Rare earth element (REE) deposits are commonly associated with carbonatites and (per)alkaline rocks where hydrothermal magmatic fluids can play a significant role in REE mobilization and deposition [1]. Thermodynamic modeling permits predicting the evolution of ore-forming fluids and can be used to test different controls on hydrothermal REE mobility including temperature, pressure, the solubility of REE minerals, aqueous REE speciation and pH evolution associated with fluid-rock interaction. Previous modeling studies either focused on REE fluoride/chloride complexation in acidic aqueous fluids [2] or near neutral/alkaline fluids associated with calcite vein formation [3]. Such models were also applied to interpret field observations in REE deposits Bayan Obo in China and Bear Lodge in Wyoming [3,4]. Recent hydrothermal calcite-fluid REE partitioning experiments provide new data to simulate the solubility of REE in calcite, REE carbonates/fluorocarbonates at high temperatures [5, 6].
We studied the competing effects controlling the mobility of REE in hydrothermal fluids between 100 and 400 °C at 500 bar. Speciation calculations were carried out in the Ca-F-CO2-Na-Cl-H2O system using the GEMS code package [7]. The properties of minerals and aqueous species were taken from the MINES thermodynamic database [3,5]. The Gallinas Mountains hydrothermal REE deposit in New Mexico was used as a field analogue to compare our models with the formation of calcite-fluorite veins hosting bastnäsite. Previous fluid inclusion studies hypothesized that the REE were transported as fluoride complexes [8] but more recent modeling studies have shown that fluoride essentially acts as a depositing ligand [2]. Here we show more detailed simulations predicting the stability of fluorite, calcite and REE minerals relevant to ore-forming processes in carbonatites and alkaline systems.
[1] Gysi et al. (2016), Econ. Geol. 111, 1241-1276; [2] Migdisov and Williams-Jones (2014), Mineral. Deposita 49, 987-997. [3] Perry and Gysi (2018), Geofluids; [4] Liu et al. (2020), Minerals 10, 495; [5] Perry and Gysi (2020), Geochim. Cosmochim. Acta 286, 177-197; [6] Gysi and Williams-Jones (2015) Chem. Geol. 392, 87-101;[7] Kulik et al. (2013), Computat. Geosci. 17, 1-24; [8] Williams-Jones et al. (2000), Econ. Geol. 95, 327-341
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Hydrothermal REE partitioning between fluorite and aqueous fluids: insights from experiments and natural fluid inclusions
Rare earth element (REE) deposits are found in association with carbonatite and alkaline systems, where metasomatism plays a significant role in the late-stage transport and enrichment of REE [1]. Fluorite is a common gangue mineral in these mineral deposits and can incorporate varying REE concentrations by substitutions of REE3+ for Ca2+. Fluorite-hosted fluid inclusions contain significant REE concentrations [2], providing a potential record of the hydrothermal ore-forming fluids. The fluorite-fluid REE partitioning mechanisms, however, are largely unknown. To date, only one study [3] measured the partitioning of REE between fluorite and aqueous fluid at 60 °C. Here, we evaluate these REE partitioning mechanisms by combining laboratory experiments with characteristics of natural fluid inclusions that provide a range of salinities and homogenization temperatures relevant to natural systems.
Batch-type experiments will be conducted between 100 and 250 °C in Teflon-lined reactors, in which millimeter-sized natural fluorite crystals (Cooke’s Peak, New Mexico) will be reacted with fluids of varying initial REE concentration, pH, and salinity. Kinetic experiments were carried out at 150 °C to test for attainment of a steady state between the fluorite crystals and the aqueous solutions. The reacted fluorite crystals will be studied using SEM, CL and EMPA. Major cations and anions in the quenched fluids will be analyzed using IC and ICP-OES; REE will be determined using solution ICP-MS. These results will permit deriving REE fluorite-fluid partition coefficients.
Fluid inclusions in hydrothermal fluorite veins from the fluorite-bastnäsite REE deposits in the Gallinas Mountains in New Mexico are studied to constrain temperatures, salinities, and REE concentrations of hydrothermal ore-forming fluids in alkaline systems. Fluid inclusion assemblages were identified in growth zones and will be further studied using microthermometry. Previous studies found maximum temperatures of 400 °C in sulfate-rich NaCl-KCl brines [4]. The goal will be to link partition coefficients derived from the experiments to the REE partitioning behavior found in the natural fluorite.
[1] Gysi et al. (2016), Econ. Geol. 111, 1241-1276; [2] Vasyukova and Williams-Jones (2018) Chem. Geol. 483, 385-396; [3] van Hinsberg et al. (2010), Geology 38, 847-850; [4] Williams-Jones et al. (2000), Econ. Geol. 95, 327-341.
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- Award ID(s):
- 2039674
- NSF-PAR ID:
- 10321000
- Date Published:
- Journal Name:
- Goldschmidt
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Accepted Manuscript1.0
- Conference Paper:
- https://doi.org/10.7185/gold2021.4834
