U-Pb dating of bastnäsite from the Vuoriyarvi massif: An example application for assessing the REE potential of carbonatite-related deposits

Abstract

The Vuoriyarvi massif is a Devonian multistage alkaline-ultrabasic carbonatite complex within the Kola alkaline province. Dolomite carbonatites of the Vuoriyarvi massif contain abundant rare-earth mineralization mainly represented by ancylite-(Ce) and bastnäsite-(Ce). Ancylite was previously shown to have probably formed in the Devonian (ca. 365 Ma) during an early postmagmatic overprint. Previous geological observations have revealed a much later crystallization of bastnäsite but have not been able to specify the exact age of the mineralization. The in situ U-Pb dating of bastnäsite allowed us to constrain its genesis. Bastnäsite for this study was extracted from two varieties of dolomite carbonatite breccias cemented by (1) quartz-bastnäsite and (2) strontianite aggregates (hereafter bastnäsite-rich and strontianite-rich carbonatites – BRC and SRC, respectively). The obtained age estimations (237.7 ± 9.8 Ma and 239.9 ± 4.1 Ma, respectively) indicate that both studied rocks were formed during a single event. The revealed age difference (∼125 Ma) excludes the genetic link between the bastnäsite origin and regional alkaline magmatism, pointing out an additional source for the Vuoriyarvi bastnäsite-bearing rocks. Moreover, the obtained U-Pb ages provide strong evidence that a Triassic event is responsible for the occurrence of bastnäsite mineralization due to hydrothermal REE redistribution from the Devonian ancylite-rich carbonatites. Most of the REEs released during this process via dissolution of ancylite were precipitated in situ as bastnäsite, while strontium was transported and incorporated into strontianite. The Pb isotopic characteristics of bastnäsite (²⁰⁶Pb/²⁰⁴Pb = 18.1 ± 0.1, ²⁰⁷Pb/²⁰⁴Pb = 15.3 ± 0.1, and ²⁰⁷Pb/²⁰⁶Pb = 0.84 ± 0.01) are most probably inherited from the Devonian host rocks of the Vuoriyarvi massif involved in the Triassic overprint. Isotopic signatures of Pb, Sr, and Nd show that the depleted mantle and lower crust played the leading role in formation of the Vuoriyarvi alkaline complex. Taken together, the results of the present study negate the supergene origin of the Vuoriyarvi bastnäsite, implying that the bastnäsite mineralization is not confined to near-surface layers and, therefore, may be dispersed more broadly throughout the complex. These findings raise the question on underestimation of the probable REE reserves and lay the groundwork for a reassessment of the economic potential of the Vuoriyarvi complex.

Keywords

Bastnäsite / REE / Carbonatites / U-Pb dating / Vuoriyarvi / Kola alkaline province

CRediT authorship contribution statement

Evgeniy N. Kozlov: Writing – original draft, Investigation, Formal analysis, Supervision, Validation, Visualization, Funding acquisition, Project administration. Ekaterina N. Fomina: Writing – review & editing, Supervision, Formal analysis, Validation. Qiuli Li: Writing – review & editing, Validation, Supervision, Funding acquisition, Data curation. Jiao Li: Writing – review & editing, Supervision, Validation, Investigation.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

Authors are deeply grateful to M. Anenburg and an unknown reviewer for helpful comments. The SIMS dating of bastnäsite was financially supported by the National Natural Science Foundation of China (Grant No. 42241105). The research was funded by the Russian Science Foundation (Grant No. 19-77-10039-P, study of the geology of bastnäsite ores and their economic potential). Preliminary investigations were supported by the Geological Institute KSC RAS, state order number FMEZ-2024-0004. We thank M.Yu. Sidorov (GI KSC RAS) and N.S. Vlasenko (RC “Geomodel” SPSU) for their assistance with EDS analyses. H.X. Ma, Y. Liu, and X.X. Ling (Institute of Geology and Geophysics, Chinese Academy of Sciences) helped with technical assistance during the SIMS test. Special thanks are due to N.M. Korolev for discussion of the manuscript.

