with crustal fluids, and metasomatism. Some of the silicate rocks also show evidence of assimilation of wall rock as part of their petrogenetic evolution. During the last stages of its evolution in carbonatites, the fluid source transited from the depleted mantle to the crust and we speculate that this resulted in a violent explosive eruption creating the diatreme-shaped, HREE-rich polygenic breccia.
Mineralogical Magazine, Vol. 79, 5, pp. 1231-1244.
Russia
Carbonatite
Abstract: Anzaite-(Ce), ideally Formula Fe2+Ti6O18(OH)2, is a new, structurally complex mineral occurring as scarce minute crystals in hydrothermally altered silicocarbonatites in the Afrikanda alkali-ultramafic complex of the Kola Peninsula, Russia. The mineral is a late hydrothermal phase associated with titanite, hibschite, clinochlore and calcite replacing the primary magmatic paragenesis. The rare-earth elements (REE) (dominated by Ce), Ti and Fe incorporated in anzaite-(Ce) were derived from primary Ti oxides abundant in the host rock. Anzaite-(Ce) is brittle and lacks cleavage; the density calculated on the basis of structural data is 5.054(6) g cm?3. The mineral is opaque and grey with a bluish hue in reflected light; its reflectance values range from 15-16% at 440 nm to 13-14% at 700 nm. Its infrared spectrum shows a prominent absorption band at 3475 cm?1 indicative of OH? groups. The average chemical composition of anzaite-(Ce) gives the following empirical formula calculated on the basis of 18 oxygen atoms and two OH? groups: (Ce2.18Nd0.85La0.41Pr0.26Sm0.08Ca0.36Th0.01)?4.15Fe0.97(Ti5.68Nb0.22Si0.04)?5.94O18(OH)2. The mineral is monoclinic, space group C2/m, a = 5.290(2), b = 14.575(6), c = 5.234(2) Å, ? = 97.233(7)°, V = 400.4(5) Å3, Z = 1. The ten strongest lines in the X-ray micro-diffraction pattern are [dobs in Å (I) hkl]: 2.596 (100) 002; 1.935 (18) 170; 1.506 (14) 133; 1.286 (13) 1.11.0; 2.046 (12) 2?41; 1.730 (12) 003; 1.272 (12) 0.10.2; 3.814 (11) 1?11; 2.206 (9) 061; 1.518 (9) 172. The structure of anzaite-(Ce), refined by single-crystal techniques to R1 = 2.1%, consists of alternating layers of type 1, populated by REE (+ minor Ca) in a square antiprismatic coordination and octahedrally coordinated Fe2+, and type 2, built of five-coordinate and octahedral Ti, stacked parallel to (001). This atomic arrangement is complicated by significant disorder affecting the Fe2+, five-coordinate Ti and two of the four anion sites. The order-disorder pattern is such that only one half of these positions in total occupy any given (010) plane, and the disordered (010) planes are separated by ordered domains comprising REE, octahedral Ti and two anion sites occupied by O2?. Structural and stoichiometric relations between anzaite-(Ce) and other REE-Ti (±Nb, Ta) oxides are discussed. The name anzaite-(Ce) is in honour of Anatoly N. Zaitsev of St Petersburg State University (Russia) and The Natural History Museum (UK), in recognition of his contribution to the study of carbonatites and REE minerals. The modifier reflects the prevalence of Ce over other REE in the composition of the new mineral.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 241-244.
Canada, British Columbia
Carbonatite
Abstract: Carbonatites host economic deposits of niobium (Nb), rare earth elements (REE), phosphate, baddeleyite (natural zirconia), vermiculite, and fl uorspar, and historically, supplied copper, uranium, carbonate (for cement industries) and sodalite (Pell, 1994 and Simandl, this volume). The Upper Fir carbonatite is in southeastern British Columbia, approximately 200 km north of Kamloops (Fig. 1). It is one ofmany known carbonatite occurrences in the British Columbia alkaline province, which follows the Rocky Mountain Trench and extends from the southeastern tip of British Columbia to its northern boundaries with the Yukon and Northwest Territories (Pell, 1994). The Upper Fir is a strongly deformed carbonatite with an indicated mineral resource of 48.4 million tonnes at 197 ppm of Ta2O5 and 1,610 ppm of Nb2O5, and an inferred resource of 5.4 million tonnes at 191 ppm of Ta2O5 and 1760 ppm of Nb2O5 (Kulla et al. 2013). The Nb, Ta, and vermiculite mineralization is described by Simandl et al. (2002, 2010), Chong, et al, (2012), and Chudy (2014). In this document we present the results of an orientation survey designed to determine the biogechemical signature of a typical carbonatite in the Canadian Cordillera. This survey suggests that needles and twigs of White Spruce (Picea glauca) and Subalpine Fir (Abies lasio carpa) are suitable sampling media to explore for carbonatites and carbonatite-related rare earth elements (REE), niobium (Nb), and tantalum (Ta) deposits.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 245-250.
Technology
Carbonatite
Abstract: We measured 10 major (SiO2, TiO2, Al2O3, total Fe2O3, MnO, MgO, CaO, Na2O, K2O, and P2O5) and 32 trace (Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Pb, Th, and U) elements in 16 geochemical reference samples (AGV-1, AGV-2, BCR-1, BCR- 2, BHVO-2, BIR-1a, DNC-1a, G-2, GSP-1, GSP-2, MAG-1, QLO-1, RGM-1, RGM-2, SGR-1b, and STM-1) distributed by United States Geological Survey (USGS) and three reference rock samples (SY-2, SY-3, and MRG-1) provided by Canadian Certifi ed Reference Materials Project (CCRMP) using inductively coupled plasma -mass spectrometry coupled with the femtosecond laser ablation sample introduction technique (fsLA-ICP-MS). Before the elemental analysis, fused glassbeads were prepared from the mixture of sample powder and high-purity alkali fl ux with a mixing ratio of 1:10. The abundances of the major and trace elements were externally calibrated by using glass beads containing the major and trace elements prepared from 17 Geological Survey of Japan (GSJ) geochemical reference samples (JB-1, JB-1a, JB-2, JB-3, JA-1, JA-2, JA-3, JR-1, JR-2, JR-3, JP-1, JGb-1, JGb-2, JG-1a, JG- 2, JG-3, and JSy-1). Typical analysis repeatabilities for these geochemical reference samples were better than 3% for Al2O3 and Na2O; <5% for SiO2, TiO2, total Fe2O3, MnO, MgO, CaO, K2O, P2O5, Zn, Rb, Sr, Zr, Nb, Ba, Nd, and U; <8% for Sc, V, Cr, Co, Y, Cs, La, Ce, Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Pb, and Th; <11% for Ni and Cu. These data clearly demonstrate that high analytical repeatability can be achieved by the fsLA-ICP-MS technique with glass beads made from 0.5 g larger samples.
Doklady Earth Sciences, Vol. 464, 2, pp. 1029-1032.
Russia
Carbonatite
Abstract: The isotopic -geochronological features of thorianite and baddeleyite from carbonatites of the Guli massif, located within Maimecha -Kotui province in the north of the Siberian Platform, are characterized for the first time. The economic complex platinum-group element (PGE) and gold placer deposits are closely related to the Guli massif. Similar geochronological data for thorianite (250.1 ± 2.9 Ma, MSWD = 0.09, n = 36) and baddeleyite (250.8 ± 1.2 Ma, MSWD = 0.2, n = 6) obtained by two different methods indicate that carbonatites were formed close to the Permian -Triassic boundary and are synchronous with tholeiitic flood basalts of the Siberian Platform.
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 31-38.
Global
Carbonatite
Abstract: Mineralized carbonatite systems are multi-commodity, highly sought after, but poorly understood exploration targets (Mariano, 1989a, b; Pell, 1996; Birkett and Simandl, 1999). They are the main sources of niobium and rare earth elements (REE), which are considered critical metals for some key economic sectors (European Commission, 2014), and have become popular exploration targets for junior mining companies worldwide. Carbonatites also contribute to our understanding of the Earth’s mantle (e.g., Bell and Tilton, 2001, 2002). Herein, we discuss the defi nition and classifi cation of carbonatites; summarize information pertinent for carbonatite exploration such as tectonic setting, shape, geophysical signature, associated rocks, alteration, and temporal distribution; and highlight the multi-commodity aspect of carbonatiterelated exploration targets and mineral prospectivity. 2. Defi nition and classifi cation Carbonatites are defi ned by the International Union of Geological Sciences (IUGS) as igneous rocks containing more than 50% modal primary carbonates (Le Maitre, 2002). Depending on the predominant carbonate mineral, a carbonatite is referred to as a ‘calcite carbonatite’ (sövite), ‘dolomite carbonatite’ (beforsite) or ‘ankerite carbonatite’. If more than one carbonate mineral is present, the carbonates are named in order of increasing modal concentrations, for example a ‘calcite-dolomite carbonatite’ is composed predominately of dolomite. If non-essential minerals (e.g., biotite) are present, this can be refl ected in the name as ‘biotite-calcite carbonatite’. Where the modal classifi cation cannot be applied, the IUGS chemical classifi cation is used (Fig. 1). This classifi cation subdivides carbonatites into calciocarbonatites, magnesiocarbonatites, and ferrocarbonatites. For calciocarbonatites, the ratio of CaO/(CaO+MgO+FeO +Fe2O3+MnO) is greater than 0.8. The remaining carbonatites are subdivided (based on wt.% ratios) into magnesiocarbonatite [MgO > (FeO+Fe2O3+MnO)] and ferrocarbonatite [MgO < (FeO+Fe2O3+MnO)] (Woolley and Kempe, 1989; Le Maitre, 2002). If the SiO2 content of the rock exceeds 20%, the rock is referred to as silicocarbonatite. When the IUGS chemical classifi cation is used, care should be taken to ensure that magnetite and hematite-rich calciocarbonates or magnesiocarbonatites are not erroneously classifi ed as ferrocarbonatites (Gittins and Harmer, 1997). A refi nement to the IUGS chemical classifi cation based on molar proportions (Gittins and Harmer, 1997), introduced ‘ferrugineous’ carbonatites (Fig. 2). The boundary separating calciocarbonatites from magnesiocarbonatites and ‘ferrugineous’ carbonatites is set at 0.75, above which carbonatites contain more than 50% calcite on a molar basis. Although not universally accepted, Gittins and Harmer’s classifi cation is commonly used in studies of carbonatitehosted ore deposits. A mineralogical-genetic classifi cation of carbonatites was proposed by Mitchell (2005). His paper points to pitfalls of the IUGS classifi cation and subdivides carbonatites into ‘primary carbonatites’ and ‘carbothermal residua’. The introduction of the term ‘carbothermal residua’ is signifi cant as it alerts mantle specialists to fundamental processes involved in the formation of many carbonatite-related deposits, and reduces rifts between camps of ore deposit geologists, petrologists, and mantle specialists. From the exploration
Symposium on critical and strategic materials, British Columbia Geological Survey Paper 2015-3, held Nov. 13-14, pp. 65-74.
Global
Carbonatite
Abstract: For nearly 50 years, carbonatites have been the primary sources of niobium and rare earth elements (REEs), particularly the light REEs including La, Ce, Pr, and Nd. In addition, carbonatites may be enriched in other critical elements and have the potential to be future sources. Currently, only fi ve of the more than 500 known carbonatites in the world are being mined for REEs: Bayan Obo (Inner Mongolia, China); Maoniuping (Sichuan, China); Dalucao (or Daluxiang, Sichuan, China); and Mountain Pass (California, USA), and the carbonatite-derived laterite at Mount Weld (Australia). To achieve ore-grade REE enrichment, initial carbonatitic magmas require an adequate endowment of REEs and need to evolve in ways for these elements to concentrate in REE-bearing mineral phases. Radiogenic isotope studies of carbonatites clearly point to a mantle origin, but a wide range in isotopic compositions has led to contrasting views about the specifi c mantle reservoir(s) that sourced carbonatites. In this study we use the neodymium and strontium isotopic compositions of a suite of mineralized carbonatites to establish the nature of the source magmas. We examine samples that span a wide range in age (~23 Ma to 1385 Ma), Nd concentrations (3720 to 32,900 ppm), and Sr concentrations (2290 to 167,900 ppm). Our Nd and Sr isotopic data include multiple samples from Mountain Pass (USA; ?Nd i = -3.1 to -5.4, Sri = 0.70512 to 0.70594), Elk Creek (USA; ~?Nd i = 1.7, Sri = 0.7035), and Maoniuping (China; ?Nd i = -4.1 and -4.2, Sri = 0.70627 and 0.70645), and one sample each from Bear Lodge (USA; ?Nd i = 0.1, Sri = 0.70441), Kangankunde (Malawi; ?Nd i = 3.3, Sri = 0.70310), Adiounedj (Mali; ?Nd i = -0.1, Sri = 0.70558), and Mushgai Khudag (Mongolia; ?Nd i = -1.3, Sri = 0.70636). Isotopic data from two producing carbonatite REE deposits (Mountain Pass and Maoniuping) have broadly similar isotopic compositions (?Nd i = -3.1 to -5.4 and Sri = 0.7051 to 0.7065), and these compositions point to a carbonated source in the lithospheric mantle. Mineralized but unmined carbonatites have higher Nd initial isotopic compositions (?Nd i = -1.3 to 3.3) and a wider range in Sr isotopic compositions (Sri = 0.70310 to 0.70637), but these data are consistent with a lithospheric mantle reservoir.
Mineralogy and Petrology, in press available, 17p.
Africa, Burundi
Carbonatite
Abstract: The Matongo carbonatite intrusive body in the Neoproterozoic Upper Ruvubu alkaline plutonic complex (URAPC) in Burundi is overlain by an economic phosphate ore deposit that is present as breccia lenses. The ore exhibits evidence of supergene enrichment but also preserves textures related to the concentration of fluorapatite in the carbonatitic system. Magmatic fluorapatite is abundant in the ore and commonly occurs as millimeter-sized aggregates. It is enriched in light rare earth elements (LREE), which is especially apparent in the final generation of magmatic fluorapatite (up to 1.32 wt% LREE2O3). After an episode of metasomatism (fenitization), which led to the formation of K-feldspar and albite, the fluorapatite-rich rocks were partly brecciated. Oxygen and carbon isotope compositions obtained on the calcite forming the breccia matrix (?18O?=?22.1?‰ and ?13C?=??1.5?‰) are consistent with the involvement of a fluid resulting from the mixing of magmatic-derived fluids with a metamorphic fluid originating from the country rocks. In a subsequent postmagmatic event, the carbonates hosting fluorapatite were dissolved, leading to intense brecciation of the fluorapatite-rich rocks. Secondary carbonate-fluorapatite (less enriched in LREE with 0.07-0.24 wt% LREE2O3 but locally associated with monazite) and coeval siderite constitute the matrix of these breccias. Siderite has ?18O values between 25.4 and 27.7?‰ and very low ?13C values (from ?12.4 to ?9.2?‰), which are consistent with the contribution of organic-derived low ?13C carbon from groundwater. These signatures emphasize supergene alteration. Finally, the remaining voids were filled with a LREE-poor fibrous fluorapatite (0.01 wt% LREE2O3), forming hardened phosphorite, still under supergene conditions. Pyrochlore and vanadiferous magnetite are other minerals accumulated in the eluvial horizons. As a consequence of the supergene processes and fluorapatite accumulation, the phosphate ore, which contains 0.72 to 38.01 wt% P2O5, is also enriched in LREE (LaN/YbN from 47.1 to 83.5; ?REE between 165 and 5486 ppm), Nb (up to 656 ppm), and V (up to 1232 ppm). In the case of phosphate exploitation at Matongo, REE could prove to have a subeconomic potential to be exploited as by-products of phosphates.
Abstract: This study presents compositional data for a statistically significant number (n = 180) of heated and quenched (recreated) carbonate melt inclusions trapped in magnetite and clinopyroxene in jacupirangite from Kerimasi volcano (Tanzania). On the basis of homogenization experiments for clinopyroxene-hosted melt inclusions and forsterite-monticellite-calcite phase relations, a range of 1000 to 900 °C is estimated for their crystallization temperatures. Petrographic observations and geochemical data show that during jacupirangite crystallization, a CaO-rich and alkali-"poor" carbonate melt (relative to Oldoinyo Lengai natrocarbonatite) existed and was entrapped in the precipitating magnetite, forming primary melt inclusions, and was also enclosed in previously crystallized clinopyroxene as secondary melt inclusions. The composition of the trapped carbonate melts in magnetite and clinopyroxene is very similar to the parental melt of Kerimasi calciocarbonatite; i.e., enriched in Na2O, K2O, F, Cl and S, but depleted in SiO2 and P2O5 relative to carbonate melts entrapped at an earlier stage and higher temperature (1050-1100 °C) during the formation of Kerimasi afrikandite. Significant compositional variation is shown by the major minerals of Kerimasi plutonic rocks (afrikandite, jacupirangite and calciocarbonatite). Magnetite and clinopyroxene in the jacupirangite are typically transitional in composition between those of afrikandite and calciocarbonatite. These data suggest that the jacupirangite represents an intermediate stage between the formation of afrikandite and calciocarbonatite. Jacupirangite most probably formed when immiscible silicate and carbonate melts separated from the afrikandite body, although the carbonate melt was not separated completely from the silicate melt fraction. In general, during the evolution of the carbonate melt at Kerimasi, concentrations of P2O5 and SiO2 decreased, whereas volatile content (alkalis, S, F, Cl and H2O) increased. Volatiles were incorporated principally in nyerereite, shortite, burbankite, nahcolite and sulfohalite as identified by Raman spectrometry. These extremely unstable minerals cannot be found in the bulk rock, because of alteration by secondary processes. On the basis of these data, an evolutionary model is developed for Kerimasi plutonic rocks.
International Journal of Mineral Processing, Vol. 144, pp. 1-10.
South America, Brazil
Carbonatite
Abstract: The rare earth elements (REE) are essential for a wide range of applications, from strategic assets (e.g. petroleum cracking, magnets for wind turbines) to popular merchandise, as smartphones. Since 2010, when China, the worlds close to exclusive REE supplier, imposed export quotas, several old and new deposits have been evaluated to compensate market shortage, taking advantage of significant price rises. The Araxá rare earth elements prospect boast a large reserve (6.34Mt @ 5.01% REO), as well as phosphate and niobium, in a deeply weathered ore of carbonatitic origin. The mineralogy and the ore properties are unconventional for rare earth elements, and require a detailed mineralogical and technological characterisation as starting point to develop a feasible processing route. Rare earths are predominantly carried by monazite (over 70%), and by a solid solution of the plumbogummite group minerals where the barium-rich term gorceixite predominates, while cerianite and bastnaesite account for less than 1% each. Minerals of the pyrochlore supergroup are the main Nb carriers, but phosphate is also due to monazite and the plumbogummite group minerals, as apatite has barely been detected. Goethite, high-Al hematite and quartz are the main gangue minerals, and goethite is thoroughly intergrown with the other phases. Fine particle size (P50 close to 45?m) and 47.4% of the REE in the ?20?m size fraction is another feature typical of this kind of ore. The mineralogical and textural complexity of the ore required a comprehensive technological characterisation in order to evaluate processing options. Based on textural measurements, the concentration of monazite, the concentration of the REE carrying minerals and the reverse removal of quartz, as processing option for this ore, have been simulated. Incomplete liberation of monazite does limit its grade in an ideal concentrate to 80%, and its recovery to 70%. The low monazite recovery must be added to the loss of REE carried by other phases, reducing the overall REE recovery to below 45%. Monazite has also a very limited exposition of the mineral on the particle's surfaces, supposed to impair process efficiency enough to keep experimental results significantly far from the simulated ones. The concentration of the REE-bearing minerals might be efficient from the liberation point of view, and over 90% of the REE carriers can be recovered to a 97% grade concentrate. Due to the low REE grade of predominant gorceixite (3.3%), however, the concentrate's grade of 14% REE is just slightly above the double of the ore's grade. For the REE-bearing minerals taken together, the process efficiency might be hampered by selectivity due to the complex mineralogy. The major gangue minerals, goethite and hematite, are strongly intergrown with the other minerals of the assemblage, to an extent that evaluating reverse processing considering these phases was not feasible. The removal of quartz by reverse processing is quite straightforward, and 95% of the mineral might be removed to a high-grade quartz concentrate of 93%, with loss of REE of only 0.14%. The mass discharge of 8.7%, however, rises the grade of the concentrate only to 7.3% REE. Complex mineralogy and the fine crystals and particles with strong intergrowth that characterise the ore hamper efficient concentration for the Araxá REE ore, and direct hydrometallurgical processing of the whole was adopted. The results are in agreement with the few other published attempts to concentrate the rare earth minerals from residual lateritic ores related to carbonatites
Physics and Chemistry of Minerals, Vol. 42, pp. 817-824.
Mantle
Carbonatite, diamond genesis
Abstract: Carbonatic components of parental melts of the deeper mantle diamonds are inferred from their primary inclusions of (Mg, Fe, Ca, Na)-carbonate minerals trapped at PT conditions of the Earth’s transition zone and lower mantle. PT phase diagrams of MgCO3-FeCO3-CaCO3-Na2CO3 system and its ternary MgCO3-FeCO3-Na2CO3 boundary join were studied at pressures between 12 and 24 GPa and high temperatures. Experimental data point to eutectic solidus phase relations and indicate liquidus boundaries for completely miscible (Mg, Fe, Ca, Na)- and (Mg, Fe, Ca)-carbonate melts. PT fields for partial carbonate melts associated with (Mg, Fe)-, (Ca, Fe, Na)-, and (Na2Ca, Na2Fe)-carbonate solid solution phases are determined. Effective nucleation and mass crystallization of deeper mantle diamonds are realized in multicomponent (Mg, Fe, Ca, Na)-carbonatite-carbon melts at 18 and 26 GPa. The multicomponent carbonate systems were melted at temperatures that are lower than the geothermal ones. This gives an evidence for generation of diamond-parental carbonatite melts and formation of diamonds at the PT conditions of transition zone and lower mantle.
Mineralogy and Petrology, In press available, 24p.
Australia
Carbonatite
Abstract: In situ SHRIMP U-Pb dating of zirconolite in clinopyroxenite from the Cummins Range Carbonatite Complex, situated in the southern Halls Creek Orogen, Kimberley region, Western Australia, has provided a reliable 207Pb/206Pb age of emplacement of 1009 ± 16 Ma. Variably metamict and recrystallised zircons from co-magmatic carbonatites, including a megacryst ~1.5 cm long, gave a range of ages from ~1043-998 Ma, reflecting partial isotopic resetting during post-emplacement deformation and alteration. Monazite-(Ce) in a strongly foliated dolomite carbonatite produced U-Th-Pb dates ranging from ~900-590 Ma. Although the monazite-(Ce) data cannot give any definitive ages, they clearly reflect a long history of hydrothermal alteration/recrystallisation, over at least 300 million years. This is consistent with the apparent resetting of the Rb-Sr and K-Ar isotopic systems by a post-emplacement thermal event at ~900 Ma during the intracratonic Yampi Orogeny. The emplacement of the Cummins Range Carbonatite Complex probably resulted from the reactivation of a deep crustal structure within the Halls Creek Orogen during the amalgamation of Proterozoic Australia with Rodinia over the period ~1000-950 Ma. This may have allowed an alkaline carbonated silicate magma that was parental to the Cummins Range carbonatites, and generated by redox and/or decompression partial melting of the asthenospheric mantle, to ascend from the base of the continental lithosphere along the lithospheric discontinuity constituted by the southern edge of the Halls Creek Orogen. There is no evidence of a link between the emplacement of the Cummins Range Carbonatite Complex and mafic large igneous province magmatism indicative of mantle plume activity. Rather, patterns of Proterozoic alkaline magmatism in the Kimberley Craton may have been controlled by changing plate motions during the Nuna-Rodinia supercontinent cycles (~1200-800 Ma).
Contributions to Mineralogy and Petrology, Vol. 171, 12p.
Mantle
Carbonatite
Abstract: Carbonatites host some unique ore deposits, especially rare earth elements (REE). Hydrothermal fluids have been proposed to play a significant role in the concentration and transport of REE and other rare metals in carbonatites, but experimental constraints on fluid-melt equilibria in carbonatitic systems are sparse. Here we present an experimental study of trace element (REE, Ba, Sr, Mo and W) partitioning between hydrous fluids and carbonatitic melts, bearing on potential hydrothermal activity associated with carbonatite ore-forming systems. The experiments were performed on mixtures of synthetic carbonate melts and aqueous fluids at 700-800 °C and 100-200 MPa using rapid-quench cold-seal pressure vessels and double-capsule assemblages with diamond traps for analyzing fluid precipitates in the outer capsule. Starting mixtures were composed of Ca, Mg and Na carbonates spiked with trace elements. Small amounts of F or Cl were added to some of the mixtures to study the effects of halogens on the element distribution. The results show that REE, Ba, Sr, Mo and W all preferentially partition into carbonatite melt and have fluid-melt distribution coefficients (D f/m) below unity. The REE partitioning is slightly dependent on the major element (Ca, Mg and Na) composition of the starting mixtures, and it is influenced by temperature, pressure, and the presence of halogens. The fluid-melt D values of individual REE vary from 0.02 to 0.15 with Df/mLu being larger than Df/mLa by a factor of 1.1-2. The halogens F and Cl have strong and opposite effects on the REE partitioning. Fluid-melt D REE are about three times higher in F-bearing compositions and ten times lower in Cl-bearing compositions than in halogen-free systems. Df/mW and Df/mMo are the highest among the studied elements and vary between 0.6 and 0.7; Df/mBa is between 0.05 and 0.09, whereas Df/mSr is at about 0.01-0.02. The results imply that carbonatite-related REE deposits were probably formed by fractional crystallization of carbonatitic melts rather than from exsolved hydrothermal fluids. The same appears to be true for a carbonatite-related Mo deposit recently discovered in China.
Abstract: In response to rising demand of the rare earth elements (REE), recent exploration of the British Columbia alkaline province has identified the Wicheeda Carbonatite, which contains an estimated 11.3 million tons of light REE-enriched ore grading 1.95 wt.% TREO, to be the highest-grade prospect known in British Columbia. However, research of the deposit is restricted to one paper describing mineralization in carbonatite dikes adjacent to the main plug. This study describes the nature and origin of REEmineralization in the Wicheeda plug. The carbonatite was emplaced in metasedimentary limestone and argillaceous limestone belonging to the Kechika Group, which has been altered to potassic fenite immediately adjacent to the carbonatite and to sodic fenite at greater distances from it. The carbonatite comprises a ferroan dolomite core, which passes outwards gradationally into calcite carbonatite. Three texturally distinct varieties of dolomite have been recognized. Dolomite 1 constitutes most of the carbonatite; Dolomite 2 replaced Dolomite 1 near veins and vugs; Dolomite 3 occurs as a fracture and vug-lining phase with the REE mineralization. Stable carbon and oxygen isotopic ratios indicate that the calcite carbonatite is of mantle origin, that Dolomite 1 is of primary igneous origin, that Dolomite 2 is largely primary igneous with minor hydrothermal signature contamination, and that Dolomite 3 is of hydrothermal origin. Rare-metal mineralization in the deposit is, with the exception of pyrochlore, which occurs in the calcite carbonatite, restricted to veins and vugs in the dolomite carbonatite. There it occurs as hydrothermal veins and in vugs infilled by REE-fluorocarbonates, i.e., bastnäsite-(Ce), ancylite-(Ce), and monazite- (Ce) together with accessory pyrite, barite, molybdenite, and thorite. A model is proposed in which calcite carbonatite was the earliest magmatic phase to crystallize. The calcite carbonatite magma saturated with niobium relatively early, precipitating pyrochlore. The magma later evolved to a dolomite carbonatite composition which, upon cooling exsolved an aqueous carbonic fluid, which altered the Kechika metasediments to potassic fenite and mixed with formational waters further from the carbonatite to produce sodic fenite. This fluid mobilized the REE as chloride complexes into vugs and fractures in the dolomite carbonatite. Upon progressive fluid-rock interaction, the REE precipitated largely in response to cooling and pH. Hydrothermal concentration led to remarkable grade consistency, with virtually all of the dolomite carbonatite containing >1 wt.% TREO, making the Wicheeda Carbonatite a very attractive exploration target.
Abstract: This study presents compositional data for a statistically significant number (n = 180) of heated and quenched (recreated) carbonate melt inclusions trapped in magnetite and clinopyroxene in jacupirangite from Kerimasi volcano (Tanzania). On the basis of homogenization experiments for clinopyroxene-hosted melt inclusions and forsterite-monticellite-calcite phase relations, a range of 1000 to 900 °C is estimated for their crystallization temperatures. Petrographic observations and geochemical data show that during jacupirangite crystallization, a CaO-rich and alkali-"poor" carbonate melt (relative to Oldoinyo Lengai natrocarbonatite) existed and was entrapped in the precipitating magnetite, forming primary melt inclusions, and was also enclosed in previously crystallized clinopyroxene as secondary melt inclusions. The composition of the trapped carbonate melts in magnetite and clinopyroxene is very similar to the parental melt of Kerimasi calciocarbonatite; i.e., enriched in Na2O, K2O, F, Cl and S, but depleted in SiO2 and P2O5 relative to carbonate melts entrapped at an earlier stage and higher temperature (1050-1100 °C) during the formation of Kerimasi afrikandite. Significant compositional variation is shown by the major minerals of Kerimasi plutonic rocks (afrikandite, jacupirangite and calciocarbonatite). Magnetite and clinopyroxene in the jacupirangite are typically transitional in composition between those of afrikandite and calciocarbonatite. These data suggest that the jacupirangite represents an intermediate stage between the formation of afrikandite and calciocarbonatite. Jacupirangite most probably formed when immiscible silicate and carbonate melts separated from the afrikandite body, although the carbonate melt was not separated completely from the silicate melt fraction. In general, during the evolution of the carbonate melt at Kerimasi, concentrations of P2O5 and SiO2 decreased, whereas volatile content (alkalis, S, F, Cl and H2O) increased. Volatiles were incorporated principally in nyerereite, shortite, burbankite, nahcolite and sulfohalite as identified by Raman spectrometry. These extremely unstable minerals cannot be found in the bulk rock, because of alteration by secondary processes. On the basis of these data, an evolutionary model is developed for Kerimasi plutonic rocks.
Abstract: The Oulad Dlim Massif of the Western Reguibat Shield contains several carbonatite complexes of previously unknown age. The largest and best studied are Gleibat Lafhouda, composed of magnesiocarbonatites, and Twihinate, composed of calciocarbonatites. Gleibat Lafhouda is hosted by Archean gneisses and schists. It has a SHRIMP U-Th-Pb zircon crystallization age of 1.85 ± 0.03 Ga, a Nd model age of TCR = 1.89 ± 0.03 Ga, and a Sm-Nd age of 1.85 ± 0.39 Ga. It forms part of the West Reguibat Alkaline province. Twihinate, on the other hand, is much younger. It is hosted by Late Silurian to Early Devonian deformed granites and has a zircon crystallization age of 104 ± 4 Ma, which is within error of the age of the carbonatites of the famous Richat Structure in the southwest Reguibat Shield. Like these, the Twihinate carbonatites are part of the Mid-Cretaceous Peri-Atlantic Alkaline Pulse. The Twihinate carbonatites contain abundant inherited zircons with ages that peak at ca. 420 Ma, 620 Ma, 2050 Ma, 2466 Ma, and 2830 Ma. This indicates that their substratum has West African rather than, as previously suggested, Avalonian affinities. It has, however, a Paleoproterozoic component that is not found in the neighboring western Reguibat Shield. The 421 Ma to 410 Ma gneissic granites hosting Twihinate are epidote + biotite + Ca-rich garnet deformed I-type to A-type granites derived from magmas of deep origin compatible, therefore, with being generated in a subduction environment. These granites form a body of unknown dimensions and petrogenesis, the study of which will be of key importance for understanding the geology and crustal architecture of this region.
Abstract: The Tundulu and Kangankunde carbonatite complexes in the Chilwa Alkaline Province, Malawi, contain late-stage, apatite-rich lithologies termed quartz-apatite rocks. Apatite in these rocks can reach up to 90 modal% and displays a distinctive texture of turbid cores and euhedral rims. Previous studies of the paragenesis and rare earth element (REE) content of the apatite suggest that heavy REE (HREE)-enrichment occurred during the late-stages of crystallization. This is a highly unusual occurrence in intrusions that are otherwise light REE (LREE) enriched. In this contribution, the paragenesis and formation of the quartz-apatite rocks from each intrusion is investigated and re-evaluated, supported by new electron microprobe (EPMA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data to better understand the mechanism of HREE enrichment. In contrast to the previous work at Tundulu, we recognize three separate stages of apatite formation, comprising an “original” euhedral apatite, “turbid” apatite, and “overgrowths” of euhedral late apatite. The crystallization of synchysite-(Ce) is interpreted to have occurred subsequent to all phases of apatite crystallization. The REE concentrations and distributions in the different minerals vary, but generally higher REE contents are found in later-stage apatite generations. These generations are also more LREE-enriched, relative to apatite that formed earlier. A similar pattern of increasing LREE-enrichment and increased REE concentrations toward later stages of the paragenetic sequence is observed at Kangankunde, where two generations of apatite are observed, the second showing higher REE concentrations, and relatively higher LREE contents. The changing REE distribution in the apatite, from early to late in the paragenetic sequence, is interpreted to be caused by a combination of dissolution-reprecipitation of the original apatite and the preferential transport of the LREE complexes by F- and Cl-bearing hydrothermal fluids. Successive pulses of these fluids transport the LREE out of the original apatite, preferentially re-precipitating it on the rim. Some LREE remained in solution, precipitating later in the paragenetic sequence, as synchysite-(Ce). The presence of F is supported by the F content of the apatites, and presence of REE-fluorcarbonates. Cl is not detected in the apatite structure, but the role of Cl is suggested from comparison with apatite dissolution experiments, where CaCl2 or NaCl cause the reprecipitation of apatite without associated monazite. This study implies that, despite the typically LREE enriched nature of carbonatites, significant degrees of hydrothermal alteration can lead to certain phases becoming residually enriched in the HREE. Although at Tundulu the LREE-bearing products are re-precipitated relatively close to the REE source, it is possible that extensive hydrothermal activity in other carbonatite complexes could lead to significant, late-stage fractionation of the REE and the formation of HREE minerals.
Abstract: Here we report field, petrographic, and geochemical analyses of the southeast Missouri Avon Volcanic District intrusive rocks and present the first combined textural and geochemical evidence for the presence of a primary magmatic carbonatite phase among ultramafic dikes, pipes, and diatremes of olivine melilitite, alnöite, and calciocarbonatite. The ?13CVPDB values measured for primary calciocarbonatite as well as carbonates in olivine melilitite and alnöite rocks range from ? 3.8‰ to ? 8.2‰, which are within the typical range of mantle values and are distinct from values of the carbonate country rocks, 0.0‰ to ? 1.3‰. The carbonate oxygen isotope compositions for the intrusive lithologies are in the range of 21.5‰ to 26.2‰ (VSMOW), consistent with post-emplacement low temperature hydrothermal alteration or kinetic fractionation effects associated with decompression and devolatilization. Metasomatized country rock and breccia-contaminated igneous lithologies have carbonate ?13CVPDB values gradational between primary carbonatite values and country rock values. Unaltered sedimentary dolomite breccia and mafic spheroids entrained by calciocarbonatite and the lack of microstratigraphic crystal growth typical of carbonate replacement, also exclude the possibility of hydrothermal replacement as the cause of the magmatic-textured carbonates. Rare earth element (REE) patterns for the alnöite, olivine melilitite, and carbonatite are similar to each other with strong light REE enrichment and heavy REE depletion relative to MORB. These patterns are distinct from those of country rock rhyolite and sedimentary carbonate. These data suggest that rocks of the Avon Volcanic District represent a single ultramafic-carbonatite intrusive complex possibly derived from a single mantle source.
Abstract: Igneous intrusions, notably carbonatitic-alkalic intrusions, peralkaline intrusions, and pegmatites, represent significant sources of rare-earth metals. Geophysical exploration for and of such intrusions has met with considerable success. Examples of the application of the gravity, magnetic, and radiometric methods in the search for rare metals are presented and described. Ground gravity surveys defining small positive gravity anomalies helped outline the shape and depth of the Nechalacho (formerly Lake) deposit within the Blatchford Lake alkaline complex, Northwest Territories, and of spodumene-rich mineralization associated with the Tanco deposit, Manitoba, within the hosting Tanco pegmatite. Based on density considerations, the bastnaesite-bearing main ore body within the Mountain Pass carbonatite, California, should produce a gravity high similar in amplitude to those associated with the Nechalacho and Tanco deposits. Gravity also has utility in modelling hosting carbonatite intrusions, such as the Mount Weld intrusion, Western Australia, and Elk Creek intrusion, Nebraska. The magnetic method is probably the most successful geophysical technique for locating carbonatitic-alkalic host intrusions, which are typically characterized by intense positive, circular to sub-circular, crescentic, or annular anomalies. Intrusions found by this technique include the Mount Weld carbonatite and the Misery Lake alkali complex, Quebec. Two potential carbonatitic-alkalic intrusions are proposed in the Grenville Province of Eastern Quebec, where application of an automatic technique to locate circular magnetic anomalies identified several examples. Two in particular displayed strong similarities in magnetic pattern to anomalies accompanying known carbonatitic or alkalic intrusions hosting rare-metal mineralization and are proposed to have a similar origin. Discovery of carbonatitic-alkalic hosts of rare metals has also been achieved by the radiometric method. The Thor Lake group of rare-earth metal deposits, which includes the Nechalacho deposit, were found by follow-up investigations of strong equivalent thorium and uranium peaks defined by an airborne survey. Prominent linear radiometric anomalies associated with glacial till in the Canadian Shield have provided vectors based on ice flow directions to source intrusions. The Allan Lake carbonatite in the Grenville Province of Ontario is one such intrusion found by this method. Although not discovered by its radiometric characteristics, the Strange Lake alkali intrusion on the Quebec-Labrador border is associated with prominent linear thorium and uranium anomalies extending at least 50 km down ice from the intrusion. Radiometric exploration of rare metals hosted by pegmatites is evaluated through examination of radiometric signatures of peraluminous pegmatitic granites in the area of the Tanco pegmatite.
Doklady Earth Sciences, Vol. 466, 2, Feb. pp. 135-137.
Russia
Carbonatite
Abstract: The first data on variations of the isotope composition and element ratios of carbon, nitrogen, and argon in carbonatites of different generations and ultrabasic rocks of the Guli massif obtained by the method of step crushing are reported. It is shown that early carbonatite differs significantly from the later ones by the concentration of highly volatile components, as well as by the isotope compositions of carbon (CO2), argon, and hydrogen (H2O). The data obtained allow us to conclude that the mantle component predominated in the fluid at the early stages of formation of rocks of the Guli massif, whereas the late stages of carbonatite formation were characterized by an additional fluid source, which introduced atmospheric argon, and most likely a high portion of carbon dioxide with isotopically heavy carbon.
Abstract: A high-temperature rheometer equipped with a graphite furnace, characterized by an air-bearing-supported synchronous motor, has been enhanced by a custom-made Pt-Au concentric cylinder assembly. With this adaptation, viscosity measurements of highly fluid melts can be achieved at high temperatures, up to 1273 K. Due to the air-bearing-supported motor, this apparatus can perform measurements of extremely low torque ranging between 0.01 ?Nm and 230 mNm (resolution of 0.1 nNm), extending the typical range of viscosity measurements accessible in the present configuration to 10?3.5-103.5 Pa•s and shear rates up to 102 of s?1. We calibrated the system with distilled water, silicone oils, and the DGG-1 standard glass. We further present new data for the viscosity of Na2CO3, K2CO3, and Li2CO3 liquids. Finally, a comparison between our results and literature data is provided, to illustrate the effect of chemical composition and oxygen fugacity on the viscosity of alkali carbonate melts, which serve as analogs for both carbonatitic melts and molten carbonates of industrial relevance. This study substantially improves the database of alkali carbonate melts and dramatically increases the accuracy with respect to previous measurement attempts. The very low viscosity range data and their temperature dependence also helps to constrain very well the activation energy of these highly fluid systems and confirms the estimate of a universal pre-exponential factor for non-Arrhenian viscosity-temperature relationships.
Abstract: The comprehensive petrographical, petrochemical and mineralogical study of the Kovdor magnetite-apatite-baddeleyite deposit in the phoscorite-carbonatite complex (Murmansk Region, Russia) revealed a spatial distribution of grain size and chemical composition of three economically extractable minerals — magnetite, apatite, and baddeleyite, showing that zonal distribution of mineral properties mimics both concentric and vertical zonation of the carbonatite-phoscorite pipe. The marginal zone of the pipe consists of (apatite)-forsterite phoscorite carrying fine grains of Ti-Mn-Si-rich magnetite with ilmenite exsolution lamellae, fine grains of Fe-Mg-rich apatite and finest grains of baddeleyite, enriched in Mg, Fe, Si and Mn. The intermediate zone accommodates carbonate-free magnetite-rich phoscorites that carry medium to coarse grains of Mg-Al-rich magnetite with exsolution inclusions of spinel, medium-grained pure apatite and baddeleyite. The axial zone hosts carbonate-rich phoscorites and phoscorite-related carbonatites bearing medium-grained Ti-V-Ca-rich magnetite with exsolution inclusions of geikielite-ilmenite, fine grains of Ba-Sr-Ln-rich apatite and comparatively large grains of baddeleyite, enriched in Hf, Ta, Nb and Sc. The collected data enable us to predict such important mineralogical characteristics of the multicomponent ore as chemical composition and grain size of economic and associated minerals, presence of contaminating inclusions, etc. We have identified potential areas of maximum concentration of such by-products as scandium, niobium and hafnium in baddeleyite and REEs in apatite.
Abstract: In the Kay?köy area of Isparta-Gölcük district, Inner Isparta Angle, SW Anatolia, Turkey, a small volume of newly discovered K-rich mafic potassic magma was emplaced in the form of dome in the vicinity of graben structures under Pliocene (3.68 ± 0.5 Ma) extensional tectonics. Kay?köy leucite ankaratrites are made up of abundant diopside, barian phlogopite and leucite, and lesser olivine, that rarely contains Cr-spinel, nepheline and haüyne, with abundant magnetite. They have low SiO2 (44.00-46.04 wt.%) and Al2O3 (12.10-12.64 wt.%) with high K2O (4.00-4.42 wt.%), CaO (13.50-14.40 wt.%) and MgO (8.52-9.36 wt.%), with high Cr (397-547 ppm) and moderate Ni (57-74 ppm) contents. They represent the less evolved silica-undersaturated mafic potassic magmas within the Isparta-Gölcük volcanic province, and may be considered another parental source to the wide spectrum of the K-rich rocks. They are highly enriched in most of the incompatible elements (e.g., Ba, 2761 to > 10,000 ppm; Sr, 3700-4074 ppm; Th, 33.60-36.99 ppm; Zr, 274-321 ppm) with high LREEs, low HREEs and elevated LREEs/HREEs ratios [(La/Yb)N, 73-80] and are comparable with kamafugite and carbonatites. Trace element patterns have negative P, Ti and Nb-Ta anomalies in common with the Italian kamafugite province and lack of a Eu anomaly, in contrast to the negative Eu anomaly of the Italian province. Their Sr87/86-Nd143/144 (0.703877-0.512765) isotopic compositions, together with those of other potassic volcanics from the Inner Isparta Angle, coincide with the West Quinling (China) kamafugites with highly depleted mantle signatures, and young East African carbonatites. Olivine-Cr-spinel pairs, high Mg# (0.69-0.73) numbers and Cr values, and high incompatible and LREE contents in Kay?köy leucite ankaratritic magma are consistent with near-primary magmas equilibrated with enriched and heterogeneous (peridotitic/pyroxenitic) mantle sources. On the basis of (i) their geochemical signatures [low Ti/Eu, elevated CaO/Al2O3 and (La/Yb)N ratios], (ii) consistency of parental magma compositions with experimental melt compositions for carbonated peridotites, and (iii) geochemical and isotopic affinities to kamafugites and carbonatites, it is inferred that the carbonatitic melts infiltrated the mantle sources of Kay?köy leucite ankaratritic magma, and induced the depletion of its SiO2 contents. Carbonate-bearing phonolitic parental melts formed by mixing of both silicate and carbonate-asthenospheric melts from convecting mantle, react with wall-rock peridotite to form diopside + phlogopite + olivine + apatite metasomatic veins as wehrlitic metasomes. Partial melting of such newly generated wehrlitic metasomes in the subcontinental lithospheric mantle resulted in the parental melts of Kay?köy leucite ankaratrites. Results also imply that the nature and composition of asthenosphere-derived silicate melts (basanitic, phonolitic or tephriphonolitic in composition) and percentage of mixed carbonatitic melts lead to the formation of discrete mantle metasomes within the Inner Isparta Angle lithospheric mantle. These metasomes are conducive to the generation of coeval potassic magmas with contrasting geochemical signatures (e.g., lamproitic, lamprophyric, kamafugitic) in a single tectonic setting.
Abstract: Generation of ultra-alkaline melts by the interaction of lherzolite with cardonatites of various genesis was simulated at the P-T parameters typical of the base of the subcratonic lithosphere. Experiments with a duration of 150 h were performed at 5.5 and 6.3 GPa and 1350°C. The concentrations of CaO and MgO in melts are buffered by the phases of peridotite, and the concentrations of alkalis and FeO depend on the composition of the starting carbonatite. Melts are characterized by a low (<7 wt %) concentration of SiO2 and Ca# from 0.40 to 0.47. It is demonstrated that only high-Mg groups of carbonatitic inclusions in fibrous diamonds have a composition close to that of carbonatitic melts in equilibrium with lherzolite. Most likely, the formation of kimberlite-like melts relatively enriched in SiO2 requires an additional source of heat from mantle plumes and probably H2O fluid.
Contributions to Mineralogy and Petrology, Vol. 171, pp. 43-50.
Europe, Cape Verde Islands
Carbonatite
Abstract: The carbonatites of Brava Island, Cape Verde hot spot, allow to investigate whether they represent small mantle melt fractions or form through extreme fractionation and/or liquid immiscibility from CO2-bearing silicate magmas. The intrusive carbonatites on Brava Island are part of a strongly silica-undersaturated pyroxenite, ijolite, nephelinite, nepheline syenite, combeite-foiditite, carbonatite series. The major and trace element composition of this suite is reproduced by a model fractionating olivine, clinopyroxene, perovskite, biotite, apatite, titanite, sodalite and FeTi oxides, all present as phenocrysts in the rocks corresponding to their fractionation interval. Fractionation of ~90 wt% crystals reproduces the observed geochemical trend from the least evolved ultramafic dikes (bulk X Mg = 0.64) to syenitic compositions. The modelled fractional crystallization leads to alkali enrichment, driving the melt into the carbonatite-silicate miscibility gap. An initial CO2 content of 4000 ppm is sufficient to saturate in CO2 at the point where the rock record suggests continuing unmixing carbonatites from nephelinites to nepheline syenites after 61 wt% fractionation. Such immiscibility is also manifested in carbonatite and silicate domains on a hand-specimen scale. Furthermore, almost identical primary clinopyroxene, biotite and carbonate compositions from carbonatites and nephelinites to nepheline syenites substantiate their conjugate character and our unmixing model. The modelled carbonatite compositions correspond to the natural ones except for their much higher alkali contents. The alkali-poor character of the carbonatites on Brava and elsewhere is likely a consequence of the release of alkali-rich CO2 + H2O fluids during final crystallization, which cause fenitization in adjacent rocks. We propose a general model for carbonatite generation during alkaline magmatism, where the fractionation of heavily Si-undersaturated, alkaline parent melts results in alkali and CO2 enrichment in the evolving melt, ultimately leading to immiscibility between carbonatites and evolved Si-undersaturated alkaline melts. Early saturation in feldspathoids or feldspars would limit alkali enrichment preventing the formation of carbonatites. The complete and continuous fractionation line from almost primitive melts to syenitic compositions on Brava underlines the possibly important role of intrusives for hot spot volcanism.
Depositional evolution of southwest Gondwana Neoproterozoic paleobasins based on Sr, C and O isotopic compositions of carbonatic rocks from the Sul-Riograndense shield, Brazil.
Abstract: A dike -vein complex of potassic type of alkalinity recently discovered in the Baikal ledge, western Baikal area, southern Siberian craton, includes calcite and dolomite -ankerite carbonatites, silicate-bearing carbonatite, phlogopite metapicrite, and phoscorite. The most reliable 40Ar -39Ar dating of the rocks on magnesioriebeckite from alkaline metasomatite at contact with carbonatite yields a statistically significant plateau age of 1017.4 ± 3.2 Ma. The carbonatite is characterized by elevated SiO2 concentrations and is rich in K2O (K2O/Na2O ratio is 21 on average for the calcite carbonatite and 2.5 for the dolomite -ankerite carbonatite), TiO2, P2O5 (up to 9 wt %), REE (up to 3300 ppm), Nb (up to 400 ppm), Zr (up to 800 ppm), Fe, Cr, V, Ni, and Co at relatively low Sr concentrations. Both the metapicrite and the carbonatite are hundreds of times or even more enriched in Ta, Nb, K, and LREE relative to the mantle and are tens of times richer in Rb, Ba, Zr, Hf, and Ti. The high (Gd/Yb)CN ratios of the metapicrite (4.5 -11) and carbonatite (4.5 -17) testify that their source contained residual garnet, and the high K2O/Na2O ratios of the metapicrite (9 -15) and carbonatite suggest that the source also contained phlogopite. The Nd isotopic ratios of the carbonatite suggest that the mantle source of the carbonatite was mildly depleted and similar to an average OIB source. The carbonatites of various mineral composition are believed to be formed via the crystallization differentiation of ferrocarbonatite melt, which segregated from ultramafic alkaline melt.
Contributions to Mineralogy and Petrology, Vol. 171, 7, 9p.
Mantle
Carbonatite, kimberlite
Abstract: Kimberlites are rare diamond-bearing volcanic rocks that originate as melts in the Earth’s mantle. The original composition of kimberlitic melt is poorly constrained because of mantle and crustal contamination, exsolution of volatiles during ascent, and pervasive alteration during and after emplacement. One recent model (Russell et al. in Nature 481(7381):352 -356, 2012. doi:10.1038/nature10740) proposes that kimberlite melts are initially carbonatitic and evolve to kimberlite during ascent through continuous assimilation of orthopyroxene and exsolution of CO2. In high-temperature, high-pressure experiments designed to test this model, assimilation of orthopyroxene commences between 2.5 and 3.5 GPa by a reaction in which orthopyroxene reacts with the melt to form olivine, clinopyroxene, and CO2. No assimilation occurs at 3.5 GPa and above. We propose that the clinopyroxene produced in this reaction can react with the melt at lower pressure in a second reaction that produces olivine, calcite, and CO2, which would explain the absence of clinopyroxene phenocrysts in kimberlites. These experiments do not confirm that assimilation of orthopyroxene for the entirety of kimberlite ascent takes place, but rather two reactions at lower pressures (<3.5 GPa) cause assimilation of orthopyroxene and then clinopyroxene, evolving carbonatitic melts to kimberlite and causing CO2 exsolution that drives rapid ascent.
Journal of the Geological Society of India, Vol. 87, 6, pp. 709-715.
India
Carbonatite
Abstract: The Siriwasan carbonatite-sill along with associated alkaline rocks and fenites is located about 10 km north of the well-known Amba Dongar carbonatite-alkaline rocks diatreme, in the Chhota Udaipur carbonatite-alkaline province. Carbonatite has intruded as a sill into the Bagh sandstone and overlying Deccan basalt. This resulted in the formation of carbonatite breccia with enclosed fragments of basement metamorphics, sandstone and fenites in the matrix of ankeritic carbonatite. The most significant are the plugs of sovite with varied mineralogy that include pyroxene, amphibole, apatite, pyrochlore, perovskite and sphene. REE in sovites is related to the content of pyrochlore, perovskite and apatite. The carbon and oxygen isotopic compositions of some sovite samples and an ankeritic carbonatite plot in the "mantle box" pointing to their mantle origin. However, there is also evidence for mixing of the erupting carbonatite magma with the overlying Bagh limestone. The carbonatites of Siriwasan and Amba Dongar have the same Sr and Nd isotopic ratios and radiometric age, suggesting the same magma source. On the basis of available chemical analyses this paper is aimed to give some details of the Siriwasan carbonatites. The carbonatite complex has good potential for an economic mineral deposit but this is the most neglected carbonatite of the Chhota Udaipur province.
Abstract: Stable (C and O) isotope data from carbonates are one of the most important methods used to infer genetic processes in carbonatites. However despite their ubiquitous use in geological studies, it is suspected that carbonates are susceptible to dissolution-reprecipitation and isotopic resetting, especially in shallow intrusions, and may not be the best records of either igneous or hydrothermal processes. Apatite, however, should be much less susceptible to these resetting problems but has not been used for O isotope analysis. In this contribution, a novel bulk-carbonatite method for the analysis of O isotopes in the apatite PO4 site demonstrates a more robust record of stable isotope values. Analyses of apatite from five carbonatites with magmatic textures establishes a preliminary Primary Igneous Apatite (PIA) field of ?18O = + 2.5 to + 6.0‰ (VSMOW), comparable to Primary Igneous Carbonatite (PIC) compositions from carbonates. Carbonate and apatite stable isotope data are compared in 10 carbonatite samples from Songwe Hill, Malawi. Apatite is heavy rare earth element (HREE) enriched at Songwe and, therefore, oxygen isotope analyses of this mineral are ideal for understanding HREE-related mineralisation in carbonatites. Carbonate C and O isotope ratios show a general trend, from early to late in the evolution, towards higher ?18O values (+ 7.8 to + 26.7‰, VSMOW), with a slight increase in ?13C (? 4.6 to ? 0.1‰, VPDB). Oxygen isotope ratios from apatite show a contrary trend, decreasing from a PIA field towards more negative values (+ 2.5 to ? 0.7‰, VSMOW). The contrasting results are interpreted as the product of the different minerals recording fluid interaction at different temperatures and compositions. Modelling indicates the possibility of both a CO2 rich fluid and mixing between meteoric and deuteric waters. A model is proposed where brecciation leads to depressurisation and rapid apatite precipitation. Subsequently, a convection cell develops from a carbonatite, interacting with surrounding meteoric water. REE are likely to be transported in this convection cell and precipitate owing to decreasing salinity and/or temperature.
Journal of South American Earth Sciences, Vol. 71, pp. 248-261.
South America, Paraguay
Carbonatite
Abstract: This work describes rare accessory minerals in volcanic and subvolcanic silica-undersaturated peralkaline and agpaitic rocks from the Permo-Triassic Cerro Boggiani complex (Eastern Paraguay) in the Alto Paraguay Alkaline Province. These accessory phases consist of various minerals including Th-U oxides/silicates, Nb-oxide, REE-Sr-Ba bearing carbonates-fluorcarbonates-phosphates-silicates and Zr-Na rich silicates. They form a late-stage magmatic to deuteric/metasomatic assemblage in agpaitic nepheline syenites and phonolite dykes/lava flows made of sodalite, analcime, albite, fluorite, calcite, ilmenite-pyrophanite, titanite and zircon. It is inferred that carbonatitic fluids rich in F, Na and REE percolated into the subvolcanic system and metasomatically interacted with the Cerro Boggiani peralkaline and agpaitic silicate melts at the thermal boundary layers of the magma chamber, during and shortly after their late-stage magmatic crystallization and hydrothermal deuteric alteration.
Abstract: Among orogenic peridotites, dunites suffer the weakest crustal metasomatism at the slab-mantle interface and are the best lithology to trace the origins of orogenic peridotites and their initial geodynamic processes. Petrological and geochemical investigations of the Lijiatun dunites from the Sulu ultrahigh-pressure (UHP) terrane indicate a complex petrogenetic history involving melt extraction and multistage metasomatism (carbonatitic melt and slab-derived fluid). The Lijiatun dunites consist mainly of olivine (Fo = 92.0-92.6, Ca = 42-115 ppm), porphyroblastic orthopyroxene (En = 91.8-92.8), Cr-spinel (Cr# = 50.4-73.0, TiO2 < 0.2 wt.%) and serpentine. They are characterized by refractory bulk-rock compositions with high MgO (45.31-47.07 wt.%) and Mg# (91.5-91.9), and low Al2O3 (0.48-0.70 wt.%), CaO (0.25-0.44 wt.%) and TiO2 (< 0.03 wt.%) contents. Whole-rock platinum group elements (PGE) are similar to those of cratonic mantle peridotites and Re-Os isotopic data suggest that dunites formed in the early Proterozoic (~ 2.2 Ga). These data indicate that the Lijiatun dunites were the residues of ~ 30% partial melting and were derived from the subcontinental lithospheric mantle (SCLM) beneath the North China craton (NCC). Subsequent carbonatitic metasomatism is characterized by the formation of olivine-rich (Fo = 91.6-92.6, Ca = 233-311 ppm), clinopyroxene-bearing (Mg# = 95.9-96.7, Ti/Eu = 104-838) veins cutting orthopyroxene porphyroblasts. Based on the occurrence of dolomite, mass-balance calculation and thermodynamic modeling, carbonatitic metasomatism had occurred within the shallow SCLM (low-P and high-T conditions) before dunites were incorporated into the continental subduction channel. These dunites then suffered weak metasomatism by slab-derived fluids, forming pargasitic amphibole after pyroxene. This work indicates that modification of the SCLM beneath the eastern margin of the NCC had already taken place before the Triassic continental subduction. Orogenic peridotites derived from such a lithospheric mantle wedge may be heterogeneously modified prior to their incorporation into the subduction channel, which would set up a barrier for investigation of the mass transfer from the subducted crust to the mantle wedge through orogenic peridotites.
Abstract: The Okorusu Alkaline Igneous-Carbonatite Complex is located about 50 km north of Otjiwarongo in North-Central Namibia. The complex was intruded during early Cretaceous into late Precambrian Damaran Series metasedimentary rocks. It is nearly circular in plan view with a diameter of about 8 km. Coarse-grained nepheline syenites and foyaites are exposed in low hills near the northern edge of the complex. Early alkalie-rich fluids pervasively fenitized the metasedimentary rocks along the southern margin of the complex forming an east-west ridge of resistant hills that include Okorusu Mountain. The fenites were subsequently brecciated and intruded by several carbonatites, especially medium-grained iron-rich diopside pyroxene carbonitite and very coarse-grained pegmatitic carbonatite. In addition to predominant calcite, the carbonatites contain titaniferous vanadiferous magnetite crystals and diopside crystals as large as one-third meter and hexagonal pyrrhotite crystals as long as one meter. For the past two decades, Okoruru has been the leading carbonatite-related fluorspar producer in the world. Fluorspar has been mined from five separate ore deposits in open pits A, B, C, D, and E. The deposits formed principally by the replacement of carbonatite as shown by local unreplaced remnants of carbonatite in the fluorspar ores, goethite pseudomorphs in fluorspar ores after carbonatite magnetite, diopside, and pyrrhotite crystals, transitions of the ores into carbonatite, and by elevated phosphorus contents resulting from carbonatite apatite crystals that were incompletely replaced by fluorite. Locally, marbles also are replaced by fluorite to form fluorspar ores that are distinguished from carbonatite-replacement fluorspar ores by their finer grain size and lack of phosphorus contents. Fluid inclusions in the fluorite crystals indicate that the fluorspar ores were deposited from 166 to 128oC from fluids of low salinity with less than 5% NaCl equivalent. The genesis of the fluorspar ores is interpreted to have resulted from deeply circulated ground waters that dissolved fluorine from carbonatite at depth. The fluorine in those ore fluids combined with calcium released during the replacement of calcite in carbonatite and marbles at the sites of the fluorspar ore deposition.
Abstract: The Magnet Cove Alkaline Intrusive Complex contains several silica-undersaturated igneous rock types (e.g. nepheline syenite, ijolite, carbonatite) that form a concentric ring map pattern approximately 4.6 square miles in area. These rings, which are likely the result of several nearly contemporaneous magma injection events during the mid Cretaceous, become increasingly silica-undersaturated from rim to core, and have been previously mapped as separate geologic units. The outer ring contains nepheline syenite, the intermediate ring contains both garnet ijolite and garnet biotite ijolite, and the core contains carbonatite. Though the detailed modal mineralogy differs somewhat between the silicate (i.e. syenite and ijolite) rock types, they all have in common the presence of mica group minerals. The purpose of this study is to examine and characterize the diversity of mica group minerals found in the silica-undersaturated rocks of Magnet Cove. Syenite and ijolite rock samples were collected from several locations within the complex, and thin sections were prepared for petrographic and electron microscope analysis using facilities and equipment at the UALR Rock Preparation Laboratory. Overall mineralogy from these samples indicates the presence of potassium feldspar, plagioclase feldspar, several feldspathoid minerals (nepheline, sodalite, altered leucite), amphiboles, pyroxenes (primarily aegerine and aegerine-augite), black Ti-bearing garnets (melanite, schorlomite), and various opaque minerals (e.g. magnetite, pyrite). Previously, micas in these rocks have been labeled simply as “biotite”. However, the ranges of color (yellowish-brown to bluish-green), crystal size (millimeter to several centimeters in diameter), and crystal habit (clusters of euhedral grains) in hand sample and variable pleochroism, ranging interference colors, reaction coronas, and zoning in thin section indicate a more interesting and complex chemical history.
Abstract: The southeast Mojave Desert hosts one of the world’s largest rare earth element (REE) deposits at Mountain Pass, California. Although surface geology has been studied, a full understanding of the carbonatite and associated intrusive suite complex requires subsurface geophysical characterization. In this study, a combination of geophysical methods, including magnetotelluric (MT), magnetics, and gravity are used to create a two-dimensional (2D) geophysical model to a depth of about 10 km. An electrically conductive body is found 2-3 km below and west of the deposit that is associated with a magnetic high that could be connected to a deeper (10 km) conductive body related to possible intrusions or hydrothermal systems. The carbonatite body coincides with a steep magnetic gradient and a bench or terrace in the gravity data that may reflect relative lower-density intrusive rocks. Although carbonatite rocks are typically magnetic, the carbonatite rocks, associated intrusive suite, and host rocks in this area are essentially non-magnetic. Combined geophysical data indicate that the enriched REE deposit may be related to a regional extensive hydrothermal alteration event.
Progress in Earth and Planetary Science, Vol. 3, 18p.
Mantle
Carbonatite
Abstract: Current knowledge on the solidus temperature for carbonated eclogites suggests that carbonatitic liquids should not form from a subducted oceanic lithosphere at sub-arc depth. However, the oceanic crust includes a range of gabbroic rocks, altered on rifts and transforms, with large amounts of anorthite-rich plagioclase forming epidote on metamorphism. Epidote disappearance with pressure depends on the normative anorthite content of the bulk composition; we therefore expect that altered gabbros might display a much wider pressure range where epidote persists, potentially affecting the solidus relationships. A set of experimental data up to 4.6 GPa, and 1000 °C, including new syntheses on mafic eclogites with 36.8 % normative anorthite, is discussed to unravel the effect of variable bulk and volatile compositions in model eclogites, enriched in the normative anorthite component (An 37 and An 45). Experiments are performed in piston cylinder and multianvil machines. Garnet, clinopyroxene, and coesite form in all syntheses. Lawsonite was found to persist at 3.7 GPa, 750 °C, with both dolomite and magnesite; at 3.8 GPa, 775-800 °C, fluid-saturated conditions, epidote coexists with kyanite, dolomite, and magnesite. The anhydrous assemblage garnet, omphacite, aragonite, and kyanite is found at 4.2 GPa, 850 °C. At 900 °C, a silicate glass of granitoid composition, a carbonatitic precipitate, and Na-carbonate are observed. Precipitates are interpreted as evidence of hydrous carbonatitic liquids at run conditions; these liquids produced are richer in Ca compared to experimental carbonatites from anhydrous experiments, consistently with the dramatic role of H2O in depressing the solidus temperature for CaCO3. The fluid-absent melting of the assemblage epidote + dolomite, enlarged in its pressure stability for An-rich gabbros, is expected to promote the generation of carbonatitic liquids. The subsolidus breakdown of epidote in the presence of carbonates at depths exceeding 120 km provides a major source of C-O-H volatiles at sub-arc depth. In warm subduction zones, the possibility of extracting carbonatitic liquids from a variety of gabbroic rocks and epidosites offers new scenarios on the metasomatic processes in the lithospheric wedge of subduction zones and a new mechanism for recycling carbon.
Abstract: Among orogenic peridotites, dunites suffer the weakest crustal metasomatism at the slab-mantle interface and are the best lithology to trace the origins of orogenic peridotites and their initial geodynamic processes. Petrological and geochemical investigations of the Lijiatun dunites from the Sulu ultrahigh-pressure (UHP) terrane indicate a complex petrogenetic history involving melt extraction and multistage metasomatism (carbonatitic melt and slab-derived fluid). The Lijiatun dunites consist mainly of olivine (Fo = 92.0-92.6, Ca = 42-115 ppm), porphyroblastic orthopyroxene (En = 91.8-92.8), Cr-spinel (Cr# = 50.4-73.0, TiO2 < 0.2 wt.%) and serpentine. They are characterized by refractory bulk-rock compositions with high MgO (45.31-47.07 wt.%) and Mg# (91.5-91.9), and low Al2O3 (0.48-0.70 wt.%), CaO (0.25-0.44 wt.%) and TiO2 (< 0.03 wt.%) contents. Whole-rock platinum group elements (PGE) are similar to those of cratonic mantle peridotites and Re-Os isotopic data suggest that dunites formed in the early Proterozoic (~ 2.2 Ga). These data indicate that the Lijiatun dunites were the residues of ~ 30% partial melting and were derived from the subcontinental lithospheric mantle (SCLM) beneath the North China craton (NCC). Subsequent carbonatitic metasomatism is characterized by the formation of olivine-rich (Fo = 91.6-92.6, Ca = 233-311 ppm), clinopyroxene-bearing (Mg# = 95.9-96.7, Ti/Eu = 104-838) veins cutting orthopyroxene porphyroblasts. Based on the occurrence of dolomite, mass-balance calculation and thermodynamic modeling, carbonatitic metasomatism had occurred within the shallow SCLM (low-P and high-T conditions) before dunites were incorporated into the continental subduction channel. These dunites then suffered weak metasomatism by slab-derived fluids, forming pargasitic amphibole after pyroxene. This work indicates that modification of the SCLM beneath the eastern margin of the NCC had already taken place before the Triassic continental subduction. Orogenic peridotites derived from such a lithospheric mantle wedge may be heterogeneously modified prior to their incorporation into the subduction channel, which would set up a barrier for investigation of the mas
Abstract: Rare earth element (REE) ore-bearing carbonatite dikes and a stock at Mountain Pass, California, are spatially associated with a suite of ultrapotassic plutonic rocks, and it has been proposed that the two are genetically related. This hypothesis is problematic, given that existing geochronological constraints indicate that the carbonatite is ?15-25 Myr younger than the ultrapotassic rocks, requiring alternative models for the formation of the REE ore-bearing carbonatite during a separate event and/or via a different mechanism. New laser ablation split-stream inductively coupled plasma mass spectrometry (LASS-ICP-MS) petrochronological data from ultrapotassic intrusive rocks from Mountain Pass yield titanite and zircon U-Pb dates from 1429?±?10 to 1385?±?18?Ma, expanding the age range of the ultrapotassic rocks in the complex by ?20 Myr. The ages of the youngest ultrapotassic rocks overlap monazite Th-Pb ages from a carbonatite dike and the main carbonatite ore body (1396?±?16 and 1371?±?10?Ma, respectively). The Hf isotope compositions of zircon in the ultrapotassic rocks are uniform, both within and between samples, with a weighted mean ?Hfi of 1•9?±?0•2 (MSWD?=?0•9), indicating derivation from a common, isotopically homogeneous source. In contrast, in situ Nd isotopic data for titanite in the ultrapotassic rocks are variable (?Ndi?=?-3•5 to -12), suggesting variable contamination by an isotopically enriched source. The most primitive ?Ndi isotopic signatures, however, do overlap ?Ndi from monazite (?Ndi?=?-2•8?±?0•2) and bastnäsite (?Ndi?=?-3•2?±?0•3) in the ore-bearing carbonatite, suggesting derivation from a common source. The data presented here indicate that ultrapotassic magmatism occurred in up to three phases at Mountain Pass (?1425, ?1405, and ?1380?Ma). The latter two stages were coeval with carbonatite magmatism, revealing previously unrecognized synchronicity in ultrapotassic and carbonatite magmatism at Mountain Pass. Despite this temporal overlap, major and trace element geochemical data are inconsistent with derivation of the carbonatite and ultrapotassic rocks by liquid immiscibility or fractional crystallization from common parental magma. Instead, we propose that the carbonatite was generated as a primary melt from the same source as the ultrapotassic rocks, and that although it is unique, the Mountain Pass ultrapotassic and carbonatite suite is broadly similar to other alkaline silicate-carbonatite occurrences in which the two rock types were generated as separate mantle melts.
