The mixing of multi-source fluids in the Wusihe Zn–Pb ore deposit in Sichuan Province, Southwestern China

  • Hongjie Zhang
  • Haifeng FanEmail author
  • Chaoyi Xiao
  • Hanjie Wen
  • Lin Ye
  • Zhilong Huang
  • Jiaxi Zhou
  • Qingjun Guo
Original Article


The Sichuan–Yunnan–Guizhou (SYG) metallogenic province of southwest China is one of the most important Zn–Pb ore zones in China, with ~ 200 Mt Zn–Pb ores at mean grades of 10 wt.% Zn and 5 wt.% Pb. The source and mechanism of the regional Zn–Pb mineralization remain controversial despite many investigations that have been conducted. The Wusihe Zn–Pb deposit is a representative large-scale Zn–Pb deposit in the northern SYG, which mainly occurs in the Dengying Formation and yields Zn–Pb resources of ~ 3.7 Mt. In this paper, Zn and S isotopes, and Fe and Cd contents of sphalerite from the Wusihe deposit were investigated in an attempt to constrain the controls on Zn and S isotopic variations, the potential sources of ore-forming components, and the possible mineralization mechanisms. Both the δ66Zn and δ34S values in sphalerite from the Wusihe deposit increase systematically from the bottom to the top of the strata-bound orebodies. Such spatial evolution in δ66Zn and δ34S values of sphalerite can be attributed to isotopic Rayleigh fractionation during sphalerite precipitation with temperature variations. The strong correlations between the Zn–S isotopic compositions and Fe–Cd concentrations in sphalerite suggest that their variations were dominated by a similar mechanism. However, the Rayleigh fractionation mechanism cannot explain the spatial variations of Fe and Cd concentrations of sphalerite in this deposit. It is noted that the bottom and top sphalerites from the strata-bound orebodies document contrasting Zn and S isotopic compositions which correspond to the Zn and S isotopic characteristics of basement rocks and host rocks, respectively. Therefore, the mixing of two-source fluids with distinct Zn–S isotopic signatures was responsible for the spatial variations of Zn–S isotopic compositions of sphalerite from the Wusihe deposit. The fluids from basement rocks are characterized by relatively lighter Zn (~ 0.2 ‰) and S (~ 5 ‰) isotopic compositions while the fluids from host rocks are marked by relatively heavier Zn (~ 0.6 ‰) and S (~ 15 ‰) isotopic compositions.


Sichuan–Yunnan–Guizhou Wusihe Zn–Pb deposit Zn–S isotopes Fe–Cd contents Two-source fluids 



This project was funded by the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (XDB18030302), the National Key R&D Program of China (2017YFC0602503), the National Natural Science Foundation of China (U1812402, 41430315, 41573011, 41625006). We give thanks to the two reviewers for reviewing the manuscript and the editor for providing comments and editorial reversions.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflicts of interest.


  1. Archer C, Vance D, Butler I (2004) Abiotic Zn isotope fractionations associated with ZnS precipitation. Geochim Cosmochim Acta 68:A325Google Scholar
  2. Belissont R, Boiron MC, Luais B, Cathelineau M (2014) LA-ICP-MS analyses of minor and trace elements and bulk Ge isotopes in zoned Ge-rich sphalerites from the Noailhac–Saint–Salvy deposit (France): insights on incorporation mechanisms and ore deposition processes. Geochim Cosmochim Acta 126:518–540CrossRefGoogle Scholar
  3. Bethke PH, Borton PB (1971) Distribution of some minor elements between coexisting sulfide minerals. Econ Geol 66:140–165CrossRefGoogle Scholar
  4. Bortnikov NS, Dobrovol’skaya MG, Genkin AD, Naumov VB, Shapenko VV (1995) Sphalerite-galena geothermometers: distribution of cadmium, manganese, and the fractionation of sulfur isotopes. Econ Geol 90:155–180CrossRefGoogle Scholar
