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REE geochemistry of gangue minerals and their geological significance in the Muli antimony ore deposit in Yunnan, China

  • Zhenchun Han
  • Jiasheng WangEmail author
  • Chao LiEmail author
  • Kaidi Qiao
  • Jinyang Chang
Original Article
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Abstract

The Muli antimony deposit is located in the Au–Sb polymetallic metallogenic belt in south-eastern Yunnan, China. In this paper, we investigated the concentrations of trace elements in gangue minerals, mainly calcite, quartz, and pyrite, which were formed at different metallogenic stages. Meanwhile, the host rocks, predominantly composed of limestone, are also analysed for comparison. The calcite from the Nadan ore section is enriched with medium-heavy rare earth elements (M-HREEs), likely due to the presence of a high concentration of Fe and Mn impurities, which results in the preferential enrichment of M-HREEs in the calcite. Alternatively, the calcite may be precipitated from the M-HREE-rich granitic leaching fluid. In the Muli ore section, both quartz and pyrite in the metallogenic period show enrichment with light rare earth elements (LREEs), and the wall rock is also enriched with LREEs, which indicates that the wall rock material was involved in the metallogenic process. The W-shaped tetrad effect of quartz in the late metallogenic stage was interpreted to determine extensive fluid–rock interactions in highly fractionated Si-rich systems. Fe and Mn impurities cause M-HREE to be preferentially enriched with calcite to some extent. Whether mineralization is related to granite deserves further study. Eu and Ce anomalies of different types of gangue minerals indicate that the temperature and the fO2 were constantly changing during mineralization, and the temperature of the main ore-stage was higher than 200 °C in an oxidized state. The various REE patterns, LREE/HREE and (La/Yb)N values, reveal that there may be multi-sources and multi-stage hydrothermal activities in the Muli antimony deposit. The REE distribution patterns of minerals are likely interfered with by many internal and external factors. Studies on REE characteristics of calcite, quartz, pyrite and limestone in the Muli antimony deposit have greatly improved the understanding of ore-forming fluids. When we traced the origin and evolution of ore-forming fluids by means of mineral REE distribution patterns, in addition to the determination of inclusions of ore minerals related to mineralization and the in situ analysis methods performed by LA-ICP-MS, we should also combine the REE characteristics of various minerals or trace the ore-forming fluids with multiple methods.

Keywords

Muli antimony deposit Ore-forming fluids REE Calcite Pyrite Quartz 

Notes

Acknowledgements

This research is jointly supported by the National Natural Science Foundation of China (Grant Nos. 41772070, 41303038), Open Fund of State Key Laboratory of Ore Deposit Geochemistry (201502). Special thanks are due to the geological engineers from the Yunnan Muli Antimony Industry Co., Ltd and Mr. Dazhou Chen for their enthusiastic help during our field investigation. We are grateful to Ms. Jing Hu and Ms. Yan Huang for their warmhearted experimental guidance and instrumentation support. We would like to thank Professors A.U. Ugarkar and Chuanwei Zhu, for their valuable suggestions and insightful comments on this manuscript.

