Description: We report new major, trace and volatile element contents (H2O, CO2, F, S, Cl), and new Sr, Nd, Pb and He isotopes on submarine glasses from the Galapagos Archipelago from several dredging expeditions. Four groups are distinguishable on the basis of composition and geographical distribution: the Fernandina group (3He/4He 〉 22 RA), which is similar to the less degassed primitive mantle; the Sierra Negra group (enriched Pb and Sr isotopes, 3He/4He = 8–20 RA), produced by mixing the Floreana (HIMU-type) and Fernandina end-members; the Pinta group (high Δ7/4, Δ8/4 and Th/La ratios, 3He/4He = 6–9 RA), an enriched mantle (EM)-type mantle indicative of recycled material in the source; and the depleted mantle (DM) group, characterized by an isotopic composition similar to mid-ocean ridge basalts (MORB). Only a single submarine glass with the isotopic composition of the Floreana end-member has been identified in the sample suite. Degassing has significantly lowered the glass CO2 content with little effect on the H2O concentration. Volatile data for oceanic basalts reveal that CO2–H2O gas–melt equilibration at eruption depth is common in ocean island basalts (OIB) and rare in MORB, suggesting different ratios of melt transport to bubble formation and gas–melt equilibration. The Galapagos glasses range from sulfide saturated to undersaturated, and a subset of samples indicate that S degasses at pressures ≤ 400 bars. Assimilation of hydrothermally altered material affected the volatile contents of a number of samples in the groups. Once shallow-level processes have been accounted for, we evaluate the volatile contents in the different Galapagos mantle sources. Ratios between volatile and refractory elements with similar incompatibilities are used to estimate the volatile budget of the Galapagos mantle plume. Most of the glasses from the Fernandina, Sierra Negra and Pinta groups have high volatile/refractory element ratios, whereas a few pristine DM group lavas have ratios similar to those measured in MORB. The volatile/refractory element ratios are consistent with previous reports for the high 3He/4He, HIMU and MORB components. The values measured for the Pinta group, however, are higher than those found in other OIB associated with the presence of recycled material (EM-type). Our data suggest that mixing between the different mantle components is pervasive throughout the archipelago, which acts to normalize the volatile data between the groups. The Fernandina component can be modeled by a 6–20% mixture of the high 3He/4He primitive mantle component with the MORB source, assuming a two-layered mantle and using existing estimates of helium concentrations. The resulting estimated volatile content and H/C mass ratio for the high 3He/4He primitive mantle are consistent with previous estimates, but calculated C/3He ratios are lower than the canonical ratio. This indicates the following: (1) the estimates require ∼20–50 times higher C or lower 3He contents, which is difficult to reconcile with the measured volatile/refractory ratios in oceanic basalts; (2) the C/3He ratio is not constant throughout the mantle; (3) an impact erosion model, rather than a two-layered mantle model, is more consistent with the relatively constant C/3He ratios observed in oceanic basalts, although it is unclear how representative oceanic basalts are of the lower mantle. The high volatile content of the high 3He/4He component will affect mantle dynamics and melt migration during plume–ridge interaction as this component would be predicted to be less viscous than the ambient mantle. The lower viscosity material would have an enhanced vertical upwelling, which could explain the buoyancy flux of the Galapagos plume without the need for a temperature anomaly. A lower viscosity, high 3He/4He component could also provide an explanation for the lack of high 3He/4He in Galapagos Spreading Center lavas erupting in the vicinity of the Galapagos plume.

