journal article·2026-07-02Open access

In Situ Trace Element Composition of Sphalerite and Its Geological Significance: A Case Study from the Huize Ge-Rich Pb-Zn Deposit, NE Yunnan

Fenghao Li, Runsheng Han, Yan Zhang, Hongwei Liu, Hanzhang Gu, Jiuli Yu, Lihui Zhu, Baosheng Huang, Ticai Hu

Applied Sciences· Volume 16· Issue 13

Abstract

The Huize Ge-rich Pb-Zn deposit is an important part of the Sichuan–Yunnan–Guizhou carbonate-hosted Pb-Zn metallogenic area and is one of the most representative super-large deposits in the northeastern Yunnan Pb-Zn ore concentration area. The orebodies mainly occur in NE-trending interlayer fault zones. The Pb-Zn mineralization process of this deposit can be divided into the dolomite stage (I), sphalerite-galena stage (II), galena-sphalerite stage (III), and pyrite-calcite stage (IV). Based on a study of the deposit geology, we utilized LA-ICP-MS for in situ microanalysis of trace element compositions and element mapping of sphalerite from different stages to reveal the characteristics of the sphalerite trace element composition and occurrence mechanisms, understand the mineralization process, and constrain the genetic type of the deposit. This research shows that sphalerite color variations result from the multi-factor coupling of multiple trace element contents, element associations, and isomorphic substitutions among elements. Trace elements such as Mn, Fe, Cu, Ga, Ge, Ag, Cd, In, Sn, Sb, and Hg occur in the sphalerite lattice in the form of isomorphic substitutions or nanoscale mineral inclusions, whereas Pb occurs mainly as microscopic mineral inclusions (galena) in sphalerite. From the early to late stages of mineralization (SpI → SpII → SpIII), the mineralization temperature (132–205 °C) and sulfur fugacity (log10 fS2 = −15.29 to −19.89) both show a gradual decrease. During sphalerite crystallization in different stages, multiple trace elements exhibit coupled multi-element substitutions at the microscale: SpI: Zn2+ ↔ (Fe2+, Mn2+, Cd2+), 2Zn2+ ↔ 2Ag+ + Ge2+; SpII: Zn2+ ↔ (Fe2+, Cd2+), 2Zn2+ ↔ 2Ag+ + Ge2+, 3Zn2+ ↔ 2Cu2+ + Ge2+, 3Zn2+ ↔ 2(Cu, Ag)2+ + Ge2+, 2Zn2+ ↔ Ga3+ + Cu+, 2Zn2+ ↔ Ga3+ + (Cu, Ag)+; and SpIII: Zn2+ ↔ (Fe2+, Mn2+), 3Zn2+ ↔ 2Cu2+ + Ge2+, 3Zn2+ ↔ 2(Cu, Ag)2+ + Ge2+). Mn, Fe, and Ge are mainly enriched in SpI; Ga and Ag are mainly enriched in SpII; and Cd is mainly enriched in both SpI and SpII. By comparing the sphalerite trace elements signature of the Huize Ge-rich deposit with those of global typical MVT, SEDEX, VMS, epithermal, and skarn-type Pb-Zn deposits, and considering the deposit’s geological and geochemical characteristics, we suggest that the Huize Pb-Zn deposit is best classified as a medium- to low-temperature, carbonate-hosted Pb-Zn deposit.
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Geological and Geochemical Analysis · Geochemistry and Geologic Mapping · Mineralogy and Gemology Studies

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Faculty of Land Resources Engineering, Kunming University of Science and Technology, Kunming 650093, China

South–West Institute of Geological Survey, Geological Survey Center for Nonferrous Metals Resources, Kunming 650093, China

Yunnan Chihong Zn & Ge Co., Ltd., Qujing 655011, China

Geological Survey of Gansu Province, Lanzhou 730000, China

Funding

National Natural Science Foundation of China · Yunnan Science and Technology Plan Project · Yunnan Mineral Resources Prediction and Evaluation Engineering Research Center · Kunming University of Science and Technology

References (100+)

