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1. Using Trace Elements in Olivine Phenocrysts to Test Models of Melt Differentiation at Convergent Margins: Constraints from Times Series in Monogenetic Volcanoes in the Central Transmexican Volcanic Belt

   Fleming, W.; Straub, S.M.; Gomez-Tuena, A.; Espinasa-Pereña, R.; Bindeman, I.N.; Stuart, F.M.; Batanova, V.G. (December 2019, AGU Fall Meeting 2019)

   Models of subduction zone magmatism ascribe the andesitic composition of arc magmas to crustal processes, such as crustal assimilation and/or fractional crystallization, that basaltic mantle melts experience during their ascent through the upper plate crust. However, results from time series study of olivine-phyric high-Nb basalts and basaltic andesites from two monogenetic arc volcanoes (V. Chichinautzin and Texcal Flow) that are constructed on the ~45 km thick continental basement of the central Transmexican Volcanic Belt (TMVB) are inconsistent with this model. Instead, ratios of radiogenic isotope and incompatible trace elements suggest that these volcanoes were constructed through multiple individual melt batches ascending from a progressively changing mantle source. Moreover, the high Ni contents of the olivine phenocrysts, together with their high mantle-like 3He/4Heoliv =7-8 Ra with high crustal δ18O oliv = +5.5 to +6.5‰ (n=12) point to the presence of secondary ‘reaction pyroxenites’ in the mantle source that create primary silicic arc magmas through melt-rock reaction processes in the mantle [1, 2] . Here we present additional trace element concentration of the high-Ni olivines by electron microprobe (Mn, Ca) and laser-ablation ICPMS (Li, Cr and V) analysis in order to test this model. Olivine Li (2-7 ppm) and Mn (1170- 2810 ppm) increase with decreasing fosterite (Fo89 to Fo75), while Cr (29-364 ppm), V (4-11 ppm) and Ca (825-2390 ppm) decrease. Quantitative modeling shows that these trends in their entirety cannot be controlled by fractional crystallization under variable melt water H2O or oxygen fugacity (fO2), or co-crystallization of Cr-spinel. Instead, the variations support the existence of compositionally distinct melt batches during earliest melt evolution. Moreover, the trace element trends are qualitatively consistent with a model of progressive source depletion by serial melting (shown in olivine Ca, V and Cr) that is triggered by the repetitive addition of silicic slab components (shown by olivine Li). These findings suggest mantle source variations are not eliminated despite the thick crust these magmas pass during ascent. [1] Straub et al. (2013) J Petrol 54 (4): 665-701; [2] Straub et al. (2015) Geochim Cosmochim Acta 166: 29-52. 

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2. 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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3. Post-melting oxidation of highly primitive basalts from the southern Andes

   https://doi.org/10.1016/j.gca.2020.01.042  

   Tassara, S. (January 2020, Geochimica et cosmochimica acta)

   null (Ed.)

   The oxygen fugacity (fO2) of the Earth’s upper mantle and its melting products is an important parameter in the geochemical evolution of arc magmas and their connection with the continental crustal construction and growth. Several works have focused on the fO2 of peridotite xenoliths, primitive melts in relatively young arc settings, and mid-ocean ridge basalts (MORB) but few studies have attempted to examine the early redox history of primitive magmas in mature arcs. Hence, our understanding of the nature and evolution of fO2 during the subduction cycle remains limited. Here, we investigate the basaltic tephra from the Los Hornitos monogenetic cones in central-southern Chile, which are among the most primitive materials reported in the Southern Andes (olivine Mg#
   92.5, and Ni
   5000 mgg1). These features offer a unique opportunity to explore the fO2 conditions below the Andean arc by studying olivine phenocrysts and their contained crystal and melt inclusions. We integrated EPMA, LA-ICP-MS, and m-XANES analyses to constrain the redox conditions recorded in the basaltic tephra by three different and self-reliant methods. First, we determined the fO2 based on the olivine-spinel equilibrium, yielding average values DFMQ + 1.3 ± 0.4 (1r). Second, we constrained the fO2 conditions of melt inclusions using Fe m-XANES data and the redox dependent olivine-melt vanadium partitioning. After correcting for post-entrapment crystallization and diffusive iron loss, the Fe m-XANES data indicate that the melt inclusions were trapped in average at DFMQ +2.5 ± 0.5 (1r). Results using the olivine-melt vanadium partitioning oxybarometer in melt inclusions are in agreement with Fe m-XANES data, yielding average DFMQ values of +2.6 ± 0.3 (1r). In order to test the potential effects of other postentrapment modifications of the melt inclusions that could have affected the fO2 prior to eruption, we assessed the residence time of these magmas using Mg-Fe interdiffusion modelling in olivine. The short residence times (<200 days) compared to vanadium re-equilibration models strongly suggest that the melt inclusions preserve the prevailing fO2 conditions during their entrapment. Correlations between melt inclusions major element composition and their fO2 determined by Fe m-XANES, as well as V/Sc modelling reveal a case of post-melting oxidation of the LHC magmas. We argue that primitive arc magmas behave as an open system with respect to fO2 during their early geochemical evolution. Our data indicate a complex fO2 early history of primitive melts in the southern Andes and provide a cautionary note on the direct extrapolation of primitive melts fO2 values to that of their mantle source. 

