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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Fluid-mediated calcium metasomatism is often associated with strong silica mobility and the presence of chlorides in solution. To help quantify mass transfer at lower crustal and upper mantle conditions, we measured quartz solubility in H2O-CaCl2 solutions at 0.6–1.4 GPa, 600–900 °C, and salt concentrations to 50 mol%. Solubility was determined by weight loss of single-crystals using hydrothermal piston-cylinder methods. All experiments were conducted at salinity lower than salt saturation. Quartz solubility declines exponentially with added CaCl2 at all conditions investigated, with no evidence for complexing between silica and Ca. The decline in solubility is similar to that in H2O-CO2 but substantially greater than that in H2O-NaCl at the same pressure and temperature. At each temperature, quartz solubility at low salinity (XCaCl2 < 0.1) depends strongly on pressure, whereas at higher XCaCl2 it is nearly pressure independent. This behavior is consistent with a transition from an aqueous solvent to a molten salt near XCaCl2 ~0.1. The solubility data were used to develop a thermodynamic model of H2O-CaCl2 fluids. Assuming ideal molten-salt behavior and utilizing previous models for polymerization of hydrous silica, we derived values for the activity of H2O (aH2O), and for the CaCl2 dissociation factor (α), which may vary from 0 (fully associated) to 2 (fully dissociated). The model accurately reproduces our data along with those of previous work and implies that, at conditions of this study, CaCl2 is largely associated (<0.2) at H2O density <0.85 g/cm3. Dissociation rises isothermally with increasing density, reaching ~1.4 at 600 °C, 1.4 GPa. The variation in silica molality with aH2O in H2O-CaCl2 is nearly identical to that in H2O-CO2 solutions at 800 °C and 1.0 GPa, consistent with the absence of Ca-silicate complexing. The results suggest that the ionization state of the salt solution is an important determinant of aH2O, and that H2O-CaCl2 fluids exhibit nearly ideal molecular mixing over a wider range of conditions than implied by previous modeling. The new data help interpret natural examples of large-scale Ca-metasomatism in a wide range of lower crustal and upper mantle settings.
more » « less- Award ID(s):
- 2124650
- NSF-PAR ID:
- 10484770
- Publisher / Repository:
- Mineralogical Society of America
- Date Published:
- Journal Name:
- American Mineralogist
- Volume:
- 108
- Issue:
- 10
- ISSN:
- 0003-004X
- Page Range / eLocation ID:
- 1852 to 1861
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The solubility of CO2 in hydrous basaltic andesite was examined in fO2-controlled experiments at a temperature of 1125 °C and pressures between 310–1200 MPa. Concentrations of dissolved H2O and CO2 in experimental glasses were determined by ion microprobe calibrated on a subset of run glasses analyzed by high-temperature vacuum manometry. Assuming that the solubility of H2O in mafic melt is relatively well known, estimates of XH2Ofluid and PH2Ofluid in the saturating fluid were modeled, and by difference, values for XCO2fluid and PCO2fluid were obtained (XCO2 ~0.5–0.9); fCO2 could be then calculated from the fluid composition, temperature, and pressure. Dissolved H2O over a range of 2.3–5.5 wt% had no unequivocal influence on the dissolution of CO2 at the pressures and fluid compositions examined. For these H2O concentrations, dissolved CO2 increases with fCO2 following an empirical power-law relation: dissolved CO2 (ppmw) = 14.9−3.5+4.5[fCO2 (MPa)]0.7±0.03. The highest-pressure results plot farthest from this equation but are within its 1 standard-error uncertainty envelope. We compare our experimental data with three recent CO2-H2O solubility models: Papale et al. (2006); Iacono-Marziano et al. (2012); and Ghiorso and Gualda (2015). The Papale et al. (2006) and Iacono-Marizano et al. (2012) models give similar results, both over-predicting the solubility of CO2 in a melt of the Pavlof basaltic andesite composition across the fCO2 range, whereas the Ghiorso and Gualda (2015) model under-predicts CO2 solubility. All three solubility