Show source-provided references
1. Origin of the newly discovered ore bodies in the Upper Sinian Dengying Formation of the Huize Pb-Zn deposit in Yunnan: Constraints from C-O-Sr isotopes
2. Geochemistry of germanium and its resources reserves
3. The giant Upper Yangtze Pb-Zn province in SW China: Reviews, new advances and a new genetic model10.1016/j.jseaes.2017.12.032 ↗
4. New research progresses of metallogenic theory for rich Zn-Pb-(Ag-Ge) deposits in the Sichuang–Yunnan–Guizhou Triangle (SYGT) area, southwestern
5. The main successive strategic bases of resources for Pb-Zn deposits in China
6. Mineralization-alteration zoning regularity and structural ore-controlling role in the Huize super-large sized Ge-Ag-rich Pb-Zn deposit, Yunnan Province
7. The control effect of metallotectonic system on lead-zinc metallogenic system: A case study of the Huize deposit, Yunnan Province
8. Sulfur and lead isotopic compositions of ores from the Dengying Formation and their prospecting implications in the Huize Pb-Zn deposit, Yunnan Province
9. Zhang, W.J. (1984). Discussion on genesis and forming law of Pb-Zn deposits in Northeast Yunnan. Geol. Prospect., 11–16. Available online: https://kns.cnki.net/kcms2/article/abstract?v=YwS3ffssB6iH5bc3ZH1FiaaD66_SUn9S9XM540Yt_NuNT9cRRPHOZhm7JgrKLjRbNBQP6NeOZ8m0K838ebeFq9t7rkexLCOhc79c-V2UDkKrHg9-ZLYURteCkVrA7Sp4KIdpL22IS8EKicBbcbg_K9DzIw1G0-cU&uniplatform=NZKPT.
10. Chen, S.J. (1986). Research on the Genesis of Lead-Zinc Ore-Deposits in Western Guizhou and Northeastern. Geol. Guizhou, 211–222. Available online: https://kns.cnki.net/kcms2/article/abstract?v=YwS3ffssB6hFD6WZ1kBy8grB5YB3zI5lNwzeEPV8qmGSpSsEn5iIdvfBnTzr19mSE1MAqm1b0UUPj3yD71IKXFiLZxQ8NjvkUQJNDIEI5NjwRcIBvjWNnvMq93xMXo7kK3JVK1wFQXINMOrjS36iFLHpFOfJwiLV&uniplatform=NZKPT.
11. Liu, H.C., and Lin, W.D. (1999). Regularity Research of Lead-Zinc-Silver Deposits in Northeastern Yunnan Province, Yunnan University Press. (In Chinese).
12. Zhang, C.Q., Mao, J.W., Wu, S.P., Li, H.M., Liu, F., Guo, B.J., and Gao, D.R. (2005). Distribution characteristics and genesis of Mississippi Valley-Type lead-zinc deposits in Sichuan–Yunnan–Guizhou area. Miner. Depos., 336–348. (In Chinese with English abstract).
13. The source of metals in the Qilinchang Zn-Pb deposit, northeastern Yunnan, China: Pb-Sr isotope constraints10.2113/gsecongeo.96.3.583 ↗
14. Deposit model of germanium-rich silver-lead-zinc polymetallic ore concentration area in northeastern Yunnan
15. Trace and minor elements in sphalerite: A LA-ICPMS study10.1016/j.gca.2009.05.045 ↗
16. Trace and minor elements in sphalerite from base metal deposits in South China: A LA-ICPMS study10.1016/j.oregeorev.2011.03.001 ↗
17. 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 into incorporation mechanisms and ore deposition processes10.1016/j.gca.2013.10.052 ↗
18. The trace(dispersed) elements in pyrite from the Fule Pb-Zn deposit, Yunnan Province, China, and its genetic information: A LA-ICPMS study
19. The sources of ore-forming elements of the Maoping large-scale Pb-Zn deposit, Yunnan Province: Constrains from in-situ S and Pb isotopes
20. REE geochemistry of altered fault tectonites of Huize-type Zn-Pb-(Ge-Ag) deposit, Yunnan Province, China10.1144/1467-7873/10-MINDEP-053 ↗
