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Licensed Unlicensed Requires Authentication Published by De Gruyter July 27, 2019

Comparison of fluid processes in coexisting wolframite and quartz from a giant vein-type tungsten deposit, South China: Insights from detailed petrography and LA-ICP-MS analysis of fluid inclusions

  • Jun-Yi Pan , Pei Ni EMAIL logo and Ru-Cheng Wang
From the journal American Mineralogist


Granite-related wolframite-quartz veins are the world’s most important tungsten mineralization and production resource. Recent progress in revealing their hydrothermal processes has been greatly facilitated by the use of infrared microscopy and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis of both quartz- and wolframite-hosted fluid inclusions. However, owing to the paucity of detailed petrography, previous fluid inclusion studies on coexisting wolframite and quartz are associated with a certain degree of ambiguity. To better understand the fluid processes forming these two minerals, free-grown crystals of intergrown wolframite and quartz from the giant Yaogangxian W deposit in South China were studied using integrated in situ analytical methods including cathodoluminescence (CL) imaging, infrared microthermometry, Raman microspectroscopy, and fluid inclusion LA-ICP-MS analysis. Detailed crystal-scale petrography with critical help from CL imaging shows repetition of quartz, wolframite, and muscovite in the depositional sequence, which comprises a paragenesis far more complex than previous comparable studies. The reconstruction of fluid history in coexisting wolframite and quartz recognizes at least four successive fluid inclusion generations, two of which were entrapped concurrently with wolframite deposition.

Fluctuations of fluid temperature and salinity during precipitation of coexisting wolframite and quartz are reflected by our microthermometry results, according to which wolframite-hosted fluid inclusions do not display higher homogenization temperature or salinity than those in quartz. However, LA-ICP-MS analysis shows that both primary fluid inclusions in wolframite and quartz-hosted fluid inclusions associated intimately with wolframite deposition are characterized by strong enrichment in Sr and depletion in B and As compared to quartz-hosted fluid inclusions that are not associated with wolframite deposition. The chemical similarity between the two fluid inclusion generations associated with wolframite deposition implies episodic tungsten mineralization derived from fluids exhibiting distinct chemical signatures. Multiple chemical criteria including incompatible elements and Br/Cl ratios of fluid inclusions in both minerals suggest a magmatic-sourced fluid with the possible addition of sedimentary and meteoric water. Combined with microthermometry and Raman results, fluid chemical evolution in terms of B, As, S, Sr, W, Mn, Fe, and carbonic volatiles collectively imply fluid phase separation and mixing with sedimentary fluid may have played important roles in wolframite deposition, whereas fluid cooling and addition of Fe and Mn do not appear to be the major driving factor.

This study also shows that fluid inclusions in both wolframite and coexisting quartz may contain a substantial amount of carbonic volatiles (CO2 ± CH4) and H3BO3. Ignoring the occurrence of these components can result in significant overestimation of apparent salinity and miscalculation of LA-ICP-MS elemental concentrations. We suggest that these effects should be considered critically to avoid misinterpretation of fluid inclusion data, especially for granite-related tungsten-tin deposits.

  1. Funding: This work is financially supported by a Key Project of National Nature Science Foundation of China (Grant No. 41830426), a National Key R&D Program of China (Grant No. 2016YFC0600205), and a Fundamental Research Funds for the Central Universities (Grant No. 0206-14380065).


We are especially grateful to Chris Heinrich, Markus Wälle, Marcel Guillong, and Oscar Laurent at ETH Zurich who provided unreserved technical support to the establishment of the fluid inclusion LA-ICP-MS lab in Nanjing University. Tao Yang, Junying Ding, and Zhe Chi at Nanjing University and Wenchao Su at Institute of Geochemistry, Chinese Academy of Science are thanked for their assistance in lab design and instrumental update. Discussion on the data interpretation with C. Heinrich is also acknowledged. We thank Wensheng Li for helping with field sampling and collection of geological documents. Xiaoping He from the Yaogangxian Mine is appreciated for providing complete access to the mine and allowing us to collect crystal samples from vein cavities. Dengping Liu is especially thanked for making us fine-polished fluid inclusion thin sections that are critical for high quality SEM, infrared microthermometry, and LA-ICP-MS analysis.

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Received: 2019-01-13
Accepted: 2019-05-03
Published Online: 2019-07-27
Published in Print: 2019-08-27

© 2019 Walter de Gruyter GmbH, Berlin/Boston

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