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Ti‐isotope fractionation on the most Ti‐rich minerals on Earth has not been reported. Therefore, we present a chemical preparation and separation technique for Ti‐rich minerals for mineralogic, petrologic, and economic geologic studies. A two‐stage ion‐exchange column procedure modified from the previous literature is used in the current study to separate Ti from Fe‐rich samples, while α‐TiO2 does not require chemical separation. Purified solutions in conjunction with solution standards were measured on two different instruments with dry plasma and medium‐resolution mode providing mass‐dependent results with the lowest errors. 49/47TiOL‐Ti for the solution and solids analyzed here demonstrate a range of >5‰ far greater than the whole procedural 1 error of 0.10‰ for a synthetic compound and 0.07‰ for the mineral magnetite; thus, the procedure produces results is resolvable within the current range of measured Ti‐isotope fractionation in these minerals.

Renewed economic interest in iron oxide–apatite (IOA) deposits — containing tens to hundreds of millions of tonnes of Fe and substantial amounts of rare earth elements, P, Co and V — has emerged to supply the sustainable energy transition. However, the mechanisms that efficiently concentrate dense iron- rich minerals (for example, in ores up to ~90% magnetite) at the Earth’s near- surface are widely debated. In this Review, we discuss synergistic combinations of magmatic and hydrothermal iron- enrichment processes that can explain the available geochemical, petrological and geological IOA data. IOA deposits typically evolve from subductionrelated water- rich and chlorine- rich intermediate magmas under a wide temperature range, almost spanning the whole igneous–hydrothermal spectrum (from ~1,000 to 300 °C). Magmatic– hydrothermal fluids could efficiently scavenge Fe from magmas to form large IOA deposits (>100 million tonnes of Fe), whereas crystal fractionation and liquid immiscibility processes might account for more minor Fe mineralization occurrences. Igneous magnetite crystallization, volatile exsolution and highly focused transport of Fe- rich hydrothermal fluids through the crust under extensional tectonic conditions could be key factors enabling concentration of dense magnetite minerals in the less- dense upper crust. Future research should target both fertile and barren mafic–intermediate magmaticmore »suites for distinctive signatures diagnostic of metallogenic fertility, to help unravel the genetic linkage between IOA and iron oxide–copper–gold systems.« less

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, themore »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.« less

Sulfur is a key element in terrestrial magmatic processes yet its geochemical behavior remains one of the most difficult to model due to its heterovalent chemistry. The maximum amount of sulfur a silicate melt can dissolve before saturating with sulfide (e.g., pyrrhotite) or sulfate (e.g., anhydrite) changes with the redox state of the system and has important implications for the sulfur budget of a magmatic system. Several empirical models have been developed to predict the sulfur content of a silicate melt at either sulfide (under reducing conditions) or sulfate (under oxidizing conditions) saturation, but only one model existed that systematically assessed how the sulfur content of a basaltic melt changes as a function of oxygen fugacity (fO2) across the transition from sulfide- to sulfate-dominated conditions. The applicability of that model to intermediate and felsic melts rests on the assumption that changes in melt composition do not affect how sulfide or sulfate dissolves in the melt. Here, we report new experimental data that constrain the sulfur concentration at sulfide saturation (SCSS) and the sulfur concentration at anhydrite saturation (SCAS) in a dacitic melt as a function of fO2. The experiments were conducted using a H2Osaturated natural dacitic melt at 1000  C,more »300 MPa, and at log fO2 varying over four orders of magnitude encompassing the sulfide-sulfate transition (log fO2 = DFMQ 0.7, DFMQ+0, DFMQ+0.5, DFMQ+1, DFMQ+1.48, DFMQ+1.54, DFMQ +1.75, DFMQ+2.08 and DFMQ+3.3). New SCSS and SCAS data and modeling for dacitic melts reveals that the sulfidesulfate transition occurs at DFMQ+1.81 ± 0.56, defined by the following equations to predict the sulfur content of intermediate to evolved silicate melts as a function of fO2: SCSSdacitic = [S2 ] (1 + 10(2.00DFMQ – 3.05)) SCASdacitic = [S6+] (1 + e(1.26 – 2.00DFMQ)) The results presented here demonstrate that the basaltic-derived SCSS-SCAS model is not appropriate for dacitic melts and that the sulfide-sulfate transition is shifted to higher fO2 in more evolved silicate melts. Implications include the stability of sulfides to higher fO2 in more evolved silicate melts and the potential for a narrower transition from a sulfide- to a sulfate-dominated melt than that predicted by thermodynamics.« less

