Hyper-enrichment of heavy rare earth elements in highly evolved granites through multiple hydrothermal mobilizations
-
Martin Yan Hei Li
and
Mei-Fu Zhou
Abstract
Highly evolved granites can be important hosts of rare earth element (REE) resources, and more importantly, they commonly serve as the protolith for regolith-hosted REE deposits to form during weathering. Highly evolved granites in the Zudong pluton, South China, are extremely rich in the heavy (H)REE (up to 8000 ppm total HREE), and display significant REE fractionation. Moreover, the HREE enrichment is positively correlated with the degree of REE fractionation, indicating a unique process in preferentially enriching the HREE during the evolution of the granites. Multiple stages of hydrothermal re-mobilization of the REE can account for the HREE mineralization, and these are recorded in the texture and composition of the zircon. In these processes, fluctuations in the F activity of the fluid caused alternating dissolution-reprecipitation and continuous growth of the zircon. REE were repeatedly mobilized and enriched in the fluid to precipitate the major HREE mineral synchysite-(Y), and partially incorporated into the growth zone of zircon, while other elements were largely lost to the fluid during the extensive dissolution of the rock-forming minerals. LREE were also likely substantially mobilized in the late hydrothermal stage and lost through complexation with Cl, causing the significant LREE depletion and, thus REE fractionation. This process continuously enriched host granites in the HREE to a potentially economic grade, making them favorable protoliths for subsequent supergene regolith-hosted HREE deposits.
Acknowledgments and Funding
We thank Xiao Fu for the support on XRF and EPMA analyses. Editorial handling and comments by Associate Editor Paul Tomascak and constructive reviews by El Saeed R. Lasheen and an anonymous reviewer are very much appreciated. This study was supported financially by the Natural Science Foundation of China (Grant No. 92162323, 91962216) and the Guangdong Basic and Applied Basic Research Foundation (Grant No. 2021A1515011524) to M.-F.Z.
References cited
Anenburg, M. and Williams, M.J. (2022) Quantifying the tetrad effect, shape components, and Ce-Eu-Gd anomalies in rare earth element patterns. Mathematical Geosciences, 54, 47–70, https://doi.org/10.1007/s11004-021-09959-5.Search in Google Scholar
Bau, M. (1996) Controls on the fractionation of isovalent trace elements in magmatic and aqueous systems: Evidence from Y/Ho, Zr/Hf, and lanthanide tetrad effect. Contributions to Mineralogy and Petrology, 123, 323–333, https://doi.org/10.1007/s004100050159.Search in Google Scholar
Bau, M. and Dulski, P. (1995) Comparative study of yttrium and rare-earth element behaviours in fluorine-rich hydrothermal fluids. Contributions to Mineralogy and Petrology, 119, 213–223, https://doi.org/10.1007/BF00307282.Search in Google Scholar
Bea, F. (1996) Residence of REE, Y, Th and U in granites and crustal protoliths: Implications for the chemistry of crustal melts. Journal of Petrology, 37, 521–552, https://doi.org/10.1093/petrology/37.3.521.Search in Google Scholar
Bea, F., Pereira, M., Corretgé, L., and Fershtater, G. (1994) Differentiation of strongly peraluminous, perphosphorus granites: The Pedrobernardo pluton, central Spain. Geochimica et Cosmochimica Acta, 58, 2609–2627, https://doi.org/10.1016/0016-7037(94)90132-5.Search in Google Scholar
