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The use of fluorite geochemistry and machine learning to identify critical mineral systems

Fluorite (CaF 2 ) is a potential pathfinder to critical mineral and rare earth element (REE) deposits but its application has been limited to a narrow range of mineralization types. I show that fluorite is a robust recorder of mineralization fertility by applying statistical and machine-learning methods to a new global fluorite geochemical database. Distinct median rare earth and trace element patterns are observed among deposit types and genetic environments. Fluorite associated with carbonatites and REE deposits are relatively enriched in Sr and have minimal Eu anomalies. These characteristics define new bivariate discrimination diagrams that correctly identify 78% of carbonatite-related fluorite and 88% of fluorite from REE deposits. Random forest classifiers were developed for a wide range of mineralization types and genetic settings. Trained solely on rare earth element patterns, these models achieve accuracies of 77–79%. Higher classification accuracies (up to 88–96%) are obtained when including elements such as Sr, highlighting the significance of trace elements for optimal fluorite classification. The recognition of diagnostic fluorite compositional fingerprints, particularly in REE-fertile systems, underscores its potential as a pathfinder and indicator for critical mineral exploration in F-bearing environments.

Mineralium Deposita

Microtextural characteristics of adularia in banded quartz veins from the Midas low-sulfidation epithermal deposit, Nevada

High-grade ores at the Miocene Midas low-sulfidation epithermal deposit in northern Nevada are confined to crustiform quartz veins containing abundant adularia. Micro-X-ray fluorescence elemental mapping reveals that adularia is a common gangue mineral occurring in colloform bands, bands showing bladed textures, and bands with dendritic terminations. The adularia aggregates have delicate shapes and are comprised of stacked, submillimeter crystals hosted by fine-grained quartz. The textural evidence suggests that the adularia aggregates originally formed within a gel-like, noncrystalline silica matrix, which subsequently transformed into quartz. This indicates that the adularia did not precipitate in open space along the vein walls. Correlative microscopy, involving scanning electron microscopy-based automated mineralogy and optical petrography, demonstrates that bands containing abundant adularia are not the primary host to ore minerals. The ore minerals occur in different bands within the crustiform veins, implying that adularia and ore mineral precipitation did not always occur simultaneously. It is hypothesized here that fluid flow at Midas involved intermittent short-lived events of fluid flashing, causing rapid solute supersaturation in the liquid. During each flashing event, different amounts of vapor were produced along a given vein. Compositional differences between adjacent bands in the crustiform quartz veins may, therefore, be linked to variations in the amount of vapor formed during each flash event.

Nevada

Noble and base metal distribution and processes affecting ore tenors in the disrupted lower stratigraphy of the Stillwater Complex, USA

Exploration continues for contact-style Ni-Cu sulfide and chromitite-associated PGE mineralization in ultramafic rocks of the Stillwater Complex. At the Iron and Chrome Mountain areas, massive sulfides occur along the complex’s footwall contact and anomalous concentrations of PGE+Au are associated with the three lowermost chromitite seams. Southeast of Chrome Mountain, magmatic layering is highly disrupted by the presence of faults, magmatic breccias, serpentinized discordant dunites, pyroxenite pegmatoids, and disaggregated chromitite seams. The bulk rock chemistry, sulfide chemistry, and noble metal mineralogy of samples from this area were examined to determine the deportment of PGE and processes that led to enrichments in PGE, Au, Cu, Co and Ni. Results show that a sulfide liquid was the principal collector of PGE. If sulfide liquid was initially deposited with chromite, it was disaggregated or redistributed by subsequent melt or fluid infiltration, which may have resulted in the offset of peak PGE(+Cu, Ni) from peak Cr 2 O 3 concentrations, and upgraded PGE tenors. Upon cooling, PGE exsolved from sulfides to form discrete bismuth tellurides, arsenides, arsenic sulfides, antimonides, and alloys, commonly along the margins of sulfide globules. Calculated metal tenors are highest in the disseminated sulfides southwest of Chrome Mountain, whereas massive and net-textured sulfides near the Iron Mountain-Camp zone represent monosulfide solid solution cumulates. At progressively shallower levels, higher metal tenors combined with lower S/Se ratios are consistent with increasing R-factors from 100 to 100,000. Serpentinization and talc-tremolite alteration resulted in S loss through partial replacement of sulfides by secondary silicate+carbonate+magnetite+sulfide assemblages, further upgrading Ni-Cu-PGE tenors. The present work shows that processes responsible for the disruption of magmatic layering and post-magmatic fluid alteration along the intrusion’s lower contact led to noble and base metal enrichments.