Abstract: The global boron geochemical cycle is closely linked to recycling of geologic material via subduction processes that have occurred over billions of years of Earth’s history. The origin of carbonatites, unique melts derived from carbon-rich and carbonate-rich regions of the upper mantle, has been linked to a variety of mantle-related processes, including subduction and plume-lithosphere interaction. Here we present boron isotope (?11B) compositions for carbonatites from locations worldwide that span a wide range of emplacement ages (between ~40 and ~2,600?Ma). Hence, they provide insight into the temporal evolution of their mantle sources for ~2.6 billion years of Earth’s history. Boron isotope values are highly variable and range between ?8.6 and +5.5, with all of the young (<300?Ma) carbonatites characterized by more positive ?11B values (>?4.0‰ whereas most of the older carbonatite samples record lower B isotope values. Given the ?11B value for asthenospheric mantle of ?7 ± 1‰ the B isotope compositions for young carbonatites require the involvement of an enriched (crustal) component. Recycled crustal components may be sampled by carbonatite melts associated with mantle plume activity coincident with major tectonic events, and linked to past episodes of significant subduction associated with supercontinent formation.
International Geology Review, Vol. 58, 12, pp. 1461-1480.
India
Carbonatite
Abstract: The South Indian Granulite Terrane (SGT) is a collage of Archaean to Neoproterozoic age granulite facies blocks that are sutured by an anastomosing network of large-scale shear systems. Besides several Neoproterozoic carbonatite complexes emplaced within the Archaean granulites, there are also smaller Paleoproterozoic (2.4 Ga, Hogenakkal) carbonatite intrusions within two NE-trending pyroxenite dikes. The Hogenakkal carbonatites, further discriminated into sövite and silicate sövite, have high Sr and Ba contents and extreme light rare earth element (LREE) enrichment with steep slopes typical of carbonatites. The C- and O-isotopic ratios [?13CVPDB = ?6.7 to ?5.8‰ and ?18OVSMOW = 7.5-8.7‰ except a single 18O-enriched sample (?18O = 20.0‰)] represent unmodified mantle compositions. The ?Nd values indicate two groupings for the Hogenakkal carbonatites; most samples show positive ?Nd values, close to CHUR (?Nd = ?0.35 to 2.94) and named high-?Nd group while the low-?Nd group samples show negative values (?5.69 to ?8.86), corresponding to depleted and enriched source components, respectively. The 87Sr/86Sri ratios of the two groups also can be distinguished: the high-?Nd ones have low 87Sr/86Sri ratios (0.70161-0.70244) while the low-?Nd group shows higher ratios (0.70247-0.70319). We consider the Nd-Sr ratios as primary and infer derivation from a heterogeneous mantle source. The emplacement of the Hogenakkal carbonatites may be related to Paleoproterozoic plume induced large-scale rifting and fracturing related to initiation of break-up of the Neoarchean supercontinent Kenorland.
Abstract: Compared to all published data from carbonatites and granitoids, the fluorapatite compositions in the Songwe Hill carbonatite, determined by EPMA and LA ICP-MS, have the highest heavy (H)REE concentration of any carbonatite apatite described so far. A combination of this fluorapatite and the REE fluorocarbonates, synchysite-(Ce) and parisite-(Ce), which are the other principal REE bearing minerals at Songwe, gives a REE deposit with a high proportion of Nd and a higher proportion of HREE (Eu-Lu including Y) than most other carbonatites. Since Nd and HREE are currently the most sought REE for commercial applications, the conditions that give rise to this REE profile are particularly important to understand. Multiple apatite crystallisation stages have been differentiated texturally and geochemically at Songwe and fluorapatite is divided into five different types (Ap-0-4). While Ap-0 and Ap-1 are typical of apatite found in fenite and calcite-carbonatite, Ap-2, -3 and -4 are texturally atypical of apatite from carbonatite and are progressively HREE-enriched in later paragenetic stages. Ap-3 and Ap-4 exhibit anhedral, stringer-like textures and their REE distributions display an Y anomaly. These features attest to formation in a hydrothermal environment and fluid inclusion homogenisation temperatures indicate crystallisation occurred between 200-350 °C. Ap-3 crystallisation is succeeded by a light (L)REE mineral assemblage of synchysite-(Ce), strontianite and baryte. Finally, late-stage Ap-4 is associated with minor xenotime-(Y) mineralisation and HREE-enriched fluorite. Fluid inclusions in the fluorite constrain the minimum HREE mineralisation temperature to approximately 160 °C. A model is suggested where sub-solidus, carbonatite-derived, (carbo)-hydrothermal fluids remobilise and fractionate the REE. Chloride or fluoride complexes retain LREE in solution while rapid precipitation of apatite, owing to its low solubility, leads to destabilisation of HREE complexes and substitution into the apatite structure. The LREE are retained in solution, subsequently forming synchysite-(Ce). This model will be applicable to help guide exploration in other carbonatite complexes.
Abstract: In situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and electron probe microanalysis (EPMA) are used to characterize magnetite and ilmenite of the phoscorite-carbonatite association at Phalaborwa. We trace the behavior of the compatible elements for two different generations of magnetite related to (1) a magmatic stage, with variable Ti-V content, which pre-dates the copper mineralization, and (2) a late hydrothermal, low-Ti, low-temperature event, mostly post-dating sulfide formation. Magnetite is shown to be a robust petrogenetic indicator; no influence on its chemical composition is detected from the intergrowth with the accompanying phases, including the interaction with coexisting sulfides. High spatial resolution EPMA characterize the tiny late-stage hydrothermal magnetite veins, as well as the ilmenite granular and lamellar exsolutions mostly developed in the magnetite from the phoscorite. By combining geochemical data with geothermo-oxybarometry calculations for magnetite-ilmenite pairs, we infer that the most primitive magnetite probably formed at oxygen fugacity above the nickel nickel oxide (NNO) buffer, revealing an evolutionary trend of decreasing temperature and oxygen fugacity. Geochemical similarity exists between magnetite from phoscorite and carbonatite, thus supporting a common mantle source for the phoscorite-carbonatite association.
Abstract: Fe-rich carbonatites with a mineral assemblage of ankerite-calcite or siderite are widespread in southern Siberia, Russia. The siderite carbonatites are associated with F-Ba-Sr-REE mineralization and have a 40Ar/39Ar age of 117.2 ± 1.3 Ma. Melt and fluid inclusions suggest that the carbonatites formed from volatile-rich alkali- and chloride-bearing carbonate melts. Ankerite-calcite carbonatites formed from carbonatite melt at a temperature of more than 790 °C. The ferrocarbonatites (the second phase of carbonatite intrusion) formed from a sulfate-carbonate-chloride fluid phase (brine-melt) at >650 °C and ?360 MPa. The brine-melt fluid phase had high concentrations of Fe and LREEs. A subsequent hydrothermal overprint contributed to the formation of economically important barite-Sr-fluorite-REE mineralization in polymict siderite breccia.
Doklady Earth Sciences, Vol. 471, 1, pp. 1140-1143.
Russia
Carbonatite
Abstract: Apatite and biotite from dolomite?ankerite and calcite?dolomite carbonatite dikes emplaced into the Paleoproterozoic metamorphic rock complex in the southern part of the Siberian Craton are dated by the U-Pb (LA-ICP-MS) and 40Ar-39Ar methods, respectively. Proceeding from the lower intercept of discordia with concordia, the age of apatite from calcite?dolomite carbonatite is estimated to be 972 ± 21 Ma and that for apatite from dolomite?ankerite carbonatite, as 929 ± 37 Ma. Values derived from their upper intercept have no geological sense. The ages obtained for biotite by the 40Ar-39Ar method are 965 ± 9 and 975 ± 14 Ma. It means that the formation of carbonatites reflects the earliest phases of the Neoproterozoic stage in extension of the continental lithosphere.
Abstract: A comprehensive study including new field, petrological and geochemical data is reported on the Jacupiranga alkaline-carbonatite complex (133-131 Ma) which, together with other alkaline complexes, occurs in southern Brazil and is coeval with the Paraná CFB province. It consists of a shallow intrusion (ca. 65 km2) in the Precambrian crystalline basement, and can be subdivided in two main diachronous plutonic bodies: an older dunite-gabbro-syenite in the NW and a younger clinopyroxenite-ijolite (s.l.) in the SE, later injected by a carbonatitic core (ca. 1 km2). An integrated petrogenetic model, based on bulk rock major and trace element analyses, mineral chemistry and Sr-Nd-Pb-C isotopic data, suggests that the two silicate intrusions generated from different mantle-derived magmas that evolved at shallow level (2-3 km depth) in two zoned cup-shaped plutonic bodies growing incrementally from independent feeding systems. The first intrusion was generated by OIB-like alkaline to mildly alkaline parental basalts that initially led to the formation of a dunitic adcumulate core, discontinuously surrounded by gabbroic cumulates, in turn injected by subanular syenite intrusive and phonolite dykes. Nephelinitic (± melilite) melts - likely generated deep in the lithosphere at ? 3 GPa - were the parental magmas of the second intrusion and gave rise to large coarse-grained clinopyroxenite ad- to meso-cumulates, in turn surrounded, and partially cut, by semi-annular fine-layered melteigite-ijolite-urtite ortho-cumulates. The available isotopic data do not evidence genetic links between carbonatites and the associated silicate intrusions, thus favouring an independent source from the mantle. Moreover, it may be suggested that, unlike gabbro-syenites and carbonatites, mostly generated from lithospheric mantle sources, the parental magmas of the ijolite-clinopyroxenite intrusion also record the influence of sublithospheric (plume-related?) geochemical components.
Abstract: The Late Cretaceous (ca. 100 Ma) diamondiferous Fort à la Corne (FALC) kimberlite field in the Saskatchewan (Sask) craton, Canada, is one of the largest known kimberlite fields on Earth comprising essentially pyroclastic kimberlites. Despite its discovery more than two decades ago, petrological, geochemical and petrogenetic aspects of the kimberlites in this field are largely unknown. We present here the first detailed petrological and geochemical data combined with reconnaissance Nd isotope data on drill-hole samples of five major kimberlite bodies. Petrography of the studied samples reveals that they are loosely packed, clast-supported and variably sorted, and characterised by the presence of juvenile lapilli, crystals of olivine, xenocrystal garnet (peridotitic as well as eclogitic paragenesis) and Mg-ilmenite. Interclast material is made of serpentine, phlogopite, spinel, carbonate, perovskite and rutile. The mineral compositions, whole-rock geochemistry and Nd isotopic composition (Nd: + 0.62 to ? 0.37) are indistinguishable from those known from archetypal hypabyssal kimberlites. Appreciably lower bulk-rock CaO (mostly < 5 wt%) and higher La/Sm ratios (12-15; resembling those of orangeites) are a characteristic feature of these rocks. Their geochemical composition excludes any effects of significant crustal and mantle contamination/assimilation. The fractionation trends displayed suggest a primary kimberlite melt composition indistinguishable from global estimates of primary kimberlite melt, and highlight the dominance of a kimberlite magma component in the pyroclastic variants. The lack of Nb-Ta-Ti anomalies precludes any significant role of subduction-related melts/fluids in the metasomatism of the FALC kimberlite mantle source region. Their incompatible trace elements (e.g., Nb/U) have OIB-type affinities whereas the Nd isotope composition indicates a near-chondritic to slightly depleted Nd isotope composition. The Neoproterozoic (~ 0.6-0.7 Ga) depleted mantle (TDM) Nd model ages coincide with the emplacement age (ca. 673 Ma) of the Amon kimberlite sills (Baffin Island, Rae craton, Canada) and have been related to upwelling protokimberlite melts during the break-up of the Rodinia supercontinent and its separation from Laurentia (North American cratonic shield). REE inversion modelling for the FALC kimberlites as well as for the Jericho (ca. 173 Ma) and Snap Lake (ca. 537 Ma) kimberlites from the neighbouring Slave craton, Canada, indicate all of their source regions to have been extensively depleted (~ 24%) before being subjected to metasomatic enrichment (1.3-2.2%) and subsequent small-degree partial melting. These findings are similar to those previously obtained on Mesozoic kimberlites (Kaapvaal craton, southern Africa) and Mesoproterozoic kimberlites (Dharwar craton, southern India). The striking similarity in the genesis of kimberlites emplaced over broad geological time and across different supercontinents of Laurentia, Gondwanaland and Rodinia, highlights the dominant petrogenetic role of the sub-continental lithosphere. The emplacement of the FALC kimberlites can be explained both by the extensive subduction system in western North America that was established at ca. 150 Ma as well as by far-field effects of the opening of the North Atlantic ocean during the Late Cretaceous.
Journal of Asian Earth Sciences, in press available, 134p.
China, Tibet
Carbonatite
Abstract: The Cenozoic Mianning-Dechang (MD) rare earth element (REE) belt in eastern Tibet is an important source of light REE in southwest China. The belt is 270 km long and 15 km wide. The total REE resources are >3 Mt of light rare earth oxides (REO), including 3.17 Mt of REO at Maoniuping (average grade = 2.95 wt.%), 81,556 t at Dalucao (average grade = 5.21 wt.%), 0.1 Mt at Muluozhai (average grade = 3.97 wt.%), and 5764 t of REO at Lizhuang (average grade = 2.38 wt.%). Recent results from detailed geological surveys, and studies of petrographic features, ore-forming ages, ore forming conditions, and wallrock alteration are synthesized in this paper. REE mineralization within this belt is associated with carbonatite-syenite complexes, with syenites occurring as stocks intruded by carbonatitic sills or dikes. The mineralization is present as complex vein systems that contain veinlet, stringer, stockwork, and brecciated pipe type mineralization. Carbonatites in these carbonatite-related REE deposits (CARDs) are extremely rich in light REEs, Sr (>5000 ppm), and Ba (>1000 ppm), and have low Sr/Ba and high Ba/Th ratios, and radiogenic Sr-Nd isotopic compositions. These fertile magmas, which may lead to the formation of REE deposits, were generated by the partial melting of sub-continental lithospheric mantle (SCLM) that was metasomatized by REE- and CO2-rich fluids derived from subducted marine sediments. We suggest that this refertilization occurred along cratonic margins and, in particular, at a convergent margin where small-volume carbonatitic melts ascended along trans-lithospheric faults and transported REEs into the overlying crust, leading to the formation of the CARDs. The formation of fertile carbonatites requires a thick lithosphere and/or high pressures (>25 kbar), a metasomatized and enriched mantle source, and favorable pathways for magma to ascend into the overlying crust where REE-rich fluids exsolve from cooling magma. The optimal combination of these three factors only occurs along the margins of a craton with a continental root, rather than in modern subduction zones where the lithosphere is relatively thin. U-Pb zircon dating indicates that the Maoniuping, Lizhuang, and Muluozhai alkali igneous complexes in the northern part of the belt formed at 27-22 Ma, whereas the Dalucao complex in the southern part of the belt formed at 12-11 Ma. Biotite and arfvedsonite in Lizhuang and Maoniuping REE deposit have 40Ar/39Ar ages of 30.8 ± 0.4 Ma (MSWD = 0.98) and 27.6 ± 2.0 Ma (MSWD = 0.06), respectively. Biotitaion alteration in syenite and fenitization caused by the relatively amount of carbonatite on syenite and host rocks is the main alteration along the whole belt. Initial Sr (0.7059-0.7079), 143Nd/144Nd (0.5123-0.5127), and 207Pb/204Pb (15.601-15.628) and 208Pb/204Pb (38.422-38.604) isotopic compositions of fluorite, barite, celestite, and calcite in the MD belt are similar to those of the associated syenite and carbonatite. Given the relatively high contents of Cl, F, SO42-, and CO2 in the rocks of the complexes, it is likely that the REEs were transported by these ligands within hydrothermal fluids, and the presence of bastnäsite indicates that the REEs were precipitated as fluorocarbonates. Petrographic, fluid inclusion, and field studies of the ores indicate that bastnäsite and other REE minerals formed during the final stages (<300°C) of the evolution of magmatic-hydrothermal systems in the belt. The mineralization formed from magmatic and meteoric fluids containing CO2 derived from the decarbonation of carbonatite, as indicated by C-O isotopic values of hydrothermal calcite and bastnäsite (?13C= -4.8 to -8.7 and ?18O = 5.8 to 12.5 ‰) and O-H isotopic values of quartz (330°C) and arfvedsonite (260°C), which correspond to fluid isotope compositions of ?18O = 0.3 to 9.8‰ and ?D = -70.0 to -152.8‰ in the belt. This study indicates that formation the largest REE deposits are related to voluminous carbonatite-syenite complexes, compositionally similar ore-forming fluids, extensive alteration, multiple stages of REE mineralization, and tectonic setting.
Abstract: SiC and associated ultra-reduced minerals were reported in various geological settings, however, their genesis and preservation mechanism are poorly understood. Here, we reported a SiC-dominated ultra-reduced mineral assemblage, including SiC, TiC, native metals (Si, Fe, and Ni) and iron silicide, from carbonatitic xenoliths in Dalihu, Inner Mongolia. All minerals were identified in situ in polished/thin sections. SiC is 20-50 ?m in size, blue to colorless in color, and usually identified in the micro-cavities within the carbonatitic xenolith. Four types of SiC polytypes were identified, which are dominated by ?-SiC (3C polytype) and 4H polytype followed by 15R and 6H. These SiC are featured by 13C-depleted isotopic compositions (?13C = ?13.2 to ?22.8‰, average = ?17.7‰) with obvious spatial variation. We provided a numerical modeling method to prove that the C isotopic composition of the Dalihu SiC can be well-yielded by degassing. Our modeling results showed that degassing reaction between graphite and silicate can readily produce the low ?13C value of SiC, and the spatial variations in C isotopic composition could have been formed in the progressive growth process of SiC. The detailed in situ occurring information is beneficial for our understanding of the preservation mechanism of the Dalihu ultra-reduced phase. The predominant occurrence of SiC in micro-cavities implies that exsolution and filling of CO2 and/or CO in the micro-cavities during the diapir rising process of carbonatitic melt could have buffered the reducing environment and separated SiC from the surrounding oxidizing phases. The fast cooling of host rock, which would leave insufficient time for the complete elimination of SiC, could have also contributed to the preservation of SiC.
Abstract: Alkaline rock and carbonatite complexes, including the Prairie Lake complex (NW Ontario), are widely distributed in the Canadian region of the Midcontinent Rift in North America. It has been suggested that these complexes were emplaced during the main stage of rifting magmatism and are related to a mantle plume. The Prairie Lake complex is composed of carbonatite, ijolite and potassic nepheline syenite. Two samples of baddeleyite from the carbonatite yield U-Pb ages of 1157.2±2.3 and 1158.2±3.8 Ma, identical to the age of 1163.6±3.6 Ma obtained for baddeleyite from the ijolite. Apatite from the carbonatite yields the same U-Pb age of ~1160 Ma using TIMS, SIMS and laser ablation techniques. These ages indicate that the various rocks within the complex were synchronously emplaced at about 1160 Ma. The carbonatite, ijolite and syenite have identical Sr, Nd and Hf isotopic compositions with a 87Sr/86Sr ratio of ~0.70254, and positive ?Nd(t)1160 and ?Hf(t)1160 values of ~+3.5 and ~+4.6, respectively, indicating that the silicate and carbonatitic rocks are co-genetic and related by simple fractional crystallization from a magma derived from a weakly depleted mantle. These age determinations extend the period of magmatism in the Midcontinent Rift in the Lake Superior area to 1160 Ma, but do not indicate whether the magmatism is associated with passive continental rifting or the initial stages of plume-induced rifting.
Journal of Asian Earth Sciences, Vol. 137, pp. 35-79.
China, Tibet
Carbonatite
Abstract: he Cenozoic Mianning-Dechang (MD) rare earth element (REE) belt in eastern Tibet is an important source of light REE in southwest China. The belt is 270 km long and 15 km wide. The total REE resources are >3 Mt of light rare earth oxides (REO), including 3.17 Mt of REO at Maoniuping (average grade = 2.95 wt.%), 81,556 t at Dalucao (average grade = 5.21 wt.%), 0.1 Mt at Muluozhai (average grade = 3.97 wt.%), and 5764 t of REO at Lizhuang (average grade = 2.38 wt.%). Recent results from detailed geological surveys, and studies of petrographic features, ore-forming ages, ore forming conditions, and wallrock alteration are synthesized in this paper. REE mineralization within this belt is associated with carbonatite-syenite complexes, with syenites occurring as stocks intruded by carbonatitic sills or dikes. The mineralization is present as complex vein systems that contain veinlet, stringer, stockwork, and brecciated pipe type mineralization. Carbonatites in these carbonatite-related REE deposits (CARDs) are extremely rich in light REEs, Sr (>5000 ppm), and Ba (>1000 ppm), and have low Sr/Ba and high Ba/Th ratios, and radiogenic Sr-Nd isotopic compositions. These fertile magmas, which may lead to the formation of REE deposits, were generated by the partial melting of sub-continental lithospheric mantle (SCLM) that was metasomatized by REE- and CO2-rich fluids derived from subducted marine sediments. We suggest that this refertilization occurred along cratonic margins and, in particular, at a convergent margin where small-volume carbonatitic melts ascended along trans-lithospheric faults and transported REEs into the overlying crust, leading to the formation of the CARDs. The formation of fertile carbonatites requires a thick lithosphere and/or high pressures (>25 kbar), a metasomatized and enriched mantle source, and favorable pathways for magma to ascend into the overlying crust where REE-rich fluids exsolve from cooling magma. The optimal combination of these three factors only occurs along the margins of a craton with a continental root, rather than in modern subduction zones where the lithosphere is relatively thin.
Abstract: Metasomatic processes are responsible for many of the heterogeneities found in the upper mantle. To better understand the metasomatism in the lithospheric mantle and to illustrate the differences between metasomatism caused by hydrous silicate and carbonate-rich melts, we performed various interaction experiments: (1) Reactions between hydrous eclogite-derived melts and peridotite at 2.2-2.5 GPa and 900-1000 °C reproduce the metasomatism in the mantle wedge above subduction zones. (2) Reactions between carbonate-rich melts and peridotite at 2.5 GPa and 1050-1000 °C, and at 6 GPa and 1200-1250 °C simulate metasomatism of carbonatite and ultramafic silicate-carbonate melts in different regions of cratonic lithosphere. Our experimental results show that partial melting of hydrous eclogite produces hydrous Si- and Al-rich melts that react with peridotite and form bi-mineralic assemblages of Al-rich orthopyroxene and Mg-rich amphibole. We also found that carbonate-rich melts with different compositions react with peridotite and form new metasomatic wehrlitic mineral assemblages. Metasomatic reactions caused by Ca-rich carbonatite melt consume the primary peridotite and produce large amounts of metasomatic clinopyroxene; on the other hand, metasomatism caused by ultramafic silicate-carbonate melts produces less clinopyroxene. Furthermore, our experiments show that ultramafic silicate-carbonate melts react strongly with peridotite and cause crystallization of large amounts of metasomatic Fe-Ti oxides. The reactions of metasomatic melts with peridotite also change the melt composition. For instance, if the carbonatite melt is not entirely consumed during the metasomatic reactions, its melt composition may change dramatically, generating an alkali-rich carbonated silicate melt that is similar in composition to type I kimberlites.
Contributions to Mineralogy and Petrology, in press available 22p.
Mantle
Metasomatism, magmatism, carbonatite
Abstract: Hydrous K-rich kimberlite-like systems are studied experimentally at 5.5-7.5 GPa and 1200-1450 °C in terms of phase relations and conditions for formation and stability of phlogopite. The starting samples are phlogopite-carbonatite-phlogopite sandwiches and harzburgite-carbonatite mixtures consisting of Ol + Grt + Cpx + L (±Opx), according to the previous experimental results obtained at the same P-T parameters but in water-free systems. Carbonatite is represented by a K- and Ca-rich composition that may form at the top of a slab. In the presence of carbonatitic melt, phlogopite can partly melt in a peritectic reaction at 5.5 GPa and 1200-1350 °C, as well as at 6.3-7.0 GPa and 1200 °C: 2Phl + CaCO3 (L)?Cpx + Ol + Grt + K2CO3 (L) + 2H2O (L). Synthesis of phlogopite at 5.5 GPa and 1200-1350 °C, with an initial mixture of H2O-bearing harzburgite and carbonatite, demonstrates experimentally that equilibrium in this reaction can be shifted from right to left. Therefore, phlogopite can equilibrate with ultrapotassic carbonate-silicate melts in a ? 150 °C region between 1200 and 1350 °C at 5.5 GPa. On the other hand, it can exist but cannot nucleate spontaneously and crystallize in the presence of such melts in quite a large pressure range in experiments at 6.3-7.0 GPa and 1200 °C. Thus, phlogopite can result from metasomatism of peridotite at the base of continental lithospheric mantle (CLM) by ultrapotassic carbonatite agents at depths shallower than 180-195 km, which creates a mechanism of water retaining in CLM. Kimberlite formation can begin at 5.5 GPa and 1350 °C in a phlogopite-bearing peridotite source generating a hydrous carbonate-silicate melt with 10-15 wt% SiO2, Ca# from 45 to 60, and high K enrichment. Upon further heating to 1450 °C due to the effect of a mantle plume at the CLM base, phlogopite disappears and a kimberlite-like melt forms with SiO2 to 20 wt% and Ca# = 35-40.
Abstract: Many carbonatites are associated both spatially and temporally with large igneous provinces (LIPs), and considered to originate from a mantle plume source lacking any contribution from recycled crustal materials. Here, we report an occurrence of carbonatite enriched in rare-earth elements (REE) and associated with the Tarim LIP in northwestern China. The Tarim LIP comprises intrusive and volcanic products of mantle plume activity spanning from ~ 300 to 280 Ma. The carbonatites at Wajilitage in the northwestern part of Tarim are dominated by calcite and dolomite varieties, and contain abundant REE minerals (principally, monazite and REE-fluorcarbonates). Th-Pb age determination of monazite yielded an emplacement age of 266 ± 5.3 Ma, i.e. appreciably younger than the eruption age of flood basalts at ~ 290 Ma. The carbonatites show low initial 87Sr/86Sr (0.7037-0.7041) and high ?Nd(t) (1.2-4) values, which depart from the isotopic characteristics of plume-derived basalts and high-Mg picrites from the same area. This indicates that the Wajilitage carbonatites derived from a mantle source isotopically distinct from the one responsible for the voluminous (ultra)mafic volcanism at Tarim. The carbonatites show ?26MgDSM3 values (? 0.99 to ? 0.65‰) that are significantly lower than those in typical mantle-derived rocks and rift carbonatites, but close to marine sediments and orogenic carbonatites. We propose that the carbonatites in the Tarim LIP formed by decompressional melting of recycled sediments mixed with the ambient mantle peridotite. The enriched components in the Tarim plume could be accounted for by the presence of recycled sedimentary components in the subcontinental mantle.
Earth and Planetary science Letters, Vol. 466, pp. 152-167.
Mantle
Metasomatism, magma, carbonatite
Abstract: Kimberlite and carbonatite magmas that intrude cratonic lithosphere are among the deepest probes of the terrestrial carbon cycle. Their co-existence on thick continental shields is commonly attributed to continuous partial melting sequences of carbonated peridotite at >150 km depths, possibly as deep as the mantle transition zone. At Tikiusaaq on the North Atlantic craton in West Greenland, approximately 160 Ma old ultrafresh kimberlite dykes and carbonatite sheets provide a rare opportunity to study the origin and evolution of carbonate-rich melts beneath cratons. Although their Sr-Nd-Hf-Pb-Li isotopic compositions suggest a common convecting upper mantle source that includes depleted and recycled oceanic crust components (e.g., negative ??Hf??Hf coupled with View the MathML source>+5‰?7Li), incompatible trace element modelling identifies only the kimberlites as near-primary low-degree partial melts (0.05-3%) of carbonated peridotite. In contrast, the trace element systematics of the carbonatites are difficult to reproduce by partial melting of carbonated peridotite, and the heavy carbon isotopic signatures (?3.6 to View the MathML source?2.4‰?13C for carbonatites versus ?5.7 to View the MathML source?3.6‰?13C for kimberlites) require open-system fractionation at magmatic temperatures.
Given that the oxidation state of Earth's mantle at >150 km depth is too reduced to enable larger volumes of ‘pure’ carbonate melt to migrate, it is reasonable to speculate that percolating near-solidus melts of carbonated peridotite must be silicate-dominated with only dilute carbonate contents, similar to the Tikiusaaq kimberlite compositions (e.g., 16-33 wt.% SiO2). This concept is supported by our findings from the North Atlantic craton where kimberlite and other deeply derived carbonated silicate melts, such as aillikites, exsolve their carbonate components within the shallow lithosphere en route to the Earth's surface, thereby producing carbonatite magmas. The relative abundances of trace elements of such highly differentiated ‘cratonic carbonatites’ have only little in common with those of metasomatic agents that act on the deeper lithosphere. Consequently, carbonatite trace element systematics should only be used with caution when constraining carbon mobility and metasomatism at mantle depths. Regardless of the exact nature of carbonate-bearing melts within the mantle lithosphere, they play an important role in enrichment processes, thereby decreasing the stability of buoyant cratons and promoting rift initiation - as exemplified by the Mesozoic-Cenozoic breakup of the North Atlantic craton.
Contributions to Mineralogy and Petrology, Vol. 172, 32p.
Russia, Kola Peninsula
Carbonatite
Abstract: The Lovozero alkaline massif—an agpaitic nepheline syenite layered intrusion—is located in the central part of the Kola Peninsula, Russia, and belongs to the Kola ultramafic alkaline and carbonatitic province (KACP) of Devonian age. Associated loparite and eudialyte deposits, which contain immense resources of REE, Nb, Ta, and Zr, constitute a world class mineral district. Previous Sr, Nd, and Hf isotope investigations demonstrated that these rocks and mineral deposits were derived from a depleted mantle source. However, because the Sr, Nd, and Hf abundances in the Kola alkaline rocks are significantly elevated, their isotopic compositions were relatively insensitive to contamination by the underlying crustal rocks through which the intruding magmas passed. Pb occurring in relatively lower abundance in the KACP rocks, by contrast, would have been a more sensitive indicator of an acquired crustal component. Here, we investigate the lead isotopic signature of representative types of Lovozero rocks in order to further characterize their sources. The measured Pb isotopic composition was corrected using the determined U and Th concentrations to the age of the crystallization of the intrusion (376?±?28 Ma, based on a 206Pb/204Pb versus 238U/204Pb isochron and 373?±?9 Ma, from a 208Pb/204Pb versus 232Th/204Pb isochron). Unlike the previously investigated Sr, Nd, and Hf isotopes, the lead isotopic composition plot was well outside the FOZO field. The 206Pb/204Pb values fall within the depleted MORB field, with some rocks having lower 207Pb/204Pb but higher 208Pb/204Pb values. Together with other related carbonatites having both lower and higher 206Pb/204Pb values, the combined KACP rocks form an extended linear array defining either a?~2.5-Ga secondary isochron or a mixing line. The projection of this isotopic array toward the very unradiogenic composition of underlying 2.4-2.5-Ga basaltic rocks of the Matachewan superplume and associated Archean granulite facies country rock provides strong evidence that this old lower crust was the contaminant responsible for the deviation of the Lovozero rocks from a presumed original FOZO lead isotopic composition. Evaluating the presence of such a lower crustal component in the Lovozero rock samples suggests a 5-10% contamination by such rocks. Contamination by upper crustal rock is limited to only a negligible amount.
Abstract: In the central part of the European part of Russia in the southeastern part of the Kursk tectonic block, some deposits and occurrences of apatite genetically related to the alkaline-carbonatite complex have been revealed. The results of U-Pb analysis of titanite provided the first confident age estimate of silicate-carbonate (phoscorite) rocks in the Dubravin alkaline-ultramafic-carbonatite massif: they formed no later than 2080 ±13 Ma, which indicates their crystallization in the pre-Oskol time during the final stage of the Early Paleoproterozoic (post-Kursk time) stabilization phase of the Kursk block of Sarmatia (about 2.3-2.1 Ga).
Abstract: Carbonatites are rare igneous carbonate-rich rocks. Most carbonatites contain a large number of accessory oxide, sulfide, and silicate minerals. Baddeleyite (ZrO2) and zircon (ZrSiO4) are common accessory minerals in carbonatites and because these minerals host high concentrations of U and Th, they are often used to determine the ages of formation of the carbonatite. In an experimental study, we constrain the stability fields of baddeleyite and zircon in Ca-rich carbonate melts with different silica concentrations. Our results show that SiO2-free and low silica carbonate melts crystallize baddeleyite, whereas zircon only crystallizes in melts with higher concentration of SiO2. We also find that the zirconsilicate baghdadite (Ca3ZrSi2O9) crystallizes in intermediate compositions. Our experiments indicate that zircon may not be a primary mineral in a low-silica carbonatite melt and care must be taken when interpreting zircon ages from low-silica carbonatite rocks.
Abstract: This study presents geochemical data on organic-rich rock samples collected from Riphean—Lower Paleozoic strata (potential source rocks) of the southern Siberian Platform and compositional data on hydrocarbon biomarkers (steranes, terpanes, n-alkanes, 12- and 13-methylalkanes, isoprenanes) and diamondoid hyrocarbons from core samples collected from the Kulindinskaya-1 well, which was drilled by RN-Exploration in 2012 within the Katanga saddle.
Abstract: Experimental studies of melting relations in the system ilmenite-K-Na-Mg-Fe-Ca carbonatite-carbon at 8 GPa and 1600°C provide evidence for the effect of liquid immiscibility between ilmenite and carbonatite melts. It is shown that the solubility of ilmenite in carbonatitic melts is negligible and does not depend on its concentration in experimental samples within 25-75 wt %. However, carbonatite-carbon melts are characterized by a high diamond-forming efficiency. This means that the correlation between the concentration of TiO2 and diamond content is problematic for mantle chambers and requires further, more complex, experimental studies.
Abstract: The Ashram Zone, which is host to the Ashram Rare Earth Element (REE) Deposit, occurs within the Eldor Carbonatite Complex, Québec, Canada. The complex is located within the Paleoproterozoic New Québec Orogen (Labrador Trough), and has been subjected to greenschist metamorphism and folding during the Hudsonian Orogeny at 1.75 Ga. To date, consanguineous undersaturated alkaline rocks have not been recognized within or adjacent to the complex. It is evident that the bulk compositions of the rocks, essentially magnesiocarbonatites and ferrocarbonatites, do not represent those of liquid compositions, as many are complex breccias which have been subjected to later hydrothermal activity. The Ashram Zone is dominated by diverse textural varieties of carbonatite which include: fluorite-rich schlieren carbonatites; coarse-to-medium grained granular carbonatites; fine grained, commonly mosaic-textured, quartz-bearing carbonatites; and colloform carbonatites. Compositional and textural data are provided for the minerals present in the carbonatites. The major rock-forming minerals are diverse Ca-Mg-Fe carbonates, fluorite, and quartz. The carbonates range in their compositional evolution from rare dolomite through ferrodolomite and magnesian siderite to siderite. The principal REE-bearing minerals of the Ashram Deposit are monazite-(Ce) and monazite-(Nd), with lesser amounts of bastnaesite-(Ce) and bastnaesite-(Nd). The minor and accessory mineral suite is characterized by the presence of apatite, phlogopite, xenotime, diverse Sc- and sn-bearing Nb-Ti-minerals (niobian rutile, nioboaeschynite, samarskite), barite, sphalerite, several uncommon, but here relatively abundant, Ba- and Ba-Be minerals (bafertisite, magbasite, barylite, betrandite, sanbornite, cebaite), yangzhumingite, cassiterite, galena, pyrite, and rare magnetite and potassium feldspar. Pyrochlore is absent and the Nb-Ti oxide assemblage is similar to that found in NYF-pegmatites associated with F-rich, A-type granitoids. The mineralogy of the Ashram Deposit, compared to that of other carbonatites associated with undersaturated silicate rocks is unique, especially with respect to the abundance of fluorite and monazite (commonly with Nd-enrichment), Ba-Be-enrichment, the NYF-type Nb-Ti oxide assemblage (especially xenotime, Y-Nb-aeschynite, samarskite), phlogopite-potassium feldspar quartz-rich residua with granitoid characteristics, paucity of magnetite, pyrochlore, and Sr-bearing carbonates. The Ashram Deposit is considered to be a late-magmatic-to-hydrothermal F-REE magnesio-to-ferrocarbonatite derived from as yet unknown consanguineous antecedents.
Abstract: The more than 500 fossil Ca-carbonatite occurrences on Earth are at odds with the only active East African Rift carbonatite volcano, Oldoinyo Lengai (Tanzania), which produces Na-carbonatite magmas. The volcano's recent major explosive eruptions yielded a mix of nephelinitic and carbonatite melts, supporting the hypothesis that carbonatites and spatially associated peralkaline silicate lavas are related through liquid immiscibility. Nevertheless, previous eruption temperatures of Na-carbonatites were 490-595 °C, which is 250-450 °C lower than for any suitable conjugate silicate liquid. This study demonstrates experimentally that moderately alkaline Ca-carbonatite melts evolve to Na-carbonatites through crystal fractionation. The thermal barrier of the synthetic Na-Ca-carbonate system, held to preclude an evolution from Ca-carbonatites to Na-carbonatites, vanishes in the natural system, where continuous fractionation of calcite + apatite leads to Na-carbonatites, as observed at Oldoinyo Lengai. Furthermore, saturating the Na-carbonatite with minerals present in possible conjugate nephelinites yields a parent carbonatite with total alkali contents of 8-9 wt%, i.e., concentrations that are realistic for immiscible separation from nephelinitic liquids at 1000-1050 °C. Modeling the liquid line of descent along the calcite surface requires a total fractionation of ?48% calcite, ?12% apatite, and ?2 wt% clinopyroxene. SiO2 solubility only increases from 0.2 to 2.9 wt% at 750-1200 °C, leaving little leeway for crystallization of silicates. The experimental results suggest a moderately alkaline parent to the Oldoinyo Lengai carbonatites and therefore a common origin for carbonatites related to alkaline magmatism.
Abstract: Carbonatites are carbonate-dominated igneous rocks derived by low-degree partial melting of metasomatized mantle, although the geodynamic processes responsible for their emplacement into the crust are disputed. Current models favor either reactivation of lithospheric structures in response to plate movements, or the impingement of mantle plumes. Geochronology provides a means of testing these models, but constraining the age of carbonatites and related metasomatic events is rarely straightforward. We use in situ U-Th-Pb analysis of monazite by SHRIMP to constrain the emplacement age and hydrothermal history of the rare earth element-bearing Gifford Creek Carbonatite Complex in Western Australia, which has been linked to plume magmatism at ca. 1075 Ma. Monazite in carbonatites and related metasomatic rocks (fenites) from the carbonatite complex dates the initial emplacement of the carbonatite at 1361 ± 10 Ma (n = 22, MSWD = 0.91). The complex was subjected to multiple stages of magmatic/hydrothermal overprinting from ca. 1300 Ma to 900 Ma during later regional tectonothermal events. Carbonatite emplacement at ca. 1360 Ma appears to be an isolated igneous event in the region, and occurred about 300 million years before intrusion of the ca. 1075 Ma Warakurna large igneous province, thus precluding a genetic connection. The Gifford Creek Carbonatite Complex occurs within a major crustal suture, and probably formed in response to reactivation of this suture during plate reorganization. Our study demonstrates the veracity of monazite geochronology in determining the magmatic and hydrothermal histories of a carbonatite complex, critical for evaluating competing geodynamic models for carbonatites. The approach involving in situ SHRIMP U-Th-Pb dating of monazite from a wide spectrum of rocks in a carbonatite complex is best suited to establishing the intrusive age and hydrothermal history of carbonatites.
Abstract: Two Neoproterozoic carbonatite suites of spatially related carbonatites and associated silicate alkaline rocks from Sevattur and Samalpatti, south India, have been investigated in terms of petrography, chemistry and radiogenic–stable isotopic compositions in order to provide further constraints on their genesis. The cumulative evidence indicates that the Sevattur suite is derived from an enriched mantle source without significant post-emplacement modifications through crustal contamination and hydrothermal overprint. The stable (C, O) isotopic compositions confirm mantle origin of Sevattur carbonatites with only a modest difference to Paleoproterozoic Hogenakal carbonatite, emplaced in the same tectonic setting. On the contrary, multiple processes have shaped the petrography, chemistry and isotopic systematics of the Samalpatti suite. These include pre-emplacement interaction with the ambient crustal materials with more pronounced signatures of such a process in silicocarbonatites. Calc-silicate marbles present in the Samalpatti area could represent a possible evolved end member due to the inability of common silicate rocks (pyroxenites, granites, diorites) to comply with radiogenic isotopic constraints. In addition, Samalpatti carbonatites show a range of C–O isotopic compositions, and ?13CV-PDB values between + 1.8 and + 4.1‰ found for a sub-suite of Samalpatti carbonatites belong to the highest values ever reported for magmatic carbonates. These heavy C–O isotopic signatures in Samalpatti carbonatites could be indicative of massive hydrothermal interaction with carbonated fluids. Unusual high-Cr silicocarbonatites, discovered at Samalpatti, seek their origin in the reaction of pyroxenites with enriched mantle-derived alkali-CO2-rich melts, as also evidenced by mantle-like O isotopic compositions. Field and petrographic observations as well as isotopic constraints must, however, be combined with the complex chemistry of incompatible trace elements as indicated from their non-uniform systematics in carbonatites and their individual fractions. We emphasise that, beside common carriers of REE like apatite, other phases may be important for incompatible element budgets, such as mckelveyite–(Nd) and kosmochlor, found in these carbonatites. Future targeted studies, including in-situ techniques, could help further constrain temporal and petrologic conditions of formation of Sevattur and Samalpatti carbonatite bodies.
Abstract: Two Neoproterozoic carbonatite suites of spatially related carbonatites and associated silicate alkaline rocks from Sevattur and Samalpatti, south India, have been investigated in terms of petrography, chemistry and radiogenic–stable isotopic compositions in order to provide further constraints on their genesis. The cumulative evidence indicates that the Sevattur suite is derived from an enriched mantle source without significant post-emplacement modifications through crustal contamination and hydrothermal overprint. The stable (C, O) isotopic compositions confirm mantle origin of Sevattur carbonatites with only a modest difference to Paleoproterozoic Hogenakal carbonatite, emplaced in the same tectonic setting. On the contrary, multiple processes have shaped the petrography, chemistry and isotopic systematics of the Samalpatti suite. These include pre-emplacement interaction with the ambient crustal materials with more pronounced signatures of such a process in silicocarbonatites. Calc-silicate marbles present in the Samalpatti area could represent a possible evolved end member due to the inability of common silicate rocks (pyroxenites, granites, diorites) to comply with radiogenic isotopic constraints. In addition, Samalpatti carbonatites show a range of C–O isotopic compositions, and ?13CV-PDB values between + 1.8 and + 4.1‰ found for a sub-suite of Samalpatti carbonatites belong to the highest values ever reported for magmatic carbonates. These heavy C–O isotopic signatures in Samalpatti carbonatites could be indicative of massive hydrothermal interaction with carbonated fluids. Unusual high-Cr silicocarbonatites, discovered at Samalpatti, seek their origin in the reaction of pyroxenites with enriched mantle-derived alkali-CO2-rich melts, as also evidenced by mantle-like O isotopic compositions. Field and petrographic observations as well as isotopic constraints must, however, be combined with the complex chemistry of incompatible trace elements as indicated from their non-uniform systematics in carbonatites and their individual fractions. We emphasise that, beside common carriers of REE like apatite, other phases may be important for incompatible element budgets, such as mckelveyite–(Nd) and kosmochlor, found in these carbonatites. Future targeted studies, including in-situ techniques, could help further constrain temporal and petrologic conditions of formation of Sevattur and Samalpatti carbonatite bodies.
Journal of African Earth Sciences, Vol. 134, pp. 10-23.
Africa, Malawi
carbonatite - Songwe Hill
Abstract: Songwe Hill, Malawi, is one of the least studied carbonatites but has now become particularly important as it hosts a relatively large rare earth deposit. The results of new mapping, petrography, geochemistry and geochronology indicate that the 0.8 km diameter Songwe Hill is distinct from the other Chilwa Alkaline Province carbonatites in that it intruded the side of the much larger (4 x 6 km) and slightly older (134.6 ± 4.4 Ma) Mauze nepheline syenite and then evolved through three different carbonatite compositions (C1–C3). Early C1 carbonatite is scarce and is composed of medium–coarse-grained calcite carbonatite containing zircons with a U–Pb age of 132.9 ± 6.7 Ma. It is similar to magmatic carbonatite in other carbonatite complexes at Chilwa Island and Tundulu in the Chilwa Alkaline Province and others worldwide. The fine-grained calcite carbonatite (C2) is the most abundant stage at Songwe Hill, followed by a more REE- and Sr-rich ferroan calcite carbonatite (C3). Both stages C2 and C3 display evidence of extensive (carbo)-hydrothermal overprinting that has produced apatite enriched in HREE (<2000 ppm Y) and, in C3, synchysite-(Ce). The final stages comprise HREE-rich apatite fluorite veins and Mn-Fe-rich veins. Widespread brecciation and incorporation of fenite into carbonatite, brittle fracturing, rounded clasts and a fenite carapace at the top of the hill indicate a shallow level of emplacement into the crust. This shallow intrusion level acted as a reservoir for multiple stages of carbonatite-derived fluid and HREE-enriched apatite mineralisation as well as LREE-enriched synchysite-(Ce). The close proximity and similar age of the large Mauze nepheline syenite suggests it may have acted as a heat source driving a hydrothermal system that has differentiated Songwe Hill from other Chilwa carbonatites.
Geochemistry International, Vol. 55, 5, pp. 457-464.
Russia
carbonatite - Guli
Abstract: For better understanding of the fluid phase sources of carbonatites of Guli alkaline-ultrabasic intrusion (Maymecha-Kotuy complex) we have studied isotope composition of He and Ne in the carbonatites of different formation stages. The data definitely point to the subcontinental lithospheric mantle (SCLM) as a primary source of fluid phase of Guli carbonatites. The absence of plume signature in such a plume-like object (from petrological point of view) could be explained in terms that Guli carbonatites have been formed at the waning stage of plume magmatic activity with an essential input of SCLM components.
Abstract: The integrated evaluation of soil geochemistry, aerogammaspectrometry (eTh), geological and structural mapping associated with the description of boreholes and outcrops in the Caçapava do Sul region, southernmost Brazil, led to the discovery of two carbonatite bodies. They are located near the eastern and southeastern border of Caçapava do Sul Granite and intrude the Passo Feio Complex. The carbonatite system is composed of early pink-colored alvikite followed by late white beforsite dikes. The carbonatites are tabular bodies concordant with the deformed host rocks. Petrographic and scanning electron microscopy show that the alvikites are dominantly composed of calcite with subordinate apatite, magnetite, ilmenite, biotite, baddeleyite, zircon, rutile, pyrochlore-like and rare earth element minerals. Beforsite is composed of dolomite and has the same minor and accessory minerals as the alvikite. U-Pb zircon geochronology via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was performed on a beforsite sample, yielding a 603.2 ± 4.5 Ma crystallization age. The carbonatite was emplaced an Ediacaran post-collisional environment with transpressive tectonism and volcanic activity marked by shoshonitic affinity.
Abstract: Zoned crystals of carbocernaite occur in hydrothermally reworked burbankite-fluorapatite-bearing calcite carbonatite at Bear Lodge, Wyoming. The mineral is paragenetically associated with pyrite, strontianite, barite, ancylite-(Ce), and late-stage calcite, and is interpreted to have precipitated from sulfate-bearing fluids derived from an external source and enriched in Na, Ca, Sr, Ba, and rare-earth elements (REE) through dissolution of the primary calcite and burbankite. The crystals of carbocernaite show a complex juxtaposition of core-rim, sectoral, and oscillatory zoning patterns arising from significant variations in the content of all major cations, which can be expressed by the empirical formula (Ca0.43–0.91Sr0.40–0.69REE0.18–0.59Na0.18–0.53Ba0–0.08)?1.96–2.00(CO3)2. Interelement correlations indicate that the examined crystals can be viewed as a solid solution between two hypothetical end-members, CaSr(CO3)2 and NaREE(CO3)2, with the most Na-REE-rich areas in pyramidal (morphologically speaking) growth sectors representing a probable new mineral species. Although the Bear Lodge carbocernaite is consistently enriched in light REE relative to heavy REE and Y (chondrite-normalized La/Er = 500–4200), the pyramidal sectors exhibit a greater degree of fractionation between these two groups of elements relative to their associated prismatic sectors. A sample approaching the solid-solution midline [(Ca0.57Na0.42)?0.99(Sr0.50REE0.47Ba0.01)?0.98(CO3)2] was studied by single-crystal X-ray diffraction and shown to have a monoclinic symmetry [space group P11m, a = 6.434(4), b = 7.266(5), c = 5.220(3) Å, ? = 89.979(17)°, Z = 2] as opposed to the orthorhombic symmetry (space group Pb21m) proposed in earlier studies. The symmetry reduction is due to partial cation order in sevenfold-coordinated sites occupied predominantly by Ca and Na, and in tenfold-coordinated sites hosting Sr, REE, and Ba. The ordering also causes splitting of carbonate vibrational modes at 690–740 and 1080–1100 cm?1 in Raman spectra. Using Raman micro-spectroscopy, carbocernaite can be readily distinguished from burbankite- and ancylite-group carbonates characterized by similar energy-dispersive spectra.
Abstract: The 2060 Ma old Palabora Carbonatite Complex (PCC), South Africa, comprises diverse REE mineral assemblages formed during different stages and reflects an outstanding instance to understand the evolution of a carbonatite-related REE mineralization from orthomagmatic to late-magmatic stages and their secondary post-magmatic overprint. The 10 rare earth element minerals monazite, REE-F-carbonates (bastnäsite, parisite, synchysite), ancylite, britholite, cordylite, fergusonite, REE-Ti-betafite, and anzaite are texturally described and related to the evolutionary stages of the PCC. The identification of the latter five REE minerals during this study represents their first described occurrences in the PCC as well as in a carbonatite complex in South Africa. The variable REE mineral assemblages reflect a multi-stage origin: (1) fergusonite and REE-Ti-betafite occur as inclusions in primary magnetite. Bastnäsite is enclosed in primary calcite and dolomite. These three REE minerals are interpreted as orthomagmatic crystallization products. (2) The most common REE minerals are monazite replacing primary apatite, and britholite texturally related to the serpentinization of forsterite or the replacement of forsterite by chondrodite. Textural relationships suggest that these two REE-minerals precipitated from internally derived late-magmatic to hydrothermal fluids. Their presence seems to be locally controlled by favorable chemical conditions (e.g., presence of precursor minerals that contributed the necessary anions and/or cations for their formation). (3) Late-stage (post-magmatic) REE minerals include ancylite and cordylite replacing primary magmatic REE-Sr-carbonates, anzaite associated with the dissolution of ilmenite, and secondary REE-F-carbonates. The formation of these post-magmatic REE minerals depends on the local availability of a fluid, whose composition is at least partly controlled by the dissolution of primary minerals (e.g., REE-fluorocarbonates). This multi-stage REE mineralization reflects the interplay of magmatic differentiation, destabilization of early magmatic minerals during subsequent evolutionary stages of the carbonatitic system, and late-stage fluid-induced remobilization and re-/precipitation of precursor REE minerals. Based on our findings, the Palabora Carbonatite Complex experienced at least two successive stages of intense fluid–rock interaction.
The Canadian Mineralogist, Vol. 54, pp. 1285-1291.
China, Mongolia
carbonatite - Bayan Obo
Abstract: Fluorcalciopyrochlore, ideally (Ca,Na)2Nb2O6F, cubic, is a new mineral species (IMA2013-055) occurring in the Bayan Obo Fe-Nb-REE deposit, Inner Mongolia, People's Republic of China. The mineral is found in a dolomite-type niobium rare-earth ore deposit. Associated minerals are dolomite, aegirine, riebeckite, diopside, fluorite, baryte, phlogopite, britholite-(Ce), bastnäsite-(Ce), zircon, magnetite, pyrite, fersmite, columbite-(Fe), monazite-(Ce), rutile, and others. Crystals mostly form as octahedra {111}, dodecahedra {110}, and cubes {100}, or combinations thereof, and generally range in size from 0.01 to 0.3 mm. It is brownish-yellow to reddish-orange in color with a light yellow streak. Crystals of fluorcalciopyrochlore are translucent to transparent with an adamantine to greasy luster on fractured surfaces. It has a conchoidal fracture. No parting or cleavage was observed. The Mohs hardness is 5, and the calculated density is 4.34(1) g/cm3. The empirical formula is (Ca1.14Na0.74Ce0.06Sr0.03Th0.01Fe0.01Y0.01La0.01Nd0.01)?2.02(Nb1.68Ti0.29Zr0.02Sn0.01)?2.00O6.00(F0.92O0.08)?1.00 on the basis of 7(O,F) anions pfu. The simplified formula is (Ca,Na)2Nb2O6F. The strongest four reflections in the X-ray powder-diffraction pattern [d in Å (I) hkl] are: 6.040 (9) 1 1 1, 3.017 (100) 2 2 2, 2.613 (17) 0 0 4, 1.843 (29) 0 4 4, and 1.571 (15) 2 2 6. The unit-cell parameters are a 10.4164(9) Å, V 1130.2(2) Å3, Z = 8. The structure was solved and refined in space group FdEmbedded Image m with R = 0.05. The type material is deposited in the Geological Museum of China, Beijing, People's Republic of China, catalogue number M12182.
Abstract: Near Meech Lake, Québec, the edges of Mesoproterozoic carbonatite dikes are composed of calcite, dolomite, fluorapatite, phlogopite, amphibole, and pyrochlore. The carbonatite is separated from amphibole-fenite by a narrow, fine-grained reaction selvage of phlogopite pierced with long prisms of amphibole. The amphibole is mainly richterite, but it extends to magnesio-arfvedsonite (overgrowth, crystal rim). Uranium-rich pyrochlore is metamict and ranges from calciopyrochlore to kenopyrochlore with Ta-U enrichment in crystal rims. Chemical characteristics of the suite are: (1) F and Nb highest in the selvage, and (2) decline of Sr and Ce outwards from the carbonatite. A similar pattern (this research) is found at Fen, Norway. Rare earths are enriched in LREE with smooth downward-sloping patterns, in chondrite-normalized curves, to HREE. Two major surges of mineralization are suggested: (1) early, metasomatic-alkalic, creating fenites with enrichment in Mg, Na, and K; and (2) later igneous depositing carbonatites and introducing first F, P, and Nb, then Ca, Sr, and Ce. Thermochemical and geochronological data place carbonate equilibration at 700 °C and the emplacement at 1026 Ma b.p. Calciocarbonatites, in monzonitic orthogneiss, are enriched in Ba and Ce. They are composed of baryte, calcite, phlogopite, fluorapatite, magnesio-riebeckite, and non-metamict allanite-(Ce). A mica selvage is present, but amphibole fenite is almost completely lacking. Magnesiocarbonatite has a well-developed selvage against granite but lacks significant amphibole fenite. In breccia cement at nearby Fortune Lake, pyrochlore is associated with abundant fluorapatite but lacks carbonates. The Cambro-Proterozoic calciocarbonatite near Fen, Norway is particularly Nb-rich in breccia zones, and pyroxene fenite takes the place of amphibole fenite at Meech Lake. In contrast to a relatively anorogenic regime during carbonatite petrogenesis at Fen, metamorphism has obscured pyrochlore zonation and enhanced amphibole growth at Meech Lake
Abstract: Apatites from the Verity, Fir, Gum, Howard Creek and Felix carbonatites of the Blue River (British Columbia, Canada) area have been investigated with respect to their paragenesis, cathodoluminescence, trace element and Sr–Nd isotopic composition. Although all of the Blue River carbonatites were emplaced as sills prior to amphibolite grade metamorphism and have undergone deformation, in many instances magmatic textures and mineralogy are retained. Attempts to constrain the U–Pb age of the carbonatites by SIMS, TIMS and LA–ICP-MS studies of zircon and titanite were inconclusive as all samples investigated have experienced significant Pb loss during metamorphism. The carbonatites are associated with undersaturated calcite–titanite amphibole nepheline syenite only at Howard Creek although most contain clasts of disaggregated phoscorite-like rocks. Apatite from each intrusion is characterized by distinct, but wide ranges, in trace element composition. The Sr and Nd isotopic compositions define an array on a 87Sr/86Sr vs²Nd diagram at 350 Ma indicating derivation from depleted sub-lithospheric mantle. This array could reflect mixing of Sr and Nd derived from HIMU and EM1 mantle sources, and implies that depleted mantle underlies the Canadian Cordillera. Although individual occurrences of carbonatites in the Blue River region are mineralogically and geochemically similar they are not identical and thus cannot be considered as rocks formed from a single batch of parental magma at the same stage of magmatic evolution. However, a common origin is highly probable. The variations in the trace element content and isotopic composition of apatite from each occurrence suggest that each carbonatite represents a combination of derivation of the parental magma(s) from mineralogically and isotopically heterogeneous depleted mantle sources coupled with different stages of limited differentiation and mixing of these magmas. We do not consider these carbonatites as primary direct partial melts of the sub-lithospheric mantle which have ascended from the asthenosphere without modification of their composition.
Abstract: The Samchampi (26° 13?N: 93° 18?E)-Samteran (26° 11?N: 93° 25?E) alkaline complex (SSAC) occurs as an intrusion within Precambrian basement gneisses in the Karbi-Anglong district of Assam, Northeastern India. This intrusive complex comprises a wide spectrum of lithologies including syenite, ijolite-melteigite, alkali pyroxenite, alkali gabbro, nepheline syenite and carbonatite (nepheline syenites and carbonatites are later intrusives). In this paper, we present new major, trace, REE and Sr-Nd isotope data for different lithologies of SSAC and discuss integrated petrological and whole rock geochemical observations with Sr-Nd isotope systematics to understand the petrogenetic evolution of the complex. Pronounced LILE and LREE enrichment of the alkaline-carbonatite rocks together with steep LREE/HREE profile and flat HREE-chondrite normalized patterns provide evidence for parent magma generation from low degree partial melting of a metasomatized garnet peridotite mantle source. LILE, HFSE and LREE enrichments of the alkaline-silicate rocks and carbonatites are in agreement with the involvement of a mantle plume in their genesis. Nb-Th-La systematics with incompatible trace element abundance patterns marked by positive Nb-Ta anomalies and negative K, Th and Sr anomalies suggest contribution from plume-derived OIB-type mantle with recycled subduction component and a rift-controlled, intraplate tectonic setting for alkaline-carbonatite magmatism giving rise to the SSAC. This observation is corroborated by enriched 87Sr/86Srinitial (0.705562 to 0.709416) and 143Nd/144Ndinitial (0.512187 to 0.512449) ratios for the alkaline-carbonatite rocks that attest to a plume-related enriched mantle (~ EM II) source in relation to the origin of Samchampi-Samteran alkaline complex. Trace element chemistry and variations in isotopic data invoke periodic melting of an isotopically heterogeneous, metasomatized mantle and generation of isotopically distinct melt batches that were parental to the different rocks of SSAC. Various extents of plume-lithosphere interaction also accounts for the trace element and isotopic variations of SSAC. The Srinitial and Ndinitial (105 Ma) isotopic compositions (corresponding to ?Nd values of ? 6.37 to ? 1.27) of SSAC are consistent with those of Sung Valley, Jasra, Rajmahal tholeiites (Group II), Sylhet Traps and Kerguelen plateau basalts.
Abstract: Although kimberlite magma carries large amounts of mantle-derived xenocrysts and xenoliths (with sizes up to meters), this magma ascends from the Earth's mantle (> 150–250 km) to the surface in a matter of hours or days, which enables diamonds to survive. The recently proposed assimilation-fuelled buoyancy model for kimberlite magma ascent emphasizes the importance of fluid CO2 that is produced via the reactive dissolution of mantle-derived orthopyroxene xenocrysts into kimberlite melt, which initially has carbonatitic composition. Here, we use a series of high-pressure experiments to test this model by studying the interaction of orthopyroxene (Opx) with an alkali-dolomitic melt (simplified to 0.7Na2CO3 + 0.3K2CO3 + 2CaMg(CO3)2), which is close to the melt that is produced by the partial melting of a kimberlite source, at P = 3.1–6.5 GPa and T = 1200–1600 °C, i.e., up to pressures that correspond to depths (~ 200 km) from where the ascent of kimberlite magma would start. During the first set of experiments, we study the reaction between powdered Opx and model carbonate melt in a homogeneous mixture. During the second set of experiments, we investigate the mechanism and kinetics of the dissolution of Opx crystals in alkali-dolomitic melt. Depending on the P-T conditions, Opx dissolves in the alkali-dolomitic melt (CL) either congruently or incongruently via the following reactions: Mg2Si2O6 (Opx) + CaMg(CO3)2 (CL) = CaMgSi2O6 (clinopyroxene) + 2MgCO3 (CL) and Mg2Si2O6 (Opx) = Mg2SiO4 (olivine) + SiO2 (CL). The experiments confirm that the dissolution of Opx causes gradual SiO2 enrichment in the initial carbonate melt, as previously suggested. However, the assimilation of Opx by carbonate melt does not produce fluid CO2 in the experiments because the CO2 is totally dissolved in the evolved melt. Thus, our results clearly demonstrate the absence of exsolved CO2 fluid at 3.1–6.5 GPa in ascending kimberlite magma and disprove the assimilation-fuelled buoyancy model for kimberlite magma ascent in the lithospheric mantle. We alternatively suggest that the extreme buoyancy of kimberlite magma at depths of 100–250 km is an exclusive consequence of the unique physical properties (i.e., low density, ultra-low viscosity and, thus, high mobility) of the kimberlite melt, which are dictated by its carbonatitic composition.
Abstract: Many carbonatites are associated both spatially and temporally with large igneous provinces (LIPs), and considered to originate from a mantle plume source lacking any contribution from recycled crustal materials. Here, we report an occurrence of carbonatite enriched in rare-earth elements (REE) and associated with the Tarim LIP in northwestern China. The Tarim LIP comprises intrusive and volcanic products of mantle plume activity spanning from ~ 300 to 280 Ma. The carbonatites at Wajilitage in the northwestern part of Tarim are dominated by calcite and dolomite varieties, and contain abundant REE minerals (principally, monazite and REE-fluorcarbonates). Th–Pb age determination of monazite yielded an emplacement age of 266 ± 5.3 Ma, i.e. appreciably younger than the eruption age of flood basalts at ~ 290 Ma. The carbonatites show low initial 87Sr/86Sr (0.7037–0.7041) and high ?Nd(t) (1.2–4) values, which depart from the isotopic characteristics of plume-derived basalts and high-Mg picrites from the same area. This indicates that the Wajilitage carbonatites derived from a mantle source isotopically distinct from the one responsible for the voluminous (ultra)mafic volcanism at Tarim. The carbonatites show ?26MgDSM3 values (? 0.99 to ? 0.65‰) that are significantly lower than those in typical mantle-derived rocks and rift carbonatites, but close to marine sediments and orogenic carbonatites. We propose that the carbonatites in the Tarim LIP formed by decompressional melting of recycled sediments mixed with the ambient mantle peridotite. The enriched components in the Tarim plume could be accounted for by the presence of recycled sedimentary components in the subcontinental mantle.
Abstract: The more than 500 fossil Ca-carbonatite occurrences on Earth are at odds with the only active East African Rift carbonatite volcano, Oldoinyo Lengai (Tanzania), which produces Na-carbonatite magmas. The volcano’s recent major explosive eruptions yielded a mix of nephelinitic and carbonatite melts, supporting the hypothesis that carbonatites and spatially associated peralkaline silicate lavas are related through liquid immiscibility. Nevertheless, previous eruption temperatures of Na-carbonatites were 490–595 °C, which is 250–450 °C lower than for any suitable conjugate silicate liquid. This study demonstrates experimentally that moderately alkaline Ca-carbonatite melts evolve to Na-carbonatites through crystal fractionation. The thermal barrier of the synthetic Na-Ca-carbonate system, held to preclude an evolution from Ca-carbonatites to Na-carbonatites, vanishes in the natural system, where continuous fractionation of calcite + apatite leads to Na-carbonatites, as observed at Oldoinyo Lengai. Furthermore, saturating the Na-carbonatite with minerals present in possible conjugate nephelinites yields a parent carbonatite with total alkali contents of 8–9 wt%, i.e., concentrations that are realistic for immiscible separation from nephelinitic liquids at 1000–1050 °C. Modeling the liquid line of descent along the calcite surface requires a total fractionation of ?48% calcite, ?12% apatite, and ?2 wt% clinopyroxene. SiO2 solubility only increases from 0.2 to 2.9 wt% at 750–1200 °C, leaving little leeway for crystallization of silicates. The experimental results suggest a moderately alkaline parent to the Oldoinyo Lengai carbonatites and therefore a common origin for carbonatites related to alkaline magmatism.
Abstract: The more than 500 fossil Ca-carbonatite occurrences on Earth are at odds with the only active East African Rift carbonatite volcano, Oldoinyo Lengai (Tanzania), which produces Na-carbonatite magmas. The volcano’s recent major explosive eruptions yielded a mix of nephelinitic and carbonatite melts, supporting the hypothesis that carbonatites and spatially associated peralkaline silicate lavas are related through liquid immiscibility. Nevertheless, previous eruption temperatures of Na-carbonatites were 490–595 °C, which is 250–450 °C lower than for any suitable conjugate silicate liquid. This study demonstrates experimentally that moderately alkaline Ca-carbonatite melts evolve to Na-carbonatites through crystal fractionation. The thermal barrier of the synthetic Na-Ca-carbonate system, held to preclude an evolution from Ca-carbonatites to Na-carbonatites, vanishes in the natural system, where continuous fractionation of calcite + apatite leads to Na-carbonatites, as observed at Oldoinyo Lengai. Furthermore, saturating the Na-carbonatite with minerals present in possible conjugate nephelinites yields a parent carbonatite with total alkali contents of 8–9 wt%, i.e., concentrations that are realistic for immiscible separation from nephelinitic liquids at 1000–1050 °C. Modeling the liquid line of descent along the calcite surface requires a total fractionation of ?48% calcite, ?12% apatite, and ?2 wt% clinopyroxene. SiO2 solubility only increases from 0.2 to 2.9 wt% at 750–1200 °C, leaving little leeway for crystallization of silicates. The experimental results suggest a moderately alkaline parent to the Oldoinyo Lengai carbonatites and therefore a common origin for carbonatites related to alkaline magmatism.
Abstract: Baddeleyite has been recognized as a key mineral to determine the crystallization age of silica-undersaturated igneous rocks. Here we report a new occurrence of baddeleyite identified from REE-Nb-Th-rich carbonatite in the world's largest REE deposit, Bayan Obo, in the North China Craton (China). U-Th-Pb dating of three baddeleyite samples yields crystallization ages of 310–270 Ma with the best estimated crystallization age of ca. 280 Ma. These ages are significantly younger than the ca. 1300 Ma Bayan Obo carbonatites, but broadly coeval to nearby Permian granitoids intruding into the carbonatites. Hence, the Bayan Obo baddeleyite did not crystallize from the carbonatitic magma that led to the formation of the Bayan Obo carbonatites and related REE-Nb-Th deposit. Instead, it crystallized from hydrothermal fluids and/or a reaction involving zircon and dolomite during contact metamorphism related to the Permian granitoid emplacement. This is in agreement with the results of electron microprobe analysis that show humite inclusions in baddeleyite, since humite is a typical magnesian skarn mineral and occurs in close proximity to the intrusive contacts between carbonatites and granitoids. Our results show that baddeleyite can be used for dating hydrothermal and contact metamorphic processes.
