Home Hydrothermal alteration of magmatic titanite: Implications for REE remobilization and the formation of ion-adsorption HREE deposits, South China
Article
Licensed
Unlicensed Requires Authentication

Hydrothermal alteration of magmatic titanite: Implications for REE remobilization and the formation of ion-adsorption HREE deposits, South China

  • Yuzhou Feng , Yuanming Pan , Bing Xiao , Gaobin Chu and Huayong Chen
Published/Copyright: October 28, 2023
Become an author with De Gruyter Brill
Author Information
American Mineralogist
From the journal American Mineralogist Volume 108 Issue 11

Abstract

Ion-adsorption rare earth element (REE) deposits in South China are currently the main source of heavy rare earth elements (HREE). The Gucheng deposit in western Guangdong Province is one example of HREE mineralization hosted in weathered coarse-grained biotite granites (CGBG). Titanite is a common accessory mineral in the CGBG and contains significant amounts of total REE (31 621 to 38 431 ppm), especially HREE (18 906 to 22 249 ppm). Titanite with a U-Pb age of 102.6 ± 1.9 Ma in the CGBG crystallized under relatively high temperatures (722–798 °C), high f H 2 O , and high f O 2 conditions in the late magmatic stage, and has similar Nd isotopic compositions similar to the host CGBG: 143Nd/144Nd = 0.512062 to 0.512125 and εNd(t) = –7.4 to –8.6.

Backscattered electron (BSE) imaging and TESCAN integrated mineral analyzer (TIMA) measurements show that titanite in the CGBG has been altered partly to fergusonite-(Y), rutile, calcite, quartz, and fluorite. The hydrothermal fluid responsible for titanite alteration was enriched in C O 3 2 − and F, and was probably exsolved from the granitic magma. HREE released from the alteration of titanite were mostly scavenged by fergusonite-(Y) and rutile, which have been further replaced by gadolinite-(Y) and synchysite-(Ce). In addition, gadolinite-(Y) in the alteration assemblages exhibits further alteration and is characterized by elevated P O 4 3 − a n d S O 4 2 − contents in the altered parts. These results demonstrate that magmatic titanite in the CGBG underwent complex hydrothermal alteration, with a preferential accumulation of HREE in fergusonite-(Y) and gadolinite-(Y) in the alteration assemblages. Preferential HREE enrichments in magmatic titanite, and its alteration assemblages, are shown to play significant roles in the formation of the Gucheng HREE deposit.

Keywords: Titanite; metasomatic alteration; REE-rich mineral; REE remobilization; ion-adsorption deposit

Acknowledgments and funding

This study was funded by the Guangdong Major Project of Basic and Applied Basic Research (No. 2019B030302013), the National Natural Science Foundation of China (No. 41725009, 42103058, 41921003, 42173065), and Science and Technology Planning of Guangdong Province, China (2020B1212060055). Staff of the Key Geology Bureau for Nonferrous Metals of Guangdong Province are thanked for supporting the research and for providing access to drill cores and sample collection.

References cited

Aleinikoff, J.N., Wintsch, R.P., Fanning, C.M., and Dorais, M.J. (2002) U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, U. S.A.: An integrated SEM, EMPA, TIMS, and SHRIMP study. Chemical Geology, 188, 125–147, https://doi.org/10.1016/S0009-2541(02)00076-1.Search in Google Scholar

Bao, Z.W. and Zhao, Z.H. (2003) Geochemistry and tectonic setting of the Fogang aluminous A-type granite, Guangdong Province, China—A preliminary study. Geology Geochemistry, 31, 52–61 (in Chinese with English abstract).Search in Google Scholar

Bern, C.R., Yesavage, T., and Foley, N.K. (2017) Ion-adsorption REEs in regolith of the Liberty Hill pluton, South Carolina, U.S.A.: An effect of hydrothermal alteration. Journal of Geochemical Exploration, 172, 29–40, https://doi.org/10.1016/j.gexplo.2016.09.009.Search in Google Scholar

Broska, I., Harlov, D., Tropper, P., and Siman, P. (2007) Formation of magmatic titanite and titanite–ilmenite phase relations during granite alteration in the Tribeč Mountains, Western Carpathians, Slovakia. Lithos, 95, 58–71, https://doi.org/10.1016/j.lithos.2006.07.012.Search in Google Scholar

Bruque, S., Mozas, T., and Rodriguez, A. (1980) Factors influencing retention of lanthanide ions by montmorillonite. Clay Minerals, 15, 413–420, https://doi.org/10.1180/claymin.1980.015.4.08.Search in Google Scholar

