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Abstract The redox state of arc mantle has been considered to be more oxidized and diverse than that of the mid-ocean ridge, but the cause of the variation is debated. We examine the redox state of the Cenozoic global arc mantle by compiling measured/calculatedfO₂of olivine-hosted melt inclusions from arc magma and modeledfO₂based on V/Sc and Cu/Zr ratios of arc basaltic rocks. The results indicate that the redox state of Cenozoic arc mantle is latitude dependent, with less oxidized arc mantle in the low latitudes, contrasting with a near constant across-latitude trend in the mid-ocean ridges. We propose that such a latitude-dependent pattern in the arc mantle may be controlled by the variation in the redox state of subducted sediment, possibly related to a latitudinal variation in the primary production of phytoplankton, which results in more organic carbon and sulfide deposited on the low-latitude ocean floor. Our findings provide evidence for the impact of the surface environment on Earth’s upper mantle. 

Titanite (CaTiSiO5) is a commonly occurring and versatile accessory mineral with broad applications in petrochronology. In situ U-Pb and trace element analyses via SIMS and LA-ICPMS are routinely performed using a matrix-matched reference material for U-Pb and standard glasses (non-matrix matched reference material) for elemental abundance determination. We report U-Pb isotopic ratios and major and trace element concentrations for three titanite samples (Ecstall, McClure and FCT) which are commonly used as reference materials in petrochronology studies. In addition, we characterize two new samples which can potentially serve as matrixmatched reference materials for titanite trace element geochemistry (BLR-2 and BRA-1). Based on electron microprobe analysis, samples BLR-1 and BLR-2 are homogeneous and suitable for use as a primary reference material for trace element concentrations. Whereas Ecstall, McClure, and FCT titanite reference materials show high intra-grain heterogeneity, yielding relative standard deviations for most trace elements between 5% and 40%, with higher standard deviations for U of 70% for Ecstall (n = 26), 265% for McClure (n = 22), and 202% for FCT (n = 26). Therefore, we suggest that these grains are unsuited to serve as reference materials for trace element quantification. The BRA-1 titanite has low trace element concentrations and is chemically heterogeneous (total REE abundances of 40 ppm for the rim and 95 ppm for the core of the grain), thus is not suitable for standardization of chemical composition using LA-ICPMS. It is commonly asserted that a matrix-matched standardization provides a more robust downhole fractionation correction compared to a non-matrix matched standardization. However, it remains unclear which standardization approach (matrix-matched vs non-matrix matched/glass) is more accurate for titanite trace element quantification. To resolve this, we tested several standardization approaches for trace element quantification, comparing matrix-matched (BLR-1) and nonmatrix- matched (NIST612) standardizations with different internal elemental standards (IES; Ca, Si and Ti) and without internal standardization (semi-quantitative). To provide an independent constraint on the accuracy of the various trace element standardization techniques we compared results to trace element concentrations obtained via solution Q-ICPMS on crushed BLR-2 and BRA-1 aliquots. The matrix-matched standardization using Si as the IES yields the best reproducibility of trace element concentrations followed by the matrix-matched reduction using Ti as the IES. Moreover, the matrix-matched semi-quantitative correction yielded the lowest weighted percentage of difference compared to reference trace composition quantified by solution ICPMS. Finally, in this contribution we also benchmark sampling-size for precise U-Pb dating of common-Pb rich phases like titanite. 

Abstract Arc magmatism is thought to be driven by peridotite melting in the mantle wedge. Yet pyroxenites are ubiquitous in the melting region beneath magmatic arcs. Because they typically have lower solidi temperatures and higher melt productivities compared to peridotite, pyroxenites likely play a significant role in magma generation. Here, we use the Zn/Fe ratios of a global database of Pliocene–Holocene primitive arc magmas to show that, as the crustal thickness of the overlying plate increases, so does the proportion of pyroxenite-derived melts relative to peridotite-derived melts. In fact, at arcs with crustal thicknesses >40 km, the majority of magmas are sourced from pyroxenite. Major and trace element geochemistry of pyroxenite melts is consistent with derivation from mafic magmas frozen in the mantle en route to the surface. We hypothesize that, as the thickness of the continental crust increases, the mantle wedge is displaced toward higher pressures and cooler temperatures, thereby lowering the extent of peridotite melting and allowing magmas sourced from the pyroxeniteveined mantle to dominate the arc budget. 

Granitic rocks, interpreted to be related to crustal melting, were emplaced into regions of thickened crust in southern Arizona during the Laramide orogeny (80–40 Ma). Laramide-age anatectic rocks are exposed as plutons, sills, and dike networks that are commonly found in the exhumed footwalls of metamorphic core complexes. This study investigates newly discovered exposures of granodioritic–leucogranitic rocks from three intrusive phases in the footwall of the Pinaleño–Jackson Mountain metamorphic core complex of southeastern Arizona, called the Relleno suite. Zircon U–Pb geochronology indicates that the suite was emplaced from 58 to 52 Ma. Zircon Lu/Hf isotope geochemistry, whole-rock Sr and Nd isotope geochemistry, and mineral O isotope geochemistry were used to investigate the source of these rocks and evaluate whether they are related to crustal anatexis. Average zircon εHf(t) values of the suite range from −4.7 to −7.9, whole-rock εNd(i) and 87Sr/86Sr(i) values range from −9.4 to −11.8 and 0.7064 to 0.7094 respectively, and quartz δ18OVSMOW values range from 6.8 to 9.4 ‰. Isotopic and geochemical data of these rocks are consistent with derivation from and assimilation of intermediate–mafic (meta)igneous rocks, at deep crustal levels, and are supported by thermodynamic melt models of Proterozoic igneous rocks equivalent to those exposed in the Pinaleño Mountains. In comparison with other Laramide-age anatectic granites in SE Arizona, those exposed in the Pinaleño Mountains are temporally similar but present compositional and isotopic differences that reflect melting and assimilation of different lithologies, producing distinct mineralogical and isotopic characteristics. The results suggest that crustal melting during this interval was not limited to metasedimentary protoliths and may have affected large portions of the deep crust. The early Paleogene Relleno suite in the Pinaleño Mountains strengthens the relationship between crustal melting and regions of thickened crust associated with the Sevier and Laramide orogenies. 

Zircons widely occur in magmatic rocks and often display internal zonation finely recording the magmatic history. Here, we presented in situ high-precision (2SD <0.15‰ for δ 94 Zr) and high–spatial-resolution (20 µm) stable Zr isotope compositions of magmatic zircons in a suite of calc-alkaline plutonic rocks from the juvenile part of the Gangdese arc, southern Tibet. These zircon grains are internally zoned with Zr isotopically light cores and increasingly heavier rims. Our data suggest the preferential incorporation of lighter Zr isotopes in zircon from the melt, which would drive the residual melt to heavier values. The Rayleigh distillation model can well explain the observed internal zoning in single zircon grains, and the best-fit models gave average zircon–melt fractionation factors for each sample ranging from 0.99955 to 0.99988. The average fractionation factors are positively correlated with the median Ti-in-zircon temperatures, indicating a strong temperature dependence of Zr isotopic fractionation. The results demonstrate that in situ Zr isotope analyses would be another powerful contribution to the geochemical toolbox related to zircon. The findings of this study solve the fundamental issue on how zircon fractionates Zr isotopes in calc-alkaline magmas, the major type of magmas that led to forming continental crust over time. The results also show the great potential of stable Zr isotopes in tracing magmatic thermal and chemical evolution and thus possibly continental crustal differentiation.