  5. Böttcher ME, Smock AM, Cypionka H (1998) Sulfur isotope fractionation during experimental precipitation of iron (II) and manganese (II) sulfide at room temperature. Chem Geol 146:127–134CrossRefGoogle Scholar
  6. Chaussidon M, Albarède F, Sheppard SMF (1989) Sulphur isotope variations in the mantle from ion microprobe analyses of micro-sulphide inclusions. Earth Planet Sci Lett 92:144–156CrossRefGoogle Scholar
  7. Feng JQ, Li Y, Liu WZ (2009) Geological features and ore control conditions for the Tianbaoshan Zn–Pb deposit in Huili. Acta Geologica Sichuan 29(4):426–430 (In Chinese with English abstract) Google Scholar
  8. Fujii T, Moynier F, Pons ML, Albarède F (2011) The origin of Zn isotope fractionation in sulfides. Geochim Cosmochim Acta 75(23):7632–7643CrossRefGoogle Scholar
  9. Gagnevin D, Boyce AJ, Barrie CD, Menuge JF, Blakeman RJ (2012) Zn, Fe and S isotope fractionation in a large hydrothermal system. Geochim Cosmochim Acta 88:183–198CrossRefGoogle Scholar
  10. Gao ZF, Zhu XK, Sun J, Luo ZH, Bao C, Tang C, Ma JX (2017) Spatial evolution of Zn–Fe–Pb isotopes of sphalerite within a single ore body: a case study from the Dongshengmiao ore deposit, Inner Mongolia, China. Miner Deposita 15:1–11Google Scholar
  11. Guan SP, Li ZX (1999) Lead-sulfur isotope study of carbonate-hosted lead-zinc deposits at the eastern margin of the Kangdian axis. Geol Geochem 27:45–54 (In Chinese with English abstract) Google Scholar
  12. Han RS, Liu CQ, Huang ZL, Chen J, Ma DY, Lei L, Ma GS (2007) Geological features and origin of the Huize carbonate-hosted Zn–Pb–(Ag) district, Yunnan, South China. Ore Geol Rev 31:360–383CrossRefGoogle Scholar
  13. He CZ, Xiao CY, Wen HJ, Zhou T, Zhu CW, Fan HF (2016) Zn–S isotopic compositions of the Tianbaoshan carbonate-hosted Zn–Pb deposit in Sichuan, China: implications for source of ore components. Acta Petrol Sin 32:3394–3406 (In Chinese with English abstract) Google Scholar
  14. Herzog GF, Moynier F, Albarede F, Berezhnoy AA (2009) Isotopic and elemental abundances of copper and zinc in lunar samples, Zagami, Pele’s hairs, and a terrestrial basalt. Geochim Cosmochim Acta 73:5884–5904CrossRefGoogle Scholar
  15. Hu RZ, Fu SL, Huang Y, Zhou MY, Fu SH, Zhao CH, Wang YJ, Bi XW, Xiao JF (2017) The giant South China Mesozoic low-temperature metallogenic domain: reviews and a new geodynamic model. J Asian Earth Sci 137:9–34CrossRefGoogle Scholar
  16. Huang ZL, Li WB, Chen J, Han RS, Liu CQ, Xu C, Guan T (2003) Carbon and oxygen isotope constraints on the mantle fluids join the mineralization of the Huize superlarge Pb–Zn deposits, Yunnan Province, China. J Geochem Explor 78(79):637–642CrossRefGoogle Scholar
  17. John SG, Rouxel OJ, Craddock PR, Engwall AM, Boyle EA (2008) Zinc stable isotopes in seafloor hydrothermal vent fluids and chimneys. Earth Planet Sci Lett 269:17–28CrossRefGoogle Scholar
  18. Kelley KD, Wilkinson JJ, Chapman JB, Crowther HL, Weiss DJ (2009) Zinc isotopes in sphalerite from base metal deposits on the red dog district, northern Alaska. Econ Geol 104:767–773CrossRefGoogle Scholar
  19. Li SZ, Zhu XK, Tang SH, He XX, Cai JJ (2008) The application of MC-ICP-MS to high-precision measurement of Zn isotope ratios. Acta Petrol Mineral 27:273–278 (In Chinese with English abstract) Google Scholar
  20. Lin FC (2005) Hydrothermal exhalative metallogeny of stratiform Zn–Pb deposits on western margin of the Yangtze craton. Ph.D. Dissertation, Chengdu University of Technology, Chengdu, pp 1–113 (in Chinese with English abstract)Google Scholar
  21. Liu HC, Lin WD (1999) Study on the law of Zn–Pb–Ag Ore deposit in northeast Yunnan. China. Yunnan University Press, Kunming, pp 1–468 (in Chinese) Google Scholar
  22. Liu TG, Ye L, Zhou JX, Shao SX (2012) The correlativity of mineralization stages and Cd, Fe contents in the sphalerite. Bull Mineral Petrol Geochem 31:79–81 (In Chinese with English abstract) Google Scholar