Montana

Insights into Mountain Pass carbonatite formation from in-situ sulfur isotopes and geochemistry of sulfate and sulfide minerals

The Mountain Pass carbonatite stock hosts a world-class rare earth element deposit and may be classified as a carbonate-sulfate igneous rock, as it contains on average > 50 volume percent carbonate minerals and 20 to 30 volume percent sulfate minerals. The sulfates range in composition from barite to celestine and locally occur with sparse sulfide minerals. We investigate the origin of sulfur enrichment and the occurrence of sulfur-bearing minerals in the Mountain Pass carbonatite with in-situ sulfur isotope and mineral chemistry. Barite cores with δ 34 S of 1 to 3‰ do not coexist with sulfides, whereas celestine rims with δ 34 S of > 3‰ are associated with sulfides with δ 34 S < -10‰. We propose a model in which sulfur-bearing sediments were subducted during episodes of plate convergence in the Mojave Province that preceded Mountain Pass magmatism. Metasomatism of the overlying mantle by melts derived from the subducted sediments generated an unusually carbon- and sulfur-rich source to yield carbonatite magmas. Sulfur from primary carbonatite magmas and ~ 1 to 7% sulfur from subducted sediment melts yielded a slightly enriched δ 34 S composition (relative to depleted mantle δ 34 S of -1‰) for early crystallizing barite. Celestine rims on magmatic barite cores formed at low, hydrothermal temperatures (< 350 °C) based on S isotope thermometry for equilibrium celestine-galena and celestine-pyrite pairs. The sparse sulfides in the carbonatite stock are not in equilibrium with the primary barite cores and therefore do not permit S isotope thermometry estimates of magmatic temperatures. The S/Se ratios of sulfide minerals (> 3,400) typically exceed primitive mantle values (S/Se of 3,340), also consistent with their derivation from hydrothermal fluids. Trace occurrences of sulfide and sulfate minerals in alkaline silicate stocks related to the carbonatite stock have similar δ 34 S compositions and yield similarly low formation temperatures, suggesting regionally extensive and chemically similar sulfur-bearing hydrothermal fluids that imparted lithologically diverse rocks with a consistent sulfur isotope fingerprint.

California, Nevada

A time-space model of graphite mineral systems

Increasing demand for graphite in energy storage systems warrants review of graphite ore genesis in a mineral systems framework. Orogenic graphite encompasses the metamorphic and orogenic mineral systems that produce flake graphite and hydrothermal vein (lump and chip) graphite deposits, respectively. A common feature of orogenic graphite deposits is an association with upper amphibolite- to granulite-facies metasedimentary rocks in continent-continent or continent-island arc collisional orogens. Orogenic flake graphite deposits form primarily through graphitization of organic carbon during regional metamorphism, but strain localization and partial melting of pelitic protoliths are likely important processes for graphite grade and quality enrichment. Orogenic vein graphite deposits precipitate from hydrothermal fluids, possibly derived from metamorphism or anatexis at depth. Decarbonation reactions in mixed calcareous-carbonaceous metasedimentary sequences are the most likely carbon sources for the veins. In contrast, intrusion-related graphite includes magmatic-hydrothermal and metamorphic mineral systems that form primarily in continental arc settings via the interaction of magmas with carbonaceous sedimentary packages. Magmatic-hydrothermal flake graphite deposits are hosted in plutonic and volcanic rocks, and result from the exsolution of CO 2 -CH 4 -rich fluids from melts contaminated by such packages. Contact metamorphism of carbonaceous sedimentary rocks by plutons produces some microcrystalline (amorphous) graphite deposits, including many in China. Compilation of geologic data from known graphite deposits globally suggests that pulses of carbon deposition in the Paleoproterozoic, Mesoproterozoic, and Neoproterozoic provided source carbon material. Subsequent supercontinent orogenesis at ca. 2,100 to 1,700 Ma (Columbia), ca. 1,300 to 1,000 Ma (Rodinia), and ca. 650 to 500 Ma (Gondwana) resulted in the genesis of orogenic flake and vein graphite deposits, where favorable geologic components overlapped with organic ± carbonate carbon-rich strata. Cryogenian deposition of graphite protoliths and Cryogenian – Cambrian metamorphic mineralization account for nearly 75% of all known resources globally and coincide with profound carbon isotope excursions and climate variability, implying a link with the global carbon budget. Comparatively few graphite deposits are associated with Pangea-forming orogens, attributed to less exhumation and/or denudation. High-temperature metasedimentary belts containing organic carbon-rich protoliths are most favorable for hosting orogenic flake graphite deposits, whereas sequences that also contain carbonate protoliths are favorable for orogenic graphite veins. Continent-scale orogenic belts may host both deposit types along with vanadium deposits. Use of a time-space mineral systems framework for graphite deposits can improve exploration models needed to ensure future supply of this critical mineral and provide insights into Earth’s long-term carbon cycle.