models would indicate a strong enhancement of CO2 solubility with increasing dissolved H2O not apparent in our results. We also examine our results in the context of previous high-pressure CO2 solubility experiments on basaltic melts. Dissolved CO2 correlates positively with mole fraction (Na+K+Ca)/Al across a compositional spectrum of trachybasalt-alkali basalt-tholeiite-icelandite-basaltic andesite. Shortcomings of current solubility models for a widespread arc magma type indicate that our understanding of degassing in the deep crust and uppermost mantle remains semi-quantitative. Experimental studies systematically varying concentrations of melt components (Mg, Ca, Na, K, Al, Si) may be necessary to identify solubility reactions, quantify their equilibrium constants, and thereby build an accurate and generally applicable solubility model.more » « less
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Abstract A collection of quaternary, high-MgO (≤13.4 wt%) basanite and minette cinder and lava cones, with an enhanced arc geochemical signature, are located along the northern margin of the N–S Colima rift in western Mexico. The Colima rift overlies the lithospheric suture between the Jalisco block and Guerrero terrane, as well as the tear between the Rivera and Cocos subducting oceanic plates. From the literature, volatile analyses of olivine-hosted melt inclusions in the Colima cone samples document notably high concentrations of dissolved H2O in the melt (≤ 7.0 wt%) as well as degassing-induced phenocryst growth over a range of depths ≤25 km. In this study, it is shown that the high-MgO character of the Colima suite reflects liquid compositions, consistent with evidence for their rapid transit to the surface, without stalling in a crustal magma chamber. The most Mg-rich olivine analyzed in each sample matches the equilibrium composition at the liquidus based on olivine-melt Mn–Mg and Fe2+–Mg exchange coefficients. Application of both a Mg- and Ni-based olivine-melt thermometer, calibrated on the same experimental data set, to the Colima cone suite provides the temperature and dissolved H2O content at the liquidus. Because the Ni thermometer is insensitive to dissolved H2O in the melt, it gives the actual temperature at the onset of olivine phenocryst growth. For the nine Colima samples that range from 13.4–9.2 wt% MgO, resulting temperatures range from 1221°C to 1056°C (± 6–11°C). In contrast, the Mg thermometer is sensitive to dissolved H2O in the melt, and its application (without a correction of H2O) gives the temperature of olivine crystallization under anhydrous conditions. When the Mg- and Ni-based temperatures are paired, the depression of the liquidus (∆T = TMg–TNi) due to dissolved H2O can be obtained. For the high-MgO (>9 wt%) Colima samples, ∆T values range from 188°C to 109°C. Corrections for the effect of pressure (i.e. evidence that phenocryst growth began at ~700 MPa), increase ∆T by ~21°C. An updated model calibration (on experiments from the literature) that relates ∆T with dissolved H2O in the melt shows that the best fit (R2 = 0.95) is linear, wt% H2O = 0.047*∆T, with a standard error of ±0.5 wt%. Although the experimental data set spans a wide range of melt composition (e.g. 47–58 wt% SiO2, 4.4–10.2 wt% MgO, 1.3–4.9 wt% Na2O, 0.1–5.0 wt% K2O, 0.3–5.3 wt% H2O), no dependence on anhydrous melt composition is resolved. Application of this updated model to the Colima suite gives H2O contents of 5.1–8.8 wt% H2O, consistent with those analyzed in olivine-hosted MIs from the literature. When the thermometry and hygrometry results for the Colima cone suite are compared to those for the adjacent calc–alkaline basalts from the Tancítaro Volcanic Field (TVF) in Michoacán, two distinct linear trends in a plot of wt% H2O vs. temperature are found, indicative of different mantle sources. It is proposed that the high-MgO (>11 wt%) Colima cone melts were derived from a phlogopite-bearing harzburgitic mantle at the base of the Jalisco block lithosphere, whereas both TVF and Colima melts with ≤10 wt% MgO were derived from the asthenosphere (i.e. arc mantle wedge). In both mantle sources, slab-derived fluids were an important source of H2O.