21. Tu, G.Z., Gao, Z.M., Hu, R.Z., Zhang, Q., Li, C.Y., Zhao, Z.H., and Zhang, B.G. (2003). Dispersed element Geochemistry and metallogenic mechanism. Geol. Publ. House, 4–22. Available online: https://wenku.baidu.com/view/aa8426e3b84cf7ec4afe04a1b0717fd5360cb28e.html?_wkts_=1782495487376&needWelcomeRecommand=1.
22. Reviews and new metallogenic models of mineral deposits in South China: An introduction10.1016/j.jseaes.2017.02.035 ↗
23. The geological setting, characters and origin of Mississippi Valley-Type Pb-Zn deposits in Sichuan and Yunnan Province
24. Zhang, C.Q. (2008). The genetic model of Mississippi Valley-type deposits in the boundary area of Sichuan, Yunnan and Guizhou provinces, China. Chin. Acad. Geol. Sci., 1–167. Available online: https://kns.cnki.net/kcms2/article/abstract?v=YwS3ffssB6h3UiAhsSImQL_CfNlNHxCgLlz7hw-VPxo5gAVOImkpJIBvXDo5ieGga9-9DMqpEQBZFDQ9y1Gnc9FjfGe0-hZYWVBXxTmXuUnlYw80I2okeVZ-IoZBFL306xKAQs5ix8jIalDWjNEmZLS3UpI9WIugW4pCkTYs6cY=&uniplatform=NZKPT.
25. Huang, F.X. (2011). Filling process and evolutionary model of sedimentary sequence in middle-upper Yangtze cratonic basin. Kunming Univ. Sci. Technol., 1–153. Available online: https://kns.cnki.net/kcms2/article/abstract?v=YwS3ffssB6idFURP7R9-8eNdBsLO3bxIRe3bskKdqgAcNAGCFSOnGqEdQk4m_KxnQcq1QWfAgD8eKezR_MZZuz8ezIYzCAo6dtqs0AE2nfWJWpfjiwEPWwPpcGBOAj6TxmQLxBmq_zxBSka87iijYMgk66f7S3Ahbk_huBp8HyI=&uniplatform=NZKPT.
26. Study on Mantle Plume and Large Igneous Provinces in China: An Overview and Perspectives
27. The Basin Translation from Late Paleozoic to Triassic of the Youjiang Basin and Its Tectonic Signification
28. Sulfur isotope analysis of carbonate-hosted Zn-Pb deposits in northwestern Guizhou Province, Southwest China: Implications for the source of reduced sulfur10.1016/j.gexplo.2017.06.023 ↗
29. Deformation record of the change from Indosinian collision-related tectonic system to Yanshanian subduction-related tectonic system in South China during the Early Mesozoic
30. Wu, Y. (2013). The age and ore-forming process of MVT deposits in the boundary area of Sichuan–Yunnan–Guizhou provinces, Southwest China. China Univ. Geosci., 1–167. Available online: https://kns.cnki.net/kcms2/article/abstract?v=YwS3ffssB6h1Xj8X5YJMsgkHo8qbOI8M5O_HO9Qnf8plbY8FNSsbbg-H7gIuxZ2KCiiCM48X9wgL0FJiO81l9hLZrT_kPdf1QUwBXLK9tFHakfGY79bsOzY0DT911u-ERF4oagcP-W1YYgMaq9qsfjXRZo_MzL-wRHzhNhPjVqQ=&uniplatform=NZKPT.
31. New insights into the origin of early Cambrian carbonate-hosted Pb-Zn deposits in South China: A case study of the Maliping Pb-Zn deposit10.1016/j.gr.2018.12.015 ↗
32. Geological features and origin of the Huize carbonate-hosted Zn-Pb-(Ag) district, Yunnan, South China10.1016/j.oregeorev.2006.03.003 ↗
33. Metallogenic structure dynamics and chronological constraints of the Huize-type (HZT) germanium-rich silver-lead-zinc deposit
34. Han, R.S., Chen, J., Huang, Z.L., Ma, D.Y., Xue, C.D., and Li, Y. (2006). Tectonic mineralization dynamics and concealed deposit location prediction: A case study of the super-large lead-zinc (silver, germanium) deposit in huize. Beijing Sci. Press, 1–185. Available online: https://book.sciencereading.cn/shop/book/Booksimple/show.do?id=B3A2FC1643BC74B6F9AD4A89BA054519A000.
35. In situ analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard10.1016/j.chemgeo.2008.08.004 ↗
36. Development of sulfide calibration standards for the laser ablation inductively-coupled plasma mass spectrometry technique10.1039/B108787H ↗
