scholarly journals Rare Earth Elements in Mineral Deposits: Speciation in Hydrothermal Fluids and Partitioning in Calcite

Geofluids ◽  
2018 ◽  
Vol 2018 ◽  
pp. 1-19 ◽  
Author(s):  
Emily P. Perry ◽  
Alexander P. Gysi
Keyword(s):  
Rare Earth ◽  
Rare Earth Elements ◽  
Hydrothermal Fluids ◽  
Mineral Deposits ◽  
Chloride Complexes ◽  
Natural Systems ◽  
Low Salinity ◽  
Numerical Predictions ◽  
Hydrothermal Processes ◽  
Bayan Obo

Studying the speciation and mineral-fluid partitioning of the rare earth elements (REE) allows us to delineate the key processes responsible for the formation of economic REE mineral deposits in natural systems. Hydrothermal REE-bearing calcite is typically hosted in carbonatites and alkaline rocks, such as the giant Bayan Obo REE deposit in China and potential REE deposits such as Bear Lodge, WY. The compositions of these hydrothermal veins yield valuable information regarding pressure (P), temperature (T), salinity, and other physicochemical conditions under which the REE can be fractionated and concentrated in crustal fluids. This study presents numerical simulation results of the speciation of REE in aqueous NaCl-H2O-CO2-bearing hydrothermal fluids and a new partitioning model between calcite and fluids at different P-T-x conditions. Results show that, in a high CO2 and low salinity system, bicarbonate/carbonate are the main transporting ligands for the REE, but predominance shifts to chloride complexes in systems with high CO2 and high salinity. Hydroxyl REE complexes may be important for the solubility and transport of the REE in alkaline fluids. These numerical predictions allow us to make quantitative interpretations of hydrothermal processes in REE mineral deposits, particularly in carbonatites, and show where future experimental work will be essential in improving our modeling capabilities for these ore-forming processes.

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

Minerals ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 495
Author(s):  
Shang Liu ◽  
Lin Ding ◽  
Hong-Rui Fan
Keyword(s):  
Rare Earth ◽  
Aqueous System ◽  
Hydrothermal Fluids ◽  
Fluid Composition ◽  
Physico Chemical ◽  
Composition Variation ◽  
Bayan Obo ◽  
Chemical Conditions ◽  
The Cost ◽  
Hydrothermal Activities

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.

scholarly journals Allanite Geochemical Response to Hydrothermal Alteration by Alkaline, Low-Temperature Fluids

Minerals ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 392 ◽  
Author(s):  
Katarzyna Gros ◽  
Ewa Słaby ◽  
Petras Jokubauskas ◽  
Jiří Sláma ◽  
Gabriela Kozub-Budzyń
Keyword(s):  
Rare Earth ◽  
Low Temperature ◽  
Rare Earth Elements ◽  
Geochemical Evolution ◽  
Additional Component ◽  
Second Stage ◽  
Ce Anomaly ◽  
Hydrothermal Processes ◽  
Fluid Infiltration ◽  
Two Stages

Allanite is one of the main rare earth elements (REE)-rich accessory minerals in composite dykes from the granitoid pluton of Karkonosze. These dykes differ in composition from the bulk of the pluton by elevated rare earth elements (REE), Y, Zr, and alkali contents, suggesting contribution of an additional component. Allanite exhibits complex alteration textures, which can be divided into two stages. The first stage is represented by allanite mantles, formed by fluid infiltration into previously crystallized magmatic allanite. These zones have low totals, are Ca-, Al-, Mg-, and light REE (LREE)-depleted, and Y-, heavy REE (HREE)-, Th-, Ti-, and alkali-enriched. The fractionation between LREE and HREE was caused by different mobility of complexes formed by these elements in aqueous fluids. The second stage includes recrystallized LREE-poor, Y-HREE-rich allanite with variable Ca, Al, Mg, and REE-fluorocarbonates. The alteration products from both stages demonstrate higher Fe3+/(Fe2+ + Fe3+) ratios and a negative Ce anomaly. These features point to the alkaline, low-temperature, and oxidized nature of the fluids. The differences in mobility and solubility of respective ligands show that the fluids from the first stage may have been dominated by Cl, whereas those of the second stage may have been dominated by F and CO2 (and PO4 in case of one sample). The inferred chemistry of the fluids resembles the overall geochemical signature of the composite dykes, indicating a major contribution of the hydrothermal processes to their geochemical evolution.

Research on the Reaction Behavior of Rare Earth Elements in Reduction

2012 ◽  
Vol 454 ◽  
pp. 268-272 ◽  
Author(s):  
Peng Gao ◽  
Yue Xin Han ◽  
Yong Sheng Sun ◽  
Chao Chen
Keyword(s):  
Rare Earth ◽  
Rare Earth Elements ◽  
Magnetic Separation ◽  
Sem Images ◽  
Reaction Behavior ◽  
Rare Earth Minerals ◽  
Iron Phase ◽  
Occurrence State ◽  
Bayan Obo ◽  
Depth Reduction

Occurrence state of rare earth elements in the different deoxidization stages and the behavior of rare earth elements in the process of depth reduction were studied by analyzing XRD and SEM images of Bayan Obo oxide ore in different deoxidization time. The results showed that deoxidization time had a great effect on the occurrence state of rare earth elements. With the increase of deoxidization time, rare earth minerals gradually translated from bastnaesite and urdite into (CaO•2Ce2O3•3SiO2).This phase was white with a small size. It was columnar or massive in most cases and could be easily separated from the iron phase. 97.18% of the rare earth elements, which could be recovered by flotation, gravity separation and magnetic separation, entered the iron tailings.

Mixed borohydride-chloride complexes of the rare earth elements

2010 ◽  
Vol 13 (6-7) ◽  
pp. 603-607 ◽  
Author(s):  
Peter W. Roesky ◽  
Jelena Jenter ◽  
Ralf Köppe
Keyword(s):  
Rare Earth ◽  
Rare Earth Elements ◽  
Chloride Complexes ◽  
The Rare Earth
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