Abstract: Carbonatites are carbonate-dominated igneous rocks derived by low-degree partial melting of metasomatized mantle, although the geodynamic processes responsible for their emplacement into the crust are disputed. Current models favor either reactivation of lithospheric structures in response to plate movements, or the impingement of mantle plumes. Geochronology provides a means of testing these models, but constraining the age of carbonatites and related metasomatic events is rarely straightforward. We use in situ U-Th-Pb analysis of monazite by SHRIMP to constrain the emplacement age and hydrothermal history of the rare earth element-bearing Gifford Creek Carbonatite Complex in Western Australia, which has been linked to plume magmatism at ca. 1075 Ma. Monazite in carbonatites and related metasomatic rocks (fenites) from the carbonatite complex dates the initial emplacement of the carbonatite at 1361 ± 10 Ma (n = 22, MSWD = 0.91). The complex was subjected to multiple stages of magmatic/hydrothermal overprinting from ca. 1300 Ma to 900 Ma during later regional tectonothermal events. Carbonatite emplacement at ca. 1360 Ma appears to be an isolated igneous event in the region, and occurred about 300 million years before intrusion of the ca. 1075 Ma Warakurna large igneous province, thus precluding a genetic connection. The Gifford Creek Carbonatite Complex occurs within a major crustal suture, and probably formed in response to reactivation of this suture during plate reorganization. Our study demonstrates the veracity of monazite geochronology in determining the magmatic and hydrothermal histories of a carbonatite complex, critical for evaluating competing geodynamic models for carbonatites. The approach involving in situ SHRIMP U-Th-Pb dating of monazite from a wide spectrum of rocks in a carbonatite complex is best suited to establishing the intrusive age and hydrothermal history of carbonatites.
Abstract: Carbonatites are carbonate-dominated igneous rocks derived by low-degree partial melting of metasomatized mantle, although the geodynamic processes responsible for their emplacement into the crust are disputed. Current models favor either reactivation of lithospheric structures in response to plate movements, or the impingement of mantle plumes. Geochronology provides a means of testing these models, but constraining the age of carbonatites and related metasomatic events is rarely straightforward. We use in situ U-Th-Pb analysis of monazite by SHRIMP to constrain the emplacement age and hydrothermal history of the rare earth element-bearing Gifford Creek Carbonatite Complex in Western Australia, which has been linked to plume magmatism at ca. 1075 Ma. Monazite in carbonatites and related metasomatic rocks (fenites) from the carbonatite complex dates the initial emplacement of the carbonatite at 1361 ± 10 Ma (n = 22, MSWD = 0.91). The complex was subjected to multiple stages of magmatic/hydrothermal overprinting from ca. 1300 Ma to 900 Ma during later regional tectonothermal events. Carbonatite emplacement at ca. 1360 Ma appears to be an isolated igneous event in the region, and occurred about 300 million years before intrusion of the ca. 1075 Ma Warakurna large igneous province, thus precluding a genetic connection. The Gifford Creek Carbonatite Complex occurs within a major crustal suture, and probably formed in response to reactivation of this suture during plate reorganization. Our study demonstrates the veracity of monazite geochronology in determining the magmatic and hydrothermal histories of a carbonatite complex, critical for evaluating competing geodynamic models for carbonatites. The approach involving in situ SHRIMP U-Th-Pb dating of monazite from a wide spectrum of rocks in a carbonatite complex is best suited to establishing the intrusive age and hydrothermal history of carbonatites.
Abstract: The Eocene (ca. 55–38 Ma) Bear Lodge alkaline complex in the northern Black Hills region of northeastern Wyoming (USA) is host to stockwork-style carbonatite dikes and veins with high concentrations of rare earth elements (e.g., La: 4140–21000 ppm, Ce: 9220–35800 ppm, Nd: 4800–13900 ppm). The central carbonatite dike swarm is characterized by zones of variable REE content, with peripheral zones enriched in HREE including yttrium. The principle REE-bearing phases in unoxidized carbonatite are ancylite and carbocernaite, with subordinate monazite, fluorapatite, burbankite, and Ca-REE fluorocarbonates. In oxidized carbonatite, REE are hosted primarily by Ca-REE fluorocarbonates (bastnäsite, parisite, synchysite, and mixed varieties), with lesser REE phosphates (rhabdophane and monazite), fluorapatite, and cerianite. REE abundances were substantially upgraded (e.g., La: 54500–66800 ppm, Ce: 11500–92100 ppm, Nd: 4740–31200 ppm) in carbonatite that was altered by oxidizing hydrothermal and supergene processes. Vertical, near surface increases in REE concentrations correlate with replacement of REE(±Sr,Ca,Na,Ba) carbonate minerals by Ca-REE fluorocarbonate minerals, dissolution of matrix calcite, development of Fe- and Mn-rich gossan, crystallization of cerianite and accompanying negative Ce anomalies in secondary fluorocarbonates and phosphates, and increasing ?18O values. These vertical changes demonstrate the importance of oxidizing meteoric water during the most recent modifications to the carbonatite stockwork. Scanning electron microscopy, energy dispersive spectroscopy, and electron probe microanalysis were used to investigate variations in mineral chemistry controlling the lateral complex-wide geochemical heterogeneity. HREE-enrichment in some peripheral zones can be attributed to an increase in the abundance of secondary REE phosphates (rhabdophane group, monazite, and fluorapatite), while HREE-enrichment in other zones is a result of HREE substitution in the otherwise LREE-selective fluorocarbonate minerals. Microprobe analyses show that HREE substitution is most pronounced in Ca-rich fluorocarbonates (parisite, synchysite, and mixed syntaxial varieties). Peripheral, late-stage HREE-enrichment is attributed to: 1) fractionation during early crystallization of LREE selective minerals, such as ancylite, carbocernaite, and Ca-REE fluorocarbonates in the central Bull Hill dike swarm, 2) REE liberated during breakdown of primary calcite and apatite with higher HREE/LREE ratios, and 3) differential transport of REE in fluids with higher PO43?/CO32? and F?/CO32? ratios, leading to phosphate and pseudomorphic fluorocarbonate mineralization. Supergene weathering processes were important at the stratigraphically highest peripheral REE occurrence, which consists of fine, acicular monazite, jarosite, rutile/pseudorutile, barite, and plumbopyrochlore, an assemblage mineralogically similar to carbonatite laterites in tropical regions.
Abstract: Stable calcium isotopic composition (44/40Ca) of silicate rock standards show limited variability [c.f., 1] although, fractionation between co-exiting ortho- and clino-pyroxenes have been reported [2]. Variability in 44/40Ca in Hawaiian shield stage tholeiites have been interpreted as evidence of subducted ancient marine carbonates, with very low 44/40Ca, into the Hawaiian plume [3]. Carbonatites are unique mantlederived carbonate-bearing igneous rocks with limited spatial but wide temporal occurrences. Few available measurements (n=5) of 44/40Ca in whole rock and leached carbonatites show a 0.2 ‰ range but broadly overlapping values with mantle-derived silicate rocks from different tectonic settings [1,4]. However, boron isotopic composition of global carbonatites suggest the contribution of subducted crustal component to the mantle source of relatively young carbonatites (<300 Ma old) [5], a signature which should potentially be traceable using Ca isotopes. We report 44/40Ca of global carbonatites ranging in age from Proterozoic to recent. The samples were analyzed using a 43Ca- 48Ca double spike on a Thermo Fischer Triton Plus Thermal Ionization Mass Spectrometer (TIMS) at IISc. 44/40Ca in the carbonatites (n = 11) range from 0.47 - 0.97 ‰ (w.r.t. SRM 915a). Our external reproducibility, estimated from multiple analyses of NIST standards SRM 915a, SRM 915b and seawater (NASS6), is better than 0.1 ‰ (2SD). 44/40Ca of the ~65 Ma old Ambadongar carbonatites of India, associated with eruption of the Deccan Traps, show correlations with Nb/Yb, K/Rb as well as with Sr/Nb, Sr/Zr. These variations suggest the role of phlogopite versus amphibole in the mantle source as well as subducted carbonates in controlling the 44/40Ca of these carbonatites.
Abstract: A growing number of studies have suggested that hydrothermal remobilization is crucial for the formation of carbonatite-hosted rare earth element (REE) deposits [1-3]. The Ashram REE deposit, hosted by the Paleoproterozoic Eldor Carbonatite Complex [4], is an example of a REE deposit formed mainly due to hydrothermal processes in magnesio- and ferro-carbonatite. The REE minerals in the Ashram deposit, monazite-(Ce), bastnäsite-(Ce), xenotime- (Y) and minor aeschynite-(Y), are secondary, and were precipitated from hydrothermal fluids. They occur mainly as disseminations, in breccia matrices and veins, and as vug fillings. Hydrothermal apatite and fluorite are also present in appreciable quantities in REE-mineralized zones. Monazite- (Ce) was the earliest REE mineral to form, and was followed by xenotime-(Y) and bastnäsite-(Ce). The compositions of the main REE minerals vary with location in the deposit, particularly in respect to their Nd2O3 and ThO2 contents. Two generations of monazite-(Ce) have been distinguished on the basis of their Nd content. Early, low-Nd monazite-(Ce) formed by replacing apatite through the substitution of 3REE3+ for 5Ca2+ + F- ; low-Nd apatite is LREE-enriched compared to apatite. In contrast, the later high-Nd generation, which has a chondrite-normalized REE profile almost perfectly parallel to that of the apatite, is interpreted to have formed by dissolving the Ca2+ and F- of the apatite and reconstituting the REE and phosphate as monazite-(Ce): Ca4.94REE0.060(PO4)3F = 0.060REEPO4 + F- + 4.94Ca2+ + 2.94PO4 3- Bastnäsite-(Ce) developed as a replacement of monazite- (Ce) through ligand exchange (F- and CO3 2- for PO4 3- ), while preserving the original REE chemistry. A combination of magmatic zone-refinement and hydrothermal remobilization, involving a chloride-bearing fluid, contributed to the formation of a carbonatite-hosted REE deposit.
Abstract: Carbonate-fluorapatite (also known as staffelite and/or francolite) can become a rock-forming mineral in the upper levels of some carbonatite complexes, such as at Sokli, Finland, and Kovdor, Russia. Carbonate-fluorapatite rocks are recognised as an important phosphate resource, but there is little consensus on their genesis. Two principal models are favoured: (1) a hydrothermal origin, from a late-stage, carbonatite-derived fluid or, (2) formation through supergene dissolution of carbonate and re-precipitation of apatite. In this contribution, we have investigated the texture and composition of different carbonate-fluorapatite generations (using cathodoluminescence microsopy and LA ICP MS) in order to evaluate the aforementioned formation mechanisms. Four carbonate-fluorapatite growth generations were identified: (1) primary apatite grains, with a rounded/euhedral habit and luminescing purple; (2) strongly luminescent epitactic rims on primary grains; (3) ‘aggregate’ apatite, forming a fine-grained groundmass, typically luminescing blue; (4) botryoidal growth zones, commonly luminescing blue, but in places green or non-luminescent. REE contents in secondary carbonate-fluorapatite generations (2–4) are markedly low, with some analyses below detection limit (typically <1 ppm). Furthermore, many of these analyses exhibit both positive and negative Ce anomalies, indicative of an oxidising environment. The low REE contents of the different carbonatefluorapatite generations indicates that negligible REE transfer occurred between different growth events, contrasting with hydrothermal apatite in other carbonatite complexes. Furthermore, the lack of any significant fractionation between subsequent carbonate-fluorapatite generations is interpreted as circumstantial evidence that these rocks did not form through hydrothermal alteration. This is compounded by the presence of a Ce anomaly, which is commonly interpreted as a weathering feature. While hydrothermal formation under different conditions, causing complete removal of the REE, cannot be ruled out, we conclude that the locations were, most-likely, formed in a supergene environment. Continued investigation of weathered carbonate-fluorapatite material from other localities is underway to assess this conclusion.
Abstract: Carbonatites are the primary source of LREE worldwide. Here we describe evidence from the Okorusu mine in NorthCentral Namibia, based on results from a suite of techniques including SEM-EDS and SEM-CL imaging, EPMA, LA-ICPMS on minerals and fluid inclusions, bulk rock chemistry and microthermometry. This provides indications of hydrothermal reworking in a carbonatite-related REE deposit. The Okorusu deposit is part of a ring complex consisting of syenites, nepheline syenites, and carbonatite with hydrothermal fluorite ore mineralisation formed principally by replacing carbonatite bodies. The primary carbonatites show a typical LREE enriched pattern. Primary REE mineralisation is contained in the magmatic phases apatite, pyrochlore and calcite. These phases have been partially broken down by hydrothermal activity. Most of the REE in the carbonatite samples now occur in secondary hydrothermal phases, mainly synchysite-(Ce). The REE occur also as synchysite-(Ce) in the hydrothermal fluorite but additionally they are incorporated into the fluorite structure resulting in cathodoluminescence zoning. Fluid inclusions are observed in both magmatic phases (apatite, calcite and clinopyroxene) and in hydrothermal phases (fluorite, calcite and quartz). The fluid inclusions associated with secondary REE mineralisation in fluorite consist of liquid-vapour inclusion with a constant liquid/bubble ratio and often a small daughter mineral. This suggests that the REE were transported by a relatively concentrated aqueous fluid. Fluid and melt inclusions hosted in the magmatic phases show a wider range in composition. The Okorusu carbonatite deposit shows primary and secondary features common to carbonatite deposits worldwide, and so the results reported here may be of wider significance.
Abstract: The deep carbon cycle and the origin of carbonatitic melts into the Earth’s mantle have been studied through the effect of CO2 on phase equilibria within carbonated eclogitic assemblage in the last decades. However the effect of temperature (T), pressure (P) and oxygen fugacity (fO2) on the melt composition remains unclear. This study aims to determine the melt composition of CO2-rich melts at fO2 buffered by the C/carbonate equilibrium as function of P and T. Experiments were performed using the Voggenreiter 840 t, Walker-type multi anvil press available at HP/HT Lab at National Institute of Geophysics and Volcanology (INGV) in Rome. The starting material employed for all the experiments is a mixture of synthetic omphacitic glass, quartz, dolomite and graphite representative of the Dolomite-CoesiteDiopside-Graphite buffering assemblage [DCDG; 1], doped with ilmenite and rutile and ~3 wt% iridium used as redox sensor to monitorate the oxygen fugacity during the experiment. The recovered quenched samples were polished for textural and chemical analysis of the mineral phases using Field emission scanning electron microscope and electron microprobe at the INGV. Preliminary results were combined with previous published data [2], and the determined fo2 compared with thermodynamic predictions. The obtained data show that at 800°C run product consists of a subsolidus mineral assemblage representative of the DCDG mineral assemblage. With increasing temperature, a carbonatitic melt forms with 1-5 wt% SiO2 at 900 °C, then evolves to a carbonate-silicate melt with 25 wt% SiO2 at 1100 °C, and to a silicate melt with ~32 wt% SiO2 at 1200 °C. Preliminary results demonstrate that magmas with compositions from carbonatitic to carbonate-silicate (hybrid) melts can form within less than 1 log unit of fO2 by redox melting of elemental carbon-bearing eclogite rocks.
Abstract: We have studied noble gases in carbonates and apatites from three carbonatites of South India, namely Hogenakal (2400 Ma), Sevattur (770 Ma) and Khambamettuu (523 Ma) by vacuum crushing. Apatite has also been analysed by pyrolysis. Vacuum crushing mostly releases the trapped gas components. The ratios 21Ne/20Ne, 22Ne/20Ne and 40Ar/36Ar increase with progressive crushing due to preservation of different composition gases in smaller inclusions released in later steps. This heterogeneity of isotopic composition of fluid inclusions is a consequence of the involvement of magmas carrying different noble gas signatures. The inclusions with lower ratios suggest the presence of a subducted atmospheric component, while the higher 21Ne/20Ne, 22Ne/20Ne and 40Ar/36Ar can be attributed to the presence of an enriched lithospheric mantle component. In addition, very minor trapped gases from less degassed, deeper mantle may also be present but overprinted by lithospheric and/or nucleogenic components. We propose that these carbonatites were generated only in an advanced stage of magmatism when this lithospheric component overwhelmed any contribution from the deeper mantle source. The lithospheric mantle underwent enrichment during an ancient subduction process through mantle metasomatism manifested in nucleogenic/radiogenic isotopic ratios of 21Ne/20Ne, 22Ne/20Ne and 40Ar/36Ar. The apatites analysed by pyrolysis clearly show nucleogenic 21Ne from 18O(?,n) reaction. We have demonstrated the potential of using U,Th–21Ne systematics as a thermo-chronometer in conjunction with the established U,Th–4He and U–136Xe clocks. While for Hogenakal, the U,Th–21Ne age of 845 ± 127 Ma is in agreement with the age of emplacement of other adjacent younger carbonatites, syenites and alkali granites, for the Sevattur apatite (738 ± 111 Ma) it indicates the crystallisation age.
Abstract: Ihouhaouene area in In Ouzzal terrane (Hoggar, South Algeria) is exceptional by numerous carbonatite complexes systematically associated to syenites. They constitute one of the oldest carbonatite emplaced at 2 Ga. Various types of carbonatites are distinguished by their successive placement and pegmatitic to brecciated appearance. The first-generation of carbonatites are always brecciated with elements of syenite and carbonate cement with calcite, apatite, alkali feldspar, wollastonite, clinopyroxene +/- sphene, allanite, quartz and garnet. Late carbonatite intrusions appear in small pegmatitic veins rich in apatite (3-50 mm). All carbonatites are calciocarbonatites (38-50 wt% CaO) with silica content ranging from 5 to 21 wt% SiO2. The high silica content is interpreted as assimilation of syenite material during emplacement. Carbonatites have high Rare Earth Element (REE) concentrations with high Ligh REE/Heavy REE fractionation (e.g. 1088 ppm La, La/Yb= 144-198) and variable concentrations in Th (26.5-197 ppm). The REE concentrations are mainly controlled by apatite phenocrysts (30-40 vol.%) with 4-9 wt% REE. In late pegmatitic carbonatite, REE-rich apatites are green-yellow phenocrysts with britholite exsolution (up to 40 vol.%, Ca4(REE)6 (SiO4,PO4)6 (OH,F,Cl)2). Britholites are hexagonal and occur as fine lamellar exsolutions (<10 um) in the same crystallographic axis (001) than apatites or as irregularshaped grains (10-200 um). All britholites contain 8-16 wt% La, 21-43 wt% Ce and 7-12 wt% Nd. The apatite-britholite exsolutions correspond to a substitution of the trivalent rareearth elements (REE3+) and Si4+ for Ca2+ and P5+. The REE substitution is accompanied by a change in volatile composition with F-rich apatite and Cl-rich britholite indicating that Si and Cl-rich hydrothermal fluids are present at the late stage of carbonatite evolution leading to REEenrichment and the crystallization of REE minerals.
Abstract: The Palabora Carbonatite Complex (PCC) in South Africa intruded at 2060 Ma into Archean basement. The tripartite pipe-like intrusion is represented by a northern and southern pyroxenite and the central Loolekop pipe. Carbonatites and phoscorites of the Loolekop pipe experienced at least 4 stages of mineralization, recrystallization and redistibution reflected by an (1) orthomagmatic, (2) late-magmatic, (3) sulphide and (4) post-magmatic phase (Giebel et al., 2017). These four stages exhibit considerable variability of REE mineralization and especially stages 2 and 4 show intense fluid-rock interaction textures. We present microtextural and compositional data on apatite and phlogopite along a 2 km depth profile through the Loolekop pipe and investigate how these data reflect fluidmineral interaction with depth during stage (2). A special focus lies on understanding the behaviour, sources and sinks of REE elements. While fluid-apatite interaction causes a dissolution of apatite coupled with a precipitation of monazite at apatite rims, the fluid-phlogopite interaction induces a chloritization of phlogopite and an occasional formation of britholite along strongly dissolved phlogopite rims. We suspect that REE are transported into the system by this late-magmatic fluid rather than being released by the dissolution of orthomagmatic REE-bearing minerals. Combining these observations with fluid inclusion textures and microthermometry, we will investigate the nature and composition of the involved fluids and will try to model REE mineralisation processes during late-magmatic fluidmineral ineraction
Abstract: The origin of intraplate carbonatitic to alkaline volcanism in Africa is controversial. A tectonic control, i.e., decompression melting associated with far-field stress, is suggested by correlation with lithospheric sutures, repeated magmatic cycles in the same areas over several million years, synchronicity across the plate, and lack of clear age progression patterns. Conversely, a dominant role for mantle convection is supported by the coincidence of Cenozoic volcanism with regions of lithospheric uplift, positive free-air gravity anomalies, and slow seismic velocities. To improve constraints on the genesis of African volcanism, here we report the first radiometric and isotopic results for the Catanda complex, which hosts the only extrusive carbonatites in Angola. Apatite (U-Th-Sm)/He and phlogopite 40Ar/39Ar ages of Catanda aillikite lavas indicate eruption at ca. 500–800 ka, more than 100 m.y. after emplacement of abundant kimberlites and carbonatites in this region. The lavas share similar high-? (HIMU)–like Sr-Nd-Pb-Hf isotope compositions with other young mantle-derived volcanics from Africa (e.g., Northern Kenya Rift; Cameroon Line). The position of the Catanda complex in the Lucapa corridor, a long-lived extensional structure, suggests a possible tectonic control for the volcanism. The complex is also located on the Bié Dome, a broad region of fast Pleistocene uplift attributed to mantle upwelling. Seismic tomography models indicate convection of deep hot material beneath regions of active volcanism in Africa, including a large area encompassing Angola and northern Namibia. This is strong evidence that intraplate late Cenozoic volcanism, including the Catanda complex, resulted from the interplay between mantle convection and preexisting lithospheric heterogeneities.
Abstract: The rare earth elements (REE) are critical metals that have been the subject of considerable recent research. In the published literature, REE deposits are typically divided into classes, which commonly include ‘alkaline igneous rocks’ and ‘carbonatites’ [1]. However, our recent work, carried out as part of the EURARE and HiTech AlkCarb projects, suggests that many deposits of the REE and other critical metals may be formed where late-stage carbonatites and associated fluids interact with alkaline igneous rocks. A key question is whether these carbonatites are formed by liquid immiscibility from the host alkaline magmas, or whether they are introduced from other sources. A classic example of a mineral deposit formed in this way is at Ivigtut in Greenland, where late-stage F and CO2 rich fluids interacted with alkali granitic melts to form a cryolite (Na3AlF6) deposit, with associated metasomatism and REE mobilisation. Isotopic evidence indicates that these late-stage fluids may have been carbonatite-derived [2]. Our more recent work indicates that REE enrichment in many alkaline igneous complexes may be generated by a similar mechanism. In the alkaline igneous province of NW Scotland, late-stage metasomatism by CO2-rich fluids has generated metasomatised veins with TREO up to 2 wt% [3]. Similar features are observed in the Ditra? Alkaline Igneous complex in Romania, where REE mineralisation is represented by monazite- and carbonate-rich veins cutting syenitic host rocks [4]; and at the Kizilcaören REE deposit in Turkey. This talk will provide an overview of the formation of REE mineralisation in this type of magmatic-hydrothermal system and consider future research questions.
International Journal of Earth Sciences, Vol. 106, 6, pp. 1963-1989.
South America, Brazil
carbonatite - Catalao II
Abstract: The Catalão II carbonatitic complex is part of the Alto Paranaíba Igneous Province (APIP), central Brazil, close to the Catalão I complex. Drill-hole sampling and detailed mineralogical and geochemical study point out the existence of ultramafic lamprophyres (phlogopite-picrites), calciocarbonatites, ferrocarbonatites, magnetitites, apatitites, phlogopitites and fenites, most of them of cumulitic origin. U–Pb data have constrained the age of Catalão I carbonatitic complex between 78 ± 1 and 81 ± 4 Ma. The initial strontium, neodymium and hafnium isotopic data of Catalão II (87Sr/86Sri= 0.70503–0.70599; ?Ndi= ?6.8 to ?4.7; 176Hf/177Hf = 0.28248–0.28249; ?Hfi= ?10.33 to ?10.8) are similar to the isotopic composition of the Catalão I complex and fall within the field of APIP kimberlites, kamafugites and phlogopite-picrites, indicating the provenance from an old lithospheric mantle source. Carbon isotopic data for Catalão II carbonatites (?13C = ?6.35 to ?5.68 ‰) confirm the mantle origin of the carbon for these rocks. The origin of Catalão II cumulitic rocks is thought to be caused by differential settling of the heavy phases (magnetite, apatite, pyrochlore and sulphides) in a magma chamber repeatedly filled by carbonatitic/ferrocarbonatitic liquids (s.l.). The Sr–Nd isotopic composition of the Catalão II rocks matches those of APIP rocks and is markedly different from the isotopic features of alkaline-carbonatitic complexes in the southernmost Brazil. The differences are also observed in the lithologies and the magmatic affinity of the igneous rocks found in the two areas, thus demonstrating the existence of regional-scale heterogeneity in the mantle sources underneath the Brazilian platform.
Abstract: We report preliminary data for sulfur isotopes from two spatially related Neoproterozoic carbonatite complexes in Tamil Nadu, S India, with the aim of getting further insights into their magmatic and/or post-emplacement histories [1]. The major sulfide phase in these rocks is pyrite, with minor chalcopyrite, whereas sulfate occurs as barite. A bimodal distribution of G34Ssulfide is found for Samalpatti (13.5 to 14.0‰), and Sevattur (?2.1 to 1.4‰) carbonatites. A significantly larger range of G34Ssulfide values is found for the associated Samalpatti silicate rocks (?5.2 to 7.4‰) relative to Sevattur pyroxenites and gabbros (?1.1 to 2.1‰). High G34Ssulfide values for Samalpatti carbonatites are unsual [2,3] but could reflect hydrothermal post-emplacement modification [1] of S isotopes. The low G34Ssulfide values for Sevattur may represent a mantle source signature. The G34Ssulfate is uniformly positive for both complexes, with most data falling in a narrow range (5.7 to 7.8‰) and one datum for a pyroxenite yielding more positive G34Ssulfate = 13.3‰. Data for '33S varies outside of analytical uncertainty (?0.07 to 0.04‰), indicating contribution from a source with a surface-derrived component. The small range of '33S values does not allow us to determine whether these sources contain S fractionated by biogeochemical (mass-dependent) or photochemical (mass-independent, pre GOE) processes. Data for '36S is positive, and varies within uncertainty (0.28 ± 0.15‰). Variations of this magnitude have been observed in other localities, and are not diagnostic of any unique source or process. The sulfur isotope data imply addition of crustal sulfur to Samalpatti. In contrast, sulfur from Sevattur has a mantle-like G34S but '33S with anomalous character. These observations support the idea of a different evolutionary story for these complexes, possibly more complex than previously thought.
Abstract: We report preliminary data for sulfur isotopes from two spatially related Neoproterozoic carbonatite complexes in Tamil Nadu, S India, with the aim of getting further insights into their magmatic and/or post-emplacement histories [1]. The major sulfide phase in these rocks is pyrite, with minor chalcopyrite, whereas sulfate occurs as barite. A bimodal distribution of G34Ssulfide is found for Samalpatti (13.5 to 14.0‰), and Sevattur (?2.1 to 1.4‰) carbonatites. A significantly larger range of G34Ssulfide values is found for the associated Samalpatti silicate rocks (?5.2 to 7.4‰) relative to Sevattur pyroxenites and gabbros (?1.1 to 2.1‰). High G34Ssulfide values for Samalpatti carbonatites are unsual [2,3] but could reflect hydrothermal post-emplacement modification [1] of S isotopes. The low G34Ssulfide values for Sevattur may represent a mantle source signature. The G34Ssulfate is uniformly positive for both complexes, with most data falling in a narrow range (5.7 to 7.8‰) and one datum for a pyroxenite yielding more positive G34Ssulfate = 13.3‰. Data for '33S varies outside of analytical uncertainty (?0.07 to 0.04‰), indicating contribution from a source with a surface-derrived component. The small range of '33S values does not allow us to determine whether these sources contain S fractionated by biogeochemical (mass-dependent) or photochemical (mass-independent, pre GOE) processes. Data for '36S is positive, and varies within uncertainty (0.28 ± 0.15‰). Variations of this magnitude have been observed in other localities, and are not diagnostic of any unique source or process. The sulfur isotope data imply addition of crustal sulfur to Samalpatti. In contrast, sulfur from Sevattur has a mantle-like G34S but '33S with anomalous character. These observations support the idea of a different evolutionary story for these complexes, possibly more complex than previously thought.
Abstract: Calcium isotope compositions are presented for two suites of carbonatites and associated alkaline silicate rocks from Neoproterozoic Sevattur and Samalpatti complexes in Tamil Nadu, South India. Despite their geographic proximity, the mean G44/40Ca values are different for Sevattur (G44/40Ca = 0.69 r 0.10‰, n = 7) and Samalpatti (0.81 r 0.16‰, n = 5). The former suite is derived from an enriched mantle source without significant post-emplacement modifications [1] and its Ca isotope composition falls to the lower end of Ca isotope range reported for mantle-derived rocks [2]. Some carbonatites from Samalpatti show a 44Ca-enriched signature which could reflect large-scale low-temperature modification, recognized also by their 13C–18O-enriched isotope systematics and sizeable loss of REE, when compared to pristine carbonatites from the area [1]. This is also consistent with albite–epidote metasomatic sample and shistose pyroxenite from Samalpatti, both showing a 44Ca-depleted signature. Leaching experiments confirm a systematic G44/40Ca offset with isotopically light carbonate relative to bulk sample [also 3]. Pyroxenites from Samalpatti are isotopically heavier than accompanying unmodified carbonatites and their G44/40Ca values fall into the mantle range. In contrast, pyroxenite and phosphate from Sevattur have a G44/40Ca value identical with associated carbonatites, indicating a homogeneous mantle source for the latter complex. For K-rich syenites and monzonites, 40K-decay corrections need to be considered for the intrinsic mass-dependent isotope fractionations considering the Neoproterozoic age and high K/Ca character of some samples.
Abstract: The 525 Ma Marinkas Quellen (MQ) Complex of southern Namibia, part of the Kuboos-Bremen Line (KBL) of alkaline igneous centers [1] consists of granites, nepheline syenites and carbonatites and is the only carbonatite locality in the KBL [1]. MQ carbonatite variteties include calciocarbonatites, magnesiocarbonatites and ferrocarbonatites. The enrichments in Ba, Nb and the REE vary widely in the carbonatites, with La ranging from 45 to 11154 ppm. All the carbonatites are characterised by large Zr, Hf, Ti depletions. Zr/Hf ratios ranges from 40 to 500, all greater than the chondritic value of 36. Such large Zr/Hf fractionations are often associated with carbonatite metasomatism. The values of carbon and oxygen isotope ratios of bulk carbonate in Marinkas Quellen carbonatites vary significantly (e.g., ?13C = -3.95 to -6.02‰; ?18 O = 8.84 to 22.22‰). The carbon isotope compositions are in the mantle range, while the oxygen isotope values extend to higher than typical mantle values, presumably due to interaction with hydrous fluids. All but two of the carbonatite samples have initial 87Sr/86Sr ratios falling in the range of 0.70236 to 0.70408. Of the remaining samples, one, a ferrocarbonatite, has a higher value of 0.70503 that is likely due to contamination by the surrounding rock or assimilation in the lower crust or Sr exchange with groundwater. The other, a magnesiocarbonatite, appears to have experienced an increase in its Rb/Sr ratio due to alteration, resulting in an over-corrected initial 87Sr/86Sr value. The relatively low Sr isotope ratios of most samples, plus their HNd(t) values (+3.9 to +4.8) values suggest that the carbonatite magma was generated from a long-lived low Rb/Sr, high Sm/Nd, relatively depleted mantle source. The radiogenic Pb isotope composition of the carbonatites (206Pb/204Pbi ratios from 18.06 to 22.38), suggests a high U/Pb source, akin to the HIMU mantle end member. This points to a sub-lithospheric (asthenospheric) source with only a relatively minor contribution from enriched lithospheric mantle
Abstract: North Tanzanian Divergence is the first stage of continental break-up of East African Rift and one of the most concentrated areas of carbonatite magmatism with Natron basin in the North (2 Ma-present - Lengai) and Manyara basin in the southern part (0.4-0.9 Ma). The Manyara basin has volcanic activities with mafic magmas as melilitites (Labait), Mg-nephelinites and carbonatite (Kwaraha), and more differentiated magmas as Mg-poor nephelinites (Hanang) recording deep magmatic environment and differentiation in the crust of CO2-rich alkaline magmas. Melilitite and Mg-nephelinite with olivine-cpx-phlogopite record mantle environment at 1.5 GPa-1300°C with water content in melt of 0.1- 0.4 wt% H2O (1-4 ppm in olivine, FTIR). Although fractional crystallization can be considered as an important process during ascent, leading to Mg-poor nephelinite with cpx-melanite-nepheline, complex zonation of cpx (e.g. abrupt change of Mg#, Nb/Ta, and H2O) recorded open system with multiple carbonate-rich silicate immiscibility and melilititic melt replenishment. The low water content of cpx (25 ppm H2O; FTIR) indicates that 0.3 wt% H2O was present during carbonate-rich nephelinite crystallization at crustal level (600 MPa - 1050°C). The interstitial melt entrapped as melt inclusions (MI) in nepheline evolved to CO2-rich and H2O-poor phonolitic composition with 6 wt% CO2 and 1 wt% S at logfO2=FMQ+1 to 1.5 (Fe3+/?Fe=0.3 - S6+/?S=0.55, XANES). At 200 MPa, phonolitic melt in MI reaches carbonate saturation and immiscibility process leads to trachytic melt with high CO2, S and halogen content (0.43 wt% CO2, SIMS; 2 wt% S, 0.84 wt% Cl; 2.54 wt% F) and very low H2O content (<0.1wt%, Raman) and an anhydrous Ca-Na±S,K carbonate liquid. The Ca-Na carbonatitic liquid in Mg-poor nephelinite represents an early stage of the evolution path towards carbonatitic magmatism as observed in Kwaraha and Lengai. Manyara volcanism has similarities with the Natron volcanism with multistage evolution and silicate-carbonatite magmatism but differ by their volatile components (up to 10 H2O wt% in Lengai nephelinite). This can be interpreted in term of depth of partial melting with H2O-CO2 lithospheric mantle source (Natron) and deep anhydrous CO2-rich asthenospheric mantle source in the southern part of rift initiation (Manyara) and percolation of deep CO2-rich silicate liquid leading to lithospheric mantle metasomatism.
Abstract: The Neoproterozoic Sevattur and Samalpatti alkaline– carbonatite complexes in S India were supposedly emplaced into regional metagranite at ~800 Ma [1]. Both complexes are close to each other (~4 km apart), with a similar NE–SW elongated oval shape arranged along NE–SW trending lineament formed by the Koratti–Attur tectonic zone [2]. Both complexes share a similar setting with central syenite intrusion mantled with a discontinuous ring and/or crescentshaped suites of carbonatites, pyroxenites, gabbros, and dunites. In contrast to identical tectonic position and similar structure, the two complexes differ significantly in geochemistry and Sr–Nd–Pb–O–C isotope compositions. The Sevattur suite is derived from an enriched mantle source without significant post-emplacement modification whilst extensive hydrothermal overprint by crustal fluids must have occurred to result in the observed 13C–18O-enriched systematics reported for the Samalpatti carbonatites [3]. Some Samalpatti pyroxenites, though, show a clear mantle signature [3]. We report preliminary K–Ar age-data, that indicate a prolonged period of the magmatic activity in this area. Sevattur gabbro and pyroxenite (both Bt-fraction) as well as one Samalpatti Cr-rich silicocarbonatite (Amp-fraction) yielded the range of ages at 700–800 Ma, consistent with previous reports [see 3 for details]. The new K–Ar data from syenites display significantly younger ages of 560–576 Ma for Samalpatti and 510–540 Ma for Sevattur, regardless of the mineral fraction used (Bt or Kfs). The K–Ar results are being supplemented by systematic U–Pb analyses of zircons. If proven true, the age disparity would have profound consequences on our understanding of carbonatite evolution.
Abstract: Pyrochlore is the main host of rare-metal elements of carbonatite rocks, including phoscorites, typical for prolonged history of alkaline magma crystallization at the mafic-ultramafic polyphase Kovdor massif. Pyrochlore associated with baddeleyite, zircon, zirkelite, zirkonolite and forms octahedral and cube-octahedral poikilitic crystals up to 2-5 cm, and represented by U, Ba-Sr and REE species of pyrochlore subgroup. The studied Kovdor pyrochlores are characterized by increased up to 6.5% U and an extremely high Th – up to 40%, with Th/U up to 500. Pyrochlore U-Pb SHRIMP ages of 290-364 Ma correlate with variations in U of different samples, whereas the Th and common Pb have a minor effect on this value. Obtained ages are significantly underestimated and may reflect the influence of the matrix effect or later low-temperature closing of the U-Pb pyrochlore system, as well as the actual transformations of pyrochlore crystal matrix due to the interaction with the late carbonate fluids. Thus the early pyrochlores and U-pyrochlores crystallized at 364 Ma within phoscorites and early calcite carbonatites, whereas Sr-Ba pyrochlores of late calcitedolomite carbonatite formed at 340 Ma, and Th-pyrochlore rims occured at the later stages of the interaction with metasomatizing fluids 290 m.y. ago. Kovdor baddeleyite is also charecterized by high composition heterogeneity determined by the difference in its origin from olivinites to ore-bearing foscorites and postmagmatic syenites. But baddeleyite from calcitemagnetite mineral association have uniform U: 184 ±40, Th: 6.4 ±1.7, ¦REE: 34 ±6, Hf: 7629 ± 599, Nb: 3595 ±840, Ti: 56 ±14, Y: 22 ±4 ppm, and HHf: +6.5 ±1.7 at the age of 379 ±6 Ma. The U-Pb SHRIMP age data demonstrate the concordance of all studied baddeleyite samples and the absence of a significant age difference between baddeleyites of the carbonatite phase: 379 ±3 and foscorites: 379 ±4 Ma. The weighted average age for all the studied baddeleyite samples (n = 8) is 379 ±2.4 Ma at MSWD of 0.6. This can also indicate a relatively short time-interval of magmatism in the formation of Kovdor polyphase massif which did not exceed 5 m.y. and could be related to the Devonian mantleplume activity.
Abstract: Calcic garnets are an important – although somewhat neglected – member of the garnet group. Typically, these mineral are members of complex solid solutions involving largely substitutions in the Fe3+/Al and Si sites and at least eight different end-members. The absolute majority of garnets in this family are Ti-Mg-Fe2+(± Al ± Zr)-bearing andradite transitional to morimotoite and schorlomite. Importantly, these garnets occur as common accessory minerals in a wide range of igneous and rocks, including nepheline syenites, alkali feldspar syenites, melteigite-urtites, nephelinites, melilitolites, melilitites, calcite carbonatites, ultramafic lamprophyres, orangeites, contaminated kimberlites, skarns and rodingites. Calcic garnets have a great capacity for atomic substitutions involving high-field-strength elements and, even more importantly, rare earths (up to 4000 ppm, including Y), Th and U (both up to 100 ppm) at low levels of common Pb. Their (La/Yb)cn ratio varies over two orders of magnitude (from < 0.01 to ~1), making these minerals a sensitive indicator of crystal fractionation, degassing and other magma-evolution processes. Given these unique compositional characteristics and surprising lack of interest in these minerals in the previous literature, we explored the possibility of using calcic garnets as a U-Pb geochronometer. For this purpose, we selected samples of well-crystallized igneous garnet from four very different rock types of different age, including: carbonatite (Afrikanda) from the Devonian Kola Alkaline Province, carbonatite from the Neoproterozoic Belaya Zima complex (Central-Asian mobile belt), ijolite from the Chick Ordovician igneous complex (Central-Asian mobile belt), granitic pegmatite from the Eden Lake complex in the Paleoproterozoic Trans-Hudson orogen, and feldspathoid syenite from the Cinder Lake alkaline complex in the Archean Knee Lake greenstone belt. U-Pb TIMS ages of the studied garnets are mostly concordant and reveal perfect correspondence with reported U-Pb zircon or perovskite ages as well as Sm-Nd isochrone age for these complexes. Therefore we can advertise calcic garnets as a promising tool for U-Pb geochronological studies.
Abstract: Carbonatites are carbonate-rich and SiO2-poor magmas with a low viscosity and low melting temperature (see [1]) making them amongst the most mobile and unusual melts produced on Earth. They occur worldwide in a range of tectonic settings, including continental rift (e.g. Tanzania, Kaiserstuhl), oceanic intraplate (e.g. Cape Verde), convergent margins (e.g. Italy) and cratons (e.g. Canada), with eruption ages spanning from 3 Ga (3007 Ma Tupertalik, Greenland, [2]) to present day (Oldoinyo Lengai, Tanzania). Nevertheless, their genesis and source remain poorly understood and the subject of much debate. They are considered to be either products of direct low-degree partial melting of a carbonated mantle source, products of immiscible separation from a carbonated silicate melt or formed by fractional crystallisation from a carbonated alkalirich silicate melt (see [1] and references therein). In order to gain further insight into the genesis and mantle source of these unusual magmas, we will present the first combined HSE and Os-Hf isotope systematics on a suite of carbonatites representative of their large age span and compositional range (Ca, Mg, Fe and Na-rich).
Abstract: The composition of the early Earth’s atmosphere is believed to result from significant magma outgassing during the Archaean eon. It has been widely debated whether the oxygen fugacity (fo2) of the Earth’s mantle has remained constant over the last ~3.8 Ga to levels where volatiles were mostly in their mobile form [1,2], or whether the mantle has experienced a gradual increase of its redox state [3]. Both hypotheses raise fundamental questions on the effect of composition of the early Earth’s accreting material, the origin and availability of primordial carbon in Earth’s interior, and the migration rate of CO2-rich magmas. In addition, the occurrence in nature of carbonatites (or silicate-carbonatitic rocks), diamonds and carbides indicate a dominant control of the mantle redox state on the volatile speciation over time and, maybe, on mechanisms of their formation, reaction and migration through the silicate mantle. A recent model has been developed that combines both experimental results on the fo2 of preserved carbonaceous chondrites at high pressure and thermodynamic predictions of the the temporal variation of the mantle redox state, with the CO2-bearing magmas that could form in the early asthenospheric mantle. Since any variation in melt composition is expected to cause significant changes in the physical properties (e.g., viscosity and density), the migration rate of these magmas has been determined using recent in situ viscosity data on CO2-rich melts with the falling sphere technique. Our results allow determining the composition of CO2- bearing magmas as function of the increasing mantle redox state over time, and the mechanisms and rate for exchange of carbon between mantle reservoirs.
Abstract: Deformed Alkaline Rocks and Carbonatites (DARCs) are markers of suture zones where continents have rifted apart and later amalgamated [1]. Petrological and geochronological data indicates that parts of India and East Antarctica may have been involved in several episodes of collision and breakup during the assembly of past supercontinents [2]. DARCs at the eastern margin of the Eastern Ghats Province (EGP) in India preserve the record of these amalgamation and breakup events. It is thought that the Napier Complex of East Antarctica collided with the Dharwar Craton of India at ca. 1.60 Ga forming the central and eastern Indian shield [3]. New zircon U-Pb ages from DARCs at the EGP margin show that the alkaline complexes (Kamakhyanagar: 1350±14 Ma Rairakhol: 1379±6 Ma; Khariar: 1478±5 Ma; Koraput: 1387±34 Ma; Kunavaram: 1360±5 Ma; Jojuru: 1352±6 Ma) were emplaced in a narrow time interval. The alkaline magmatism marks an episode of rifting in the Indo-Antarctic continental fragment, correlatable with breakup of the Columbia supercontinent. Metamorphic zircon from the alkaline rocks furnish age populations at 917-950 Ma, 792- 806 Ma and 562-569 Ma. The 917-950 Ma ages are correlated with the closure of an oceanic basin between the Ruker Terrane of East Antarctica and the Indian Shield during the assembly of the Rodinia supercontinent. This led to the collision of the Ruker Terrane with the combined India-Napier Complex producing the Grenville-age EGPRayner Complex orogen [2, 3]. The 792-806 Ma ages record the disintegration of Rodinia when Greater India started to break away from East Antarctica [4]. In the early Paleozoic, India reconverged towards Antarctica and Australia during Gondwanaland assembly. The 562-569 Ma zircon ages date the resulting collisions during Pan-African orogenesis.
Abstract: The geochemistry and mineralogy of REE deposits is diverse, from carbonatite-related deposits, alkaline rocks, mineral sands and ion adsorption clays to potential by-products of phosphate and bauxite, and reuse of waste materials. Despite the large number of prospects that have been explored recently, very little additional REE production has started. A major challenge is to design effective, cost-efficient and environmentally-friendly processing and extraction. Processing flow sheets have to be constructed carefully for each deposit. Translating geochemistry and mineralogy studies, including quantitative mineralogy results, into processing characteristics can be illustrated using results from the Songwe Hill carbonatite, Malawi. Combining results with other published data then allows us to make some general conclusions about the common REE ore minerals and their geological environment, including the REE fluorcarbonate series, monazite and xenotime. The use of chemicals for REE extraction is often the largest environmental burden to mitigate. A new issue is that certain REE, such as Ce, are in oversupply, and are not being recovered in some proposed processing flowsheets. It will be important to understand the environmental and commercial implications of this development.
Abstract: The Carboniferous sub-platform Tajno alkaline-carbonatite intrusion is located within a narrow alkaline magmatic belt, which trends E–W from SW Lithuania to NE Poland, along the southern rim of the Mesoproterozoic A–type Mazury Complex. The Tajno pluto–volcanic massif comprises clinopyroxenite cumulates and syenites that are crosscut by carbonatite veins of variable thickness. An emplacement age for the carbonatite has been obtained based on zircon U–Pb and pyrrhotite Re–Os from albitites crosscut by the intrusion. Both ages cluster at 354–345Ma, which corresponds to the Tournaisian Epoch of the Early Carboniferous Period. The carbonatite is 5 to 20Ma younger than the Kola Province, Russian Federation [1]. The current Tajno pluto-volcanic massif lies under ~600m of a Meso–Cenozoic cover. Carbonatite igneous systems are formed by processes of partial melting in metasomatised lithospheric mantle, and are associated with mantle plumes. This implies that a specific geochemical footprint may be spread throughout the host rocks and overlying sedimentary cover by post–emplacement processes. This is of key importance for carbonatite mineral exploration under cover. The Tajno carbonatitic veins do not contain typical accessory minerals (e.g. pyrochlore, perovskite, zirconolite, baddeleyite) that are classically found in other carbonatites. Instead, REE-bearing minerals such as burbankite, parisite, synchysite and bastnaesite are common. This explains its low Nb content. By contrast, fluorite is abundant as cement in the carbonatite breccia.This new study of alkaline-carbonatite rock assemblages is focused on: (1) characterise Tajno's isotopic, REE and HFSE footprint based on petrographic and geochemical observations of apatite and titanite; and (2) increase the understanding of Tajno–type carbonatitic intrusions in the region, and determine if such intrusions can be detected under the sedimentary cover by geochemical techniques. [1] Demaiffe et al.,(2013) The Journal of Geology 12, (1), 91–104
Central European carbonatites under cover: insights for mineral exploration from the Tajno alkaline intrusions, NE Poland.
Abstract: The Miaoya carbonatite complex in the South Qinling orogenic belt hosts one of the largest rare earth element (REE)-Nb deposits in China that is composed of carbonatite and syenite. The emplacement age of the complex and the geochronological relationship between the carbonatite and syenite have long been debated. In this study, in situ U-Th-Pb ages have been obtained for the constituent minerals zircon, monazite and columbite from carbonatite and syenite of the Miaoya complex, together with their chemical and isotopic compositions. In situ trace element compositions for zircon from carbonatite and syenite are highly variable. The zircon displays slightly heavy REE (HREE)-enriched chondrite-normalized patterns with no Eu anomaly and various light REE (LREE) contents. In situ Th-Pb dating for zircon from the Miaoya complex by laser ablation ICP-MS yields ages of 442.6 ± 4.0 Ma (n = 53) for syenite and 426.5 ± 8.0 Ma (n = 23) for carbonatite. Monazite from carbonatite and syenite shows similar chondrite-normalized REE patterns and yields a consistent Th-Pb age of ~ 240 Ma. Based on petrographic and chemical composition, columbite from the carbonatite can be identified into two groups. The columbite dispersed within carbonatite is characterized by slightly LREE-enriched chondrite-normalized REE patterns, whereas columbite associated with apatite is characterized by LREE-depleted trends. Columbite has been further determined to have a weighted mean 206Pb/238U age of 232.8 ± 4.5 Ma (n = 9) using LA-ICP-MS. Detailed geochronological and chemical investigations suggest that there were two major episodes of magmatic/metasomatic activities in the formational history of the Miaoya carbonatite complex. The early alkaline magmatism emplaced in the Silurian was related to the opening of the Mianlue Ocean, whereas the late metasomatism or hydrothermal overprint occurred during the Triassic South Qinling orogeny. The latter serves as the major ore formation period for both REE (e.g., monazite) and Nb (e.g., columbite).
Barium isotopic composition of the mantle constrained by carbonatites.
Goldschmidt Conference, 1p. Abstract
Africa, Tanzania, east Africa, Canada, Europe, Germany, Greenland
carbonatite
Abstract: Deep mantle origin and ultra-reducing conditions in podiform chromitite: diamonds, moissanite, and other unusual minerals in podiform chromitites from the Pozanti-Karsanti ophiolite, southern Turkey
Abstract: The Ust-Chulman apatite ore body is situated within the Nimnyrskaya apatite zone at the Aldan shield in Russia. The latest data confirm the carbonatitic origin of the Seligdar apatite deposit (Prokopyev et al. in Ore Geol Rev 81:296-308, 2017). The results of our investigations demonstrate that the magnetite-apatite-dolomitic rocks of the Ust-Chulman are highly similar to Seligdar-type dolomitic carbonatites in terms of the mineralogy and the fluid regime of formation. The ilmenite and spinel mineral phases occur as solid solutions with magnetite, and support the magmatic origin of the Ust-Chulman ores. The chemical composition of REE- and SO3-bearing apatite crystals and, specifically, monazite-(Ce) mineralisation and the formation of Nb-rutile, late hydrothermal sulphate minerals (barite, anhydrite) and haematite are typical for carbonatite complexes. The fluid inclusions study revealed similarities to the evolutionary trend of the Seligdar carbonatites that included changes of the hydrothermal solutions from highly concentrated chloride to medium-low concentrated chloride-sulphate and oxidized carbonate-ferrous.
Abstract: Re-Os and platinum group element analyses are reported for peridotite xenoliths from the 533 Ma Venetia kimberlite cluster situated in the Limpopo Mobile Belt, the Neoarchaean collision zone between the Kaapvaal and Zimbabwe Cratons. The Venetian xenoliths provide a rare opportunity to examine the state of the cratonic lithosphere prior to major regional metasomatic disturbance of Re-Os systematics throughout the Phanerozoic. The 32 studied xenoliths record Si-enrichment that is characteristic of the Kaapvaal lithospheric mantle and can be subdivided into five groups based on Re-Os analyses. The most pristine group I samples (n = 13) display an approximately isochronous relationship and fall on a 3.28 ± 0.17 Ga (95 % conf. int.) reference line that is based on their mean TMA age. This age overlaps with the formation age of the Limpopo crust at 3.35-3.28 Ga. The group I samples derive from ?50 to ?170 km depth, suggesting coeval melt depletion of the majority of the Venetia lithospheric mantle column. Group II and III samples have elevated Re/Os due to Re addition during kimberlite magmatism. Group II has otherwise undergone a similar evolution as the group I samples with overlapping 187Os/188Os at eruption age: 187Os/188OsEA, while group III samples have low Os concentrations, unradiogenic 187Os/188OsEA and were effectively Re-free prior to kimberlite magmatism. The other sample groups (IV and V) have disturbed Re-Os systematics and provide no reliable age information. A strong positive correlation is recorded between Os and Re concentrations for group I samples, which is extended to groups II and III after correction for kimberlite addition. This positive correlation precludes a single stage melt depletion history and indicates coupled remobilisation of Re and Os. The combination of Re-Os mobility, preservation of the isochronous relationship, correlation of 187Os/188Os with degree of melt depletion and lack of radiogenic Os addition puts tight constraints on the formation and subsequent evolution of Venetia lithosphere. First, melt depletion and remobilisation of Re and Os must have occurred within error of the 3.28 Ga mean TMA age. Second, the refractory peridotites contain significant Re despite recording >40 % melt extraction. Third, assuming that Si-enrichment and Re-Os mobility in the Venetia lithospheric mantle were linked, this process must have occurred within ?100 Myr of initial melt depletion in order to preserve the isochronous relationship. Based on the regional geological evolution, we propose a rapid recycling model with initial melt depletion at ?3.35 Ga to form a tholeiitic mafic crust that is recycled at ?3.28 Ga, resulting in the intrusion of a TTG suite and Si-enrichment of the lithospheric mantle. The non-zero primary Re contents of the Venetia xenoliths imply that TRD model ages significantly underestimate the true depletion age even for highly depleted peridotites. The overlap of the ?2.6 Ga TRD ages with the time of the Kaapvaal-Limpopo collision is purely fortuitous and has no geological significance. Hence, this study underlines the importance of scrutiny if age information is to be derived from whole rock Re-Os analyses.
Earth and Planetary Science Letters, Vol. 454, pp. 121-131.
Mantle
carbonatites
Abstract: Carbonatites are peculiar magmatic rocks with mantle-related genesis, commonly interpreted as the products of melting of CO2-bearing peridotites, or resulting from the chemical evolution of mantle-derived magmas, either through extreme differentiation or secondary immiscibility. Here we report the first finding of anatectic carbonatites of crustal origin, preserved as calcite-rich polycrystalline inclusions in garnet from low-to-medium pressure migmatites of the Oberpfalz area, SW Bohemian Massif (Central Europe). These inclusions originally trapped a melt of calciocarbonatitic composition with a characteristic enrichment in Ba, Sr and LREE. This interpretation is supported by the results of a detailed microstructural and microchemical investigation, as well as re-melting experiments using a piston cylinder apparatus. Carbonatitic inclusions coexist in the same cluster with crystallized silicate melt inclusions (nanogranites) and COH fluid inclusions, suggesting conditions of primary immiscibility between two melts and a fluid during anatexis. The production of both carbonatitic and granitic melts during the same anatectic event requires a suitable heterogeneous protolith. This may be represented by a sedimentary sequence containing marble lenses of limited extension, similar to the one still visible in the adjacent central Moldanubian Zone. The presence of CO2-rich fluid inclusions suggests furthermore that high CO2 activity during anatexis may be required to stabilize a carbonate-rich melt in a silica-dominated system. This natural occurrence displays a remarkable similarity with experiments on carbonate-silicate melt immiscibility, where CO2 saturation is a condition commonly imposed. In conclusion, this study shows how the investigation of partial melting through melt inclusion studies may unveil unexpected processes whose evidence, while preserved in stiff minerals such as garnet, is completely obliterated in the rest of the rock due to metamorphic re-equilibration. Our results thus provide invaluable new insights into the processes which shape the geochemical evolution of our planet, such as the redistribution of carbon and strategic metals during orogenesis.
Journal of Volcanology and Geothermal Research, in press available, 19p.
Africa, Angola, Democratic Republic of Congo
carbonatites
Abstract: The South Atlantic Igneous Province comprises the Paraná Basalts, Rio Grande Rise, Tristan archipelago and surrounding guyot province,Walvis Ridge, Etendeka basalts and, in somemodels, the alkaline igneous lineament in the Lucapa corridor, Angola. Although these volcanics are often considered to have a single generic origin, complexities that suggest otherwise are observed. The Paraná Basalts erupted ~5 Ma before sea-floor spreading started in the neighborhood, and far more voluminous volcanic margins were emplaced later. A continental microcontinent likely forms much of the Rio Grande Rise, and variable styles of volcanism built the Walvis Ridge and the Tristan da Cunha archipelago and guyot province. Such complexities, coupled with the northward-propagating mid-ocean ridge crossing amajor transverse transtensional intracontinental structure, suggest that fragmentation of Pangaea was complex at this latitude and that the volcanism may have occurred in response to distributed extension. The alternative model, a deep mantle plume, is less able to account for many observations and no model variant can account for all the primary features that include eruption of the Paraná Basalts in a subsiding basin, continental breakup by rift propagation that originated far to the south, the absence of a time-progressive volcanic chain between the Paraná Basalts and the Rio Grande Rise, derivation of the lavas from different sources, and the lack of evidence for a plume conduit in seismic-tomography- and magnetotelluric images. The region shares many common features with the North Atlantic Igneous Province which also features persistent, widespread volcanismwhere a propagating mid-ocean ridge crossed a transverse structural discontinuity in the disintegrating supercontinent.
International Journal of Earth Sciences, Vol. 106, pp. 2797-2813.
Africa, Namibia
carbonatites
Abstract: Rb-Sr whole-rock and mineral isotope data from nepheline syenite, tinguaite, and carbonatite samples of the Kalkfeld Complex within the Damaraland Alkaline Province, NW Namibia, indicate a date of 242?±?6.5 Ma. This is interpreted as the age of final magmatic crystallization in the complex. The geological position of the complex and the spatially close relationship to the Lower Cretaceous Etaneno Alkaline Complex document a repeated channeling of small-scale alkaline to carbonatite melt fractions along crustal fractures that served as pathways for the mantle-derived melts. This is in line with Triassic extensional tectonic activity described for the nearby Omaruru Lineament-Waterberg Fault system. The emplacement of the Kalkfeld Complex more than 100 Ma prior to the Paraná-Etendeka event and the emplacement of the Early Cretaceous Damaraland intrusive complexes excludes a genetic relationship to the Tristan Plume. The initial ?Sr-?Nd pairs of the Kalkfeld rocks are typical of younger African carbonatites and suggest a melt source, in which EM I and HIMU represent dominant components.
Contributions to Mineralogy and Petrology, Vol. 172, 96
Africa, Malawi
carbonatite
Abstract: Carbonatites host some of the largest and highest grade rare earth element (REE) deposits but the composition and source of their REE-mineralising fluids remains enigmatic. Using C, O and 87Sr/86Sr isotope data together with major and trace element compositions for the REE-rich Kangankunde carbonatite (Malawi), we show that the commonly observed, dark brown, Fe-rich carbonatite that hosts REE minerals in many carbonatites is decoupled from the REE mineral assemblage. REE-rich ferroan dolomite carbonatites, containing 8-15 wt% REE2O3, comprise assemblages of monazite-(Ce), strontianite and baryte forming hexagonal pseudomorphs after probable burbankite. The 87Sr/86Sr values (0.70302-0.70307) affirm a carbonatitic origin for these pseudomorph-forming fluids. Carbon and oxygen isotope ratios of strontianite, representing the REE mineral assemblage, indicate equilibrium between these assemblages and a carbonatite-derived, deuteric fluid between 250 and 400 °C (?18O + 3 to + 5‰VSMOW and ?13C ? 3.5 to ? 3.2‰VPDB). In contrast, dolomite in the same samples has similar ?13C values but much higher ?18O, corresponding to increasing degrees of exchange with low-temperature fluids (< 125 °C), causing exsolution of Fe oxides resulting in the dark colour of these rocks. REE-rich quartz rocks, which occur outside of the intrusion, have similar ?18O and 87Sr/86Sr to those of the main complex, indicating both are carbonatite-derived and, locally, REE mineralisation can extend up to 1.5 km away from the intrusion. Early, REE-poor apatite-bearing dolomite carbonatite (beforsite: ?18O + 7.7 to + 10.3‰ and ?13C ?5.2 to ?6.0‰; 87Sr/86Sr 0.70296-0.70298) is not directly linked with the REE mineralisation.
Russian Geology and Geophysics, Vol. 58, pp. 1222-1231.
Russia
carbonatite
Abstract: We present results of U-Pb (SHRIMP II) and Ar-Ar geochronological study of the rocks of the Chuktukon massif, which is part of the Chadobets alkaline-carbonatite complex, and of the weathering crust developed after them. Perovskite from picrites and monazite from the weathering crust were dated by the U-Pb (SHRIMP II) method, and rippite from carbonatites, by the Ar-Ar method. Rippite has first been used as a geochronometer. The estimated ages (252 ± 12 and 231 ± 2.7 Ma) testify to two magmatism pulses close in time (within the estimation error) to the stages of alkaline magmatism in the Siberian Platform (250-245 and 238-234 Ma). These pulses characterize, most likely, the processes accompanying and completing the activity of the mantle superplume that formed the Siberian Igneous Province at 250-248 Ma. The monazite-estimated age (102.6 ± 2.9 Ma) reflects the time of formation of the ore-bearing weathering crust on the massif rocks.
Journal of South American Earth Sciences, Vol. 80, pp. 1-17.
South America, Brazil
carbonatite
Abstract: We present results of U-Pb dating (by MC-ICP-MS) of zircons from samples that cover all of the known lithotypes in the Seis Lagos Carbonatite Complex and associated lateritic mineralization (the Morro dos Seis Lagos Nb deposit). The host rock (gneiss) yielded an age of 1828 ± 09 Ma interpreted as the crystallization time of this unit. The altered feldspar vein in the same gneiss yielded an age of 1839 ± 29 Ma. Carbonatite samples provided 3 groups of ages. The first group comprises inherited zircons with ages compatible with the gneissic host rock: 1819 ± 10 Ma (superior intercept), 1826 ± 5 Ma (concordant age), and 1812 ± 27 Ma (superior intercept), all from the Orosirian. The second and the third group of ages are from the same carbonatite sample: the superior intercept age of 1525 ± 21 Ma (MSWD ¼ 0.77) and the superior intercept age of 1328 ± 58 Ma (MSWD ¼ 1.4). The mineralogical study indicates that the ~1.3 Ga zircons have affinity with carbonatite. It is, however, a tendence rather than a well-defined result. The data allow state that the age of 1328 ± 58 Ma represents the maximum age of the carbonatite. Without the same certainty, we consider that the data suggest that this age may be the carbonatite age, whose emplacement would have been related to the evolution of the K'Mudku belt. The best age obtained in laterite samples (a superior intercept age of 1828 ± 12 Ma) is considered the age of the main source for the inherited zircons related to the gneissic host rock.
Ackerman, L., Magna, T., Rapprich, V., Upadhyay, D., Kratky, O., Cejkova, B., Erban, V., Kochergina, Y.V., Hrstka, T.
Contrasting petrogenesis of spatially related carbonatites from Samalpatti and Sevattur, Tamil Nadu, India: insights from trace element and isotopic geochemistry.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 31-33.
India
deposit - Samalpatti, Sevattur
Abstract: The Tamil Nadu region in southern India hosts several carbonatite bodies (e.g., Hogenakal, Samalpatti, Sevattur, Pakkanadu-Mulakkadu) which are closely associated with alkaline silicate rocks such as syenites, pyroxenites or dunites (e.g, Kumar et al., 1998; Schleicher et al., 1998; Srivastava, 1998). This is in contrast to the carbonatite occurrences in north-western India associated with the Deccan Trap basalts (e.g., Amba Dongar) or Proterozoic Newania dolomitic carbonatites. We have studied two, spatially related, Neoproterozoic carbonatite-silico(carbonatite) suites in association with alkaline silicate rocks (e.g., pyroxenite, gabbro) from Sevattur and Samalpatti in terms of petrography, chemistry and radiogenic-stable isotopic compositions in order to provide constraints on their genesis and evolution. In these two bodies, several different carbonatite types have been reported previously with striking differences in their trace element and isotopic compositions (Srivastava, 1998; Viladkar and Subramanian, 1995; Schleicher et al., 1998; Pandit et al., 2002). Collected data for previously poorly studied calcite carbonatites from the Sevattur representing the first carbonatite magmas on this locality, indicate similar geochemical characteristics to those of dolomitic carbonatites, such as high LREE/HREE ratios, very high Sr and Ba contents, large amounts of apatite and magnetite, identical Sr-Nd-C-O isotopic compositions. Thus, they were derived from an enriched mantle source without significant post-emplacement modifications through crustal contamination and hydrothermal overprint, in agreement with previous studies (e.g., Schleicher et al., 1998). Detailed microprobe analyses revealed that high levels of some incompatible elements (e.g., REE, Y, Sr, Ba) cannot be accounted by matrix calcite hosting only significant amounts of SrO (~0.6-1.2 wt.%). On the other hand, abundant micro- to nano-scale exsolution lamellae and/or inclusions of mckelveyite-(Nd) appear to host a significant fraction of LREE in parallel with apatite. Distribution of Sr is most likely influenced also by common but heterogeneously dispersed barite and strontianite. Newly acquired as well as detailed inspection of available geochemical data permits distinguish two different types of carbonatites in Samalpatti: (1) Type I similar to Sevattur carbonatites in terms of mineralogy, trace element and radiogenic-stable isotopic compositions and (2) Type II with remarkably low concentrations of REE and other incompatible trace elements, more radiogenic Sr isotopic compositions and extremely variable C–O isotopic values. The petrogenesis of the Type II seems to be intimately associated with the presence of silicocarbonatites and abundant silicate mineral domains. Instead of liquid immiscible separation from a silicate magma, elevated SiO2 contents observed in silico-carbonatites may have resulted from the interaction of primary carbonatitic melts and crustal rocks prior to and/or during magma emplacement. Arguments for such hypothesis include variable, but radiogenic Sr isotopic compositions correlated with SiO2 and other lithophile elements (e.g., Ti, Y, Zr, REE). Calc-silicate marbles present in the Samalpatti area could represent a possible evolved crustal end member for such process due to the inability of common silicate rocks (pyroxenites, granites, diorites) to comply with radiogenic isotopic constraints. The wide range of C-O isotopic compositions found in Samalpatti carbonatites belong to the highest values ever reported for magmatic carbonates and can be best explained by massive hydrothermal interaction with carbonated fluids. Unusual high-Cr silicocarbonatites were discovered at Samalpatti forming centimetre to decimetre-sized enclaves enclosed in pyroxenites with sharp contacts at hand specimen scale. Detailed microprobe analyses revealed peculiar chemical compositions of the Mgamphibole with predominantly sodic composition embaying and replacing Na-Cr-rich pyroxene (kosmochlor), accompanied by the common presence of Cr-spinel and titanite. Such association have been reported for hydrous metasomatism by Na-rich carbonatitic melts at upper mantle conditions (Ali and Arai, 2013). However, the mineralogy and the mode of occurrence of Samalpatti Mg–-r-rich silicocarbonatites argue against such origin. We explain the petrogenesis of these rocks through the reaction of pyroxenites with enriched mantle-derived alkali-CO2-rich melts, as also evidenced by mantle-like O and Hf isotopic compositions.
A secular variation of stable isotope record in global carbonatite magma.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p.11.
Global
carbonatites
Abstract: Carbonatites are magmatic rocks, origin of these relates to the involvement of mantle fluid. Thus they provide indirect method to understand the sub-continental upper mantle fluid composition. The first report on carbonatites and the later eruption of the natrocarbonatite paved way for investigating the heterogeneity of the mantle with depth and since then, many other occurrences have been found worldwide, offering suitable samples for probing the mantle. We present record of stable isotopic composition of carbonatites spanning Precambrian, Proterozoic to Phanerozoic to Recent time based on their temporal occurrences and global distribution in the geological record. We consider the various tectonic settings from which carbonatites have been reported, the underlying eruption mechanisms taking into account the tectonic significance of their occurrence and their imprints on surrounding rocks. This account covers carbonatites and associated rocks from different continents with a prime focus on carbon and oxygen isotopes. Carbon and oxygen isotope composition vary significantly within time spans. These variations depend on other factors besides mantle composition i.e. carbonate mineralogy and alteration processes that can cause a shift from original compositions. We envisage the use of stable isotope records to address the secular variation of crustal mixing / contamination process in geological time. Many of these secular variation are abrupt and probably indicate shift in the tectonic forcing - a vital factor responsible for driving the secular trend.
Abstract: The origin of intraplate carbonatitic to alkaline volcanism in Africa is controversial. A tectonic control, i.e., decompression melting associated with far-field stress, is suggested by correlation with lithospheric sutures, repeated magmatic cycles in the same areas over several million years, synchronicity across the plate, and lack of clear age progression patterns. Conversely, a dominant role for mantle convection is supported by the coincidence of Cenozoic volcanism with regions of lithospheric uplift, positive free-air gravity anomalies, and slow seismic velocities. To improve constraints on the genesis of African volcanism, here we report the first radiometric and isotopic results for the Catanda complex, which hosts the only extrusive carbonatites in Angola. Apatite (U-Th-Sm)/He and phlogopite 40Ar/39Ar ages of Catanda aillikite lavas indicate eruption at ca. 500-800 ka, more than 100 m.y. after emplacement of abundant kimberlites and carbonatites in this region. The lavas share similar high-? (HIMU)-like Sr-Nd-Pb-Hf isotope compositions with other young mantle-derived volcanics from Africa (e.g., Northern Kenya Rift; Cameroon Line). The position of the Catanda complex in the Lucapa corridor, a long-lived extensional structure, suggests a possible tectonic control for the volcanism. The complex is also located on the Bié Dome, a broad region of fast Pleistocene uplift attributed to mantle upwelling. Seismic tomography models indicate convection of deep hot material beneath regions of active volcanism in Africa, including a large area encompassing Angola and northern Namibia. This is strong evidence that intraplate late Cenozoic volcanism, including the Catanda complex, resulted from the interplay between mantle convection and preexisting lithospheric heterogeneities.