37. Routine quantitative multi-element analysis of sulphide minerals by laser ablation ICP-MS: Standard development and consideration of matrix effects10.1144/1467-7873/09-244 ↗
38. Iolite: Freeware for the visualisation and processing of mass spectrometric data10.1039/c1ja10172b ↗
39. Chu, G.B., Chen, H.Y., Zhang, S.T., Zhang, Y., and Cheng, J.M. (2022). Geochemistry and Geochronology of Multi-Generation Garnet: New Insights on the Genesis and Fluid Evolution of Prograde Skarn Formation. Geosci. Front., 14.10.1016/j.gsf.2022.101495 ↗
40. Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis
41. Dmitrijeva, M., Cook, N.J., Ehrig, K., Ciobanu, C.L., Metcalfe, A.V., Kamenetsky, M., Kamenetsky, V.S., and Gilbert, S. (2020). Multivariate Statistical Analysis of Trace Elements in Pyrite: Prediction, Bias and Artefacts in Defining Mineral Signatures. Minerals, 10.10.3390/min10010061 ↗
42. Cd content in sphalerite with different color
43. Liu, Y.J., Cao, L.M., Li, Z.L., Wang, H.N., Chu, T.Q., and Zhang, J.R. (1984). Element Geochemistry, Science Press. (In Chinese).
44. A genetic mineralogical study of sphalerite in the Fankou Pb-Zn ore district
45. Sphalerite color banding: Lack of correlation with iron content, Pine Point, Northwest Territories, Canada
46. Self-organized banded sphalerite and branching galena in the Pine Point ore deposit, Northwest Territories
47. Commentary on the sphalerite geobarometer
48. Minor elements in layered sphalerite as a record of fluid origin, mixing, and crystallization in the Navan Zn-Pb ore deposit, Ireland10.2113/econgeo.109.6.1513 ↗
49. Trace element distribution (Cu, Ga, Ge, Cd, and Fe) in sphalerite from the Tennessee MVT deposits, USA, by combined EMPA, LA-ICP-MS, Raman spectroscopy, and crystallography10.3749/canmin.1500104 ↗
50. Van Den Boogaart, K.G., and Tolosana-Delgado, R. (2013). Analyzing Compositional Data with R, Springer.10.1007/978-3-642-36809-7 ↗
51. Textural control on gold distribution in As-free pyrite from the Dongping, Huangtuliang and Hougou gold deposits, North China Craton (Hebei Province, China)10.1016/j.chemgeo.2009.02.020 ↗
52. Constraints on the solid solubility of Hg, Tl, and Cd in arsenian pyrite10.2138/am-2016-5603 ↗
53. Trace metal nanoparticles in pyrite10.1016/j.oregeorev.2011.03.003 ↗
54. Deciphering the Hydrothermal Evolution of a VMS System by LA-ICP-MS Using Trace Elements in Pyrite: An Example from the Bracemac-McLeod Deposits, Abitbi, Canada, and Implications for Exploration10.2113/econgeo.110.8.2087 ↗
55. Pyrite as a record of hydrothermal fluid evolution in a porphyry copper system: A SIMS/EMPA trace element study10.1016/j.gca.2012.11.006 ↗
56. Copper-arsenic decoupling in an active geothermal system: A link between pyrite and fluid composition10.1016/j.gca.2017.01.044 ↗
57. Trace element systematics and ore-forming processes in mafic VMS deposits: Evidence from the Troodos ophiolite, Cyprus10.1016/j.oregeorev.2019.01.024 ↗
58. Element enrichment characteristics: Insights from element geochemistry of sphalerite in Daliangzi Pb-Zn deposit, Sichuan, Southwest China10.1016/j.gexplo.2017.12.014 ↗
59. Genetic discrimination of the Dingjiashan Pb-Zn deposit, SE China, based on sphalerite chemistry10.1016/j.oregeorev.2021.104212 ↗
60. Halogens in hydrothermal sphalerite record origin of ore-forming fluids10.1130/G47087.1 ↗