References

  1. Abedini A, Calagari AA, Naseri H (2016) Mineralization and REE geochemistry of hydrothermal quartz and calcite of the Helmesi vein-type copper deposit, NW Iran. Neues Jahrbuch für Geologie und Paläontologie-Abhandlungen 281(2):123–134Google Scholar
  2. Bao GP, Cui YL, Gao JG (2013) REE geochemical features of hydrothermal calcite from Maozu Pb–Zn deposit, northeastern Yunnan province, China. Acta Mineral Sin 33(4):681–685Google Scholar
  3. Bau M, Dulski P (1995) Comparative study of yttrium and rare-earth element behaviours in fluorine-rich hydrothermal fluids. Contrib Mineral Petrol 119(2–3):213–223Google Scholar
  4. Bau M, Möller P (1992) Rare earth element fractionation in metamorphogenic hydrothermal calcite, magnesite and siderite. Mineral Petrol 45(45):231–246Google Scholar
  5. Bau M, Koschinsky A, Dulski P, Hein JR (1996) Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater. Geochim Cosmochim Acta 60(10):1709–1725Google Scholar
  6. Bi XW, Hu RZ, Peng JT, Wu KX (2004) REE and HFSE geochemical characteristics of pyrites in Yao’an gold deposit: tracing ore forming fluid signatures. Bull Mineral Petrol Geochem 23(1):1–4Google Scholar
  7. Brugger J, Meisser N (2006) Manganese-rich assemblages in the Barrhorn unit, Turtmanntal, central Alps, Switzerland. Can Mineral 44(1):229–248Google Scholar
  8. Cao JC (1995) REE geochemical characteristics of epithermal vein fluorite deposits in south China. Geochimica 24(3):225–234Google Scholar
  9. Cao HW, Zhang ST, Gao YZ, Ma Y, Zeng ZF, Gao F, Zou H (2014) REE geochemistry of fluorite from Linxi fluorite deposit and its geological implications, Inner Mongolia Autonomous Region. Geochimica 43(2):131–140Google Scholar
  10. Chen MH, Wu LL, Phillip JU, Tony N, Zheng JM, Qin YZ (2007) REE features of arsenian pyrite and vein quartz and their fluid inclusions in the Jinfeng (Lannigou) gold deposit, Guizhou province, China. Acta Petrol Sin 23(10):2423–2433Google Scholar
  11. Chesley JT, Halliday AN, Scrivener RC (1991) Samarium–neodymium direct dating of fluorite mineralization. Science 252(5008):949–951Google Scholar
  12. Chesley JT, Halliday AN, Kyser TK, Spry PG (1994) Direct dating of MVT mineralization: use of Sm–Nd in fluorite. Econ Geol 89(5):1192–1199Google Scholar
  13. Debruyne D, Hulsbosch N, Muchez P (2016) Unraveling rare earth element signatures in hydrothermal carbonate minerals using a source–sink system. Ore Geol Rev 72:232–252Google Scholar
  14. Deng H, Huang ZL, Xiao XG, Ding W (2014) REE geochemistry of gangue calcite from Banpo deposit in Dushan antimony ore field, Guizhou province, China. Acta Mineral Sin 34(2):208–216Google Scholar
  15. Dromgoole EL, Walter LM (1990) Iron and manganese incorporation into calcite: effects of growth kinetics, temperature and solution chemistry. Chem Geol 81(4):311–336Google Scholar
  16. Elderfield H, Sholkovitz ER (1987) Rare earth elements in the pore waters of reducing nearshore sediments. Earth Planet Sci Lett 82(3–4):280–288Google Scholar
  17. Fan JG, Ni P, Su WC, Qi L, Tian JH (2000) Characteristics and significance of rare earth elements in quartz of Sidaogou hydrothermal gold deposit, Liaoning. Acta Petrol Sin 16(4):587–590Google Scholar
  18. Feng CX, Bi XW, Wu LY, Zou ZC, Tang YY (2011) Significance and characteristics of REE geochemistry in calcite in the eastern ore belt of the Baiyangping poly-metallic metallogenic province, northwestern Yunnan province, China. J Jilin Univ Earth Sci Ed 41(5):1397–1406Google Scholar
  19. Feng CX, Bi XW, Liu S, Hu RZ (2014) Fluid inclusion, rare earth element geochemistry, and isotopic characteristics of the eastern ore zone of the Baiyangping polymetallic Ore district, northwestern Yunnan Province, China. J Asian Earth Sci 85(2):140–153Google Scholar
  20. Gagnon JE, Samson IM, Fryer BJ et al (2003) Compositional heterogeneity in fluorite and the genesis of fluorite deposits: insights from LA-ICP-MS analysis. Can Mineral 41(2):365–382Google Scholar
  21. Ghaderi M, Palin JM, Campbell IH, Sylvester PJ (1999) Rare earth element systematics in scheelite from hydrothermal gold deposits in the Kalgoorlie-Norseman region, Western Australia. Econ Geol 94(3):423–437Google Scholar