Doklady Earth Sciences, Vol. 477, 1, pp. 1291-1294.
Russia
kimberlite, alnoite, carbonatite
Abstract: The results of geochemical typification of kimberlites and related rocks (alneites and carbonatites) of the North Anabar region are presented with consideration of the geochemical specification of their source and estimation of their potential for diamonds. The content of representative trace elements indicates the predominant contribution of an asthenospheric component (kimberlites and carbonatites) in their source, with a subordinate contribution of vein metasomatic formations containing Cr-diopside and ilmenite. A significant contribution of water-bearing potassium metasomatic parageneses is not recognized. According to the complex of geochemical data, the studied rocks are not industrially diamondiferous.
Carbonatites of India: part 1. Field relations, petrology, mineralogy and economic aspects.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 1-2.
India
carbonatites
Abstract: Carbonatites of India have been reviewed by Krishnamurthy (1988; 2008) and Viladkar (2001). The present review in two parts incorporates all the developments in the field of carbonatites from India since 1963. Carbonatites of India occur in some well-defined geological environments and structural set-ups, and belong to four age groups namely, Palaeoproterozoic, Neoproterozoic, Cretaceous and Palaeocene. The Proterozoic ones are found in the three shield areas, namely southern (e.g., Hogenakal, Sevathur, Samalpatti, Pakkanadu, Khambammettu and Munnar), eastern (e.g. Beldi-Kutni and others) and north-western (e.g., Newania) India, often associated with deep faults and shear zones that may define terrain boundaries (e.g. carbonatites of Tamil Nadu between the Dharwar granite-greenstone schist belt and the southern Indian granulite zone). The Cretaceous and Palaeocene ones (e.g., Amba Dongar, Sirivasan, Sung Valley, Samchampi, Sarnu-Dandali-Kamthai and others) have been found to be related to the flood basalt provinces of Rajmahal, Sylhet (eastern and north-eastern India) and the Deccan (western India). Based on the field relations and associated rock types, the carbonatite-alkaline rock complexes can be grouped into four major types, namely: (a) syenite-dominated complexes with subordinate pyroxenites ± dunites (e.g. Sevathur, Samalpatti, Pakkanadu, and Samchampi); (b) pyroxenite/gabbro dominated ± dunite, ijolite, melteigite with minor syenite (e.g. Sung Valley, Swangre; Mer-Mundwara); (c) carbonatite dominated ringcomplexes or dykes with minor nephelinite and phonolite (e.g. Amba Dongar, Sarnu- Dandali, Kamthai); (d) Sheet-like, minor dykes and veins of carbonatites either alone or with syenites (e.g., Newania, Kunavaram, Eichuru, Munnar and others). Carbonatitekimberlite- lamproite-lamprophyre association has been clearly seen in the Precambrian Wajrakarur kimberlite field (e.g. Chelima dykes and Khaderpet cluster, Andhra Pradesh) and in the Jungal Valley (Mahakhoshal Group, Uttar Pradesh). Such an association from the Cretaceous Deccan basalt province has been shown to exist from Kutch, Gujarat and the Chhatishgargh-Odhisha areas. A wide variety of fenites, notably the syenitic types comprising sodic, sodic-potassic, and potassic variants have been noticed from several complexes, such as Amba Dongar, Newania, Sevattur, Samchampi, and Sung Valley. Fenitisation is attributed to both carbonatite and alkaline rocks as at Amba Dongar, Sevattur, Sung Valley, and Samchampi or to carbonatite alone (e.g. Newania and others).Among the carbonatite types, sovites (calcitic types) are the most common in most of the localities. Beforsitic (dolomitic) and ankeritic/sideritic types occur in complexes which manifest well developed differentiation trends that range from sovite to beforsite or to ankeritic and sideritic types, as exemplified by complexes such as Amba Dongar, Sevattur, Samalpatti, Newania and Sung Valley. Associated alkaline rocks, as mentioned above, enable the grouping of the complexes into four types. Heterogeneity in terms of structures, mineralogy, and chemistry is characteristic of many carbonatite bodies. Apart from the dominant carbonate-minerals such as calcite, dolomite, ankerite and siderite in the major carbonatite types, a variety of minor minerals have also been found in them. Early phase apatite-magnetite and silicate minerals (olivine, aegirineaugite, ritcherite, riebeckite, phlogopite and others) are well-developed in deep-seated plutonic complexes such as Sevattur, Newania, Sung Valley, Samalpatti, Pakkanadu, and Hogenekal. Some uncommon carbonatite types include those containing Fe-Nb rutile and benstonite from Samalpatti and eschynite, monazite, cerianite, celestite, and allanitebearing types from Pakkanadu, and magnesite from Newania. Minerals of economic importance, often in workable concentrations, occur in several complexes. These include: 1. REE minerals consisting of bastnaesite-(La) and daqingshanite-(Ce), bastnaesite-(Ce), ancylite and synchysite occur at Kamthai; bastnaesite and parasite from ankeritic carbonatites at Amba Dongar; bastnaesite-(Ce), ancylite-(Ce), belovite-(Ce), and britholite-(Ce) at Sung Valley. REE also occur as substituted elements in apatite in many complexes. 2. Pyrochlore - often uraniferous, occur at Sevathur, Sung Valley, Newania and Samchampi; 3. Apatite and/or phosphatic rocks (e.g. Beldih-Kutni, Samchampi, Sung, Sevathur and Newania). 4. Ti-magnetite/ hematite deposit at Samchampi. In addition a large fluorite deposit occurs at Amba Dongar and both vermiculite and apatite are mined from the fenitised-pyroxenite envelope to the north of the Sevathur carbonatite-complex. Evaluation of field association of pyroxenite-fenites in carbonatite-syenite association along with development of carbo-thermal and/or pegmatitic and skarn-rock facies in some complexes such as Samalpatti and Pakkanadu in Tamil Nadu suggests strong possibilities of Sc mineralization in some (e.g. 0.02% Sc from Pakkanadu pyroxenite) or Sc along with possible HREE associations.
Carbonatites of India: part 2. Geochemistry, stable and unstable isotopes and petrogenesis.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 26-28.
India
carbonatites
Abstract: Geochemically carbonatites and genetically associated alkaline rocks represent an anomalous association of both large-ion lithophile (LIL) elements including the highfield strength (HFS) elements group such as Sr, Ba, Zr, Nb, REE, Y, Sc, Th, and U (excluding Rb) often from trace (< 0.1%) to minor/major components (> 0.1-1%) besides Ca, Mg, Fe, Mn, Si, Ti, Al, P, Na, K and CO2 in major components. Extreme heterogeneity in terms of elemental abundances is in fact a characteristic feature, often at a single outcrop level, in many carbonatite complexes (e.g. Amba Dongar, Sevathur, Sung Valley). Such apparent chemical diversity is related to the mineralogical heterogeneity that is not uncommon in many carbonatite complexes, leading to diverse mineral prefixes in carbonatite types such as apatite-sovite, apatite-magnetite soviet, riebeckite beforsite, silico-carbonatite and numerous other types (e.g. Sevathur, Samalpatti and Pakkanadu). The most diagnostic geochemical character of carbonatites stem from their geochemical features, especially the higher abundances of LIL and HFS elements, often the highest among the diverse igneous rock types as also compared to the primitive mantle or sedimentary or metamorphosed limestone/or marble or calc-silicate rocks. This has been shown from several studies of Indian carbonatites (Krishnamurthy, 1988; Schleicher et. al. 1998 and others). Radiogenic and stable isotopic ratios have been used since the mid 1990’s on Indian carbonatites which range in age from mid Proterozoic to Cretaceous in both rift related settings and associated with large igneous provinces, apparently related to deep mantleplumes, to provide constraints on the evolution of the sub-continental mantle through time. Various mantle reservoirs like HIMU (A mantle source enriched in U and Th believed to be due to recycling of ancient altered oceanic crust into the mantle), DMM (Depleted MORB mantle), EM1 (Enriched Mantle 1, generated either by recycling of lower crustal material or enrichment by mantle metasomatism) and EM2 (Enriched Mantle 2, possibly formed by recycling of continentally derived sediment, or ocean island crust into the mantle by subduction processes) with distinct isotopic signatures in the Sr- Nd-Pb isotopic space have been invoked to explain the observed variations in isotopic ratios in carbonatites worldwide (Zindler and Hart, 1984 and others). Stable isotopes of Indian carbonatites have been comprehensively reviewed by Ray and Ramesh (2009). Based on ?13C and ?18O variations, carbonatites have been grouped by them into: 1. Primary, unaltered ?18O values (5.3-7.5‰) which indicate mantle signatures that ensue from batch crystallization under plutonic conditions, as observed at Hogenakal, Sung Valley and Samchampi. ?13C values, however, appear to be more enriched (-6 to - 3.1‰) than expected for the mantle. Such a feature of enrichment probably happened sometime around ~2.4 Ga, as a sequel to metasomatism by fluids derived from recycled oceanic crust through subduction that carried enriched carbon of lithospheric mantle. 2. Secondary, altered carbonatites’ (e.g. mainly Amba Dongar and others) showing wide variations in ?13C and ?18 O values apparently results from low temperature alteration by either meteoric water or CO2-bearing aqueous fluids. The values of ??Sr (+5.3 to +7.8), ??Nd ( +1.7 to + 2.3) and initial Pb ratios (19.02, 15.67 and 39.0) for the Sung Valley complex and ?Sr (+3.0 to + 9.3) and ?Nd (+0.45 to +2.3) and initial Pb ratios ( 206Pb/204Pb= 19.12, 207Pb/204Pb= 15.66 and 208Pb/204Pb= 39.56) for the Samchampi alkaline complex are well constrained and indicate that they have originated from isotopically similar source regions that are characterised by somewhat higher Rb/Sr ratio relative to bulk earth, minor LREE depletion with respect to CHUR and time integrated enhancement of the U/Pb ratio relative to bulk earth. However, carbonatites from Sirivasan and Amba Dongar (Srivatsava and Taylor, 1996, Simonetti et al., 1995, Ray and Ramesh, 2006) indicate higher values with ?Sr = +14.6 to +21.8, ?Nd = -0.6 to -1.84 and measured 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios of 19.0, 15.6 and 39.3 and indicate greater enrichment in terms of higher Rb/Sr ratios and LREE enrichment with respect to CHUR. Differences in the north eastern complexes and western complexes are also seen in the stable isotopic data wherein, data for both Sung Valley and Samchampi are constrained with average values of -3.1 ± 0.1‰ for ?13C and 6.33 ± 0.2‰ and -3.1 ± 0.2‰ for ?13C and 7.34 ± 0.7‰ for ?18O respectively whereas data from Amba Dongar and Sirivasan have ?13C of -2.6 to -8.6 ‰ and ?18O of 7.62 to 26.8 ‰. Heterogeneous mantle source has been proposed for the Hogenakal carbonatites with two groups one having high ??Nd and low ??Sr and the other having low ??Nd and high ??Sr. Carbonatites from Sevattur are more enriched with ??Sr (22 to 23), ??Nd ( -5.1 to -5.7) and ?13C ( -4.8 to -6.2‰) and ?18O (6.7 to 7.6 ‰) (Schleicher et.al., 1996, Pandit., et al. 2016). Petrogenetic models of the different carbonatite complexes are reviewed in the light of geochemical and isotopic characteristics. These include models that invoke mantle plumes of both the Kerguelen (e.g. Sung Valley and Samchampi) and Reunion (e.g. Amba Dongar, Sarnu-Dandali and others related to the Deccan volcanism) and their influence on the subcontinental lithosphere. Enriched mantle sources have been indicated for many of the Proterozoic complexes of Tamil Nadu. Evaluations of the different carbonatite complexes in terms of the three known genetic models, listed as follows, have also been elucidated. These include: (a) Direct partial melts from enriched, carbonatedperidotitic sources; (b. Immiscible carbonate and silicate magma after differentiation of the primary, carbonated peridotitic magma; (c) Extreme stage of differentiation of the ultra-alkaline, nephelinite magma. Such approaches also lead us to understand the temporal evolution of the mantle source regions of carbonatites of India since Palaeoproterozoic times. The petrogenetic link between carbonatite-kimberlite-lamproitelamprophyre in the Indian scenario is also briefly reviewed.
Magna, T., Rapprich, V., Wittke, A., Gussone, N., Upadhyay, D., Mikova, J., Pecskay, Z.
Calcium isotope systematics and K-Ar and U-Pb temporal constraints on the genesis of Sevattur Samalpatti carbonatite silicate alkaline complexes.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 34-35.
India
deposit - Samalpatti, Sevattur
Abstract: We present the first systematic survey of Ca isotope compositions in carbonatites and associated silicate rocks from Samalpatti and Sevattur, two Neoproterozoic complexes in Tamil Nadu, south India. Despite their close geographic proximity, their genesis and post-emplacement histories differ (Ackerman et al. 2017). The Sevattur complex appears to have been derived from an enriched mantle source with a limited post-magmatic disturbance. In contrast, carbonatites from Samalpatti show a record of extensive late-stage post-magmatic overprint, also apparent from unusually heavy C-O isotope compositions in a sub-suite of carbonatites (Ackerman et al. 2017). The mean ?44/40Ca = 0.69 ± 0.10‰ is slightly lighter than the average of fertile, unmetasomatized peridotites at ?44/40Ca = 0.95 ± 0.05‰ (Kang et al. 2017). This difference may attest to the general difference between carbonates and silicates (see Kang et al. 2017). It could also reflect Ca isotope fractionation between isotopically heavy silicate and isotopically light carbonate (e.g., John et al. 2012), though to a somewhat minor extent. This is supported by leaching experiments in this study where the extent of silicate-carbonate fractionation (44/40Casilicate-carbonate) has been investigated. The values at ~0.1-0.2‰ are expectedly lower than those reported earlier (~0.6‰; John et al. 2012) and may reflect high-temperature Ca isotope fractionation. The variability in ?44/40Ca values of carbonatites and silico-carbonatites from the Samalpatti complex is larger (0.70- 1.14‰) and appears to be in accord with extensive post-emplacement disturbance. Significant loss of REE and 13C-18O-enriched signature are combined with high ?44/40Ca values, which could reflect massive exchange with metasomatic aqueous fluids. The 40Kdecay correction was applied to K-rich rocks (syenites, monzonites). Given the antiquity of the complex dated at ca. ~800 Ma (Schleicher et al. 1997) and considering high-K/Ca character of some rocks, the resulting ?44/40Ca800 Myr correction was up to ~+1.2‰. In this regard, it is crucial to constrain the age history of the entire region. The nearby Hogenakal carbonatite body was dated at ~2.4 Ga which is much older than Rb-Sr and Sm-Nd age of Sevattur (Kumar et al. 1998) from the same fault system. We have acquired K-Ar mineral (K-feldspar, biotite, amphibole) and U-Pb zircon data from Sevattur and Samalpatti. The K-Ar ages span a range between ~800 and ~510 Ma (~800 Ma for amphiboles and biotites from silico-carbonatites and mafic silicate rocks and ~570-510 Ma for K-feldspars and biotites from syenites), dating two high-grade regional tectono-thermal overprint events, documented earlier. The complex nature of this process is indicated by concordant U-Pb zircon age at ~2.5 Ga yielded for a melatonalite, for which K-Ar biotite age of ~802 Ma was measured. This fits into the age bracket of basement of the Eastern Dharwar Craton. The age distribution bimodality at ~2.5 Ga and ~800 Ma has been found for several other samples, suggesting a pulsed thermal history of the area, associated with a significant overprint by fluids likely derived from the local crust. Particularly high U concentrations in zircons (thousands ppm), combined with a range of K-Ar ages, attest to such multi-episodic history.
Abstract: Long-term cycles in Earth’s climate are thought to be primarily controlled by changes in atmospheric CO2 concentrations. Changes in carbon emissions from volcanic activity can create an imbalance in the carbon cycle. Large-scale changes in volcanic activity have been inferred from proxies such as the age abundance of detrital zircons, but the magnitude of carbon emissions depends on the style of volcanism as well as the amount. Here we analyse U-Pb age and trace element data of detrital zircons from Antarctica and compare the results with the global rock record. We identify a spike in CO2-rich carbonatite and alkaline magmatism during the Ediacaran period. Before the Ediacaran, secular cooling of the mantle and the advent of cooler subduction regimes promoted the sequestration of carbon derived from decarbonation of subducting oceanic slabs in the mantle. We infer that subsequent magmatism led to the extensive release of carbon that may at least in part be recorded in the Shuram-Wonoka carbon isotope excursion. We therefore suggest that this pulse of alkaline volcanism reflects a profound reorganization of the Neoproterozoic deep and surface carbon cycles and promoted planetary warming before the Cambrian radiation.
Abstract: Alkaline and carbonatite rocks are relatively rare but offer the opportunity to study the contribution of fluids in the genesis of mantle and crustal rocks because they are commonly affected by metasomatism. Carbonate minerals represent versatile archives of mantle and crustal magmatic-hydrothermal processes because they can have magmatic, metasomatic or hydrothermal origins and because they host the trace elements, stable and radiogenic isotopes required to unravel their petrogenesis. Previous studies have shown that the 1894 Ma Montviel alkaline?carbonatite complex was emplaced through four injections of volatile-saturated, mantle magmas which evolved through fractional crystallization, mixing of mantle and crustal fluids and metasomatism. Trace element analyses and ?18O, ?13C, 87Sr/86Sr and 143Nd/144Nd isotope compositions of metasomatic and hydrothermal carbonates further support that each magma injection was accompanied by a volatile phase. Variations in trace element concentrations suggest that the carbonatite might have exsolved from a metasomatized mantle or hybrid silicate?carbonatite magma, and that the fluid composition evolved towards higher REE and lower HFSE with increasing degree of segregation of the carbonatite magma and the silicate source. A strong correlation between the C-O-Sr isotopic systems show that mantle fluids mixed with crustal fluids, increasing the 87Sr/86Sr from mantle to crustal values, and driving the C and O isotopic ratios towards respectively lighter and heavier values. The Sm/Nd isotopic system was weakly coupled with the other isotopic systems as depleted mantle fluids mixed with crustal fluids and metasomatized the crystallizing magmas, thereby redistributing the REE and affecting their Sm/Nd ratios. The Nd isotopes suggest that the mixed mantle/crustal fluids redistributed the rare earth elements, producing ultra-depleted (?Nd = + 10), normally depleted (?Nd = + 4) and slightly enriched (?Nd = ? 2) isotopic compositions.
Natali, C., Beccaluva, L., Bianchini, G., Siena, F.
Coexistence of alkaline carbonatite complexes and high MgO CFB in the Parana-Etendeka province: insights on plume lithosphere interactions in the Gondwana realm.
Apatites from Sri Lankan carbonatites: petrogenetic implications.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 19.
Asia, Sri Lanka
carbonatites
Abstract: Carbonatite exposures are found near the boundary of Highland and Wanni Complexes that are major lithotectonic units of Precambrian basement of Sri Lanka. Larger bodies of carbonatite are found at Eppawala, in northcentral part of the island and smaller intrusions with associated apatite rich silicate dykes are present at Kawisigamuwa, in the Northwestern part. Both carbonatite complexes appear mostly as dykes and have calcite-dolomite-magnetite-apatite assemblages. The aim of present study is to decipher the petrogenetic history of carbonatite via the compositional and petrographical investigations of apatite. The size of apatite varies from fine grained to mega size (up to 1m). Cathodoluminescence and compositional data of apatite from two carbonatite occurrences and associated dykes are variable. Apatite grains of Eppawala are rich in F and Fe with relatively persistent chemical composition of all sizes. However, over growth zones of crystals show highly variable chemical compositions. Kawisigamuwa apatite is characterized by higher concentrations of Cl, Sr and light rare earth elements (LREE). Higher concentrations of Fe and F with lower Sr levels are measured from apatite crystals in silicate dykes. Results of present study are indicative of composition of parent magma and post magmatic fluid activities on the generation of apatite.
Platinum group element and rhenium osmium geochemistry of selected carbonatites from India, USA and East africa.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 22-23.
India, United States, Africa, East Africa
carbonatites
Abstract: Carbonatites and associated alkaline silicate rocks might have potential economic impact for a large variety of metals such as Cu, Ni, Fe and platinum-group elements (PGE - Os, Ir, Ru, Pd, Pt) as it is demonstrated in South Africa (Phalaborwa; Taylor et al. 2009) or Brazil (Ipanema; Fontana 2006). In addition, determined PGE contents along with Re-Os isotopic compositions may also provide important information about PGE fractionation during the genesis of upper mantle-derived carbonatitic melts and nature of their sources. Nevertheless, the existing PGE data for carbonatites are extremely rare, limited mostly to Chinese localities and they are not paralleled by Re-Os isotopic data (Xu et al. 2008). Therefore, in this study, we present the first complete PGE datasets together with Re-Os determinations for a suite of selected carbonatite bodies worldwide. We have chosen eight carbonatite sites with different alkaline rock association, age and geotectonic position. Among these, the youngest samples are from East African rift system and include Oldoinyo Dili, Tanzania with an age spanning from ~0 to 45 Ma; same as Tororo and Sukulu in Uganda (Woolley and Kjarsgaard 2008). These carbonatites are in association with pyroxenites and nepheline syenites. Another young carbonatitic complex is Amba Dongar in west India with Cretaceous age of ~65 Ma associated with alkaline volcanic rocks such as trachybasalts within Deccan Traps (Sukheswala and Udas 1963). Proterozoic bodies are represented by Iron Hill, USA carbonatites associated with pyroxenite, melitolite and ijolite with age ranging from ~520 to 580 Ma (Nash 1972). These carbonatites are famous for their intensive and varied fenitization. Last and the oldest carbonatites in this study comes from Samalpatti and Sevattur, South India having the age of ~800 Ma (Schleicher et al. 1997) and outcropping as small bodies within alkaline rocks such as pyroxenite, syenite and gabbro. The PGE concentrations and Re-Os isotopic ratios were determined by standard methods consisting of decarbonatization using HCl, decomposition of samples in Carius Tubes in the presence of reverse aqua regia and spikes (isotopic dilution), separation of Os by CHCl3 followed by N-TIMS measurements and Ir, Ru, Pd, Pt, Re isolation by anion exchange chromatography followed by ICP-MS measurements. All analysed carbonatites exhibit extremely low PGE contents (? PGE up to 1 ppb), even in the samples with high S contents (up to 1.5 wt. %). Such values are much lower than other determined so far for upper mantle-derived melts such as basalts, komatiites, etc. (Day et al. 2016). Such signatures indicate very low partitioning of PGE into carbonatitic melts and/or early separation of PGE-bearing fraction. Elements from iridium-group I-PGE; Os, Ir and Ru; mostly < 0.1 ppb) are distinctly lower compared to palladiumgroup elements and Re (PPGE; Pt, Pd, Re; mostly > 0.1 ppb) with some rocks being largely enriched in Re (up to ~6 ppb). Most of the analysed carbonatites exhibit progressive enrichment from Os to Re and consequently, PdN/ReN < 0.1 except south India carbonatites and associated alkaline rocks (> 0.30). Rocks analysed so far for Os have OsN/IrN up to 6.2 that might suggest that the carbonatites might concentrate Os over Ir. The highest HSEtot contents have been found in Mg-Cr-rich silicocarbonatites from South India (up to 40 ppb) and taking into account their only slightly radiogenic 187Os/188Os ratios (0.14-0.57), these rocks represents mixture of CO2-rich alkaline mantle melts and country rocks. Very high concentrations of HSE have been also found in magnetite separated from Fe-carbonatite from Amba Dongar, India (0.2-0.5 ppb of I-PGE and 0.9-9 ppb of P-PGE). The 187Os/188Os ratios determined so far for carbonatites from South India vary from 0.24 to 6.5 and calculated ?Os values range from +100 up to +5000. Such wide range of values suggest extremely heterogenous source of the melts and/or possible contamination by 187Os-rich crustal materials.
Carbonatite occurrences in Munnar area, Kerala, southern India.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 36-37.
India
carbonatites
Abstract: Carbonatites, usually associated with alkaline complexes and emplaced within continental rifting environment, are the rarest of all the igneous rocks. Carbonatite and alkaline intrusive complexes, as well as their weathering products, are the primary sources of REEs (Long et.al. 2010). Carbonatites are defined by the International Union of Geological Sciences (IUGS) system of igneous rock classification as having more than 50 modal percent primary carbonate minerals, such as calcite, dolomite, and ankerite, and less than 20 percent SiO2 (Le Maitre, 2002). Southern India has several carbonatite occurrences and the alkaline complex of Munnar in southern India comprises of an alkali granite plutons with minor patches of charnockite, syenite and carbonatite emplaced within Precambrian gneisses (Nair et.al., 1983, 1984; Santosh et.al., 1987, Nair et.al., 1984). Gneissic layering and foliation are apparent in all but the least deformed granitic rocks in the study area. The Munnar granite body is situated in the western part of the Madurai block in Southern Granulite Terrane (SGT) of Peninsular India, within the newly defined Western Madurai Domain. The complex is spatially related to the intersection zone of Karur-Kambam-Painavu-Trissur lineament. The alkali granite of the complex has been dated at 740±30 my (Odom, 1982) and 804±6 Ma (Brandt et. al., 2014). Present study deals with examining the nature of the carbonatites and takes a relook at its major and REE contents, and for the first time, looks at the stable isotope signatures of these rocks, in an attempt to check whether these rocks are indeed carbonatites. The geology and geochemistry of the rock types in and around Munnar area have been mapped with special focus on carbonatites. Extensive field mapping was carried out and a base map was prepared and all the geological and structural features were recorded in the base map. Intra- and inter-relationships of various rock units were examined. Field photographs of interesting geological features have been recorded. Carbonatites in Munnar area are exposed as two minor patches. The one which occurs towards north of the Munnar town and is seen as patches, lens and veins of 30 cm to 1 m thickness, cutting coarse grained syenite which occurs as a NW- SE along a body. Exposures are found about 15 km from Munnar on the Udumalpet road. The second exposure occurs towards the east of the Munnar town, near at the Ellapatty estate 24 km from Munnar on the road to top station where coarse grained cabonatites occurs as lenticular bodies up to 1.5 m thick within granite. In both the localities, the carbonatite bodies show sharp and discordant margins with absence of any pseudomorphs within them. Fenitisation is characterised by the development of pink K-feldspar megacrystals in the country rock at the contact. The carbonatites are fresh and homogenous and represent two varieties. A coarse grained holocrystalline type and yellowish calcite crystals constituting 90% of the rock, with pyroxene apatite and magnetite correspond to sovite (Streckeisen, 1979). The second variety which contains highly coarse calcite crystals (up to 1 cm) and associated dolomite with mafic minerals constituting 30% of the rock corresponds to alvikite. The sovite exhibits an interlocking crystals mosaic of calcite in thin section. The calcite crystals of alvikite show exsolution blebs of dolomite. The major mafic component in both varieties is aegirine-augite which forms euhedral- subhedral laths (Santosh et al., 1984). The opaque phase is dominantly magnetite. Rarely phlogopite, biotite and minor laths of albite are also noted, small crystals of euhedral apatite are found occluded in calcite grain although alkaline complexes with carbonatite of Munnar devoid of related mafic differentiates like gabbros or lamprophyres may be considered unique. The immiscibility of carbonatitic and alkalic silicate liquids can be physically explained as the separation of a less viscous carbonate liquid from a more viscous polymerized silicate phase. The carbonate liquid would be lower in density because of higher content of H2O and this contrast in density could cause phase separation due to earth’s gravitational field alone (Moller et al., 1980). The pre-requisite to establish separation of immiscible silicate-saturated carbonatite liquid and the associated carbonate-saturated silicate melt is achieved as follows; Large-scale volatile outgassing occurs during crustal wrapping and distention prior to rifting which trigger mantle degassing (Bailey, 1974). An imprint of such large-scale volatile influx is recognised in the Kerala region (Nair et al., 1984). Rapid ascent volatiles enriched in CO2 liberated from the mantle cause partial melting at shallower levels of the mantle.
Reguir, E.P., Chakhmouradian, A.R., Zaitsev, A.N., Yang, P.
Trace element variations and zoning in phlogopite from carbonatites and phoscorites.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 8-9.
carbonatites
Abstract: Phlogopite from carbonatites and phoscorites worldwide shows three major types of core-to-rim trends of compositional variation: Ba+Al-, Fe and Fe+Al enrichment. These major-element trends are accompanied by largely consistent changes in traceelement abundances. Uptake of Rb, Sr, Ba, Sc, V, Mn and HFSE by phlogopite is susceptible to changes in the availability of these elements due to precipitation of other early silicate and oxide phases (especially, magnetite, apatite and niobates). In rare cases, more complex oscillatory and sector patterns are juxtaposed over the principal evolutionary trend, indicating kinetic and crystal-chemical controls over element uptake. Phlogopite is a common accessory to major constituent of carbonatites and genetically related rocks (including phoscorites). Major-element variations of phlogopite from these rocks have been addressed in much detail in the literature (for references, see Reguir et al. 2009), whereas its trace-element characteristics and zoning patterns have so far received little attention. In this work, we examined the compositional variation of phlogopite from 23 carbonatite and phoscorite localities worldwide. The major-element compositions were determined using wavelength-dispersive X-ray spectrometry (WDS) and trace-element abundances by laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICPMS). Previously, two major core-to-rim zoning trends have been identified in micas from calcite carbonatites (Reguir et al. 2009, 2010). Phlogopite from Oka (Canada) and Iron Hill (USA), for example, involves an increase in kinoshitalite component rim-ward, accompanied by enrichment in high-field-strength elements (HFSE = Zr, Nb, Ta), Sr and Sc. At most other carbonatite localities (e.g., Kovdor in Russia, or Prairie Lake in Canada), phlogopite crystals exhibit rim-ward enrichment in Fe. In the present work, we confirmed these two common types of zoning, and identified new patterns that have not been reported in the previous literature. In addition to the common Fe-enrichment trend, which occurs in both carbonatites (e.g., Guli in Russia and Sokli in Finland) and phoscorites (e.g., Aley in Canada), we identified a Fe-Al-enrichment subtype of this zoning pattern observed, for example, in samples from the Shiaxiondong calcite carbonatite (China). Overall, the Fe-enrichment pattern is accompanied by rim-ward depletion in Ba, Rb and HFSE, coupled with enrichment in Mn. Other trace elements exhibit no consistent variation among the studied samples. The Shiaxiondong material is characterized by the highest recorded Rb values, ranging from 1120 to 660 ppm. Phlogopite from the Kovdor calcite-forsterite-magnetite phoscorite contains the highest recorded levels of Nb and Ta, ranging from 320 ppm and 40 ppm, respectively, in the core to 85 ppm and 4 ppm in the rim. The maximum levels of Zr (up to 50 ppm) were observed in the core of Prairie Lake phlogopite, whereas its rim contains the highest measured Mn content (up to 4100 ppm). The levels of Sc are typically below 100 ppm in samples from calcite and dolomite carbonatites, but may reach 280 ppm in phoscorites. Interestingly, phlogopite from phoscorites shows rim-ward enrichment in Sc, whereas the opposite trend is observed in carbonatitic micas. Phlogopite from calcite carbonatites at Zibo (China) and Valentine Township (Canada), and from phoscorites at Aley (Canada) shows an unusual zoning pattern involving depletion in Fe, which is accompanied by a decrease in Al, Ba, Sr, Zr, Hf, Y, Sc and V abundances. The concentrations of other trace elements, including Nb and Ta show inconsistent variations. In the Aley phoscorite, phlogopite is enriched in Ba (up to 15000 ppm in the core and < 7500 ppm in the rim), but poor in Sr (80 and 35 ppm in the core and rim, respectively) relative to those from the Zibo and Valentine carbonatites. Zirconium levels reach 200 and 170 ppm in the core, and drop to < 40 and 60 ppm in the rim of the Valentine and Zibo samples, respectively. In the Aley sample, the content of Zr does not exceed 55 ppm. The Zibo sample is also enriched in V (up to 230 and 160 ppm in the core and rim, respectively) relative to the two other samples (< 100 ppm V). The Sc and Hf levels are consistently low (less than 30 and 4 ppm, respectively). In addition to simple core-rim patterns, phlogopite from carbonatites and phoscorites may exhibit oscillatory zoning, which involves periodic variations in Fe/Mg ratio. Iron-rich zones are relatively depleted in Mn, but enriched in Nb. One sample of phoscoritic phlogopite (Aley) exhibits striking sector zoning juxtaposed over the overall Feenrichment trend and Fe-Mg oscillations. In terms of major elements, basal sectors perpendicular to [001] are enriched in Fe and Al, but depleted in Mg and K relative to the flank sectors. This enrichment is accompanied by higher Ba, Sr and HFSE levels in the basal sector. Our data confirm that there is no universal pattern of zoning in carbonatitic or phoscoritic phlogopite, and variations in the content of most trace elements are strongly coupled to major-element patterns. Three major core-to-rim variation trends, as well as juxtaposed oscillatory and sector patterns, can be recognized. The observed compositional variations indicate that, in the majority of cases, the trace-element composition of phlogopite is controlled by partitioning of Rb, Sr, Ba, Sc, V, Mn and HFSE between this mineral, its parental magma, and co-precipitating early phases. Among the latter, magnetite, apatite and niobates appear to exert the greatest influence on element distributions. More complex oscillatory and sector patterns imply the presence of kinetic and crystal-chemical controls over element uptake in certain carbonatitic systems
Petrographic studies in understanding carbonatites.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 48-49.
India
carbonatites
Abstract: Carbonatites are mantle derived carbonate rich rocks of igneous origin. Carbonatites are often spatially associated with alkaline rocks and typically confined to continental rift related tectonic setting. Mineralogically, carbonatites are predominantly composed of primary carbonate minerals (calcite, dolomite), while, oxides, hydroxides, silicates, phosphate and sulphide minerals are also found as associated minerals in variable amounts. Although geochemical and isotope geology studies significantly contribute to understand the genetic aspects of these rare REE rich rocks of economic significance; petrographic studies with the aid of polarizing microscope play a critical role in (i) identification of the constituent minerals (ii) ascertain the relative abundance of various minerals and (iii) to recognise the textures. All these three aspects along with geochemical, isotope and mineral inclusion studies are extremely important to understand carbonatite petrogenesis. As per the IUGS classification scheme, the primary carbonate minerals [calcite CaCO3, dolomite (Ca, Mg) CO3, ankerite Ca (Fe, Mg, Mn) (CO3)2] constitute > 50 % by mode in carbonatites, while the SiO2 is < 20 % (Le Maitre, 2002). Though the primary mineralogy in carbonatite is variable, petrographic studies do help in establishing the presence of REE rich phases like apatite and pyrochlore; presence of mineral phases like phlogopite, perovskite, olivine, fluorite (transmitted light) and opaque oxides; eg. magnetite (reflected light) in carbonate rich rock with crystalline texture; as an initial stage for identification of a carbonatite. Based on the chemical composition, the carbonatites are classified as calciocarbonatites, magnesiocarbonatites and ferrocarbonatites (Woolley, 1982); the calciocarbonatites are further classified as sovite and alvikite (Le Bas, 1999). Based on the mineralogical-genetic criteria, carbonatites are divided into primary carbonatites and carbothermal residua (Mitchell, 2007). Petrographic studies help to initially identify the chemically distinct calciocarbonatites; sovite or alvikite. Sovite is texturally coarse grained, while alvikite is relatively fine grained. The coarse grained nature of the calciocarbonatites (average grain size of the carbonate minerals ranging from 1 to 5 mm) coupled with their equigranular nature makes them texturally distinct. Calcite and dolomite can be distinguished with the aid of staining techniques (Dickson, 1965). Staining technique will be useful for rapid estimation of the modal contents of the carbonate phases (calcite, ferroan calcite, dolomite,) in carbonatites. Though less abundant, the ferrocarbonatites are charecterised by the presence of clearly relatively large magnetite grains. Often the porphyritic appearance in the ferrocarbonatites is due to the presence of aggregates of celadonite and phlogopite leaving olivine and pyroxene as relict phases. Late stage magmatic-hydrothermal fluids can play a role in alteration of the textural and mineralogy in carbonatites (Duraiswami and Shaikh, 2014). Study the primary magmatic inclusions in silicates phases in carbonatites with the aid of optical and scanning electron microscopy provide critical information to understand the petrogenetic aspects of carbonatites (e.g. Nisbett and Kelly, 1977). Petrographic studies also contribute in identification of textures indicating crystal-melt interaction in carbonatites (Sesha Sai and Sengupta, 2017). Field and laboratory studies leading to chronological understanding of the geotectonic events in a given area, along with petrographic analyses with detailed mineralogical and textural descriptions, not only contribute to understand the fundamental aspects of carbonatites, but also form a solid substratum to build an acceptable petrogenetic model, by synthesising the information obtained by the geochemical, isotope geology and mineral inclusion studies.
Journal of the Geological Society of India, Vol. 90, 5, pp. 524-530.
Russia
carbonatite
Abstract: Secondary multiphase inclusions were studied in olivine from olivine-pyrochlore varieties of calcite carbonatites of the Belaya Zima alkaline complex, Eastern Sayan, Siberia, Russia. The inclusions form trails cross-cutting the host olivine. Their composition varies from carbonate to silicate-carbonate species. Multiphase silicate-carbonate inclusions contain Na-Ca-carbonates (shortite, nyerereite), Na-Mg-carbonates (northupite, eitelite, bradleyite), common carbonates (calcite, dolomite), Ba-Sr-rich carbonates (olekminskite, burbankite, strontianite), tetraferriphlogopite, magnetite, humite-clinohumite and other mineral phases. Na-Ca-carbonates, tetraferriphlogopite, humiteclinohumite and magnetite are omnipresent and dominant phases within the inclusions. The phase composition of secondary olivinehosted inclusions seems to reflect evolutionary features for the Belaya Zima carbonatites at their late stages of formation. During crystallization calciocarbonatite melt gradually evolved toward enrichment in alkalis (mainly, in sodium) and volatile components (Cl, F and H2O).
in: Ferbey, T. Plouffe, A., Hickein, A.S. eds. Indicator minerals in tills and stream sediments of the Canadian Cordillera. Geological Association of Canada Special Paper,, Vol. 50, pp. 175-190.
Canada, British Columbia
carbonatite - Aley, Lonnie, Wicheeda
Abstract: This volume consists of a series of papers of importance to indicator minerals in the Canadian Cordillera. Topics include the glacial history of the Cordilleran Ice Sheet, drift prospecting methods, the evolution of survey sampling strategies, new analytical methods, and recent advances in applying indicators minerals to mineral exploration. This volume fills a notable knowledge gap on the use of indicator minerals in the Canadian Cordillera. We hope that the volume serves as a user guide, encouraging the wider application of indicator minerals by the exploration community.
Nd, Sr, Pb and B isotopic investigation of carbonatite/alkaline centers in west central India: insights into plume driven vs lithospheric controlled magmatism.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 17.
India
carbonatites
Abstract: The exact origin of carbonatite magmas remains debatable as there are two main hypothesis proposed; one relates magmatism to asthenospheric upwellings and/or mantle plumes, whereas the other argues for generation from metasomatized lithosphere. However, proponents of the latter rarely describe in detail the origin of the metasomatic agents required to generate the high concentrations of rare earth and highly incompatible elements present in carbonatite magmas. In a recent study, Boron isotopic signatures of carbonatite complexes worldwide, ranging in age from ~2600 to ~65 million years old, indicate greater input of recycled (subducted), crustal material and plume activity with increasing geologic age of the Earth. More positive Boron isotopic values with increasing geologic time were attributed to the change of Earth’s geodynamics to a modern style of plate tectonics. In this study, the radiogenic (Sr, Nd, Pb) and B isotope systematics of carbonatites and alkaline rocks from west-central India are reported and discussed with reference to the plume-lithosphere interaction model previously proposed for the generation of Deccan-related alkaline centers in this region of the Indian sub-continent
Pyrochlore group minerals from Paleozoic carbonatite massifs of the Kola Peninsula: composition and evolution.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 20-21.
Russia, Kola Peninsula
carbonatites
Abstract: Chemical composition and evolution of pyrochlore-group minerals (Nb?Ta?Ti) from the early phoscorites and calcite carbonatites, and late rare-earth dolomite carbonatites from Seblyavr and Vuorijarvi Paleozoic massifs have been studied. There are two trends in pyrochlore composition evolution: the change of U, Ti, and Ta enriched varieties by calcium high-Nb, and the change of early calcium varieties by barium-strontium pyrochlores. The substitutions are described by the typical reactions: 2Ti4+ + U4+ ? 2Nb5+ + Ca2+; Ta5+ ? Nb5+; U4+ + v (vacancy) ? 2Ca2+. The Ca ranges in pyrochlores are explained by isomorphic occupation of the cation position A with Ba, Sr, and REE, the total concentration of which increases as the carbonatite melt evolved and reaches a maximum in rare-earth dolomite carbonatites. The formation of barium pyrochlore is mainly due to successive crystallization from the Ba and Sr enriched melt (oscillatory zoning crystals), or with the secondary replacement of grain margins of the calcium pyrochlore, as an additional mechanism of formation. High enrichments in LREE2O3 (up to 6 wt.%) are identified. The fluorine content in pyrochlore group minerals varies widely. A high concentration (up to 8 wt.%) is found in central and marginal zones of crystals from calcite carbonatites, while it decreases in the pyrochlore from dolomite carbonatites. Fluorine in the crystal lattice has sufficient stability during cation-exchange processes and it is not lost in the case of developing of late carbonatites over the earlier ones. In the late mineral populations the relics enriched by this component are observed. There is a positive correlation of fluorine with sodium. The marginal and fractured zones of pyrochlore crystals from all rock types are represented by phases with a cation deficiency in position A and an increased Si. The evolution of mineral composition depends on the alkaline-ultramafic melt crystallization differentiation, enrichment of the late melts by alkalis and alkaline earth metals at the high fluorine activity. It is determined that the fluorine sharply increases from the early pyroxenites to the carbonatite rocks of the massif. The foscorites and carbonatites of the early stages of crystallization are the most enriched in fluorine, while the late dolomite carbonatites are depleted by this component and enriched in chlorine and water. The fluorine saturation of the early stages of carbonatite melting leads to the formation of fluorapatite and pyrochlore minerals which are the main mineralsconcentrators of fluorine. Pyrochlore group minerals from the Paleozoic carbonatite complexes of the Kola Peninsula are characterized by decreasing Pb, Th and U, and Th/U ratios in the transition from the early foscorites to later calcite carbonatites and hydrothermal dolomite carbonatites. The pyrochlore age varies within the 420-320 m.y. interval (U-Pb SHRIMPII data), while the rocks of the earliest magmatic stages has an individual grain age of 423 ± 15 Ma, but pyrochlore ages for calcite and dolomite carbonatites are younger: 351 ± 8.0 Ma and 324 ± 6.1 Ma, respectively. Such a dispersion of the age data is apparently associated with a disturbed Th/U ratio due to high ability for cation-exchange processes of pyrochlore crystalline matrix including secondary transformations. The research was done within the framework of the scientific program of Russian Academy of Sciences and state contract K41.2014.014 with Sevzapnedra.
Carbonatites-alkaline rocks, and associated economic mineral deposits: a view from beneficiation.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 3.
India
carbonatites
Abstract: Among the known 20 carbonatite-alkaline rock associations in India, eight contain potentially economic deposits, major among them are: fluorite at Amba Dongar, Gujaratand hematite, Nb, apatite etc. at Samchampi Complex, Assam, Amba Dongar complex is estimated to host 11.6 million tonnes of fluorite ore. In the broad region of the entire Amba Dongar-Mogra-Sedivasan Carbonatite complex, fluorite mineralization has been reported, particularly on the northern and southern flanks as isolated pockets. Starting from 1964, numerous agencies like Geological Survey of India, Directorate of Geology & Mining and, finally GMDC have carried out exploration activities from time to time. The deposit is hydrothermal, mainly in form of vug filling, cavity filling and dissemination and exhibits large variations in grade, in terms of CaF2, CaCO3 and SiO2% as well as in thickness. This being the only commercially viable fluorite deposit in India, GMDC set up a 500 TPD Beneficiation Plant to produce acid/metallurgical grades in 1970. Typical problems of Fine dissemination of major part of fluorite grains, intimate association of fluorite with silica, interstitial presence of apatite in fluorite matrix are some major issues giving rise to difficulties encountered in upgrading the ore. Major setback for the Project has been deteriorating grade of 30% CaF2 at the top to current 20% CaF2 after excavating 90 meters. Having recently found more selective Collector of fluorite from silica and carbonate, an operation of 1000 TPD is now under implementation. Current mine is associated with sovite carbonatite as overburden which are reported to have appreciable amount of RE Elements like Nb, La, Ce etc. simultaneous development of which can provide a strong base for enhancing commercial aspects of the combined Project.
Journal of the Geological Society of India, Vol. 90, 5, pp. 591-594.
India
carbonatite
Abstract: The present paper for the first times gives details of pyroxenesövites of Amba Dongar and discusses significance of these pyroxenes in evolution of carbonatite magma in Amba Dongar. Calciocarbonatite (sövite) forms the major mass of carbonatite in Amba Dongar complex. It shows large variation in texture and mineral composition and has complex evolutionary history. Three types of compositional variations are observed in sövite samples, (1) monomineralic sövites are coarse grained with 99% calcite, (2) sövites with abundant apatite, barite, pyrochlore, magnetite and zirconolite and (3) silico-sövite with of clinopyroxene and phlogopite. In the crystallization history of various sövite types, silico-sövite seems to have crystallized as an earlier phase and was later caught up in major sövite mass. Both, phlogopite-sövite and pyroxene-sövite are coarse grained and exhibit hypidiomorphic texture. Phlogopite is strongly zoned with Mg-rich core to Fe-rich rims. Pyroxenes also exhibit zoning with decrease in Ca and Mg and increase in Fe and Na from core to rim. In general composition of clinopyroxene varies from diopsidic to aegirine-augite. Pyroxenesövites show good concentration of Ba, Sr, Nb and LREE. Elevated concentrations of LREE are found in two aegirine-sövites.
Journal of Asian Earth Sciences, in press availabe, 30p.
Asia, Tien Shan
carbonatites
Abstract: Postorogenic intrusions of essexites and alkaline and nepheline syenites in the Turkestan-Alai segment of the Kyrgyz Southern Tien Shan coexist with dikes and veins of carbonatites dated at ?220?Ma by the Ar-Ar and Rb-Sr age methods. They are mainly composed of calcite and dolomite (60-85%), as well as sodic amphibole, phlogopite, clinopyroxene, microcline, albite, apatite, and magnetite, with accessory niobate, ilmenite, Nb-rutile, titanite, zircon, baddeleyite, monazite-(Ce), barite, and sulfides. The rocks share mineralogical and geochemical similarity with carbonatites that originated by liquid immiscibility at high temperatures above 500?°C. Alkaline silicate and salt-carbonate melts are derived from sources with mainly negative bulk ?Nd(t) ? from ?11 to 0 and high initial 87Sr/86Sr ratios (?0.7061-0.7095) which may be due to mixing of PREMA and EM?type mantle material. Pb isotopic ratios in accessory pyrrhotite (206Pb/204Pb?=?18.38; 207Pb/204Pb?=?15.64; 208Pb/204Pb?=?38.41) exhibit an EM2 trend. The intrusions bear signatures of significant crustal contamination as a result of magma genesis by syntexis and hybridism. Concordant isotope composition changes of ?13C (?6.5 to ?1.9‰), ?18O (9.2-23‰), ?D (?58 to ?41‰), and ?34S (12.6-12.8‰) in minerals and rocks indicate inputs of crustal material at the stage of melting and effect of hot fluids released during dehydration of metamorphosed oceanic basalts or sediments. The observed HFSE patterns of the oldest alkaline gabbro may be due to interaction of the primary mafic magma with IAB-type material. The isotope similarity of alkaline rocks with spatially proximal basalts of the Tarim large igneous province does not contradict the evolution of the Turkestan-Alai Triassic magmatism as the “last echo” of the Tarim mantle plume.
Preservation model for Kola alkaline province for Paleozoic and Paleoproterozoic alkaline magmatism volume comparing.
Carbonatite-alkaline rocks and associated mineral deposits , Dec. 8-11, abstract p. 13.
Russia, Kola Peninsula
carbonatites
Abstract: Northern part of the Fennoscandian Shield in Kola Peninsula and Northern Karelia was intruded by alkaline magmatic complexes during the two main episodes. Paleoproterozoic alkaline province consisting from five alkaline massifs and Paleozoic alkaline province, consisting from twenty alkaline-ultramafic rock complexes, together with two giant nepheline syenite complexes are practically overlap. Based on the data about morphology and internal structure of the Paleozoic alkaline and ultramaficcarbonatite intrusions and their average denudation rates, the model of alkaline province destruction was developed. This model allows forecasting, how many intrusions of Kola Paleozoic alkaline province will remain and calculate preservation ratio for any moment of future. The dependence of preservation ratio on the age of province allow to compare the initial numbers of massifs in alkaline provinces and conclude that Paleoproterozoic event of alkaline magmatism in Kola peninsula was even more powerful than Paleozoic one.
Mineralogical Magazine, Vol. 81, 6, pp. 1367-1395.
Africa, Malawi
carbonatite - Chilwa
Abstract: Carbonatites are enriched in critical raw materials such as the rare earth elements (REE), niobium, fluorspar and phosphate. A better understanding of their fluid regimes will improve our knowledge of how to target and exploit economic deposits. This study shows that multiple fluid phases penetrated the surrounding fenite aureole during carbonatite emplacement at Chilwa Island, Malawi. The first alkaline fluids formed the main fenite assemblage and later microscopic vein networks contain the minerals of potential economic interest such as pyrochlore in high-grade fenite and RE minerals throughout the aureole. Seventeen samples of fenite rock from the metasomatic aureole around the Chilwa Island carbonatite complex were chosen for study (Natural History Museum, London collection BM1968 P37). In addition to the main fenite assemblage of feldspar and aegirine ± arfvedsonite, riebeckite and richterite, the fenite contains micro-mineral assemblages including apatite, ilmenite, rutile, magnetite, zircon, RE minerals and pyrochlore in vein networks. Petrography using SEM-EDX showed that the RE minerals (monazite, bastnäsite and parisite) formed later than the fenite feldspar, aegirine and apatite and provide evidence of REE mobility into all grades of fenite. Fenite apatite has a distinct negative Eu anomaly (determined by LA-ICP-MS) that is rare in carbonatite-associated rocks and interpreted as related to pre-crystallisation of plagioclase and co-crystallisation with K-feldspar in the fenite. The fenite minerals have consistently higher mid REE/light REE ratios (La/Sm = ~1.3 monazite, ~1.9 bastnäsite, ~1.2 parisite) than their counterparts in the carbonatites (La/Sm = ~2.5 monazite, ~4.2 bastnäsite, ~3.4 parisite). Quartz in the low- and medium-grade fenite hosts fluid inclusions, typically a few µm in diameter, secondary and extremely heterogeneous. Single phase, 2- and 3-phase, single solid and multi solid-bearing examples are present, with 2-phase the most abundant. Calcite, nahcolite, burbankite and barite were found in the inclusions. Decrepitation of inclusions occurred at around 200?C before homogenisation but melting temperature data indicate that the inclusions contain relatively pure CO2. A minimum salinity of around 24 wt.% NaCl equivalent was determined. Among the trace elements in whole rock analyses, enrichment in Ba, Mo, Nb, Pb, Sr, Th and Y and depletion in Co, Hf and V are common to carbonatite and fenite but enrichment in carbonatitic type elements (Ba, Nb, Sr, Th, Y, and REE) generally increases towards the inner parts of the aureole. A schematic model contains multiple fluid events, related to first and second boiling of the magma, accompanying intrusion of the carbonatites at Chilwa Island, each contributing to the mineralogy and chemistry of the fenite. The presence of distinct RE mineral micro-assemblages in fenite at some distance from carbonatite could be developed as an exploration indicator of REE enrichment.
Abstract: Carbonatites and alkaline-silicate rocks are the most important sources of rare earth elements (REE) and niobium (Nb), both of which are metals imperative to technological advancement and associated with high risks of supply interruption. Cooling and crystallizing carbonatitic and alkaline melts expel multiple pulses of alkali-rich aqueous fluids which metasomatize the surrounding country rocks, forming fenites during a process called fenitization. These alkalis and volatiles are original constituents of the magma that are not recorded in the carbonatite rock, and therefore fenites should not be dismissed during the description of a carbonatite system. This paper reviews the existing literature, focusing on 17 worldwide carbonatite complexes whose attributes are used to discuss the main features and processes of fenitization. Although many attempts have been made in the literature to categorize and name fenites, it is recommended that the IUGS metamorphic nomenclature be used to describe predominant mineralogy and textures. Complexing anions greatly enhance the solubility of REE and Nb in these fenitizing fluids, mobilizing them into the surrounding country rock, and precipitating REE- and Nb-enriched micro-mineral assemblages. As such, fenites have significant potential to be used as an exploration tool to find mineralized intrusions in a similar way alteration patterns are used in other ore systems, such as porphyry copper deposits. Strong trends have been identified between the presence of more complex veining textures, mineralogy and brecciation in fenites with intermediate stage Nb-enriched and later stage REE-enriched magmas. However, compiling this evidence has also highlighted large gaps in the literature relating to fenitization. These need to be addressed before fenite can be used as a comprehensive and effective exploration tool.
Mineralogy and Petrology, in press available, 10p.
Russia, Aldan shield
carbonatites
Abstract: The Ust-Chulman apatite ore body is situated within the Nimnyrskaya apatite zone at the Aldan shield in Russia. The latest data confirm the carbonatitic origin of the Seligdar apatite deposit (Prokopyev et al. in Ore Geol Rev 81:296-308, 2017). The results of our investigations demonstrate that the magnetite-apatite-dolomitic rocks of the Ust-Chulman are highly similar to Seligdar-type dolomitic carbonatites in terms of the mineralogy and the fluid regime of formation. The ilmenite and spinel mineral phases occur as solid solutions with magnetite, and support the magmatic origin of the Ust-Chulman ores. The chemical composition of REE- and SO3-bearing apatite crystals and, specifically, monazite-(Ce) mineralisation and the formation of Nb-rutile, late hydrothermal sulphate minerals (barite, anhydrite) and haematite are typical for carbonatite complexes. The fluid inclusions study revealed similarities to the evolutionary trend of the Seligdar carbonatites that included changes of the hydrothermal solutions from highly concentrated chloride to medium-low concentrated chloride-sulphate and oxidized carbonate-ferrous.
Abstract: The oxygen fugacity of the upper mantle is 3-4 orders of magnitude higher than that of the lower mantle and this has been attributed to Fe2 + disproportionating into Fe3 + plus Fe0 at pressures > 24 GPa. The upper mantle might therefore have been expected to have evolved to more oxidizing compositions through geological time, but it appears that the oxygen fugacity of the upper mantle has remained constant for the last 3.5 billion years. Thus, it indicates that the mantle has been actively buffered from the accumulation of Fe3 +, and that this is linked to oxidation of diamond to carbonate coupled with reduction of Fe3 + to Fe2 +. When subducted plates penetrate into the lower mantle, compensational upwelling transports bridgmanite into the transition zone, where it breaks down to ringwoodite and majorite, releasing the ferric iron. The system returns to equilibrium through oxidation of diamond. Early in Earth history, diamond may have been enriched at the base of the transition zone in the Magma Ocean, because it is denser than peridotite melts at depths shallower than 660 km, and it is more buoyant below. Ongoing oxidation of diamond forms carbonate, leading to relatively high carbonate concentrations in the source of ocean island basalts.
Journal of Asian Earth Sciences, Vol. 153, pp. 252-281.
Asia
carbonatite
Abstract: Postorogenic intrusions of essexites and alkaline and nepheline syenites in the Turkestan-Alai segment of the Kyrgyz Southern Tien Shan coexist with dikes and veins of carbonatites dated at ?220?Ma by the Ar-Ar and Rb-Sr age methods. They are mainly composed of calcite and dolomite (60-85%), as well as sodic amphibole, phlogopite, clinopyroxene, microcline, albite, apatite, and magnetite, with accessory niobate, ilmenite, Nb-rutile, titanite, zircon, baddeleyite, monazite-(Ce), barite, and sulfides. The rocks share mineralogical and geochemical similarity with carbonatites that originated by liquid immiscibility at high temperatures above 500?°C. Alkaline silicate and salt-carbonate melts are derived from sources with mainly negative bulk ?Nd(t) ? from ?11 to 0 and high initial 87Sr/86Sr ratios (?0.7061-0.7095) which may be due to mixing of PREMA and EM?type mantle material. Pb isotopic ratios in accessory pyrrhotite (206Pb/204Pb?=?18.38; 207Pb/204Pb?=?15.64; 208Pb/204Pb?=?38.41) exhibit an EM2 trend. The intrusions bear signatures of significant crustal contamination as a result of magma genesis by syntexis and hybridism. Concordant isotope composition changes of ?13C (?6.5 to ?1.9‰), ?18O (9.2-23‰), ?D (?58 to ?41‰), and ?34S (12.6-12.8‰) in minerals and rocks indicate inputs of crustal material at the stage of melting and effect of hot fluids released during dehydration of metamorphosed oceanic basalts or sediments. The observed HFSE patterns of the oldest alkaline gabbro may be due to interaction of the primary mafic magma with IAB-type material. The isotope similarity of alkaline rocks with spatially proximal basalts of the Tarim large igneous province does not contradict the evolution of the Turkestan-Alai Triassic magmatism as the “last echo” of the Tarim mantle plume.
Geological Society of London Special Publication, No. 463, pp. 137-169.
India
carbonatite
Abstract: The genetic connection between Large Igneous Province (LIP) and carbonatite is controversial. Here, we present new major and trace element data for carbonatites, nephelinites and Deccan basalts from Amba Dongar in western India, and probe the linkage between carbonatite and the Deccan LIP. Carbonatites are classified into calciocarbonatite (CaO, 39.5-55.9 wt%; BaO, 0.02-3.41 wt%; ?REE, 1025-12 317 ppm) and ferrocarbonatite (CaO, 15.6-31 wt%; BaO, 0.3-7 wt%; ?REE, 6839-31 117 ppm). Primitive-mantle-normalized trace element patterns of carbonatites show distinct negative Ti, Zr-Hf, Pb, K and U anomalies, similar to that observed in carbonatites globally. Chondrite-normalized REE patterns reveal high LREE/HREE fractionation; average (La/Yb)N values of 175 in carbonatites and approximately 50 in nephelinites suggest very-low-degree melting of the source. Trace element modelling indicates the possibility of primary carbonatite melt generated from a subcontinental lithospheric mantle (SCLM) source, although it does not explain the entire range of trace element enrichment observed in the Amba Dongar carbonatites. We suggest that CO2-rich fluids and heat from the Deccan plume contributed towards metasomatism of the SCLM source. Melting of this SCLM generated primary carbonated silicate magma that underwent liquid immiscibility at crustal depths, forming two compositionally distinct carbonatite and nephelinite magmas.
Journal of Asian Earth Sciences, Vol. 154, pp. 354-368.
Russia, Yakutia
carbonatite -Seligdar
Abstract: The Paleoproterozoic Seligdar magnesiocarbonatite intrusion of the Aldan-Stanovoy shield in Russia underwent extensive postmagmatic hydrothermal alteration and metamorphic events. This study comprises new isotopic (Sr, Nd, C and O) data, whole-rock major and trace element compositions and trace element characteristics of the major minerals to gain a better understanding of the source and the formation process of the carbonatites. The Seligdar carbonatites have high concentrations of P2O5 (up to 18?wt%) and low concentrations of Na, K, Sr and Ba. The chondrite-normalized REE patterns of these carbonatites display significant enrichments of LREE relative to HREE with an average La/Ybcn ratio of 95. Hydrothermal and metamorphic overprints changed the trace element characteristics of the carbonatites and their minerals. These alteration processes were responsible for Sr loss and the shifting of the Sr isotopic compositions towards more radiogenic values. The altered carbonatites are further characterized by distinct 18O- and 13C-enrichments compared to the primary igneous carbonatites. The alteration most likely resulted from both the percolation of crustal-derived hydrothermal fluids and subsequent metamorphic processes accompanied by interaction with limestone-derived CO2. The narrow range of negative ?Nd(T) values indicates that the Seligdar carbonatites are dominated by a homogenous enriched mantle source component that was separated from the depleted mantle during the Archean.
Mineralogical Magazine, Vol. 81, 6, pp. 1367-1395.
Africa, Malawi
carbonatite
Abstract: Carbonatites are enriched in critical raw materials such as the rare earth elements (REE), niobium, fluorspar and phosphate. A better understanding of their fluid regimes will improve our knowledge of how to target and exploit economic deposits. This study shows that multiple fluid phases penetrated the surrounding fenite aureole during carbonatite emplacement at Chilwa Island, Malawi. The first alkaline fluids formed the main fenite assemblage and later microscopic vein networks contain the minerals of potential economic interest such as pyrochlore in high-grade fenite and RE minerals throughout the aureole. Seventeen samples of fenite rock from the metasomatic aureole around the Chilwa Island carbonatite complex were chosen for study (Natural History Museum, London collection BM1968 P37). In addition to the main fenite assemblage of feldspar and aegirine ± arfvedsonite, riebeckite and richterite, the fenite contains micro-mineral assemblages including apatite, ilmenite, rutile, magnetite, zircon, RE minerals and pyrochlore in vein networks. Petrography using SEM-EDX showed that the RE minerals (monazite, bastnäsite and parisite) formed later than the fenite feldspar, aegirine and apatite and provide evidence of REE mobility into all grades of fenite. Fenite apatite has a distinct negative Eu anomaly (determined by LA-ICP-MS) that is rare in carbonatite-associated rocks and interpreted as related to pre-crystallisation of plagioclase and co-crystallisation with K-feldspar in the fenite. The fenite minerals have consistently higher mid REE/light REE ratios (La/Sm = ~1.3 monazite, ~1.9 bastnäsite, ~1.2 parisite) than their counterparts in the carbonatites (La/Sm = ~2.5 monazite, ~4.2 bastnäsite, ~3.4 parisite). Quartz in the low- and medium-grade fenite hosts fluid inclusions, typically a few µm in diameter, secondary and extremely heterogeneous. Single phase, 2- and 3-phase, single solid and multi solid-bearing examples are present, with 2-phase the most abundant. Calcite, nahcolite, burbankite and barite were found in the inclusions. Decrepitation of inclusions occurred at around 200?C before homogenisation but melting temperature data indicate that the inclusions contain relatively pure CO2. A minimum salinity of around 24 wt.% NaCl equivalent was determined. Among the trace elements in whole rock analyses, enrichment in Ba, Mo, Nb, Pb, Sr, Th and Y and depletion in Co, Hf and V are common to carbonatite and fenite but enrichment in carbonatitic type elements (Ba, Nb, Sr, Th, Y, and REE) generally increases towards the inner parts of the aureole. A schematic model contains multiple fluid events, related to first and second boiling of the magma, accompanying intrusion of the carbonatites at Chilwa Island, each contributing to the mineralogy and chemistry of the fenite. The presence of distinct RE mineral micro-assemblages in fenite at some distance from carbonatite could be developed as an exploration indicator of REE enrichment.
International Journal of Earth Sciences, Vol. 106, 8, pp. 2797-2813.
Africa, Namibia
carbonatite
Abstract: Rb-Sr whole-rock and mineral isotope data from nepheline syenite, tinguaite, and carbonatite samples of the Kalkfeld Complex within the Damaraland Alkaline Province, NW Namibia, indicate a date of 242 ± 6.5 Ma. This is interpreted as the age of final magmatic crystallization in the complex. The geological position of the complex and the spatially close relationship to the Lower Cretaceous Etaneno Alkaline Complex document a repeated channeling of small-scale alkaline to carbonatite melt fractions along crustal fractures that served as pathways for the mantle-derived melts. This is in line with Triassic extensional tectonic activity described for the nearby Omaruru Lineament-Waterberg Fault system. The emplacement of the Kalkfeld Complex more than 100 Ma prior to the Paraná-Etendeka event and the emplacement of the Early Cretaceous Damaraland intrusive complexes excludes a genetic relationship to the Tristan Plume. The initial ?Sr-?Nd pairs of the Kalkfeld rocks are typical of younger African carbonatites and suggest a melt source, in which EM I and HIMU represent dominant components.
Mineralogy and geochemistry of Triassic carbonatites in the Matcha alkaline intrusive complex ( Turkestan Alai Ridge, Kyrgyz southern Tien Shan), SW central Asian orogenic belt.
Journal of Asian Earth Sciences, Vol. 153, pp. 252-281.
Kampelite, Ba3Mg1.5,Sc4(PO4)6(OH)3.4H2O, a new very complex Ba-Sc phosphate mineral from the Kovdor phoscorite-carbonatite complex ( Kola Peninsula) Russia.
Contribution to Mineralogy and Petrology, Vol. 173, 22p.
Mantle
carbonatite
Abstract: We performed an experimental study, designed to reproduce the formation of an unusual merwinite?+?olivine-bearing mantle assemblage recently described as a part of a Ca-rich suite of inclusions in sublithospheric diamonds, through the interaction of peridotite with an alkali-rich Ca-carbonatite melt, derived from deeply subducted oceanic crust. In the first set of experiments, we studied the reaction between powdered Mg-silicates, olivine and orthopyroxene, and a model Ca-carbonate melt (molar Na:K:Ca?=?1:1:2), in a homogeneous mixture, at 3.1 and 6.5 GPa. In these equilibration experiments, we observed the formation of a merwinite?+?olivine-bearing assemblage at 3.1 GPa and 1200 °C and at 6.5 GPa and 1300-1400 °C. The melts coexisting with this assemblage have a low Si and high Ca content (Ca#?=?molar 100?×?Ca/(Ca?+?Mg)?>?0.57). In the second set of experiments, we investigated reaction rims produced by interaction of the same Ca-carbonate melt (molar Na:K:Ca?=?1:1:2) with Mg-silicate, olivine and orthopyroxene, single crystals at 3.1 GPa and 1300 °C and at 6.5 GPa and 1400 °C. The interaction of the Ca-carbonate melt with olivine leads to merwinite formation through the expected reaction: 2Mg2SiO4 (olivine)?+?6CaCO3 (liquid)?=?Ca3MgSi2O8 (merwinite)?+?3CaMg(CO3)2 (liquid). Thus, our experiments confirm the idea that merwinite in the upper mantle may originate via interaction of peridotite with Ca-rich carbonatite melt, and that diamonds hosting merwinite may have a metasomatic origin. It is remarkable that the interaction of the Ca-carbonate melt with orthopyroxene crystals does not produce merwinite both at 3.1 and 6.5 GPa. This indicates that olivine grain boundaries are preferable for merwinite formation in the upper mantle.
Earth Planetary Science Letters, Vol. 492, pp. 186-196.
India
carbonatite
Abstract: Within a stepwise crushing study we determined the noble gas composition of several calcite separates, one aegirine and one pyrochlore-aegirine separate of the carbonatite ring dyke complex of Amba Dongar and carbonatite sill complex of Siriwasan, India. Both carbonatites are related to the waning stages of volcanic activity of the Deccan Igneous Province ca. 65 Ma ago. Major observations are a clear radiogenic 4He and nucleogenic 21Ne imprint related to in situ production from U and Th in mineral impurities, most likely minute apatite grains, or late incorporation of crustal fluids. However, in first crushing steps of most calcites from Amba Dongar a well-resolvable mantle neon signal is observed, with lowest air-corrected mantle 21Ne/22Ne-compositions equivalent to the Réunion hotspot mantle source. In case of the aegirine separate from Siriwasan we found a neon composition similar to the Loihi hotspot mantle source. This transition from a mantle plume signal in first crushing step to a more nucleogenic signature with progressive crushing indicates the presence of an external (crustal) or in situ nucleogenic component unrelated and superposed to the initial mantle neon component whose composition is best approximated by results of first crushing step(s). This contradicts previous models of a lithospheric mantle source of the carbonatitic magmas from Amba Dongar containing recycled crustal components which base on nucleogenic neon compositions. Instead, the mantle source of both investigated carbonatite complexes is related to a primitive mantle plume source that we tentatively ascribe to the postulated Deccan mantle plume. If, as is commonly suggested, the present location of the Deccan mantle plume source is below Réunion Island, the currently observed more nucleogenic neon isotopic composition of the Réunion hotspot might be obliterated by significant upper mantle contributions. In addition, compared with other carbonatite complexes worldwide a rather significant contribution of atmospheric noble gases is observed. This is documented in cut-off 20Ne/22Ne-ratios of ca. 10.2 (Amba Dongar) and 10.45 (Siriwasan) and cut-off 40Ar/36Ar-ratios of about 1500. This atmospheric component had been added at shallow levels during the emplacement process or later during hydrothermal alteration. However, understanding the late-stage interaction between atmospheric gases and magmatic mantle fluids still requires further investigation.
