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1. Multicomponent diffusion in a basaltic melt: Temperature dependence

   https://doi.org/10.1016/j.chemgeo.2020.119700  

   Guo, Chenghuan Zhang (September 2020, Chemical geology)

   Eighteen successful diffusion couple experiments in 8-component SiO2–TiO2–Al2O3–FeO–MgO–CaO–Na2O–K2O basaltic melts were conducted at 1260°C and 0.5 GPa and at 1500°C and 1.0 GPa. These experiments are combined with previous data at 1350°C and 1.0 GPa (Guo and Zhang, 2018) to study the temperature dependence of multicomponent diffusion in basaltic melts. Effective binary diffusion coefficients of components with monotonic diffusion profiles were extracted and show a strong dependence on their counter-diffusing component even though the average (or interface) compositions are the same. The diffusion matrix at 1260°C was obtained by simultaneously fitting diffusion profiles of all diffusion couple experiments as well as appropriate data from the literature. All features of concentration profiles in both diffusion couples and mineral dissolution are well reproduced by this new diffusion matrix. At 1500°C, only diffusion couple experiments are used to obtain the diffusion matrix. Eigenvectors of the diffusion matrix are used to discuss the diffusion (exchange) mechanism, and eigenvalues characterize the diffusion rate. Diffusion mechanisms at both 1260 and 1500°C are inferred from eigenvectors of diffusion matrices and compared with those at 1350°C reported in Guo and Zhang (2018). There is indication that diffusion eigenvectors in basaltic melts do not depend much on temperature, but complexity is present for some eigenvectors. The two slowest eigenvectors involve the exchange of SiO2 and/or Al2O3 with nonalkalis. The third slowest eigenvector is due to the exchange of divalent oxides with other oxides. The fastest eigenvector is due to the exchange of Na2O with other oxide components. Some eigenvalues differ from each other by less than 1/3, and their eigenvectors are less well defined. We define small difference in eigenvalues as near degeneracy. In strict mathematical degeneracy, eigenvectors are not uniquely defined because any linear combination of two eigenvectors is also an eigenvector. In the case of near degeneracy, more constraints either in terms of higher data quality or more experiments are needed to resolve the eigenvectors. We made a trial effort to generate a set of average eigenvectors, which are assumed to be constant as temperature varies. The corresponding eigenvalues are roughly Arrhenian. Thus, the temperature-dependent diffusion matrix can be roughly predicted. The method is applied to predict experimental diffusion profiles in basaltic melts during olivine and anorthite dissolution at ~1400°C with preliminary success. We further applied our diffusion matrix to investigate multicomponent diffusion during magma mixing in the Bushveld Complex and found such diffusion may result in an increased likelihood of sulfide and Fe-Ti oxide mineralization. 

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2. Insights from elastic thermobarometry into exhumation of high-pressure metamorphic rocks from Syros, Greece

   https://doi.org/10.5194/se-12-1335-2021  

   Cisneros, Miguel; Barnes, Jaime D.; Behr, Whitney M.; Kotowski, Alissa J.; Stockli, Daniel F.; Soukis, Konstantinos (January 2021, Solid Earth)

   Abstract. Retrograde metamorphic rocks provide key insights into the pressure–temperature (P–T) evolution of exhumed material, and resultant P–T constraints have direct implications for the mechanical and thermal conditions of subduction interfaces. However, constraining P–T conditions of retrograde metamorphic rocks has historically been challenging and has resulted in debate about the conditions experienced by these rocks. In this work, we combine elastic thermobarometry with oxygen isotope thermometry to quantify the P–T evolution of retrograde metamorphic rocks of the Cycladic Blueschist Unit (CBU), an exhumed subduction complex exposed on Syros, Greece. We employ quartz-in-garnet and quartz-in-epidote barometry to constrain pressures of garnet and epidote growth near peak subduction conditions and during exhumation, respectively. Oxygen isotope thermometry of quartz and calcite within boudin necks was used to estimate temperatures during exhumation and to refine pressure estimates. Three distinct pressure groups are related to different metamorphic events and fabrics: high-pressure garnet growth at ∼1.4–1.7 GPa between 500–550 ∘C, retrograde epidote growth at ∼1.3–1.5 GPa between 400–500 ∘C, and a second stage of retrograde epidote growth at ∼1.0 GPa and 400 ∘C. These results are consistent with different stages of deformation inferred from field and microstructural observations, recording prograde subduction to blueschist–eclogite facies and subsequent retrogression under blueschist–greenschist facies conditions. Our new results indicate that the CBU experienced cooling during decompression after reaching maximum high-pressure–low-temperature conditions. These P–T conditions and structural observations are consistent with exhumation and cooling within the subduction channel in proximity to the refrigerating subducting plate, prior to Miocene core-complex formation. This study also illustrates the potential of using elastic thermobarometry in combination with structural and microstructural constraints, to better understand the P–T-deformation conditions of retrograde mineral growth in high-pressure–low-temperature (HP/LT) metamorphic terranes. 