Cao, M.J., Qin, K.Z., Li, G.M., Evans, N.J., and Jin, L.Y. (2015) In situ LA-(MC)-ICP-MS trace element and Nd isotopic compositions and genesis of polygenetic titanite from the Baogutu reduced porphyry Cu deposit, Western Junggar, NW China. Ore Geology Reviews, 65, 940–954, https://doi.org/10.1016/j.oregeorev.2014.07.014.Search in Google Scholar

Chakhmouradian, A.R. (2004) Crystal chemistry and paragenesis of compositionally unique (Al-, Fe-, Nb-, and Zr-rich) titanite from Afrikanda, Russia. American Mineralogist, 89, 1752–1762, https://doi.org/10.2138/am-2004-11-1222.Search in Google Scholar

Chakhmouradian, A.R. and Zaitsev, A.N. (2002) Calcite-amphibole-clinopyroxene rock from the Afrikanda complex, Kola Peninsula, Russia: Mineralogy and a possible link to carbonatites. III. Silicate minerals. Canadian Mineralogist, 40, 1347–1374, https://doi.org/10.2113/gscanmin.40.5.1347.Search in Google Scholar

Chi, R., Tian, J., Luo, X., Xu, Z., and He, Z. (2012) The basic research on the weathered crust elution-deposited rare earth ores. Nonferrous Metals Science and Engineering, 3, 1–13 (in Chinese with English abstract).Search in Google Scholar

Feng, Y.Z., Xiao, B., Chu, G.B., Li, S.S., Wang, J., and Wen, Z.Q. (2022) Late Mesozoic magmatism in the Gucheng district: Implications for REE metallogenesis in South China. Ore Geology Reviews, 148, 105034, https://doi.org/10.1016/j.oregeorev.2022.105034.Search in Google Scholar

Fu, Y., Sun, X.M., Zhou, H.Y., Lin, H., and Yang, T.J. (2016) In-situ LA-ICP-MS U-Pb geochronology and trace elements analysis of polygenetic titanite from the giant Beiya gold-polymetallic deposit in Yunnan Province, Southwest China. Ore Geology Reviews, 77, 43–56, https://doi.org/10.1016/j.oregeorev.2016.02.001.Search in Google Scholar

Gao, X.Y., Zheng, Y.F., Chen, Y.X., and Guo, J.L. (2012) Geochemical and U-Pb age constraints on the occurrence of polygenetic titanites in UHP metagranite in the Dabie orogen. Lithos, 136–139, 93–108, https://doi.org/10.1016/j.lithos.2011.03.020.Search in Google Scholar

Harlov, D., Tropper, P., Seifert, W., Nijland, T., and Forster, H.J. (2006) Formation of Al-rich titanite (CaTiSiO4O-CaAlSiO4OH) reaction rims on ilmenite in metamorphic rocks as a function of f H 2 O , and fO2. Lithos, 88, 72–84, https://doi.org/10.1016/j.lithos.2005.08.005.Search in Google Scholar

Hayden, L.A., Watson, E.B., and Wark, D.A. (2008) A thermobarometer for sphene (titanite). Contributions to Mineralogy and Petrology, 155, 529–540, https://doi.org/10.1007/s00410-007-0256-y.Search in Google Scholar

Hu, Z., Zhang, W., Liu, Y., Gao, S., Li, M., Zong, K., Chen, H., and Hu, S. (2015) “Wave” signal-smoothing and mercury-removing device for laser ablation quadrupole and multiple collector ICPMS analysis: Application to lead isotope analysis. Analytical Chemistry, 87, 1152–1157, https://doi.org/10.1021/ac503749k.Search in Google Scholar

Huang, D.H., Wu, C.Y., and Han, J.Z. (1988) REE geochemistry and mineralization characteristics of the Zudong and Guanxi granites, Jiangxi Province. Acta Geologica Sinica, 2, 139–157.Search in Google Scholar

Ichimura, K., Sanematsu, K., Kon, Y., Takagi, T., and Murakami, T. (2020) REE redistributions during granite weathering: Implications for Ce anomaly as a proxy for paleoredox states. American Mineralogist, 105, 848–859, https://doi.org/10.2138/am-2020-7148.Search in Google Scholar

Ishihara, S., Hua, R., Hoshino, M., and Murakami, H. (2008) REE abundance and REE minerals in granitic rocks in the Nanling Range, Jiangxi Province, Southern China, and generation of the REE-rich weathered crust deposits. Resource Geology, 58, 355–372, https://doi.org/10.1111/j.1751-3928.2008.00070.x.Search in Google Scholar

Jamtveit, B. (1991) Oscillatory zonation patterns in hydrothermal grossular-andradite garnet; nonlinear dynamics in regions of immiscibility. American Mineralogist, 76, 1319–1327.Search in Google Scholar

Jowitt, S., Wong, V., Wilson, S., and Gore, O. (2017) Critical metals in the critical zone: Controls, resources and future prospectivity of regolith-hosted rare earth elements. Australian Journal of Earth Sciences, 64, 1045–1054, https://doi.org/10.1080/08120099.2017.1380701.Search in Google Scholar