Abstract: Carbonatites (sensu stricto) are igneous rocks typically associated with continental rifts, being emplaced at relatively shallow crustal levels or as extrusive rocks. Some carbonatites are, however, related to subduction and lithospheric collision zones, but so far no carbonatite has been reported from ultrahigh-pressure (UHP) metamorphic terranes. In this study, we present detailed petrological and geochemical data on carbonatites from the Tromsø Nappe—a UHP metamorphic terrane in the Scandinavian Caledonides. Massive to weakly foliated silicate-rich carbonate rocks, comprising the high-P mineral assemblage of Mg-Fe-calcite?±?Fe-dolomite?+?garnet?+?omphacitic clinopyroxene?+?phlogopite?+?apatite?+?rutile?+?ilmenite, are inferred to be carbonatites. They show apparent intrusive relationships to eclogite, garnet pyroxenite, garnet-mica gneiss, foliated calc-silicate marble and massive marble. Large grains of omphacitic pyroxene and megacrysts (up to 5?cm across) of Cr-diopside in the carbonatite contain rods of phlogopite oriented parallel to the c-axis, the density of rods being highest in the central part of the megacrysts. Garnet contains numerous inclusions of all the other phases of the carbonatite, and, in places, composite polyphase inclusions. Zircon, monazite and allanite are common accessory phases. Locally, veins of silicate-poor carbonatite (up to 10?cm across) occur. Extensive fenitization by K-rich fluids, with enrichment in phlogopite along contacts between carbonatite and silicate country rocks, is common. Primitive mantle-normalized incompatible element patterns for the carbonatite document a strong enrichment of light rare earth elements, Ba and Rb, and negative anomalies in Th, Nb, Ta, Zr and Hf. The carbon and oxygen isotope compositions of the carbonatite are distinctly different from those of the spatially associated calc-silicate marble, but also from mantle-derived carbonatites elsewhere. Neodymium and Sr isotope data coupled with the trace element distribution indicate a similarity of the Tromsø carbonatite to orogenic (off-craton) carbonatites rather than to anorogenic (on-craton) ones. U-Pb dating of relatively U-rich prismatic, oscillatory-zoned zircon gives an age of 454•5?±?1•1?Ma. We suggest that the primary carbonatite magma resulted from partial melting of a carbonated eclogite at UHP, in a deeply subducted continental slab.
Abstract: The silico?carbonatite dykes of the Huanglongpu area, Lesser Qinling, China, are unusual in that they are quartz-bearing, Mo-mineralised and enriched in the heavy rare earth elements (HREE) relative to typical carbonatites. The textures of REE minerals indicate crystallisation of monazite-(Ce), bastnäsite-(Ce), parisite-(Ce) and aeschynite-(Ce) as magmatic phases. Burbankite was also potentially an early crystallising phase. Monazite-(Ce) was subsequently altered to produce a second generation of apatite, which was in turn replaced and overgrown by britholite-(Ce), accompanied by the formation of allanite-(Ce). Bastnäsite and parisite where replaced by synchysite-(Ce) and röntgenite-(Ce). Aeschynite-(Ce) was altered to uranopyrochlore and then pyrochlore with uraninite inclusions. The mineralogical evolution reflects the evolution from magmatic carbonatite, to more silica-rich conditions during early hydrothermal processes, to fully hydrothermal conditions accompanied by the formation of sulphate minerals. Each alteration stage resulted in the preferential leaching of the LREE and enrichment in the HREE. Mass balance considerations indicate hydrothermal fluids must have contributed HREE to the mineralisation. The evolution of the fluorcarbonate mineral assemblage requires an increase in aCa2+ and aCO32? in the metasomatic fluid (where a is activity), and breakdown of HREE-enriched calcite may have been the HREE source. Leaching in the presence of strong, LREE-selective ligands (Cl?) may account for the depletion in late stage minerals in the LREE, but cannot account for subsequent preferential HREE addition. Fluid inclusion data indicate the presence of sulphate-rich brines during alteration, and hence sulphate complexation may have been important for preferential HREE transport. Alongside HREE-enriched magmatic sources, and enrichment during magmatic processes, late stage alteration with non-LREE-selective ligands may be critical in forming HREE-enriched carbonatites.
Abstract: An analysis of the global array of ocean island volcanics shows that carbonatites only form in those hotspots that have the lowest Si- and highest alkali-contents among their primitive melts, such as the Cape Verde and Canary (Islands) hotspots. Fractionated melts from these two hotspots reach, at any given SiO2, several wt% higher total alkali contents than for ocean islands without carbonatites. This is because their strongly silica-undersaturated primitive melts fractionate at low SiO2 to high alkali contents, driving the evolving melt into the silicate-carbonatite miscibility gap. Instead, moderately alkaline magmas fractionate toward the alkali-feldspar thermal divide and do not reach liquid immiscibility. Low SiO2 and high alkalis are the combined result of comparatively deep and low-degree mantle melting, the latter is corroborated by the highest high-field-strength and rare earth element concentrations in the Cape Verde and Canary primitive melts. CO2 in the source facilitates low melt SiO2, but enrichment in CO2 relative to other hotspots is not required. The oceanic hotspots with carbonatites are among those with the thickest thermal lithosphere supporting a deep origin of their asthenospheric parent melts, an argument that could be expanded to continental hotspot settings.
Mineralogical Magazine Open access special publication Critical metal mineralogy and ore genesis, Vol. 82 (S1) pp. S115-S131.
Europe, Norway
carbonatite
Abstract: The Fen Complex in Norway consists of a ~583 Ma composite carbonatite-ijolite-pyroxenite diatreme intrusion. Locally, high grades (up to 1.6 wt.% total REE) of rare-earth elements (REE) are found in a hydrothermally altered, hematite-rich carbonatite known as rødbergite. The progressive transformation of primary igneous carbonatite to rødbergite was studied here using scanning electron microscopy and inductively coupled plasma-mass spectrometry trace-element analysis of 23 bulk samples taken along a key geological transect. A primary mineral assemblage of calcite, dolomite, apatite, pyrite, magnetite and columbite with accessory quartz, baryte, pyrochlore, fluorite and REE fluorocarbonates was found to have transformed progressively into a secondary assemblage of dolomite, Fe-dolomite, baryte, Ba-bearing phlogopite, hematite with accessory apatite, calcite, monazite-(Ce) and quartz. Textural evidence is presented for REE fluorocarbonates and apatite breaking down in igneous carbonatite, and monazite-(Ce) precipitating in rødbergite. The importance of micro-veins, interpreted as feeder fractures, containing secondary monazite and allanite, is highlighted. Textural evidence for included relics of primary apatite-rich carbonatite are also presented. These acted as a trap for monazite-(Ce) precipitation, a mechanism predicted by physical-chemical experiments. The transformation of carbonatite to rødbergite is accompanied by a 10-fold increase in REE concentrations. The highest light REE (LREE) concentrations are found in transitional vein-rich rødbergite, whereas the highest heavy REE (HREE) and Th concentrations are found within the rødbergites, suggesting partial decoupling of LREE and HREE due to the lower stability of HREE complexes in the aqueous hydrothermal fluid. The hydrothermal fluid involved in the formation of rødbergite was oxidizing and had probably interacted with country-rock gneisses. An ore deposit model for the REE-rich rødbergites is presented here which will better inform exploration strategies in the complex, and has implications for carbonatite-hosted REE resources around the world.
Journal of Volcanology and Geothermal Research, Vol. 358, pp. 262-272.
Africa, Tanzania
carbonatite
Abstract: Hanang volcano is the southern volcano of, the southern area of the east part of the East African Rift (the North Tanzanian Divergence) and represents volcanic activity of the first stage of continental break-up. In this study, we investigate glassy melt inclusions in nepheline phenocrysts to constrain the late stage of Mg-poor nephelinite evolution and the behaviour of volatiles (CO2, H2O, S, F, Cl) during magma storage and ascent during early stage rifting. The melt inclusions have a green silicate glass, a carbonate phase and a shrinkage bubble free of gas phase indicating that carbonatite:silicate (18:82) liquid immiscibility occurred during nephelinite magmatic evolution. The silicate glasses have trachytic composition (Na?+?K/Al?=?1.6-7.2, SiO2?=?54-65.5?wt%) with high CO2 (0.43?wt% CO2), sulfur (0.21-0.92?wt% S) and halogens (0.28-0.84?wt% Cl; 0.35-2.54?wt% F) contents and very low H2O content (<0.1?wt%). The carbonate phase is an anhydrous Ca-Na-K-S carbonate with 33?wt% CaO, 20?wt% Na2O, 3?wt% K2O, and 3?wt% S. The entrapped melt in nepheline corresponds to evolved interstitial CO2-rich phonolitic composition (Na?+?K/Al?=?6.2-6.9) with 6?±?1.5?wt% CO2 at pressure of 800?±?200?MPa after crystallization of cpx (17%), nepheline (40%) garnet (6.5%) and apatite (1.7%) from Mg-rich nephelinitic magma. During ascent, immiscibility in phonolitic melt inclusions leads to Ca-Na carbonate melt with composition within the range of carbonate melt from Oldoinyo Lengai and Kerimasi, in equilibrium with trachytic silicate melt (closed-system, P?
Abstract: Geochemical characterization including mineralogical measurements and kinetic testing was completed on samples from the Montviel carbonatite deposit, located in Quebec (Canada). Three main lithological units representing both waste and ore grades were sampled from drill core. A rare earth element (REE) concentrate was produced through a combination of gravity and magnetic separation. All samples were characterized using different mineralogical techniques (i.e., quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN), X-ray diffraction (XRD), and scanning electron microscopy with X-ray microanalysis (SEM-EDS)) in order to quantify modal mineralogy, liberation, REE deportment and composition of REE-bearing phases. The REE concentrate was then submitted for kinetic testing (weathering cell) in order to investigate the REE leaching potential. The mineralogical results indicate that: (i) the main REE-bearing minerals in all samples are burbankite, kukharenkoite-Ce, monazite, and apatite; (ii) the samples are dominated by REE-free carbonates (i.e., calcite, ankerite, and siderite); and (iii) LREE is more abundant than HREE. Grades of REE minerals, sulfides and oxides are richer in the concentrate than in the host lithologies. The geochemical test results show that low concentrations of light REE are leached under kinetic testing conditions (8.8-139.6 ?g/L total light REE). These results are explained by a low reactivity of the REE-bearing carbonates in the kinetic testing conditions, low amounts of REE in solids, and by precipitation of secondary REE minerals.
Abstract: Carbonatites are rare igneous rocks that have a high content of carbonate minerals and nearly no silica. Carbonatitic magmas are derived from carbonated mantle sources but the origin of the carbonates (recycling of surface material or primary mantle source) is still debated. While mafic igneous rocks present a ?44/40Ca around 0.8-1.2‰ normalised to SRM, surface carbonates have ?44/40Ca ~ 0‰. Ca isotopes are therefore well suited to study the origin of Ca in carbonatites. We analysed the Ca isotopic composition of 25 carbonatites from continental and oceanic locations and from different ages (from 2 Ga to present day). The large majority of the carbonatites are isotopically light (?44/40Ca down to 0.07‰) compared to mantle derived rocks. On the other hand, the natrocarbonatite from Oldoinyo Lengai is isotopically heavier (?44/40Ca =0.82‰), similarly to basalts. Three mechanisms can explain the very light isotopic composition of the calciocarbonatites i) A very low degree of partial melting of the mantle may enrich the melt in light isotopes, yet there is no evidence of such large isotopic fractionation during partial melting. ii) The mantle source for the calciocarbonatites is enriched in light Ca likely due to recycling of surface material. iii) aqueous alteration has enriched the calciocarbonatites in the lighter isotopes. On the other hand, the natrocarbonatite from Oldoinyo Lengai have a MORB-like Ca isotopic composition. The difference of ?44/40Ca between natro- and calcio-carbonatite would then suggest that they either have different mantle sources, were formed from different degree of partial melting and/or that aqueous alteration has modified the Ca isotopic composition of calciocarbonatites.
Abstract: Carbonatite and related alkaline silicate rocks contain one of the most significant rare earth element (REE) reserves in the world. It is well-known that these REE deposits are characterized by a strong light REE enrichment with a steep fractionation from La to Lu in the chondrite-normalized diagram. However, the origin of their REE enrichment remains debatable. The Shaxiongdong (SXD) carbonatite in the South Qinling orogenic belt hosts one of the most important REE deposits in central China. In this study, in situ chemical and isotopic data have been obtained for carbonate minerals from the complex. Our results show that calcite has variable trace element abundances, especially REEs. In situ Pb isotope data for calcite reveal extreme variations of 206Pb/204Pb (18.05-31.71) and 207Pb/204Pb (15.49-16.36) ratios. Interestingly, Pb isotope variations display positive correlations with REE enrichments [i.e., (La/Yb)N and (La/Nd)N]. Calcite with extreme radiogenic Pb isotopic compositions displays upper mantle C and O isotopic compositions (?13Cavg?=??5.74‰, ?18Oavg?=?7.13‰) and depleted 87Sr/86Sr isotopic ratios (~0.7030). The observed various REE enrichments accompanying the variable Pb isotopic composition within SXD calcite possibly result from a closed-system metasomatic event. The U-bearing mineral (i.e., pyrochlore) accumulating abundant uranogenic lead since their Silurian formation serves as the radiogenic Pb and LREE source for the metasomatism. Alternatively, the chemical and isotopic composition observed might suggest involvement of two mantle sources (PREMA and the distinct radiogenic Pb mantle reservoir).
Abstract: Carbonatites are few but significant to understand carbon recycling of the earth, the crust-mantle interactions, deep mantle magmatism and regional continental evolution. The Lijiahe carbonatite intrusion, located at the Micangshan Mountains along the NW margin of the Yangtze block, South China was emplaced into the Paleoproterozoic strata, but the timing of the igneous event has long been unknown. Dating by U-Pb apatite was carried out by this work, and it gives an age of 766 ± 11 Ma (MSWD=0.15) for the carbonatitic magmatism of the region. The carbonatite comprises mainly of calcite, magnitite and apatite with minor minerals of salite, biotite, tremolite, hornblende and muscovite and accessary minerals of pyrrhotite, silver marcasite, niobite, spinel and zircon. Its spatial distribution was obviously controlled by regional tectonics. Besides, ultra-alkaline silicate intrusive complex in the region has been reported by us and other works, and mostly consists of iolite, urtite and jacupirangite with ages of ~890-875 Ma. Furthermore, a large number of gabbro and diorite plutons are found in the Micangshan Mountains and dated at ~780-760 Ma. NW margin of the Yangtze block is connected with the South Qinling orogenic belt generally thought having an affinity of the Yangtze block during the Neoproterozoic. Our works revealed that the South Qinling is discriminated from the NW Yangtze by intensive ~680 Ma igneous activities which are poorly reported in the interior of South China. Given that a ~815 Ma collision between the South Qinling ribbon and NW Yangtze margin is recognized by our recent work, the regional massive mantle-derived magmatism including the Lijiahe carbonatitic pluton is explained to indicate a drifting of South Qinling terrane from the NW margin of Yangtze block along previous weak-tectonic zones during the Rodinia breakup caused by continental rifting.
Abstract: Sedimentary carbonate rocks, which exist extensively in the oceanic realm, are subducted to differing degrees during the closure of oceanic basins. However, very few observational data exist to provide details on the mechanisms of transport of carbonate materials from the surface to mantle depths and back to the Earth’s surface. Here we presented a series of diamond-bearing carbonatite xenoliths, carbonatite intrusions and carbonatite veins along the northern margin of the North China Craton (NCC). These carbonatites show geochemical features of recycled limestone (similar trace element patterns and high 87Sr/86Sr ratios of 0.705-0.709), indicating that they had a sedimentary limestone precursor. However, the presence of diamond, reduced minerals (e.g., moissanite), mantle-derived silicate minerals (eg., Cpx and Opx), and high Ni content and 143Nd/144Nd ratio indicate their staying for a time in the mantle. Combining with the zircon age spectrums of the carbonatite xenoliths and intrusions and the extensive high-87Sr/86Sr (up to 0.708) carbonatite metasomatism in the lithospheric mantle along the northern margin of NCC, we suggest that the limestone precursor could have been derived from the Paleo-Asian Ocean, and these carbonatites mark the subduction of a carbonate platform of the Paleo-Asian Oceanic slab to mantle depths beneath the NCC. Extensive mantle recycling of sedimentary carbonate could have contributed to the modification of the lithospheric mantle along the northern margin of the North China Craton.
Abstract: The contribution of magmatic and hydrothermal processes to rare earth element (REE) mineralization of carbonatites remains an area of considerable interest. With the aim of better understanding REE mineralization mechanisms, we conducted a detailed study on the petrology, mineralogy and C-O isotopes of the Bachu carbonatites, NW China. The Bachu carbonatites are composed predominantly of magnesiocarbonatite with minor calciocarbonatite. The two types of carbonatite have primarily holocrystalline textures dominated by dolomite and calcite, respectively. Monazite-(Ce) and bastnäsite-(Ce), the major REE minerals, occur as euhedral grains and interstitial phases in the carbonatites. Melt inclusions in the dolomite partially rehomogenize at temperatures above 800?°C, and those in apatite have homogenization temperatures (Th) ranging from 645 to 785?°C. Oxygen isotope ratios of the calciocarbonatite intrusions (?18OV-SMOW?=?6.4‰ to 8.3‰), similar to the magnesiocarbonatites, indicate the parental magma is mantle-derived, and that they may derive from a more evolved stage of carbonatite fractionation. The magnesiocarbonatites are slightly enriched in LREE whereas calciocarbonatites have higher HREE concentrations. Both dolomite and calcite have low total REE (TREE) contents ranging from 112 to 436?ppm and 88 to 336?ppm, respectively, much lower than the bulk rock composition of the carbonatites (371 to 36,965?ppm). Hence, the fractional crystallization of carbonates is expected to elevate REE concentrations in the residual magma. Rocks from the Bachu deposit with the highest TREE concentration (up to 20?wt%) occur as small size (2?mm to 3 cm) red rare earth-rich veins (RRV) with barite + celestine + fluorapatite + monazite-(Ce) associations. These rocks are interpreted to have a hydrothermal origin, confirmed by the fluid inclusions in barite with Th in the range 198-267?°C. Hydrothermal processes may also explain the existence of interstitial textures in the carbonatites with similar mineral assemblages. The C-O isotopic compositions of the RRV (?13CV-PDB?=??3.6 to ?4.3‰, ?18OV-SMOW?=?7.6 to 9.8‰) are consistent with an origin resulting from fluid exsolution at the end of the high temperature fractionation trend. A two-stage model involving fractional crystallization and hydrothermal fluids is proposed for the mineralization of the Bachu REE deposit.
Geochemistry International, Vol. 56, 8, pp. 766-783.
Russia, Siberia
carbonatite
Abstract: In this study we present a fresh isotopic data, as well as U-Pb ages from different REE-minerals in carbonatites and phoscorites of Guli massif using in situ LA-ICPMS technique. The analyses were conducted on apatites and perovskites from calcio-carbonatite and phoscorite units, as well as on pyrochlores and baddeleyites from the carbonatites. The 87Sr/86Sr ratios obtained from apatites and perovskites from the phoscorites are 0.70308-0.70314 and 0.70306-0.70313, respectively; and 0.70310-0.70325 and 0.70314-0.70327, for the pyrochlores and apatites from the carbonatites, respectively. Furthermore, the in situ laser ablation analyses of apatites and perovskites from the phoscorite yield ?Nd from 3.6 (±1) to 5.1 (±0.5) and from 3.8 (±0.5) to 4.9 (±0.5), respectively; ?Nd of apatites, perovskites and pyrochlores from carbonatite ranges from 3.2 (±0.7) to 4.9 (±0.9), 3.9 (±0.6) to 4.5 (±0.8) and 3.2 (±0.4) to 4.4 (±0.8), respectively. Laser ablation analyses of baddeleyites yielded an eHf(t)d of +8.5 (± 0.18); prior to this study Hf isotopic characteristic of Guli massif was not known. Our new in situ ?Nd, 87Sr/86Sr and eHf data on minerals in the Guli carbonatites imply a depleted source with a long time integrated high Lu/Hf, Sm/Nd, Sr/Rb ratios. In situ U-Pb age determination was performed on perovskites from the carbonatites and phoscorites and also on pyrochlores and baddeleyites from carbonatites. The co-existing pyrochlores, perovskites and baddeleyites in carbonatites yielded ages of 252.3 ± 1.9, 252.5 ± 1.5 and 250.8 ± 1.4 Ma, respectively. The perovskites from the phoscorites yielded an age of 253.8 ± 1.9 Ma. The obtained age for Guli carbonatites and phoscorites lies within the range of ages previously reported for the Siberian Flood Basalts and suggest essentially synchronous emplacement with the Permian-Triassic boundary.
Physics and Chemistry of Minerals, doi.org/10.1007/s00269-018-0995-5 16p.
Mantle
carbonatite
Abstract: Thermodynamic modeling offers a powerful framework for studying melting reactions of carbonated mantle systems across a wide range of compositions, pressures, and temperatures. Such modeling requires knowledge of the standard state thermodynamic properties of the pure alkaline earth carbonate liquid components, which are difficult to determine experimentally due to their instability at 1 bar. Atomistic simulations offer a solution to these experimental difficulties by providing access to metastable states and supplying constraints on thermodynamic properties. We developed an empirically-derived potential model for the simulation of alkaline earth carbonates (MgCO3, CaCO3, SrCO3 and BaCO3), emphasizing the accurate simulation of the standard state thermodynamic properties of carbonate liquids. Molecular dynamics (MD) simulations of liquids in the CaCO3-SrCO3-BaCO3 system are performed over a geologically relevant temperature-pressure range (1100-3400 K and 0-43 GPa). Simulation data for each of these three components (up to a maximum of 2300 K and 30 GPa) are fitted to a temperature-dependent third-order Birch-Murnaghan equation-of-state to estimate their standard state thermodynamic properties. With a few exceptions, calculated properties agree well with available estimates from experiments and/or first-principles MD simulations. Exploration of binary mixtures supports ideal mixing of volumes, heat capacities, and compressibilities, reflecting the common liquid structure and pressure-temperature evolution for these three components. The success of this new model for CaCO3-SrCO3-BaCO3 liquids suggests that it can accurately predict the properties of MgCO3-bearing liquids, where experimental data are unavailable.
Abstract: Rare-earth deposits associated with intrusive carbonatite complexes are the world’s most important source of these elements (REE). One of the largest deposits of this type is Maoniuping in the Mianning-Dechang metallogenic belt of eastern Tibet (Sichuan, China). In the currently mined central part of the deposit (Dagudao section), REE mineralization is hosted by a structurally and mineralogically complex Late Oligocene (26.4 ±?1.2 Ma, 40Ar/39Ar age of fluorphlogopite associated with bastnäsite) hydrothermal vein system developed in a coeval syenite intrusion. Low-grade stockworks of multiple veinlets and breccias in the lower part of the orebody grade upwards into progressively thicker veins (up to 12 m in width) that are typically zoned and comprise ferromagnesian micas (biotite to fluorphlogopite), sodium clinopyroxenes (aegirine to aegirine-augite), sodium amphiboles (magnesio-arfvedsonite to fluororichterite), K-feldspar, fluorite, barite, calcite, and bastnäsite. The latter four minerals are most common in the uppermost 80 m of the Dagudao section and represent the climax of hydrothermal activity. Systematic variations in the fluid inclusion data indicate a continuous hydrothermal evolution from about 230-400 °C (fluid inclusions in feldspar, clinopyroxene, and amphibole) to 140-240 °C (fluid inclusions in bastnäsite, fluorite, calcite). Hydrothermal REE transport was probably controlled by F?, (SO4)2?, Cl?, and (CO3)2? as complexing ligands. We propose that at Dagudao, silicate magmas produced orthomagmatic fluids that explored and expanded a fissure system generated by strike-slip faulting. Initially, the fluids had appreciable capacity to transport REE and, consequently, no major mineralization developed. The earliest minerals to precipitate were alkali- and Fe-rich silicates containing low levels of F, which caused progressive enrichment of the fluid in Ca, Mg, F, Cl, REE, (SO4)2?, and (CO3)2?, leading to the crystallization of aegirine-augite, fluororichterite, fluorphlogopite, fluorite, barite, calcite, and bastnäsite gradually. Barite, fluorite, calcite, and bastnäsite are the most common minerals in typical ores, and bastnäsite generally postdates these gangue minerals. Thus, it is very probable that fluid cooling and formation of large amount of fluorite, barite, and calcite triggered bastnäsite precipitation in the waning stage of hydrothermal activity.
Contributions to Mineralogy and Petrology, Vol. 173, 26p. Doi.org/10.1007/s00410-018-1505-y
Europe, Greenland
carbonatite
Abstract: Petrogenetic studies of carbonatites are challenging, because carbonatite mineral assemblages and mineral chemistry typically reflect both variable pressure-temperature conditions during crystallization and fluid-rock interaction caused by magmatic-hydrothermal fluids. However, this complexity results in recognizable alteration textures and trace-element signatures in the mineral archive that can be used to reconstruct the magmatic evolution and fluid-rock interaction history of carbonatites. We present new LA-ICP-MS trace-element data for magnetite, calcite, siderite, and ankerite-dolomite-kutnohorite from the iron-rich carbonatites of the 1.3 Ga Grønnedal-Íka alkaline complex, Southwest Greenland. We use these data, in combination with detailed cathodoluminescence imaging, to identify magmatic and secondary geochemical fingerprints preserved in these minerals. The chemical and textural gradients show that a 55 m-thick basaltic dike that crosscuts the carbonatite intrusion has acted as the pathway for hydrothermal fluids enriched in F and CO2, which have caused mobilization of the LREEs, Nb, Ta, Ba, Sr, Mn, and P. These fluids reacted with and altered the composition of the surrounding carbonatites up to a distance of 40 m from the dike contact and caused formation of magnetite through oxidation of siderite. Our results can be used for discrimination between primary magmatic minerals and later alteration-related assemblages in carbonatites in general, which can lead to a better understanding of how these rare rocks are formed. Our data provide evidence that siderite-bearing ferrocarbonatites can form during late stages of calciocarbonatitic magma evolution.
Abstract: Pyrochlore from the Kaiserstuhl volcanic complex (SW Germany) shows textural and compositional differences between various coarse-grained calcite-carbonatite bodies (Badberg, Degenmatt, Haselschacher Buck, Orberg) and extrusive carbonatites (Henkenberg, Kirchberg). Oscillatory-zoned F-rich pyrochlore with up to 69?wt% Nb2O5 is common in all coarse-grained calcite-carbonatite bodies and probably formed during magmatic conditions. However, only in some of the samples from the Badberg, partly resorbed U- and Ta-enriched pyrochlore cores with up to 22?wt% UO2 and 9?wt% Ta2O5 have been identified, which are interpreted as being inherited from underlying nosean syenites. Pyrochlore data from a drill core penetrating the Badberg indicate increasing contents of REE, U, and Ta with depth, while Nb, F and Na contents decrease. This may reflect the combined effects of fractional crystallization and assimilation (AFC) or indicates a multi-stage emplacement of the carbonatitic magma. Patchy-zoned ceriopyrochlore and REE- and Th-enriched pyrochlore with up to 19?wt% total REE2O3 and 6.5?wt% ThO2 is largely restricted to samples from the Orberg and probably formed during hydrothermal conditions. This can be related to the relatively evolved character of the Orberg carbonatites, based on their relatively high whole-rock Nb/Ta and Zr/Hf mass ratios. This study demonstrates that the textural and compositional variation of pyrochlore in carbonatites is a powerful tool to distinguish magmatic, hydrothermal and weathering processes in carbonatitic systems.
Abstract: Mantle-derived carbonatites provide a unique window in the understanding of mantle characteristics and dynamics, as well as insight into the assembly and breakup of supercontinents. As a petrological indicator of extensional tectonic regimes, Archean/Proterozoic carbonatites provide important constraints on the timing of the breakup of ancient supercontinents. The majority of the carbonatites reported worldwide are Phanerozoic, in part because of the difficulty in recognizing Archean/Proterozoic carbonatites, which are characterized by strong foliation and recrystallization, and share broad petrologic similarities with metamorphosed sedimentary lithologies. Here, we report the recognition of a ~1.85?Ga carbonatite in Chaihulanzi area of Chifeng in north China based on systematic geological, petrological, geochemical, and baddeleyite U-Pb geochronological results. The carbonatite occurs as dikes or sills emplaced in Archean metasedimentary rocks and underwent intense deformation. Petrological and SEM/EDS results show that calcite and dolomite are the dominant carbonate minerals along with minor and varied amounts of Mg-rich mafic minerals, including forsterite (with Fo?>?98), phlogopite, diopside, and an accessory amount of apatite, baddeleyite, spinel, monazite, and ilmenite. The relatively high silica content together with the non-arc and OIB-like trace element signatures of the carbonatite indicates a hot mantle plume as the likely magma source. The depleted Nd isotopic signatures suggest that plume upwelling might be triggered by the accumulation of recycled crust in the deep mantle. As a part of the global-scale Columbia supercontinent, the Proterozoic tectonic evolution of the North China Craton (NCC) provides important insights into the geodynamics governing amalgamation and fragmentation of the supercontinent. The Paleo-Mesoproterozoic boundary is the key point of tectonic transition from compressional to extensional settings in the NCC. The newly identified ~1.85?Ga carbonatite provides a direct link between the long-lasting supercontinental breakup and plume activity, which might be sourced from the “slab graveyard,” continental crustal slabs subducted into asthenosphere, beneath the supercontinent. The carbonatite provides a precise constraint of the initiation of the continental breakup at ~1.85?Ga.
Abstract: Magmatism of the Povungnituk Group of the Cape Smith Belt, northern Superior craton, was formed in three stages: (i)early alkaline magmatism and associated carbonatites (undated), (ii) a main flood basalt sequence (Beauparlant Formation) (constrained between 2040 and 1991?Ma), and (iii) a late stage alkaline pulse (Cecilia Formation) (ca. 1959?Ma). We suggest that the main stage of magmatic activity (middle pulse) was of short duration. A new UPb baddeleyite age of 1998?±?6?Ma is obtained from a dolerite sill intruding the uppermost section of the Beauparlant Formation. This age has regional significance because it matches the previously obtained 1998?±?2?Ma age for the Watts Group (Purtuniq) ophiolite of the northern Cape Smith Belt and the 1998?±?2?Ma?U-Pb age of the Minto dykes intruding the craton to the south. These coeval units, along with additional units correlated on paleomagnetic grounds (Eskimo Formation), are interpreted to define a large igneous province (LIP), extending over an area of >400,000?km2, which we herein define as the Minto-Povungnituk LIP. Geochemical comparison between the Watts Group ophiolite, Minto dykes and the mafic Povungnituk Group shows significant differences allowing these data to be divided into two groups and domains within the LIP. A northern domain, comprising the Povungnituk and Watts groups, shows mixing between a depleted mantle source and a more enriched mantle plume-sourced melt. A southern domain comprising the Minto dykes and the paleomagnetically linked Eskimo Formation shows signs of an even more enriched source, while these magmas also show the effect of crustal contamination. Two distinct source mechanisms can be responsible for the observed geochemical differences between the two domains. First, a difference in lithospheric sources, where melting of different portions of Superior craton lithosphere caused the different melt signatures in the interior of the craton. In this case magmatism in the two domains is only related by having the same heat source (e.g.,a mantle plume) interpreted to be located on the northwestern side of the northern Superior craton. Second, two distinct deep mantle sources that remained separated within the ascending plume. This is analogous to some current hotspots interpreted to sample both large low shear velocity provinces (LLSVP) and adjacent ambient deep mantle. This latter interpretation would allow for the use of bilateral chemistry in LIPs as a potential tool for the recognition and mapping of the LLSVP boundaries throughout Earth's history.
Abstract: Carbonatitic magmatism in subduction zones provides extremely valuable information on the cycling, behavior and storage of deep carbon within the Earth. It may also shed light on insights into crust-mantle interaction and mantle metasomatism within subduction zones. Origin of carbonatite has long been debated: all hypotheses need to reflect the different mineral assemblages and geochemical compositions of carbonatites and their diverse tectonic settings. Here we present a petrological, geochronological, geochemical and isotopic study of carbonatite bodies associated with orogenic peridotites, which occur as stocks or dykes with widths of tens to hundreds of meters in the Luliangshan region, North Qaidam, northern Tibet, China. On the basis of modal olivine (Ol) content, the studied samples were subdivided into two groups: Ol-poor carbonatite and Ol-rich carbonatite. Zircon grains from the Ol-poor carbonatite show detrital features, and yield a wide age spectrum between 400?Ma and 1000?Ma with a pronounced peak at ca. 410-430?Ma. By contrast, oscillatory zoned zircons and inherited cores show two relatively small Neoproterozoic age peaks at ca. 920 and 830?Ma. Zircon grains from the Ol-rich carbonatite sample are also distributed in a wide spectrum between 400 and 1000?Ma, with a pronounced peak at ca. 440?Ma and a slightly inferior peak at ca. 410?Ma. The oscillatory zoned zircons and inherited cores exhibit a smaller Neoproterozoic age peak at ca. 740?Ma. The pronounced peaks ranging from 430 to 410?Ma are consistent with the deep subduction and mantle metasomatic events recorded in associated ultramafic rocks. Both groups of carbonatites are characterized by enrichment of light rare earth elements (LREEs) with high (La/Yb)N values and pronounced negative Eu anomalies. They show high 87Sr/86Sr values (0.708156-0.709004), low 143Nd/144Nd values (0.511932-0.512013) and high ?18OV-SMOW values (+17.9 to +21.3‰). This geochemical and isotopic evidence suggests that these carbonatites were derived from remobilized sedimentary carbonate rocks. We propose that the primary carbonatite magma was formed by partial melting of sedimentary carbonates with mantle contributions. Sedimentary carbonates were subducted into the shallow upper mantle where they melted and formed diapirs that moved upwards through the hot mantle wedge. The case presented provides a rare example of carbonatite originating from sedimentary carbonates with mantle contributions and relevant information on the mantle metasomatism within a subduction zone.
Abstract: Knowledge of the rheology of molten materials at high pressure and temperature is required to understand magma mobility and ascent rate at conditions of the Earth's interior. We determined the viscosity of nominally anhydrous sodium carbonate (Na2CO3), an analogue and ubiquitous component of natural carbonatitic magmas, by the in situ “falling sphere” technique at 1.7, 2.4 and 4.6?GPa, at 1200 to 1700?°C, using the Paris-Edinburgh press. We find that the viscosity of liquid Na2CO3 is between 0.0028?±?0.0001?Pa•s and 0.0073?±?0.0001?Pa•s in the investigated pressure-temperature range. Combination of our results with those from recent experimental studies indicate a negligible dependence on pressure from 1?atm to 4.6?GPa, and a small compositional dependence between molten alkali metal-bearing and alkaline earth metal-bearing carbonates. Based on our results, the viscosity of Na2CO3 is consistent with available viscosity data of both molten calcite (determined at high pressure and temperature) and Na2CO3 at ambient pressure. Molten Na2CO3 is a valid experimental analogue for study of the rheology of natural and/or synthetic near-solidus carbonatitic melts. Estimated values of the mobility and ascent velocity of carbonatitic melts at upper conditions are between 70 and 300?g?cm?3•Pa?1•s?1 and 330-1450?m•year?1, respectively, when using recently proposed densities for carbonatitic melts. The relatively slow migration rate allows magma-rock interaction over time causing seismic anomalies and chemical redox exchange.
Abstract: Mantle-derived carbonatites provide a unique window in the understanding of mantle characteristics and dynamics, as well as insight into the assembly and breakup of supercontinents. As a petrological indicator of extensional tectonic regimes, Precambrian carbonatites provide important constraints on the timing of the breakup of ancient supercontinents. The majority of the carbonatites reported worldwide are Phanerozoic, in part because of the difficulty in recognizing Precambrian carbonatites, which are characterized by strong foliation and recrystallization, and share broad petrologic similarities with metamorphosed sedimentary lithologies. Here we report the recognition of a ~1.85?Ga carbonatite in Chaihulanzi area of Chifeng in north China based on systematic geological, petrological, geochemical, and baddeleyite U-Pb geochronological results. The carbonatite occurs as dikes or sills emplaced in Archean metasedimentary rocks and underwent intense deformation. Petrological and SEM/EDS results show that calcite and dolomite are the dominant carbonate minerals along with minor and varied amounts of Mg-rich mafic minerals, including forsterite (with Fo?>?98), phlogopite, diopside, and an accessory amount of apatite, baddeleyite, spinel, monazite, and ilmenite. The relatively high silica content together with the non-arc and OIB-like trace element signatures of the carbonatite indicates a hot mantle plume as the likely magma source. The depleted Nd isotopic signatures suggest that plume upwelling might be triggered by the accumulation of recycled crust in the deep mantle. As a part of the global-scale Columbia supercontinent, the Proteozoic tectonic evolution of the North China Craton (NCC) provides important insights into the geodynamics governing amalgamation and fragmentation of the supercontinent. The Paleo-Mesoproterozoic boundary is the key point of tectonic transition from compressional to extensional settings in the NCC. The newly-identified ~1.85?Ga carbonatite provides a direct link between the long-lasting supercontinental breakup and plume activity, which might be sourced from the “slab graveyard”, continental crustal slabs subducted into asthenosphere, beneath the supercontinent. The carbonatite provides a precise constraint of the initiation of the continental breakup at ~1.85?Ga.
Contributions to Mineralogy and Petrology, Vol. 174, 4, doi.org/10. 1007/s00410-018-1530-x 13p.
Mantle
carbonatite
Abstract: Here we present an experimental study of the distribution of a broad range of trace elements between carbonatite melt, calcite and fluorite. The experiments were performed in the CaCO3 + CaF2 + Na2CO3 ± Ca3(PO4)2 synthetic system at 650-900 °C and 100 MPa using rapid-quench cold-seal pressure vessels. Starting mixtures were composed of reagent-grade oxides, carbonates, Ca3(PO4)2 and CaF2 doped with 1 wt% REE-HFSE mixture. The results show that the distribution coefficients of all the analyzed trace elements for calcite and fluorite are below 1, with the highest values observed for Sr (0.48-0.8 for calcite and 0.14-0.3 for fluorite) and Y (0.18-0.3). The partition coefficients of REE gradually increase with increasing atomic number from La to Lu. The solubility of Zr, Hf, Nb and Ta in the synthetic F-rich carbonatitic melts, which were used in our experiments, is low and limited by crystallization of baddeleyite and Nb-bearing perovskite.
Abstract: Mantle-derived carbonatites provide a unique window in the understanding of mantle characteristics and dynamics, as well as insight into the assembly and breakup of supercontinents. As a petrological indicator of extensional tectonic regimes, Precambrian carbonatites provide important constraints on the timing of the breakup of ancient supercontinents. The majority of the carbonatites reported worldwide are Phanerozoic, in part because of the difficulty in recognizing Precambrian carbonatites, which are characterized by strong foliation and recrystallization, and share broad petrologic similarities with metamorphosed sedimentary lithologies. Here we report the recognition of a ~1.85?Ga carbonatite in Chaihulanzi area of Chifeng in north China based on systematic geological, petrological, geochemical, and baddeleyite U-Pb geochronological results. The carbonatite occurs as dikes or sills emplaced in Archean metasedimentary rocks and underwent intense deformation. Petrological and SEM/EDS results show that calcite and dolomite are the dominant carbonate minerals along with minor and varied amounts of Mg-rich mafic minerals, including forsterite (with Fo?>?98), phlogopite, diopside, and an accessory amount of apatite, baddeleyite, spinel, monazite, and ilmenite. The relatively high silica content together with the non-arc and OIB-like trace element signatures of the carbonatite indicates a hot mantle plume as the likely magma source. The depleted Nd isotopic signatures suggest that plume upwelling might be triggered by the accumulation of recycled crust in the deep mantle. As a part of the global-scale Columbia supercontinent, the Proteozoic tectonic evolution of the North China Craton (NCC) provides important insights into the geodynamics governing amalgamation and fragmentation of the supercontinent. The Paleo-Mesoproterozoic boundary is the key point of tectonic transition from compressional to extensional settings in the NCC. The newly-identified ~1.85?Ga carbonatite provides a direct link between the long-lasting supercontinental breakup and plume activity, which might be sourced from the “slab graveyard”, continental crustal slabs subducted into asthenosphere, beneath the supercontinent. The carbonatite provides a precise constraint of the initiation of the continental breakup at ~1.85?Ga.
Abstract: Major, trace element concentrations and Nd, Sr and Ca stable isotopic compositions (?44/40Ca and ?44/42Ca w.r.t. NIST SRM915a) of carbonatites and associated igneous silicate rocks from the ~65?Ma old Ambadongar carbonatite complex and the surrounding Phenai Mata igneous complex of western India are reported. Samples of fluorspar from Ambadongar and the Bagh Limestone and Sandstone, which are part of the country rocks at Ambadongar, have also been analysed. The Ambadongar carbonatites are primarily calcio- and ferro-carbonatites while the silicate rocks from these two complexes are alkaline and tholeiitic in composition. The ?44/40Ca values of the carbonatites (0.58-1.1‰, n?=?7) and the associated igneous silicate rocks (0.50-0.92‰, n?=?14) show a broad range. The low K/Ca values of the carbonatites (<0.2) and silicate rocks (<2) along with their young eruption age (~65 Ma) rule out any effect of radiogenic 40Ca ingrowth due to decay of 40K on the ?44/40Ca values. The lack of correlations between ?44/40Ca and Mg# as well as La/Yb(N) values suggest that the variability in ?44/40Ca is not controlled by the degree of partial melting. The ?44/40Ca values of the carbonatites (0.58-1.1‰) overlap with that of the upper mantle/Bulk Silicate Earth and is mostly higher than the ?44/40Ca value of the Bagh Limestone (0.66‰) suggesting that assimilation of these crustal limestones by the magma is unlikely to have caused the variability in ?44/40Ca of the carbonatites. In plots of ?44/40Ca versus ?Nd(t) and 87Sr/86Sr(t), the igneous silicate rocks from the Ambadongar and Phenai Mata complexes plot on a mixing trend between a primitive (plume) mantle source and the continental crustal basement suggesting the role of continental crustal contamination during eruption of the Reunion plume. While simple binary mixing calculations yield unrealistically high amounts of crustal contamination (40%), assimilation and fractional crystallization (AFC) models suggest up to 20% contribution from a heterogeneous basement for these igneous silicate rocks. The role of continental crustal contamination in the genesis of the igneous silicate rocks is further supported by their unradiogenic ?Nd(t), radiogenic 87Sr/86Sr(t) and low Ce/Pb values. In contrast, carbonatites plot away from the mixing trend between a primitive mantle (plume) source and continental crust in Ca-Sr-Nd isotopic diagrams suggesting that the Ca isotopic variability of carbonatites is not caused by continental crustal contamination. In contrast, the isotopic composition of the carbonatites can be explained by mixing of the plume end-member with up to 20% of ~160?Ma-old recycled carbonates suggesting their derivation from a highly heterogeneous, recycled carbonate-bearing plume mantle source. The composition of one carbonatite sample showing unusually high ?44/40Ca and highly radiogenic 87Sr/86Sr(t) is explained by hydrothermal alteration which is also invoked for the formation of massive fluorspar deposits with high ?44/40Ca (1.44‰) at Ambadongar. In a plot of ?44/40Ca versus K/Rb, the carbonatites plot towards the phlogopite end-member (?44/40Ca?=?1‰, K/Rb?=?40-450) while the igneous silicate rocks plot towards the amphibole end-member (?44/40Ca?=?0.44‰, K/Rb >1000). Phlogopite, especially if F-rich, is stable at greater depths in the mantle compared to amphibole. Hence, the correlated ?44/40Ca and K/Rb values of the carbonatites and associated igneous silicate rocks suggest the derivation of these carbonatites from a relatively deeper mantle source compared to the silicate rocks, both within the Reunion mantle plume. The origin of the carbonatites from the F-rich phlogopite-bearing mantle is also consistent with the occurrence of large fluorspar deposits within the Ambadongar carbonatite complex.
Geochimica et Cosmochimica Acta, Vol. 248, pp. 1-13.
Russia, Siberia
carbonatite
Abstract: Ca isotopes can be strongly fractionated at the Earth’s surface and thus may be tracers of subducted carbonates and other Ca-rich surface materials in mantle rocks, magmas and fluids. However, the ?44/40Ca range in the mantle and the scope of intra-mantle isotope fractionation are poorly constrained. We report Ca isotope analyses for 22 mantle xenoliths: four basalt-hosted refractory peridotites from Tariat in Mongolia and 18 samples from the Obnazhennaya (Obn) kimberlite on the NE Siberian craton. Obn peridotites are Paleoproterozoic to Archean melting residues metasomatised by carbonate-rich and/or silicate melts including unique xenoliths that contain texturally equilibrated carbonates. ?44/40Ca in 15 Obn xenoliths shows limited variation (0.74-0.97‰) that overlaps the value (0.94?±?0.05‰) inferred for the bulk silicate Earth from data on fertile lherzolites, but is lower than ?44/40Ca for non-metasomatised refractory peridotites from Mongolia (1.10?±?0.03‰). Bulk ?44/40Ca in four Obn peridotites containing metasomatic carbonates ranges from 0.81?±?0.08‰ to 0.83?±?0.06‰, with similar values in acid-leachates and leaching residues, indicating isotopic equilibration of the carbonates with host rocks. We infer that (a) metasomatism tends to decrease ?44/40Ca values of the mantle, but its effects are usually limited (?0.3‰); (b) Ca isotopes cannot distinguish "carbonatite" and "silicate" types of mantle metasomatism. The lowest ?44/40Ca value (0.56‰) was obtained for a phlogopite-bearing Obn peridotite with a very high Ca/Al of 8 suggesting that the greatest metasomatism-induced Ca isotope shifts may be seen in rocks initially low in Ca that experienced significant Ca input leading to high Ca/Al. Two Obn peridotites, a dunite (melt channel material) and a veined spinel wehrlite, have high ?44/40Ca values (1.22‰ and 1.38‰), which may be due to isotope fractionation by diffusion during silicate melt intrusion and percolation in the host mantle. Overall, we find no evidence that recycling of crustal carbonates may greatly affect Ca isotope values in the global mantle or on a regional scale.
Researchgate preprint, 10.31223/ofs.io/uh5c8 40p. Pdf
Mantle
carbonatite
Abstract: Over the last decades, many experimental studies have focused on the effect of CO2 on phase equilibria and melting behavior of synthetic eclogite and peridotite rocks as function of pressure and temperature. These studies have been of fundamental importance to understanding the origin of carbonated magmas varying in composition from carbonatitic to kimberlitic. The occurrence of diamonds in natural rocks is a further evidence of the presence of (reduced) carbon in the Earth’s interior. The oxygenation of the Earth’s interior (i.e. its redox state) through time has strongly influenced the speciation of carbon from the mantle to mantle-derived magmas and, in turn, to the released volcanic gases to the atmosphere. This paper explains how the knowledge of the oxygen fugacity recorded by mantle rocks and determined through the use of appropriate oxy-thermobarometers allows modeling the speciation of carbon in the mantle, its mobilization in the asthenospheric mantle by redox partial melting, and its sequestration and storage during subduction by redox freezing processes. The effect of a gradual increase of the mantle fo2 on the mobilization of C is here discussed along with the main variables affecting its transport by subduction down to the mantle.
Abstract: This paper focuses on formation of subcalcic Cr-rich garnet (up to 14.25?wt% Cr2O3) in the model ultramafic system corresponding to natural harzburgite with the presence of REE-bearing fluid phase. The experiments were carried out using a “split-sphere” type multi-anvil high-pressure apparatus (BARS) at a pressure of 5?GPa and a temperature of 1300?°C. Natural serpentine, chromite, corundum and REE-carbonatite were used as starting components. Crystallization of garnet occurred in subsolidus conditions by the reaction of orthopyroxene and spinel in the presence of fluid phase. Composition of fluid was controlled by interaction of water released by decomposition of serpentine with carbonate. By using different amounts of carbonatite (0.5 and 1.5?wt%) as a source of calcium and REE, subcalcic Cr-rich garnets with up to 3.5?wt% CaO were crystallized, which are typical for inclusions of harzburgitic paragenesis in natural diamonds. The experiments demonstrated that the rare earth elements (REE) released from the initial carbonatite were transported by the fluid and were incorporated into the newly formed garnet. The distribution of REE in garnet revealed a vivid enrichment toward the heavy REE (HREE), showing the pattern with a very steep slope. These results confirmed high partitioning of HREE into garnet. The present study indicates that the mantle carbonatites, which contain very high proportions of light REE (LREE) to HREE, can play an important role as source material in formation of REE-rich fluids to crystallize garnets with typical REE patterns in mantle peridotites.
Geochimica et Cosmochimica Acta, Vol. 248, pp. 1-13.
Mantle
carbonatite
Abstract: Ca isotopes can be strongly fractionated at the Earth’s surface and thus may be tracers of subducted carbonates and other Ca-rich surface materials in mantle rocks, magmas and fluids. However, the ?44/40Ca range in the mantle and the scope of intra-mantle isotope fractionation are poorly constrained. We report Ca isotope analyses for 22 mantle xenoliths: four basalt-hosted refractory peridotites from Tariat in Mongolia and 18 samples from the Obnazhennaya (Obn) kimberlite on the NE Siberian craton. Obn peridotites are Paleoproterozoic to Archean melting residues metasomatised by carbonate-rich and/or silicate melts including unique xenoliths that contain texturally equilibrated carbonates. ?44/40Ca in 15 Obn xenoliths shows limited variation (0.74-0.97‰) that overlaps the value (0.94?±?0.05‰) inferred for the bulk silicate Earth from data on fertile lherzolites, but is lower than ?44/40Ca for non-metasomatised refractory peridotites from Mongolia (1.10?±?0.03‰). Bulk ?44/40Ca in four Obn peridotites containing metasomatic carbonates ranges from 0.81?±?0.08‰ to 0.83?±?0.06‰, with similar values in acid-leachates and leaching residues, indicating isotopic equilibration of the carbonates with host rocks. We infer that (a) metasomatism tends to decrease ?44/40Ca values of the mantle, but its effects are usually limited (?0.3‰); (b) Ca isotopes cannot distinguish "carbonatite" and "silicate" types of mantle metasomatism. The lowest ?44/40Ca value (0.56‰) was obtained for a phlogopite-bearing Obn peridotite with a very high Ca/Al of 8 suggesting that the greatest metasomatism-induced Ca isotope shifts may be seen in rocks initially low in Ca that experienced significant Ca input leading to high Ca/Al. Two Obn peridotites, a dunite (melt channel material) and a veined spinel wehrlite, have high ?44/40Ca values (1.22‰ and 1.38‰), which may be due to isotope fractionation by diffusion during silicate melt intrusion and percolation in the host mantle. Overall, we find no evidence that recycling of crustal carbonates may greatly affect Ca isotope values in the global mantle or on a regional scale.
Abstract: Identification of the Late Mesozoic carbonatite province in Central Asia is herein discussed. Its regional extent and distribution is investigated, and the areas with manifestations of carbonatite magmatism are described. It is shown that they were developed in terranes with heterogeneous and heterochronous basements: Siberian (Aldan Shield) and North China cratons; Early Paleozoic (Caledonian) and Middle-Late Paleozoic (Hercynian) structures of the Central Asian fold belt (Transbaikal and Tuva zones in Russia; Mongolia). Irrespective of the structural position, the carbonatites were generated within a relatively narrow time interval (150-118?Ma). The geochemical (Sr, LREE, Ba, F and P) specialization of carbonatites of the province is reflected in their mineral composition. Some rocks of the carbonatite complexes always include one or more distinctive minerals: fluorite, Ba-Sr sulfates, Ba-Sr-Ca carbonates, LREE fluorocarbonates, or apatite. Compared to counterparts from other age groups (for example, Maimecha-Kotui group in North Asia), these carbonatites are depleted in Ti, Nb, Ta, Zr and Hf. It is shown that the Sr and Nd isotope composition of carbonatites correlates with the geological age of the host crust. Rocks of carbonatite complexes associated with cratons are characterized by the lowest ?Nd(T) and highest ISr(T) values, indicating that their formation involved an ancient lithospheric material. Carbonatite magmatism occurred simultaneously with the largest plateau basalts 130-120?Ma ago in rift zones in the Late Mesozoic intraplate volcanic province of Central Asia. This interval corresponds to timing of global activation of intraplate magmatism processes, suggesting a link of the carbonatite province with these processes. It is shown that fields with the carbonatite magmatism were controlled by small mantle plumes (“hot fingers”) responsible for the Central Asian mantle plume events.
Abstract: The phase relations in the system Na2CO3?CaCO3?MgCO3 have been studied at 3?GPa and 700-1285?°C using a Kawai-type multianvil press. At 700?°C, the system has five intermediate compounds: dolomite, Mg-bearing Na2Ca4(CO3)5 burbankite, Na2Ca3(CO3)4, Na4Ca(CO3)3, and eitelite. As temperature increases to 800?°C, the system is complicated by an appearance of Ca-dolomite and Mg-bearing shortite, while Na2Ca4(CO3)5 disappears. At 850?°C, Na4Ca(CO3)3 decomposes to produce Na carbonate and nyerereite. The latter melts incongruently at 875?±?25?°C to form Na2Ca3(CO3)4. Incongruent melting of eitelite to magnesite and liquid, occurs at 925?±?25 °C. Mg-bearing shortite melts incongruently at 950?±?50?°C, producing Na2Ca3(CO3)4 and liquid. Na2Ca3(CO3)4 disappears at 1000?°C via incongruent melting to calcite and liquid. The liquidus projection of the studied ternary system has seven primary solidification phase regions for magnesite, dolomite-calcite solid solutions, Na2Ca3(CO3)4, Mg-bearing shortite, nyerereite, eitelite, and Na carbonate. The primary solidification regions are separated by five peritectic and three cotectic monovariant lines. The system has six ternary peritectic points and one minimum on the liquidus at 850?°C and 52Na2CO3?48(Ca0.62Mg0.38)CO3. The minimum point resembles a eutectic controlled by a four-phase reaction, by which, on cooling, a liquid transforms into three solid phases: shortite, Na carbonate, and eitelite. Since the system has a single eutectic at 3?GPa, there is no thermal barrier preventing continuous liquid fractionation from Na-poor toward Na-rich dolomitic compositions more alkaline than eitelite and nyerereite. Considering the present results and previous data, a range of Na-Ca-Mg double carbonates changes in the following sequence upon pressure and temperature increase: Na2Ca2(CO3)3 (Amm2) shortite, Na2Ca(CO3)2 (P21ca) nyerereite, Na2Mg(CO3)2 () eitelite (0.1?GPa)???Na2(Ca0.97-0.98Mg0.02-0.03)4(CO3)5 (P63mc), Na2(Ca?0.91Mg?0.09)3(CO3)4 (P1n1), Na2(Ca???0.81?Mg0?0.19)(CO3)2 () nyerereite, Na2(Ca0.77-0.93Mg0.07-0.23)2(CO3)3 (Amm2) shortite, Na4(Ca0.90-0.98Mg0.02-0.10)(CO3)3 (Ia3d), Na2(Mg?0.9Ca0?0.1)(CO3)2 (P21ca) eitelite (3?GPa)???Na2(Ca?0.87Mg0?0.13)4(CO3)5 (P63mc), Na2(Ca?0.89Mg?0.11)3(CO3)4 (P1n1), Na4(Ca???0.7?Mg0?0.3)(CO3)3 (Ia3d), Na2(Mg?0.92Ca0?0.08)(CO3)2 (P21ca) eitelite (6?GPa). Using the present results at 3?GPa and previous data at 6?GPa in the Na2CO3?CaCO3?MgCO3 system, we constrained isopleths of the Na2CO3 content in melt coexisting with Ca-Mg carbonates. We found that the cratonic geotherms cross the isopleths so that the carbonatite melt percolating upward via the continental mantle lithosphere should become progressively enriched in Na, evolving from alkali-poor dolomitic composition at depths exceeding 200?km toward sodic dolomitic with the ~52?mol% Na2CO3 at 80-120?km depths.
Abstract: Magnetite (Fe3O4) is one of the most common accessory minerals in magmatic rocks, and it can accommodate a wide variety of major, minor and trace elements that can be measured by laser ablation ICP-MS. In this study, we investigate the chemical compositions of magnetite from four carbonatite complexes (Oka, Mushgai Khudag, Hongcheon and Bayan Obo). The minor elements (Mg, Ti, Al, Mn) in magnetite vary significantly both within and between different complexes. High field strength elements (Zr, Hf, Nb, Ta, U, Th) are generally depleted in magnetite from carbonatite complexes, whereas K, Rb, Cs, Ca and P are commonly below detection limits. V and Zn display significant variations from tens to thousands of ppm. Co, Ni and Ga are present in ppm or tens of ppm, whereas Cu, Sr, Y, Ba and Pb are characterized by sub-ppm levels. Mo and Ge are identified at the ppm level, whereas a consistent concentration of 2-5?ppm is observed for Ge. The determined chemical compositions of magnetite from carbonatite complexes are quite distinguishable compared to those formed in silicate and sulfide melts. This is clearly shown using multielement variation diagrams, and the distinct signatures of carbonatite-related magnetite include strong positive anomalies of Mn and Zn and negative anomalies of Cu, Co and Ga. The discriminant diagrams of Ti vs. Zr?+?Hf, Ti vs. Nb?+?Ta and Ni/Cr vs. Ti are applicable for distinguishing magmatic and hydrothermal magnetite in carbonatite-related environments. In addition, the discriminant diagram of Zn/Co vs. Cu/Mo and Cu vs. Zr?+?Hf can be used to distinguish carbonatite-related magnetite from magnetite that formed in other environments.
Abstract: The Upper Ruvubu Alkaline Plutonic Complex (URAPC) in Burundi consists of three separate intrusions, each with a specific emplacement age and petrological composition. Three main units are recognized: an outer unit with silica-saturated plutonic rocks (from gabbro to granite), an inner unit with silica-undersaturated plutonic rocks (feldspathoidal syenite with subordinate feldspathoidal monzonite and ijolite) and a carbonatitic body in the subsoil, known by drilling. The URAPC is quite large in size (?24?km long and up to 10?km wide). It is considered to have been intruded syntectonically in an overall extensional context, thanks to the kilometric shear zones that accommodated its emplacement. Radiometric ages from literature range from 748 to 705?Ma and point to structurally-controlled magmatic differentiation followed by long-lived circulations of late-stage fluids postdating the emplacement of a part of the undersaturated rocks and the carbonatites. In the north-western part of the outer unit, gabbro likely has been emplaced at a deeper structural level than the granite, which represents a more apical structural level of emplacement. This petrological, geochemical and isotopic (Sr-Nd-Hf) study concentrates on the processes that generated the URAPC: (i) fractional crystallization, evidenced by the chemical evolution trends of the major and trace elements, and by marked P, Ti and Ba anomalies in the trace element patterns; (ii) crustal assimilation/contamination, as shown by the wide range of Nd isotope compositions and the general increase of the Sr isotope ratios with increasing SiO2 contents, and (iii) late-magmatic/hydrothermal alteration inducing an increase of the Sr isotope composition without changing significantly the Nd isotope composition. The isotopic data are consistent with an asthenospheric mantle source, though less depleted than the Depleted Mantle (DM), contaminated by the Subcontinental Lithospheric Mantle (SCLM). The silicate and carbonate magmatic series are cogenetic. The outer unit is clearly more contaminated than the inner unit, whereas the carbonatitic body could have evolved by liquid immiscibility. The URAPC lies within East Africa’s Western Rift Valley, which is marked by 23 alkaline plutonic complexes. Their emplacement has been ascribed to reactivation of Proterozoic lithospheric weakness zones resulting from the breakup of the Neoproterozoic supercontinent Rodinia supercontinent.
Abstract: We report on pipe-like bodies and dikes of carbonate rocks related to sodic alkaline intrusions and amphibole mantle peridotites in the Ivrea zone (European Southern Alps). The carbonate rocks have bulk trace-element concentrations typical of low-rare earth element carbonatites interpreted as cumulates of carbonatite melts. Faintly zoned zircons from these carbonate rocks contain calcite inclusions and have trace-element compositions akin to those of carbonatite zircons. Laser ablation-inductively coupled plasma-mass spectrometry U-Pb zircon dating yields concordant ages of 187 ± 2.4 and 192 ± 2.5 Ma, coeval with sodic alkaline magmatism in the Ivrea zone. Cross-cutting relations, ages, as well as bulk and zircon geochemistry indicate that the carbonate rocks are carbonatites, the first ones reported from the Alps. Carbonatites and alkaline intrusions are comagmatic and were emplaced in the nascent passive margin of Adria during the Early Jurassic breakup of Pangea. Extension caused partial melting of amphibole-rich mantle domains, yielding sodic alkaline magmas whose fractionation led to carbonatite-silicate melt immiscibility. Similar occurrences in other rifts suggest that small-scale, sodic and CO2-rich alkaline magmatism is a typical result of extension and decompression-driven reactivation of amphibole-bearing lithospheric mantle during passive continental breakup and the evolution of magma-poor rifts.
Abstract: Bastnäsite is the main ore mineral in many carbonatite-related rare earth element (REE) deposits, which account for ?51% of rare-earth oxide reserves worldwide. However, the occurrence, geochemistry, and genetic significance of bastnäsite has not been methodically investigated. The Cenozoic Mianning-Dechang (MD) REE belt in Sichuan Province, SW China, contains the Maoniuping, Dalucao, Lizhuang, and Muluozhai deposits as well as numerous smaller REE occurrences. Individual deposits within the belt contain different types of bastnäsite-bearing ore, which provides a unique opportunity to explore in detail the common mechanisms controlling the formation of bastnäsite-rich REE deposits. Here, we present detailed results from field observations and petrographic, geochemical, and fluid inclusion studies of bastnäsite from the main MD deposits. Calcite, fluorite, and barite form stable mineral assemblages that are commonly overprinted by bastnäsite. Homogenization temperatures of fluid inclusions in bastnäsite of ?150-270?°C (Dalucao and Lizhuang deposits) and 155-210?°C (Maoniuping deposit) are systematically lower than those of fluid inclusions in gangue minerals. Therefore, the petrographic studies and homogenization temperatures both show that large-scale crystallization of bastnäsite took place during the later stage of the hydrothermal system. The bastnäsite, relatively geochemically homogeneous within all of the MD deposits, is enriched in Ba (293-8425?ppm), Th (16.4-2527?ppm), and U (4.19-92.7?ppm), and relatively depleted in high field strength elements such as Nb (0.15-17.4?ppm), Ta (0.06-6.48?ppm), Zr (0.71-31.1?ppm), Hf (0.62-5.65?ppm), and Ti (<60?ppm), the same to carbonatite, and ore veins. In comparison, the samples from the study area show an increase in average REE contents from syenites to carbonatites to ore veins (i.e., bastnäsite-bearing ores) and finally to bastnäsite. Lanthanum and Ce were commonly substituted by Th, U, Sc, Ba, and Sr supplied by more evolved hydrothermal fluids. Combining the present results with existing data, we present a three-stage model for the formation of carbonatite-related REE deposits. First, partial melting of metasomatized sub-continental lithospheric mantle, fluxed by REE- and CO2-rich fluids, forms the parental carbonatite-syenite magma. Second, Sr, Ba, and REEs are strongly partitioned into carbonatite melts during liquid immiscibility in the carbonatite-syenite magmatic system. Third, hydrothermal fluids exsolved from the crystalizing syenite and carbonatite magmas form ore veins with early gangue minerals and later bastnäsite overgrowths. Consequently, barite, calcite, and fluorite assemblages are a valuable guide in REE exploration.
Geochimica et Cosmochimica Acta, in press available 38p.
Mantle
carbonatite
Abstract: Carbon isotope exchange between carbon-bearing high temperature phases records carbon (re-) processing in the Earth's interior, where the vast majority of global carbon is stored. Redox reactions between carbonate phases and elemental carbon govern the mobility of carbon, which then can be traced by its isotopes. We determined the carbon isotope fractionation factor between graphite and a Na2CO3-CaCO3 melt at 900-1500 °C, 1 GPa using a piston-cylinder device. The failure to isotopically equilibrate preexisting graphite led us to synthesize graphite anew from organic material during the melting of the carbonate mixture. Graphite growth proceeds by (1) decomposition of organic material into globular amorphous carbon, (2) restructuring into nano-crystalline graphite, and (3) recrystallization into hexagonal graphite flakes. Each transition is accompanied by carbon isotope exchange with the carbonate melt. High-temperature (1200 - 1500 °C) equilibrium isotope fractionation with type (3) graphite can be described by (temperature T in K). As the experiments do not yield equilibrated graphite at lower temperatures, we combined the ?1200 °C experimental data with those derived from upper amphibolite and lower granulite facies carbonate-graphite pairs (Kitchen and Valley, 1995, Valley and O'Neil, 1981). This yields the general fractionation function usable as a geothermometer for solid or liquid carbonate at ? 600 °C. Similar to previous observations, lower-temperature experiments (?1100 °C) deviate from equilibrium. By comparing our results to diffusion and growth rates in graphite, we show that at ?1100 °C carbon diffusion is slower than graphite growth, hence equilibrium surface isotope effects govern isotope fractionation between graphite and carbonate melt and determine the isotopic composition of newly formed graphite. The competition between diffusive isotope exchange and growth rates requires a more careful interpretation of isotope zoning in graphite and diamond. Based on graphite crystallization rates and bulk isotope equilibration, a minimum diffusivity of Dgraphite = 2x10-17 m2s-1 for T >1150 °C is required. This value is significantly higher than calculated from experimental carbon self-diffusion constants (?1.6x10-29 m2s-1) but in good agreement with the value calculated for mono-vacancy migration (?2.8x10-16 m2s-1).
Abstract: In Brazil, alkaline intrusions are source rocks for several commodities (bauxite, phosphate, niobium and barite, to mention a few), including mineral water. The present study aims to understand by means of chemical and stable isotope analyses, the residence time, circulation and hydrochemical facies of the groundwater systems from the alkaline-carbonatitic complex of Barreiro (State of Minas Gerais, Brazil). This Mesozoic alkaline complex is located in the Brazilian tropical region characterized by weathered soils and fractured rocks, which play an important role in the groundwater dynamics. To assess this influence, groundwater samples from 12 points and water samples from 3 artificial lakes were collected for the determination of chemical element and natural isotope (18O, deuterium and 13C) concentrations and 14C and tritium dating. Two main groundwater categories were revealed: (a) a local, acidic and sub-modern groundwater system developed in thick, poorly mineralized weathered soil from the inner part of ACCB, and (b) a basic, hypothermal, ca. 40-ky-old fractured aquifer developed in mineralized fenitized quartzites. The younger and shallower groundwater circulation is controlled by the present intrusion relief and is prone to environmental impacts. The older, hypothermal groundwater system indicates existing geothermal residual heat provided by the Mesozoic alkaline intrusion.
Journal of the Geological Society of India, Vol. 93, 3, pp. 305-312.
India
carbonatite
Abstract: Inclusions of calcite within large euhedral apatite crystals from the pyroxenite-carbonatite-syenite complex of Sevattur, Tamil Nadu, south India, were identified to represent inclusions of a primary carbonatitic melt (calcite I) from which the apatites have crystallized. The apatites themselves are embedded into a younger batch of calcite-carbonatitic melt (calcite II). Using the synchrotron XRF microprobe at beamline L at HASYLAB/DESY (Hamburg), the concentrations of the trace elements Ba, Sr, Y, Zr, Th, La, Ce, Nd, Sm, Gd, Dy, and Er were determined both in melt inclusions as well as in host apatites and younger carbonatite matrix. Unexpected high REE concentrations were found not only in apatite but also in calcite, especially of the younger matrix phase, in agreement with the whole rock geochemistry. The data reveal an equilibrium distribution between melt inclusions and host apatite that allows the calculation of partition coefficients D = CiAp/CiCc=melt for elements of interest. Assuming 9% crystallization of the melt, which can be calculated from the whole rock analyses, the composition of the primary carbonatite melt prior to apatite crystallization can be determined. This composition is, with the exception of only few elements, nearly equal to that of the younger matrix carbonatite melt (calcite II), and thus gives evidence for the existence of different pulses of carbonatite melt during crystallization and consolidation of the carbonatite body. The results allow new insights into the processes of trace element and REE distribution between the two major igneous components of carbonatites and thus into the question of carbonatitic fractionation processes. The data reveal that mere apatite crystallization and fractionation does not lead to enriched REE compositions during carbonatite evolution but lowers their concentrations in the residual melts. But alternatively, if segregated apatite is collected and incorporated by a new melt batch, the overall REE of this melt will be increased.
