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1. Fluid-mineral titanium isotope fractionation: Computational and empirical results with implications for mineral deposits

   Emproto, C; Mathur, R; Sun, M; Simon, AC; Godfrey, L (February 2025, Geochimica et Cosmochimica Acta)

   Titanium (Ti) typically exhibits low mobility in geologic fluids due to the low aqueous solubility of common (Fe-)Ti oxide minerals. Consequently, Ti isotope variations (δ49/47Ti, given as δ49Ti) in geologic systems are primarily attributed to magmatic differentiation. Thus, the potential for fluid-mineral fractionation has received less attention. However, ligand-rich fluids are capable of mobilizing Ti as observed in natural systems and laboratory studies. As hydrothermal ore mineralization is commonly associated with ligand-rich brines capable of transporting significant quantities of metals, Ti isotopes may aid in understanding mineralization and alteration in complex hydrothermal systems. Here we present data from computational modeling of various Ti coordination complexes theorized to exist in geologic systems and/or under relevant experimental conditions as well as computed fractionation factors for various Ti-bearing crystalline phases to investigate the basic mechanics of equilibrium fluid-mineral Ti isotope fractionation. These results indicate that equilibrium fluid-mineral Ti isotope exchange between our modeled Ti complexes and phases with 6-coordinated Ti is predicted to generally lead to enrichment of heavy Ti isotopes in the fluid. Because minerals with 6-coordinated Ti (such as magnetite and ilmenite) are the most important reservoirs of Ti in the solid Earth, Ti isotope equilibration between terrestrial rocks and fluids can be generalized to enrich the fluid in heavy Ti isotopes. We also performed magnetite-ülvospinel leaching experiments to investigate fluid-mineral Ti isotope fractionation in this phase. Mineral leaching experiments varying acid strength, leaching temperature, and reaction time with HCl and HF qualitatively support the prediction that the fluid phase will become enriched in heavy Ti isotopes during fluid-mineral interactions that approach equilibrium with Ti-rich magnetite. Additionally, the leaching data also suggest that the fluid becomes slightly enriched in lighter Ti isotopes when Ti exchange is limited—potentially due to kinetic effects. Therefore, magnetite from natural systems may be depleted in heavy Ti isotopes during regenerative mineral replacement involving equilibration with fluids or may possibly become depleted in light Ti isotopes under a kinetic fractionation regime—leading to mineral δ49Ti values that are insufficiently explained by magmatic differentiation or inter-mineral fractionation. These results are a first look at fluid-mineral interactions that may affect Ti isotope fractionation in hydrothermal mineral systems, and Ti isotopes should be further studied as a potential method of understanding aqueous metal transport and tracing alteration in mineral deposits. 

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2. Thermodynamic modeling of hydrothermal REE partitioning in critical mineral deposits

   Gysi, A.P.; Hurtig, N.; Water, L.; Migdisov, A.; Dub, P.; Zhu, C. (July 2022, Goldschmidt)

   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. 

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3. Paleothermometry of an enigmatic travertine deposit: Cottonwood Travertine, Stillwater Range, NV

   Jackson, A. (February 2023, Proceedings 48th Workshop on Geothermal Reservoir Engineering, Stanford University, Stanford, California.)

   ABSTRACT Hot and cold spring travertine deposits record integrated histories reflecting changing hydrologic conditions, informing our understanding of the driving forces behind factors impacting local hydrology. We present results from a geologic and geochemical investigation of Cottonwood Travertine, located in Dixie Valley, NV, where it is unclear if the paleospring system that deposited the travertine was driven by deeply sourced hydrothermal fluids, or high fluid flow driven by wetter paleoclimate conditions. The temperature of the spring water that precipitated the Cottonwood Travertine has implications for the relative importance of hydrothermal versus climatic processes influencing the formation and cessation of this enigmatic deposit. We identified four groups of samples based on geologic setting, sample textures, and stable and clumped isotopic analysis: 1) calcite cemented upper gravels, 2) a mound area at the upper bench of the deposit, 3) samples from the flanks and from vuggy veins and fault zone cements from the base of the deposit, and 4) fibrous sub-travertine veins. The calcite-cemented gravels yielded δ18OC values as low as -18.4‰ (VPDB) and apparent TΔ47 of 52°C. The top mound of the deposit returned calcite δ18OC values between -12.8‰ and -11.7‰ (VPDB) and clumped isotope temperatures (TD47) of 24 – 32°C. Higher d13C and d18Oc values at the mound site are interpreted to reflect off gassing of CO2 and disequilibrium conditions. δ18OC and TD47 values from the slopes and base of the deposit are between -15.9‰ and -14.5‰ (VPDB) and around 20°C, respectively. Structurally, texturally, and isotopically (δ18OC = -29.4‰ (VPDB); TΔ47 = 93°C), the fibrous sub-travertine veins are more consistent with the local Jurassic host rock and probably do not reflect recent hot spring conditions. Our analysis suggests that, despite the impressive volume, Cottonwood Travertine formed from springs that were not particularly hot, and the deposit instead reflects vigorous warm spring activity in a wetter climactic regime rather than fluid flow from an extinct higher temperature hydrothermal system. 