Breiter, K., Frýda, J., Seltmann, R., and Thomas, R. (1997) Mineralogical evidence for two magmatic stages in the evolution of an extremely fractionated P-rich rare-metal granite: The Podlesí stock, Krušné hory, Czech Republic. Journal of Petrology, 38, 1723–1739, https://doi.org/10.1093/petroj/38.12.1723.Search in Google Scholar
Burnham, A.D. (2020) Key concepts in interpreting the concentrations of the rare earth elements in zircon. Chemical Geology, 551, 119765, https://doi.org/10.1016/j.chemgeo.2020.119765.Search in Google Scholar
Chen, W.T. and Zhou, M.-F. (2017) Hydrothermal alteration of magmatic zircon related to NaCl-rich brines: Diffusion-reaction and dissolution-reprecipitation processes. American Journal of Science, 317, 177–215, https://doi.org/10.2475/02.2017.02.Search in Google Scholar
Claridge, R., Mackle, K., Sutton, G., and Tennant, W. (1994) 10 K EPR of an oxygen-hole aluminium centre, [AlO4]0, in X-irradiated zircon, ZrSiO4. Journal of Physics: Condensed Matter, 6, 10415–10422, https://doi.org/10.1088/0953-8984/6/47/024.Search in Google Scholar
Eby, G.N. (1990) The A-type granitoids: A review of their occurrence and chemical characteristics and speculations on their petrogenesis. Lithos, 26, 115–134, https://doi.org/10.1016/0024-4937(90)90043-Z.Search in Google Scholar
Erdmann, S., Wodicka, N., Jackson, S., and Corrigan, D. (2013) Zircon textures and composition: Refractory recorders of magmatic volatile evolution? Contributions to Mineralogy and Petrology, 165, 45–71, https://doi.org/10.1007/s00410-012-0791-z.Search in Google Scholar
Ersay, L., Greenough, J.D., Larson, K.P., and Dostal, J. (2022) Zircon reveals multistage, magmatic and hydrothermal Rare Earth Element mineralization at Debert Lake, Nova Scotia, Canada. Ore Geology Reviews, 144, 104780, https://doi.org/10.1016/j.oregeorev.2022.104780.Search in Google Scholar
Fan, C., Xu, C., Shi, A., Smith, M.P., Kynicky, J., and Wei, C. (2023) Origin of heavy rare earth elements in highly fractionated peraluminous granites. Geochimica et Cosmochimica Acta, 343, 371–383, https://doi.org/10.1016/j.gca.2022.12.019.Search in Google Scholar
Förster, H.-J. (2001) Synchysite-(Y)–synchysite-(Ce) solid solutions from Markersbach, Erzgebirge, Germany: REE and Th mobility during high-T alteration of highly fractionated aluminous A-type granites. Mineralogy and Petrology, 72, 259–280, https://doi.org/10.1007/s007100170019.Search in Google Scholar
Fu, B., Mernagh, T.P., Kita, N.T., Kemp, A.I., and Valley, J.W. (2009) Distinguishing magmatic zircon from hydrothermal zircon: A case study from the Gidginbung high-sulphidation Au-Ag-(Cu) deposit, SE Australia. Chemical Geology, 259, 131–142, https://doi.org/10.1016/j.chemgeo.2008.10.035.Search in Google Scholar
Gagnevin, D., Daly, J.S., and Kronz, A. (2010) Zircon texture and chemical composition as a guide to magmatic processes and mixing in a granitic environment and coeval volcanic system. Contributions to Mineralogy and Petrology, 159, 579–596, https://doi.org/10.1007/s00410-009-0443-0.Search in Google Scholar
Geisler, T., Pidgeon, R.T., Kurtz, R., Van Bronswijk, W., and Schleicher, H. (2003a) Experimental hydrothermal alteration of partially metamict zircon. American Mineralogist, 88, 1496–1513, https://doi.org/10.2138/am-2003-1013.Search in Google Scholar
Geisler, T., Rashwan, A., Rahn, M., Poller, U., Zwingmann, H., Pidgeon, R., Schleicher, H., and Tomaschek, F. (2003b) Low-temperature hydrothermal alteration of natural metamict zircons from the Eastern Desert, Egypt. Mineralogical Magazine, 67, 485–508, https://doi.org/10.1180/0026461036730112.Search in Google Scholar