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3. Phase Relations of a Depleted Peridotite Fluxed by a CO ₂ ‐H ₂ O Fluid—Implications for the Stability of Partial Melts Versus Volatile‐Bearing Mineral Phases in the Cratonic Mantle

   https://doi.org/10.1029/2019JB017653  

   Saha, Sriparna; Dasgupta, Rajdeep (October 2019, Journal of Geophysical Research: Solid Earth)

   Abstract We present phase‐equilibria experiments of a K‐bearing, depleted peridotite (Mg# 92) fluxed with a mixed CO₂‐H₂O fluid (0.5 wt.% CO₂and 0.94 wt.% H₂O in the bulk) to gain insight into the stability of volatile‐bearing partial melts versus volatile‐bearing mineral phases in a depleted peridotite system. Experiments were performed at 850–1150 °C and 2–4 GPa using a piston‐cylinder and a multianvil apparatus. Olivine, orthopyroxene, clinopyroxene, and spinel/garnet are present at all experimental conditions. Textural confirmation of partial melt is made at temperatures as low as 1000 °C at 2 GPa, 950 °C at 3 GPa, and 1000 °C at 4 GPa marking the onset of melting at 900–1000 °C at 2 GPa, 850–950 °C at 3 GPa, and 950–1000 °C at 3 GPa. Phlogopite and magnesite breakdown at 900–1000 °C at 2 GPa, 950–1000 °C at 3 GPa, and 1000–1050 °C at 4 GPa. Comparison with previously published experiments in depleted peridotite system with identical CO₂‐H₂O content introduced via a silicic melt show that introduction of CO₂‐H₂O as fluid lowers the temperature of phlogopite breakdown by 150–200 °C at 2–4 GPa and stabilizes partial melts at lower temperatures. Our study thus, shows that the volatile‐bearing phase present in the cratonic mantle is controlled by bulk composition and is affected by the process of volatile addition during craton formation in a subduction zone. In addition, volatile introduction via melt versus aqueous fluid, leads to different proportion of anhydrous phases such as olivine and orthopyroxene. Considering the agent of metasomatism is thus critical to evaluate how the bulk composition of depleted peridotite is modified, leading to potential stability of volatile‐bearing phases as the cause of anomalously low shear wave velocity in mantle domains such as mid lithospheric discontinuities beneath continents. 

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4. Pronounced and rapid exhumation of the Connecticut Valley Trough revealed through quartz in garnet Raman barometry and diffusion modelling of garnet dissolution–reprecipitation reactions

   https://doi.org/10.1111/jmg.12601  

   Wolfe, Oliver M.; Spear, Frank S.; Harrison, T. Mark (April 2021, Journal of Metamorphic Geology)

   Abstract Metamorphic rocks from the Connecticut Valley Trough (CVT), Vermont, and Massachusetts, have been examined using quartz‐in‐garnet (QuiG) and conventional thermobarometry, thermodynamic reaction modelling, diffusion modelling, and⁴⁰Ar/³⁹Ar thermochronology to constrain theirP–T–tpaths during Acadian metamorphism and subsequent exhumation. Numerous samples, collected in the vicinity of the Acadian domes, contain garnet porphyroblasts that display cloudy zones characterized by numerous fluid inclusions and modified garnet compositions associated with the replacement of the original garnet by biotite±muscovite±plagioclase±quartz±lowX_grs/enrichedX_sps. QuiG and conventional thermobarometry constrain both the conditions of garnet nucleation and peakP–Tconditions to have occurred at ~0.85–1.05 GPa, ~550–600°C. Most notably, QuiG barometry was performed on inclusions adjacent to these reaction zones in conjunction with Gibbs method reaction modelling to reveal that these dissolution–reprecipitation reactions occurred during nearly isothermal decompression from the peakP–Tconditions to around ~0.3 GPa, 550°C. Diffusion modelling reveals that the Mn zoning profiles created during garnet resorption that accompanied decompression formed in less thanc. 3 Ma, which constrains the tectonic exhumation to have occurred at 8–10 mm/year. Subsequent cooling to 500°C occurred rapidly at a rate of 100°C/Ma, followed by slower cooling reaching 1.7°C /Ma by the mid Carboniferous. This is the first reported example of QuiG barometry revealing a multi‐stage metamorphic history and highlights the utility of this method for unravelling complex metamorphic terranes. 