Abstract: New in-situ U-Pb ages and Sr-Nd-Hf isotopic data on mineral phases of the Sung Valley and Jasra ultramafic-alkaline-(carbonatite) intrusions (Shillong Plateau, India) shed new light on the petrogenetic processes of volcanism in north-eastern India during the Cretaceous. Perovskites of Sung Valley dunite, ijolite and uncompahgrite yielded U-Pb ages of 109.1?±?1.6, 104.0?±?1.3 and 101.7?±?3.6?Ma, respectively. A U-Pb age of 106.8?±?1.5?Ma was obtained on zircons of a Sung Valley nepheline syenite. Perovskite of a Jasra clinopyroxenite yielded an age of 101.6?±?1.2?Ma, different from the U-Pb age of 106.8?±?0.8?Ma on zircon of Jasra syenites. The variation in Sr-Nd-Hf isotopic compositions [initial 87Sr/86Sr?=?0.70472 to 0.71080; ?Nd i?=??10.85 to +0.86; ?Hf i?=??7.43 to +1.52] matches the bulk-rock isotopic composition of the different rock units of Sung Valley and Jasra. Calcite and apatite in the carbonatites, the perovskite in a dunite, and the bulk-rock carbonatites of Sung Valley intrusion have the lowest initial 87Sr/86Sr and ?Nd, taken to be the best proxies of the mantle source composition, which is dominated by components derived from the lithospheric mantle. The alkaline intrusions of north-eastern India are significantly younger than the Sylhet tholeiitic magmatism. The silicate rocks of both intrusions have isotopic composition trending to that of the underlying Shillong crust, indicating the effects of fractional crystallization and low-pressure crustal contamination during the emplacement of the various intrusive magma pulses.
Journal of the Geological Society of London, Vol. 176, pp. 375-387.
Global
carbonatite
Abstract: Over the last decades, many experimental studies have focused on the effect of CO2 on phase equilibria and melting behavior of synthetic eclogite and peridotite rocks as function of pressure and temperature. These studies have been of fundamental importance to understanding the origin of carbonated magmas varying in composition from carbonatitic to kimberlitic. The occurrence of diamonds in natural rocks is a further evidence of the presence of (reduced) carbon in the Earth’s interior. The oxygenation of the Earth’s interior (i.e. its redox state) through time has strongly influenced the speciation of carbon from the mantle to mantle-derived magmas and, in turn, to the released volcanic gases to the atmosphere. This paper explains how the knowledge of the oxygen fugacity recorded by mantle rocks and determined through the use of appropriate oxy-thermobarometers allows modeling the speciation of carbon in the mantle, its mobilization in the asthenospheric mantle by redox partial melting, and its sequestration and storage during subduction by redox freezing processes. The effect of a gradual increase of the mantle fo2 on the mobilization of C is here discussed along with the main variables affecting its transport by subduction down to the mantle.
Abstract: Carbonatite-related rare-earth element (REE) deposits (CARDs) are the major global source of REEs. The ore-forming fluids of CARDs usually comprise multiple components and record complicated evolutions. The Maoniuping REE deposit, located in the eastern Tibetan Plateau, is the second-largest CARD in China and contains total reserves of 3.17?Mt of light rare-earth oxides (REOs). Geochronological and geological data show that the deposit was formed at ?25?Ma and was only moderately affected by tectonic and hydrothermal activities, thereby allowing us to study the evolution of ore fluids as well as the mechanisms of REE mineralization. The Maoniuping REE deposit is spatially associated with a carbonatite-syenite complex and includes two sections: Guangtoushan and Dagudao. The Dagudao section is the main focus of exploration and hosts well-developed vein systems. In the uppermost vein system, minerals are zoned from the syenite wall-rock contact to the vein centers in the order of biotite, aegirine-augite, arfvedsonite, calcite, quartz, barite, fluorite, and bastnäsite-(Ce). Based on geological observations and the petrography of fluid inclusions, the mineralization processes are classified into magmatic, pegmatitic, hydrothermal I, hydrothermal II, and REE stages. The inclusions in these stages include melt (M), melt-fluid (M-L), pure CO2 (C), aqueous-CO2 (L-C), aqueous-CO2 with crystals (L???C?+?S), liquid-vapor aqueous with crystals (L???V?+?S), and liquid-vapor (L-V) type inclusions. The magmatic stage is marked by a carbonatite-syenite complex with minor bastnäsite-(Ce), whereas the pegmatitic stage consists of coarse-grained calcite, barite, fluorite, and quartz that contain M, M-L, and L-C type inclusions with a fluid system of NaCl-Na2SO4-H2O-CO2 at high temperature (>600?°C) and high salinity (>45?wt% NaCl equiv.). The hydrothermal I stage is characterized by fenitization and is marked by aegirine-augite and arfvedsonite containing abundant L-V and few L-C type inclusions. This stage is characterized by high temperatures (?480?°C) and moderate salinity (10.2-17.9?wt% NaCl equiv.), with a fluid system of NaCl-Na2SO4-H2O and minor CO2 and CH4?+?C2H6. The hydrothermal II stage is dominated by L-C, L???C?+?S, L???V?+?S, and L-V type inclusions that are hosted in barite, calcite, fluorite, and quartz, and formed at moderate to high temperatures (260-350?°C), with a wide range of salinity (9.4-47.8?wt% NaCl equiv.), a fluid system of NaCl-Na2SO4-CO2-H2O, and abundant CH4?+?C2H6. During the REE stage, pervasive bastnäsite-(Ce) containing abundant L-V type and few L-C type inclusions crystallized under low temperatures (160-240?°C) and low salinities (8.8-13.1?wt% NaCl equiv.) with a fluid system of NaCl-H2O and minor CO2 and CH4?+?C2H6. The results of ion-chromatographic analysis show that the ore fluids are rich in Na+, K+, Cl?, F?, and (SO4)2?, and have low Cl?/(SO4)2? ratios (0.78-2.00), showing a marked contrast with the fluids of granite-related REE deposits (Cl?/(SO4)2??>?50) and a similarity to subcontinental lithospheric mantle (SCLM). The ?D and ?18Ofluid values and the high N2/Ar ratios indicate that the ore fluids originated from carbonatitic magma and were dominated by magmatic water during the hydrothermal I stage, whereas magmatic and meteoric water co-existed during the hydrothermal II and REE stages. Moreover, the higher ratios of CO2/N2 (9-64) and CO2/CH4 (17-472) and the higher concentrations of CO2, CH4, C2H6, and N2 in the hydrothermal II stage compared with the hydrothermal I stage are attributed to intense immiscibility that resulted from decompression and is constrained to temperatures of 310-350?°C and pressures of 2.0-2.4?kbar. In contrast, microthermometric data and low CH4, C2H6, and N2 contents for the REE stage show that fluid cooling and mixing with meteoric water played an important role during the intensive mineralization of this stage, which occurred under shallow open-system conditions at temperatures of ?200?°C and pressures of <0.5?kbar. The mineral assemblages, together with experimental petrology results, suggest that the REE transport capability of the hydrothermal fluids was due to the high contents of (SO4)2?, Cl?, and F? complexes. In addition, CO2 that separates during immiscibility is known to act as a buffer that constrains the pH of ore fluids. Thus, immiscibility during the hydrothermal II stage could have provided favorable conditions for the migration of REEs. The subsequent cooling of fluids, the involvement of meteoric water, and increased fluid pH, favored the precipitation of REEs in the Maoniuping deposit.
Abstract: The Lower Cretaceous Jacupiranga complex, in the central-southeastern portion of the South American Platform, includes carbonatites in close association with silicate rocks (i.e. strongly and mildly silica-undersaturated series). Here we document the first hafnium isotope data on the Jacupiranga complex, together with new trace element and Pb isotope compositions. Even though liquid immiscibility from a carbonated silicate melt has been proposed for the genesis of several Brazilian carbonatites, isotopic and geochemical (e.g., Ba/La ratios, lack of pronounced Zr-Hf and Nb-Ta decoupling) information argues against a petrogenetic relationship between Jacupiranga carbonatites and their associated silicate rocks. Thus, an origin by direct partial melting of the mantle is considered. The isotopic compositions of the investigated silicate samples are coherent with a heterogeneously enriched subcontinental lithospheric mantle (SCLM) source of rather complex evolution. At least two metasomatic processes are constrained: (1) a first enrichment event, presumably derived from slab-related fluids introduced into the SCLM during Neoproterozoic times, as indicated by consistently old TDM ages and lamprophyre trace signatures, and (2) a Mesozoic carbonatite metasomatism episode of sub-lithospheric origin, as suggested by ?Nd-?Hf values inside the width of the terrestrial array. The Jacupiranga parental magmas might thus derive by partial melting of distinct generations of metasomatic vein assemblages that were hybridized with garnet peridotite wall-rocks.
Abstract: The petrogenesis of temporally and spatially associated carbonatitic and deeply derived carbonated alkaline silicate magmas provides an opportunity to gain insights into the nature of the deepest lithospheric mantle. The Chuktukon massif, which is part of the Chadobets alkaline ultramafic carbonatite complex (Chadobets upland, Siberian craton) is a carbonatite-melilitite-damtjernite intrusion, whose emplacement was coeval with the Siberian Traps large igneous province (LIP). In this study, the sources of the primary melts are examined, the petrogenetic evolution of the complex is reconstructed and the relationship with the Siberian LIP is also discussed. Isotopic and geochemical information indicate that the source for the Chuktukon primary melts was isotopically moderately depleted and the primarymelts were formed by lowdegree partial melting of garnet carbonated peridotite. Hydrothermal processes caused 18O- and 13C- enrichment. The weathering process was accompanied by trace element re-distribution and enrichment of the weathering crust in Zn, Th, U, Nb, Pb and REE, relative to the Chuktukon rocks and a change in radiogenic (Sr, Nd) isotope compositions.
Abstract: Earth’s only active natrocarbonatite volcanism, occurring at Oldoinyo Lengai (OL), Tanzania, suggests that natrocarbonatite melts are formed through a unique geological process. In the East African Rift, the extinct Kerimasi (KER) volcano is a neighbor of OL and also contains nephelinites hosting melt and fluid inclusions that preserve the igneous processes associated with formation of natrocarbonatite melts. Here, we present evidence for the presence of coexisting nephelinite melt, fluorine-rich carbonate melt, and alkali carbonate fluid. The compositions of these phases differ from the composition of OL natrocarbonatites; therefore, it is unlikely that natrocarbonatites formed directly from one of these phases. Instead, mixing of the outgassing alkali carbonate fluid and the fluorine-rich carbonate melt can yield natrocarbonatite compositions at temperatures close to subsolidus temperatures of nephelinite (<630-650 °C). Moreover, the high halogen content (6-16 wt%) in the carbonate melt precludes saturation of calcite (i.e., formation of calciocarbonatite) and maintains the carbonate melt in the liquid state with 28-41 wt% CaO at temperatures ?600 °C. Our study suggests that alkali carbonate fluids and melts could have commonly formed in the geological past, but it is unlikely they precipitated calcite that facilitates fossilization. Instead, alkali carbonates likely precipitated that were not preserved in the fossil nephelinite rocks. Thus, alkali carbonate fluids and melts have been so far overlooked in the geological record because of the lack of previous detailed inclusion studies.
Abstract: Hydroxynatropyrochlore, (Na,?a,Ce)2Nb2O6(OH), is a new Na-Nb-OH-dominant member of the pyrochlore supergroup from the Kovdor phoscorite-carbonatite pipe (Kola Peninsula, Russia). It is cubic, Fd-3m, a = 10.3211(3) Å, V = 1099.46 (8) Å3, Z = 8 (from powder diffraction data) or a = 10.3276(5) Å, V = 1101.5(2) Å3, Z = 8 (from single-crystal diffraction data). Hydroxynatropyrochlore is a characteristic accessory mineral of low-carbonate phoscorite of the contact zone of the phoscorite-carbonatite pipe with host foidolite as well as of carbonate-rich phoscorite and carbonatite of the pipe axial zone. It usually forms zonal cubic or cubooctahedral crystals (up to 0.5 mm in diameter) with irregularly shaped relics of amorphous U-Ta-rich hydroxykenopyrochlore inside. Characteristic associated minerals include rockforming calcite, dolomite, forsterite, hydroxylapatite, magnetite,and phlogopite, accessory baddeleyite, baryte, barytocalcite, chalcopyrite, chamosite-clinochlore, galena, gladiusite, juonniite, ilmenite, magnesite, pyrite, pyrrhotite, quintinite, spinel, strontianite, valleriite, and zirconolite. Hydroxynatropyrochlore is pale-brown, with an adamantine to greasy lustre and a white streak. The cleavage is average on {111}, the fracture is conchoidal. Mohs hardness is about 5. In transmitted light, the mineral is light brown, isotropic, n = 2.10(5) (??= 589 nm). The calculated and measured densities are 4.77 and 4.60(5) g•cm-3, respectively. The mean chemical composition determined by electron microprobe is: F 0.05, Na2O 7.97, CaO 10.38, TiO2 4.71, FeO 0.42, Nb2O5 56.44, Ce2O3 3.56, Ta2O5 4.73, ThO2 5.73, UO2 3.66, total 97.65 wt. %. The empirical formula calculated on the basis of Nb+Ta+Ti = 2 apfu is (Na1.02Ca0.73Ce0.09Th0.09 U0.05Fe2+0.02)?2.00 (Nb1.68Ti0.23Ta0.09)?2.00O6.03(OH1.04F0.01)?1.05. The simplified formula is (Na, Ca,Ce)2Nb2O6(OH). The mineral slowly dissolves in hot HCl. The strongest X-ray powderdiffraction lines [listed as (d in Å)(I)(hkl)] are as follows: 5.96(47)(111), 3.110(30)(311), 2.580(100)(222), 2.368(19)(400), 1.9875(6)(333), 1.8257(25)(440) and 1.5561(14)(622). The crystal structure of hydroxynatropyrochlore was refined to R1 = 0.026 on the basis of 1819 unique observed reflections. The mineral belongs to the pyrochlore structure type A2B2O6Y1 with octahedral framework of corner-sharing BO6 octahedra with A cations and OH groups in the interstices. The Raman spectrum of hydroxynatropyrochlore contains characteristic bands of the lattice, BO6, B-O and O-H vibrations and no characteristic bands of the H2O vibrations. Within the Kovdor phoscorite-carbonatite pipe, hydroxynatropyrochlore is the latest hydrothermal mineral of the pyrochlore supergroup, which forms external rims around grains of earlier U-rich hydroxykenopyrochlore and separated crystals in voids of dolomite carbonatite veins. The mineral is named in accordance with the pyrochlore supergroup nomenclature.
Abstract: Three models of geodynamic regimes of carbonatite formation are now actively being developed because of the high trace metal potential of this rock type: carbonatite melt generation within the lithosphere mantle; carbonatite relation to orogenic zones; the formation of carbonatite complexes as a result of the ascent of deep mantle plumes. The application for the first time of a modern model of “absolute” paleotectonic reconstructions combined with databases (both our own and published) demonstrates the general relationship of occurrences of the Phanerozoic carbonatite magmatism to Large Low S-wave Velocity Provinces: those are allocated in the lower mantle and are zones of generation of deep mantle plumes.
Abstract: The phase relations in the system Na2CO3?CaCO3?MgCO3 have been studied at 3?GPa and 700-1285?°C using a Kawai-type multianvil press. At 700?°C, the system has five intermediate compounds: dolomite, Mg-bearing Na2Ca4(CO3)5 burbankite, Na2Ca3(CO3)4, Na4Ca(CO3)3, and eitelite. As temperature increases to 800?°C, the system is complicated by an appearance of Ca-dolomite and Mg-bearing shortite, while Na2Ca4(CO3)5 disappears. At 850?°C, Na4Ca(CO3)3 decomposes to produce Na carbonate and nyerereite. The latter melts incongruently at 875?±?25?°C to form Na2Ca3(CO3)4. Incongruent melting of eitelite to magnesite and liquid, occurs at 925?±?25 °C. Mg-bearing shortite melts incongruently at 950?±?50?°C, producing Na2Ca3(CO3)4 and liquid. Na2Ca3(CO3)4 disappears at 1000?°C via incongruent melting to calcite and liquid. The liquidus projection of the studied ternary system has seven primary solidification phase regions for magnesite, dolomite-calcite solid solutions, Na2Ca3(CO3)4, Mg-bearing shortite, nyerereite, eitelite, and Na carbonate. The primary solidification regions are separated by five peritectic and three cotectic monovariant lines. The system has six ternary peritectic points and one minimum on the liquidus at 850?°C and 52Na2CO3?48(Ca0.62Mg0.38)CO3. The minimum point resembles a eutectic controlled by a four-phase reaction, by which, on cooling, a liquid transforms into three solid phases: shortite, Na carbonate, and eitelite. Since the system has a single eutectic at 3?GPa, there is no thermal barrier preventing continuous liquid fractionation from Na-poor toward Na-rich dolomitic compositions more alkaline than eitelite and nyerereite. Considering the present results and previous data, a range of Na-Ca-Mg double carbonates changes in the following sequence upon pressure and temperature increase: Na2Ca2(CO3)3 (Amm2) shortite, Na2Ca(CO3)2 (P21ca) nyerereite, Na2Mg(CO3)2 () eitelite (0.1?GPa)???Na2(Ca0.97-0.98Mg0.02-0.03)4(CO3)5 (P63mc), Na2(Ca?0.91Mg?0.09)3(CO3)4 (P1n1), Na2(Ca???0.81?Mg0?0.19)(CO3)2 () nyerereite, Na2(Ca0.77-0.93Mg0.07-0.23)2(CO3)3 (Amm2) shortite, Na4(Ca0.90-0.98Mg0.02-0.10)(CO3)3 (Ia3d), Na2(Mg?0.9Ca0?0.1)(CO3)2 (P21ca) eitelite (3?GPa)???Na2(Ca?0.87Mg0?0.13)4(CO3)5 (P63mc), Na2(Ca?0.89Mg?0.11)3(CO3)4 (P1n1), Na4(Ca???0.7?Mg0?0.3)(CO3)3 (Ia3d), Na2(Mg?0.92Ca0?0.08)(CO3)2 (P21ca) eitelite (6?GPa). Using the present results at 3?GPa and previous data at 6?GPa in the Na2CO3?CaCO3?MgCO3 system, we constrained isopleths of the Na2CO3 content in melt coexisting with Ca-Mg carbonates. We found that the cratonic geotherms cross the isopleths so that the carbonatite melt percolating upward via the continental mantle lithosphere should become progressively enriched in Na, evolving from alkali-poor dolomitic composition at depths exceeding 200?km toward sodic dolomitic with the ~52?mol% Na2CO3 at 80-120?km depths.
Petrography, mineralogy and SIMS U-Pb geochronology of 1.0 - 1.8 Ga carbonatites and associated alkaline rocks of the Central Aldan magnesiocarbonatite province ( South Yakutia, Russia).
Mineralogy and Petrology, Doi.org/a0.1007/ s00710-019-00661-3 24p.
Abstract: The Saint-Honoré alkaline complex located near the Saguenay River (Grenville Province, Québec) has a syenite outer rim and concentric units of calcio-, magnesio- to ferro-carbonatite moving towards the centre. The Mg-carbonatite hosts a niobium deposit, and the Fe-carbonatite hosts a rare earth-rich zone at its centre. The Nb mineralization has a close spatial relationship to the syenite enclaves suggesting that the syenites may have played a critical role in concentrating the pyrochlore (Pcl). There are two forms of Nb mineralization: high- and low-grade. Low-grade mineralization is characterized by highly variable Pcl chemistry with higher U concentrations and a low abundance of fluoroapatite (Ap), whereas high-grade mineralization has a consistent Pcl chemistry (low-U), abundant Ap (with many acicular crystals) and more abundant phlogopite and magnetite. Some of the Pcl crystals have been altered to columbite by hydrothermal processes. It is interpreted that the metamict Pcl (rich in radioactive elements) was altered more readily than the Pcl having undamaged crystal structure. The high-grade mineralization is generally located near the syenite enclaves. Syenite enclaves (from a centimetre scale to several tens of metres in size) reacted with the carbonatite magma to produce a phlogopite rim. Ap is also abundant along the immediate contact between the enclaves and Mg-carbonatite. Large enclaves show hydro-fracturing by the carbonatite suggesting they were crystalline enough to be brittle. There are smaller textures (3-6 mm in diameter) that share many similarities with the syenite enclaves; however, these textures are rounded and could be interpreted as being related to liquid immiscibility. The interaction of carbonatite magma with syenite enclaves is interpreted to have started with abundant crystallization of acicular Ap which depleted the magma in F and lowered the magma's Nb-solubility. Pcl then crystallized in abundance in the vicinity of the syenite enclaves to create the economic Nb-rich zone.
Abstract: Manitoba, with its 400 000 km2 of exposed Precambrian basement, remains the most conspicuous "white spot" on the map of Canadian kimberlites. The apparent absence of these rocks from the regional geological record seems all the more paradoxical, given the existence of large Phanerozoic kimberlite fields just across the provincial border in eastern Saskatchewan, and abundant evidence of mantle-derived carbonate-rich magmatism (carbonatites and ultramafic lamprophyres) across central Manitoba. Interestingly, rocks of this type were first identified in the Province in 1983 at Wekusko Lake, where they crosscut supracrustal assemblages of the Paleoproterozoic Flin Flon belt, and were tentatively logged as kimberlites. This interpretation, based to a large extent on their high Cr + Ni contents and the presence of indicator minerals in their modal composition, was challenged in subsequent research. Similar rocks have been recognized recently in similar settings south of Wekusko Lake. These discoveries expanded not only the area of known post-Paleoproterozoic mantle magmatism, but also the petrographic and geochemical spectrum of its products. The primary carbonate phase in these rocks is dolomite that shows a variable degree of subsolidus isotopic re-equilibration under CO2-rich conditions. Fluid-rock interaction was also responsible for the replacement of olivine, phlogopite and groundmass perovskite by secondary minerals and deposition of hydrothermal carbonates in fractures, although the relative timing of these processes with respect to dike emplacement is poorly understood at present. Notably, indicator minerals indistinguishable from those in bona fide kimberlites are common in all of the examined dikes. These recent discoveries may hold key to understanding the genetic relations between kimberlites and primitive carbonatites, and have practical implications for heavy-mineral-based diamond exploration.
Abstract: The Fen Complex is a 2 km-wide subcircular intrusion composed mainly of sovite, Fe-dolomite carbonatite, damtjernite (lamprophyre) and minor alkaline rocks such as nepheline syenite and ijolite, emplaced at 580 Ma through Mesoproterozoic orthogneisses forming the Fennoscandian Shield. Previous bulk-rock isotopic study indicates that the carbonatite magma originated in the upper mantle [(87Sr/86Sr)i = 0.7029] and underwent contamination during its ascent throughout the crust. This study focuses on two deep cores (1000 m and 700 m), drilled to assess the distribution of REE mineralizations in the Fe-dolomite carbonatite. Hyperspectral data, allowing investigators to log cores objectively and quantify lithologies, were acquired using a SisuRock Gen 2 system composed of three cameras gathering data in the following wavelengths: RGB, Near-Visible Short-Wave Infrared (VN-SWIR) and Long-Wave Infrared (LWIR). In addition, every meter of the first core and 500 m of the second one were analyzed for bulk-rock geochemistry to characterize the distribution of elements. In this study, we compare the results obtained by the imaging technique with the bulk-rock data and present preliminary results of the textural variations observed in rare-earth mineralizations. Preliminary results indicate that neither of the deep bore holes reached the fenitized host-rock and that the Fe-dolomite carbonatite continues at depth. In both cores, the dominant carbonate is Fe-rich dolomite, although calcite and Fe-Mg carbonate have been observed locally. REE-minerals, composed mainly of bastnäsite, parisite/synchisite and monazite, display variable textural relationships and often occur together in clusters associated with barite and minor Fe-oxides, sulfides (pyrite ± sphalerite) and locally thorite.
Abstract: The petrogenesis of temporally and spatially associated carbonatitic and deeply derived carbonated alkaline silicate magmas provides an opportunity to gain insights into the nature of the deepest lithospheric mantle. The Chuktukon massif, which is part of the Chadobets alkaline ultramafic carbonatite complex (Chadobets upland, Siberian craton) is a carbonatite-melilitite-damtjernite intrusion, whose emplacement was coeval with the Siberian Traps large igneous province (LIP). In this study, the sources of the primary melts are examined, the petrogenetic evolution of the complex is reconstructed and the relationship with the Siberian LIP is also discussed. Isotopic and geochemical information indicate that the source for the Chuktukon primary melts was isotopically moderately depleted and the primary melts were formed by low degree partial melting of garnet carbonated peridotite. Hydrothermal processes caused 18 O- and 13 C- enrichment. The weathering process was accompanied by trace element re-distribution and enrichment of the weathering crust in Zn, Th, U, Nb, Pb and REE, relative to the Chuktukon rocks and a change in radiogenic (Sr, Nd) isotope compositions.
Abstract: The Saguenay City alkali province (~ 580 Ma) comprises the Saint-Honoré alkaline complex (carbonatite-syenite), lesser-known minor subsurface carbonatite intrusions and several sets of lamprophyre (sl) dykes. Flat-lying, north-dipping dykes (l-100 cm) that crop out close the Saguenay River/Fjord were formed by multiple intrusions of a very fluid magma. The dykes are continuously variable in composition from carbonatite to ultramafic lamprophyre. Olivine phenocrysts (l-3 mm) are pseudomorphed by serpentine but phlogopite phenocrysts (l-5 mm) are well preserved in a matrix of a fine-grained serpentine, chlorite and carbonate. A few dykes are phoscorites, with abundant phenocrysts of phlogopite, oxides, apatite and accessory baddeleyite. In all dykes, the matrix may have been originally fine-grained or even glassy, and subsequently altered by water dissolved in the original magma. Several dykes contain abundant xenoliths: mostly crustal and possibly one of mantle origin. Low-carbonate dykes have a narrow range in Sr isotopes (0.7030-0.7033) versus the wider range of high-carbonate dykes (0.7032-0.7046), but this distinction is not seen in ?Nd (3.4-4.9). Overall, it appears that each batch of magma was small and came from independent mantle sources. Recently, we found a new set of vertical, NW-directed lamprophyres around the Baie des Ha! Ha!, about 15 km south of the main swarm. They have phlogopite phenocrysts to 50 mm and olivine pseudomorphs. Their contrasting orientation suggests that they have a different age to the Saguenay River dykes, but they have yet to be dated. The overall pattern is of an extensive mantle source that delivered small volumes of volatile-rich ultramafic magmas over a long period. We consider that some of these magma batches accumulated and differentiated in a magma chamber beneath the Saint-Honoré alkaline complex, whereas others rose uninterrupted to high levels of the crust where they were emplaced as dykes.
Abstract: Geodynamic origin of carbonatites is debated for several decades. One of hypotheses links their origin to large-volume mantle plumes rising from the core-mantle boundary (CMB). Some evidence exists for temporal and spatial relationships between the occurrences of carbonatites and large igneous provinces (LIPs), and both carbonatites and LIPs can be related to mantle plumes. A good example is the carbonatites of the Maymecha-Kotuy Province in the Polar Siberia, which were formed at the same time as the Siberian superplume event at ca. 250 Ma. In this study we use a recently published absolute plate kinematic modelling to reconstruct the position of 155 Phanerozoic carbonatites at the time of their emplacement. We demonstrate that 69% of carbonatites may be projected onto the central or peripheral parts of the large low shear-wave velocity provinces (LLSVPs) in the lowermost mantle. This correlation provides a strong evidence for the link between the carbonatite genesis and the locations of deep-mantle plumes. A large group of carbonatites (31%) has no obvious links to LLSVPs and, on the contrary, they plot above the "faster-than-average S-wave" zones in the deep mantle, currently located beneath North and Central America and China. We propose that their origin may be associated with remnants of subducted slabs in the mantle.
Journal of the Geological Society of India, extended abstract of Monthly Scientific Lecture March 12, 1p.
India
carbonatites
Abstract: Carbonatites, defined as carbonate-rich rocks of igneous origin, pose considerable challenges in understanding their genesis and evolution. These mantle-derived, rare, magmatic rocks are enigmatic in many facets compared to their associated co-magmatic rocks. These include: (a) The very-low viscous, water-soluble, Na- and K-carbonate (nyererieite and gregoryite respectively)-bearing lavas with low temperature (500-600°C) of eruption with only one active volcano as an example (e.g. Ol Doinyo Lengai, Tanzania) in contrast to the numerous acid and basic lava eruptive centres that are well-known around the world. (b). Carbonatites show very high solubilities of many elements considered rare in silicate magmas, and they have the highest known melt capacities for dissolving water and other volatile species like halogens at crustal pressures. With such ‘fluxing and fusing’ characters, carbonatite magma, actively reacts and ‘fenitises’ the country rocks through Na and K metasomatism when they get emplaced. Thus the carbonatite magma loses its Na and K, a feature rare to other magmatic rocks. (c) Primary mineralogy is highly variable from simple carbonate species to a variety of silicate, oxide, phosphate, niobates, rare-earth carbonates and others not found in more common igneous rocks. This feature, unlike other magmatic rocks, influences the variety and size of mineral deposits including the formation of ‘super-giant’ resources such as Nb (Araxa, Brazil) and rare-earths (Bayan Obo, China). (d) They can be direct partial melts or comagmatic with a variety of mantle-derived silicate magmas such as nephelinite, melilitite, kimberlite, phonolite, trachyte, basanite, alkali pyroxenite, ijolite and others from which they can form through liquidimmiscibility or through crystal-liquid differentiation. (e) Carbonatites can also be formed as low-temperature, carbo-thermal residual fluids rich in CO2, H2O and fluorine forming calcite-barite-fluorite veins which may lack the higher abundances of some trace elements. Carbonatites of India, found in some twenty four (24) localities, are associated with a variety of rocks as mentioned above and range in age from late Achaean (e.g. Hogenakal and Khambamettu, Tamil Nadu) to late Cretaceous (e.g. Amba Dongar, Gujarat). These are briefly reviewed with regard to their anomalous features.
Abstract: The formation of Iron Oxide-Apatite (IOA) systems has long been enigmatic. The compositions of both magnetite and apatite and the other component elements suggest derivation from high temperature (T) magmatic systems, with genetic models including iron oxide magmas or igneous magnetite and apatite flotation. Ideas related to the role of H2O and associated oxidative mechanisms have resurfaced from models of the late 1960s. As such, salt melts forming in open, differentially degassing systems could represent an end-member to the formation of IOA deposits. Another end-member involves autometasomatic decarbonation reactions involving ferroan carbonatites with co-genetic melts or host rocks generating CO2 capable of oxidizing carbonatites to enhance magnetite-apatite saturation. The syntectic decarbonation end-member presented here examines the reactions of carbonate melts of mantle origin or from syntectic reactions with limestone, with cogenetic silicate magmas. Although carbonate and silicate melts can coexist at magmatic pressure (P) and T, their compositions must be peralkalic. However, as P decreases, immiscibility or reactivity between these melts is such that CO2 is exsolved (decarbonation) to the point that at near surface conditions, decarbonation is complete. The addition of CO2 to silicate melt will drive the conversion of FeO to Fe2O3 in order to make carbon monoxide (CO), thus shifting the redox equilibria. For most silicate magmas, the amount of dissolved carbonate and CO2 is quite limited, and differential CO2 degassing results. These carbonate: silicate melt reactions then may result in oxidation of the silicate magma, to enhance immiscibility of IOA (liquation) and elemental partitioning associated with liquid-liquid immiscibility. This could be an oxidative mechanism for Fe-Ti tholeiites (ferrobasalts) and diorites to reach a two-liquid field and form IOA melts via liquation. Carbonates would typically be consumed in these reactions, although CO2 is an important degassing product that would substantially increase ?V of the reaction, which has implications during high-level emplacement.
Petrography, mineralogy and SIMS U-Pb geochronology of 1.9-1.8 Ha carbonatites and associated alkaline rocks of the Central-Aldan magnesiocarbonatite province ( South Yakutia, Russia).
Geostandards and Geoanalytical Research, Vol. 43, 2, pp. 291-300.
Global
carbonatites
Abstract: This study presents a high?precision method to measure barium (Ba) isotope compositions of international carbonate reference materials and natural carbonates. Barium was purified using chromatographic columns filled with cation exchange resin (AG50W?X12, 200-400 mesh). Barium isotopes were measured by MC?ICP?MS, using a 135Ba-136Ba double?spike to correct mass?dependent fractionation during purification and instrumental measurement. The precision and accuracy were monitored by measuring Ba isotope compositions of the reference material JCp?1 (coral) and a synthetic solution obtained by mixing NIST SRM 3104a with other matrix elements. The mean ?137/134Ba values of JCp?1 and the synthetic solution relative to NIST SRM 3104a were 0.21 ± 0.03‰ (2s, n = 16) and 0.02 ± 0.03‰ (2s, n = 6), respectively. Replicate measurements of NIST SRM 915b, COQ?1, natural coral and stalagmite samples gave average ?137/134Ba values of 0.10 ± 0.04‰ (2s, n = 18), 0.08 ± 0.04‰ (2s, n = 20), 0.27 ± 0.04‰ (2s, n = 16) and 0.04 ± 0.03‰ (2s, n = 20), respectively. Barium mass fractions and Ba isotopes of subsamples drilled from one stalagmite profile were also measured. Although Ba mass fractions varied significantly along the profile, Ba isotope signatures were homogeneous, indicating that Ba isotope compositions of stalagmites could be a potential tool (in addition to Ba mass fractions) to constrain the source of Ba in carbonate rocks and minerals.
Abstract: The Archean (~2.6?Ga) Siilinjärvi carbonatite complex in east-central Finland is crosscut by a few ultramafic lamprophyre dykes, together with a broad array of more evolved mafic dykes that range in composition from foidites to various types of alkali basalts. A possible genetic link between the primitive lamprophyres and the carbonatite complex has previously been hypothesised, but their exact relations have been unclear due to the regional metamorphic overprint (i.e., greenschist facies). Here we focus on the petrology and petrography of the mafic dykes, and integrate the data to present a coherent model that can explain the genesis of the Siilinjärvi carbonatite complex. Field-relations, in combination with petrography and geochemistry, indicate that there are at least three generations of mafic dykes present. The oldest dykes (Generation I) are strongly deformed, and inferred to have been emplaced shortly after the formation of the complex itself. These dykes can be divided into two groups (i.e., ultramafic lamprophyres and Group A), where Group A comprises foidites characterised by low SiO2 (41.4-51.5?wt%) and high alkali (>10?wt% K2O) content. We interpret the foiditic magmas to have evolved from primitive ultramafic lamprophyres by fractionating a clinopyroxene-olivine dominated mineral assemblage that was devoid of feldspar. This fractionation path forced alkali-enrichment in the magmas belonging to Group A, which pushed them into the miscibility gap, and resulted in liquid immiscibility that produced moderately alkaline conjugate carbonatite(s). Subsequent fractionation of the conjugate carbonatite by predominantly calcite and apatite produced the mineralogically homogeneous carbonatite cumulate that is exposed at Siilinjärvi. Younger, less deformed, mafic dykes (belonging to Generations II and III) exhibit trace element characteristics, broadly similar to basaltic dyke swarms in the region. The younger dykes are characterised by the presence of large plagioclase crystals in thin sections. Crystallisation of a feldspar-bearing mineral assemblage resulted in only moderate enrichment of alkalis with increased fractionation, which caused the younger dykes to evolve along the more common basalt-to-trachyte series. Thus, the magmas belonging to Generations II and III at Siilinjärvi never fulfilled the conditions required to produce carbonatites by liquid immiscibility.
International Geology Review, Vol. 58, 12, pp. 1461-1480.
India
carbonatites
Abstract: The South Indian Granulite Terrane (SGT) is a collage of Archaean to Neoproterozoic age granulite facies blocks that are sutured by an anastomosing network of large-scale shear systems. Besides several Neoproterozoic carbonatite complexes emplaced within the Archaean granulites, there are also smaller Paleoproterozoic (2.4 Ga, Hogenakkal) carbonatite intrusions within two NE-trending pyroxenite dikes. The Hogenakkal carbonatites, further discriminated into sövite and silicate sövite, have high Sr and Ba contents and extreme light rare earth element (LREE) enrichment with steep slopes typical of carbonatites. The C- and O-isotopic ratios [?13CVPDB = ?6.7 to ?5.8‰ and ?18OVSMOW = 7.5-8.7‰ except a single 18O-enriched sample (?18O = 20.0‰)] represent unmodified mantle compositions. The ?Nd values indicate two groupings for the Hogenakkal carbonatites; most samples show positive ?Nd values, close to CHUR (?Nd = ?0.35 to 2.94) and named high-?Nd group while the low-?Nd group samples show negative values (?5.69 to ?8.86), corresponding to depleted and enriched source components, respectively. The 87Sr/86Sri ratios of the two groups also can be distinguished: the high-?Nd ones have low 87Sr/86Sri ratios (0.70161-0.70244) while the low-?Nd group shows higher ratios (0.70247-0.70319). We consider the Nd-Sr ratios as primary and infer derivation from a heterogeneous mantle source. The emplacement of the Hogenakkal carbonatites may be related to Paleoproterozoic plume induced large-scale rifting and fracturing related to initiation of break-up of the Neoarchean supercontinent Kenorland.
Abstract: Most carbonatite-related REE (rare earth element) deposits record two stages of REE enrichment: magmatic and magmatic-hydrothermal. It is generally accepted that the first stage of enrichment, which occurs in magmas associated with carbonatite-syenite complexes, is a prerequisite to the formation of REE deposits. The magmatic-hydrothermal process is also important, as demonstrated by the fact that many fertile carbonatite-syenite complexes do not produce REE deposits. The Miaoya carbonatite-syenite complex is prospective for REE and is ideal for studies of the formation of REE deposits. The Miaoya REE prospect lies in the western member of the Wudan Terrane of the Qinling Belt, China, and is hosted by a carbonatite-syenite complex that was intruded along a fault zone between schist of the lower Silurian Meiziya Group and adjacent Proterozoic quartzite. Mineralization at the Miaoya REE prospect includes carbonatite-, syenite-, and mixed-type, all low grade (about 1%). Results of X-ray diffraction (XRD) and electron probe micro-analyzer (EMPA) analyses reveal that modes of REE minerals are low in all samples (<5%), which is consistent with the fact that less monazite, bastnäsite and other REE minerals have been found in the Miaoya REE prospect. REE mineralization is less likely to occur as an overprint on gangue minerals. Results of Photon Laser Ablation Inductively-Coupled-Plasma Mass-Spectrometer (LA-ICP-MS) analyses reveal that apatite and calcite in carbonatite have the highest REE concentrations which are responsible for the relatively high concentration in carbonatite rather than because of the presence of REE minerals. The consistence of Sr-Nd isotopes ratios between altered host rocks and fresh hosted rocks suggested REE mineralization originates directly from the unmineralized carbonatite-syenite complex rather than other host rocks. Carbon and oxygen isotope ratios of hydrothermal calcite are consistent with low-temperature alteration subsequent to ore. Trace element ratios for the Miaoya carbonatite-syenite complex lie in the barren carbonatite field (REEs vs. CaO/MgO, FeO/MgO, Ba and Sr/Ba) compared with those of other giant or large carbonatite-syenite complex related REE deposits, just below the boundary between fields for fertile and barren carbonatites. This suggests that the carbonatite-syenite complex at the Miaoya prospect did not have the potential to produce large or giant REE deposits. The low REE of the Miaoya prospect compared with other carbonatite-syenite hosted deposits may reflect: 1) as supported by petrography, minimal tectonic deformation in the area resulting in 2) restricted cycling of hydrothermal solutions that led to 3) minimal fluid scavenging from REE-rich apatite and calcite for local REE re-deposition and concentration.
Abstract: The Lower Cretaceous Jacupiranga complex, in the central-southeastern portion of the South American Platform, includes carbonatites in close association with silicate rocks (i.e. strongly and mildly silica-undersaturated series). Here we document the first hafnium isotope data on the Jacupiranga complex, together with new trace element and Pb isotope compositions. Even though liquid immiscibility from a carbonated silicate melt has been proposed for the genesis of several Brazilian carbonatites, isotopic and geochemical (e.g., Ba/La ratios, lack of pronounced Zr-Hf and Nb-Ta decoupling) information argues against a petrogenetic relationship between Jacupiranga carbonatites and their associated silicate rocks. Thus, an origin by direct partial melting of the mantle is considered. The isotopic compositions of the investigated silicate samples are coherent with a heterogeneously enriched subcontinental lithospheric mantle (SCLM) source of rather complex evolution. At least two metasomatic processes are constrained: (1) a first enrichment event, presumably derived from slab-related fluids introduced into the SCLM during Neoproterozoic times, as indicated by consistently old TDM ages and lamprophyre trace signatures, and (2) a Mesozoic carbonatite metasomatism episode of sub-lithospheric origin, as suggested by ?Nd-?Hf values inside the width of the terrestrial array. The Jacupiranga parental magmas might thus derive by partial melting of distinct generations of metasomatic vein assemblages that were hybridized with garnet peridotite wall-rocks.
Journal of the Geological Society, Vol. 176, 4, pp. 620-628.
Canada, British Columbia
carbonatite
Abstract: Paleozoic continental margin strata in the western Foreland Belt of the Canadian Cordillera are characterized in part by alkaline volcanic sequences, carbonatite intrusions, coarse clastic sedimentary units, and erosional unconformities. These strata also contain a record of mid-Paleozoic contractional deformation unseen in coeval passive margin strata in the eastern Foreland Belt. In order to test potential genetic links between Paleozoic alkaline igneous activity, active margin sedimentation, and deformation in the western Foreland Belt, and better understand their implications for the evolution of the Foreland Belt as a whole, we have undertaken a detailed mapping and structural study of the Aley carbonatite intrusion and its host strata in the western Foreland Belt of NE British Columbia. Our work demonstrates that carbonatite emplacement was coeval with a Late Devonian contractional nappe-forming tectonic event. Interpreting tectonism as associated with continental collision along a long-lived active margin provides the best explanation for our structural and stratigraphic observations, and suggests that the western Foreland Belt is far-travelled and exotic relative to coeval passive margin strata in the eastern Foreland Belt. Deformed alkaline-carbonatite intrusions that characterize continental suture zones in Africa may provide an analogue for the Aley carbonatite and correlative alkaline-carbonatite complexes in the western Foreland Belt.
Evolution of the carbonatite Mo-HREE deposits in the Lesser Qinling orogen: insights from in situ geochemical investigation of the calcite and sulfate. Huanglongpu, Huangshuian
Geochemical and Nd-Sr-Ca isotopic compositions of carbonatites and alkaline igneous rocks from the Deccan Igneous Province: role of recycled carbonates, crustal assimilation and plume heterogeneity.
Abstract: Alkaline complexes consist of variable mantle-derived silicate rocks, ranging from primitive alkali basalts, melilitites, nephelinites and basanites towards tephrites and more evolved phonolites, respectively their plutonic equivalents. This lithological variance is also expressed by a wide range of redox conditions that vary by several log units around the synthetic fayalite-magnetite-quartz (FMQ) buffer. However, only some of these complexes are characterized by the occurrence of carbonatites which must be related to specific formation conditions. Based on textural, mineralogical and geochemical observations, we calculated the redox conditions of carbonatites and associated silicate rocks for seven alkaline complexes (Kaiserstuhl, Sokli, Kovdor, Palabora, Magnet Cove, Oka, Jacupiranga) which are considered to represent typical carbonatite-alkaline silicate rock associations. In combination with a comprehensive literature review, we demonstrate that carbonatite-bearing alkaline complexes formed under highly oxidized conditions and hence, belong to the most oxidized alkaline rocks at all. This is consistent with the prerequisite of a carbonated mantle as the source region for carbonatite complexes, which requires redox conditions distinctively above that for mean lithospheric or asthenospheric mantle. Carbonatitemetasomatized peridotites also show high redox conditions and might not only reflect an interaction between peridotite and carbonatitic melts/fluids, but at least partly represent the carbonated mantle source for crustally emplaced carbonatite complexes. We therefore suggest that the oxidation state of carbonatites and associated silicate rocks provides direct information about an extraordinary oxidized parental mantle source.
Mineralogical Magazine, in press available 54p. Pdf
Africa, Namibia
carbonatite - Okorusu
Abstract: The Cretaceous Okorusu carbonatite, Namibia, includes diopside-bearing and pegmatitic calcite carbonatites, both exhibiting hydrothermally altered mineral assemblages. In unaltered carbonatite, REE, Sr and Ba are largely hosted by calcite and fluorapatite. However, in hydrothermally altered carbonatites, small (< 50 ?m) parisite-(Ce) grains are the dominant REE host, while Ba and Sr are hosted in baryte, celestine, strontianite and witherite. Hydrothermal calcite has a much lower trace element content than the original, magmatic calcite. Despite the low REE contents of the hydrothermal calcite, the REE patterns are similar to those of parisite-(Ce), and magmatic minerals and mafic rocks associated with the carbonatites. These similarities suggest that hydrothermal alteration remobilised REE from magmatic minerals, predominantly calcite, without significant fractionation or addition from an external source. Ba and Sr released during alteration were mainly reprecipitated as sulfates. The breakdown of magmatic pyrite into Fe-hydroxide is inferred to be the main source of sulfate. The behaviour of sulfur suggests that the hydrothermal fluid was somewhat oxidising and it may have been part of a geothermal circulation system. Late hydrothermal massive fluorite replaced the calcite carbonatites at Okorusu and resulted in extensive chemical change, suggesting continued magmatic contributions to the fluid system.
Journal of Petrology , Vol. 60, 6, pp. 1119--1134.
India
carbonatite
Abstract: There are disparate views about the origin of global rift- or plume-related carbonatites. The Amba Dongar carbonatite complex, Gujarat, India, which intruded into the basalts of the Deccan Large Igneous Province (LIP), is a typical example. On the basis of new comprehensive major and trace element and Sr-Nd-Pb isotope data, we propose that low-degree primary carbonated melts from off-center of the Deccan-Réunion mantle plume migrate upwards and metasomatize part of the subcontinental lithospheric mantle (SCLM). Low-degree partial melting (?2%) of this metasomatized SCLM source generates a parental carbonated silicate magma, which becomes contaminated with the local Archean basement during its ascent. Calcite globules in a nephelinite from Amba Dongar provide evidence that the carbonatites originated by liquid immiscibility from a parental carbonated silicate magma. Liquid immiscibility at crustal depths produces two chemically distinct, but isotopically similar magmas: the carbonatites (20% by volume) and nephelinites (80% by volume). Owing to their low heat capacity, the carbonatite melts solidified as thin carbonate veins at crustal depths. Secondary melting of these carbonate-rich veins during subsequent rifting generated the carbonatites and ferrocarbonatites now exposed at Amba Dongar. Carbonatites, if formed by liquid immiscibility from carbonated silicate magmas, can inherit a wide range of isotopic signatures that result from crustal contamination of their parental carbonated silicate magmas. In rift or plume-related settings, they can, therefore, display a much larger range of isotope signatures than their original asthenosphere or mantle plume source.
Chemical Geology, doi.org/10.1016/j.chemgeo.2019.07.015 59p.
Canada, British Columbia
carbonatite - Blue River
Abstract: This study reports the combined major, minor and trace element compositions, and stable (C, O), radiogenic (Nd, Pb, and Sr) isotopic compositions, and first ?11B isotopic data for the Fir, Felix, Gum, and Howard Creek carbonatites from the Blue River Region, British Columbia (Canada). These sill-like occurrences were intruded into Late Proterozoic strata during rifting and extensional episodes during the Late Cambrian and Devonian -Mississippian, and subsequently deformed and metamorphosed to amphibolite grade in relation to a collisional-type tectonic environment. The carbonatites at Fir, Gum, and Felix contain both calcite and dolomite, whereas the carbonatite at Howard Creek contains only calcite. The dolomite compositions reported here are consistent with those experimentally determined by direct partial melting of metasomatized peridotitic mantle. The combined major and trace element compositions and ?13CPDB (?5.37 to ?4.85‰) and ?18OSMOW (9.14 to 9.62‰) values for all the samples investigated are consistent with those for primary igneous carbonate and support their mantle origin. However, these signatures cannot be attributed to closed system melt differentiation from a single parental melt. The initial Nd, Pb, and Sr isotopic ratios are highly variable and suggest generation from multiple, small degree parental melts derived from a heterogeneous mantle source. The ?11B values for carbonates from Felix, Gum, and Howard Creek vary between ?8.67 and ?6.36‰, and overlap the range for asthenospheric mantle (?7.1?±?0.9‰), whereas two samples from Fir yield heavier values of ?3.98 and ?2.47‰. The latter indicate the presence of recycled crustal carbon in their mantle source region, which is consistent with those for young (<300?Ma) carbonatites worldwide. The radiogenic and B isotope results for the Blue River carbonatites are compared to those from contrasting, anorogenic tectonic settings at Chipman Lake, Fen, and Jacupiranga, and indicate that similar upper mantle sources are being tapped for carbonatite melt generation. The pristine, mantle-like ?11B values reported here for the Blue River carbonatites clearly demonstrate that this isotope system is robust and was not perturbed by post-solidification tectono-metamorphic events. This observation indicates that B isotope signatures are a valuable tool for deciphering the nature of the upper mantle sources for carbonates of igneous origin.
Abstract: Carbonatites and syenites from Ihouhaouene (2 Ga; In Ouzzal terrane, Hoggar, South of Algeria) have close spatial relationships. Their analogous mineral assemblages with diopside/hedenbergite (cpx), apatite, wollastonite +/- calcite and alkali-feldspar suggest that they were emplaced from a common igneous parental event. Carbonatites from In Ouzzal terrane are calciocarbonatites and form a continuous range of whole-rock major and trace element composition from Sipoor carbonatite (<20 wt.% SiO2; 24-36 wt.% CO2) to Si-rich carbonatite (20-35 wt.% SiO2; 11-24 wt.% CO2) then white syenite (52-58 wt.% SiO2; 0.1-6.5 wt.% CO2) and red syenite (57-65 wt.% SiO2; 0.1-0.4 wt.% CO2). Equilibrium calculations reveal that apatite (Ce/Lu= 1690-6182; Nb/Ta >50) and cpx (Ce/Lu= 49-234; Nb/Ta<10) from Si-rich carbonatites and white syenites crystallized from a REEenriched carbonate melt and an evolved silicate melt, respectively. Likewise, Si-poor carbonatites have a higher REE contents in calculated apatite equilibrium melts than in their cpx and a wide range of Nb/Ta ratios with a majority of subchondritic value (<10) that reflects the segregation of the carbonate fraction from an evolved parental melt. Otherwise, red syenites have similar REE contents in apatite and clinopyroxene equilibrium melts (Nb/Ta>10) suggesting an origin from homogeneous evolved melt batches. Both mineralogical and geochemical features reveal the intimate link between carbonatites and syenites and their cogenetic signature. Immiscibility and fractional crystallization processes modelling explain the trace element contents and low Nb/Ta ratio in minerals. These processes were partly counterbalanced by intermingling of partially crystallized melt fractions and hybridization of segregated minerals during the progressive cooling of a silico-carbonated mantle melt.
Abstract: Carbonatite and alkaline magma constitute one of the principal resources of rare metals (REE, Nb, Ti, Zr). Carbonatite rare metals enrichment is mainly considered as the result of hydrothermal or supergen processes. However, the magmatic processes linked to carbonatites genesis and differentiation are still debated and whether these processes can significantly impact on the rare metal concentrations remains unclear. Experimental studies have shown that immiscibility processes between carbonate and silicate melts can lead to both REE enrichments and depletions in carbonatites. Anionic species (F, Cl, P or S) and water may impact both melt compositions and expand the immiscibility gap. Morever, anionic species are assumed to play an important role in REE behaviour in carbonate melts [1]. Indeed, halogens may occur in carbonatites as immiscible salt melts in melt inclusions [2] and primary REE- fluoride minerals have been identified as magmatic phases in carbonatites. Such occurrences thus question on the role of salt (carbonate, phosphate, fluoride and chloride) melts in REE and other rare metals partitioning. F, Cl, P and also H2O may all significantly increase the window of primary REE enrichment in carbonatites. Here we present high pressure and high temperature experiments made in piston-cylinder (850 to 1050°C, 8kb) simulating the immiscibility between carbonate and differentiated alkaline melts. We added F, Cl, P and H2O in order to assess the effect of salts and water on the immiscibility gap and on the rare metals partitoning between carbonatite and evolved silicate melts. The partitioning data are analysed using LA-ICP-MS, nano-SIMS, FTIR and RAMAN. The characterization of rare metal partition coefficients allow to determine the relative importance of F, Cl, P and H2O on carbonatites rare metal enrichments at evolved magmatic stage.
Abstract: A detailed electron microprobe study has been carried out on the compositional variations of mica and apatite from carbonatites, phoscorites and associated pyroxenites (and fenites) of the Loolekop deposit, Palabora Carbonatite Complex (South Africa). Mica in pyroxenites and fenites is Mg-rich biotite, whilst micas in carbonatites and phoscorites are compositionally diverse including phlogopite, Ba-rich phlogopite (up to 30% kinoshitalite component), IVAl-rich phlogopite (up to 30% eastonite component) and tetraferriphlogopite. The various types of phlogopites are interpreted as orthomagmatic phases, whereas tetraferriphlogopite precipitation was a late-magmatic to hydrothermal process that additionally introduced REE into the system. Orthomagmatic apatite is generally REE- and Sr-poor fluorapatite and does not show large compositional differences between rock types. Apatite associated with the late-stage tetraferriphlogopite mineralization reaches higher levels of REE (up to 4.9?wt%), Si (up to 1.5?wt% SiO2), Sr (up to 2.6?wt% SrO) and Na (up to 1.0?wt% Na2O). The compositional variation of micas and apatites, which is affiliated with distinct rock types, reflects the multi-stage evolution of the Loolekop deposit and provides detailed insight into the relationships of the carbonatite-phoscorite assemblage. The obtained data support the separation of phoscorite and carbonatite by immiscibility from a common parental magma, which may happen due to a decrease of temperature and/or pressure during the ascent of the magma. This results in a density contrast between the carbonatitic and phoscoritic components that will lead to descending phoscorite accumulations at the outer zones of the magma channel and a jet-like ascent (further promoted by its extremely low viscosity) of the carbonatite magma. The genetic model deduced here explains the peculiar association of carbonatites, phoscorites and silicate rocks in many alkaline complexes worldwide.
Abstract: The mineralogy and mineral chemistry of the four major sövite bodies (Badberg, Degenmatt, Haselschacher Buck and Orberg), calcite foidolite/nosean syenite xenoliths (enclosed in the Badberg sövite only) and rare extrusive carbonatites of the Kaiserstuhl Volcanic Complex in Southern Germany provide evidence for contamination processes in the carbonatitic magma system of the Kaiserstuhl. Based on textures and composition, garnet and clinopyroxene in extrusive carbonatites represent xenocrysts entrained from the associated silicate rocks. In contrast, forsterite, monticellite and mica in sövites from Degenmatt, Haselschacher Buck and Orberg probably crystallized from the carbonatitic magma. Clinopyroxene and abundant mica crystallization in the Badberg sövite, however, was induced by the interaction between calcite foidolite xenoliths and the carbonatite melt. Apatite and micas in the various sövite bodies reveal clear compositional differences: apatite from Badberg is higher in REE, Si and Sr than apatite from the other sövite bodies. Mica from Badberg is biotite- and comparatively Fe2+-rich (Mg# = 72-88). Mica from the other sövites, however, is phlogopite (Mg# up to 97), as is typical of carbonatites in general. The typical enrichment of Ba due to the kinoshitalite substitution is observed in all sövites, although it is subordinate in the Badberg samples. Instead, Badberg biotites are strongly enriched in IVAl (eastonite substitution) which is less important in the other sövites. The compositional variations of apatite and mica within and between the different sövite bodies reflect the combined effects of fractional crystallization and carbonatite-wall rock interaction during emplacement. The latter process is especially important for the Badberg sövites, where metasomatic interaction released significant amounts of K, Fe, Ti, Al and Si from earlier crystallized nosean syenites. This resulted in a number of mineral reactions that transformed these rocks into calcite foidolites. Moreover, this triggered the crystallization of compositionally distinct mica and clinopyroxene crystals around the xenoliths and within the Badberg sövite itself. Thus, the presence and composition of clinopyroxene and mica in carbonatites may be useful indicators for contamination processes during their emplacement. Moreover, the local increase of silica activity during contamination enabled strong REE enrichment in apatite via a coupled substitution involving Si, which demonstrates the influence of contamination on REE mineralization in carbonatites.
Journal of the Geological Society of India, Vol. 94, 2, pp. 117-138.
India
carbonatite
Abstract: Based on the field relations, associated rock types and age, the carbonatite-alkaline rock complexes of India, that are spatially related to deep main faults, rifts and shear zones, have been classified in to two major groups, namely: 1. Middle — late Cretaceous, subvolcanic -volcanic complexes (Amba Dongar, Siriwasan, Swangkre, Mer-Mundwara, Sarnu-Dandali-Kamthai) and 2. Paleo-Neoproterozoic plutonic complexes (Newania, Sevathur, Samalpatti, Hogenakal, Kollegal, Pakkanadu, Udaiyapatti, Munnar, and Khambamettu). The middle Cretaceous Sung Valley and Samchampi complexes also belong to this plutonic group. Three minor associations, belonging to these two age groups include, the Neoproterzoic, late stage veins of carbonatites in peralkaline syenite complexes (e.g., Kunavaram, Elchuru), the diamond-bearing carbonatite and kimberlite at Khaderpet and the lamprophyre-lamproite association (e.g., Pachcham Is. Upper Cretaceous, Deccan Volcanic Province, and the Proterozoic Chitrangi Group). Petrological associations include carbonatite-nephelinite-phonolite (e.g. Amba Dongar, Sarnu-Dandali-Kamthai), dunite-peridotite-pyroxenite-ijolitemelilitite (e.g. Sung Valley), miaskitic syenite-pyroxenite ± dunite (e.g. Sevathur, Samalpatti, Pakkanadu), carbonatite alone with fenites (e.g. Newania), besides those minor associations mentioned above. Sovites (calico-carbonatites) occur as the most dominant type in some ten (10) complexes. Beforsite (magnesio-carbonatite) is the dominant type at Newania and ankeritic-sideritic types are mainly found at Amba Dongar, Siriwasan and Newania. The rare benstonite-bearing carbonatites are found at Jokkipatti and Udaiyapatti in Tamil Nadu. Mineralogically and chemically the carbonatites show considerable diversity. Fenitised zones and types of fenites (Na, K and mixed) vary widely since the carbonatites are emplaced in a variety of hostrocks ranging from granitic, mafic, ultramafic, charnockitic types besides basalts and sandstones. Stable (?13C and ?18O) and radiogenic (Sr, Nd and Pb) isotopes clearly indicate their mantle origin and also the diverse types of sources (both depleted HIMU and enriched EM 1 and 2). Petrogenetic considerations reveal three types of carbonatites, namely direct partial melts from metasomatised mantle (e.g. Newania), liquid immiscibility from carbonatite-nephelinite association (e.g. Amba Dongar) and through fractionation of ultra-alkaline ultramafic and mafic association (e.g. Sung Valley). Carbonatites of India that host significant resources include Amba Dongar (Fluorite, REE, Nb, P, Ba, Sr), Kamthai (REE), Sevathur (Nb, P, vermiculite), Beldih (P, Fe), Sung Valley (P, Nb, REE, Fe) and Samchampi (P, Nb, Fe, REE).
Abstract: uncommon type of magmatic rocks dominates by carbonate, are broadly enriched in rare earth elements (REE) relative to the majority of igneous silicate rocks. While more than 500 carbonatites are referenced worldwide [1], only a few contain economic REE concentrations that are widely considered as resulting from late magmatic-hydrothermal or supergene processes. Magmatic pre-enrichment, linked to the igneous processes at the origin of carbonatites, are, however, likely to contribute to the REE fertilisation. Field observations [1] and experimental surveys [2, 3] suggest that a large part of the carbonatite melts can be produced as immiscible liquids with silicate magmas. Experimental constraints reveals that such immiscibility processes can lead to both REE enrichments and depletions in carbonatites [2, 3], making the magmatic processes controlling REE enrichments unclear. Here we present results of high-pressure and hightemperature experiments, simultaneously addressing crystal fractionation of alkaline magmas and immiscibility between carbonate and silicate melts. The experimental data reveal that the degree of differentiation, controlling the chemical composition of alkaline melts is a key factor ruling the REE concentration of the coexisting immiscible carbonatites. The parameterization of the experimental data together with the compilation of geochemical data from various alkaline provinces show that REE concentrations similar to those of highly REE enriched carbonatites (?REE > 30000 ppm) can be produced by immiscibility with phono-trachytic melt compositions, while more primitive alkaline magma can only be immiscible with carbonatites that are not significantly enriched in REE.
Abstract: The Tiksheozero ultramafic-alkaline-carbonatite intrusive complex, like numerous carbonatite-bearing complexes of similar composition, is a part of a large igneous province related to the ascent of a thermochemical mantle plume. The geochemical and isotopic data indicate that the formation of the ultramafic and alkaline rocks was related to crystallization differentiation of a primary alkali picritic melt, whereas carbonatite magmas were derived from an independent mantle source. We suggest that the origin of parental magmas of the Tiksheozero Complex, as well as other ultramafic-alkaline-carbonatite complexes, was provided by two-stage melting of the mantle-plume head: (1) adiabatic melting of its inner part generated moderately alkaline picrites, the subsequent fractional crystallization of which led to the appearance of alkaline magmas, and (2) incongruent melting of the upper cooled margin of the plume head under the influence of CO2-rich fluids, which arrived from underlying adiabatic melting zone, gave rise to carbonatite magmas.
Abstract: A new discovery of carbonatites at Pianciano, Ficoreto and Forcinelle in the Roman Region demonstrates that Italian carbonatites are not just isolated, mantle xenoliths-bearing, primitive diatremic rocks but also evolved sub-type fluor-calciocarbonatite (F?10 wt.%) associated with fluor ore (F?30 wt.%). New data constrain a multi-stage petrogenetic process, 1-orthomagmatic, 2-carbothermal, 3-hydrothermal. Petrography and geochemistry are conducive to processes of immiscibility and decarbonation, rather than assimilation and crystal fractionation. A CO2-rich, ultra-alkaline magma is inferred to produce immiscible melilite leucitite and carbonatite melts, at lithospheric mantle depths. At the crustal level and in the presence of massive CO2 exsolution, decarbonation reactions may be the dominant processes. Decarbonation consumes dolomite and produces calcite and periclase, which, in turn, react with silica to produce forsterite and Ca silicates (monticellite, melilite, andradite). Under carbothermal conditions, carbonate breakdown releases Sr, Ba and LREE; F and S become concentrated in residual fluids, allowing precipitation of fluorite and barite, as well as celestine and anhydrite. Fluor-calciocarbonatite is the best candidate to exsolve fluids able to deposit fluor ore, which has a smaller volume. At the hydrothermal stage, REE concentration and temperature dropping allow the formation of LREEF2+ and LREECO3+ ligands, which control the precipitation of interstitial LREE fluorcarbonate and silicates -(bastnäsite-(Ce)- Ce(CO3)F and -britholite-(Ce)- (Ce,Ca)5(SiO4,PO4)3(OH,F) . Vanadates such as wakefieldite, CeVO4, vanadinite, Pb5(VO4)3Cl and coronadite Pb(Mn4+6 Mn3+2)O16 characterise the matrix. At temperatures of ?100°C analcime, halloysite, quartz, barren calcite, and zeolites (K-Ca) precipitate in expansion fractures, veins and dyke aureoles.
Abstract: Jebel Dumbier is the first-identified carbonatite-bearing alkaline complex in Sudan. It is located on the northeastern margin of the Nuba Mountains in the south part of Sudan. The complex exposed as small elliptical hills with outcrops of around 8 km2. It is composed of dominant orthoclasite and ditroite and subdominant carbonatite and fluorite dykes. The fluorite dykes are mined and together with the carbonatite dykes are controlled by a NNE strike-slip fault system. Orthoclasite is the dominant rock type, comprising of orthoclase, kalsilite, few interstitial biotite and calcium carbonate and accesserary minerals of fluorite, apatite and zircon. Ditroite consists of perthite, aegirine-augite, nepheline, sodalite, and minor annite-phlogopite and richterite, with common accessories of fluorite, titanite, apatite and zircon. Zircon U-Pb dating reveals that both orthoclasite and ditroite emplaced at around 600 Ma. Relative to orthoclasites, ditroites display higher FeOtotal and MgO and lower Al2O3 contents, contain higher volatiles (F, Cl, Br, S), and are more depleted in LILEs (Rb, Sr, Ba) and enriched in HFSEs (Nb, Ta, Zr, Hf, Th, U) and REEs. Isotopic data imply that the ditoite, orthoclasite, fluorite and carbonatite dyke originated from a common source of depleted mantle affinities, with identical low initial 87Sr/86Sr ratios (0.7033-0.7037) and high ?Nd (t) values (1.6-2.7). The carbonatites display ?13C(V-PDB) of -5.8 to -6.7‰ and ?18O(SMOW) of 9.1 to 11.3‰, typical of primary igneous carbonatite worldwide. We propose that the orthoclasite, ditroite, carbonatite, and fluorite association in Jebel Dumbier is product of variable degrees of fractional crystallization of mantlederived volatile-rich magma. Magma immiscibility among silicates, carbonates and fluorates may proceed. The Jebel Dumbier alkaline-carbonatite complex represents the postorogenic alkaline magmatism during the end evolution of Pan-African orogen (650-550 Ma) at Arabian-Nubian Shield.
Earth and Planetary Science letters, Vol. 520, pp. 175-187.
India
carbonatites
Abstract: Carbonatite metasomatism has been widely implicated for worldwide mafic mantle suites but so far, no combined data have been available for highly siderophile element systematics (HSE - Os, Ir, Ru, Pt, Pd, Re) and Re-Os isotopic compositions in carbonatites themselves. We present the first systematic survey of the HSE and Re-Os isotopic compositions in a suite of well-characterized Neoproterozoic carbonatites, silicocarbonatites and associated silicate rocks (pyroxenites, monzogabbros, syenites) from south India in order to place constraints on the HSE systematics in carbonatite magmas, anchoring possible mantle sources of carbonatites and relationship to the ambient crustal lithologies as well as preliminary constraints on carbonatite metasomatism in Earth's mantle. The most plausible explanation for generally low HSE contents in calciocarbonatites from Tamil Nadu (?HSE < 1.22 ppb) involves a low-degree (<1%) partial melting of the mantle source producing sulfur-saturated carbonatitic magmas leaving behind sulfide phases retaining HSE. The new data also indicate a strong FeO control on the distribution of Os and Pt during segregation of carbonatite melt from its enriched mantle source and/or melt differentiation. The combined 187Re/188Os values (from 0.10 to 217), 187Os/188Os ratios (0.186-10.4) and initial ?Os values back-calculated to 800 Ma (from +0.1 to +6052) predict that most Tamil Nadu calciocarbonatites were plausibly derived from a carbonated peridotite source with <10% recycled component. This model would thus provide significant constraints on the origin/source of carbonatites, irrespective of their post-emplacement history. The unusual, volumetrically rare, Mg-Cr-rich silicocarbonatites (?HSE = 14-41 ppb) display almost identical HSE patterns with those of host pyroxenites and predominantly high Pt (up to 38 ppb), the origin of which remains unknown. Positive co-variations between Pt, Pd and Re, and the well-developed positive correlation between Pt and MgO in these Mg-Cr-rich silicocarbonatites argue for a source coming predominantly from the upper mantle. The Re-Os isotopic systematics agree with direct incorporation of enriched mantle-derived material into parental melts but variable incorporation of potassium-rich crustal materials is evidenced by highly positive ?Os800 Ma values for a sub-suite of Mg-Cr-rich silicocarbonatites, indicating intense fenitization. The highly radiogenic Os isotopic compositions of monzogabbros and a syenite argue for their derivation from crustal lithologies with no or only negligible contribution of mantle material. Collectively, low Ir, Ru, Pt and Pd contents found in the Tamil Nadu carbonatites appear to indicate the incapability to significantly modify the total budget of these elements in the Earth's mantle during carbonatite metasomatism. In contrast, very high Re/Os ratios found in some of the analyzed carbonatites, paralleled by extremely radiogenic 187Os/188Os signature, can produce large modification of the Re-Os isotopic composition of mantle peridotites during carbonatite melt percolation when high melt/rock ratios are achieved.