References

[1] B.V. Afanasyev. Mineral Resources of the Alkaline-Ultramafic Massifs of the Kola Peninsula. Roza Vetrov, St. Petersburg, Russia (in Russian) (2011)

[2] J.N. Aleinikoff, R.P. Wintsch, C.M. Fanning, M.J. Dorais. U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, USA: an integrated SEM, EMPA, TIMS, and SHRIMP study. Chem. Geol., 188 (2002), pp. 125-147,

[3] Y. Amelin, A.N. Zaitsev. Precise geochronology of phoscorites and carbonatites. Geochim. Cosmochim. Acta, 66 (2002), pp. 2399-2419,

[4] A.K. Andersen, J.G. Clark, P.B. Larson, J.J. Donovan. REE fractionation, mineral speciation, and supergene enrichment of the Bear Lodge carbonatites, Wyoming, USA. Ore Geol. Rev., 89 (2017), pp. 780-807,

[5] A.K. Andersen, P.B. Larson, M.A. Cosca. C-O stable isotope geochemistry and 40Ar/39Ar geochronology of the Bear Lodge carbonatite stockwork, Wyoming, USA. Lithos, 324–325 (2019), pp. 640-660,

[6] M. Anenburg, J.A. Mavrogenes, C. Frigo, F. Wall. Rare earth element mobility in and around carbonatites controlled by sodium, potassium, and silica. Sci. Adv., 6 (2020), p. eabb6570,

[7] M. Anenburg, S. Broom-Fendley, W. Chen. Formation of rare earth deposits in carbonatites. Elements, 17 (2021), pp. 327-332,

[8] K. Bell, A.N. Zaitsev, J. Spratt, S. Fröjdö, A.S. Rukhlov. Elemental, lead and sulfur isotopic compositions of galena from Kola carbonatites, Russia – implications for melt and mantle evolution. Mineral. Mag., 79 (2015), pp. 219-241,

[9] K. Binnemans, P.T. Jones, K. Van Acker, B. Blanpain, B. Mishra, D. Apelian. Rare-earth economics: The balance problem. JOM, 65 (2013), pp. 846-848,

[10] A.G. Bulakh, A.R. Nesterov, A.N. Zaitsev, A.N. Pilipiuk, F. Wall, A.S. Kirillov. Sulfur-containing monazite-(Ce) from late-stage mineral assemblages at the Kandaguba and Vuoriyarvi carbonatite complexes, Kola peninsula, Russia. Neues Jahrb. Fur Mineral., 5 (2000), pp. 217-233 (in Russian)

[11] S.B. Castor. The Mountain Pass rare-earth carbonatite and associated ultrapotassic rocks, California. Can. Mineral., 46 (2008), pp. 779-806,

[12] T. Cerva-Alves, M.V.D. Remus, N. Dani, M.A.S. Basei. Integrated field, mineralogical and geochemical characteristics of Caçapava do Sul alvikite and beforsite intrusions: A new Ediacaran carbonatite complex in southernmost Brazil. Ore Geol. Rev., 88 (2017), pp. 352-369,

[13] A.R. Chakhmouradian, F. Wall. Rare earth elements: Minerals, mines, magnets (and more). Elements, 8 (2012), pp. 333-340,

[14] N.D. Chau, P. Jadwiga, P. Adam, D.V. Hao, L.K. Phon, J. Paweł. General characteristics of rare earth and radioactive elements in Dong Pao deposit, Lai Chau, Vietnam. Vietnam J. Earth Sci., 39 (2017), pp. 14-26, 10.15625/0866-7187/39/1/9181

[15] D.M. Chew, P.J. Sylvester, M.N. Tubrett. U-Pb and Th–Pb dating of apatite by LA-ICPMS. Chem. Geol., 280 (2011), pp. 200-216,

[16] C.A.F. Dietzel, T. Kristandt, S. Dahlgren, R.J. Giebel, M.A.W. Marks, T. Wenzel, G. Markl. Hydrothermal processes in the Fen alkaline-carbonatite complex, southern Norway. Ore Geol. Rev., 111 (2019), Article 102969,

[17] A.G. Doroshkevich, S.G. Viladkar, G.S. Ripp, M.V. Burtseva. Hydrothermal REE mineralization in the Amba Dongar carbonatite complex, Gujarat, India. Can. Mineral., 47 (2009), pp. 1105-1116,