Geisler, T., Schaltegger, U., and Tomaschek, F. (2007) Re-equilibration of zircon in aqueous fluids and melts. Elements, 3, 43–50, https://doi.org/10.2113/gselements.3.1.43.Search in Google Scholar
Han, J., Chen, H., Hollings, P., Jiang, H., Xu, H., Zhang, L., Xiao, B., Xing, C., and Tan, Z. (2019) The formation of modified zircons in F-rich highly-evolved granites: An example from the Shuangji granites in Eastern Tianshan, China. Lithos, 324-325, 776–788, https://doi.org/10.1016/j.lithos.2018.12.009.Search in Google Scholar
Hanchar, J.M. and Van Westrenen, W. (2007) Rare earth element behavior in zircon-melt systems. Elements, 3, 37–42, https://doi.org/10.2113/gselements.3.1.37.Search in Google Scholar
Hay, D. and Dempster, T. (2009) Zircon behaviour during low-temperature metamorphism. Journal of Petrology, 50, 571–589, https://doi.org/10.1093/petrology/egp011.Search in Google Scholar
Henderson, P., Ed. (2013) Rare Earth Element Geochemistry, 510 p. Elsevier.Search in Google Scholar
Hoskin, P.W. (2005) Trace-element composition of hydrothermal zircon and the alteration of Hadean zircon from the Jack Hills, Australia. Geochimica et Cosmochimica Acta, 69, 637–648, https://doi.org/10.1016/j.gca.2004.07.006.Search in Google Scholar
Hoskin, P.W. and Schaltegger, U. (2003) The composition of zircon and igneous and metamorphic petrogenesis. Reviews in Mineralogy and Geochemistry, 53, 27–62, https://doi.org/10.2113/0530027.Search in Google Scholar
Huang, D., Wu, C., and Han, J. (1989) REE geochemistry and mineralization characteristics of the Zudong and Guanxi granites, Jiangxi Province. Acta Geologica Sinica—English Edition, 2, 139–157, https://doi.org/10.1111/j.1755-6724.1989.mp2002004.x.Search in Google Scholar
Irber, W. (1999) The lanthanide tetrad effect and its correlation with K/Rb, Eu/Eu*, Sr/Eu, Y/Ho, and Zr/Hf of evolving peraluminous granite suites. Geochimica et Cosmochimica Acta, 63, 489–508, https://doi.org/10.1016/S0016-7037(99)00027-7.Search in Google Scholar
Keppler, H. (1993) Influence of fluorine on the enrichment of high field strength trace elements in granitic rocks. Contributions to Mineralogy and Petrology, 114, 479–488, https://doi.org/10.1007/BF00321752.Search in Google Scholar
Kozlik, M., Raith, J.G., and Gerdes, A. (2016) U-Pb, Lu-Hf and trace element characteristics of zircon from the Felbertal scheelite deposit (Austria): New constraints on timing and source of W mineralization. Chemical Geology, 421, 112–126, https://doi.org/10.1016/j.chemgeo.2015.11.018.Search in Google Scholar
Li, Y.H.M., Zhao, W.W., and Zhou, M.-F. (2017) Nature of parent rocks, mineralization styles and ore genesis of regolith-hosted REE deposits in South China: An integrated genetic model. Journal of Asian Earth Sciences, 148, 65–95, https://doi.org/10.1016/j.jseaes.2017.08.004.Search in Google Scholar
Li, M.Y.H., Zhou, M.-F., and Williams-Jones, A.E. (2019) The genesis of regolith-hosted heavy rare earth element deposits: Insights from the world-class Zudong deposit in Jiangxi Province, South China. Economic Geology and the Bulletin of the Society of Economic Geologists, 114, 541–568, https://doi.org/10.5382/econgeo.4642.Search in Google Scholar
Li, M.Y.H., Kwong, H.T., Williams-Jones, A.E., and Zhou, M.-F. (2022) The thermodynamics of rare earth element liberation, mobilization and supergene enrichment during groundwater-regolith interaction. Geochimica et Cosmochimica Acta, 330, 258–277, https://doi.org/10.1016/j.gca.2021.05.002.Search in Google Scholar
