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Open AccessArticle

Thermodynamic Constraints on REE Mineral Paragenesis in the Bayan Obo REE-Nb-Fe Deposit, China

by Shang Liu 1,*, Lin Ding 1,2 and Hong-Rui Fan 3,4,5
School of Earth Sciences, Lanzhou University and Key Laboratory of Mineral Resources in Western China (Gansu Province), Lanzhou 730000, China
Institute of Tibetan Plateau Research, Chinese Academy of Sciences, Beijing 100101, China
Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
College of Earth and Planetary Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
Innovation Academy for Earth Science, Chinese Academy of Sciences, Beijing 100029, China
Author to whom correspondence should be addressed.
Minerals 2020, 10(6), 495;
Received: 6 May 2020 / Revised: 27 May 2020 / Accepted: 28 May 2020 / Published: 29 May 2020
Hydrothermal processes have played a significant role in rare earth element (REE) precipitation in the Bayan Obo REE-Nb-Fe deposit. The poor preservation of primary fluid inclusions and superposition or modification by multiphase hydrothermal activities have made identification of physico-chemical conditions of ore-forming fluids extremely difficult. Fortunately, with more and more reliable thermodynamic properties of aqueous REE species and REE minerals reported in recent years, a series of thermodynamic calculations are conducted in this study to provide constraints on REE precipitation in hydrothermal solutions, and provide an explanation of typical paragenesis of REE and gangue minerals at Bayan Obo. During the competition between fluocerite and monazite for LREE in the modelled solution (0.1 M HCl, 0.1 M HF and 0.1 M trichloride of light rare earth elements (LREE) from La to Sm), all LREE would eventually be hosted by monazite at a temperature over 300 °C, with continuous introduction of H3PO4. Additionally, monazite of heavier LREE would precipitate earlier, indicating that the Ce- and La-enriched monazite at Bayan Obo was crystallized from Ce and La pre-enriched hydrothermal fluids. The fractionation among LREE occurred before the ore-forming fluids infiltrating ore-hosting dolomite. When CO2 (aq) was introduced to the aqueous system (model 1), bastnaesite would eventually and completely replace monazite-(Ce). Cooling of hot hydrothermal fluids (>400 °C) would significantly promote this replacement, with only about one third the cost of CO2 for the entire replacement when temperature dropped from 430 °C to 400 °C. Sole dolomite addition (model 2) would make bastnaesite replace monazite and then be replaced by parisite. The monazite-(Ce) replaced by associated bastnaesite and apatite is an indicator of very hot hydrothermal fluids (>400 °C) and specific dolomite/fluid ratios (e.g., initial dolomite at 1 kbar: 0.049–0.068 M and 0.083–0.105 M at 400 °C and 430 °C). In hot solution (>430 °C) that continuously interacts with dolomite, apatite precipitates predating the bastnaesite, but it behaves oppositely at <400 °C. The former paragenesis is in accord with petrography observed in this study. Some mineral pairs, such as monazite-(Ce)-fluorite and monazite-(Ce)-parisite would never co-precipitate at any calculated temperature or pressure. Therefore, their association implies multiphase hydrothermal activities. Pressure variation would have rather limited influence on the paragenesis of REE minerals. However, temperature and fluid composition variation (e.g., CO2 (aq), dolomite, H3PO4) would cause significantly different associations between REE and gangue minerals. View Full-Text
Keywords: REE precipitation; thermodynamic modelling; Bayan Obo REE-Nb-Fe deposit REE precipitation; thermodynamic modelling; Bayan Obo REE-Nb-Fe deposit
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MDPI and ACS Style

Liu, S.; Ding, L.; Fan, H.-R. Thermodynamic Constraints on REE Mineral Paragenesis in the Bayan Obo REE-Nb-Fe Deposit, China. Minerals 2020, 10, 495.

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