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 ΔFMQ, using zircon geochemistry indicate that the fO2 values of the St-Jude, Côté Gold, and Clifford magmas increase from ΔFMQ -0.3 ± 0.6, ΔFMQ +0.8 ± 0.4, 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 amphibole may overestimate the fO2 of intrusive rocks by up to one 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 the 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 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.
EXAFS Determination of Clay Minerals in Martian Meteorite Allan Hills 84001 and Its Implication for the Noachian Aqueous Environment