Most known porphyry Cu±Au deposits are associated with moderately oxidized and sulfur-rich, calc-alkaline to mildly alkalic arc-related magmas in the Phanerozoic. In contrast, sodium-enriched tonalite–trondhjemite–granodiorite–diorite (TTG) magmas predominant in the Archean are hypothesized to be unoxidized and sulfur-poor, which together preclude porphyry Cu deposit formation. Here, we test this hypothesis by interrogating the causative magmas for the ∼2·7 Ga TTG-related Côté Gold, St-Jude, and Clifford porphyry-type Cu±Au deposit settings in the Neoarchean southern Abitibi subprovince. New and previously published geochronological results constrain the age of emplacement of the causative magmas at ∼2·74 Ga, ∼2·70 Ga, and∼2·69 Ga, respectively. The dioritic and trondhjemitic magmas associated with Côté Gold and St-Jude evolved along a plagioclase-dominated fractionation trend, in contrast to amphibole-dominated fractionation for tonalitic magma at Clifford. Analyses of zircon grains from the Côté Gold, St-Jude, and Clifford igneous rocks yielded εHf(t)±SD values of 4·5±0·3, 4·2±0·6, and 4·3±0·4, and δ18O±SD values of 5·40±0·11  , 3·91±0·13  , and 4·83±0·12  , respectively. These isotopic signatures indicate that, although these magmas are mantle-sourced with minimal crustal contamination, for the St- Jude and Clifford settings the magmas or their sources may have undergone variable alteration by heated seawater or meteoric fluids. Primary barometric minerals (i.e. zircon,more »amphibole, apatite, and magnetite–ilmenite) that survived variable alteration and metamorphism (up to greenschist facies) were used for estimating fO2 of the causative magmas. Estimation of magmatic fO2 values, reported relative to the fayalite–magnetite–quartz buffer as  FMQ, using zircon geochemistry indicates that the fO2 values of the St-Jude, Côté Gold, and Clifford magmas increase from  FMQ –0·3±0·6 to  FMQ +0·8±0·4 and to  FMQ +1·2±0·4, respectively. In contrast, amphibole chemistry yielded systematically higher fO2 values of  FMQ +1·6±0·3 and  FMQ +2·6±0·1 for Côté Gold and Clifford, respectively, which are consistent with previous studies that indicate that amphibole may overestimate the fO2 of intrusive rocks by up to 1 log unit. Micro X-ray absorption near edge structure (μ-XANES) spectrometric determination of sulfur (i.e. S6+/ S) in primary apatite yielded ≥ FMQ−0·3 and FMQ+1·4–1·8 for St-Jude and Clifford, respectively. The magnetite–ilmenite mineral pairs from the Clifford tonalite yielded  FMQ +3·3±1·3 at equilibrium temperatures of 634±21 ◦C, recording the redox state of the late stage of magma crystallization. Electron probe microanalyses revealed that apatite grains from Clifford are enriched in S (up to 0·1 wt%) relative to those of Côté Gold and St-Jude (below the detection limit), which is attributed to either relatively oxidized or sulfur-rich features of the Clifford tonalite. We interpret these results to indicate that the deposits at Côté Gold and Clifford formed from mildly (∼ FMQ +0·8±0·4) to moderately (∼ FMQ +1·5) oxidized magmas where voluminous early sulfide saturation was probably limited, whereas the St-Jude deposit represents a rare case whereby the ingress of externally derived hydrothermal fluids facilitated metal fertility in a relatively reduced magma chamber (∼ FMQ +0). Furthermore, we conclude that variable modes of formation for these deposits and, in addition, the apparent rarity of porphyry-type Cu–Au deposits in the Archean may be attributed to either local restriction of favorable metallogenic conditions, and/or preservation, or an exploration bias.« less