Alkaline rocks and carbonatites of the World, Part 4: Antarctica, Asia and Europe ( excluding the former USSR), Australasia and Oceanic Islands.
geolsoc.org.uk, Book MPAR4 approx 150.00
Antarctica, Asia, Europe
carbonatites
Abstract: The alkaline igneous rocks and carbonatites are compositionally and mineralogically the most diverse of all igneous rocks and, apart from their scientific interest, are of major, and growing, economic importance. They are important repositories of certain metals and commodities, indeed the only significant sources of some of them, and include Nb, the rare earths, Cu, V, diamond, phosphate, vermiculite, bauxite, raw materials for the manufacture of ceramics, and potentially Th and U. The economic potential of these rocks is now widely appreciated, particularly since the commencement of the mining of the Palabora carbonatite for copper and a host of valuable by-products. Similarly, the crucial economic dominance of rare earth production from carbonatite-related occurrences in China, has stimulated the world-wide hunt for similar deposits. This volume describes and provides ready access to the literature for all known occurrences of alkaline igneous rocks and carbonatites of Antarctica, Asia and Europe excluding the former USSR, Australasia and oceanic islands. More than 1,200 occurrences from 59 countries are outlined together with those of 57 oceanic islands and island groups. The descriptions include geographical coordinates and information on general geology, rock types, petrography, mineralogy, age and economic aspects with the principal references cited. There are 429 geological and distribution maps and a locality index. As has been demonstrated by the three earlier volumes, the present book is likely to be of considerable interest to mineral exploration companies, as there are no comprehensive published reviews of the economic aspects of the alkaline rocks. It will also interest research scientists in the fields of igneous petrology and volcanology, and geologists concerned with the regional distribution of igneous rocks and their geodynamic relationships.
Abstract: Recent exploration work in South Morocco revealed the occurrence of several carbonatite bodies, including the Paleoproterozoic Gleibat Lafhouda magnesiocarbonatite and its associated iron oxide mineralization, recognized here as iron-oxide-apatite (IOA) deposit type. The Gleibat Lafhouda intrusion is hosted by Archean gneiss and schist and not visibly associated with alkaline rocks. Metasomatized micaceous rocks occur locally at the margins of the carbonatite outcrop and were identified as glimmerite fenite type. Rare earth element (REE) and Nb mineralization is mainly linked to the associated IOA mineralization and is represented by monazite-(Ce) and columbite-(Fe) as major ore minerals. The IOA mineralization mainly consists of magnetite and hematite that usually contain large apatite crystals, quartz and some dolomite. Monazite-(Ce) is closely associated with fluorapatite and occurs as inclusions within the altered parts of apatite and along cracks or as separate phases near apatite. Monazite shows no zonation patterns and very low Th contents (<0.4?wt%), which would be beneficial for commercial extraction of the REE and which indicates monazite formation from apatite as a result of hydrothermal volatile-rich fluids. Similar monazite-apatite mineralization and chemistry also occurs at depth within the carbonatite, although the outcropping carbonatite is barren, suggesting an irregular REE ore distribution within the carbonatite body. The barren carbonatite contains some tiny unidentified secondary Nb-Ta-U phases, synchysite and monazite. Niobium mineralization is commonly represented by anhedral minerals of columbite-(Fe) which occur closely associated with magnetite-hematite and host up to 78?wt% Nb2O5, 7?wt% Ta2O5 and 1.6?wt% Sc2O3. This association may suggest that columbite-(Fe) precipitated by an interaction of Nb-rich fluids with pre-existing Fe-rich minerals or as pseudomorphs after pre-existing Nb minerals like pyrochlore. Our results most strongly suggest that the studied mineralization is economically important and warrants both, further research and exploration with the ultimate goal of mineral extraction.
Journal of South American Earth Sciences, Vol. 94, 102208 13p. Pdf
South America, Brazil
carbonatite
Abstract: Carbonatites are peculiar igneous rocks, consisting mainly of greater than 50% carbonate minerals, which arouse an economic interest due to the potentiality of high phosphate content and Light Rare Earth Elements (LREE) associated with their occurrence. The Passo Feio Carbonatite (PFC) is located 17?km Southwest of Caçapava do Sul city and constitutes NW dipping body, which is interposed with Passo Feio Formation metamorphic rocks. The PFC varies texturally from massive to foliated, being mainly composed of calcites and dolomites and on a smaller scale by apatites, phlogopites and tremolites. The opaque minerals correspond to hematites, magnetites, pyrites and barites, while the accessory minerals are represented by zircons, monazites- (Ce) and aeschynites- (Ce). Probably those REE mineral phases correspond to a hydrothermal stage, with the REE remobilization from apatites into those latter REE-rich mineral phases - this hypothesis is corroborated by geochemistry, mineral chemistry and microtextures found. Considering the results of mineral chemistry and taking into account the textural criteria, it was possible to classify carbonatite as an alvikite, with geochemical patterns that do not indicate economic potential for REE. However, soil geochemistry showed an important enrichment in REE, reflecting a probable concentration of monazites- (Ce) and aeschynites- (Ce), and because of this, it was possible to establish a zone in which the Passo Feio Carbonatite would probably be extended. In the stable isotope analyzes, the ?13C values varied between ?4.14 and ?3.89‰ while those of ?18O between 10.01 and 11.32‰ which can be attributed to the cooling of the magma itself, without suggesting metamorphic processes or subsequent changes. The deformation found in this carbonatite was probably developed in late-magmatic conditions, guided by tectonics associated with horizontal movements in shear zones. Thus, this work suggests that this carbonatite was the product of the reactivation of mantle sources, within a post-collision magmatic context of the Sul-Riograndense Shield.
Abstract: Permian dikes, sills, and diatremes in southern Illinois and northwestern Kentucky (the Omaha, Wildcat Hills, Cottage Grove, Will Scarlet, Williams, Grant, and Clay Lick intrusions) share similar geochemistry and are classified as ultramafic lamprophyres. Major element compositions are 30-35 wt% SiO2, 6-7% Al2O3, 12-14% FeOt, 16-19% MgO, 3-5% TiO2, 11-16% CaO, 0.1-0.7% Na2O, 1.2-2.7% K2O, and 0.4-1.3% P2O5. The Grant Intrusive Breccia is an exception, with lower SiO2, Al2O3, FeOt, MgO, TiO2, and higher CaO. Typically, these rocks are fine grained, with phlogopite, serpentinized olivine ( Fo88), diopside, perovskite, Fe-Ti-spinel, apatite, and calcite. Blocky and lath-shaped pseudomorphs in some samples probably represent melilite, which would make the rocks alnöites. The Grant and Williams diatremes contain sedimentary and igneous clasts (including amphibole megacrysts) within a carbonate-rich matrix. The Grant exhibits pelletal lapilli and is characterized as a lamprophyre?carbonatite tuffisite. Trace element patterns exhibit enrichment of LREE, strong REE fractionation, and relative depletions of K, Sr, Zr, and Hf, closely matching those of the mela-aillikites of Aillik Bay, Labrador. The Grant Intrusive exhibits even greater REE enrichment and notable peaks at Nb, La, and Ce. Geochemical characteristics, including distributions of 143Nd/144Nd and 87Sr/86Sr, are consistent with near-primary melts from a metasomatized peridotite source containing phlogopite-rich veins. Derivation of the lamprophyres from carbonate-rich parental melts similar to the Grant Intrusive could be achieved by separation of carbonatite. A narrow range of initial 87Sr/86Sr (0.70301-0.70449), and initial ?Nd (3.7-5.1), suggests a uniform mantle source close to Bulk Earth. T-depleted mantle model ages range from 540 to 625 Ma, and might correlate with timing of enrichment of a lithospheric mantle source during the breakup of Rodinia.
Abstract: We have investigated a locality very well known to mineral collectors, the Yates U-Th prospect near Otter Lake, Québec. There, dikes of orange to pink calcite enclose euhedral prisms of fluorapatite, locally aligned. Early investigators pointed out the importance of micro-inclusions in the prisms. We describe and image the micro-inclusions in two polished sections of fluorapatite prisms, one of them with a millimetric globule of orange calcite similar to that in the matrix. We interpret the globule to have been an inclusion of melt trapped during growth. Micro-globules disseminated in the fluorapatite are interpreted to have crystallized in situ from aliquots of the boundary-layer melt enriched in constituents rejected by the fluorapatite; the micro-globules contain a complex jigsawed assemblage of carbonate, silicate, and sulfate minerals. Early minerals to crystallize are commonly partly dissolved and partly replaced by lower-temperature phases. Such jigsawed assemblages seem to be absent in the carbonate matrix sampled away from the fluorapatite prisms. The pressure and temperature attained at the Rigolet stage of the Grenville collisional orogeny were conducive to the anatexis of marble in the presence of H2O. The carbonate melt is considered to have become silicocarbonatitic by assimilation of the enclosing gneisses, which were also close to their melting point. Degassing was important, and the melt froze quickly. The evidence points to a magmatic origin for the carbonate dikes and the associated clinopyroxenite, rather than a skarn-related association.
Abstract: A new discovery of carbonatites at Pianciano, Ficoreto and Forcinelle in the Roman Region demonstrates that Italian carbonatites are not just isolated, mantle xenoliths-bearing, primitive diatremic rocks but also evolved sub-type fluor-calciocarbonatite (F~10 wt.%) associated with fluor ore (F~30 wt.%). New data constrain a multi-stage petrogenetic process, 1-orthomagmatic, 2-carbothermal, 3-hydrothermal. Petrography and geochemistry are conducive to processes of immiscibility and decarbonation, rather than assimilation and crystal fractionation. A CO2-rich, ultra-alkaline magma is inferred to produce immiscible melilite leucitite and carbonatite melts, at lithospheric mantle depths. At the crustal level and in the presence of massive CO2 exsolution, decarbonation reactions may be the dominant processes. Decarbonation consumes dolomite and produces calcite and periclase, which, in turn, react with silica to produce forsterite and Ca silicates (monticellite, melilite, andradite). Under carbothermal conditions, carbonate breakdown releases Sr, Ba and LREE; F and S become concentrated in residual fluids, allowing precipitation of fluorite and barite, as well as celestine and anhydrite. Fluor-calciocarbonatite is the best candidate to exsolve fluids able to deposit fluor ore, which has a smaller volume. At the hydrothermal stage, REE concentration and temperature dropping allow the formation of LREEF2+ and LREECO3+ ligands, which control the precipitation of interstitial LREE fluorcarbonate and silicates -(bastnäsite-(Ce)- Ce(CO3)F and -britholite-(Ce)- (Ce,Ca)5(SiO4,PO4)3(OH,F) . Vanadates such as wakefieldite, CeVO4, vanadinite, Pb5(VO4)3Cl and coronadite Pb(Mn4+6 Mn3+2)O16 characterise the matrix. At temperatures of =100°C analcime, halloysite, quartz, barren calcite, and zeolites (K-Ca) precipitate in expansion fractures, veins and dyke aureoles.
Toscani, L., Salvioli-Mariani, E., Mattioli, M., Tellini, C., Boschetti, T., Iacumin, P., Selmo, E.
The pyroclastic breccia of the Cabezo Negro de Tallant ( SE Spain): the first finding of carbonatite volcanism in the internal domain of the Betic Cordillera.
Abstract: Geodynamic origin of carbonatites is debated for several decades. One of hypotheses links their origin to large-volume mantle plumes rising from the core-mantle boundary (CMB). Some evidence exists for temporal and spatial relationships between the occurrences of carbonatites and large igneous provinces (LIPs), and both carbonatites and LIPs can be related to mantle plumes. A good example is the carbonatites of the Maymecha-Kotuy Province in the Polar Siberia, which were formed at the same time as the Siberian superplume event at ca. 250 Ma. In this study we use a recently published absolute plate kinematic modelling to reconstruct the position of 155 Phanerozoic carbonatites at the time of their emplacement. We demonstrate that 69% of carbonatites may be projected onto the central or peripheral parts of the large low shear-wave velocity provinces (LLSVPs) in the lowermost mantle. This correlation provides a strong evidence for the link between the carbonatite genesis and the locations of deep-mantle plumes. A large group of carbonatites (31%) has no obvious links to LLSVPs and, on the contrary, they plot above the "faster-than-average S-wave" zones in the deep mantle, currently located beneath North and Central America and China. We propose that their origin may be associated with remnants of subducted slabs in the mantle.
Geochemistry International, Vol. 57, 11, pp. 1125-1146.
Russia, Siberia
carbonatite
Abstract: We report the first combined investigation (neutron activation, X-ray fluorescence, and electron microprobe analysis) of mineral forms of Au and Ag and noble metal distribution in the sulfide-bearing phoscorites and carbonatites of the Guli alkaline ultrabasic massif (Polar Siberia) and magnetite and sulfide separates from these rocks. The highest noble metal contents were observed in the sulfide separates from the carbonatites: up to 2.93 Pt, 61.6 Au, and 3.61 ppm Ag. Pyrrhotite, djerfisherite, chalcopyrite, and pyrite are the most abundant sulfides and the main hosts for Au and Ag. The latest assemblage of chalcopyrite, Ag-rich djerfisherite, lenaite, sternbergite, and native silver shows significant Ag concentrations. The wide occurrence of K sulfides and presence of multiphase inclusions in pyrrhotite consisting of rasvumite, K?Na–Ca carbonate, carbocernaite, strontianite, galena, chalcopyrite, sternbergite, lenaite, and native silver suggest that the sulfides were formed at high activities of K, Na, Sr, LREE, F, Cl, and S. Chlorine shows high complex-forming capacity to Ag and could be an agent of noble metal transport in the carbonatites. Crystallization of the early djerfisherite–pyrrhotite assemblages of the phoscorites and carbonatites began at a temperature not lower than 500°C and continued up to the formation of late Ag-bearing sulfides at temperatures not higher than 150°C. The carbonatite-series rocks could be enriched in Au and Ag during late low-temperature stages and serve as a source for Au placers.
Earth and Planetary Science Letters, Vol. 533, 11p. Pdf
Mantle
carbonatite
Abstract: A detailed investigation on seven carbonatites and associated alkaline rock complexes (Kaiserstuhl, Sokli, Kovdor, Palabora, Oka, Magnet Cove, Jacupiranga), together with a world-wide comparison between carbonatites, alkaline silicate rocks and mantle xenoliths, implies peculiar redox conditions for carbonatite-bearing alkaline complexes: Carbonatites and associated alkaline rocks in continental settings crystallize from relatively oxidized magmas, on average 1.4 log units () and 1.3 log units () above the synthetic fayalite-magnetite-quartz (FMQ) buffer. In contrast, alkaline rocks in continental settings that lack associated carbonatites reveal rather reduced conditions (mean ; ). The calculated redox conditions for carbonatites and associated silicate rocks demonstrate that these crystallize from relatively oxidized mantle-derived melts compared to the general range found for alkaline rocks in continental settings.
Earth and Planetary Science Letters, Vol. 531, 10p. Pdf
Mantle
carbonatite
Abstract: MgCO3 is one of the most important components of mantle-derived carbonatite melts, and yet also one of the most difficult to study experimentally. Attempts to constrain its thermodynamic properties are hampered by decarbonation, which occurs at only ?500 °C, far below its metastable 1 bar melting temperature. Molecular dynamic simulations, however, can predict the thermodynamic properties of the MgCO3 liquid component in spite of experimental challenges. Using the recently developed empirical potential model for high-pressure alkaline-earth carbonate liquids (Hurt and Wolf, 2018), we simulate melts in the MgCO3-CaCO3-SrCO3-BaCO3 system from 773 to 2373 K up to 20 GPa. At 1 bar, MgCO3 liquid assumes a novel topology characterized by a 4-fold coordination of the metal cation (Mg) with both the carbonate molecule and oxygen ion; this is distinct from the other alkaline-earth carbonate liquids in which the metal cation is in ?6- and ?8-fold coordination with carbonate and oxygen. With increasing pressure, MgCO3 liquid structure becomes progressively more like that of (Ca, Sr, Ba)CO3 liquids with approaching 6-fold coordination with carbonate groups. The novel network topology of MgCO3 liquid results in a melt that is significantly more buoyant and compressible than other alkaline-earth carbonate liquids. Simulations of mixed MgCO3-bearing melts show that metal cation coordination with O and C is independent of bulk composition. Mixed simulation also reveal that molar volume, compressibility, enthalpy and heat capacity do not mix ideally with (Ca, Sr, Ba)CO3 liquids at 1 bar, a consequence of preferential metal-cation ordering in MgCO3-bearing mixtures. As pressure increases, however, mixing progressively approaches ideality with respect to molar volume, becoming nearly ideal by 12 GPa. The model is further applied to mantle-derived primary carbonatite melts with compositions, temperatures and pressures determined by published phase equilibrium experiments. The voluminous structure of liquid MgCO3 results in a buoyant melt that inhibits a density crossover with the surrounding mantle. Assuming FeCO3 liquid also adopts the same anomalous high-volume structure as MgCO3, we predict that even the most Fe-rich ferrocarbonatites would remain buoyant and be barred from sinking or stagnating in the mantle.
Abstract: The origin of dolomite that hosts the Bayan Obo REE-Nb-Fe deposit (57.4 Mt.@6% REE2O3, 2.16 [email protected]% Nb2O5, and >1500 Mt.@35% iron oxides) has been controversial for decades, but it is integral to understanding of the genesis of this giant deposit. In this study, based on the textures and in situ major and trace element composition of its carbonates, the dolomite was proved to be initially generated from magnesio-ferro?carbonatite melts. It subsequently experienced magmatic-hydrothermal alteration and recrystallization in a low strain environment, caused by calcio?carbonatitic fluids, with formation of finer-grained dolomite, interstitial calcite and increasing amounts of associated fluorocarbonates. Available stable isotope analyses indicate that the recrystallized ore-hosting dolomite has higher ?13C and ?18O ratios compared to its igneous coarse-grained precursor. Rayleigh fractionation during the recrystallization process, rather than crustal contamination, played a major role in the highly-variable stable isotope composition of carbonates in the dolomite. Low-T alteration increased variability with apparently random increases in ?18O within carbonates. The REE, Ba and Sr were added simultaneously with the elevated (La/Yb)cn from magnesio-ferro?carbonatite melts to calcio?carbonatitic fluids, and to carbonatite-derived aqueous fluids, through which extensive fluorine metasomatism and alkali alteration overlapped the recrystallization of the ore-hosting dolomite. Therefore, the multi-stage REE mineralization at Bayan Obo is closely related to metasomatism by calcio?carbonatitic fluids of previously-emplaced intrusive magnesio-ferro?carbonatite bodies during late evolution of the Bayan Obo carbonatite complex. Then, the ore-hosting dolomitic carbonatite was subjected to compressive tectonics during a Paleozoic subduction event, and suffered intense, largely brittle, deformation, which partially obscured the earlier recrystallization process. The complex, multi-stage evolution of the ore-hosting dolomite is responsible for the uniqueness, high grade and giant size of the Bayan Obo deposit, the world's largest single REE resource with million tonnes of REE oxides.
Abstract: Sulfur-bearing monazite-(Ce) occurs in silicified carbonatite at Eureka, Namibia, forming rims up to ~0.5 mm thick on earlier-formed monazite-(Ce) megacrysts. We present X-ray photoelectron spectroscopy data demonstrating that sulfur is accommodated predominantly in monazite-(Ce) as sulfate, via a clino-anhydrite-type coupled substitution mechanism. Minor sulfide and sulfite peaks in the X-ray photoelectron spectra, however, also indicate that more complex substitution mechanisms incorporating S2 and S4+ are possible. Incorporation of S6+ through clino-anhydrite-type substitution results in an excess of M2+ cations, which previous workers have suggested is accommodated by auxiliary substitution of OH for O2. However, Raman data show no indication of OH, and instead we suggest charge imbalance is accommodated through F substituting for O2. The accommodation of S in the monazite-(Ce) results in considerable structural distortion that may account for relatively high contents of ions with radii beyond those normally found in monazite-(Ce), such as the heavy rare earth elements, Mo, Zr and V. In contrast to S-bearing monazite-(Ce) in other carbonatites, S-bearing monazite-(Ce) at Eureka formed via a dissolutionprecipitation mechanism during prolonged weathering, with S derived from an aeolian source. While large S-bearing monazite-(Ce) grains are likely to be rare in the geological record, formation of secondary S-bearing monazite-(Ce) in these conditions may be a feasible mineral for dating palaeo-weathering horizons.
South African Journal of Geology, Vol. 122, 4, pp. 397-420.
India
alkaline, carbonatites
Abstract:
On the last page of his 1937 book “Our Wandering Continents” Alex Du Toit advised the geological community to develop the field of “comparative geology”, which he defined as “the study of continental fragments”. This is precisely the theme of this paper, which outlines my research activities for the past 28 years, on the continental fragments of the Indian Ocean. In the early 1990s, my colleagues and I were working in Madagascar, and we recognized the need to appreciate the excellent geological mapping (pioneered in the 1950s by Henri Besairie) in a more modern geodynamic context, by applying new ideas and analytical techniques, to a large and understudied piece of continental crust. One result of this work was the identification of a 700 to 800 Ma belt of plutons and volcanic equivalents, about 450 km long, which we suggested might represent an Andean-type arc, produced by Neoproterozoic subduction. We wondered if similar examples of this magmatic belt might be present elsewhere, and we began working in the Seychelles, where late Precambrian granites are exposed on about 40 of the >100 islands in the archipelago. Based on our new petrological, geochemical and geochronological measurements, we built a case that these ~750 Ma rocks also represent an Andean-type arc, coeval with and equivalent to the one present in Madagascar. By using similar types of approaches, we tracked this arc even further, into the Malani Igneous Province of Rajasthan, in northwest India. Our paleomagnetic data place these three entities adjacent to each other at ~750 Ma, and were positioned at the margins, rather than in the central parts of the Rodinia supercontinent, further supporting their formation in a subduction-related continental arc. A widespread view is that in the Neoproterozoic, Rodinia began to break apart, and the more familiar Gondwana supercontinent was assembled by Pan-African (~500 to 600 Ma) continental collisions, marked by the highly deformed and metamorphosed rocks of the East African Orogen. It was my mentor, Kevin Burke, who suggested that the present-day locations of Alkaline Rocks and Carbonatites (called “ARCs”) and their Deformed equivalents (called “DARCs”), might mark the outlines of two well-defined parts of the Wilson cycle. We can be confident that ARCs formed originally in intracontinental rift settings, and we postulated that DARCs represent suture zones, where vanished oceans have closed. We also found that the isotopic record of these events can be preserved in DARC minerals. In a nepheline syenite gneiss from Malawi, the U-Pb age of zircons is 730 Ma (marking the rifting of Rodinia), and that of monazites is 522 Ma (marking the collisional construction of Gondwana). A general outline of how and when Gondwana broke apart into the current configuration of continental entities, starting at about 165 Ma, has been known for some time, because this record is preserved in the magnetic properties of ocean-floor basalts, which can be precisely dated. A current topic of active research is the role that deep mantle plumes may have played in initiating, or assisting, continental fragmentation. I am part of a group of colleagues and students who are applying complementary datasets to understand how the Karoo (182 Ma), Etendeka (132 Ma), Marion (90 Ma) and Réunion (65 Ma) plumes influenced the break-up of Gondwana and the development of the Indian Ocean. Shortly after the impingement of the Karoo plume at 182 Ma, Gondwana fragmentation began as Madagascar + India + Antarctica separated from Africa, and drifted southward. Only after 90 Ma, when Madagascar was blanketed by lavas of the Marion plume, did India begin to rift, and rapidly drifted northward, assisted by the Marion and Deccan (65 Ma) plumes, eventually colliding with Asia to produce the Himalayas. It is interesting that a record of these plate kinematics is preserved in the large Permian - Eocene sedimentary basins of western Madagascar: transtensional pull-apart structures are dextral in Jurassic rocks (recording initial southward drift with respect to Africa), but change to sinistral in the Eocene, recording India’s northward drift. Our latest work has begun to reveal that small continental fragments are present in unexpected places. In the young (max. 9 Ma) plume-related, volcanic island of Mauritius, we found Precambrian zircons with ages between 660 and 3000 Ma, in beach sands and trachytic lavas. This can only mean that a fragment of ancient continent must exist beneath the young volcanoes there, and that the old zircons were picked up by ascending magmas on their way to surface eruption sites. We speculate, based on gravity inversion modelling, that continental fragments may also be present beneath the Nazareth, Saya de Malha and Chagos Banks, as well as the Maldives and Laccadives. These were once joined together in a microcontinent we called "Mauritia", and became scattered across the Indian Ocean during Gondwana break-up, probably by mid-ocean ridge "jumps". This work, widely reported in international news media, allows a more refined reconstruction of Gondwana, suggests that continental break-up is far more complex than previously perceived, and has important implications for regional geological correlations and exploration models. Our results, as interesting as they may be, are merely follow-ups that build upon the prescient and pioneering ideas of Alex Du Toit, whose legacy I appreciatively acknowledge.
Geochimica et Cosmochimica Acta, Vol. 274, pp. 118-135.
India
carbonatite
Abstract: Carbonatites crystallise along a wide range of solidus temperatures and are commonly affected by post-magmatic textural re-equilibration and diagenesis. Further insights into the formation and modification of carbonatites are provided using carbon, oxygen and clumped isotope (?47) data of rocks from spatially associated Amba Dongar and Siriwasan alkaline complexes in the north-western Deccan igneous province, India. We derive apparent equilibrium blocking temperatures to help constrain the thermal evolution of the different rock types found within the alkaline complexes in a petrographic context. The apparent temperatures for the carbonatites are significantly low but are consistent with reports on other global carbonatites and model predictions. Rapidly cooled Oldoinyo Lengai natrocarbonatite yielded similar low temperatures, even in the absence of bulk isotopic alteration. The isotopic proxies and petrographic observations favour both isotopic exchange reactions and diagenesis in altering ?47 values in calciocarbonatites. Diagenetic reactions are however strongly favoured, as secondary calcites in nephelinites and ferrocarbonatites record much lower temperatures than in the calciocarbonatites, highlighting the effect of fluids and diagenetic reactions in 13C18O bond ordering in carbonatites. Variations in the CO isotope data reveal the coupling of fractional crystallisation and post-magmatic fluid-rock interactions on bulk rock composition. After emplacement, the resetting of clumped isotope signatures in carbonatites is facilitated by post-magmatic processes in both open and closed systems.
Earth and Planetary Science Letters, Vol. 535, 116076 11p. Pdf
Russia, Siberia
carbonatite
Abstract: Large igneous province (LIP) eruptions have been linked in some cases to major perturbations of Earth's carbon cycle. However, few observations directly constrain the isotopic composition of carbon released by LIP magmas because carbon isotopes fractionate during degassing, which hampers understanding of the relative roles of mantle versus crustal carbon reservoirs. Carbonatite magmatism associated with LIPs provides a unique window into the isotopic systematics of LIP carbon because the majority of carbon in carbonatites crystalizes rather than degassing. Although the volume of such carbonatites is small, they offer one of the few available constraints on the mantle carbon originally hosted in other more voluminous magma types. Here, we present new data for the Guli carbonatites in the Siberian Traps. In addition, we compile ?260 published measurements of from carbonatites related to the Deccan Traps and the Paraná-Etendeka. We find no evidence for magmas with carbon isotope ratios lighter than depleted mantle values of ‰ from any of these LIPs, though some carbonatites range to heavier . We attribute relatively heavy in some carbonatites to either slightly 13C-enriched domains in the mantle lithosphere or carbon isotope fractionation in deep, carbon-saturated LIP magma reservoirs. The absence of a light component in LIP magmas supports the view that lithospheric carbon reservoirs must be tapped during cases of LIP magmatism linked with sharp negative carbon isotope excursions and mass extinctions.
Abstract: The Morro dos Seis Lagos niobium rare earth element, Ti-bearing lateritic deposit (Amazonas, Brazil) is derived from a primary siderite carbonatite. The complex is the only example of a Nb deposit in which Nb-rich rutile is the main Nb ore mineral. Apart from the laterites, at the current level of exposure the complex consists only of siderite carbonatite; silicate rocks are absent. Three types of siderite carbonatite are recognized: (1) a brecciated and oxidized core siderite carbonatite consisting of up to 95 vol% siderite together with: hematite; pyrochlore; Nb-brookite; Ti-maghemite; and thorobastnäsite; (2) a REE- and P-rich variety of the core siderite carbonatite consisting of siderite (up to 95 vol%), hematite, minor pyrochlore, monazite and bastnäsite; (3) a border hydrothermal siderite carbonatite with ~70 vol% siderite, barite (~15 vol%), gorceixite (~7 vol%) and minor rhabdophane and pyrochlore. The country rock gneiss in which the carbonatite was emplaced was affected by potassic fenitization, with the formation of phlogopite and orthoclase together with monazite, fluorapatite and bastnäsite. The siderite carbonatites exhibit a wide variation of ?13C (?5.39‰ to ?1.40‰), accompanied by a significant variation in ?18O (17.13‰ to 31.33‰), especially in the REE-rich core siderite carbonatite, and are explained as due to the presence of both H2O and CO2 in the magma. The core siderite carbonatite is the richest in Fe (48.64-70.85 wt% Fe2O3) and the poorest in Ca (up 0.82 wt% CaO) example of a siderite carbonatite yet recognized The ferrocarbonatite has significant contents of Mn, Ba, Th, Pb and LREE, and a very high Nb (up to 7667 ppm) content due to the presence of Nb-brookite. The substitution 3Ti4+ = Fe2+ + 2Nb5+ recognized in Nb-rich brookite explains enrichment of Nb in the core siderite carbonatite and indicates formation in a reducing environment. The high Nb/Ta ratio (1408-11,459) of the carbonatite is compatible with residual liquids derived by fractional crystallization. The 87Sr/86Sr (0.70411-0.70573) and 144Nd/143Nd (0.512663-0.512715) isotopic data suggest the carbonatite is mantle-derived with essentially no crustal contamination and is younger than the maximum age of 1328 ± 58 Ma (UPb in zircon). We suggest that the Morro dos Seis Lagos carbonatite complex represents the upper-most parts of a differentiated carbonatite magmatic system, and that the siderite carbonatite is related to late-magmatic-to-carbo-hydrothermal processes.
Contributions to Mineralogy and Petrology, Vol. 175, 28p. Pdf.
Australia
carbonatite
Abstract: The 1370 Ma Gifford Creek Carbonatite Complex (GCCC) comprises a diverse suite of alkaline dyke and sill complexes that cover an area of?~?250 km2 in the Gascoyne Province, Western Australia. Most carbonatite types are interpreted to be related products of fractional crystallisation, with calcite carbonatites representing cumulate rocks and dolomite carbonatites representing crystallised products of the derivative liquids. Genetic relationships between these carbonatites and other alkaline igneous units are less clear. The ankerite-siderite carbonatites and magnetite-biotite dykes are likely of related magmatic origin as both have distinctly high LREE and low HFSE contents. The ankerite-siderite carbonatites have mantle-like ?13C isotope values of ? 6.1 to ? 7.1‰ and similar geochemistry to other known magmatic ferrocarbonatites. Silica-rich alkaline veins found near the centre of the complex have trace element signatures that are antithetic to the magnetite-biotite dykes, so these veins are interpreted to represent products of alkali- and F-rich magmatic-hydrothermal fluids exsolved from the magnetite-biotite dykes during their emplacement. Carbon, O, Sr, and Nd isotope data are consistent with an enriched mantle source for the origin of the GCCC, with mantle enrichment likely caused by plate convergence processes associated with the c. 2.0 Ga Glenburgh Orogeny. There is no evidence to link mantle plume activity with formation of the GCCC; rather, alkaline magmatism is interpreted to result from low degree melting of the metasomatised mantle during reactivation of the crustal suture zone at 1370 Ma. The carbonatitic magmas utilised the Lyons River Fault to traverse the crust to be emplaced as the GCCC. Post magmatic alteration has variably modified the O and Sr isotope compositions of carbonates from these rocks. We therefore appeal for careful evaluation of isotopic data from ancient carbonatites, as isotopic resetting may be more common than currently recognised.
Journal of South American Earth Sciences, Vol. 97, 102416, 7p. Pdf
South America, Brazil, Minas Gerais
carbonatite
Abstract: The Alto Parnaíba Igneous Province (APIP) is a voluminous magmatic province composed of various alkaline-carbonatite complexes emplaced in the Brasilia Mobile Belt during the Cretaceous. Relative timing of emplacement of silicate and carbonate magmas in most of these complexes remains mostly unresolved due to conflicting geochronological results. To determine the duration of magmatism and to test the possible existence of multiple magmatic events, we employ 40Ar/39Ar phlogopite single crystal dating to determine the history of magma emplacement at the Tapira alkaline-carbonatite complex, Minas Gerais, Brazil. The new single crystal data indicate at least two magmatic events during the emplacement of this complex, the first at > 96.2 ± 0.8 Ma and the second at 79.15 ± 0.6 Ma. The first igneous event was responsible for emplacement of the silicate plutonic series, while the second event corresponds to the emplacement of primarily carbonatitic magmas, generating metasomatic phlogopite alteration in bebedourites. The ages of intrusion and cooling of the alkaline-carbonatite complexes in the APIP must be investigated in other complexes to determine if intrusion intervals of ~17 Ma or more are common regionally. Protracted intrusive events, if related to magma generation by passage of South America over a stationary Trindade plume, requires complex ponding and lateral magma flow below a slow-moving continent.
Contributions to Mineralogy and Petrology, Vol. 175, 34 31p. Pdf
Africa, South Africa
carbonatite
Abstract: The Phalaborwa world-class phosphate deposit (South Africa) is hosted by a Paleoproterozoic alkaline complex mainly composed of phoscorite, carbonatite, pyroxenitic rocks, and subordinate fenite. In addition, syenite and trachyte occur in numerous satellite bodies. New petrological and in-situ geochemical data along with O and Sr isotope data obtained on apatite demonstrate that apatite is in the principal host rocks (pyroxenitic rocks, phoscorite and carbonatite) formed primarily by igneous processes from mantle-derived carbonatitic magmas. Early-formed magmatic apatite is particularly enriched in light rare earth elements (LREE), with a decrease in the REE content ascribed to magma differentiation and early apatite fractionation in isolated interstitial melt pockets. Rayleigh fractionation favored a slight increase in ?18O (below 1%) at a constant Sr isotopic composition. Intrusion of fresh carbonatitic magma into earlier-formed carbonatite bodies locally induced re-equilibration of early apatite with REE enrichment but at constant O and Sr isotopic compositions. In fenite, syenite and trachyte, apatite displays alteration textures and LREE depletion, reflecting interaction with fluids. A marked decrease in ?18O in apatite from syenite and trachyte indicates a contribution from ?18O-depleted meteoric fluids. This is consistent with the epizonal emplacement of the satellite bodies. The general increase of the Sr isotope ratios in apatite in these rocks reflects progressive interaction with the country rocks over time. This study made it possible to decipher, with unmatched precision, the succession of geological processes that led to one of the most important phosphate deposits worldwide.
Journal of Asian Earth Sciences, Vol. 188, 26p. Pdf
Russia, Siberia
carbonatite
Abstract: The Cambrian Kharly alkaline plutonic complex composed mainly of foidolite and nepheline syenite makes up a small intrusive field in the Sangilen Plateau in Tuva (southern Siberia). The rocks show large ranges of major oxides (38-58 wt% SiO2; 1-18 wt% Na2O + K2O; 11-28 wt% Al2O3; 1.5-20 wt% CaO; 0.1-8 wt% MgO; 2-12 wt% Fe2O3) controlled by variable percentages of minerals: clinopyroxenes, calcic amphiboles, micas, nepheline and feldspars. Alkaline rocks are cut by carbonatite veins composed of predominant calcite coexisting with femic minerals (10-15% of aegirine-ferrosalite-hedenbergite, sodic-calcic amphiboles, ferrobiotite, Ti-garnet), Na-K feldspar and nepheline (up to 15-20%), fluorapatite (up to 20-25%), Sr-apatite, and accessory carbocernaite, titanite, Ti-magnetite and ilmenite. Carbonatites (4057-8859 ppm Sr, 426-1901 ppm Ba (Sr/Ba ? 2), 290-980 ppm REE + Y, 2 to 100 ppm Zr, and 0.5 to 15 ppm Nb) possibly originated at high (?500-650 °C) temperatures as a result of liquid immiscibility. The isotope systematics of rocks and minerals (?Nd(t) from ~2.9 to 6.5; 207Pb/206Pbin = 0.89; 208Pb/206Pbin = 2.15; 87Sr/86Sr(t) = 0.70567-0.70733, ?18OV-SMOW ? 7.2-19.5‰, and ?13CV-PDB from ?6.0 to ?1.4‰) suggest mixing of PREMA and EM 1 material during magma generation and crustal contamination of the evolving melts. The rocks bear signatures of interaction with “magmatic-equilibrated” fluids or heated meteoric waters. LILE/HFSE ratios indicate mixed magma sources that involved the material of IAB and OIB, as well as a crustal component, possibly, due to interaction of a mantle plume with rock complexes on the active continental margin.
Geochimica et Cosmochimica Acta, in press available 57p. Pdf
Mantle
carbonatite
Abstract: Rare earth element (REE) enrichments in carbonatites are often described as resulting from late magmatic-hydrothermal or supergene processes. However, magmatic pre-enrichment linked to the igneous processes at the origin of carbonatites are likely to contribute to the REE fertilisation. Experimental constraints reveals that immiscibility processes between carbonate and silicate melts can lead to both REE enrichments and depletions in carbonatites making the magmatic processes controlling REE enrichments unclear.
We link REE contents of carbonatites to the magmatic stage at which carbonatites are separated from silicate magma in their course of differentiation. We present results of experiments made at pressure and temperature conditions of alkaline magmas and associated carbonatites differentiation (0.2-1.5 GPa; 725-975?°C; FMQ to FMQ?+?2.5), simultaneously addressing crystal fractionation of alkaline magmas and immiscibility between carbonate (calcio-carbonate type) and silicate melts (nephelinite to phonolite type). The experimental data shows that the degree of differentiation, controlling the chemical composition of alkaline melts, is a key factor ruling the REE concentration of the coexisting immiscible carbonate melts. In order to predict carbonate melt REE enrichments during alkaline magma differentiation, we performed a parameterisation of experimental data on immiscible silicate and carbonate melts, based exclusively on the silica content, the alumina saturation index and the alkali/alkaline-earth elements ratio of silicate melts. This parameterisation is applied to more than 1600 geochemical data of silicate magmas from various alkaline provinces (East African Rift, Canary and Cape Verde Islands) and show that REE concentrations of their potential coeval carbonatite melts can reach concentration ranges similar to those of highly REE enriched carbonatites (?REE?>?30 000?ppm) by immiscibility with phonolitic/phono-trachytic melt compositions, while more primitive alkaline magmas can only be immiscible with carbonatites that are not significantly enriched in REE.
Abstract: Carbonates of the Tomtor complex of ultramafic alkaline rocks and carbonatites (the northern part of the Republic of Sakha Yakutia) are distinguished by a wide range of carbon isotopic composition ?13C from +2 to -59.9‰. The geological position, localization patterns, mineral and chemical compositions and the relationship with REE mineralization of samples with values of ?13C carbonates from -25 to -59‰ are characterized. The formation of abnormally low ?13C in carbonates is determined by the biogenic oxidation of methane from ?13Cmet to -70‰.
Geochimica et Cosmochimica Acta, Vol. 277, pp. 224-242. pdf
Europe, Germany
carbonatite
Abstract: Studies of fluid inclusions in carbonatitic rocks are essential for understanding physicochemical processes involved in carbonatite-related hydrothermal ore mineralization and fenitization. However, the composition of many carbonatite-derived fluids is challenging to quantify, which hampers their detailed interpretation. Here, we present a systematic study of microthermometry of fluid inclusions found in carbonatites from the Kaiserstuhl (SW Germany), and a simple numerical model to estimate the compositions of such fluids, which are typical of numerous carbonatites worldwide. Four types of fluid inclusions have been identified in the Kaiserstuhl carbonatites: (I) vapor-poor H2O-NaCl fluids with <50?wt.% salinity; (II) vapor-rich H2O-NaCl-CO2 fluids with <5?wt.% salinity; (III) multi-component fluids with high salinity and high CO2 contents; and (IV) multi-component fluids with high salinity but little to no CO2. At present, it is only possible to quantify fluid compositions for types I and II. For the complex types III and IV, we conducted predictive modeling of the liquidus surface based on the Margules equations. The results suggest that carbonatite melts predominantly exsolve Na-K-sulfate-carbonate/bicarbonate-chloride brines (types III or IV). Such fluid inclusions may represent immiscible fluids that were trapped after segregation by boiling from a parental highly saline brine (type I). Fluid boiling, in turn, was probably triggered by a rapid pressure release during melt ascent. The present model enables quantification of fluid compositions associated with carbonatitic magmatism.
Abstract: Mineral zoning in fenites around miaskite intrusions of the Vishnevye Mountains complex can be interpreted as a magmatic-replacement zonal metasomatic aureole (in D.S. Korzhinskii’s understanding): the metasomatic transformations of the fenitized gneisses under the effect of deep alkaline fluid eventually resulted in the derivation of nepheline syenite eutectic melt. Based on the P-T-fO2 parameters calculated from the composition of minerals coexisting in the successive zones, isobaric-isothermal fO2-aSiO2 and µNa2O-µAl2O3 sections were constructed with the Perplex program package to model how the fenites interacted with H2O-CO2 fluid (in the Na-K-Al-Si-Ca-Ti-Fe-Mg-O-H-C system). The results indicate that the fluid-rock interaction mechanisms are different in the outer (fenite) and inner (migmatite) parts of the zonal aureole. Its outer portion was dominated by desilication of rocks, which led, first, to quartz disappearance from these rocks and then to an increase in the Al# of the coexisting minerals (biotite and clinopyroxene). In the inner part of the aureole, fenite transformations into biotite-feldspathic metasomatic rocks and nepheline migmatite were triggered by an increase in the Na and Al activities in the system alkaline H2O-CO2 fluid-rock. As a consequence, the metasomatites were progressively enriched in Al2O3 and alkalis, and these transformations led to the development of biotite in equilibrium with K-Na feldspar and calcite at the sacrifice of pyroxene. The further introduction of alkalis led to the melting of the biotite-feldspathic metasomatites and the origin of nepheline migmatites. The simulated model sequence of metasomatic zones that developed when the gneiss was fenitized and geochemical features of the successive zones (differences in the LILE and REE concentrations in the rocks and minerals of the fenitization aureole and the Sm-Nd isotope systematics of the rocks of the alkaline complex) indicate that the source of the fluid responsible for the origin of zonal fenite-miaskite complexes may have been carbonatite, a derivative of mantle magmas, whereas the miaskites were produced by metasomatic transformations of gneisses and subsequent melting under the effect of fluid derived from carbonatite magmas.
Abstract: The origin of carbonatites—igneous rocks with more than 50% of carbonate minerals—and whether they originate from a primary mantle source or from recycling of surface materials are still debated. Calcium isotopes have the potential to resolve the origin of carbonatites, since marine carbonates are enriched in the lighter isotopes of Ca compared to the mantle. Here, we report the Ca isotopic compositions for 74 carbonatites and associated silicate rocks from continental and oceanic settings, spanning from 3 billion years ago to the present day, together with O and C isotopic ratios for 37 samples. Calcium-, Mg-, and Fe-rich carbonatites have isotopically lighter Ca than mantle-derived rocks such as basalts and fall within the range of isotopically light Ca from ancient marine carbonates. This signature reflects the composition of the source, which is isotopically light and is consistent with recycling of surface carbonate materials into the mantle.
Geochimica et Cosmochimica Acta, Vol. 278, pp. 235-243.
Mantle
carbonatite
Abstract: To investigate the behaviour of Ba isotopes during carbonatite petrogenesis and to explore the possibility of using carbonatites to constrain the Ba isotopic composition of the mantle, we report high-precision Ba isotopic analyses of: (1) carbonatites and associated silicate rocks from the only active carbonatite volcano, Oldoinyo Lengai, Tanzania, and (2) Archean to Cenozoic carbonatites from Canada, East Africa, Germany and Greenland. Carbonatites and associated phonolites and nephelinites from Oldoinyo Lengai have similar ?137/134Ba values that range from +0.01 to +0.03‰, indicating that Ba isotope fractionation during carbonatite petrogenesis is negligible. The limited variation in ?137/134Ba values from ?0.03 to +0.09‰ for most carbonatite samples suggests that their mantle sources have a relatively homogeneous Ba isotopic composition. Based on the carbonatites investigated in this work, the average ?137/134Ba value of their mantle sources is estimated to be +0.04?±?0.06‰ (2SD, n?=?16), which is similar to the average value of +0.05?±?0.06‰ for mid-ocean ridge basalts. The lower ?137/134Ba value of ?0.08‰ in a Canadian sample and higher ?137/134Ba values of +0.14‰ and?+?0.23‰ in two Greenland samples suggest local mantle isotopic heterogeneity that may reflect the incorporation of recycled crustal materials in their sources.
Earth and Planetary Science Letters, Vol. 544, 116365 14p. Pdf
Australia
carbonatite
Abstract: Petrological and geochemical studies have revealed the contribution of garnet pyroxenites in basalt petrogenesis. However, whether primary mantle melts are produced with such signature or acquired it subsequently remains somewhat controversial. We here integrate new major-, trace-element and Sr-Nd-Hf isotopic compositions of garnet pyroxenite xenoliths in Holocene alkali basalts from Lakes Bullenmerri and Gnotuk, Southeastern Australia, to relate their petrogenesis to mantle-wedge melt circulation and subsequent lithospheric evolution. Results show that the clinopyroxenites have lower MgO and Cr2O3 contents than the associated websterites, and range in compositions from depleted LREE patterns and highly radiogenic Nd and Hf isotopic signatures in relatively low-MgO samples (Type 1), to enriched REE patterns with negative HFSE anomalies, unradiogenic Nd and Hf isotopes, and extremely radiogenic Sr-isotopic ratios in samples with higher MgO (Type 2). Such compositional variabilities suggest that these pyroxenites represent segregates from melts derived from a recycled oceanic lithosphere with a potential contribution from pelagic sediments. Variable LREE contents and isotopic compositions between those of Type 1 and 2 clinopyroxenites are observed in amphibole-bearing samples (Type 3), which are interpreted as Type 1-like protoliths metasomatized by the basaltic and carbonatitic melts, possibly parental to Type 2 clinopyroxenites. The lithosphere beneath Southeastern Australia thus has received variable melt contributions from a heterogeneous mantle-wedge source, which notably includes a subducted oceanic slab package that has retained its integrity during subduction. On this basis, we suggest that the compositional heterogeneity and temporal evolution of the subsequent Southeastern Australian basaltic magmatism were probably affected by the presence of pyroxenite fragments in the basalt source and formed by the tectonic reactivation of this lithosphere during Cenozoic rifting. This interpretation is notably consistent with a trend of Nd-Pb isotopes towards EMII in Older Volcanic Provinces (OVP basalts) and limited Sr-Nd-Pb isotopic variations towards HIMU in the Newer Volcanic Provinces (NVP basalts, including the host lavas), which also exhibit low SiO2, high FeO and high CaO/Al2O3 commonly interpreted as due to pyroxenite contributions. Therefore, the identification of a subduction signature in these rift-related lavas attests to a "lithospheric memory" of earlier subduction episodes (as documented by the xenoliths), rather than a reflection of contemporaneous subduction tectonics.
Abstract: The recently discovered REE and Nb mineralization in the Twihinat area in the western part of the Oulad Dlim Massif (Adrar Souttouf) in South Morocco is linked to a Cretaceous calciocarbonatite intrusion which was likely formed in an intracontinental rift setting and crops out locally within a ring structure that mainly consists of massive Fe-oxide mineralization and silica breccia. The carbonatite shows intensively metasomatized zones, which contain bastnaesite and pyrochlore-group minerals as the main REE and Nb ore minerals. They are usually associated with apatite, quartz and Fe-oxides, or trapped in calcite voids, suggesting a secondary ore formation. Within the associated Fe-oxide mineralization, pyrochlore and monazite-(Ce) are the main ore minerals occurring closely associated with quartz and magnetite or hematite. The silica breccia also shows significant subsequent infill of barite, bastnaesite-(Ce) and hydrated ceriopyrochlore, which was identified by EPMA and Raman spectroscopy. Bastnaesite commonly forms prismatic aggregates whereas pyrochlore and ceriopyrochlore usually display subhedral grains along tiny fractures. Structural and textural relationships clearly indicate epigenetic ore formation induced by multiple stages of hydrothermal fluid flow and fracturing. Ore precipitation likely resulted from interaction between low-pH mineralizing hydrothermal fluids and the wall-rock. The latter efficiently buffered the acidity of the fluids and allowed significant amounts of REE and Nb ore minerals to precipitate. Trace element ICP-MS analyses show very high REE and Nb concentrations of up to 0.76 wt% ?REE and 0.21 wt% Nb in carbonatite and up to 3 wt% ?REE and 1.3 wt% Nb in the associated silica and Fe-oxide mineralization. The results clearly demonstrate that the Twihinat REE-Nb deposits are significant and represent a potential new high-grade resource for these critical metals.
Abstract: The Mushgai-Khudag alkaline?carbonatite complex, located in southern Mongolia within the Central Asian Orogenic Belt (CAOB), comprises a broad range of volcanic and subvolcanic alkaline silicate rocks (melanephelinite-trachyte and shonkinite-alkaline syenite, respectively). Magnetite-apatite rocks, carbonatites, and fluorite mineralization are also manifested in this area. The complex formed between 145 and 133 Ma and is contemporaneous with late Mesozoic alkaline-carbonatite magmatism within the CAOB. Major and trace element characteristics of silicate rocks in the Mushgai-Khudag complex imply that these rocks were formed by the fractional crystallization of alkaline ultramafic parental magma. Magnetite-apatite rocks may be a product of silicate-Ca-Fe-P liquid immiscibility that took place during the alkaline syenite crystallization stage. The Mushgai-Khudag rocks have variable and moderately radiogenic Sr (87Sr/86Sr(i) = 0.70532-0.70614), ?Nd(t) = ?1.23 to 1.25) isotopic compositions. LILE/HFSE values and SrNd isotope compositions indicate that the parental melts of Mushgai-Khudag were derived from a lithospheric mantle source that was affected by a metasomatic agent in the form a mixture of subducted oceanic crust and its sedimentary components. The ?18OSMOW and ?18CPDB values for calcites in carbonatites range from 16.8‰ to 19.2‰ and from ?3.9‰ to 2.0‰, respectively. CO covariations in calcites of the Mushgai-Khudag carbonatites can be explained by the slight host limestone assimilation.
Abstract: The Vuoriyarvi Devonian alkaline-ultramafic complex (northwest Russia) contains magnesiocarbonatites with rare earth mineralization localized in the Petyayan-Vara area. High concentrations of rare earth elements are found in two types of these rocks: (a) ancylite-dominant magnesiocarbonatites with ancylite-baryte-strontianite-calcite-quartz (±late Ca-Fe-Mg carbonates) ore assemblage, i.e., “ancylite ores”; (b) breccias of magnesiocarbonatites with a quartz-bastnäsite matrix (±late Ca-Fe-Mg carbonates), i.e., “bastnäsite ores.” We studied fluid inclusions in quartz and late-stage Ca-Fe-Mg carbonates from these ore assemblages. Fluid inclusion data show that ore-related mineralization was formed in several stages. We propose the following TX evolution scheme for ore-related processes: (1) the formation of ancylite ores began under the influence of highly concentrated (>50 wt.%) sulphate fluids (with thenardite and anhydrite predominant in the daughter phases of inclusions) at a temperature above300-350 °C; (2) the completion of the formation of ancylite ores and their auto-metasomatic alteration occurred under the influence of concentrated (40-45 wt.%) carbonate fluids (shortite and synchysite-Ce in fluid inclusions) at a temperature above 250-275 °C; (3) bastnäsite ores deposited from low-concentrated (20-30 wt.%) hydrocarbonate-chloride fluids (halite, nahcolite, and/or gaylussite in fluid inclusions) at a temperature of 190-250 °C or higher. Later hydrothermal mineralization was related to the low-concentration hydrocarbonate-chloride fluids (<15 wt.% NaCl-equ.) at 150-200 °C. The presented data show the specific features of the mineral and fluid evolution of ore-related late-stage hydrothermal rare earth element (REE) mineralization of the Vuoriyarvi alkaline-ultramafic complex.
Abstract: Carbonatite is a magmatic rock with high carbonate and low silicate contents, which mostly originate in the mantle. It is therefore of critical importance to understand the behavior of carbon in the mantle, and consequently deep carbon recycling. However, the formation of carbonatite is largely unresolved. In particular, the source of carbonatite the carbonate remains obscure. Previous studies showed that the solidus of carbonated mantle peridotite was lower than the Earth’s geotherm in the Archean and the Early Proterozoic era, before ~1.4 Ga ago. Therefore, the mantle should have been severely decarbonated early in Earth’s history. This is consistent with the low carbon abundance in the asthenospheric mantle (~100 ppm), as indicated by low carbonate concentrations in mid-ocean ridge basalts. Consequently, carbonate in young mantle must have been mostly obtained in the post-Archean era by two processes. These are either oxidation of diamond in the mantle or recycling of sedimentary carbonates through plate subduction. Here we show that the Sr and Nd isotope variations in carbonatite may be plausibly explained by mixing of three endmembers, (1) recycled sedimentary carbonates, (2) depleted mantle, and (3) a low Sr and Nd isotopes endmember. The low Sr, Nd carbonate reservoirs for carbonatites of different ages plot roughly on the evolution line of the primitive mantle, suggesting that they were successively released from a well-preserved, non-carbonate mantle source. The preferred candidate for this endmember is carbonate formed through oxidation of diamond by ferric ion released through decomposition of bridgmanite, which is carried up from the lower mantle via background upwelling, compensational to the volume of oceanic slabs penetrating into the lower mantle1.
Abstract:
Carbonatitic magmatism plays a significant role in outgassing carbon from mantle and the formation of rare earth element (REE), rare metal (e.g., Nb and Th) and other types of deposits. The mechanism of REE mineralization associated with carbonatite have been widely studied. However, it is hard to understand U-Nb mineralization without Th enrichment associated with carbonatite. Here we report a carbonatite-hosted U-Nb deposit in Huayangchuan, located in the north Qinling Orogenic Belt. Field observation, mineralogy and geochemical analysis on a suite of drillhole samples were conducted to decipher the mineralization mechanism and its relationship with carbonatite. Huayangchuan carbonatite samples mainly consist of calcite and augite with small volume of accessory minerals (e.g., allanite, fluorapatite, barite and celestite). Betafite [(Ca,U)2(Ti,Nb,Ta)2O6(OH)] is the major ore-bearing mineral in Huayangchuan deposit. The carbonatite shows high CaO, low MgO and alkali contents, which should be products to be differentiated from primary carbonatite (high MgO and alkali contents). The immiscibility and crystallization processes could explain the high CaO/(CaO + MgO + FeO) ratios and the enrichment of LILE. Numerical modeling also indicates positive ?18OSMOW (7.29 to 15.53‰) and negative ?13CPDB (?5.26 to ?10.08‰) shifts are induced by reduced sediments assimilation from source consistent with there being enriched Sr-Nd and low Mg isotopic compositions. LA-ICP-MS zircon U-Pb dating of Huayangchuan carbonatite yielded Triassic ages of 229 ± 3 Ma, which corresponds to the post-collision stage of Qinling Orogen during the middle-late Triassic. We then proposed that the recycling of subducted sediments and later re-melting of those materials in shallow mantle generated the Huayangchuan carbonatite and subsequently formed the Huayangchuan deposit. Fluorine concentration decrease, caused by fluorapatite crystallization, ultimately resulted in betafite mineralization.
Science Advances, Vol. 6, eaba3269 June 3, 7p. Pdf
Global, Africa, Tanzania
carbonatites
Abstract: The origin of carbonatites-igneous rocks with more than 50% of carbonate minerals-and whether they originate from a primary mantle source or from recycling of surface materials are still debated. Calcium isotopes have the potential to resolve the origin of carbonatites, since marine carbonates are enriched in the lighter isotopes of Ca compared to the mantle. Here, we report the Ca isotopic compositions for 74 carbonatites and associated silicate rocks from continental and oceanic settings, spanning from 3 billion years ago to the present day, together with O and C isotopic ratios for 37 samples. Calcium-, Mg-, and Fe-rich carbonatites have isotopically lighter Ca than mantle-derived rocks such as basalts and fall within the range of isotopically light Ca from ancient marine carbonates. This signature reflects the composition of the source, which is isotopically light and is consistent with recycling of surface carbonate materials into the mantle.
Abstract:
Carbonatite melts derived from the mantle are enriched in CO2- and H2O-bearing fluids. This melt can metasomatize the peridotitic lithosphere and liberate a considerable amount of CO2. Experimental studies have also shown that a CO2-H2O-rich fluid can form Fe- and Mg-rich carbonate by reacting with olivine. The Sung Valley carbonatite of NE India is related to the Kerguelen plume and is characterized by rare occurrences of olivine. Our study shows that this olivine is resorbed forsterite of xenocrystic nature. This olivine bears inclusions of Fe-rich magnesite. Accessory apatite in the host carbonatite contains CO2-H2O fluid inclusions. Carbon and oxygen isotopic analyses indicate that the carbonatites are primary igneous carbonatites and are devoid of any alteration or fractionation. We envisage that the forsterite is a part of the lithospheric mantle that was reprecipitated in a carbonatite reservoir through dissolution-precipitation. Carbonation of this forsterite, during interaction between the lithospheric mantle and carbonatite melt, formed Fe-rich magnesite. CO2-H2O-rich fluid derived from the carbonatite magma and detected within accessory apatite caused this carbonation. Our study suggests that a significant amount of CO2 degassed from the mantle by carbonatitic magma can become entrapped in the lithosphere by forming Fe- and Mg-rich carbonates.
Geochimica et Cosmochimica Acta, Vol. 282, pp. 297-323.
Africa, East Africa
carbonatites
Abstract: Rare earth element (REE) enrichments in carbonatites are often described as resulting from late magmatic-hydrothermal or supergene processes. However, magmatic pre-enrichment linked to the igneous processes at the origin of carbonatites are likely to contribute to the REE fertilisation. Experimental constraints reveals that immiscibility processes between carbonate and silicate melts can lead to both REE enrichments and depletions in carbonatites making the magmatic processes controlling REE enrichments unclear.
We link REE contents of carbonatites to the magmatic stage at which carbonatites are separated from silicate magma in their course of differentiation. We present results of experiments made at pressure and temperature conditions of alkaline magmas and associated carbonatites differentiation (0.2-1.5 GPa; 725-975?°C; FMQ to FMQ?+?2.5), simultaneously addressing crystal fractionation of alkaline magmas and immiscibility between carbonate (calcio-carbonate type) and silicate melts (nephelinite to phonolite type). The experimental data shows that the degree of differentiation, controlling the chemical composition of alkaline melts, is a key factor ruling the REE concentration of the coexisting immiscible carbonate melts. In order to predict carbonate melt REE enrichments during alkaline magma differentiation, we performed a parameterisation of experimental data on immiscible silicate and carbonate melts, based exclusively on the silica content, the alumina saturation index and the alkali/alkaline-earth elements ratio of silicate melts. This parameterisation is applied to more than 1600 geochemical data of silicate magmas from various alkaline provinces (East African Rift, Canary and Cape Verde Islands) and show that REE concentrations of their potential coeval carbonatite melts can reach concentration ranges similar to those of highly REE enriched carbonatites (?REE?>?30 000?ppm) by immiscibility with phonolitic/phono-trachytic melt compositions, while more primitive alkaline magmas can only be immiscible with carbonatites that are not significantly enriched in REE.
Abstract: The alkaline rocks and carbonatites (ARCs) of the Great Indian Proterozoic belt bear the testimony of tectonic processes operating in the Proterozoic during the continental assembly and breakup of both Columbia and Rodinia. We present a comprehensive review, mainly focused on the petrology, geochemistry, and geochronology of 38 ARCs of Peninsular India, which are mostly concentrated within the Eastern Ghats Mobile Belt and Southern Granulite Terrain. Available geochronologic data reveals three distinct alkaline magmatic phases (2533-2340 Ma, 1510-1242 Ma, 833-572 Ma) and two metamorphic events (950-930 Ma and 570-485 Ma) that correlate with the Grenvillian and Pan-African orogeny events. Whereas clinopyroxene, amphibole, titanite and apatite fractionation seems to have affected the nephelinite, nepheline syenite and syenite, carbonatite is affected by fractionation of calcite, dolomite, ankerite, pyroxene, apatite, magnetite, mica, and pyrochlore. Trace elements and Sr-Nd-Pb-C-O isotopic compositions of these ARCs strongly suggest a subcontinental lithospheric mantle source, that is enriched either by distribution of subducted crustal material or by metasomatism of mantle-derived fluids, for the generation of ARCs. Despite some isotopic variability that can result from crustal contamination, a trend showing enrichment in 87Sr/86Sri (0.702 to 0.708) and depletion in ?Nd(i) (-1.3 to -14.1) over a 2 Gyr duration indicates temporal changes in the lithospheric/asthenospheric source of ARCs, due to periodic enrichment of the source by mantle-derived fluids. ARC generation starts in an intracontinental rift setting (beginning of Wilson cycle). These early-formed ARCs are carriedto 100 km depths during continental collision (termination stage of Wilson cycle) and undergo extensive melting because of renewed rifting along suture zones to form new generation of ARCs.
Abstract: The early Cretaceous (ca. 118-100 Ma) alkaline/ultraalkaline silicate and carbonatite magmatism, exclusively recorded in the Chhotanagpur Gneissic Complex and the Shillong Plateau-Mikir Hills in the eastern/northeastern regions of the Indian Shield, have been reviewed to understand their genetic aspects. These are thought to be associated to the Kerguelen hot spot, active in this region during ca. 118-100 Ma. The existing geochemical, geochronological and isotopic data do not support any definite emplacement order for these diverse groups of magmatic suites. It is likely that they were derived from distinct magma batches with direct or indirect involvement of the Kerguelen plume. The available data suggest their possible derivation from the depleted asthenosphere/lithosphere with negligible contribution from the Kerguelen mantle plume. It is likely that mantle plume provided additional heat necessary to melt the asthenosphere/lithosphere. These data also suggest effects of low-pressure crustal contamination, crystal accumulation and fractional crystallization, rather than mantle-derived heterogeneity. These identified magmatic events together with other known magmatic events such as southeastern Tibet, Abor volcanics, SW Australia and eastern Antarctica during ca. 140-100 Ma could be related to the Kerguelen plume and integral part of the Greater Kerguelen Large Igneous Province, and have possible impact on the breakup of East Gondwanaland.
Abstract: This Tajno alkaline massif (together with the nearby E?k and Pisz intrusions) occurs beneath a thick Mesozoic- Cenozoic sedimentary cover. It has first been recognized by geophysical (magnetic and gravity) investigations, then directly by deep drilling (12 boreholes down to 1800 m). The main rock types identified as clinopyroxenites, syenites, carbonatites, have been cut by later multiphase volcanic /subvolcanic dykes. This massif was characterized as a differentiated ultramafic, alkaline and carbonatite complex, quite comparable to the numerous massifs of the Late Devonian Kola Province of NW Russia [1,2]. Recent geochronological data (U-Pb on zircon from an albitite and Re-Os on pyrrhotite from a carbonatite) indicate that the massif was emplaced at ca. 348 Ma (Early Carboniferous). All the rocks, but more specifically the carbonatites, are enriched in Sr, Ba and LREE, like many carbonatites worldwide but depleted in high field strength elements (Ti, Nb, Ta, Zr). The initial 87Sr/86Sr (0.70370 to 0.70380) and ?Nd(t) (+3.3 to +0.7) isotopic compositions of carbonatites plot in the depleted quadrant of the Nd-Sr diagram, close to “FOcal ZOne” (FOZO) deep mantle domain [1]. The Pb isotopic data (206Pb/204Pb <18.50) do not point to an HIMU (high U/Pb) source. The ranges of C and O stable isotopic compositions of the carbonatites are quite large; some data plot in (or close to) the “Primary Igneous Carbonatite” box while others extend to much higher, typically crustal ?18O and ?13C values.
Abstract: Mineral zoning in fenites around miaskite intrusions of the Vishnevye Mountains complex can be interpreted as a magmatic-replacement zonal metasomatic aureole (in D.S. Korzhinskii’s understanding): the metasomatic transformations of the fenitized gneisses under the effect of deep alkaline fluid eventually resulted in the derivation of nepheline syenite eutectic melt. Based on the P-T-fO2 parameters calculated from the composition of minerals coexisting in the successive zones, isobaric-isothermal fO2-aSiO2 and µNa2O-µAl2O3 sections were constructed with the Perplex program package to model how the fenites interacted with H2O-CO2 fluid (in the Na-K-Al-Si-Ca-Ti-Fe-Mg-O-H-C system). The results indicate that the fluid-rock interaction mechanisms are different in the outer (fenite) and inner (migmatite) parts of the zonal aureole. Its outer portion was dominated by desilication of rocks, which led, first, to quartz disappearance from these rocks and then to an increase in the Al# of the coexisting minerals (biotite and clinopyroxene). In the inner part of the aureole, fenite transformations into biotite-feldspathic metasomatic rocks and nepheline migmatite were triggered by an increase in the Na and Al activities in the system alkaline H2O-CO2 fluid-rock. As a consequence, the metasomatites were progressively enriched in Al2O3 and alkalis, and these transformations led to the development of biotite in equilibrium with K-Na feldspar and calcite at the sacrifice of pyroxene. The further introduction of alkalis led to the melting of the biotite-feldspathic metasomatites and the origin of nepheline migmatites. The simulated model sequence of metasomatic zones that developed when the gneiss was fenitized and geochemical features of the successive zones (differences in the LILE and REE concentrations in the rocks and minerals of the fenitization aureole and the Sm-Nd isotope systematics of the rocks of the alkaline complex) indicate that the source of the fluid responsible for the origin of zonal fenite-miaskite complexes may have been carbonatite, a derivative of mantle magmas, whereas the miaskites were produced by metasomatic transformations of gneisses and subsequent melting under the effect of fluid derived from carbonatite magmas.
Abstract: Carbonates in subducting oceanic slabs can survive beyond slab dehydration and be transferred into the deep mantle. Such deep carbon cycling plays a critical role in generating carbonatitic to alkaline melts. However, whether and how this process has influenced the lithospheric mantle still remains enigmatic. To address these issues, here we provide a detailed petrographic, in-situ chemical and Sr isotopic study on two mantle xenoliths (a wehrlite and a melt pocket-bearing peridotite) entrained by the Changle Miocene basalts from the eastern China. The Changle wehrlite contains carbonate melt inclusions and apatites and is merely enriched in clinopyroxene relative to the lherzolites. The clinopyroxenes are characterized by high (La/Yb)N (4.7-41) and low Ti/Eu (873-2292) ratios and equilibrated with carbonated silicate melt-like compositions. These petrographic and chemical features indicate that the wehrlite was formed by reaction between peridotite and carbonated silicate melts. On the other hand, the Changle melt pocket-bearing peridotite is suggested to have been produced by in-situ melting/breakdown of amphiboles of an amphibole-rich dunite. Low olivine Fo (~89), presence of amphiboles with high (La/Yb)N (~50) and low Ti/Eu (~1070) ratios suggest that such amphibole-rich dunite would have been formed by reaction of peridotite with hydrous alkaline basaltic melts from a carbonated mantle. Our data, combined with previously reported data of the Changle lherzolite xenoliths, unravel a series of mantle metasomatisms by carbonatitic to alkaline melts from carbonated mantle sources. The consistently high 87Sr/86Sr ratios (up to 0.7036) of the clinopyroxenes in both the wehrlites and lherzolites indicate the carbonate components in the mantle sources were derived from the stagnant Pacific slab within the Mantle Transition Zone. This study provides a fresh perspective on the role of deep carbon cycling from subducted oceanic slabs in chemical modification of intracontinental lithospheric mantle through reaction with different types of melts.