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4. Constraints of boron and oxygen stable isotopes on dehydration fluids, sediment-derived melts, and crustal assimilation of the Toba volcanic system (Indonesia)

   https://doi.org/10.1130/G51690.1  

   Liu, Ping-Ping; Wang, Dian-Bing; Zhou, Mei-Fu; Li, Xian-Hua; Li, Qiu-Li; Gaetani, Glenn A; Monteleone, Brian; Kamenetsky, Vadim (December 2023, Geology)

   Abstract Arc magmas are produced from the mantle wedge, with possible addition of fluids and melts derived from serpentinites and sediments in the subducting slab. Identification of various sources and their relevant contributions to such magmas is challenging; in particular, at continental arcs where crustal assimilation may overprint initial geochemical signatures. This study presents oxygen isotopic compositions of zoned olivine grains from post-caldera basalts and boron contents and isotopes of these basalts and glassy melt inclusions hosted in quartz and clinopyroxene of silicic tuffs in the Toba volcanic system, Indonesia. High-magnesian (≥87 mol% Fo [forsterite]) cores of olivine in the basalts have δ18O values ranging from 5.12‰ to 6.14‰, indicating that the mantle source underneath Toba is variably enriched in 18O. Olivine with <87 mol% Fo has highly variable (4.8–7.2‰), but overall increased, δ18O values, interpreted to reflect assimilation of high δ18O crustal materials during fractional crystallization. Mass balance calculations constrain the overall volume of crustal assimilation for the basalts as ≤13%. The processes responsible for the 18O-enriched basaltic melts are further constrained by boron data that indicate the addition of <0.1 wt% fluids to the mantle, >40% of the fluids being derived from serpentinites and others from altered oceanic crust and sediments. This amount of fluids can increase δ18O of the magma by only ~0.02‰. Approximately 6–9% sediment-derived melt hybridization in the mantle wedge is further needed to yield basaltic melts with δ18O values in equilibrium with those of the high-Fo olivine cores. The cogenetic silicic tuffs, on the other hand, seem to record a higher proportion of fluid addition dominated by sediment-derived fluids to the mantle source, in addition to crustal assimilation. Our reconnaissance study therefore demonstrates the application of combined B and O isotopes to differentiate between melts and fluids derived from serpentinites and sediments in the subducted slab—an application that can be applied to arc magmas worldwide. 

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5. Trace element partitioning between olivine and melt in lunar basalts

   https://doi.org/10.2138/am-2022-7971  

   Chen, Sha; Ni, Peng; Zhang, Youxue; Gagnon, Joel (August 2022, American Mineralogist)

   Abstract Mineral/melt partition coefficients have been widely used to provide insights into magmatic processes. Olivine is one of the most abundant and important minerals in the lunar mantle and mare basalts. Yet, no systematic olivine/melt partitioning data are available for lunar conditions. We report trace element partition data between host mineral olivine and its melt inclusions in lunar basalts. Equilibrium is evaluated using the Fe-Mg exchange coefficient, leading to the choice of melt inclusion-host olivine pairs in lunar basalts 12040, 12009, 15016, 15647, and 74235. Partition coefficients of 21 elements (Li, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Co, Y, Zr, Nb, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) were measured. Except for Li, V, and Cr, these elements show no significant difference in olivine-melt partitioning compared to the data for terrestrial samples. The partition coefficient of Li between olivine and melt in some lunar basalts with low Mg# (Mg# < 0.75 in olivine, or < ~0.5 in melt) is higher than published data for terrestrial samples, which is attributed to the dependence of DLi on Mg# and the lack of literature DLi data with low Mg#. The partition coefficient of V in lunar basalts is measured to be 0.17 to 0.74, significantly higher than that in terrestrial basalts (0.003 to 0.21), which can be explained by the lower oxygen fugacity in lunar basalts. The significantly higher DV can explain why V is less enriched in evolved lunar basalts than terrestrial basalts. The partition coefficient of Cr between olivine and basalt melt in the Moon is 0.11 to 0.62, which is lower than those in terrestrial settings by a factor of ~2. This is surprising because previous authors showed that Cr partition coefficient is independent of fO2. A quasi-thermodynamically based model is developed to correlate Cr partition coefficient to olivine and melt composition and fO2. The lower Cr partition coefficient between olivine and basalt in the Moon can lead to more Cr enrichment in the lunar magma ocean, as well as more Cr enrichment in mantle-derived basalts in the Moon. Hence, even though Cr is typically a compatible element in terrestrial basalts, it is moderately incompatible in primitive lunar basalts, with a similar degree of incompatibility as V based on partition coefficients in this work, as also evidenced by the relatively constant V/Cr ratio of 0.039 ± 0.011 in lunar basalts. The confirmation of constant V/Cr ratio is important for constraining concentrations of Cr (slightly volatile and siderophile) and V (slightly siderophile) in the bulk silicate Moon. 

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