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.
Pyrite is ubiquitous in the world-class iron oxide copper-gold (IOCG) deposits of the Candelaria-Punta del Cobre district, documented from early to late stages of mineralization and observed in deep and shallow levels of mineralized bodies. Despite its abundance, the chemical and isotopic signature of pyrite from the Candelaria-Punta del Cobre district, and most IOCG deposits worldwide, remains poorly understood. We evaluated in situ chemical and isotopic variations at the grain scale in a set of pyrite-bearing samples collected throughout the district in order to characterize and further understand the nature of mineralization in this IOCG system. Our multianalytical approach integrated synchrotron micro-X-ray fluorescence (μ-XRF) mapping of pyrite grains with electron probe microanalysis and laser ablation-inductively coupled plasma-mass spectrometry data, and sulfur isotope determinations using secondary ion mass spectrometry (SIMS) complemented with bulk sulfur isotope analyses of coeval pyrite, chalcopyrite, and anhydrite. Synchrotron μ-XRF elemental concentration maps of individual pyrite grains reveal a strong zonation of Co, Ni, As, and Se. The observed relationships between Ni and Se are interpreted to reflect changes in temperature and redox conditions during ore formation and provide constraints on fluid evolution. Co and Ni concentrations and ratios suggest contributions from magmas of mafic-intermediate composition. Pyrite chemical concentrations reflect potential stratigraphic controls, where the sample from the upper part of the stratigraphy diverges from trends formed by the rest of the sample set from lower stratigraphic levels. The SIMS δ34S values of pyrite (and chalcopyrite) range between –2 up to 10‰, and bulk δ34S values of pyrite range between 4 up to 12‰. The majority of the δ34S analyses, falling between –1 and 2‰, indicate a magmatic source for sulfur and, by inference, for the hydrothermal ore fluid(s). Variation in the δ34S signature can be explained by changes in the redox conditions, fluid sources, and/or the temperature of the hydrothermal fluid. The Se/S ratio combined with δ34S values in pyrite is consistent with mixing between a magmatic-hydrothermal fluid and a fluid with a probable basinal signature. The results of this study are consistent with the hydrothermal fluids responsible for mineralization in the Candelaria-Punta del Cobre district being predominantly of magmatic origin, plausibly from mafic-intermediate magmas based on the Ni-Co content in pyrite. External fluid incursion, potentially from a basinal sedimentary source, occurred late in the evolution of the system, adding additional reduced sulfur as pyrite. There is no evidence to suggest that the late fluid added significant Cu-Au mineralization, but this cannot be ruled out. Finally, the data reveal that trace element ratios coupled with spatially resolved sulfur isotope data in pyrite are powerful proxies to track the magmatic-hydrothermal evolution of IOCG systems and help constrain the source of their contained metals.
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