Applied Earth Science Transactions of the Institute of Mining and Metallurgy, doi.org/10.1080/ 25726838.2018.1516935 32p. Pdf
Global
carbonatite
Abstract: Most carbonatites were emplaced in continental extensional settings and range in age from Archean to recent. They commonly coexist with alkaline silicate igneous rocks, forming alkaline-carbonatite complexes, but some occur as isolated pipes, sills, dikes, plugs, lava flows, and pyroclastic blankets. Incorporating cone sheets, ring dikes, radial dikes, and fenitisation-type halos into an exploration model and recognising associated alkaline silicate igneous rocks increases the footprint of the target. Undeformed complexes have circular, ring, or crescent-shaped aeromagnetic and radiometric signatures. Carbonatites can be effectively detected by soil, till, and stream-sediment geochemical surveys, as well as biogeochemical and indicator mineral surveys Carbonatites and alkaline-carbonatite complexes are the main sources of rare earth elements (REE) and Nb, and host significant deposits of apatite, vermiculite, Cu, Ti, fluorite, Th, U, natural zirconia, and Fe. Nine per cent of carbonatites and alkaline-carbonatite complexes contain active or historic mines, making them outstanding multi-commodity exploration targets.
Contributions to Mineralogy and Petrology, doi.org/10.1007/ s00410-020-01708 17p. Pdf
Mantle
carbonatite
Abstract: Carbonatite compositions resulting from melting of magnesian calcite?+?olivine?+?clinopyroxene were experimentally determined in the system CaO-MgO-SiO2-CO2-H2O as a function of temperature and bulk H2O contents at 1.0 and 1.5 GPa. The melting reaction and melt compositions were found to be highly sensitive to H-loss or -gain during experiments. We hence designed a new hydrogen-trap technique, which provided sufficient control to obtain consistent results. The nominally dry solidus temperatures at 1.0 and 1.5 GPa are 1225-1250 °C and 1275-1300 °C, respectively. At 1.0 GPa, the solidus temperature decreases with H2O increasing to 3.5 wt% (1025-1050 °C), then remains approximately constant at higher H2O concentrations. Our nominally dry solidus temperatures are up to 140 °C higher than in previous studies that did not take measures to limit hydrogen infiltration and hence suffered from H2O formation in the capsule. The near-solidus anhydrous melts have 7-8 wt% SiO2 and molar Ca/(Ca?+?Mg) of 0.78-0.82 (XCa). Melting temperatures decrease by as much as 200 °C with increasing XH2O in the coexisting COH-fluid. Concomitantly, near-solidus melt compositions change with increasing bulk H2O from siliceous Ca-rich carbonate melts to Mg-rich silico-carbonatites with up to 27.8 wt% SiO2 and 0.55 XCa. The continuous compositional array of Ca-Mg-Si carbonatites demonstrates the efficient suppression of liquid immiscibility in the alkali-free system. Diopside crystallization was found to be sensitive to temperature and bulk water contents, limiting metasomatic transformation of carbonated upper mantle to wehrlite at 1.0-1.5 GPa to?
Science Advances, Vol. 6, 11p. 10.1126/sciadv.abb6570 pdf
Global
carbonatites, REE
Abstract: Carbonatites and associated rocks are the main source of rare earth elements (REEs), metals essential to modern technologies. REE mineralization occurs in hydrothermal assemblages within or near carbonatites, suggesting aqueous transport of REE. We conducted experiments from 1200°C and 1.5 GPa to 200°C and 0.2 GPa using light (La) and heavy (Dy) REE, crystallizing fluorapatite intergrown with calcite through dolomite to ankerite. All experiments contained solutions with anions previously thought to mobilize REE (chloride, fluoride, and carbonate), but REEs were extensively soluble only when alkalis were present. Dysprosium was more soluble than lanthanum when alkali complexed. Addition of silica either traps REE in early crystallizing apatite or negates solubility increases by immobilizing alkalis in silicates. Anionic species such as halogens and carbonates are not sufficient for REE mobility. Additional complexing with alkalis is required for substantial REE transport in and around carbonatites as a precursor for economic grade-mineralization.
Abstract: Early and Late Cretaceous alkaline and alkaline-carbonatitic complexes from southern Brazil are located along the main tectonic lineaments of the South America Platform. Calcium-, magnesium-, and ferrocarbonatites are well represented and frequently associated even in the same complex. Primary carbonates present significant variations in C-O isotopic compositions, which are mainly due to isotope exchange with H2O-CO2-rich hydrothermal fluids, whereas fractional crystallization or liquid immiscibility probably affects the ?18O and ?13C values by no more than 2?‰ Our isotope exchange model implies that the most significant isotopic variations took place in a hydrothermal environment, e.g., in the range 400-80°C, involving fluids with the CO2/H2O ratio ranging from 0.8 to 1. Sr-Nd-Pb isotope systematics highlight heterogeneous mixtures between HIMU and EMI mantle components, similar to the associated alkaline rocks and the flood tholeiites from southern Brazil. In spite of the strong variation shown by C-O isotopes, Sr-Nd-Pb-Os isotopic systematics could be related to an isotopically enriched source where the chemical heterogeneities reflect a depleted mantle "metasomatized" by small-volume melts and fluids rich in incompatible elements. These fluids are expected to have promoted crystallization of K-rich phases in the mantle, which produced a veined network variously enriched in LILE and LREE. The newly formed veins (enriched component) and peridotite matrix (depleted component) underwent a different isotopic evolution with time as reflected by the carbonatites. These conclusions may be extended to the whole Paraná-Etendeka system, where isotopically distinct parent magmas were generated following two main enrichment events of the subcontinental lithospheric mantle at 2.0-1.4 and 1.0-0.5?Ga, respectively, as also supported by Re-Os systematics. The mantle sources preserved the isotopic heterogeneities over a long time, suggesting a nonconvective lithospheric mantle beneath different cratons or intercratonic regions. Overall, the data indicate that the alkaline-carbonatitic magmatism originated from a locally heterogeneous subcontinental mantle.
Abstract: Carbonatites are unusual, carbon-rich magmas thought to form either by the melting of a carbon-rich mantle source or by low-degree partial melting of a carbon-poor (<80 ppm C) mantle followed by protracted differentiation and/or immiscibility. Carbonate-bearing mantle xenoliths from Oldoinyo Lengai (East African Rift), the only active volcano erupting carbonatites, have provided key support for a C-rich mantle source. Here, we report unique microscale O and C isotopic analyses of those carbonates, which are present as interstitial grains in the silicate host lava, veins in the xenoliths, and pseudo-inclusions in olivine xenoliths. The ?18O values vary little, from 19‰ to 29, whereas ?13C values are more variable, ranging from -23‰ to +0.5‰. We show that such carbonate ?18O values result from the low-temperature precipitation of carbonate in equilibrium with meteoric water, rather than under mantle conditions. In this framework, the observed ?13C values can be reproduced by Rayleigh distillation driven by carbonate precipitation and associated degassing. Together with petrological evidence of a physical connection between the three types of carbonates, our isotopic data support the pedogenic formation of carbonates in the studied xenoliths by soil-water percolation and protracted crystallization along xenolith cracks. Our results refute a mechanism of C enrichment in the form of mantle carbonates in the mantle beneath the Natron Lake magmatic province and instead support carbonatite formation by low-degree partial melting of a C-poor mantle and subsequent protracted differentiation of alkaline magmas.
Abstract: Compositional ranges of carbonate melts stable under P-T conditions corresponding to the base of subcontinental lithospheric mantle (SCLM) are limited by alkali-rich near-eutectic compositions. In the present work, we investigated the interaction of such melts with the natural eclogite of Group A. It was found that the interaction is accompanied by decreasing Ca# in the melt (L) and increasing Ca# in garnet (Grt) according to the reaction: 3CaCO3 (L) + Mg3Al2Si3O12 (Grt) = 3MgCO3 (Mgs and/or L) + Ca3Al2Si3O12 (Grt), where Mgs is magnesite. The interaction with the Na-Ca-Mg-Fe carbonate melt increases amount of jadeite component in clinopyroxene (Cpx) consuming Al2O3 from garnet and Na2O from the melt according to the reaction: Na2CO3 (L) + CaCO3 (L) + 2Mg3Al2Si3O12 (Grt) + 2CaMgSi2O6 (Cpx) = 2NaAlSi2O6 (Cpx) + Ca3Al2Si3O12 (Grt) + 2MgCO3 (Mgs, L) + 3Mg2SiO4 (Ol). As a result, garnet and omphacite compositions evolve from eclogite Group A to eclogite Group B. A byproduct of the reaction is olivine (Ol), which may explain the formation of inclusions of “mixed” eclogite (garnet + omphacite) and peridotite (olivine) paragenesis in lithospheric diamonds. The interaction with the K-Ca-Mg-Fe carbonate melt increases the K2O content in clinopyroxene to 0.5-1.2 wt%, while the Na2O content lowers to 0.3 wt%. The following range of carbonatite melt compositions can be in equilibrium with eclogite at the base of SCLM (1100-1200 °C and 6 GPa): 18(Na0.97K0.03)2CO3?82(Ca0.63Mg0.30Fe0.07)CO2-42(Na0.97K0.03)2CO3?58(Ca0.46Mg0.45Fe0.09)CO2. Our results also suggest that the partial melting of ‘dry’ carbonated eclogite, if any, at 1100 °C and 6 GPa yields the formation of a carbonate melt with the following composition (mol%) 25(Na0.96K0.04)2CO3?75(Ca0.64Mg0.31Fe0.05)CO2, corresponding to 18-27 wt% Na2O in the melt on a volatile-free basis.
MDPI Minerals, Vol. 10, 965 doi:103390/min10110965, 26p. Pdf
China
carbonatite, REE
Abstract: The rare earth elements (REEs) have unique and diverse properties that make them function as an “industrial vitamin” and thus, many countries consider them as strategically important resources. China, responsible for more than 60% of the world’s REE production, is one of the REE-rich countries in the world. Most REE (especially light rare earth elements (LREE)) deposits are closely related to carbonatite in China. Such a type of deposit may also contain appreciable amounts of industrially critical metals, such as Nb, Th and Sc. According to the genesis, the carbonatite-related REE deposits can be divided into three types: primary magmatic type, hydrothermal type and carbonatite weathering-crust type. This paper provides an overview of the carbonatite-related endogenetic REE deposits, i.e., primary magmatic type and hydrothermal type. The carbonatite-related endogenetic REE deposits are mainly distributed in continental margin depression or rift belts, e.g., Bayan Obo REE-Nb-Fe deposit, and orogenic belts on the margin of craton such as the Miaoya Nb-REE deposit. The genesis of carbonatite-related endogenetic REE deposits is still debated. It is generally believed that the carbonatite magma is originated from the low-degree partial melting of the mantle. During the evolution process, the carbonatite rocks or dykes rich in REE were formed through the immiscibility of carbonate-silicate magma and fractional crystallization of carbonate minerals from carbonatite magma. The ore-forming elements are mainly sourced from primitive mantle, with possible contribution of crustal materials that carry a large amount of REE. In the magmatic-hydrothermal system, REEs migrate in the form of complexes, and precipitate corresponding to changes of temperature, pressure, pH and composition of the fluids. A simple magmatic evolution process cannot ensure massive enrichment of REE to economic values. Fractional crystallization of carbonate minerals and immiscibility of melts and hydrothermal fluids in the hydrothermal evolution stage play an important role in upgrading the REE mineralization. Future work of experimental petrology will be fundamental to understand the partitioning behaviors of REE in magmatic-hydrothermal system through simulation of the metallogenic geological environment. Applying "comparative metallogeny" methods to investigate both REE fertile and barren carbonatites will enhance the understanding of factors controlling the fertility.
Mineralogy and Petrology, doi.org/10.1007/ s00710-021-00736-0 11p. Pdf
Europe, Norway
carbonatite
Abstract: Carbonatites in the Fen intrusive complex (southern Norway) contain abundant burbankite (confirmed by Raman microspectroscopy) as inclusions in calcite, dolomite and, less commonly, fluorapatite and pyrochlore. Typically the inclusions occur in the core of calcite or dolomite grains relatively unaffected by subsolidus processes, and are associated with Fe-poor dolomite or Sr-rich calcite, respectively. Burbankite does not exceed 30?×?50 ?m in size and is characteristically absent from the peripheral areas of carbonate grains affected by recrystallization or interaction with fluids. Compositionally, the mineral falls within the following range: (Na1.51-2.16Ca0.58-1.21)(Sr1.50-2.42Ca0.28-0.57LREE0.05-0.64Ba0.06-0.41)(CO3)5 and contains low Th, but no detectable Mg, Fe or F (LREE?=?light rare-earth elements: Ce?>?La?>?Nd?>?Pr?>?Sm). Burbankite inclusions at Fen are interpreted as primary and indicative of Na enrichment in their parental carbonatitic magma. Dissociation of burbankite during subsolidus re-equilibration of its host phases with fluids undoubtedly served as one of the sources of LREE for the development of late-stage mineralization in the Fen complex.
Abstract: This article is devoted to the geology of titanium-rich varieties of the Petyayan-Vara rare-earth dolomitic carbonatites in Vuoriyarvi, Northwest Russia. Analogues of these varieties are present in many carbonatite complexes. The aim of this study was to investigate the behavior of high field strength elements during the late stages of carbonatite formation. We conducted a multilateral study of titanium- and niobium-bearing minerals, including a petrographic study, Raman spectroscopy, microprobe determination of chemical composition, and electron backscatter diffraction. Three TiO2-polymorphs (anatase, brookite and rutile) and three pyrochlore group members (hydroxycalcio-, fluorcalcio-, and kenoplumbopyrochlore) were found to coexist in the studied rocks. The formation of these minerals occurred in several stages. First, Nb-poor Ti-oxides were formed in the fluid-permeable zones. The overprinting of this assemblage by residual fluids led to the generation of Nb-rich brookite (the main niobium concentrator in the Petyayan-Vara) and minerals of the pyrochlore group. This process also caused niobium enrichment with of early generations of Ti oxides. Our results indicate abrupt changes in the physicochemical parameters at the late hydro (carbo) thermal stage of the carbonatite formation and high migration capacity of Ti and Nb under these conditions. The metasomatism was accompanied by the separation of these elements.
Abstract: Over recent decades, many experimental studies have focused on the effect of CO2 on phase equilibria and melting behaviour of synthetic eclogites and peridotites as a function of pressure and temperature. These studies have been of fundamental importance to understanding the origin of carbonated magmas varying in composition from carbonatitic to kimberlitic. The occurrence of diamonds in natural rocks is further evidence of the presence of (reduced) carbon in the Earth's interior. The oxygenation of the Earth's interior (i.e. its redox state) through time has strongly influenced the speciation of carbon from the mantle to mantle-derived magmas and, in turn, to the volcanic gases released to the atmosphere. This paper explains how the knowledge of the oxygen fugacity recorded by mantle rocks and determined through the use of appropriate oxy-thermobarometers allows modelling of the speciation of carbon in the mantle, its mobilization in the asthenospheric mantle by redox partial melting, and its sequestration and storage during subduction by redox freezing processes. The effect of a gradual increase of the mantle fO2 on the mobilization of C is here discussed along with the main variables affecting its transport by subduction into the mantle.
Abstract: Three types of carbonatites have been identified based on the analysis of alkaline complexes using geological, petrological, and geochemical data. It has been suggested that for distinguishing carbonatite complexes into these three types, the following criteria should be used: a) the alkalinity type (Na- or K- richer primary magmas) and b) the time when the carbonatite liquid separates from silicate melts in different stages of primary magma differentiation. The first type is genetically related to the kimberlite magmatism and the carbonatite liquid separates from ultramafic magma. The second type is associated with Na-rich alkaline ultramafic rocks and the carbonatite component separates when pyroxenites and ijolites crystallize. The third type is related to K-alkaline complexes and the carbonatite component separates when syenites and granites crystallize. In this article we discuss the geochemical characteristics of all 3 types and outline the difference between them. A model for the formation of carbonatite complexes under the influence of mantle plume processes is given. The geochemistry of C, O, Sr, and Nd isotopes shows that carbonatite complexes, depending on their geotectonic setting (platform surrounding, orogenic areas and rift zones) can originate from three types of mantle sources: depleted mantle, enriched mantle 1 (EM1), and enriched mantle 2 (EM2).
Abstract: Aillikites are carbonate-rich ultramafic lamprophyres often associated with carbonatites. Despite their common field relationships, the petrogenetic links, if any, between aillikites and carbonatites remain controversial. To address this question, this study reports the results of a detailed geochemical and isotopic examination of the Permian Wajilitag aillikites in the northwestern Tarim large igneous province, including bulk-rock major-, trace-element and Sr-Nd isotope compositions, olivine major- and trace-element and (in-situ secondary ion mass spectrometry) oxygen isotope compositions, oxygen isotope data for clinopyroxene separates, and bulk-carbonate C-O isotopic analyses. Olivine in the aillikites occurs in two textural types: (i) microcrysts, 0.3-5?mm; and (ii) macrocrysts, 0.5-2.5?cm. The microcrysts exhibit well-defined linear correlations between Fo (79-89), minor and trace elements (e.g., Ni?=?1304-3764??g/g and Mn?=?1363-3042??g/g). In contrast, the olivine macrocrysts show low Fo79-81, Ni (5.3-442??g/g) and Ca (477-1018??g/g) and very high Mn (3418-5123??g/g) contents, and are displaced from the compositional trend of the microcrysts. The microcrysts are phenocrysts crystallized from the host aillikite magmas. Conversely, the lack of mantle-derived xenoliths in these aillikites suggests that the macrocrysts probably represent cognate crystals (i.e., antecrysts) that formed from earlier, evolved aillikite melts. Olivine phenocrysts in the more primitive aillikite dykes (Dyke 1) have relatively higher Fo82-89 and mantle-like oxygen isotope values, whereas those in the more evolved dykes (Dyke 2 and 3) exhibit lower Fo79-86 and oxygen isotope values that trend toward lower than mantle ?18O values. The decreasing ?13C values of carbonate from Dyke 1 through to Dyke 2 and 3, coupled with the indistinguishable Sr-Nd isotopes of these dykes, suggest that the low ?18O values of olivine phenocrysts in Dyke 2 and 3 resulted from carbonate melt/fluid exsolution from a common progenitor melt. These lines of evidence combined with the overlapping emplacement ages and Sr-Nd isotope compositions of the aillikites and carbonatites in this area suggest that these exsolved carbonate melts probably contributed to the formation of the Tarim carbonatites thus supporting a close petrogenetic relationship between aillikites and carbonatites.
Abstract: The Quaternary carbonatite-nephelinite Kerimasi volcano is located within the Gregory rift in northern Tanzania. It is composed of nephelinitic and carbonatitic pyroclastic rocks, tuffs, tuff breccias and pyroclastic breccias, which contain blocks of different plutonic (predominantly ijolite) and volcanic (predominantly nephelinite) rocks including carbonatites. The plutonic and volcanic carbonatites both contain calcite as the major mineral with variable amounts of magnetite or magnesioferrite, apatite and forsterite. Carbonatites also contain accessory baddeleyite, kerimasite, pyrochlore and calzirtite. Zr and Nb minerals are rarely observed in rock samples, though they are abundant in eluvial deposits of carbonatite tuff/pyroclastic breccias in the Loluni and Kisete craters. Pyrochlore, ideally (CaNa)Nb 2 O 6 F, occurs as octahedral and cubo-octahedral crystals up to 300 ?m in size. Compositionally, pyrochlore from Loluni and Kisete differs. The former is enriched in U (up to 19.4 wt.% UO 2 ), light rare earth elements (up to 8.3 wt.% LREE 2 O 3 ) and Zr (up to 14.4 wt.% ZrO 2 ), and the latter contains elevated Ti (up to 7.3 wt.% TiO 2 ). All the crystals investigated were crystalline, including those with high U content ( a = 10.4152(1) Å for Loluni and a = 10.3763(1) Å for Kisete crystals). They have little or no subsolidus alteration nor low-temperature cation exchange ( A -site vacancy up to 1.5% of the site), and are suitable for single-crystal X-ray diffraction analysis ( R 1 = 0.0206 and 0.0290; for all independent reflections for Loluni and Kisete crystals, respectively). Observed variations in the pyrochlore composition, particularly Zr content, from the Loluni and Kisete craters suggest crystallisation from compositionally different carbonatitic melts. The majority of pyrochlore crystals studied exhibit exceptionally well-preserved oscillatory- and sometimes sector-type zoning. The preferential incorporation of smaller and higher charged elements into more geometrically constrained sites on the growing surfaces explains the formation of the sector zoning. The oscillatory zoning can be rationalised by considering convectional instabilities of carbonatite magmas during their emplacement.
Geochimica et Cosmochimica Acta, Vol. 299, pp. 52-68. pdf
Mantle
carbonatites
Abstract: Carbonatites are unique magmatic rocks that are essentially composed of carbonates, and they usually host a diverse suite of minor and accessory minerals. To provide additional insights on their petrogenesis, triple oxygen isotope analyses were carried out on carbonatites from sixteen localities worldwide in order to assess the behaviour of oxygen isotopes (mass-dependent fractionation) during their formation. The study evaluates the mineralogical differences, i.e., calcite, dolomite, ankerite, and Na-carbonates, and the mode of emplacement (intrusive or extrusive) in the mantle-derived carbonatites to further constrain the triple oxygen isotopic composition (??17O) of the upper mantle. ??17O values in the intrusive calcite carbonatites vary between ?0.003 to ?0.088‰ (n?=?20) and ?0.024 to ?0.085‰ (n?=?5) in the dolomite varieties. We surmise that the magnitude of isotopic fractionation in the different carbonate phases during their formation is similar and thus, the observed variations are independent of mineralogy and may be related to alteration in the rocks. Taking the samples that classify as primary igneous carbonatites altogether, the average ??17O value of the mantle is estimated as ?0.047?±?0.027‰ (1SD, n?=?18) which overlaps those of other mantle rocks, minerals and xenoliths, indicating that the mantle has a relatively homogenous oxygen isotope composition. Two ankerite carbonatites have identical ??17O values as calcite but a few samples, together with pyroclastic tuffs have significantly lower ??17O values (?0.108 to ?0.161‰). This deviation from mantle ??17O signature suggests diagenetic alteration (dissolution and recrystallisation) and mixing of carbonate sources (juvenile and secondary carbonates) which is consistent with the high ?18O and clumped isotope (?47) values recorded in the pyroclastic and ankeritic rocks. In summary, diagenetic alteration driven by fluid-rock interaction at low temperatures, sub-solidus re-equilibration with magmatic waters, and the incorporation of secondary carbonates altogether facilitate the alteration of original isotopic compositions of carbonatites, obliterating their primary mantle signatures.
Abstract: Population growth and technological progress in the last 50 years have resulted in the global demand for mineral resources increasing by 400% since 1970, and it is further expected to almost double by 2050. This context forecasts a never-seen-before market for some specific mineral commodities, termed critical metals. The resource and supply flow of critical metals would be decisive for the economic well-being of economies in near future. Carbonatites are the most prospective host rocks for Rare Earth Elements (REEs), which constitute some of the most important critical elements. This special issue aims to contribute to the debate on understanding the genesis of carbonatites and their prospectivity for REEs (including exploration strategies), by presenting a wide variety of studies on carbonatites from around the globe.
Contributions to Mineralogy and Petrology, Vol. 176, 34 21p. Pdf
Mantle
carbonatites
Abstract: The reactions between pyroxenes and carbonates have been studied in the CaMgSi2O6 + MgCO3 (Di + 2Mgs), CaMgSi2O6 + NaAlSi2O6 + 2MgCO3 (Di + Jd + 2Mgs), CaMgSi2O6 + Na2Mg(CO3)2 (Di + Eit), and CaMgSi2O6 + K2Mg(CO3)2 (Di + K2Mg) systems at pressures of 3.0 and 4.5 GPa in the temperature range 850-1300 °C and compared with those established previously at 6.0 GPa. The Di + 2Mgs solidus locates at 1220 °C / 3 GPa and 1400 °C / 6 GPa. Near-solidus melt is carbonatitic with SiO2 < 4 wt% and Ca# 56. The Di + Jd + 2Mgs solidus locates near 1050 °C at 3 GPa, rises to 1200 °C at 4.5 GPa, and 1350 °C at 6 GPa. The solidus is controlled by the reaction: 4NaAlSi2O6.2CaMgSi2O6 (clinopyroxene) + 12MgCO3 (magnesite) = 2MgAl2SiO6.5Mg2Si2O6 (clinopyroxene) + 2[Na2CO3.CaCO3.MgCO3] (liquid) + 6CO2. As pressure increases, the composition of solidus melt evolves from 26Na2CO3?74Ca0.58Mg0.42CO3 at 3 GPa to 10Na2CO3?90Ca0.50Mg0.50CO3 at 6 GPa. Melting in the Di + Eit and Di + K2Mg systems is controlled by the reactions: CaMgSi2O6 (clinopyroxene) + 2(Na or K)2 Mg(CO3)2 (eitelite) = Mg2Si2O6 (orthopyroxene) + 2[(Na or K)2CO3?Ca0.5Mg0.5CO3] (liquid). The Di + Eit solidus locates at 925 °C / 3 GPa and 1100 °C / 6 GPa, whereas the Di + K2Mg solidus is located at 50 °C lower. The resulting melts have alkali-rich carbonate compositions, (Na or K)2CO3?Ca0.4Mg0.6CO3. The obtained results suggest that most carbonates belong to the ultramafic suite would survive during subduction into the deep mantle and experience partial melting involving alkaline carbonates, eitelite or K2Mg(CO3)2, under geothermal conditions of the subcontinental lithospheric mantle (35-40 mW/m2). On the other hand, the jadeite component in clinopyroxene would be an important fluxing agent responsible for the partial melting of carbonated rocks under the rift margin geotherm (60 mW/m2) at a depth of about 100 km, yielding the formation of Na-carbonatite melt.
Mineralium Deposita, 10.1007/s00126 -021-01055-2 18p. Pdf
China
carbonatites
Abstract: The Huangshui'an deposit located in East Qinling (China) is an unusual case of a Si-rich carbonatite hosting economic Mo and minor Pb and REE mineralization. The role of mantle-sourced carbonatite melts and fluids in the formation of the Mo mineralization remains poorly understood. Our integrated study based on field geology, petrography, microthermometry, and LA-ICP-MS analysis of single fluid inclusions, and noble gas isotopes of pyrite permits to reconstruct the source characteristics, the magmatic-hydrothermal evolution of the carbonatitic fluids, and their controls on Mo mineralization. Fluid inclusions hosted in calcite in the carbonatite dikes have the highest concentrations of Mo (9.9-62 ppm), Ce (820-9700 ppm), Pb (1800-19500 ppm), and Zn (570-5800 ppm) and represent the least modified hydrothermal fluid derived from the carbonatite melt. Fluid inclusions hosted in calcite (Cal) and quartz (Qz2 and Qz3) of the stage I carbonatite dikes have different metal concentrations, suggesting that they formed from two distinct end member fluids. The FIA in calcite represent fluid A evolved from carbonatite melt with relatively high-ore metal concentrations, and those in quartz characterize fluid B having a crustal signature due to metasomatic reactions with the wall rocks. The FIA in quartz (Qz1) within the altered wall rock have overlapping elemental concentrations with those of massive quartz (Qz2) and vuggy quartz (Qz3) in carbonatite. This suggests that the volumetrically significant quartz in the Huangshui'an carbonatite has been formed by the introduction of Si by fluid B. The positive correlations between Rb, B, Al, Cl, and Sr in stage II fluid inclusions in late fluorite + quartz + calcite veins indicate that this late mineralization formed from the mixing of primary hydrothermal fluid B with meteoric water. The He-Ar isotope data, in combination with available C-O-Sr-Nd-Pb isotope data, constrain the carbonatite source as an enriched mantle source modified by contributions from crustal material which was probably the fertile lower crust in the region. This distinct source facilitated the enrichment in Mo, REE, and Pb in the primary carbonatite magma. The carbonatite magmatism and Mo mineralization at 209.5-207 Ma occurred in the regional-scale extensional setting at the postcollision stage of the Qinling Orogenic Belt.
Journal of Asian Earth Sciences, Vol. 214, 104773, 9p. Pdf
Africa, Sudan
carbonatites
Abstract: Carbonatite from the Arabian-Nubian Shield of Sudan occurs as dykes in the Nuba Mountains. It is composed of calcite with some feldspars, quartz and fluorite. CaO is the major constituent in this carbonatite and accordingly, it is classified as calico-carbonatite. The studied carbonatite shows exceptionally high concentrations of SrO (4.4 to 5.9 wt%). Ba, Pb and Y occur in relatively higher concentrations compared to other trace elements. Concentration of rare earth elements (?REEs) is relatively low (average 1550 ppm) compared to many primary igneous carbonatites. The chondrite-normalized REE patterns display higher light rare earth elements (LREEs) compared to heavy rare earth elements (HREEs) with slight negative Ce/Ce* and Eu/Eu* anomalies. The ?18OV-SMOW values range between 7.48 and 10.05‰, while ?13CV-PDB values vary from ?6.24 to ?7.38‰, which is close to the primary carbonatites values. Occurrence of carbonatite as dykes with cumulate and triple junction textures, plot of the carbonatite in the true carbonatite fields of the Ba-Sr and Ba + Sr-REE + Y diagrams, igneous-derived ?13CV-PDB and ?18OV-SMOW values and high (La/Yb)N ratios indicate its primary igneous origin. The strong positive correlation between REEs and Sr suggests the occurrence of these elements as secondary strontianite, which was confirmed by SEM and EDX analyses. This might indicate that the enrichment of REEs and Sr in the studied carbonatite is not from the primary magma and most probably took place during a sub-solidus metasomatic process after the carbonatite emplacement.
Abstract: The Yilgarn Craton and its northern margin contain a variety of petrogenetically poorly defined small-volume alkaline ultramafic rocks of Proterozoic age. This study documents the petrography, mineral and bulk-rock geochemistry and Nd-Hf-Sr-Pb isotope compositions of a selected suite of these rocks. They comprise ~2.03-2.06 Ga ultramafic lamprophyres (UML) and carbonatites from the Eastern Goldfields Superterrane (EGS), ~0.86 Ga UML from Norseman, and orangeites from the Earaheedy Basin, including samples from Jewill (~1.3 Ga), Bulljah (~1.4 Ga) and Nabberu (~1.8-1.9 Ga). The Proterozoic UML and carbonatites from the EGS and Norseman display very consistent chondritic to superchondritic Nd-Hf isotope compositions and trace-element ratios similar to modern OIBs, which are indicative of a common mantle source across this wide alkaline province. These Nd-Hf isotope compositions overlap with the evolution trends of global kimberlites through time, thus suggesting that this mantle source could be deep and ancient as that proposed for kimberlites. Conversely, the orangeites located in the Earaheedy Basin along the northern margin of the Yilgarn Craton display trace element signatures similar to subduction-related calc-alkaline magmas. Taken together with their highly enriched Sr-Nd-Hf isotope compositions, these characteristics indicate an ancient lithospheric mantle source, which was probably metasomatised by subduction-related fluids. As the ages of the Bulljah and Jewill orangeites overlap with the breakup of the Columbia supercontinent, it is proposed that orangeite magmatism was triggered by changes in plate stress conditions associated with this event. This study provides a comprehensive picture of the genesis of Proterozoic alkaline magmatism in the Yilgarn Craton, highlighting the complex tectono-magmatic evolution of this lithospheric block after its assembly in the Archean.
Geochemical Perspectives Letters, Vol. 17, pp. 11-15. pdf
Mantle
carbonatites
Abstract: Carbonatite, an unusual carbonate-rich igneous rock, is known to be sourced from the mantle which provides insights into mantle-to-crust carbon transfer. To constrain further the Ca isotopic composition of carbonatites, investigate the behaviour of Ca isotopes during their evolution, and constrain whether recycled carbonates are involved in their source regions, we report ?44/42Ca for 47 worldwide carbonatite and associated silicate rocks using a refined analytical protocol. Our results show that primary carbonatite and associated silicate rocks are rather homogeneous in Ca isotope compositions that are comparable to ?44/42Ca values of basalts, while non-primary carbonatites show detectable ?44/42Ca variations that are correlated to ?13C values. Our finding suggests that Ca isotopes fractionate during late stages of carbonatite evolution, making it a useful tool in the study of carbonatite evolution. The finding also implies that carbonatite is sourced from a mantle source without requiring the involvement of recycled carbonates.
Ore Geology Reviews, doi.org/10.1016/j.oregeorev.2021.104310, 50p. Pdf
China
carbonatite, REE
Abstract: The Huayangchuan deposit in the North Qinling alkaline province of Central China is a unique carbonatite-hosted giant U-Nb-REE polymetallic deposit. The mineralization is characterized by the presence of betafite, monazite, and allanite as the main ore minerals, but also exhibit relatively high budgets of heavy rare earth elements (HREE = Gd-Lu and Y). The origin of carbonatites has long been controversial, thus hindering our understanding of the genesis of the deposit. Here, we conducted an in-situ trace elemental, Sr-Nd isotopic, and bulk C-O isotopic analyses of multi-type calcites in the deposit. Two principal types (Cal-I and Cal-II), including three sub-types (Cal-I-1, Cal-I-2 and Cal-I-3) of calcites were identified based on crosscutting relationships and calcite textures. Texturally, Cal-I calcites in carbonatites display cumulates with the grain size decreasing from early coarse- (Cal-I-1) to medium- (Cal-I-2) and late fine-grained (Cal-I-3), whereas Cal-II calcites coexist with zeolite displaying zeolite-calcite veinlets. Geochemically, Cal-I calcites contain relatively high REE(Y) (151-2296 ppm), Sr (4947-9566 ppm) and Na (28.6-390 ppm) contents, characterized by right- to left-inclined flat distribution patterns [(La/Yb)N=0.2-4.2] with enrichment of HREE(Y) (136-774 ppm), whereas Cal-II calcites display low REE, Sr and undetectable Na contents, characterized by a right-inclined distribution pattern [(La/Yb)N=13.5, n=16]. The U-Nb-REE mineralization, accompanied with intense and extensive fenitization and biotitization, is mainly associated with the Cal-I-3 calcites which show flat to relatively left-inclined flat REE distribution patterns [(La/Yb)N=0.2-1.0]. Isotopic results show that Cal-I calcites with mantle signatures are primarily igneous in origin, whereas Cal-II are hydrothermal, postdating the U-Nb-REE mineralization. Cal-I calcites (Cal-I-1, Cal-I-2 and Cal-I-3) from mineralized and unmineralized carbonatites, displayed regular changes in REE, Na and Sr contents, but similar trace element distribution patterns and Sr-Nd-C-O isotopic signatures, indicating that these carbonatites originated from the same enriched mantle (EM1) source by low-degree partial melting of HREE-rich carbonated eclogites related to recycled marine sediments. The combination of trace elements and Sr-Nd isotopic composition of calcites further revealed that these carbonatites have undergone highly differentiated evolution. Such differentiation is conducive to the enrichment of ore-forming elements (U-Nb-REE) in the late magmatic-hydrothermal stages owing to extensive ore-forming fluids exsolved from carbonatitic melts. The massive precipitation of the U-Nb-REE minerals from ore-forming hydrothermal fluids may have been triggered by intense fluid-rock reactions indicated by extensive and intense fenitization and biotitization. Therefore, the Huayangchuan carbonatite-related U-Nb-REE deposit may have formed by a combination of processes involving recycled U-Nb-REE-rich marine sediments in the source, differentiation of the produced carbonatitic magmas, and subsequent exsolution of U-Nb-REE-rich fluids that precipitated ore minerals through reactions with wall rocks under the transitional tectonic regime from compression to extension at the end of Late Triassic.
Geochemical Perspectives Letters, Vol. 18, pp. 11-15. pdf
Russia, Siberia
carbonatite
Abstract: For the last two decades, the end of the voluminous phase of eruptions of the Siberian Traps large igneous province has been constrained by a U-Pb date of discordant baddeleyite collected from the Guli carbonatite intrusion with the assumption that the discordance resulted from unsupported 207Pb. In this study we have re-analysed baddeleyite from the same intrusion and found two types of discordance: (1) due to 207Pb-excess, and (2) radiogenic lead loss from high U mineral inclusions. The former implies that baddeleyite is an efficient scavenger of protactinium during crystallisation, leaving the magma depleted in this element. Together with a published high precision U-Pb date of 252.24?±?0.08 Ma for the Arydzhansky Formation, our new date of 250.33?±?0.38 Ma for the Guli carbonatite constrains the total duration of the voluminous eruptions of the Siberian Traps LIP at 1.91?±?0.38 million years. The lower intercept of the (231Pa)/(235U) corrected discordance line yields a date of 129.2?±?65.0 Ma, which points to the widespread Early Cretaceous rifting in East and Central Asia.
Abstract: The Arbarastakh ultramafic carbonatite complex is located in the southwestern part of the Siberian Craton and contains ore-bearing carbonatites and phoscorites with Zr-Nb-REE mineralization. Based on the modal composition, textural features, and chemical compositions of minerals, the phoscorites from Arbarastakh can be subdivided into two groups: FOS 1 and FOS 2. FOS 1 contains the primary minerals olivine, magnetite with isomorphic Ti impurities, phlogopite replaced by tetraferriphlogopite along the rims, and apatite poorly enriched in REE. Baddeleyite predominates among the accessory minerals in FOS 1. Zirconolite enriched with REE and Nb and pyrochlore are found in smaller quantities. FOS 2 has a similar mineral composition but contains much less olivine, magnetite is enriched in Mg, and the phlogopite is enriched in Ba and Al. Of the accessory minerals, pyrochlore predominates and is enriched in Ta, Th, and U; baddeleyite is subordinate and enriched in Nb. Chemical and textural differences suggest that the phoscorites were formed by the sequential introduction of different portions of the melt. The melt that formed the FOS 1 was enriched in Zr and REE relative to the FOS 2 melt; the melt that formed the FOS 2 was enriched in Al, Ba, Nb, Ta, Th, U, and, to a lesser extent, Sr.
Journal of the Geological Society , https://doi.org/10.1144/jgs2020-171
Europe, Turkey
carbonatite
Abstract: Unusual carbonate dykes, which have a thickness of up to 4 m, cross-cut the amphibolites from the high-grade metamorphic rocks in the Armutlu Peninsula (NW Turkey). They are described as carbonatites on the basis of their petrographic, geochemical and isotope-geochemical characteristics. The carbonatites, which commonly show equigranular texture, are composed of calcite and clinopyroxene with other minor phases of plagioclase, mica, garnet, K-feldspar, quartz, epidote, titanite and opaque minerals. They contain abundant xenoliths of pyroxenite and amphibolite. The geochemical characteristics of the carbonatites are significantly different from those of mantle-derived carbonatites. They have remarkably low incompatible element (e.g. Ba, Th, Nb) and total REE (11-91 ppm) contents compared with mantle-derived carbonatites. The high 87Sr/86Sr(i) (0.70797-0.70924) and low ?Nd(t) (?8.08 to ?9.57) of the carbonatites confirm that they were derived from the continental crust rather than from a mantle source. Mica from carbonatite was dated by the 40Ar/39Ar method, yielding a Late Jurassic-Early Cretaceous age (148-137 Ma). This is significantly younger than the age of adjacent amphibolites (Upper Triassic). All data from field studies, as well as petrographic, geochemical and geochronological observations, suggest that these carbonatites were formed from anatectic melting of a carbonated source area in the continental crust.
International Journal of earth Sciences, Vol. 110, pp. 1593-1609.
Canada, Ontario
carbonatite
Abstract: Igneous intrusions are important to the thermomechanical evolution of continents because they inject heat into their relatively cold host rocks, and potentially change the distribution of radiogenic heat production and thermal properties within the crust. To explore one aspect of the complex evolution of the continental crust, this paper investigates the local thermal effects of two intrusive rock types (carbonatites and anorthosites) on the Archean Superior Province of the Canadian shield. We provide new data on their contrasting properties: rock density near 298 K, thermal diffusivity, and heat capacity up to 800 K (which altogether yield thermal conductivity), plus radiogenic element contents. The volumetrically small carbonatites have widely varying radiogenic heat production (2–56 µW m?3) and moderate thermal conductivity at 298 K (~?1 to 4 W m?1 K?1) which decreases with temperature. The massive Shawmere anorthosite has nearly negligible radiogenic heat production (
Abstract: Neoarchean intraplate granitoid (2.61 Ga) and carbonatite magmatism are established in the Kursk block of Sarmatia in close spatial association. Alkaline pyroxenites, carbonatites, and syenites of the Dubravinskii complex are represented by two relatively large intrusions and a few small plutons. They underwent amphibolite facies metamorphism at about 2.07 Ga. The age of alkaline-carbonatite magmatism is 2.59 Ga according to SIMS isotope dating of zircon from syenites. The close age and spatial conjugation allow the Dubravinskii carbonatite complex to be considered to have formed in intraplate conditions. The mantle plume upwelling caused metasomatic alteration and consequent partial melting of the sublithospheric mantle and intrusion of enriched magmas into the crust. Contamination of alkaline mantle melts in the crust by Archean TTGs caused the formation of syenites melts in the form of dykes that cutting through pyroxenites and carbonatites.
Australian Journal of Earth Sciences, Vol. 66, 7, pp. 1041-1062.
China
carbonatite
Abstract: During the past 50 years, many geological and ore-deposit investigations have led to the discovery of the Fe-P-(Ti)-oxide deposits associated with mafic-ultramafic-carbonatite complexes in the Kuluketage block, northeastern Tarim Craton. In this paper, we discuss the genetic and ore-forming ages, tectonic setting, and the genesis of these deposits (Kawuliuke, Qieganbulake and Duosike). LA-ICP-MS zircon U-Pb dating yielded a weighted mean 206Pb/238U ages of 811?±?5?Ma, 811?±?4?Ma, and 840?±?5?Ma for Kawuliuke ore-bearing pyroxenite, Qieganbulake gabbro and Duosike ore-bearing pyroxenite, respectively. The CL images of the Kawuliuke apatite grains show core-rim structure, suggesting multi-phase crystallisation, whereas the apatite grains from Qieganbulake and Dusike deposits do not show any core-rim texture, suggesting a single-stage crystallisation. LA-ICP-MS apatite 207Pb-corrected U-Pb dating provided weighted mean 206Pb/238U ages of 814?±?21?Ma and 771?±?8?Ma for the Kawuliuke ores, and 810?±?7?Ma and 841?±?7?Ma for Qieganbulake and Duosike ores, respectively. The core-rim texture in apatite by CL imaging as well as two different ore-forming ages in the core and rim of the apatite indicate two metallogenic events for the Kawuliuke deposit. The first metallogenic period was magmatic in origin, and the second period was hydrothermal in origin. The initial ore-forming age of the Kawuliuke Fe-P-Ti mineralisation was ca 814?Ma and the second one was ca 771?Ma. On the other hand, the ore-forming ages of the Qieganbulake and Duosike deposits were ca 810?Ma and ca 841?Ma, respectively. Qieganbulake and Duosike deposits were of magmatic origin. Combined with previous geochronological data and the research on the tectonic background, we infer that the Kawuliuke, Qieganbulake and Duosike Fe-P-(Ti)-oxide deposits were formed in a subduction-related tectonic setting and were the product of subduction-related magmatism.
Abstract: The study reports petrography, bulk major and trace element compositions of lamprophyric Devonian dykes in three areas of the Kola Alkaline Carbonatite Province (N Europe). Dykes in one of these areas, Kandalaksha, are not associated with a massif, while dykes in Kandaguba and Turij Mys occur adjacent (< 5 km) to coeval central multiphase ultramafic alkaline?carbonatitic massifs. Kandalaksha dyke series consists of aillikites - phlogopite carbonatites and monchiquites. Kandaguba dykes range from monchiquites to nephelinites and phonolites; Turij Mys dykes represent alnöites, monchiquites, foidites, turjaites and carbonatites. Some dykes show extreme mineralogical and textural heterogeneity and layering we ascribe to fluid separation and crystal cumulation. Melt evolution of the dykes was modelled with Rhyolite-MELTS and compared with the observed order and products of the crystallization. Our results suggest that the studied rocks were related by fractional crystallization and liquid immiscibility. Primitive melts of aillikites or olivine melanephelinites initially evolved at P = 1.5-0.8 GPa without a SiO2 increase due to abundant clinopyroxene crystallization controlled by the CO2-rich fluid. At 1-1.1 GPa the Turij Mys melts separated immiscible carbonatite melt, which subsequently exsolved late carbonate-rich fluids extremely rich in trace elements. Kandaguba and Turij Mys melts continued to fractionate at lower pressures in the presence of hydrous fluid to the more evolved nephelinite and phonolite melts. The studied dykes highlight the critical role of the parent magma chamber in crystal fractionation and magma diversification. The Kandalaksha dykes may represent a carbonatite - ultramafic lamprophyre association, which fractionated at 45-20 km in narrow dykes on ascent to the surface and could not get more evolved than monchiquite. In contrast, connections of Kandaguba and Turij Mys dykes to their massif magma chambers ensured the sufficient time for fractionation, ascent and a polybaric evolution. This longevity generated more evolved rock types with the higher alkalinity and an immiscible separation of carbonatites.
Abstract: Alkaline igneous rocks and carbonatites are compositionally and mineralogically the most diverse of all igneous rocks and, apart from their scientific interest, are of major, and growing, economic importance. They are valuable repositories of certain metals and commodities - the only significant sources of some of them - and include Nb, the rare earths, Cu, V, diamond, phosphate, vermiculite, bauxite, raw materials for the manufacture of ceramics, and potentially Th and U. The economic potential of these rocks is now widely appreciated, particularly since the commencement of the mining of the Palabora carbonatite for copper and a host of valuable by-products. Similarly, the crucial economic dominance of rare earth production from carbonatite-related occurrences in China has stimulated the world-wide hunt for related deposits. This volume describes and provides ready access to the literature for all known occurrences of alkaline igneous rocks and carbonatites of Antarctica, Asia and Europe (excluding the former USSR), Australasia and the oceanic islands. More than 1200 occurrences from 59 countries are outlined, together with those of 57 oceanic islands and island groups. The descriptions include geographical coordinates and information on general geology, rock types, petrography, mineralogy, age and economic aspects, with the principal references cited. A brief description is also given of alkaline minerals in meteorites and of alkaline rocks on Mars and Venus. There are 429 geological and distribution maps and a locality index. As has been demonstrated by the three earlier volumes, Alkaline Rocks Part 4 is likely to be of considerable interest to mineral exploration companies, as there are no comprehensive published reviews of the economic aspects of the alkaline rocks. It will also interest research scientists in the fields of igneous petrology and volcanology, and geologists concerned with the regional distribution of igneous rocks and their geodynamic relationships.
Abstract: Carbonatites are rare volcanic rocks whose carbon/oxygen isotope signatures point towards a mantle origin. However there is still debate on the role of processes such as partial melting or the recycling of sediments for their generation. Carbonatite quadruple sulfur isotope measurements should be useful for deciphering the imprints of Earth’s earliest atmosphere and microbial cycling, two processes isotopically characterized by different slopes in a ?33S-?36S diagram, and thus help to better understand the origin of carbonatites, and the possiblity of sedimentary precursors, in greater detail. We report here multiple sulfur data for a wide range of carbonatite samples: 4 continents, from today to 3Ga, oceanic and continental settings. 80 measurements from 18 localities yielded sulfur in sulfides between 0 to 1wt%, with ?34S ranging from -20‰ to +10‰. The record through time seems to correlate with the sedimentary record albeit with some delay. ?33S varies between -0.1 to 0.4‰. Most of the samples display unequivocal mass-dependent fractionation, characteristic of the sedimentary record. A few samples show mass-independent fractionation. ?33S shows a temporal variation from near zero at 3Ga to positive values until 500Ma and then a broadening with both positive and negative values. This is interpreted to reflect the assimilation of surface derived sulfur in the source of carbonatites. The mixing with mantle sulfur narrows the amplitude of the variation and a crustal imprint could blur the signal as well. However coupled ?34S-?33S point toward two different stages in the sulfur isotopic signature: a long recycling before 900Ma and a much shorter residence time, on the order of 300 Myrs, after. This could be linked with a preferential recycling of sulfides in the early time and a recycling of both sulfides and sulfates later on.
Contributions to Mineralogy and Petrology, Vol. 176, 10, 15p. Pdf
Mantle
carbonatite
Abstract: The depth of melting beneath mid-ocean ridges (MORs) controls the melt composition as well as its rheology. Since mantle melting below MORs is the main mechanism of mantle degassing and CO2 emission into the atmosphere and oceans, there is an increasing interest in understanding the sub-ridge mantle conditions leading to its melting. Here we study the effect of oxygen fugacity on melting of carbonate-bearing peridotite at 3 GPa. Two metal—metal-oxide buffers (RRO and IW) were used to influence the fO2 of the experimental charge. Using Ir-Fe alloy sliding redox sensors, the fO2 of the two sets of experiments was measured. The solidus at IW?+?4.5 was found to be at 950 °C, while at IW?+?2.5 melting initiated at 1150 °C. In both sets of experiments, near-solidus carbonatitic melts evolved to carbon-bearing silicate melts with increasing temperature. This study together with previous studies suggest that increasing fO2 of a carbonate-bearing peridotite results in lowering of its melting temperature. Extrapolating these solidi to higher pressures results in initiation of melting of a relatively oxidizing mantle at?~?430 km while melting of a more reduced mantle will initiate at depth of?~?320 km. Very low velocity anomalies in the sub-ridge mantle at depth may reflect the initiation of melting, triggered by the presence of carbonate in the mantle at 1-2 log units below QFM.
Journal of African Earth Sciences, Vol. 185, 104414, 19p. Pdf
Africa, South Africa
carbonatite
Abstract: The Salpeterkop volcano is spatially part of the Sutherland Suite of alkaline rocks in the Northern Cape. It is one of the best preserved volcanoes in South Africa with part of the tuff ring still intact, remnants of the ejecta mantle outside the crater still preserved, and is host to epiclastic rocks, including ash and lapillistone and water lain sediments, inside the crater. New dates from apatites and phlogopites from Salpeterkop suggest an age close to 70 Ma. This Upper Cretaceous age is supported by the silicified wood found within the epiclastic sediments. Its relationship to the alkaline rocks in this cluster is not entirely clear but field evidence suggests that initial olivine melilitites and ultramafic bodies were followed by the main eruption that produced Salpeterkop. Clear igneous components in the associated breccias and pyroclastics are rare but indicate that this volcano was linked to an alkaline (trachytic) intrusion driven by phreatic magmatism. This is further highlighted by the presence of (nepheline?) syenite xenoliths in some carbonatite breccias and dykes that are part of the later carbonatites with its associated hydrothermal alteration products. Although the carbonatites are largely late-stage, there is evidence of earlier carbonatite activity from a precursor carbonatite dyke that has off-set an olivine melilitite dyke. Relatively unaltered pyroclastics, associated with two vents, northeast and northwest of the crater respectively, represent the final phase of this volcanic centre. Finally, the preservation of the Salpeterkop crater and its associated volcaniclastics highlights the change of intense landscape denudation, that ensued from Gondwana break-up to the end of the Cretaceous, to a period of drastically reduced erosion rates during the Cenozoic Era.
Abstract: Although a mantle origin of carbonatites has long been advocated, a few carbonatite bodies with crustal fingerprints have been identified. The Eppawala carbonatites in Sri Lanka are more similar to orogenic carbonatites than those formed in stable cratons and within plate rifts. They occur within the Pan-African orogenic belt and have a formation age of ca. 475 Ma newly obtained in this study with no contemporary mantle-related magmatism. These carbonatites have higher (87Sr/86Sr)i ratios (0•70479-0•70524) and more enriched Nd and Hf isotopic compositions than carbonatites reported in other parts of the world. Model ages (1•3-2•0 Ga) of both Nd and Hf isotopes [apatite ?Nd(t)?=??9•2 to ?4•7; rutile ?Hf(t)?=??22•0 to ?8•02] are in the age range of metamorphic basement in Sri Lanka, and the carbon and oxygen isotopic compositions (?13CPDB?=??2•36 to ?1•71; ?18OSMOW?=?13•91-15•13) lie between those of mantle-derived carbonatites and marble. These crustal signatures are compatible with the chemistry of accessory minerals in the carbonatites, such as Ni-free olivine and Al- and Cr-poor rutile. Modeling results demonstrate that the Eppawala carbonatite magmas originated from a mixture of basement gneisses and marbles, probably during regional metamorphism. This interpretation is supported by the occurrence of the carbonatites along, or near, the axes of synforms and antiforms where granitic gneiss and marble are exposed. Therefore, we propose that the Eppawala carbonatites constitute another rare example of a carbonatitic magma that was derived from melting of a sedimentary carbonate protolith. Our findings suggest that other orogenic carbonatites with similar features should be re-examined to re-evaluate their origin.
Abstract: A preliminary field evaluation of rare earth elements (REE) mineralization in the Squalus Lake Alkaline Complex (SLAC) was undertaken for 9 days in the summer of 2021. The focus of the fieldwork was on identifying and characterizing sources of historical anomalous REE assays contained in assessment and government survey reports. The Squalus Lake Alkaline Complex is a syenite-dominated concentric Proterozoic intrusion within the Archean Morose Granite. The intrusion is situated along the Phoenix Fault - a major NNE-trending crustal structure. The core of the complex coincides with a regional-scale magnetic high. These features suggest a classic concentric lithological zonation of the complex with a syenite rim and a carbonatite core. The magnetic anomaly is probably associated with a magnetite-rich ferro-carbonatite phase that typically occurs in the cores of most zoned alkaline/carbonatite complexes. During the fieldwork, evidence for several carbonatite dykes were observed, both in outcrop and in angular float. The dykes are probably emanating from a carbonatite intrusion at the core of the complex, which is interpreted to be underneath Squalus Lake. Sites with reported anomalies were visited and re-sampled. An effort was also made at sampling the different lithological units that were observed. Historically anomalous samples (obtained from the previous prospector) have been re-analyzed to confirm the results and attempts are being made at characterizing the potentials of the various host units. In classic alkaline/carbonatite complex models, high grade REE mineralization is generally associated with the younger ferro-carbonatite phase at the core of the complex. High grade REE mineralization tends to occur in late ferro-carbonatite phases. Previously collected ground-magnetic surveys provide strong discrete targets for the locations of the theorized ferro-carbonatite core, which is a primary target for REE endowment. Curiously, the ~2180 Ma age of the SLAC is similar to the age of several other alkaline complexes in the Slave structural province, including the Big Spruce Lake Complex (~2188Ma) and the Grace Lake Granite (~2176Ma). The Grace Lake Granite is part of the Blatchford Lake Intrusive Suite, which is host to Canada's first REE mine at the Nechalacho Deposit at Thor Lake.
Journal of the Geological Society of India, Vol.98, pp. 35-40.
India
carbonatite
Abstract: A new carbonatite body has been discovered from Gundlupet area, western Dharwar craton, southern India which is located at juncture of major shear zones namely, Kollegal shear zone to the east, Sargur shear zone to the west and Moyar shear zone to the south. The carbonatite and associated syenite have intruded into the peninsular gneissic complex. The southern margin of the syenite has a tectonic contact with the peninsular gneissic complex suggesting their emplacement is related to the splay shear of Moyar shear zone. The Gundlupet carbonatite is dominantly sövite with minor beforsite and iron rich carbonatite which are associated with phenocrystic magnetite, apatite, amphibole, pyroxene and monazite. Fenitisation is observed in local scale along the contact of carbonatite and syenite where metasomatic alterations took place to give rise to alkali amphibole and pyroxene rich rock. Geochemically, the carbonatite is characterised by high CaO content (48.86%-51.80%), P2O5 (0.35%-3.23%) and low SiO2 (3.09%-5.30%). The high Sr (5750-13445 ppm) content and low Ni, Cr, Zn and Cu content indicates that the melt has undergone some degree of fractionation before crystallization. Gundlupet carbonatite is enriched in LREE with values ranging from 5666 ppm to 7530 ppm and average LREE of 6248 ppm.
International Journal of Earth Science, Vol. 111, 2, 16p.
Europe, Germany
carbonatite
Abstract: The accessories perovskite, pyrochlore, zirconolite, calzirtite and melanite from carbonatites and carbonate-rich foidites from the Kaiserstuhl are variously suited for the in situ determination of their U-Pb ages and Sr, Nd- and Hf-isotope ratios by LA-ICP-MS. The 143Nd/144Nd ratios may be determined precisely in all five phases, the 176Hf/177Hf ratios only in calzirtite and the 87Sr/86Sr ratios in perovskites and pyrochlores. The carbonatites and carbonate-rich foidites belong to one of the three magmatic groups that Schleicher et al. (1990) distinguished in the Kaiserstuhl on the basis of their Sr, Nd and Pb isotope ratios. Tephrites, phonolites and essexites (nepheline monzogabbros) form the second and limburgites (nepheline basanites) and olivine nephelinites the third. Our 87Sr/86Sr isotope data from the accessories overlap with the carbonatite and olivine nephelinite fields defined by Schleicher et al. (1990) but exhibit a much narrower range. These and the ?Nd and ?Hf values plot along the mantle array in the field of oceanic island basalts relatively close to mid-ocean ridge basalts. Previously reported K-Ar, Ar-Ar and fission track ages for the Kaiserstuhl lie between 16.2 and 17.8 Ma. They stem entirely from the geologically older tephrites, phonolites and essexites. No ages existed so far for the geologically younger carbonatites and carbonate-rich foidites except for one apatite fission track age (15.8 Ma). We obtained precise U-Pb ages for zirconolites and calzirtites of 15.66, respectively 15.5 Ma (±?0.1 2?) and for pyrochlores of 15.35?±?0.24 Ma. Only the perovskites from the Badberg soevite yielded a U-P concordia age of 14.56?±?0.86 Ma while the perovskites from bergalites (haüyne melilitites) only gave 206Pb/238U and 208Pb/232Th ages of 15.26?±?0.21, respectively, 15.28?±?0.48 Ma. The main Kaiserstuhl rock types were emplaced over a time span of 1.6 Ma almost 1 million years before the carbonatites and carbonate-rich foidites. These were emplaced within only 0.32 Ma.
Abstract: This manuscript presents results of the newest petrographic, mineralogical and bulk chemical, as well as H, C and O stable isotope study of carbonatites and associated silicate rocks from the Tajno Massif (NE Poland). The Tajno Intrusion is a Tournaisian-Visean ultramafic-alkaline-carbonatite body emplaced within the Paleoproterozoic rocks of the East European Craton (EEC). Carbonatites of the Tajno Massif can be subdivided into the calciocarbonatite (calcite), ferrocarbonatite (ankerite), and breccias with an ankerite-fluorite matrix. Due to location at the cratonic margin and abundance in the REE, Tajno classifies (Hou et al., 2015) as the carbonatite-associated REE deposit (CARD), and more precisely as the Dalucao-Style orebody (the breccia-hosted orebody). High Fe2O3 (13.8 wt%), MnO (2.1 wt%), total REE (6582 ppm), Sr (43895 ppm), Ba (6426 ppm), F (greater than10000 ppm) and CO2 contents points for the involvement of the slab - including pelagic metalliferous sediments - in the carbonatites formation. Spatial relations and Sr isotope composition ((87Sr/86Sr)i = 0.7043-0.7048; Wiszniewska et al., 2020) of alkali clinopyroxenite and syenite suggest that these are products of differentiation of the magma, generated by the initial melting of the SCLM due to influx of F-rich fluids from subducted marine sediments. Carbonatites Sr isotope composition ((87Sr/86Sr)i = 0.7037-0.7038), and Ba/Th (16-20620) and Nb/Y (0.01-6.25) ratios, link their origin with a more advanced melting of the SCLM, triggered by CO2-rich fluids from the subducted AOC and melts from sediments. The Tajno Massif - and coeval mafic-alkaline intrusions - age, high potassic composition, and location along the craton margin nearly parallel the Variscan deformation front, are suggesting Variscan subduction beneath the EEC. The oxygen isotope compositions of clinopyroxene (?18O value = 5.2‰) and alkali feldspar (?18O value = 5.7‰), from alkali clinopyroxenite and foid syenite, respectively, are consistent with mantle-derived magmas. Isotopic compositions of carbonatites and breccias (carbonate ?18O = 8.7‰ to 10.7‰; ?13C = -4.8‰ to ?0.4‰) span from values of primary carbonatites to carbonatites affected by a fractionation or sedimentary contamination. The highest values (?18O = 10.7‰; ?13C = -0.4‰) were reported for breccia cut by numerous veins confirming post-magmatic hydrothermal alteration. The lowest carbonate ?18O (9.3‰ to 10.7‰) and ?13C (?5.0‰ to ?3.8‰) values are reported for veins in alkali clinopyroxenites, whereas the highest ?18O (11.2‰) and ?13C (?1.2‰ to ?1.1‰) values are for veins in syenites and trachytes. Isotopic composition of veins suggests hydrothermal origin, and interaction with host mantle-derived rocks, as well as country rocks. In silicate rocks of the Tajno Massif, fluid influx leads to the development of Pb, Zn, Cu, Ag, Au sulfide mineralization-bearing stockwork vein system, with carbonate, silicate and fluorite infilling the veins. Bulk-rock contents of molybdenum (925 ppm), rhenium (905 ppb) and palladium (29 ppb) are notable. The Re-rich molybdenite association with galena, pyrite and Th-rich bastnäsite in carbonate veins is similar as in Mo deposits associated with carbonatites, implying the mantle source of Mo and Re.
Comptes Rendus Geoscience, Vol. 353, no S2, pp. 217-231.
Global
carbonatite
Abstract: Carbonatites host Earth’s main REE deposits, with bastnaesite (LREE)CO
F being the main economic REE-bearing mineral. However, bastnaesite mineralisation processes are debated between hydrothermal or magmatic origin. This study aims to assess if bastnaesite can be magmatic, and to characterise the REE behaviour during carbonatite crystallisation. Crystallisation experiments have been performed from 900 to 600 °C at 1 kbar, on a REE-rich calciocarbonatitic composition. REE-bearing calcite is the dominant crystallising mineral, driving the residual melt towards natrocarbonatitic compositions. Both halogens (i.e., Cl and F) and water decrease the temperature of calcite saturation. REE are slightly incompatible with calcite: for all REE, partition coefficients between carbonate melt and calcite are comprised between 1 and 11, and increase with temperature decrease. Britholite (REE, Ca) (Si,P)O) (F,OH) crystallises at high temperatures (700-900 °C), while pyrochlore (Ca,Na,REE) NbO (OH,F) crystallises at low temperatures (600-700 °C), as well as REE-rich apatite (600-650 °C). No bastnaesite is found in crystallisation experiments. We thus performed a bastnaesite saturation experiment at 600 °C. The bastnaesite-saturated melt contains 20 wt% of REE: such magmatic saturation is unlikely to happen in nature. Textural evidences imply a Na, Cl, REE-rich fluid at high temperatures and hydrous conditions. We propose that fluids are the main mineralising agent for bastnaesite at hydrothermal stage (600 °C).
Comptes Rendus Geoscience, Vol. 353, no S2, pp. 233-272. pdf
Global
carbonatites
Abstract: This study presents new insights into the effects of halogens (F and Cl) and phosphorous (P) on rare earth element (REE) partitioning between carbonatite and alkaline silicate melts. F, Cl and P are elements that are abundant in carbonatites and alkaline magmatic systems and they are considered to play an important role on the REE behaviour. Nonetheless, their effect on REE partitioning between carbonate and alkaline silicate melts has not yet been constrained. Here we present new experimental data on REE partitioning between carbonate and alkaline silicate melts doped in F, Cl and P, in order to (1) test the Nabyl et al. [2020] REE partitioning model in F-, Cl- and P-rich systems, and (2) identify the possible role of F, Cl and P in carbonate melt REE enrichments during alkaline–carbonatite magma differentiation. The experiments were performed at 850–1050 °C and 0.8 GPa using piston-cylinder devices. Starting materials consisted of carbonatite and phonolite compositions doped in F, Cl and P. The experimental results show that REE partitioning is similar in F-Cl-P-rich and -poor systems. The silicate melt composition and its molecular structure (i.e. SiO contents, the alumina saturation index and the alkali/alkaline-earth element ratio), which have already been identified as controlling REE partitioning in F-, Cl- and P-poor systems, still operate in doped systems. No direct effect of the F, Cl or P melt concentrations on REE partitioning has been identified. We also propose an application to natural systems.
Abstract: As I was finishing my PhD thesis on the Borralan alkaline complex in Scotland, my professor, Basil King, who published the first account of the Napak carbonatite occurrence in Uganda, proposed that I should apply for a NERC fellowship to investigate the fenites associated with carbonatites of the Chilwa Province in Malawi (Fig. 1). After a successful application, I duly flew out to Malawi and spent three months building an extensive collection of fenites from the very large metasomatic aureoles around the carbonatites of Chilwa Island, Tundulu, and Kangankunde. Back at Bedford College (University of London, UK) I had been working on my fenites for about a year when Brian Sturt, a lecturer in the department, told me that at a council meeting of the Mineralogical Society of Great Britain and Ireland the previous day he had been told by Frank Claringbull that he, Claringbull, was looking for a petrologist to work in the Department of Mineralogy at the British Museum (Natural History), now called the Natural History Museum. I arranged to see Claringbull, was interviewed, and was fortunate enough to be appointed as a petrologist in the department.
Abstract: Carbonatites are the most silica-poor magmas known and are amongst Earth’s most enigmatic igneous rocks. They crystallise to rocks dominated by the carbonate minerals calcite and dolomite. We review models for carbonatite petrogenesis, including direct partial melting of mantle lithologies, exsolution from silica-undersaturated alkali silicate melts, or direct fractionation of carbonated silicate melts to carbonate-rich residual melts. We also briefly discuss carbonatite-mantle wall-rock reactions and other processes at mid- to upper crustal depths, including fenitisation, overprinting by carbohydrothermal fluids, and reaction between carbonatite melt and crustal lithologies.
Abstract: Reconstruction of the mechanisms of carbonatitic melt evolution is extremely important for understanding metasomatic processes at the base of the continental lithospheric mantle (CLM). We have studied the interaction between garnet lherzolite and a carbonatitic melt rich in molecular CO2 and H2O in experiments at 6.3 GPa and 1200-1450 °C. The interaction with garnet lherzolite and H2O-bearing carbonatite melt leads to wehrlitization of lherzolite, without its carbonation. Introduction of molecular CO2 and H2O initiates carbonation of olivine and clinopyroxene with the formation of orthopyroxene and magnesite. Partial carbonation leads to the formation of carbonate-silicate melts that are multiphase saturated with garnet harzburgite. Upon complete carbonation of olivine already at 1200 °C, melts with 27-31 wt% SiO2 and MgO/CaO ? 1 are formed. At 1350-1450 °C, the interaction leads to an increase in the melt fraction and the MgO/CaO ratio to 2-4 and a decrease in the SiO2 concentration. Thus, at conditions of a thermally undisturbed CLM base, molecular CO2 and H2O dissolved in metasomatic agents, due to local carbonation of peridotite, can provide the evolution of agent composition from carbonatitic to hydrous silicic, i.e., similar to the trends reconstructed for diamond-forming high density fluids (HDFs) and genetically related proto-kimberlite melts.
Abstract: Carbonatites are generally accepted as derived from the mantle, whereas viewpoint of carbonatitic melt formed at crust level is considered marginal. Here we document large-scale (?17?km2) igneous carbonate-rich rocks in the southeast Tarim Craton that were formed within the crust. These rocks exhibit clear intrusive contact with the wall-rocks and contain diverse xenolith, indicating an igneous origin. Zircon U-Pb dating reveals that they were emplaced at ca. 1.94-1.92 and 1.87-1.86?Ga, respectively. ?18O values in zircons (5.7-13.7‰) are higher than those crystallized in equilibrium with mantle melt. Total REE content is 1-2 magnitude lower than that of mantle carbonatite and shows weak fractionation of HREE. REE modeling reveals that the samples cannot be produced by partial melting of carbonated MORB at mantle conditions. The studied samples have positive ?13CV-PDB values (4.2-15.7‰), which are distinct from the mantle carbonatite but comparable to sedimentary carbonates. C-O-Sr-Nd isotope modelling indicates that the compositions of the studied samples cannot be produced by evolution of mantle carbonatite. Integrating these lines of evidence, we conclude that the studied carbonate-rich magmatic rocks were derived from partial melting of impure marble at crustal level via fluid-present melting. These carbonatites probably represent the initial magmatic record of tectonic extension of the late Paleoproterozoic collisional orogenic belt in the southern margin of the Tarim craton. The positive carbon excursion recorded by the high ?13CV-PDB values probably corresponds to the global Paleoproterozoic Lomagundi-Jatuli event. Our study implies that partial melting of sedimentary carbonates is more common than previously thought, which has significant impacts on crust rheology and global carbon cycling