  23. Liu SA, Wang ZZ, Li SG, Huang J, Yang W (2016) Zinc isotope evidence for a large-scale carbonated mantle beneath eastern China. Earth Planet Sci Lett 444:169–178CrossRefGoogle Scholar
  24. Luo K, Zhou JX, Huang ZL, Wang XC, Wilde SA, Zhou W, Tian LY (2019) New insights into the origin of early Cambrian carbonate-hosted Pb–Zn deposits in South China: a case study of the Maliping Pb–Zn deposit. Gondwana Res 70:88–103CrossRefGoogle Scholar
  25. Machel HG, Krouse HR, Sassen R (1995) Products and distinguishing criteria of bacterial and thermochemical sulfate reduction. Appl Geochem 10:373–389CrossRefGoogle Scholar
  26. Maréchal CN, Sheppard SMF (2002) Isotopic fractionation of Cu and Zn between chloride and nitrate solutions and malachite or smithsonite at 30 degrees and 50 degrees C. In: Goldschmidt conference. Geochim Cosmochim Acta 66:A484Google Scholar
  27. Maréchal CN, Télouk P, Albarède F (1999) Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chem Geol 156(1–4):251–273CrossRefGoogle Scholar
  28. Mason TFD, Weiss DJ, Chapman JB, Wilkinson JJ, Tessalina SG, Spiro B, Horstwood MSA, Spratt J, Coles BJ (2005) Zn and Cu isotopic variability in the Alexandrinka volcanic-hosted massive sulphide (VHMS) ore deposit, Urals, Russia. Chem Geol 221(3–4):170–187CrossRefGoogle Scholar
  29. Moeller K, Schoenberg R, Pedersen RB, Weiss D, Dong SF (2012) Calibration of the new certified reference materials ERM-AE633 and ERM-AE647 for copper and IRMM-3702 for zinc isotope amount ratio determinations. Geostand Geoanal Res 36(2):177–199CrossRefGoogle Scholar
  30. Pašava J, Tornos F, Chrastný V (2014) Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits, Cantabria, Spain. Miner Deposita 49:797–807CrossRefGoogle Scholar
  31. Pichat S, Douchet C, Albarède F (2003) Zinc isotope variations in deep-sea carbonates from the eastern equatorial Pacific over the last 175 ka. Earth Planet Sci Lett 210(1–2):167–178CrossRefGoogle Scholar
  32. Rye RO, Ohmoto H (1974) Sulfur and carbon isotopes and ore genesis: a review. Econ Geol 69:826–842CrossRefGoogle Scholar
  33. Samanta M, Ellwood MJ, Mortimer GE (2016) A method for determining the isotopic composition of dissolved zinc in seawater by MC-ICP-MS with 67Zn–68Zn double spike. Microchem J 126:530–537CrossRefGoogle Scholar
  34. Seewald JS, Seyfried WE (1990) The effect of temperature on metal mobility in subseafloor hydrothermal systems: constraints from basalt alteration experiments. Earth Planet Sci Lett 101:388–403CrossRefGoogle Scholar
  35. Tang SH, Zhu XK, Cai JJ, Li SZ, He XX, Wang JH (2006) Chromatographic separation of Cu, Fe and Zn using AGMP-1 anion exchange resin for isotope determination by MC-ICP-MS. Rock Miner Anal 25:5–8 (In Chinese with English abstract) Google Scholar
  36. Thiessen EJ, Gleeson SA, Bennett V, Creaser RA (2016) The Tiger deposit: a carbonate-hosted, magmatic-hydrothermal gold deposit, Central Yukon, Canada. Econ Geol 111:421–446CrossRefGoogle Scholar
  37. Toutain JP, Sonke J, Munoz M, Nonell A, Polvé M, Viers J, Freydier R, Sortino F, Joron JL, Sumarti S (2008) Evidence for Zn isotopic fractionation at Merapi Volcano. Chem Geol 253(1–2):74–82CrossRefGoogle Scholar
  38. Wang H, Sun ZJ, Cheng XY, Jiang BB (2016) The geochemical characteristics and metallogenic mechanism of the Daliangzi Pb-Zn deposit in Sichuan province. Acta Geol Sin (Engl Ed) 89:287–288Google Scholar
  39. Wen HJ, Zhu CW, Zhang YX, Cloque C, Fan HF, Fu SH (2016) Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits. Sci Rep 20:5–8. Google Scholar
  40. Wilkinson JJ, Weiss DJ, Mason TFD, Coles BJ (2005) Zinc isotope variation in hydrothermal systems: preliminary evidence from the Irish midlands ore field. Econ Geol 100(3):583–590CrossRefGoogle Scholar
  41. Xiong SF, Yao SZ, Gong YJ, Tan MT, Zeng GP, Wang W (2016) Ore-forming fluid and thermochemical sulfate reduction in the Wusihe lead-zinc deposit, Sichuan Province, China. Earth Sci 41:105–120 (In Chinese with English abstract) Google Scholar
