Magmatic compositions and source terranes estimated from melt inclusions in detrital Cr-rich spinels: An example from mid-Cretaceous sandstones in the eastern Tethys Himalaya
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Mineral redox buffer
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The redox state of silicate melts influences crystallization, element partitioning, and degassing behavior. Synchrotron-based micro-X-ray absorption near edge structure (μXANES) spectroscopy has emerged as a powerful tool for determining redox conditions through the direct measurement of speciation of multivalent elements such as iron and sulfur in silicate glasses. In particular, the high spatial resolution afforded by synchrotron μXANES makes it one of the few techniques available for determining redox conditions in melt inclusions, which can provide insights into pre-eruptive melt properties. However, the small size of melt inclusions, the deep penetration of X-rays, and irradiation-induced beam damage make μXANES measurements in melt inclusions challenging. Here we present data that show rapid Fe- and S-μXANES beam damage in experimental glasses, mid-ocean ridge basalt glasses, and olivine-hosted melt inclusions from the southern Cascade arc and Kīlauea Volcano and develop approaches to recognize and correct for beam damage through repeated rapid analyses. By applying a time-dependent correction to a series of rapid measurements (~82 s/scan) of Fe-μXANES pre-edge centroid positions, irradiation-induced photo-oxidation (Fe2+ to Fe3+) can be corrected back to undamaged initial Fe3+/ΣFe even in damage-susceptible hydrous glasses. Using this beam damage correction technique, hydrous basaltic melt inclusions from the southern Cascades have Fe3+/ΣFe that is ~0.036 lower (corresponding to -0.5 log units lower oxygen fugacity) than would have been indicated by standard Fe-μXANES measurements. Repeated, rapid analyses (150 – 300 s/scan) were used to identify S-μXANES beam damage (photo-reduction of S6+ to S4+), which was corrected with a peak fitting method to restore initial S6+/ΣS. We observe that S-μXANES beam damage can occur rapidly even in low-H2O mid-ocean ridge basaltic glasses and melt inclusions from Kīlauea Volcano, which are otherwise stable during even prolonged Fe-μXANES analyses. By mitigating and correcting for sulfur photo-reduction, we conclude that some mid-ocean ridge basaltic glasses contain 0.08 – 0.09 S6+/ΣS, which is more sulfate than might be expected based on the reduced oxidation state of these glasses (near the fayalite-magnetite-quartz oxygen buffer). Using beam damage identification and correction techniques, the valence states of iron and sulfur can be accurately measured even in beam damage-susceptible glasses and melt inclusions. Finally, using Fe-μXANES, we demonstrate the presence of Fe-oxide nanolites within otherwise glassy, naturally quenched melt inclusions, which can complicate determination of iron valence state in affected glasses.
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The metal content, volatile content and crystallization conditions of ore-related rhyolite samples from the Climax-type porphyry Mo deposits at Urad–Henderson and Silver Creek (Rico) were reconstructed based on the composition of melt inclusions, mineral inclusions, and titanium-in-quartz thermobarometry. Additional melt inclusion data were obtained from contemporaneous mafic dikes. Crystallized melt inclusions were either directly analyzed by laser ablation inductively coupled plasma mass spectrometry, or re-homogenized and then analyzed by electron microprobe. Inter-mineralization rhyolite melts at Urad–Henderson were highly evolved (four times more fractionated than average granite of the continental crust), contained 10–15 ppm Mo, 6–7 wt % H2O and 0·5–0·7 wt % F, and record crystallization conditions of 730–770°C, 1–3 kbar and an oxygen fugacity about two log units above the fayalite–magnetite–quartz buffer (FMQ + 2). Melts from two presumably syn-mineralization rhyolite dikes at Silver Creek were slightly less evolved and contained 3–5 ppm Mo, 7–8 wt % H2O and ∼0·3 wt % F, and record crystallization conditions of 780–800°C, 2–5 kbar. Both datasets are characterized by distinctly lower fluorine contents but higher temperatures and higher water contents than corresponding values reported for ore-related rhyolites at Climax. Calculated melt viscosities (log η = 3·5–4·9 Pa s) are lower than those of average granitic melts at the same temperature, which may have facilitated crystal–melt segregation and thus accumulation of large volumes of fractionated, crystal-poor melts in shallow magma chambers, a process that seems to be critical for the formation of Climax-type porphyry Mo deposits.