  22. Han ZC, Wang JS, Gao ZH (2017) Geochemical characteristics and implications of REE, carbon and oxygen isotopes of calcite from La’e mercury deposit. J Kunming Univ Sci Technol Nat Sci Ed 42(3):28–37Google Scholar
  23. Hazarika P, Mishra B, Pruseth KL (2016) Scheelite, apatite, calcite and tourmaline compositions from the late Archean Hutti orogenic gold deposit: Implications for analogous two stage ore fluids. Ore Geol Rev 72:989–1003Google Scholar
  24. Hecht L, Freiberger R, Gilg HA, Grundmann G, Kostitsyn YA (1999) Rare earth element and isotope (C, O, Sr) characteristics of hydrothermal carbonates: genetic implications for dolomite-hosted talc mineralization at Göpfersgrün (Fichtelgebirge, Germany). Chem Geol 155(1–2):115–130Google Scholar
  25. Huang DY, Lei WL (1997) The geological features and metallogenetic mechanism of Muli Sb deposit, Guangxi. Yunnan Geol 16(4):377–385Google Scholar
  26. Huang ZL, Chen J, Han RS, Li WB, Gao DR, Zhao DS, Liu CQ (2001) REE geochemistry of calcite—a gangue mineral in the Huize ore deposit, Yunnan. Acta Mineral Sin 21(4):659–666Google Scholar
  27. Huang JG, Li HJ, Li WJ, Dong L (2012) Element geochemistry of ore-bearing rock series in the Getang gold deposit, Guizhou Province. Geol China 39(5):1318–1326Google Scholar
  28. Jiang YN (1988) The distribution characteristics of the rare earth elements in phyllites and iron-bearing quartzites form Anshan district. Contr Geol Miner Resour Res 3(1):23–31Google Scholar
  29. Johannesson KH, Lyons WB, Yelken MA, Gaudette HE, Stetzenbach KJ (1996) Geochemistry of the rare-earth elements in hypersaline and dilute acidic natural terrestrial waters: Complexation behavior and middle rare-earth element enrichments. Chem Geol 133(1–4):125–144Google Scholar
  30. Klinkhammer GP, Elderfield H, Edmond JM, Mitra A (1994) Geochemical implications of rare earth element patterns in hydrothermal fluids from mid-ocean ridges. Geochim Cosmochim Acta 58(23):5105–5113Google Scholar
  31. Leng CB, Wang YH, Zhang XC, Gao JF, Zhang W, Xu XY (2018) Constraints of molybdenite Re–Os and scheelite Sm–Nd ages on mineralization time of the Kukaazi Pb–Zn–Cu–W deposit, Western Kunlun, NW China. Acta Geochim 37(1):47–59Google Scholar
  32. Leybourne MI, Goodfellow WD, Dan RB, Hall GM (2000) Rapid development of negative Ce anomalies in surface waters and contrasting REE patterns in groundwaters associated with Zn–Pb massive sulphide deposits. Appl Geochem 15(6):695–723Google Scholar
  33. Li B (1999) Origin of ore forming material of the Muli antimony deposit. Geol Explor Non-Ferr Met 8(2):103–106Google Scholar
  34. Li HM, Shen YC, Mao JW, Liu TB, Zhu HP (2003) REE features of quartz and pyrite and their fluid inclusions: an example of Jiaojia-type gold deposits, northwestern Jiaodong peninsula. Acta Petrol Sin 19(2):267–274Google Scholar
  35. Li XF, Wang G, Mao W, Wang CZ, Xiao R, Wang M (2015) Fluid inclusions, muscovite Ar–Ar age, and fluorite trace elements at the Baiyanghe volcanic Be–U–Mo deposit, Xinjiang, northwest China: implication for its genesis. Ore Geol Rev 64:387–399Google Scholar
  36. Liang T, Wang DH, Qu WJ, Cai MH, Wei KL, Huang HM, Wu DC (2007) REE geochemistry of calcites in the Dachang tin-polymetallic deposit, Guangxi. Acta Petrol Sin 23(10):2493–2503Google Scholar
  37. Lottermoser BG (1992) Rare earth elements and hydrothermal ore formation processes. Ore Geol Rev 7(1):25–41Google Scholar
  38. Mao GZ, Hua RM, Gao JF, Long GM, Lu HJ, Li WQ, Zhao KD (2006) Existence of REE in different phases of gold-bearing pyrite in the Jinshan gold deposit, Jiangxi province. Acta Mineral Sin 26(4):409–418Google Scholar
  39. Mao GZ, Hua RM, Gao JF, Zhao KD, Long GM, Lu HJ, Yao JM (2010) Rare earth element and trace element features of gold-bearing pyrite in the Jinshan Gold Deposit, Jiangxi Province. Acta Geologica Sinica 84(3):614–623Google Scholar
  40. Moller P, Morteani G (1983) On the geochemical fractionation of rare earth elements during the formation of Ca-minerals and its application to problems of the genesis of ore deposits. Bulletin De Lacadémie Nationale De Médecine 152(28):747–791Google Scholar