Iron oxide copper-gold (IOCG) deposits are major sources of Cu, contain abundant Fe oxides, and may contain Au, Ag, Co, rare earth elements (REEs), U, and other metals as economically important byproducts in some deposits. They form by hydrothermal processes, but the source of the metals and ore fluid(s) is still debated. We investigated the geochemistry of magnetite from the hydrothermal unit and manto orebodies at the Mina Justa IOCG deposit in Peru to assess the source of the iron oxides and their relationship with the economic Cu mineralization. We identified three types of magnetite: magnetite with inclusions (type I) is only found in the manto, is the richest in trace elements, and crystallized between 459° and 707°C; type Dark (D) has no visible inclusions and formed at around 543°C; and type Bright (B) has no inclusions, has the highest Fe content, and formed at around 443°C. Temperatures were estimated using the Mg content in magnetite. Magnetite samples from Mina Justa yielded an average δ56Fe ± 2σ value of 0.28 ± 0.05‰ (n = 9), an average δ18O ± 2σ value of 2.19 ± 0.45‰ (n = 9), and D’17O values that range between –0.075 and –0.047‰. Sulfide separates yieldedmore »δ65Cu values that range from –0.32 to –0.09‰. The trace element compositions and textures of magnetite, along with temperature estimations for magnetite crystallization, are consistent with the manto magnetite belonging to an iron oxide-apatite (IOA) style mineralization that was overprinted by a younger, structurally controlled IOCG event that formed the hydrothermal unit orebody. Altogether, the stable isotopic data fingerprint a magmatic-hydrothermal source for the ore fluids carrying the Fe and Cu at Mina Justa and preclude significant input from meteoric water and basinal brines.« less

Iron oxide-copper-gold (IOCG) deposits are major sources of Cu, contain abundant Fe-oxides and may contain Au, Ag, Co, rare earth elements (REE), U and other metals as economically important byproducts in some deposits. They form by hydrothermal processes, but the source of the metals and ore fluid(s) is still debated. We investigated the geochemistry of magnetite from the manto and breccia ore bodies at the Mina Justa IOCG deposit in Peru to assess the source of the iron oxides and their relationship with the economic Cu mineralization. We identified three magnetite types: Type Inclusion (I) is only found in the manto, is the richest in trace elements, and crystallized between 459 - 707 °C; Type Dark (D) has no visible inclusions and formed at around 543 °C; and Type Bright (B) has no inclusions, has the highest Fe content, and formed at around 443 °C. Magnetite samples from Mina Justa yielded an average δ56Fe ± 2σ value of 0.28 ± 0.05‰ (n=9), an average δ18O ± 2σ value 2.19 ± 0.45‰ (n=9), and Δ’17O values that range between -0.075‰ and -0.047‰. Sulfide separates yielded δ65Cu values that range from -0.32‰ to -0.09‰. The trace element compositions and textures of magnetite,more »along with temperature estimations for magnetite crystallization, are consistent with the manto magnetite belonging to an IOA style mineralization that was overprinted by a younger, structurally-controlled IOCG event that formed the breccia ore body. Altogether, the stable isotopic data fingerprint a magmatic-hydrothermal source for the ore fluids carrying the Fe and Cu at Mina Justa and preclude the input from meteoric water and basinal brines.« less

Iron oxide-copper-gold (IOCG) deposits are major sources of Cu, contain abundant Fe-oxides and may contain Au, Ag, Co, rare earth elements (REE), U and other metals as economically important byproducts in some deposits. They form by hydrothermal processes, but the source of the metals and ore fluid(s) is still debated. We investigated the geochemistry of magnetite from the manto and breccia ore bodies at the Mina Justa IOCG deposit in Peru to assess the source of the iron oxides and their relationship with the economic Cu mineralization. We identified three magnetite types: Type Inclusion (I) is only found in the manto, is the richest in trace elements, and crystallized between 459 - 707 °C; Type Dark (D) has no visible inclusions and formed at around 543 °C; and Type Bright (B) has no inclusions, has the highest Fe content, and formed at around 443 °C. Magnetite samples from Mina Justa yielded an average δ56Fe ± 2σ value of 0.28 ± 0.05‰ (n=9), an average δ18O ± 2σ value 2.19 ± 0.45‰ (n=9), and Δ’17O values that range between -0.075‰ and -0.047‰. Sulfide separates yielded δ65Cu values that range from -0.32‰ to -0.09‰. The trace element compositions and textures of magnetite,more »along with temperature estimations for magnetite crystallization, are consistent with the manto magnetite belonging to an IOA style mineralization that was overprinted by a younger, structurally-controlled IOCG event that formed the breccia ore body. Altogether, the stable isotopic data fingerprint a magmatic-hydrothermal source for the ore fluids carrying the Fe and Cu at Mina Justa and preclude the input from meteoric water and basinal brines.« less