Lee, H.G. and Byrne, R.H. (1992) Examination of comparative rare earth element complexation behavior using linear free-energy relationships. Geochimica et Cosmochimica Acta, 56, 1127–1137, https://doi.org/10.1016/0016-7037(92)90050-S.Search in Google Scholar

Li, X.C. and Zhou, M.F. (2017) Hydrothermal alteration of monazite-(Ce) and chevkinite-(Ce) from the Sin Quyen Fe-Cu-LREE-Au deposit, northwestern Vietnam. American Mineralogist, 102, 1525–1541, https://doi.org/10.2138/am-2017-5970.Search in Google Scholar

Li, M. Y.H. and Zhou, M.F. (2020) The role of clay minerals in formation of the regolithhosted heavy rare earth element deposits. American Mineralogist, 105, 92–108, https://doi.org/10.2138/am-2020-7061.Search in Google Scholar

Li, M. Y.H., 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

Murakami, H. and Ishihara, S. (2008) REE mineralization of weathered crust and clay sediment on granitic rocks in the Sanyo Belt, SW Japan and the Southern Jiangxi Province, China. Resource Geology, 58, 373–401, https://doi.org/10.1111/j.1751-3928.2008.00071.x.Search in Google Scholar

Pan, Y.M. and Fleet, M.E. (1991) Vanadian allanite-(La) and vanadian allanite-(Ce) from the Hemlo gold deposit, Ontario, Canada. Mineralogical Magazine, 55, 497–507, https://doi.org/10.1180/minmag.1991.055.381.01.Search in Google Scholar

Pan, Y.M., Fleet, M.E., and Macrae, N.D. (1993) Late alteration in titanite (CaTiSiO5): Redistribution and remobilization of rare earth elements and implications for U/Pb and Th/Pb geochronology and nuclear waster disposal. Geochimica et Cosmochimica Acta, 57, 355–367, https://doi.org/10.1016/0016-7037(93)90437-2.Search 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

Sanematsu, K., Kon, Y., Imai, A., Watanabe, K., and Watanabe, Y. (2013) Geochemical and mineralogical characteristics of ion-adsorption type REE mineralization in Phuket, Thailand. Mineralium Deposita, 48, 437–451, https://doi.org/10.1007/s00126-011-0380-5.Search in Google Scholar

Spandler, C., Hammerli, J., Sha, P., Hilbert-Wolf, H., Hu, Y., Roberts, E., and Schmitz, M. (2016) MKED1: A new titanite standard for in situ analysis of Sm-Nd isotopes and U-Pb geochronology. Chemical Geology, 425, 110–126, https://doi.org/10.1016/j.chemgeo.2016.01.002.Search in Google Scholar

Van Hinsberg, V.J., Migdisov, A.A., and Williams-Jones, A.E. (2010) Reading the mineral record of fluid composition from element partitioning. Geology, 38, 847–850, https://doi.org/10.1130/G31112.1.Search in Google Scholar

Wen, G., Li, J.W., Hofstra, A.H., Koenig, A.E., and Cui, B.Z. (2020) Textures and compositions of clinopyroxene in an Fe skarn with implications for ore-fluid evolution and mineral-fluid REE partitioning. Geochimica et Cosmochimica Acta, 290, 104–123, https://doi.org/10.1016/j.gca.2020.08.020.Search in Google Scholar

Wood, S.A. (1990) The aqueous geochemistry of the rare-earth elements and yttrium. 1. Review of available low-temperature data for inorganic complexes and the inorganic REE speciation of natural waters. Chemical Geology, 82, 159–186, https://doi.org/10.1016/0009-2541(90)90080-Q.Search in Google Scholar

Xiao, B., Pan, Y.M., Song, H., Song, W.L., Zhang, Y., and Chen, H. (2021) Hydrothermal alteration processes of fluorapatite and implications for REE remobilization and mineralization. Contributions to Mineralogy and Petrology, 176, 87, https://doi.org/10.1007/s00410-021-01849-7.Search in Google Scholar

Xie, L., Wang, R. C., Chen, J., and Zhu, J.C. (2010) Mineralogical evidence for magmatic and hydrothermal processes in the Qitianling oxidized tin-bearing granite (Hunan, South China): EMP and (MC)-LA-ICPMS investigations of three types of titanite. Chemical Geology, 276, 53–68, https://doi.org/10.1016/j.chemgeo.2010.05.020.Search in Google Scholar

Xu, L., Hu, Z.C., Zhang, W., Yang, L., Liu, Y.S., Gao, S., Luo, T., and Hu, S. (2015) In situ Nd isotope analyses in geological materials with signal enhancement and non-linear mass dependent fractionation reduction using laser ablation MC-ICP-MS. Journal of Analytical Atomic Spectrometry, 30, 232–244, https://doi.org/10.1039/C4JA00243A.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