  41. Mucci A (1988) Manganese uptake during calcite precipitation from seawater: conditions leading to the formation of a pseudokutnahorite. Geochim Cosmochim Acta 52(7):1859–1868Google Scholar
  42. Norman DI, Landis GP (1983) Source of mineralizing components in hydrothermal ore fluids as evidenced by 87Sr/86Sr and stable isotope data from the Pasto Bueno deposit, Peru. Econ Geol 78(3):451–465Google Scholar
  43. Peng JT, Hu RZ, Jiang GH (2003) Samarium–neodymium isotopic system of fluorites from the Qinglong antimony deposit, Guizhou province: constraints on the mineralizing age and ore-forming materials’ sources. Acta Petrol Sin 19(4):785–791Google Scholar
  44. Peng JT, Hu RZ, Qi L, Zhao JH, Fu YZ (2004) REE distribution pattern for the hydrothermal calcites from the Xikuangshan antimony deposit and its constraining factors. Geol Rev 50(1):25–32Google Scholar
  45. Peng JT, Fu YZ, Yuan SD, Shen NP, Zhang DL (2006) Sm–Nd isotope dating of some Ca-bearing minerals in hydrothermal deposits. Geol Rev 52(5):662–667Google Scholar
  46. Pingitore NE Jr, Eastman MP, Sandidge M, Oden K, Freiha B (1988) The coprecipitation of manganese(II) with calcite: an experimental study. Mar Chem 25(2):107–120Google Scholar
  47. Qi XX, Tian-Fu Li TF, Yu CL (2008) Rare earth element and trace element geochemistry of Shalagang antimony deposit in the southern tibet and its tracing significance for the origin of metallogenic elements. GeoSci 22(2):162–172Google Scholar
  48. Rimstidt JD, Balog A, Webb J (1998) Distribution of trace elements between carbonate minerals and aqueous solutions. Geochim Cosmochim Acta 62(11):1851–1863Google Scholar
  49. Roberts S, Palmer MR, Waller L (2006) Sm–Nd and REE characteristics of tourmaline and scheelite from the Björkdal gold deposit, northern Sweden: evidence of an intrusion-related gold deposit? Econ Geol 101(7):1415–1425Google Scholar
  50. Schönenberger J, Köhler J, Markl G (2008) REE systematics of fluorides, calcite and siderite in peralkaline plutonic rocks from the Gardar province, South Greenland. Chem Geol 247(1–2):16–35Google Scholar
  51. Schwinn G, Markl G (2005) REE systematics in hydrothermal fluorite. Chem Geol 216(3–4):225–248Google Scholar
  52. Shen NP, Cai JL, Su WC, Dong WD (2015) Characteristics and source significance of trace element geochemistry of fluorite from Chashan Sb–W deposit in Guangxi. Acta Geol Sin 89(2):384–391Google Scholar
  53. Su WC, Hu RZ, Xia B, Xia Y, Liu YP (2009) Calcite Sm–Nd isochron age of the Shuiyindong Carlin-type gold deposit, Guizhou, China. Chem Geol 258(3):269–274Google Scholar
  54. Su WC, Dong WD, Zhang XC, Shen NP, Hu RZ, Hofstra AH, Cheng LZ, Xia Y, Yang KY (2018) Carlin-type gold deposits in the Dian-Qian-Gui “Gold Triangle” of Southwest China. Rev Econ Geol 20:157–185Google Scholar
  55. Subías I, Fernández-Nieto C (1995) Hydrothermal events in the Valle de Tena (Spanish Western Pyrenees) as evidenced by fluid inclusions and trace-element distribution from fluorite deposits. Chem Geol 124(3–4):267–282Google Scholar
  56. Takahashi Y, Yoshida H, Sato N, Hama K, Yusa Y, Shimizu H (2002) W- and M-type tetrad effects in REE patterns for water-rock systems in the Tono uranium deposit, central Japan. Chem Geol 184(3):311–335Google Scholar
  57. Veksler IV, Dorfman AM, Kamenetsky M, Dulski P, Dingwell DB (2005) Partitioning of lanthanides and Y between immiscible silicate and fluoride melts, fluorite and cryolite and the origin of the lanthanide tetrad effect in igneous rocks. Geochim Cosmochim Acta 69(11):2847–2860Google Scholar
  58. Wang LJ, Man KL (1994) Analysis of ore-control geological conditions of Muli antimony deposit, Guangnan. Yunnan Geol 13(2):133–138Google Scholar
  59. Wang GZ, Hu RZ, Liu Y, Sun GS, Su WC, Liu H (2003) REE geochemical characteristics from fluorite in Qinglong antimony deposit, south-western Guizhou. J Mineral Petrol 23(2):62–65Google Scholar
  60. Wang JS, Wen HJ, Shi SH (2010) Characteristics and implications of REE, carbon and oxygen isotopes of hydrothermal calcite from the mercury metallogenic belt in Hunan and Guizhou provinces, China. Acta Mineral Sin 30(2):185–193Google Scholar