Mineralium Deposita

Geology, mineralogy, and cassiterite geochronology of the Ayawilca Zn-Pb-Ag-In-Sn-Cu deposit, Pasco, Peru

The Ayawilca deposit in Pasco, Peru, represents the most significant recent base-metal discovery in the central Andes and one of the largest undeveloped In resources globally. As of 2018, it hosts an 11.7 Mt indicated resource grading 6.9% Zn, 0.16% Pb, 15 g/t Ag, and 84 g/t In, an additional 45.0 Mt inferred resource grading 5.6% Zn, 0.23% Pb, 17 g/t Ag, and 67 g/t In, and a separate Sn-Cu-Ag inferred resource of 14.5 Mt grading 0.63% Sn, 0.21% Cu, and 18 g/t Ag. Newly obtained U–Pb dates for cassiterite by LA-ICP-MS (22.77 ± 0.41 and 23.05 ± 2.06 Ma) assign the Ayawilca deposit to the Miocene polymetallic belt of central Peru. The polymetallic mineralization occurs as up to 70-m-thick mantos hosted by carbonate rocks of the Late Triassic to Early Jurassic Pucará Group, and subordinately, as steeply dipping veins hosted by rocks of the Pucará Group and overlying Cretaceous sandstones-siltstones of the Goyllarisquizga Group. Relicts of a distal retrograde magnesian skarn and cassiterite (stage pre-A) were identified in the deepest mantos. The volumetrically most important mineralization at Ayawilca comprises a low-sulfidation assemblage (stage A) with quartz, pyrrhotite, arsenopyrite, chalcopyrite, Fe-rich sphalerite, and traces of stannite and herzenbergite. Stage A sphalerite records progressive Fe depletion, from 33 to 10 mol% FeS, which is compatible with the observed transition from low- to a subsequent intermediate-sulfidation stage (B) marked by the crystallization of abundant pyrite and marcasite. Finally, during a later intermediate-sulfidation stage (C) sphalerite (up to 11 mol% FeS), galena, native bismuth, Cu-Pb-Ag sulfosalts, siderite, Mn-Fe carbonates, kaolinite, dickite, and sericite were deposited. This paragenetic evolution shows striking similarities with that at the Cerro de Pasco Cordilleran-type polymetallic deposit, even if at Ayawilca stage C did not reach high-sulfidation conditions. The occurrence of an early retrograde skarn assemblage suggests that the manto bodies at Ayawilca formed at the transition between distal skarn and skarn-free (Cordilleran-type) carbonate-replacement mineralization. Mineral assemblages define a T- f S 2 evolutionary path close to the pyrrhotite-pyrite boundary. Buffering of hydrothermal fluids by underlying Devonian carbonaceous phyllites of the Excelsior Group imposed highly reduced conditions during stage A mineralization (log f O 2 < − 30 atm). The low f O 2 favored efficient Sn mobility during stages pre-A and A, in contrast to other known ore deposits in the polymetallic belt of central Peru, in which the occurrence of Sn minerals is minor. Subsequent cooling, progressive sealing of vein walls, and decreasing buffering potential of the host rocks promoted the shift from low- (stage A) to intermediate-sulfidation (stages B and C) states. LA-ICP-MS analyses reveal significant In contents in Fe-rich sphalerite (up to 1.7 wt%), stannite (up to 1908 ppm), and chalcopyrite (up to 1185 ppm). The highest In content was found in stage A sphalerite that precipitated along with chalcopyrite and stannite, thus pointing to the early, low-sulfidation assemblage as prospective for this high-tech metal in similar mineral systems. Indium was likely incorporated into the sphalerite crystal lattice via Cu + + In 3+ ↔ 2 Zn 2+ and (Sn, Ge) 4+ + (Ga, In) 3+ + (Cu + Ag) + ↔ 4 Zn 2+ coupled substitutions. Indium incorporation mechanisms into the stannite and chalcopyrite crystal lattices remain unclear.

Pasco