Linnen, R.L. and Keppler, H. (2002) Melt composition control of Zr/Hf fractionation in magmatic processes. Geochimica et Cosmochimica Acta, 66, 3293–3301, https://doi.org/10.1016/S0016-7037(02)00924-9.Search in Google Scholar
Migdisov, A., Williams-Jones, A., Brugger, J., and Caporuscio, F.A. (2016) Hydrothermal transport, deposition, and fractionation of the REE: Experimental data and thermodynamic calculations. Chemical Geology, 439, 13–42, https://doi.org/10.1016/j.chemgeo.2016.06.005.Search in Google Scholar
Nasdala, L., Kronz, A., Wirth, R., Váczi, T., Perez-Soba, C., Willner, A., and Kennedy, A.K. (2009) The phenomenon of deficient electron microprobe totals in radiation-damaged and altered zircon. Geochimica et Cosmochimica Acta, 73, 1637–1650, https://doi.org/10.1016/j.gca.2008.12.010.Search in Google Scholar
Ngwenya, B.T. (1994) Hydrothermal rare earth mineralisation in carbonatites of the Tundulu complex, Malawi: Processes at the fluid/rock interface. Geochimica et Cosmochimica Acta, 58, 2061–2072, https://doi.org/10.1016/0016-7037(94)90285-2.Search in Google Scholar
Pupin, J. (1980) Zircon and granite petrology. Contributions to Mineralogy and Petrology, 73, 207–220, https://doi.org/10.1007/BF00381441.Search in Google Scholar
Reed, M.H. (1997) Hydrothermal alteration and its relationship to ore fluid composition. In H. Barnes, Ed., Geochemistry of Hydrothermal Ore Deposits, p. 303–366. WileySearch in Google Scholar
Sanematsu, K. and Watanabe, Y. (2016) Characteristics and genesis of ion-adsorption type deposits. Reviews in Economic Geology, 18, 55–79.Search in Google Scholar
Sarbas, B. (2008) The GEOROC database as part of a growing geoinformatics network. Geoinformatics 2008—Data to Knowledge, 42–43. USGS.Search in Google Scholar
Schneider, D., Bachtel, J., and Schmitt, A. (2012) Zircon alteration in wall rock of Pamour and Hoyle Pond Au deposits, Abitibi greenstone belt: Constraints on timescales of fluid flow from depth-profiling techniques. Economic Geology and the Bulletin of the Society of Economic Geologists, 107, 1043–1072, https://doi.org/10.2113/econgeo.107.5.1043.Search in Google Scholar
Soman, A., Geisler, T., Tomaschek, F., Grange, M., and Berndt, J. (2010) Alteration of crystalline zircon solid solutions: A case study on zircon from an alkaline pegmatite from Zomba-Malosa, Malawi. Contributions to Mineralogy and Petrology, 160, 909–930, https://doi.org/10.1007/s00410-010-0514-2.Search in Google Scholar
Tomaschek, F., Kennedy, A.K., Villa, I.M., Lagos, M., and Ballhaus, C. (2003) Zircons from Syros, Cyclades, Greece—Recrystallization and mobilization of zircon during high-pressure metamorphism. Journal of Petrology, 44, 1977–2002, https://doi.org/10.1093/petrology/egg067.Search in Google Scholar
Trail, D., Watson, E.B., and Tailby, N.D. (2012) Ce and Eu anomalies in zircon as proxies for the oxidation state of magmas. Geochimica et Cosmochimica Acta, 97, 70–87, https://doi.org/10.1016/j.gca.2012.08.032.Search in Google Scholar
U.S. Geological Survey (2023) Mineral Commodity Summaries 2023, p. 210. U.S. Geological Survey.Search in Google Scholar
Vasyukova, O. and Williams-Jones, A. (2018) Direct measurement of metal concentrations in fluid inclusions, a tale of hydrothermal alteration and REE ore formation from Strange Lake, Canada. Chemical Geology, 483, 385–396, https://doi.org/10.1016/j.chemgeo.2018.03.003.Search in Google Scholar