  42. Xiong SF, Gong YJ, Jiang SY, Zhang XJ, Li Q, Zeng GP (2018) Ore genesis of the Wusihe carbonate-hosted Zn–Pb deposit in the Dadu River Valley district, Yangtze Block, SW China. Miner Deposita 53(7):967–979CrossRefGoogle Scholar
  43. Ye L, Cook NJ, Ciobanu CL, Liu YP, Zhang Q, Liu TG, Gao W, Yang YL, Danyushevsky L (2011) Trace and minor elements in sphalerite from base metal deposits in South China: a LA-ICPMS study. Ore Geol Rev 39:188–217CrossRefGoogle Scholar
  44. Zhang TG, Chu XL, Zhang QR, Feng LJ, Huo WG (2004) The sulfur and carbon isotopic records in carbonates of the Dengying Formation in the Yangtze Platform, China. Acta Petrol Sin 20:717–724 (in Chinese with English abstract) Google Scholar
  45. Zhang CQ, Wu Y, Hou L, Mao JW (2015) Geodynamic setting of mineralization of Mississippi Valley-type deposits in world-class Sichuan-Yunnan-Guizhou Zn–Pb triangle, southwest China: implications from age-dating studies in the past decade and the Sm–Nd age of Jinshachang deposit. J Asian Earth Sci 103:103–114CrossRefGoogle Scholar
  46. Zhang HJ, Xiao CY, Wen HJ, Zhu XK, Ye L, Huang ZL, Fan HF (2019) Homogeneous Zn isotopic compositions in the Maozu Zn–Pb ore deposit in Yunnan Province, Southwestern China. Ore Geol Rev 109:1–10CrossRefGoogle Scholar
  47. Zheng XZ (2012) Geological features and genesis of WuSiHe Zn–Pb deposit, Sichuan. M.Sc. Thesis, Chang’an University, Xi’an, pp 1–75 (in Chinese with English abstract)Google Scholar
  48. Zhou MF, Malpas J, Song XY, Robinson PT, Sun M, Kennedy AK, Lesher CM, Keays RR (2002) A temporal link between the Emeishan large igneous province (SW China) and the end-Guadalupian mass extinction. Earth Planet Sci Lett 196:113–122CrossRefGoogle Scholar
  49. Zhou JX, Huang ZL, Yan ZF (2013) The origin of the Maozu carbonate-hosted Zn–Pb deposit, southwest China: constrained by C–O–S–Pb isotopic compositions and Sm-Nd isotopic age. J Asian Earth Sci 73:39–47CrossRefGoogle Scholar
  50. Zhou JX, Huang ZL, Zhou MF, Zhu XK, Gao JG, Mirnejad H (2014a) Geology, isotope geochemistry and ore genesis of the Shanshulin carbonate-hosted Zn–Pb deposit, Southwest China. Ore Geol Rev 63:209–225CrossRefGoogle Scholar
  51. Zhou JX, Huang ZL, Zhou MF, Zhu XK, Muchez P (2014b) Zinc, sulfur and lead isotopic variations in carbonate-hosted Pb–Zn sulfide deposits, southwest China. Ore Geol Rev 58:41–54CrossRefGoogle Scholar
  52. Zhou JX, Xiang ZZ, Zhou MF, Feng YX, Luo K, Huang ZL, Wu T (2018) The giant upper Yangtze Zn–Pb province in SW China: reviews, new advances and a new genetic model. J Asian Earth Sci 154:280–315CrossRefGoogle Scholar
  53. Zhu CW, Wen HJ, Zhang YX, Fan HF (2016) Cadmium and sulfur isotopic compositions of the Tianbaoshan Zn–Pb–Cd deposit, Sichuan Province, China. Ore Geol Rev 76:152–162CrossRefGoogle Scholar
  54. Zhu CW, Wen HJ, Zhang YX, Fu SH, Fan HF, Cloquet C (2017) Cadmium isotope fractionation in the Fule Mississippi Valley-type deposit, Southwest China. Miner Deposita 52:675–686CrossRefGoogle Scholar
  55. Zhu CW, Liao SL, Wang W, Zhang YX, Yang T, Fan HF, Wen HJ (2018) Variations in Zn and S isotope chemistry of sedimentary sphalerite, Wusihe Zn–Pb deposit, Sichuan Province, China. Ore Geol Rev 95:639–648CrossRefGoogle 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.State Key Laboratory of Ore Deposit GeochemistryInstitute of Geochemistry, Chinese Academy of SciencesGuiyangChina
  2. 2.University of Chinese Academy of SciencesBeijingChina
  3. 3.School of Resource Environment and Earth SciencesYunnan UniversityKunmingChina
  4. 4.Center for Environmental Remediation, Institute of Geographic Sciences and Natural Resources ResearchChinese Academy of SciencesBeijingChina

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