Most known porphyry Cu deposits formed in the Phanerozoic and are exclusively associated with moderately oxidized, sulfur-rich, hydrous arc-related magmas derived from partial melting of the asthenospheric mantle metasomatized by slab-derived fluids. Yet, whether similar metallogenic processes also operated in the Precambrian remains obscure. Here we address the issue by investigating the origin, fO2, and S contents of calc-alkaline plutonic rocks associated with the Haib porphyry Cu deposit in the Paleoproterozoic Richtersveld Magmatic Arc (southern Namibia), an interpreted mature island-arc setting. We show that the ca. 1886–1881 Ma ore-forming magmas, originated from a mantle-dominated source with minor crustal contributions, were relatively oxidized (1‒2 log units above the fayalitemagnetite- quartz redox buffer) and sulfur-rich. These results indicate that moderately oxidized, sulfur-rich arc magma associated with porphyry Cu mineralization already existed in the late Paleoproterozoic, probably as a result of recycling of sulfate-rich seawater or sediments from the subducted oceanic lithosphere at that time.

The Chahgaz iron oxide-apatite (IOA) deposit is one of the main IOA deposits in the Bafq metallogenic province, Central Iran. The Chahgaz mineral deposit is hosted by Early Cambrian felsic to intermediate, altered subvolcanic to effusive rocks that range compositionally from granite to diorite. Geochemical, geochronologic and tectonomagmatic investigations of various host rock types in the Bafq province indicate that mineralization was the product of Early Cambrian active continental margin processes that evolved calc-alkaline felsic igneous rocks followed by formation of diabase dykes in a back-arc basin environment. Magnetite is present in massive magnetite-rich ore bodies and veinlets that cut the massive ore bodies. Detailed macro- and micro-scopic characterization of mineralized samples and host rocks reveals a paragenetic sequence containing three generations of magnetite that are distinguished from one another compositionally and texturally. The massive ores contain apatite in trace amounts, consistent with IOA deposits globally, and locally exhibit textures that are visually similar to lava flow structures, as described for the El Laco IOA deposit, Chile. The ore bodies contain miarolitic cavities that are filled by calcite, hematite and quartz. The host rocks for the Chahgaz deposit have undergone widespread hydrothermal metasomatism including Na-Ca, K-, Mg-, Si-, sericitic, argillicmore »and carbonatization alteration. The compositions of two generations of magnetite, referred to as Mag1 and Mag2, in massive ore overlap compositions reported for igneous and high-temperature magmatic-hydrothermal magnetite. The third generation of magnetite, which is referred to as Mag3 and is present in veinlets cross-cutting the massive magnetite ore bodies, overlaps compositions reported for low to moderate temperature magmatichydrothermal magnetite. Pyrite is present as disseminated grains coeval with Mag1 and micro-fracture filling in the massive magnetite-rich ore bodies. The δ18O values obtained for magnetite from representative samples of massive magnetite Mag1 ore range between 2.18 and 6.32‰ and are consistent with δ18O values reported for igneous and magmatic-hydrothermal magnetite from other deposits in the Bafq district and globally. The δ34S values for pyrite range from 22.54 to 24.94‰ and are consistent with an evaporitic sulfur source; plausibly by magma contamination with evaporitic rocks of the Early Cambrian Volcano-Sedimentary Sequence (ECVSS). The data presented here are consistent with formation of the massive magnetite-rich ore bodies in the Chahgaz IOA deposit by an iron-rich magmatichydrothermal fluid.« less