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1. The Geochemistry of Magnetite and Apatite from the El Laco Iron Oxide-Apatite Deposit, Chile: Implications for Ore Genesis

   La Cruz, N. ( November 2020 , Economic geology)

   null (Ed.)

   The textures of outcrop and near-surface exposures of the massive magnetite orebodies (>90 vol % magnetite) at the Plio-Pleistocene El Laco iron oxide-apatite (IOA) deposit in northern Chile are similar to basaltic lava flows and have compositions that overlap high- and low-temperature hydrothermal magnetite. Existing models— liquid immiscibility and complete metasomatic replacement of andesitic lava flows—attempt to explain the genesis of the orebodies by entirely igneous or entirely hydrothermal processes. Importantly, those models were developed by studying only near-surface and outcrop samples. Here, we present the results of a comprehensive study of samples from outcrop and drill core that require a new model for the evolution of the El Laco ore deposit. Backscattered electron (BSE) imaging, electron probe microanalysis (EPMA), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were used to investigate the textural and compositional variability of magnetite and apatite from surface and drill core samples in order to obtain a holistic understanding of textures and compositions laterally and vertically through the orebodies. Magnetite was analyzed from 39 surface samples from five orebodies (Cristales Grandes, Rodados Negros, San Vicente Alto, Laco Norte, and Laco Sur) and 47 drill core samples from three orebodies (Laco Norte, Laco Sur, and Extensión Laco Sur). The geochemistry of apatite from eight surface samples from three orebodies (Cristales Grandes, Rodados Negros, and Laco Sur) was investigated. Minor and trace element compositions of magnetite in these samples are similar to magnetite from igneous rocks and magmatic-hydrothermal systems. Magnetite grains from deeper zones of the orebodies contain >1 wt % titanium, as well as ilmenite oxyexsolution lamellae and interstitial ilmenite. The ilmenite oxyexsolution lamellae, interstitial ilmenite, and igneous-like trace element concentrations in titanomagnetite from the deeper parts of the orebodies are consistent with original crystallization of titanomagnetite from silicate melt or high-temperature magmatic-hydrothermal fluid. The systematic decrease of trace element concentrations in magnetite from intermediate to shallow depths is consistent with progressive growth of magnetite from a cooling magmatic-hydrothermal fluid. Apatite grains from surface outcrops are F rich (typically >3 wt %) and have compositions that overlap igneous and magmatic-hydrothermal apatite. Magnetite and fluorapatite grains contain mineral inclusions (e.g., monazite and thorite) that evince syn- or postmineralization metasomatic alteration. Magnetite grains commonly meet at triple junctions, which preserve evidence for reequilibration of the ore minerals with hydrothermal fluid during or after mineralization. The data presented here are consistent with genesis of the El Laco orebodies via shallow emplacement and eruption of magnetite-bearing magmatic-hydrothermal fluid suspensions that were mobilized by decompression- induced collapse of the volcanic edifice. The ore-forming magnetite-fluid suspension would have rheological properties similar to basaltic lava flows, which explains the textures and presence of cavities and gas escape tubes in surface outcrops. 

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2. An ab-initio study on the thermodynamics of disulfide, sulfide, and bisulfide incorporation into apatite and the development of a more comprehensive temperature, pressure, pH, and composition-dependent model for ionic substitution in minerals

   https://doi.org/10.2138/am-2022-8250  

   Kim, YoungJae ; Konecke, Brian ; Simon, Adam ; Fiege, Adrian ; Becker, Udo ( November 2022 , American Mineralogist)

   The mineral apatite, Ca10(PO4)6(F,OH,Cl)2, incorporates sulfur (S) during crystallization from S-bearing hydrothermal fluids and silicate melts. Our previous studies of natural and experimental apatite demonstrate that the oxidation state of S in apatite varies systematically as a function of oxygen fugacity (fO2). The S oxidation states –1 and –2 were quantitatively identified in apatite crystallized from reduced, S-bearing hydrothermal fluids and silicate melts by using sulfur K-edge X-ray absorption near-edge structure spectroscopy (S-XANES) where S 6+/ΣS in apatite increases from ~0 at FMQ-1 to ~1 at FMQ+2, where FMQ refers to the fayalite-magnetite-quartz fO2 buffer. In this study, we employ quantum-mechanical calculations to investigate the atomistic structure and energetics of S(-I) and S(-II) incorporated into apatite and elucidate incorporation mechanisms.