Verplanck, P., Mariano, A., and Mariano, A. Jr. (2016) Rare earth element ore geology of carbonatites. Reviews in Economic Geology, 18, 5–32, https://doi.org/10.5382/Rev.18.01.Search in Google Scholar
Wang, X.-L., Coble, M.A., Valley, J.W., Shu, X.-J., Kitajima, K., Spicuzza, M.J., and Sun, T. (2014) Influence of radiation damage on Late Jurassic zircon from southern China: Evidence from in situ measurements of oxygen isotopes, laser Raman, U-Pb ages, and trace elements. Chemical Geology, 389, 122–136, https://doi.org/10.1016/j.chemgeo.2014.09.013.Search in Google Scholar
Wang, H., He, H., Yang, W., Bao, Z., Liang, X., Zhu, J., Ma, L., and Huang, Y. (2023) Zircon texture and composition fingerprint HREE enrichment in muscovite granite bedrock of the Dabu ion-adsorption REE deposit, South China. Chemical Geology, 616, 121231, https://doi.org/10.1016/j.chemgeo.2022.121231.Search in Google Scholar
Williams-Jones, A.E. and Wood, S.A. (1992) A preliminary petrogenetic grid for REE fluorocarbonates and associated minerals. Geochimica et Cosmochimica Acta, 56, 725–738, https://doi.org/10.1016/0016-7037(92)90093-X.Search in Google Scholar
Williams-Jones, A.E., Samson, I.M., and Olivo, G.R. (2000) The genesis of hydrothermal fluorite-REE deposits in the Gallinas Mountains, New Mexico. Economic Geology and the Bulletin of the Society of Economic Geologists, 95, 327–341, https://doi.org/10.2113/gsecongeo.95.2.327.Search in Google Scholar
Williams-Jones, A.E., Migdisov, A.A., and Samson, I.M. (2012) Hydrothermal mobilisation of the rare earth elements—a tale of “ceria” and “yttria”. Elements, 8, 355–360, https://doi.org/10.2113/gselements.8.5.355.Search in Google Scholar
Xu, C., Kynický, J., Smith, M.P., Kopriva, A., Brtnický, M., Urubek, T., Yang, Y., Zhao, Z., He, C., and Song, W. (2017) Origin of heavy rare earth mineralization in South China. Nature Communications, 8, 14598, https://doi.org/10.1038/ncomms14598.Search in Google Scholar
Yang, W.-B., Niu, H.-C., Shan, Q., Sun, W.-D., Zhang, H., Li, N.-B., Jiang, Y.-H., and Yu, X.-Y. (2014) Geochemistry of magmatic and hydrothermal zircon from the highly evolved Baerzhe alkaline granite: Implications for Zr-REE-Nb mineralization. Mineralium Deposita, 49, 451–470, https://doi.org/10.1007/s00126-013-0504-1.Search in Google Scholar
Zeng, L.-J., Niu, H.-C., Bao, Z.-W., and Yang, W.-B. (2017) Chemical lattice expansion of natural zircon during the magmatic-hydrothermal evolution of A-type granite. American Mineralogist, 102, 655–665, https://doi.org/10.2138/am-2017-5840.Search in Google Scholar
Zhao, Z., Wang, D., Chen, Z., Chen, Z., Zheng, G., and Liu, X. (2014) Zircon U-Pb age, endogenic mineralization and petrogenesis of rare earth ore-bearing granite in Longnan, Jiangxi province. Acta Geoscientica Sinica, 35, 719–725.Search in Google Scholar
Zhao, W.W., Zhou, M.-F., and Chen, W.T. (2016) Growth of hydrothermal baddeleyite and zircon in different stages of skarnization. American Mineralogist, 101, 2689–2700, https://doi.org/10.2138/am-2016-5706.Search in Google Scholar
Zhou, X., Sun, T., Shen, W., Shu, L., and Niu, Y. (2006) Petrogenesis of Mesozoic granitoids and volcanic rocks in South China: A response to tectonic evolution. Episodes, 29, 26–33, https://doi.org/10.18814/epiiugs/2006/v29i1/004.Search in Google Scholar
© 2024 by Mineralogical Society of America
Articles in the same Issue
- Tetrahedral aluminum in tourmaline from a spinel-pargasite-metamorphosed mafic-ultramafic rock
