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Critical mineral deposits form through an interplay of magmatic-hydrothermal processes in carbonatites and (per)alkaline systems during their emplacement in the Earth’s crust. Hydrothermal aqueous fluids can lead to the mobilization, transport, and deposition of the rare earth elements (REE) coupled to development of alteration zones at the deposit scale [1]. However, unraveling the underlying processes that affect the solubility of REE in these geologic fluids is a challenge in high temperature and pressure fluids [2]. A holistic approach is key to understand the controls of fluid-rock interaction in mobilizing REE in critical mineral deposits. Through a joint effort, we formed a new U.S. geoscience critical minerals experimental–thermodynamic research hub between New Mexico Tech, Los Alamos National Laboratory and Indiana University. The goal of this project is to conduct frontiers research on the behavior of critical elements in supercritical aqueous fluids by integration of a wide array of high temperature solubility experiments complemented by spectroscopic measurements and molecular dynamic simulations. Here we present current advances to simulate a significant vein paragenesis of barite + fluorite +calcite +bastnäsite-(Ce) observed in many critical mineral deposits. A case study will be presented from the Gallinas Mountains REE-fluorite hydrothermal breccia deposit in New Mexico. Using the GEMS code package [3] and the MINES thermodynamic database (https://geoinfo.nmt.edu/mines-tdb), we highlight our current capabilities and limitations to simulate the behavior of REE in these hydrothermal fluids and minerals. A thermodynamic model is presented to simulate the partitioning of REE between calcite- and fluorite-fluid based on recent and ongoing experimental and thermodynamic work on the synthesis of REE doped minerals [4] and REE speciation in acidic and alkaline fluids. We further show how to integrate multiple experimental datasets and develop new thermodynamic models based on the new research efforts from the research hub and future directions to improve our prediction capabilities of REE complexation in supercritical fluids. [1] Gysi et al. (2016), Econ. Geol. 111, 1241-1276; [2] Migdisov et al. (2016), Chemical Geology 439, 13-42. [3] Kulik et al. (2013), Comput Geosci 17, 1–24. [4] Perry and Gysi (2020), Geochim. Cosmochim. Acta 286, 177-197.more » « less
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The Gallinas Mountains district located in Lincoln and Torrance Counties, New Mexico, is host to hydrothermal REE-bearing fluorite veins and breccia deposits. The rare earth elements (REE) are found in bastnäsite-(Ce) ([La,Ce]CO3F) which is also the primary ore mineral mined in several important carbonatite deposits (e.g. Mountain Pass in California; Bayan Obo in China). Minor production of REE, fluorite, Cu, Pb, Zn, Ag, and Fe has been recorded in the Gallinas Mountains district between the early 1900s and the 1950s. The REE-bearing fluorite veins and breccias are hosted in Permian sedimentary rocks as well as genetically related trachyte/syenite sills and dikes emplaced between 28-30 Ma. Previous studies have described the REE occurrences in the Gallinas Mountains but the controls of hydrothermal processes on the transport and deposition of REE in the district remain unclear. In this study, we combine microtextural observations with mineral and bulk rock chemistry of hydrothermal REE-bearing fluorite veins and breccias to determine the vein types, alteration styles and establish a detailed mineral paragenesis. The goal of this study is to determine lithogeochemical vectors towards REE enriched zones in the district by linking thin section and deposit scale observations with mineral and bulk rock geochemistry. This district is an exceptional natural laboratory for studying the role of hydrothermal processes for transport/deposition of REE in an alkaline F-rich magmatic- hydrothermal system because very few deposits worldwide have such well-preserved and exposed geology. Hand samples of hydrothermal veins and breccias containing fluorite ± calcite ± barite ± bastnäsite-(Ce) were collected from outcrops, prospect pits, and mine dumps. Optical microscopy was used to identify minerals and determine the textural features and crosscutting relationships of the different fluorite veins. The veins were classified into: i) hematite-fluorite veins; ii) barite- bearing bastnäsite-fluorite veins; iii) barite-bearing (fluorite)-calcite veins. Nearly all of the barite crystals in the fluorite veins display dissolution textures (skeletonized crystals) with infilling of mostly fluorite and minor calcite, suggesting that barite is part of an earlier paragenetic mineral assemblage. Bastnäsite-(Ce) is commonly found in veins containing barite and occurs either as disseminated crystals in the fluorite veins or together with fluorite infills around large barite crystals. A few of the barren fluorite-calcite veins display an intergrowth with euhedral barite crystals indicating that these could be part of an earlier barite paragenesis. These textural observations suggest a key control of REE mineralization in the Gallinas Mountains district by a coupled dissolution of barite-bearing (fluorite)-calcite veins and precipitation of later bastnäsite- fluorite veins. Geochemical bulk rock data collected from the New Mexico Bureau of Geology and Mineral Resources database were analyzed using the IMDEX ioGASTM program to definegeochemical signatures of rock types, alteration styles, and vein types. Preliminary data analysis indicates a positive correlation between Ba, F, and total rare earth oxides (TREO). These trends corroborate with the observed vein microtextures, suggesting that the interaction of a hydrothermal fluids with the barite-bearing (fluorite)-calcite veins represents a key process for defining geochemical vectors in the district.more » « less
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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, 327-341more » « less
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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.more » « less