   One S(-I) species (disulfide, S22−) and two S(-II) species (bisulfide, HS−, and sulfide, S2−) are investigated as possible forms of reduced S species in apatite. In configuration models for the simulation, these reduced S species are positioned along the c-axis channel, originally occupied by the column anions F, Cl, and OH in the end-member apatites. In the lowest-energy configurations of S-incorporated apatite, disulfide prefers to be positioned halfway between the mirror planes at z = 1/4 and 3/4. In contrast, the energy-optimized bisulfide is located slightly away from the mirror planes by ~0.04 fractional units in the c direction. The energetic stability of these reduced S species as a function of position along the c-axis can be explained by the geometric and electrostatic constraints of the Ca and O planes that constitute the c-axis channel.

   The thermodynamics of incorporation of disulfide and bisulfide into apatite is evaluated by using solid-state reaction equations where the apatite host and a solid S-bearing source phase (pyrite and Na2S2(s) for disulfide; troilite and Na2S(s) for sulfide) are the reactants, and the S-incorporated apatite and an anion sink phase are the products. The Gibbs free energy (ΔG) is lower for incorporation with Na-bearing phases than with Fe-bearing phases, which is attributed to the higher energetic stability of the iron sulfide minerals as a source phase for S than the sodium sulfide phases. The thermodynamics of incorporation of reduced S is also evaluated by using reaction equations involving dissolved disulfide and sulfide species [HnS(aq)(2−n) and HnS(aq)(2−n); n = 0, 1, and 2] as a source phase. The ΔG of S-incorporation increases for fluorapatite and chlorapatite, and decreases for hydroxylapatite, as these species are protonated (i.e., as n changes from 0 to 2). These thermodynamic results demonstrate that the presence of reduced S in apatite is primarily controlled by the chemistry of magmatic and hydrothermal systems where apatite forms (e.g., an abundance of Fe; solution pH). Ultimately, our methodology developed for evaluating the thermodynamics of S incorporation in apatite as a function of temperature, pH, and composition is highly applicable to predicting the trace and volatile element incorporation in minerals in a variety of geological systems. In addition to solid-solid and solid-liquid equilibria treated here at different temperatures and pH, the methodology can be easily extended to different pressure conditions by just performing the quantum-mechanical calculations at elevated pressures.

    

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3. An ab-initio study on the thermodynamics of disulfide, sulfide, and bisulfide incorporation into apatite and the development of a more comprehensive temperature, pressure, pH, and composition-dependent model for ionic substitution in minerals

   Young Jae Kim, Brian Konecke ( September 2022 , The American mineralogist)

   The mineral apatite, Ca10(PO4)6(F,OH,Cl)2, incorporates sulfur (S) during crystallization from S-bearing hydrothermal fluids and silicate melts. Our previous studies of natural and experimental apatite demonstrate that the oxidation state of S in apatite varies systematically as a function of oxygen fugacity (fO2). The S oxidation states –1 and –2 were quantitatively identified in apatite crystallized from reduced, S-bearing hydrothermal fluids and silicate melts by using sulfur K-edge X‑ray absorption near-edge structure spectroscopy (S-XANES) where S6+/ΣS in apatite increases from ~0 at FMQ-1 to ~1 at FMQ+2, where FMQ refers to the fayalite-magnetite-quartz fO2 buffer. In this study, we employ quantum-mechanical calculations to investigate the atomistic structure and energetics of S(-I) and S(-II) incorporated into apatite and elucidate incorporation mechanisms. One S(-I) species (disulfide, S22−) and two S(-II) species (bisulfide, HS−, and sulfide, S2−) are investigated as possible forms of reduced S species in apatite. In configuration models for the simulation, these reduced S species are positioned along the c-axis channel, originally occupied by the column anions F, Cl, and OH in the end-member apatites. In the lowest-energy configurations of S-incorporated apatite, disulfide prefers to be positioned halfway between the mirror planes at z = 1/4 and 3/4. In contrast, the energy-optimized bisulfide is located slightly away from the mirror planes by ~0.04 fractional units in the c direction. The energetic stability of these reduced S species as a function of position along the c-axis can be explained by the geometric and electrostatic constraints of the Ca and O planes that constitute the c-axis channel. The thermodynamics of incorporation of disulfide and bisulfide into apatite are evaluated by using solid-state reaction equations where the apatite host and a solid S-bearing source phase (pyrite and Na2S2(s) for disulfide; troilite and Na2S(s) for sulfide) are the reactants, and the S-incorporated apatite and an anion sink phase are the products. The Gibbs free energy (ΔG) is lower for incorporation with Na-bearing phases than with Fe-bearing phases, which is attributed to the higher energetic stability of the iron sulfide minerals as a source phase for S than the sodium sulfide phases. The thermodynamics of incorporation of reduced S are also evaluated by using reaction equations involving dissolved disulfide and sulfide species [HnS2(aq)(2–n) and HnS(aq)(2–n); n = 0, 1, and 2] as a source phase. The ΔG of S-incorporation increases for fluorapatite and chlorapatite and decreases for hydroxylapatite as these species are protonated (i.e., as n changes from 0 to 2). These thermodynamic results demonstrate that the presence of reduced S in apatite is primarily controlled by the chemistry of magmatic and hydrothermal systems where apatite forms (e.g., an abundance of Fe; solution pH). Ultimately, our methodology developed for evaluating the thermodynamics of S incorporation in apatite as a function of temperature, pH, and composition is highly applicable to predicting the trace and volatile element incorporation in minerals in a variety of geological systems. In addition to solid-solid and solid-liquid equilibria treated here at different temperatures and pH, the methodology can be easily extended also to different pressure conditions by just performing the quantum-mechanical calculations at elevated pressures. 

