Crystallization of late-stage MORB under varying water activities and redox conditions: Implications for the formation of highly evolved lavas and oxide gabbro in the ocean crust

Abstract In order to understand late magmatic processes that occur in the deep oceanic crust, we performed a phase-equilibria study in a representative late-stage system at a pressure of 200 MPa with a special focus on the role of water and oxygen fugacity. The starting composition for the experiments was evaluated based on a statistical approach using evolved fresh MORB glasses from the database PETDB highest in FeO and TiO2 (in average 17.92 wt% and 3.73 wt%, respectively), assumed to represent frozen liquids erupted at the seafloor generated by extensive differentiation of MORB. We conducted crystallization experiments in a range of temperatures from 850 to 1050 °C with water activities …

Reaction between Cu-bearing minerals and hydrothermal fluids at 800 °C and 200 MPa: Constraints from synthetic fluid inclusions

Abstract Transport and deposition of copper in the Earth's crust are mainly controlled by the solubility of Cu-bearing phases and the speciation of Cu in magmatic-hydrothermal fluids. To improve our understanding of copper mobilization by hydrothermal fluids, we conducted an experimental study on the interaction between Cu-bearing phases (metallic copper, Cu2O, CuCl) and aqueous chloride solutions (H2O ± NaCl ± HCl; with Cl concentrations of 0 to 4.3 mol kg-1). The experiments were run in rapid heat/rapid quench cold-seal pressure vessels at 800 °C, 200 MPa, and logfO2 ~ NNO+2.3. Either Cu or Au capsules were used as containers. The reaction products were sampled in situ by the entrapment o…

Thin crust and exposed mantle control sulfide differentiation in slow-spreading ridge magmas

Dehydration of melt inclusions in olivine and implications for the origin of silica-undersaturated island-arc melts

Highlights • New experiments with melt inclusions in olivine at 1200 °C and 300 MPa. • Coupled behavior H2O and SiO2 in inclusions during re-hydration and dehydration. • SiO2 mobility results from formation/destruction of metal vacant olivine. • SiO2-undersaturated arc melt inclusions may originate by dehydration. • New method to assess initial H2O in dehydrated inclusions. Abstract Primary subduction-related magmas build up modern continental crust and counterbalance massive recycling of crustal material into the deep mantle occurring at this tectonic setting. Melt inclusions in Mg-rich olivine are believed to be the best probes of primary subduction-related melts. However, unexpectedly, m…

Experimental calibration and implications of olivine-melt vanadium oxybarometry for hydrous basaltic arc magmas

The strong dependence of vanadium partitioning between olivine and silicate melt (DVOl-M) on redox conditions (fO2) can be used as sensitive oxybarometer in magmatic systems. Here we extend the experimental database on DVOl-M, obtained so far at high temperatures (mainly above 1250 °C), to lower temperatures that are typical for island-arc basalts. Crystallization experiments were performed using a composition from Mutnovsky volcano (Kamchatka), and the investigated temperature, pressure, and oxygen fugacity ranges were 1025–1150 °C, 0.1 and 0.3 GPa, and ΔQFM of –0.5 to +3.2, respectively. The water content in melts ranged from 0.6 to ∼6.5 wt% H2O. The data demonstrate a strong negative cor…

Sulfide enrichment at an oceanic crust-mantle transition zone: Kane Megamullion (23°N, MAR)

Abstract The Kane Megamullion oceanic core complex located along the Mid-Atlantic Ridge (23°30′N, 45°20′W) exposes lower crust and upper mantle directly on the ocean floor. We studied chalcophile elements and sulfides in the ultramafic and mafic rocks of the crust-mantle transition and the mantle underneath. We determined mineralogical and elemental composition and the Cu isotope composition of the respective sulfides along with the mineralogical and elemental composition of the respective serpentines. The rocks of the crust-mantle transition zone (i.e., plagioclase harzburgite, peridotite-gabbro contacts, and dunite) overlaid by troctolites are by one order of magnitude enriched in several…

Electron microprobe technique for the determination of iron oxidation state in silicate glasses

We present a new calibration for the determination of the iron oxidation state in silicate glasses by electron probe microanalysis (EPMA) with the "flank method." This method is based on the changes in both intensity and wavelength of the FeLα and FeLβ X-ray emission lines with iron oxidation state. The flank method utilizes the maximum difference for the FeLα and FeLβ spectra observed at the peak flanks between different standard materials, which quantitatively correlates with the Fe2+ content. Provided that this correlation is calibrated on reference materials, the Fe2+/ΣFe ratio can be determined for samples with known total Fe content. Two synthetic Fe-rich ferric and ferrous garnet end…