- Lorenz number and transport properties of Fe: Implications to the thermal conductivity at Earth’s core-mantle boundary
- Structure and equation of state of Ti-bearing davemaoite: New insights into the chemical heterogeneity in the lower mantle
- Solfataric alteration at the South Sulfur Bank, Kilauea, Hawaii, as a mechanism for the formation of sulfates, phyllosilicates, and silica on Mars
- Plastic deformation and trace element mobility in sphalerite
- Crystallographic insights into monovalent thallium incorporation: Exploring hydropyrochlore structure for environmental remediation
- Distribution of REE between amphibole and pyroxenes in the lithospheric mantle: An assessment from the lattice strain model
- Elastic anomalies across the P21nm→Pnnm structural phase transition in δ-(Al,Fe)OOH
- Hyper-enrichment of heavy rare earth elements in highly evolved granites through multiple hydrothermal mobilizations
- In-situ zircon and cassiterite LA-ICP-MS geochronology and implications for granite-hosted Sn deposit models and exploration: Insights from the Cameroon Line
- Compressibility, thermal expansion, and Raman spectroscopy of synthetic whitlockite Ca9Mg(PO3OH)(PO4)6 at high pressures and high temperatures
- Experimental determination of tin partitioning between titanite, ilmenite, and granitic melts using improved capsule designs
- Low-temperature crystallization of kumdykolite, a polymorph of albite, during mineral carbonation within fluid inclusions in hornblendite from the Dabie orogen, central China
- Louisfuchsite, Ca2(Mg4Ti2)(Al4Si2)O20, a new rhönite-type mineral from the NWA 4964 CK meteorite: A refractory phase from the solar nebula
Articles in the same Issue
- Tetrahedral aluminum in tourmaline from a spinel-pargasite-metamorphosed mafic-ultramafic rock
- Lorenz number and transport properties of Fe: Implications to the thermal conductivity at Earth’s core-mantle boundary
- Structure and equation of state of Ti-bearing davemaoite: New insights into the chemical heterogeneity in the lower mantle
- Solfataric alteration at the South Sulfur Bank, Kilauea, Hawaii, as a mechanism for the formation of sulfates, phyllosilicates, and silica on Mars
- Plastic deformation and trace element mobility in sphalerite
- Crystallographic insights into monovalent thallium incorporation: Exploring hydropyrochlore structure for environmental remediation
- Distribution of REE between amphibole and pyroxenes in the lithospheric mantle: An assessment from the lattice strain model
- Elastic anomalies across the P21nm→Pnnm structural phase transition in δ-(Al,Fe)OOH
- Hyper-enrichment of heavy rare earth elements in highly evolved granites through multiple hydrothermal mobilizations
- In-situ zircon and cassiterite LA-ICP-MS geochronology and implications for granite-hosted Sn deposit models and exploration: Insights from the Cameroon Line
- Compressibility, thermal expansion, and Raman spectroscopy of synthetic whitlockite Ca9Mg(PO3OH)(PO4)6 at high pressures and high temperatures
- Experimental determination of tin partitioning between titanite, ilmenite, and granitic melts using improved capsule designs
- Low-temperature crystallization of kumdykolite, a polymorph of albite, during mineral carbonation within fluid inclusions in hornblendite from the Dabie orogen, central China
- Louisfuchsite, Ca2(Mg4Ti2)(Al4Si2)O20, a new rhönite-type mineral from the NWA 4964 CK meteorite: A refractory phase from the solar nebula
