Search

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 ΔFMQ, using zircon geochemistry indicates that the fO2 values of the St-Jude, Côté Gold, and Clifford magmas increase from ΔFMQ –0·3 ± 0·6 to ΔFMQ +0·8 ± 0·4 and to ΔFMQ +1·2 ± 0·4, respectively. In contrast, amphibole chemistry yielded systematically higher fO2 values of ΔFMQ +1·6 ± 0·3 and ΔFMQ +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+/ΣS) in primary apatite yielded ≥ΔFMQ −0·3 and ΔFMQ +1·4–1·8 for St-Jude and Clifford, respectively. The magnetite–ilmenite mineral pairs from the Clifford tonalite yielded ΔFMQ +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 (~ΔFMQ +0·8 ± 0·4) to moderately (~ΔFMQ +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 (~ΔFMQ +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.

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 fayalite-magnetite-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., Tectonomagmatic conditions in the Precambrian were hypothesized to be unfavorable for porphyry Cu deposit formation. Here, the authors show that metallogenic processes typify Phanerozoic porphyry Cu deposits operated by ~1.88 Ga, reflecting modification of mantle lithosphere by oxidized slab-derived fluids at that time.

In the present study, we combined stable isotopes and anthropogenic tracers to investigate the origin, residence times, and evolution of thermal waters in the Lonquimay-Tolhuaca Volcanic Complex (LTVC) of the southern Chilean Andes. A total of 20 water samples from springs discharging at a broad range of temperatures (8–96 °C) were collected and analyzed for major ion geochemistry, stable isotope ratios (δ2H, δ18O, δ13CTDIC), dissolved chlorofluorocarbons (CFCs) and sulfur hexafluoride (SF6). In addition, we compiled all available data on the isotopic composition of precipitation in the region to derive the local meteoric water line. Coupled with a Rayleigh-fractionation model of precipitation, we provide constraints on the elevation at which infiltration and recharge to the system is produced. δ13CTDIC values are consistent with the bulk of dissolved inorganic carbon being derived from the addition of soil CO2 to an atmospheric source, while magma degassing and boiling processes are evidenced in samples discharging directly on the flanks of volcanoes. The isotopic composition of thermal water, once heated at depth, is further modified by CO2 degassing and carbonate precipitation during ascent. All geothermal samples contain low but detectable concentrations of CFC-11, CFC-12, CFC-113, and SF6, suggesting the addition of only a small fraction (2–22%) of modern meteoric water. The discharge temperature of naturally outflowing springs in the LTVC correlates directly with the age distribution of the water samples. This difference in residence times is attributed to the distinct subsurface circulation pathways of each water type—i.e., the shallow, diffuse flow of cold groundwater vs. the deep, focused circulation of thermal water along fault zones. Conduit flow along high vertical permeability networks allows hydrothermal fluid to remain relatively unmixed with shallow meteoric water during ascent. Data from this study confirm that fault-fracture meshes with different orientations exert a first order control on the residence times, ascent, and mixing rates of thermal waters in this segment of the Andean Cordillera, thus modulating their chemical and isotopic signature. Additionally, our results show that the combined use of conventional hydrogeochemical and isotopic data with environmental tracers, including anthropogenic CFCs and SF6, is a powerful tool to better understand the dynamics of geothermal systems.