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4. Titanite zonation records magmatic to autometamorphic transition in the Little Cottonwood stock, Utah

   Bartley, J.M. ; Stearns, M.A. ; Bowman, J.R. ; Beno, C.J. ; Saunders, E. ; Nicholas, S. ( April 2023 , Abstracts Geological Society of America)

   Granite textures are usually assumed to be unmodified igneous features, but titanite petrochronoloy records a progression from magmatic crystallization to fluid-mediated automorphism in the Little Cottonwood stock (LCS). The Wasatch Mountains expose a profile through the 36-25 Ma Wasatch Igneous Belt owing to 20° eastward tilt in the footwall of the Wasatch Fault. The LCS, Alta stock (AS) and their contact aureoles form an integrated magmatic-hydrothermal system that underpinned the cogenetic Keetley Volcanics (KV). The AS (~3-5 km depth) likely formed a conduit from the deeper LCS (~6-11 km) to the KV. The LCS formed in two phases: 1) ~36–33 Ma, coeval with the AS and KV, and 2) ~32–25 Ma, younger than KV and AS but at this time hydrothermal fluid infiltrated the AS­ to form endoskarn. LCS titanite was analyzed by LASS-ICP-MS in 16 samples of unaltered granite (s.l.) collected along transects from the roof on the east to the deepest exposures on the west and from the northern wall to the southern wall. Principal component analysis of titanite trace-element data distinguishes a magmatic group with high REE and a metamorphic group with low REE and high W, Sr, Sc, V, Cr, Fe, Al, and Pb. The metamorphic group forms BSE-dark rims that are variably developed but present in every sample. U-Pb dates indicate that, across the sample suite, there is nearly complete age overlap between magmatic and metamorphic titanite. We interpret chemical zoning of the titanite to record magmatic crystallization followed by hydrothermal modification of primary minerals. The age overlap suggests that solidified increments were infiltrated by fluid released by crystallization of nearby later increments. Infiltrating fluids also affected the feldspars: although apparently intact when examined optically, CL images reveal the feldspars to have been shattered, then healed by dissolution-reprecipitation. Exsolution of Ab component from K-feldspar to form albite selvages against adjacent plagioclase probably was part of the same process, as were biotite chloritization and exsolution of Ti from primary titanomagnetite to grow metamorphic titanite. Taken together, observations from titanite and major phases are consistent with fluid-mediated submagmatic re-equilibration throughout incremental assembly of the LCS. 

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5. Volatiles, vesicles, and vugs: Unraveling the magmatic and eruptive histories of Steno crater basalts

   https://doi.org/10.1111/maps.14086  

   Wilbur, Z. E. ; Barnes, J. J. ; Eckley, S. A. ; Ong, I. J. ; Brounce, M. ; Crow, C. A. ; Erickson, T. ; Kent, J. J. ; Boyce, J. W. ; Mosenfelder, J. L. ; et al ( October 2023 , Meteoritics & Planetary Science)

   In 1972, Apollo 17 astronauts returned 170.4 kg of lunar material. Within 1 month of their return, a subset of those samples was specially curated with the forethought that future analytical techniques would offer new insight into the formation and evolution of the Moon. Of interest in this work is sample 71036, a basalt collected from the rim of Steno crater in the Taurus–Littrow Valley, which was stored frozen and was processed and released for study 50 years later. We report, for the first time, the detailed mineralogy and petrology of 71036 and its companion samples 71035, 71037, and 71055 using a novel combination of 2‐D and 3‐D methods. We investigate lunar volatiles through in situ measurements of apatite and 3‐D measurements of vesicles to understand the degassing histories of the Steno crater basalts. Our coupled 2‐D petrography and 3‐D tomography data sets support a model of the Steno crater basalts crystallizing in the upper crust of a mare lava flow. Apatite F and OH chemistry and the late‐stage deformation of voids and formation of smaller vesicles provide evidence supporting coeval degassing of volatiles and crystallization of mesostasis apatite in Apollo 17 basalts. This work helps to close knowledge gaps surrounding the origin, magmatic evolution, emplacement, and crystallization history of high‐titanium basalts.

    

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