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5. Effects of H2O–CO2 Fluids, Temperature, and Peridotite Fertility on Partial Melting in Mantle Wedges and Generation of Primary Arc Basalts

   https://doi.org/10.1093/petrology/egad047  

   Lara, Michael; Dasgupta, Rajdeep (July 2023, Journal of Petrology)

   Abstract Many lines of evidence from high P–T experiments, thermodynamic models, and natural observations suggest that slab-derived aqueous fluids, which flux mantle wedges contain variable amounts of dissolved carbon. However, constraints on the effects of H2O–CO2 fluids on mantle melting, particularly at mantle wedge P–T conditions, are limited. Here, we present new piston cylinder experiments on fertile and depleted peridotite compositions with 3.5 wt.% H2O and XCO2 [= molar CO2 / (CO2 + H2O)] of 0.04–0.17. Experiments were performed at 2–3 GPa and 1350°C to assess how temperature, peridotite fertility, and XCO2 of slab-derived fluid affects partial melting in mantle wedges. All experiments produce olivine + orthopyroxene +7 to 41 wt.% partial melt. Our new data, along with previous lower temperature data, show that as mantle wedge temperature increases, primary melts become richer in SiO2, FeO*, and MgO and poorer CaO, Al2O3, and alkalis when influenced by H2O–CO2 fluids. At constant P–T and bulk H2O content, the extent of melting in the mantle wedge is largely controlled by peridotite fertility and XCO2 of slab-fluid. High XCO2 depleted compositions generate ~7 wt.% melt, whereas, at identical P–T, low XCO2 fertile compositions generate ~30 to 40 wt.% melt. Additionally, peridotite fertility and XCO2 have significant effects on peridotite partial melt compositions. At a constant P–T–XCO2, fertile peridotites generate melts richer in CaO and Al2O3 and poorer in SiO2, MgO + FeO, and alkalis. Similar to previous experimental studies, at a constant P–T fertility condition, as XCO2 increases, SiO2 and CaO of melts systematically decrease and increase, respectively. Such distinctive effects of oxidized form of dissolved carbon on peridotite partial melt compositions are not observed if the carbon-bearing fluid is reduced, such as CH4-bearing. Considering the large effect of XCO2 on melt SiO2 and CaO concentrations and the relatively oxidized nature of arc magmas, we compare the SiO2/CaO of our experimental melts and melts from previous peridotite + H2O ± CO2 studies to the SiO2/CaO systematics of primitive arc basalts and ultra-calcic, silica-undersaturated arc melt inclusions. From this comparison, we demonstrate that across most P–T–fertility conditions predicted for mantle wedges, partial melts from bulk compositions with XCO2 ≥ 0.11 have lower SiO2/CaO than all primitive arc melts found globally, even when correcting for olivine fractionation, whereas partial melts from bulk compositions with XCO2 = 0.04 overlap the lower end of the SiO2/CaO field defined by natural data. These results suggest that the upper XCO2 limit of slab-fluids influencing primary arc magma formation is 0.04 < XCO2 < 0.11, and this upper limit is likely to apply globally. Lastly, we show that the anomalous SiO2/CaO and CaO/Al2O3 signatures observed in ultra-calcic arc melt inclusions can be reproduced by partial melting of either CO2-bearing hydrous fertile and depleted peridotites with 0 < XCO2 < 0.11 at 2–3 GPa, or from nominally CO2-free hydrous fertile peridotites at P > 3 GPa. 

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