Iron oxide copper-gold (IOCG) and iron oxide-apatite (IOA) deposits are major sources of Fe, Cu, and Au. Magnetite is the modally dominant and commodity mineral in IOA deposits, whereas magnetite and hematite are predominant in IOCG deposits, with copper sulfides being the primary commodity minerals. It is generally accepted that IOCG deposits formed by hydrothermal processes, but there is a lack of consensus for the source of the ore fluid(s). There are multiple competing hypotheses for the formation of IOA deposits, with models that range from purely magmatic to purely hydrothermal. In the Chilean iron belt, the spatial and temporal association of IOCG and IOA deposits has led to the hypothesis that IOA and IOCG deposits are genetically connected, where S-Cu-Au–poor magnetite-dominated IOA deposits represent the stratigraphically deeper levels of S-Cu-Au–rich magnetite- and hematite-dominated IOCG deposits. Here we report minor element and Fe and O stable isotope abundances for magnetite and H stable isotope abundances for actinolite from the Candelaria IOCG deposit and Quince IOA prospect in the Chilean iron belt. Backscattered electron imaging reveals textures of igneous and magmatic-hydrothermal affinities and the exsolution of Mn-rich ilmenite from magnetite in Quince and deep levels of Candelaria (>500 m below the bottom of the open pit). Trace element concentrations in magnetite systematically increase with depth in both deposits and decrease from core to rim within magnetite grains in shallow samples from Candelaria. These results are consistent with a cooling trend for magnetite growth from deep to shallow levels in both systems. Iron isotope compositions of magnetite range from δ56Fe values of 0.11 ± 0.07 to 0.16 ± 0.05‰ for Quince and between 0.16 ± 0.03 and 0.42 ± 0.04‰ for Candelaria. Oxygen isotope compositions of magnetite range from δ18O values of 2.65 ± 0.07 to 3.33 ± 0.07‰ for Quince and between 1.16 ± 0.07 and 7.80 ± 0.07‰ for Candelaria. For cogenetic actinolite, δD values range from –41.7 ± 2.10 to –39.0 ± 2.10‰ for Quince and from –93.9 ± 2.10 to –54.0 ± 2.10‰ for Candelaria, and δ18O values range between 5.89 ± 0.23 and 6.02 ± 0.23‰ for Quince and between 7.50 ± 0.23 and 7.69 ± 0.23‰ for Candelaria. The paired Fe and O isotope compositions of magnetite and the H isotope signature of actinolite fingerprint a magmatic source reservoir for ore fluids at Candelaria and Quince. Temperature estimates from O isotope thermometry and Fe# of actinolite (Fe# = [molar Fe]/([molar Fe] + [molar Mg])) are consistent with high-temperature mineralization (600°–860°C). The reintegrated composition of primary Ti-rich magnetite is consistent with igneous magnetite and supports magmatic conditions for the formation of magnetite in the Quince prospect and the deep portion of the Candelaria deposit. The trace element variations and zonation in magnetite from shallower levels of Candelaria are consistent with magnetite growth from a cooling magmatic-hydrothermal fluid. The combined chemical and textural data are consistent with a combined igneous and magmatic-hydrothermal origin for Quince and Candelaria, where the deeper portion of Candelaria corresponds to a transitional phase between the shallower IOCG deposit and a deeper IOA system analogous to the Quince IOA prospect, providing evidence for a continuum between both deposit types.
Garnet secondary ion mass spectrometry oxygen isotopes reveal crucial roles of pulsed magmatic fluid and its mixing with meteoric water in lode gold genesis
Lode gold deposits, which are currently the world’s major gold supply, have been shown to be generated mostly by phase separation of metamorphic fluids and/or interaction between these fluids and wall rocks. Here we use garnet oxygen isotopes by secondary ion mass spectrometry to document the crucial role of magmatic hydrothermal fluids and their mixing with meteoric water in the formation of the world-class Dongping gold deposit in the North China Craton. Garnet grains from quartz veins of various paragenetic stages and the mineralized alteration envelope at Dongping have dynamic δ 18 O variations of 3.8 to −11.0‰, with large intragrain fluctuations up to 5.3‰. These values correspond to calculated δ 18 O values of 6.1 to −9.1‰ for the hydrothermal fluids from which the garnet formed. The isotope data, notably the cyclic alternation in δ 18 O within individual garnet grains, are best interpreted to reflect multiple pulses of magmatically derived fluids and subsequent mixing of each pulse with variable amounts of meteoric water. The results presented here allow us to quantify the significant interplay between magmatic hydrothermal fluids and meteoric water that spanned the entire mineralization history and triggered gold deposition of a lode gold deposit. This study highlights the potential use of in situ oxygen isotope analysis of garnet in tracing the origin and evolution of hydrothermal fluids in the Earth’s crust that may have formed other giant ore deposits.
