The redox sensitivity of Ce and Eu anomalies in zircon has been clearly demonstrated by experimental studies, and these may represent an important tool in the exploration for porphyry Cu deposits which are thought to be derived from oxidised magmas. These deposits are significant because they are the source of much of the world's copper and almost all of the molybdenum and rhenium, key elements in many modern technologies. However, Ce and Eu anomalies in zircon are also affected by the co-crystallisation of REE bearing phases, such as titanite. Here, we report the trace element chemistry of zircons from titanite-bearing intrusions associated with mineralisation at the world class Oyu Tolgoi porphyry Cu-Au deposit (Mongolia). Based on these data, we suggest that neither zircon Eu/Eu*, nor Ce4+/Ce3+ are robust proxies for melt redox conditions, because they are both too strongly dependent on melt REE concentrations, which are usually poorly constrained and controlled by the crystallisation of titanite and other REE-bearing phases. In spite of this, Eu/Eu* can broadly distinguish between fertile and barren systems, so may still be an indicator of porphyry magma fertility, and a useful tool for exploration
Protracted magma storage in the deep crust is a key stage in the formation of evolved, hydrous arc magmas that can result in explosive volcanism and the formation of economically valuable magmatic-hydrothermal ore deposits. High magmatic water content in the deep crust results in extensive amphibole ± garnet fractionation and the suppression of plagioclase crystallization as recorded by elevated Sr/Y ratios and high Eu (high Eu/Eu*) in the melt. Here, we use a novel approach to track the petrogenesis of arc magmas using apatite trace element chemistry in volcanic formations from the Cenozoic arc of central Chile. These rocks formed in a magmatic cycle that culminated in high-Sr/Y magmatism and porphyry ore deposit formation in the Miocene. We use Sr/Y, Eu/Eu*, and Mg in apatite to track discrete stages of arc magma evolution. We apply fractional crystallization modeling to show that early-crystallizing apatite can inherit a high-Sr/Y and high-Eu/Eu* melt chemistry signature that is predetermined by amphibole-dominated fractional crystallization in the lower crust. Our modeling shows that crystallization of the in situ host-rock mineral assemblage in the shallow crust causes competition for trace elements in the melt that leads to apatite compositions diverging from bulk-magma chemistry. Understanding this decoupling behavior is important for the use of apatite as an indicator of metallogenic fertility in arcs and for interpretation of provenance in detrital studies.
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