  61. Wang JJ, Hu YZ, Han RS (2011) Geochemical characteristics and its implications of trace elements in Qinglong antimony deposit, Guizhou province, China. Acta Mineral Sin 31(3):571–577Google Scholar
  62. Wang DH, Li C, Chen ZH, Wang CH, Huang F, Qu WJ (2012a) New application of molybdenite in the study on ore deposits: rare earth elements geochemistry. J Jilin Univ Earth Sci Ed 42(6):1647–1655Google Scholar
  63. Wang JS, Wen HJ, Fan HF, Zhu JJ (2012b) Sm–Nd geochronology, REE geochemistry and C and O isotope characteristics of calcites and stibnites from the Banian antimony deposit, Guizhou Province, China. Geochem J 46(5):393–407Google Scholar
  64. Wang ZP, Xia Y, Song XY, You B, Zheng XH, Wang XY (2012c) Isotopes and REE characteristic and ore-forming materials source of the Taipingdong-Zimudang gold deposit. Acta Mineral Sin 32(1):93–100Google Scholar
  65. Wang JS, Wen HJ, Li C, Jiang XJ, Zhu CW, Du SJ, Lei Z (2015) Determination of age and source constraints for the Bake quartz vein-type gold deposit in SE Guizhou using arsenopyrite Re–Os chronology and REE characteristics. Geochem J 49(1):73–81Google Scholar
  66. Wang JS, Han ZC, Li C, Gao ZH, Yang Y, Zhou GC (2018) REE, Fe and Mn contents of calcites and their prospecting significance for the Banqi carlin-type gold deposit in southwestern China. Geotect Met 42(3):494–504Google Scholar
  67. Whitney PR, Olmsted JF (1998) Rare earth element metasomatism in hydrothermal systems: the Willsboro–Lewis wollastonite ores, New York, USA. Geochim Cosmochim Acta 62(17):2965–2977Google Scholar
  68. Wood SA (1990) The aqueous geochemistry of the rare-earth elements and yttrium: 2. Theoretical predictions of speciation in hydrothermal solutions to 350 °C at saturation water vapor pressure. Chem Geol 88(1–2):99–125Google Scholar
  69. Yan SH, Wang AJ, Gao L, Zhao YQ, Chen GZ (2000) REE geochemistry and implications of stable isotopes in Dashui type gold deposits. Miner Depos 19(1):37–45Google Scholar
  70. Yu KJ (1990) Geological characteristics and exploration experience on Yunnan antimony ores. Yunnan Geology 9(2):83–94Google Scholar
  71. Zhang Y, Xia Y, Wang ZP, Yan BW, Fu ZK, Chen M (2010) REE and stable isotope geochemical characteristics of Bojitian gold deposit, Guizhou province. Geosci Front 17(2):385–395Google Scholar
  72. Zhang XD, Yang RD, Wang W, Wei HR (2011) The geochemical characteristics and significance of trace element and REE in Pingqiu gold deposits, southeastern Guizhou. J Mineral Petrol 31(1):63–69Google Scholar
  73. Zhang Y, Gu XX, Zhang YM, Cheng WB, Song YQ (2012) Geochemical characteristics of rare earth elements and its significance in the mineralization of quartz and pyrite in the Liubeigou gold deposit, Inner Mongolia. Bull Mineral Petrol Geochem 31(1):23–30Google Scholar
  74. Zhao ZH, Masuda A, Shabani MB (1992) Tetrad effects of rare-earth elements in rare-metal granites. Geochimica 3:221–233Google Scholar
  75. Zhao ZH, Xiong XL, Han XD, Wang YX, Wang Q, Bao ZW, Jahn B (2002) Controls on the REE tetrad effect in evidence from the Qianlishan and Baerzhe Granites, China. Geochem J 36(6):527–543Google Scholar
  76. Zheng J, Yu DL, Yang ZQ (2010) A study on the trace element geochemical characteristics of pyrite and arsenopyrite in Bake gold deposit, east Guizhou province, P. R. China. Acta Mineral Sin 30(1):107–114Google Scholar
  77. Zheng J, Yu DL, Wu WM, Yang ZQ, Liu Y (2011) Typomorphic characteristics of arsenopyrite in the Bake gold deposit, eastern Guizhou province. GeoSci 25(4):750–758Google Scholar
  78. Zhou H, Greig A, Tang J, You CF, Yuan DX, Tong XN, Huang Y (2012) Rare earth element patterns in a Chinese stalagmite controlled by sources and scavenging from karst groundwater. Geochim Cosmochim Acta 75(1):1–18Google Scholar
  79. Zhu JB, Fang WX, Liu JJ, Hu YZ (2010) The REE characteristics and genetic study of Qinglong antimony deposit, Guizhou. Contr Geol Miner Resour Res 25(2):118–123Google Scholar

Copyright information

© Science Press and Institute of Geochemistry, CAS and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Southwest Institute of Geological SurveyKunming University of Science and TechnologyKunmingChina
  2. 2.National Research Center for GeoanalysisBeijingChina

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