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- Award ID(s):
- 2004618
- NSF-PAR ID:
- 10397171
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 119
- Issue:
- 19
- ISSN:
- 0027-8424
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract -
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, 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.more » « less
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null (Ed.)The Plio-Pleistocene El Laco iron oxide-apatite (IOA) orebodies in northern Chile are some of the most enigmatic mineral deposits on Earth, interpreted to have formed as lava flows or by hydrothermal replacement, two radically different processes. Field observations provide some support for both processes, but ultimately fail to explain all observations. Previously proposed genetic models based on observations and study of outcrop samples include (1) magnetite crystallization from an erupting immiscible Fe- and P-rich (Si-poor) melt and (2) metasomatic replacement of andesitic lava flows by a hypogene hydrothermal fluid. A more recent investigation of outcrop and drill core samples at El Laco generated data that were used to develop a new genetic model that invokes shallow emplacement and surface venting of a magnetite-bearing magmatic-hydrothermal fluid suspension. This fluid, with rheological properties similar to basaltic lava, would have been mobilized by decompression- induced collapse of the volcanic edifice. In this study, we report oxygen, including 17O, hydrogen, and iron stable isotope ratios in magnetite and bulk iron oxide (magnetite with minor secondary hematite and minor goethite) from five of seven orebodies around the El Laco volcano, excluding San Vicente Bajo and the minor Laquito deposits. Calculated values of δ18O, Δ17O, δD, and δ56Fe fingerprint the source of the ore-forming fluid(s): Δ17Osample = δ17Osample – δ18Osample * 0.5305. Magnetite and bulk iron oxide (magnetite variably altered to goethite and hematite) from Laco Sur, Cristales Grandes, and San Vicente Alto yield δ18O values that range from 4.3 to 4.5‰ (n = 5), 3.0 to 3.9‰ (n = 5), and –8.5 to –0.5‰ (n = 5), respectively. Magnetite samples from Rodados Negros are the least altered samples and were also analyzed for 17O as well as conventional 16O and 18O, yielding calculated δ18O values that range from 2.6 to 3.8‰ (n = 9) and Δ17O values that range from –0.13 to –0.07‰ (n = 5). Bulk iron oxide from Laco Norte yielded δ18O values that range from –10.2 to +4.5‰ (avg = 0.8‰, n = 18). The δ2H values of magnetite and bulk iron oxide from all five orebodies range from –192.8 to –79.9‰ (n = 28); hydrogen is present in fluid inclusions in magnetite and iron oxide, and in minor goethite. Values of δ56Fe for magnetite and bulk iron oxide from all five orebodies range from 0.04 to 0.70‰ (avg = 0.29‰, σ = 0.15‰, n = 26). The iron and oxygen isotope data are consistent with a silicate magma source for iron and oxygen in magnetite from all sampled El Laco orebodies. Oxygen (δ18O Δ +4.4 to –10.2‰) and hydrogen (δ 2H ≃ –79.9 to –192.8‰) stable isotope data for bulk iron oxide samples that contain minor goethite from Laco Norte and San Vicente Alto reveal that magnetite has been variably altered to meteoric values, consistent with goethite in equilibrium with local δ18O and δ2H meteoric values of ≃ –15.4 and –211‰, respectively. The H2O contents of iron oxide samples from Laco Norte and San Vicente Alto systematically increase with increasing abundance of goethite and decreasing values of δ18O and δ2H. The values of δ2H (≃ –88 to –140‰) and δ18O (3.0–4.5‰) for magnetite samples from Cristales Grandes, Laco Sur, and Rodados Negros are consistent with growth of magnetite from a degassing silicate melt and/or a boiling magmatic-hydrothermal fluid; the latter is also consistent with δ18O values for quartz, and salinities and homogenization temperatures for fluid inclusions trapped in apatite and clinopyroxene coeval with magnetite. The sum of the data unequivocally fingerprint a silicate magma as the source of the ore fluids responsible for mineralization at El Laco and are consistent with a model that explains mineralization as the synergistic result of common magmatic and magmatic-hydrothermal processes during the evolution of a caldera-related explosive volcanic system.more » « less
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null (Ed.)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, 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.more » « less
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null (Ed.)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, 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.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.2116380119