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Abstract The redox condition of magma determines the stability and composition of crystallizing and volatile phases in martian meteorites, reflecting the evolution of the martian interior. In the current study, direct analyses on the oxidation states of V, Cr, and Fe were performed based on the X-ray absorption near-edge structure (XANES) measurements equipped with a micro-sized X-ray beam. We first applied the micro-XANES (μ-XANES) technique to the olivine-hosted glass inclusion and groundmass glass of martian meteorite Yamato 980459 (Y98), which is interpreted as representing a primary melt composition. Mass-balance calculations and XANES spectra comparisons indicated that, while chromite and pyroxene affected Cr and Fe K-edge XANES spectra, the contribution of these minerals was minimal for V. The pre-edge peak intensity of V K-edge XANES enabled the estimation of the oxygen fugacity for inclusion and groundmass glasses. The calculated oxygen fugacity (fO2) of the glass inclusions was near the Iron-Wüstite (IW) buffer (IW-0.07 ± 0.32) for the glass inclusion, whereas it was 0.9 log units more oxidized (IW+0.93 ± 0.56) for the groundmass glasses. This result suggests that the redox condition of the parent magma of Y98 evolved during magma ascent and emplacement. Since Y98 is interpreted to have evolved in a closed system, our finding suggests that fractional crystallization and/or ascent of magma potentially induces the fO2 increase. This study shows that the μ-XANES technique enables us to determine the fO2 by only measuring a single phase of glassy compounds, and thus, it is useful to discuss the redox condition of volcanic rocks even if they do not crystallize out several equilibrium phases of minerals.
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To decipher the petrogenesis of chromitites from the Moho Transition Zone of the Cretaceous Oman ophiolite, we carried out detailed scanning electron microscope and electron microprobe investigations of ∼500 silicate and chromite inclusions and their chromite hosts, and oxygen isotope measurements of seven chromite and olivine fractions from nodular, disseminated, and stratiform ore bodies and associated host dunites of the Maqsad area, Southern Oman. The results, coupled with laboratory homogenization experiments, allow several multiphase and microcrystal types of the chromite-hosted inclusions to be distinguished. The multiphase inclusions are composed of micron-size (1–50 μm) silicates (with rare sulphides) entrapped in high cr-number [100Cr/(Cr + Al) up to 80] chromite. The high cr-number chromite coronas and inclusions are reduced (oxygen fugacity, fO2, of ∼3 log units below the quartz–fayalite–magnetite buffer, QFM). The reduced chromites, which crystallized between 600 and 950°C at subsolidus conditions, were overgrown by more oxidized host chromite (fO2 ≈ QFM) in association with microcrystal inclusions of silicates (plagioclase An86, clinopyroxene, and pargasite) that were formed between 950 and 1050°C at 200 MPa from a hydrous hybrid mid-ocean ridge basalt (MORB) melt. Chromium concentration profiles through the chromite coronas, inclusions, and host chromites indicate non-equilibrium fractional crystallization of the chromitite system at fast cooling rates (up to ∼0·1°C a−1). Oxygen isotope compositions of the chromite grains imply involvement of a mantle protolith (e.g. serpentinite and serpentinized peridotite) altered by seawater-derived hydrothermal fluids in an oceanic setting. Our findings are consistent with a three-stage model of chromite formation involving (1) mantle protolith alteration by seawater-derived hydrothermal fluids yielding serpentinites and serpentinized harzburgites, which were probably the initial source of chromium, (2) subsolidus crystallization owing to prograde metamorphism, followed by (3) assimilation and fractional crystallization of chromite from water-saturated MORB. This study suggests that the metamorphic protolith assimilation occurring at the Moho level may dramatically affect MORB magma chemistry and lead to the formation of economic chromium deposits.
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Fayalite
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