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4. Hydrothermal Rare Earth Elements (REE) Partitioning into Fluorite: A Fluid Inclusion Study from the Gallinas Mountains REE-bearing Fluorite Deposit, NM

   https://doi.org/10.56577/SM-2024.2978  

   Velmani, Aadish; Gysi, Alexander; Hurtig, Nicole (April 2024, New Mexico Geological Society)

   are earth elements (REE) are becoming increasingly important in modern society due to their numerous uses in manufacturing of components for green and high-tech energy industries. Studying the mechanisms of REE mineral formation in geologic systems is vital for understanding where and how these mineral deposits form. Previous studies of REE mineral deposits have shown that hydrothermal fluids can play a key role in the mobilization and enrichment of REE (Williams-Jones et al., 2000; Gysi et al., 2016; Vasyukova and Williams-Jones, 2018). Fluorite is ideal to study the behavior of REE because of their compatibility in its structure and it is a ubiquitous hydrothermal vein mineral found together with REE fluorocarbonates (i.e., bastnäsite and parisite). However, the controls on hydrothermal fluid-mineral REE partitioning in these deposits are not yet fully understood. In this study, we present petrographic observations of fluorite veins and fluid inclusions from the Gallinas Mountains REE-bearing fluorite veins/breccia deposit in New Mexico (McLemore, 2010; Williams-Jones et al. 2000). The Gallinas Mountains deposit notably contains hydrothermal fluorite and bastnäsite, and is associated with ~30 Ma alkaline igneous rocks intruded into Permian sedimentary rocks (McLemore, 2010). The goal of this study is to better understand the cause of REE variations in fluorite as a function of temperature and salinity of the fluids, and to determine how the REE concentrations change in barren and mineralized veins. Optical microscopy and cold-cathode cathodoluminescence (CL) is used to distinguish different fluorite generations and fluid inclusion types. Scanning electron microscopy (SEM) is used to identify REE minerals, zonation in fluorite, and acquire elemental compositions of different vein minerals. 

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5. What controls the mobility of rare earth elements (REE) in critical mineral deposits in acidic vs. alkaline hydrothermal fluids?

   https://doi.org/10.7185/gold2023.19801  

   Gysi, Alexander; Hurtig, Nicole; Waters, Laura; Harlov, Daniel; Miron, George Dan; Migdissov, Artaches; Zhu, Chen; Kulik, Dmitrii (July 2023, European Association of Geochemistry)

   (Per)alkaline complexes and carbonatites evolve through a complex sequence of magmatic-hydrothermal processes. Most of them are overprinted by late auto-metasomatic processes which involves the mobilization, fractionation and/or enrichment of critical elements, such as the rare earth elements (REE) [1]. However, our current ability to predict the behavior of REE in high temperature aqueous fluids and interpret these natural systems using geochemical modeling depends on the availability of thermodynamic data for the REE minerals and aqueous species. Previous experimental work on REE solubility has focused on acidic aqueous fluids up to ~300 °C and considered chloride, fluoride and sulfate as important ligands for their transport [2]. However, magmatic-hydrothermal systems that form these critical mineral deposits may cover a wider range of fluid chemistries spanning acidic to alkaline pH as well as temperatures and pressures at which the fluids are supercritical. A few recently published studies have shown that other ligands (e.g., REE carbonates and/or combined fluoride species) could become important in near-neutral to alkaline fluids [3,4], and that REE mobility can also be increased in saline alkaline fluids reacted with fluorite [5]. Here we present new hydrothermal REE hydroxyl/chloride speciation data and REE phosphate/hydroxide minerals [6,7], calcite and fluorite solubility experiments as a function of pH, salinity and temperature. We use an integrated approach to link a wide array of experimental techniques (solubility, calorimetry, and spectroscopy) with thermodynamic optimizations using GEMSFITS [8], and present the development of a new experimental database for REE and its integration into the MINES thermodynamic database (https://geoinfo.nmt.edu/mines-tdb). The latter permits simulating hydrothermal fluid-rock interaction and ore-forming processes in critical mineral deposits to better understand the behavior of REE during metasomatism. 

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