[18] H. Downes, E. Balaganskaya, A. Beard, R. Liferovich, D. Demaiffe. Petrogenetic processes in the ultramafic, alkaline and carbonatitic magmatism in the Kola Alkaline Province: A review. Lithos, 85 (2005), pp. 48-75,

[19] J.-Y. Feng, L. Tang, B.-C. Yang, M. Santosh, S.-T. Zhang, B. Xu, S. Won Kim, Y.-M. Sheng. Bastnäsite U-Th-Pb age, sulfur isotope and trace elements of the Huangshui’an deposit: Implications for carbonatite-hosted Mo-Pb-REE mineralization in the Qinling Orogenic Belt, China. Ore Geol. Rev., 143 (2022), Article 104790,

[20] E.N. Fomina, E.N. Kozlov. Stable (C, O) and radiogenic (Sr, Nd) isotopic evidence for REE-carbonatite formation processes in Petyayan-Vara (Vuoriyarvi massif, NW Russia). Lithos, 398–399 (2021), Article 106282,

[21] A.L. Giovannini, R.H. Mitchell, A.C. Bastos Neto, C.A.V. Moura, V.P. Pereira, C.G. Porto. Mineralogy and geochemistry of the Morro dos Seis Lagos siderite carbonatite, Amazonas, Brazil. Lithos, 360–361 (2020), Article 105433,

[22] D. Guo, Y. Liu. Occurrence and geochemistry of bastnäsite in carbonatite-related REE deposits, Mianning–Dechang REE belt, Sichuan Province, SW China. Ore Geol. Rev., 107 (2019), pp. 266-282,

[23] J. Hong, W. Ji, X. Yang, T. Khan, R. Wang, W. Li, H. Zhang. Origin of a Miocene alkaline–carbonatite complex in the Dunkeldik area of Pamir, Tajikistan: Petrology, geochemistry, LA–ICP–MS zircon U-Pb dating, and Hf isotope analysis. Ore Geol. Rev., 107 (2019), pp. 820-836,

[24] A. Jordens, Y.P. Cheng, K.E. Waters. A review of the beneficiation of rare earth element bearing minerals. Miner. Eng., 41 (2013), pp. 97-114,

[25] Y.L. Kapustin. Structure of the Vuoriyarvi carbonatite complex. Int. Geol. Rev., 18 (1976), pp. 1296-1304,

[26] Karchevsky, P.I., Moutte, J., 2004. The phoscorite-carbonatite complex of Vuoriyarvi, northern Karelia, in: Phoscorites and Carbonatites from Mantle to Mine. Mineralogical Society of Great Britain and Ireland, pp. 163–199. Doi:

[27] E. Kozlov, E. Fomina, M. Sidorov, V. Shilovskikh, V. Bocharov, A. Chernyavsky, M. Huber. The Petyayan-Vara carbonatite-hosted rare earth deposit (Vuoriyarvi, NW Russia): Mineralogy and geochemistry. Minerals, 10 (2020), p. 73,

[28] E.N. Kozlov, E.N. Fomina. Mass balance of complementary metasomatic processes using isocon analysis. MethodsX, 9 (2022), Article 101609,

[29] U. Kramm, L.N. Kogarko, V.A. Kononova, H. Vartiainen. The Kola Alkaline Province of the CIS and Finland: Precise Rb-Sr ages define 380–360 Ma age range for all magmatism. Lithos, 30 (1993), pp. 33-44,

[30] M. Lee, J. Lee, S. Hur, Y. Kim, J. Moutte, E. Balaganskaya. Sr–Nd–Pb isotopic compositions of the Kovdor phoscorite–carbonatite complex, Kola Peninsula, NW Russia. Lithos, 91 (2006), pp. 250-261,

[31] B. Lehmann, S. Nakai, A. Höhndorf, J. Brinckmann, P. Dulski, U.F. Hein, A. Masuda. REE mineralization at Gakara, Burundi: Evidence for anomalous upper mantle in the western Rift Valley. Geochim. Cosmochim. Acta, 58 (1994), pp. 985-992,