In situ quantification of the nitrogen content of olivine-hosted melt inclusions from Klyuchevskoy volcano (Kamchatka): Implications for nitrogen recycling at subduction zones

International audience; Assessing the N content of arc magmas and their mantle source remains a challenge because the volatile element composition of melts and gases can be modified during magma ascent, storage, and eruption. Given that melt inclusions (MIs) in Mg-rich olivine represent the best proxies for primary arc melts, we applied, for the first time, an in situ high-resolution secondary ion mass spectrometry (SIMS) method to determine the N concentration in olivine-hosted MIs from Klyuchevskoy volcano in Kamchatka. To reverse the effects of post-entrapment modification processes (i.e., exsolution of volatiles into a fluid bubble), the MIs were partially to completely homogenized at h…

Composition, crystallization conditions and genesis of sulfide-saturated parental melts of olivine-phyric rocks from Kamchatsky Mys (Kamchatka, Russia)

Highlights • Parental melts of sulfide-bearing KM rocks have near primary MORB-like composition. • Crystallization of these S-saturated melts occurred in near-surface conditions. • Extensive fractionation and crustal assimilation are not the causes of S-saturation. • S content in melts can be restored by accounting for daughter sulfide globules. Abstract Sulfide liquids that immiscibly separate from silicate melts in different magmatic processes accumulate chalcophile metals and may represent important sources of the metals in Earth's crust for the formation of ore deposits. Sulfide phases commonly found in some primitive mid-ocean ridge basalts (MORB) may support the occurrence of sulfide …

High spatial resolution analysis of the iron oxidation state in silicate glasses using the electron probe

The iron oxidation state in silicate melts is important for understanding their physical properties, although it is most often used to estimate the oxygen fugacity of magmatic systems. Often high spatial resolution analyses are required, yet the available techniques, such as μrXANES and μMössbauer, require synchrotron access. The flank method is an electron probe technique with the potential to measure Fe oxidation state at high spatial resolution but requires careful method development to reduce errors related to sample damage, especially for hydrous glasses. The intensity ratios derived from measurements on the flanks of FeLα and FeLβ X-rays (FeLβf/FeLαf) over a time interval (time-depend…

Experimental determination of the phase relations of Pt and Pd antimonides and bismuthinides in the Fe-Ni-Cu sulfide systems between 1100 and 700 °C

Abstract The stability relations of Pt and Pd antimonides and bismuthinides in the Sb- and Bi-bearing Fe-Ni-Cu sulfide systems have been experimentally determined at temperatures between 1100 and 700 °C in evacuated silica tubes. Both PtSb and PdSb are stable as immiscible liquids at temperatures above 1100 and 1000 °C, respectively. The Fe-Ni-Cu-sulfide melt that coexists with the immiscible antimonide melt can dissolve up to 3.8 wt% Sb at 1100 °C, whereas monosulfide solid solution (mss) dissolves very low amounts of Sb over the entire 1100–700 °C temperature range. The liquidus of Pt-antimonides and Pdantimonides are above 980 and 750 °C, respectively. Bismuth does not form immiscible me…

Sapphire-bearing magmatic rocks trace the boundary between paleo-continents: A case study of Ilmenogorsky alkaline complex, Uralian collision zone of Russia

Abstract Metamorphic gem corundum (mainly ruby) deposits are robust indicators of continent-continent collision processes. However, a systematic link of primary magmatic blue sapphire occurrences to orogenic belts is less understood. An example is the Ilmenogorsky alkaline complex, within the Ilmen Mountains region and part of the Uralian orogenic belt. The mobile belt is a product of the collision among Kazakhstania, Laurussia, and Siberia continents prior to the closure of the Paleo-Uralian ocean and formation of the Laurasia supercontinent (330–250 Ma). It is believed that the alkaline complex became inсluded into the separate Sysertsk-Ilmenogorsk microcontinent with unconstrained border…

Corundum Anorthosites-Kyshtymites from the South Urals, Russia: A Combined Mineralogical, Geochemical, and U-Pb Zircon Geochronological Study

Kyshtymites are the unique corundum-blue sapphire-bearing variety of anorthosites of debatable geological origin found in the Ilmenogorsky-Vishnevogorsky complex (IVC) in the South Urals, Russia. Their mineral association includes corundum-sapphire, plagioclase (An61&ndash