61. Wei, C., Huang, Z.L., Yan, Z.F., Hu, Y.S., and Ye, L. (2018). Trace Element Contents in Sphalerite from the Nayongzhi Zn-Pb Deposit, Northwestern Guizhou, China: Insights into Incorporation Mechanisms, Metallogenic Temperature and Ore Genesis. Minerals, 8.10.3390/min8110490 ↗
62. Trace and minor elements in sphalerite from metamorphosed sulphide deposits10.1007/s00710-014-0346-2 ↗
63. Trace and minor elements in galena: A reconnaissance LA-ICP-MS study10.2138/am-2015-4862 ↗
64. Partitioning of trace elements in co-crystallized sphalerite-galena-chalcopyrite hydrothermal ores10.1016/j.oregeorev.2016.02.009 ↗
65. Genesis of the late Ordovician Kukaazi Pb-Zn deposit in the western Kunlun orogen, NW China: New insights from in-situ trace elemental compositions of base metal sulfides10.1016/j.jseaes.2019.103995 ↗
66. Trace elements in sulfides from the Maozu Pb-Zn deposit, Yunnan Province, China: Implications for trace-element incorporation mechanisms and ore genesis10.2138/am-2020-6950 ↗
67. Indium and germanium in the structure of sphalerite: An example of coupled substitution with Copper10.1007/BF01163036 ↗
68. Distribution and oxidation state of Ge, Cu and Fe in sphalerite by μ-XRF and K-edge μ-XANES: Insights into Ge incorporation, partitioning and oxidation state in sphalerite10.1016/j.gca.2016.01.001 ↗
69. Distribution and Substitution Mechanism of Ge in a Ge-(Fe)-Bearing Sphalerite10.3390/min5020117 ↗
70. Trace elements in sulfide from the Tianbaoshan Pb-Zn deposit, Sichuan Province, China: A LA-ICPMS study
71. Effects of temperature, sulfur, and oxygen fugacity on the composition of sphalerite from submarine hydrothermal vents10.1130/G35655.1 ↗
72. Evolution of a hydrothermal ore-forming system recorded by sulfide mineral chemistry: A case study from the Plaka Pb-Zn-Ag Deposit, Lavrion, Greece10.1007/s00126-021-01067-y ↗
73. Four Steps Type’ ore-prospecting method for deeply concealed hydrothermal ore deposits—A case study of the Maoping Zn-Pb-(Ag-Ge) deposit in Southwestern China
74. Trace element geochemistry of sphalerite in contrasting hydrothermal fluid systems of the Freiberg district, Germany: Insights from LA-ICP-MS analysis, near-infrared light microthermometry of sphalerite- hosted fluid inclusions, and sulfur isotope geochemistry10.1007/s00126-018-0850-0 ↗
75. Gallium, germanium, indium, and other trace and minor elements in sphalerite as a function of deposit type—A meta-analysis10.1016/j.oregeorev.2015.12.017 ↗
76. Germanium enrichment in supergene settings: Evidence from the Cristal nonsulfide Zn prospect, Bongará district, northern Peru10.1007/s00126-017-0781-1 ↗
77. Polymetallic sulfide and sulfosalts of the pongkor epithermal gold-sliver deposit, west Java, Indonesia10.2113/gscanmin.41.1.185 ↗
78. Thermochemistry of Sulfide Mineral Solutions10.2138/rmg.2006.61.6 ↗
79. Formation of Pb-Zn deposits in the Sichuan–Yunnan–Guizhou triangle linked to the Youjiang foreland basin: Evidence from Rb-Sr age and in situ sulfur isotope analysis of the Maoping Pb-Zn deposit in northeastern Yunnan Province, southeast China10.1016/j.oregeorev.2019.03.022 ↗
80. Zhang, Y. (2016). The metallogenic mechanism of fluid mixing in the Huize super- large lead-zinc deposit in the northeastern Yunnan ore concentration area. Kunming Univ. Sci. Technol., 1–193. Available online: https://kns.cnki.net/kcms2/article/abstract?v=YwS3ffssB6g78wNBLxSqbyxdWkac1tqo0r6LrAfqj7L8SsWLIUWQohvf2sHXZuFs5N3U7EeCqdMpPUpn4MpzHGuSgXbh8Fat3bjBVkaXO_hsEGzVzd_NnmOpS9WeIcXTObGtDTF3QPkt66YaQteKCwABQc3A1I-5pMzMp52YbiwOBEPLfBf4Xw==&uniplatform=NZKPT.