[32] Q.-L. Li, X.-H. Li, F.-Y. Wu, Q.-Z. Yin, H.-M. Ye, Y. Liu, G.-Q. Tang, C.-L. Zhang. In-situ SIMS U-Pb dating of phanerozoic apatite with low U and high common Pb. Gondwana Res., 21 (2012), pp. 745-756,

[33] Q.-L. Li, M.H. Huyskens, Y. Yue-Heng, X.-X. Ling, Q.-Z. Yin, A.V. Nikiforov, X.-H. Li. Bastnaesite K-9: A homogenous natural reference material for in-situ U-Pb and Th–Pb dating. At. Spectrosc., 41 (2020), 10.46770/AS.2020.06.001

[34] X.-C. Li, K.-F. Yang, C. Spandler, H.-R. Fan, M.-F. Zhou, J.-L. Hao, Y.-H. Yang. The effect of fluid-aided modification on the Sm-Nd and Th-Pb geochronology of monazite and bastnäsite: Implication for resolving complex isotopic age data in REE ore systems. Geochim. Cosmochim. Acta, 300 (2021), pp. 1-24,

[35] X.X. Ling, Q.L. Li, Y. Liu, Y.H. Yang, Y. Liu, G.Q. Tang, X.H. Li. In situ SIMS Th–Pb dating of bastnaesite: constraint on the mineralization time of the Himalayan Mianning–Dechang rare earth element deposits. J. Anal. At. Spectrom., 31 (2016), pp. 1680-1687,

[36] Linnen, R.L., Samson, I.M., Williams-Jones, A.E., Chakhmouradian, A.R., 2014. Geochemistry of the rare-earth element, Nb, Ta, Hf, and Zr deposits. In: Holland, H.D., Turekian, K.K. (Eds.), Treatise on Geochemistry. Elsevier, pp. 543–568. Doi:

[37] S. Liu, H.-R. Fan, Q.-W. Wang, Y.-J. Liu, W. Wei. Carbonatite-related delicate REE mineralization processes revealed by fluorocarbonates and monazite: Insights from the giant Bayan Obo REE-Nb-Fe deposit, China. Ore Geol. Rev., 157 (2023), Article 105443,

[38] Y. Liu, Z. Hou. A synthesis of mineralization styles with an integrated genetic model of carbonatite-syenite-hosted REE deposits in the Cenozoic Mianning-Dechang REE metallogenic belt, the eastern Tibetan Plateau, southwestern China. J. Asian Earth Sci., 137 (2017), pp. 35-79,

[39] M. Louvel, B. Etschmann, Q. Guan, D. Testemale, J. Brugger. Carbonate complexation enhances hydrothermal transport of rare earth elements in alkaline fluids. Nat. Commun., 13 (2022), p. 1456,

[40] R.H. Mitchell, D.L. Smith. Geology and mineralogy of the Ashram Zone carbonatite, Eldor Complex, Québec. Ore Geol. Rev., 86 (2017), pp. 784-806,

[41] V. Mollé, F. Gaillard, Z. Nabyl, J. Tuduri, I. Di Carlo, S. Erdmann. Crystallisation sequence of a REE-rich carbonate melt: an experimental approach. Comptes Rendus. Géoscience, 353 (2022), pp. 217-231,

[42] M. Moore, A.R. Chakhmouradian, A.N. Mariano, R. Sidhu. Evolution of rare-earth mineralization in the Bear Lodge carbonatite, Wyoming: Mineralogical and isotopic evidence. Ore Geol. Rev., 64 (2015), pp. 499-521,

[43] A. Néron, L. Bédard, D. Gaboury. The Saint-Honoré Carbonatite REE Zone, Québec, Canada: Combined magmatic and hydrothermal processes. Minerals, 8 (2018), p. 397,

[44] B.T. Ngwenya. Hydrothermal rare earth mineralisation in carbonatites of the Tundulu complex, Malawi: Processes at the fluid/rock interface. Geochim. Cosmochim. Acta, 58 (1994), pp. 2061-2072,

[45] A.M. Nikolenko, K.M. Stepanov, V. Roddatis, I.V. Veksler. Crystallization of bastnäsite and burbankite from carbonatite melt in the system La(CO3)F-CaCO3-Na2CO3 at 100 MPa. Am. Mineral., 107 (2022), pp. 2242-2250,