Yan, S., Zhou, R.J., Niu, H.C., Feng, Y.X., Nguyen, A.D., Zhao, Z.H., Yang, W.B., Dong, Q., and Zhao, J.X. (2020) LA-MC-ICP-MS U-Pb dating of low-U garnets reveals multiple episodes of skarn formation in the volcanic-hosted iron mineralization system, Awulale belt, Central Asia. Geological Society of America Bulletin, 132, 1031–1045, https://doi.org/10.1130/B35214.1.Search in Google Scholar

Zhang, W., Hu, Z.C., and Liu, Y.S. (2020) Iso-Compass: New freeware software for isotopic data reduction of LA-MC-ICP-MS. Journal of Analytical Atomic Spectrometry, 35, 1087–1096, https://doi.org/10.1039/D0JA00084A.Search in Google Scholar

Zhao, W.W., Zhou, M.F., Li, M.Y.H., Zhao, Z., and Gao, J.F. (2017) Genetic types, mineralization styles and geodynamic settings of Mesozoic tungsten deposits in South China. Journal of Asian Earth Sciences, 137, 109–140, https://doi.org/10.1016/j.jseaes.2016.12.047.Search in Google Scholar
Received: 2022-06-12
Accepted: 2022-11-16
Published Online: 2023-10-28
Published in Print: 2023-11-25

© 2023 by Mineralogical Society of America

Articles in the same Issue

  1. Passive carbon sequestration associated with wollastonite mining, Adirondack Mountains, New York
  2. Geochemical variation in biotite from the Devonian South Mountain Batholith, Nova Scotia: Constraints on emplacement pressure, temperature, magma redox state and the development of a magmatic vapor phase (MVP)
  3. Nanostructural domains in martian apatites that record primary subsolidus exsolution of halogens: Insights into nakhlite petrogenesis
  4. Magnetism and equation of states of fcc FeHx at high pressure
  5. Hydrothermal alteration of magmatic titanite: Implications for REE remobilization and the formation of ion-adsorption HREE deposits, South China
  6. Effects of crystal chemistry on adsorption, occurrence, and mobility of water in palygorskite tunnels
  7. Temperature-induced densification in compressed basaltic glass revealed by in-situ ultrasonic measurements
  8. X-ray absorption spectroscopic study of Pd2+ on Ni site in pentlandite
  9. Twinning in hydrous wadsleyite: Symmetry relations, origin, and consequences
  10. An experimental crystallization of the Macusani obsidian in a thermal gradient with applications to lithium-rich granitic pegmatites
  11. Amorphous Mn2SiO4: A potential manganese phase in the stagnant slab
  12. The crystal structure of feitknechtite (β-MnOOH) and a new MnOOH polymorph
  13. Yakubovichite, CaNi2Fe3+(PO4)3, a new nickel phosphate mineral of non-meteoritic origin
  14. Book Review
https://doi.org/10.2138/am-2022-8644
Keywords for this article
Titanite; metasomatic alteration; REE-rich mineral; REE remobilization; ion-adsorption deposit

Articles in the same Issue

  1. Passive carbon sequestration associated with wollastonite mining, Adirondack Mountains, New York
  2. Geochemical variation in biotite from the Devonian South Mountain Batholith, Nova Scotia: Constraints on emplacement pressure, temperature, magma redox state and the development of a magmatic vapor phase (MVP)
  3. Nanostructural domains in martian apatites that record primary subsolidus exsolution of halogens: Insights into nakhlite petrogenesis
  4. Magnetism and equation of states of fcc FeHx at high pressure
  5. Hydrothermal alteration of magmatic titanite: Implications for REE remobilization and the formation of ion-adsorption HREE deposits, South China
  6. Effects of crystal chemistry on adsorption, occurrence, and mobility of water in palygorskite tunnels
  7. Temperature-induced densification in compressed basaltic glass revealed by in-situ ultrasonic measurements
  8. X-ray absorption spectroscopic study of Pd2+ on Ni site in pentlandite
  9. Twinning in hydrous wadsleyite: Symmetry relations, origin, and consequences
  10. An experimental crystallization of the Macusani obsidian in a thermal gradient with applications to lithium-rich granitic pegmatites
  11. Amorphous Mn2SiO4: A potential manganese phase in the stagnant slab
  12. The crystal structure of feitknechtite (β-MnOOH) and a new MnOOH polymorph
  13. Yakubovichite, CaNi2Fe3+(PO4)3, a new nickel phosphate mineral of non-meteoritic origin
  14. Book Review
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 24.9.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2022-8644/html
Scroll to top button