81. Li, G.M. (2023). Metallogenic Mechanism of the Daliangzi MVT Pb-Zn (Cd) Deposit in Sichuan–Yunnan–Guizhou Metallogenic Province, SW China. China Univ. Geosci., 1–219. (In Chinese).
82. Mechanisms of Lead Transportation and Deposition in Hydrothermal Deposits
83. Cu speciation and partitioning among minerals, melts and fluids: Experimental advances and implications for ore formation10.1007/s11430-024-1493-y ↗
84. Thermodynamic properties of aqueous Ge (IV) hydroxide complexes from 25 to 350 C: Implications for the behavior of germanium and the Ge/Si ratio in hydrothermal fluids10.1016/S0016-7037(98)00081-7 ↗
85. The aqueous geochemistry of gallium, germanium, indium and scandium10.1016/j.oregeorev.2003.06.002 ↗
86. Geochemistry and Evolution of Mississippi Valley-Type Mineralizing Brines from the Tri-State and Northern Arkansas Districts Determined by LA-ICP-MS Microanalysis of Fluid Inclusions10.2113/gsecongeo.103.7.1411 ↗
87. Composition of ore fluid inclusions from the Viburnum Trend, Southeast Missouri district, United States: Implications for transport and precipitation mechanisms10.2113/econgeo.106.1.55 ↗
88. Constraints from Fluid Inclusion Compositions on the Origin of Mississippi Valley-Type Mineralization in the Illinois-Kentucky District10.2113/econgeo.110.3.787 ↗
89. New Insights into the Origin of the World-Class Jinding Sediment-Hosted Zn-Pb Deposit, Southwestern China: Evidence from LA-ICP-MS Analysis of Individual Fluid Inclusions10.5382/econgeo.4826 ↗
90. Ore genesis of the Fule Pb-Zn deposit and its relationship with the Emeishan Large Igneous Province: Evidence from mineralogy, bulk C-O-S and in situ S-Pb isotopes10.1016/j.gr.2017.11.004 ↗
91. Ore-Forming Fluid and Thermochemical Sulfate Reduction in the Wusihe Lead-Zinc Deposit, Sichuan Province, China
92. Precipitation Reaction Mechanisms of Mineral Deposits Simulated with a Fluid Mixing Model
93. The Tectonics-fluids-mineralization Coupling Processes in the Huize Ultra-large Ge-rich Pb-Zn Deposit
94. In situ trace element compositions of sulfides constraining the genesis of the worldclass Shuangjianzishan Ag-Pb-Zn deposit, NE China10.1016/j.oregeorev.2023.105675 ↗
95. Indium and other trace elements in volcanogenic massive sulfide ores from the Kuroko, Besshi and other types in Japan10.9795/bullgsj.58.7 ↗
96. Comparison of metal enrichment in pyrite framboids from a metal-enriched and metal-poor estuary10.2138/am.2014.4545 ↗
97. LA-ICP-MS trace element geochemistry of sphalerite: Metallogenic constraints on the Qingshuitang Pb–Zn deposit in the Qinhang Ore Belt, South China10.1016/j.oregeorev.2021.104659 ↗
98. Trace element characteristics of sphalerite in the Haobugao Zn-Pb deposit, Inner Mongolia, and their geological significance
99. Li, X.M., Zhang, Y.X., Li, Z.K., Zhao, X.F., Zuo, R.G., Xiao, F., and Zheng, Y. (2023). Discrimination of Pb-Zn deposit types using sphalerite geochemistry: New insights from machine learning algorithm. Geosci. Front., 14.10.1016/j.gsf.2023.101580 ↗
100. LA-ICP-MS analyses of trace elements in base metal sulfides from carbonate-hosted Zn-Pb deposits, South China: A case study of the Maoping deposit10.1016/j.oregeorev.2020.103945 ↗