[46] S. Ntiharirizwa, P. Boulvais, M. Poujol, Y. Branquet, C. Morelli, J. Ntungwanayo, G. Midende. Geology and U-Th-Pb dating of the Gakara REE deposit, Burundi. Minerals, 8 (2018), p. 394,

[47] I. Prokopyev, E. Kozlov, E. Fomina, A. Doroshkevich, M. Dyomkin. Mineralogy and fluid regime of formation of the REE-Late-Stage hydrothermal mineralization of Petyayan-Vara carbonatites (Vuoriyarvi, Kola Region, NW Russia). Minerals, 10 (2020), p. 405,

[48] I. Prokopyev, A. Doroshkevich, D. Zhumadilova, A. Starikova, Y.N. Nugumanova, N. Vladykin. Petrogenesis of Zr–Nb (REE) carbonatites from the Arbarastakh complex (Aldan Shield, Russia): Mineralogy and inclusion data. Ore Geol. Rev., 131 (2021), Article 104042,

[49] I.R. Prokopyev, A.G. Doroshkevich, A.E. Starikova, Y. Yang, V.O. Goryunova, N.A. Tomoshevich, V.F. Proskurnin, V.A. Saltanov, E.A. Kukharenko. Geochronology and origin of the carbonatites of the Central Taimyr Region, Russia (Arctica): Constraints on the F-Ba-REE mineralization and the Siberian Large Igneous Province. Lithos, 440–441 (2023), Article 107045,

[50] J.J.W. Rogers, M. Santosh. Continents and Supercontinents. Oxford University Press, Oxford (2004)

[51] E. Ruberti, G.E.R. Enrich, C.B. Gomes, P. Comin-Chiaramonti. Hydrothermal REE fluorocarbonate mineralization at Barra do Itapirapuã, a multiple stockwork carbonate, southern Brazil. Can. Mineral., 46 (2008), pp. 901-914,

[52] E.B. Sal’nikova, S.Z. Yakovleva, A.V. Nikiforov, A.B. Kotov, V.V. Yarmolyuk, I.V. Anisimova, A.M. Sugorakova, Y.V. Plotkina. Bastnaesite: a promising U-Pb geochronological tool. Dokl. Earth Sci., 430 (2010), pp. 134-136,

[53] H.-D. She, H.-R. Fan, K.-F. Yang, X.-H. Li, Z.-Y. Wang. REEs upgrading by post-carbonatite fluids in the Huangshui’an Mo-REE deposit, eastern Qinling Orogen (central China). Ore Geol. Rev., 150 (2022), Article 105177,

[54] X. Shu, Y. Liu. Fluid inclusion constraints on the hydrothermal evolution of the Dalucao carbonatite-related REE deposit, Sichuan Province, China. Ore Geol. Rev., 107 (2019), pp. 41-57,

[55] M.P. Smith, K. Moore, D. Kavecsánszki, A.A. Finch, J. Kynicky, F. Wall. From mantle to critical zone: A review of large and giant sized deposits of the rare earth elements. Geosci. Front., 7 (2016), pp. 315-334,

[56] W. Song, C. Xu, M.P. Smith, A.R. Chakhmouradian, M. Brenna, J. Kynický, W. Chen, Y. Yang, M. Deng, H. Tang. Genesis of the world’s largest rare earth element deposit, Bayan Obo, China: Protracted mineralization evolution over ∼1 b.y. Geology, 46 (4) (2018), pp. 323-326,

[57] N.O. Sorokhtin, S.L. Nikiforov, R.A. Ananiev, N.N. Dmitrevskiy, E.A. Moroz, E.A. Sukhih, N.E. Kozlov, I.V. Chikirev, A.I. Fridenberg, A.A. Koluibakin. Geodynamics of the Russian Arctic Shelf and relief-forming processes in the central Kara Basin. Oceanology, 62 (2022), pp. 540-549,

[58] J.S. Stacey, J.D. Kramers. Approximation of terrestrial lead isotope evolution by a two-stage model. Earth Planet. Sci. Lett., 26 (1975), pp. 207-221,

[59] R.H. Steiger, E. Jäger. Subcommission on geochronology: Convention on the use of decay constants in geo- and cosmochronology. Earth Planet. Sci. Lett., 36 (1977), pp. 359-362,

[60] F. Tera, G.J. Wasserburg. U-Th-Pb systematics in three Apollo 14 basalts and the problem of initial Pb in lunar rocks. Earth Planet. Sci. Lett., 14 (1972), pp. 281-304,

[61] P. Vermeesch. IsoplotR: A free and open toolbox for geochronology. Geosci. Front., 9 (2018), pp. 1479-1493,

[62] R.V. Veselovskiy, S.N. Thomson, A.A. Arzamastsev, V.S. Zakharov. Apatite fission track thermochronology of Khibina Massif (Kola Peninsula, Russia): Implications for post-Devonian Tectonics of the NE Fennoscandia. Tectonophysics, 665 (2015), pp. 157-163,

[63] C. Wang, J. Liu, H. Zhang, X. Zhang, D. Zhang, Z. Xi, Z. Wang. Geochronology and mineralogy of the Weishan carbonatite in Shandong province, eastern China. Geosci. Front., 10 (2019), pp. 769-785,

[64] Z. Weng, S.M. Jowitt, G.M. Mudd, N. Haque. A detailed assessment of global rare earth element resources: Opportunities and challenges. Econ. Geol., 110 (2015), pp. 1925-1952,

[65] Q. Weng, W.-B. Yang, H.-C. Niu, N.-B. Li, R.H. Mitchell, S. Zurevinski, D. Wu. Formation of the Maoniuping giant REE deposit: Constraints from mineralogy and in situ bastnäsite U-Pb geochronology. Am. Mineral., 107 (2022), pp. 282-293,

[66] A.E. Williams-Jones, S.A. Wood. A preliminary petrogenetic grid for REE fluorocarbonates and associated minerals. Geochim. Cosmochim. Acta, 56 (1992), pp. 725-738,

[67] W.K. Witt, D.P. Hammond, M. Hughes. Geology of the Ngualla carbonatite complex, Tanzania, and origin of the Weathered Bastnaesite Zone REE ore. Ore Geol. Rev., 105 (2019), pp. 28-54,

[68] X.-M. Yang, M.J. Le Bas. Chemical compositions of carbonate minerals from Bayan Obo, Inner Mongolia, China: implications for petrogenesis. Lithos, 72 (2004), pp. 97-116,

[69] Y.-H. Yang, F.-Y. Wu, Y. Li, J.-H. Yang, L.-W. Xie, Y. Liu, Y.-B. Zhang, C. Huang. In situ U-Pb dating of bastnaesite by LA-ICP-MS. J. Anal. at. Spectrom., 29 (2014), pp. 1017-1023,

[70] Y. Yang, F. Wu, Q. Li, Y. Rojas-Agramonte, J. Yang, Y. Li, Q. Ma, L. Xie, C. Huang, H. Fan, Z. Zhao, C. Xu. In situ U-Th-Pb dating and Sr-Nd isotope analysis of bastnäsite by LA-(MC)-ICP-MS. Geostand. Geoanalytical Res., 43 (2019), pp. 543-565,

[71] G.M. Yaxley, M. Anenburg, S. Tappe, S. Decree, T. Guzmics. Carbonatites: classification, sources, evolution, and emplacement. Annu. Rev. Earth Planet. Sci., 50 (2022), pp. 261-293,

[72] R.E. Zartman, S.M. Haines. The plumbotectonic model for Pb isotopic systematics among major terrestrial reservoirs—A case for bi-directional transport. Geochim. Cosmochim. Acta, 52 (1988), pp. 1327-1339,

[73] R.E. Zartman, L.N. Kogarko. Lead isotopic evidence for interaction between plume and lower crust during emplacement of peralkaline Lovozero rocks and related rare-metal deposits, East Fennoscandia, Kola Peninsula, Russia. Contrib. Mineral. Petrol., 172 (2017), p. 32,

[74] W. Zhang, W.T. Chen, J.-F. Gao, H.-K. Chen, J.-H. Li. Two episodes of REE mineralization in the Qinling Orogenic Belt, Central China: in-situ U-Th-Pb dating of bastnäsite and monazite. Miner. Depos., 54 (2019), pp. 1265-1280,