Description: Apatite-melt partitioning experiments were conducted in a piston-cylinder press at 1.0–1.2 GPa and 950–1000 °C using an Fe-rich basaltic starting composition and an oxygen fugacity within the range of IW-1 to IW+2. Each experiment had a unique F:Cl:OH ratio to assess the partitioning as a function of the volatile content of apatite and melt. The quenched melt and apatite were analyzed by electron probe microanalysis and secondary ion mass spectrometry techniques. The mineral-melt partition coefficients ( D values) determined in this study are as follows: D F Ap-Melt = 4.4–19, D Cl Ap-Melt = 1.1–5, D OH Ap-Melt = 0.07–0.24. This large range in values indicates that a linear relationship does not exist between the concentrations of F, Cl, or OH in apatite and F, Cl, or OH in melt, respectively. This non-Nernstian behavior is a direct consequence of F, Cl, and OH being essential structural constituents in apatite and minor to trace components in the melt. Therefore mineral-melt D values for F, Cl, and OH in apatite should not be used to directly determine the volatile abundances of coexisting silicate melts. However, the apatite-melt D values for F, Cl, and OH are necessarily interdependent given that F, Cl, and OH all mix on the same crystallographic site in apatite. Consequently, we examined the ratio of D values (exchange coefficients) for each volatile pair (OH-F, Cl-F, and OH-Cl) and observed that they display much less variability: K d Cl-F Ap-Melt = 0.21 ± 0.03, K d OH-F Ap-Melt = 0.014 ± 0.002, and K d OH-Cl Ap-Melt = 0.06 ± 0.02. However, variations with apatite composition, specifically when mole fractions of F in the apatite X-site were low ( X F 〈 0.18), were observed and warrant additional study. To implement the exchange coefficient to determine the H 2 O content of a silicate melt at the time of apatite crystallization (apatite-based melt hygrometry), the H 2 O abundance of the apatite, an apatite-melt exchange K d that includes OH (either OH-F or OH-Cl), and the abundance of F or Cl in the apatite and F or Cl in the melt at the time of apatite crystallization are needed (F if using the OH-F K d and Cl if using the OH-Cl K d ). To determine the H 2 O content of the parental melt, the F or Cl abundance of the parental melt is needed in place of the F or Cl abundance of the melt at the time of apatite crystallization. Importantly, however, exchange coefficients may vary as a function of temperature, pressure, melt composition, apatite composition, and/or oxygen fugacity, so the combined effects of these parameters must be investigated further before exchange coefficients are applied broadly to determine volatile abundances of coexisting melt from apatite volatile abundances.

Description: Clinopyroxene (Cpx) phenocrysts have the potential to record magmatic water contents and magma ascent rates through their concentration of H 2 O (incorporated as H + and commonly referred to as water). Here we investigate three issues related to the fidelity and utility of the Cpx water record: the partitioning of water between Cpx and melt, the diffusivity of water in natural Cpx phenocrysts, and the possibility for water loss in Cpx erupted in lava flows. Samples studied are from volcanic ash of the 1974 eruption of Volcán de Fuego (Guatemala) and scoria and lava from the 1977 eruption on Seguam Island (Alaska). The partitioning of water was determined by analyzing melt inclusions (MIs) and the adjacent clinopyroxene host by ion microprobe. For seven Cpx-hosted MIs from Seguam, the partition coefficient is well predicted (within 0·1 wt % H 2 O on average) using the temperature-dependent parameterization of O’Leary et al. (2010; Earth and Planetary Science Letters 297 , 111–120). For the determination of diffusivity, H 2 O concentration profiles were measured in oriented Cpx from Fuego by ion microprobe. Water decreases toward the rim, consistent with diffusive re-equilibration during ascent-driven degassing. Using previously estimated durations of ascent (7–12 min), we determined the H + diffusivity (10 –9·7 –10 –10·3 m 2 s –1 at a temperature of 1030 °C) that would satisfy these timescales. These calculated DH+Cpx values are comparable with the medial values determined for natural Cpx (Mg# 〈 92·5) in laboratory diffusion studies. Tephra and lava co-erupted on Seguam bear similar Cpx populations in their major and trace element compositions, but the lava Cpx contain 80% lower H 2 O concentrations on average than the tephra Cpx. Using the DH+Cpx values obtained from the Fuego Cpx, the difference in H 2 O between the lava and tephra Cpx can be attributed to post-eruption H 2 O loss during the estimated ~20 min the sample remained above the H + closure temperature. The results from this study indicate that clinopyroxene from slowly cooled basaltic lavas should not be used to reconstruct initial magmatic water contents. High ascent rates, rapid post-eruptive cooling, large phenocrysts, and cooler magma (e.g. andesites and rhyolites) favor better preservation of water in Cpx. In cases of H + loss, Cpx zonation can be exploited as a chronometer for syn- and post-eruptive volcanic processes.

Description: A model for the origin, ascent, and eruption of the lunar A17 orange glass magma has been constructed using petrological constraints from gas solubility experiments and from analyses of the lunar sample 74220 to better determine the nature and origin of this unique explosive eruption. Three stages of the eruption have been identified. Stage 1 of the eruption model extends from ~550 km, the A17 orange glass magma source region based on phase equilibria studies, to 50 km depth in the Moon. Stage 2 extends from ~50 km to 500 m, where a C-O-H-S gas phase formed and grew in volume based on melt inclusion analyses and measurements. The volume of the gas phase at 500 m depth below the surface is calculated to be 7 to 15 vol% of the magma (closed-system) using the minimum and maximum estimates of CO, H 2 O, and S loss from the melt. In Stage 3, depths shallower than ~450 m, the rising magma exsolved an additional 800–900 ppm H 2 O and 300 ppm S, increasing the moles in the gas by a factor of 3 to 4. The closed-system gas phase is calculated to reach ~70 vol% at ~130 m depth, enough to fragment the magma and form pyroclastic beads. However, fragmentation (bead formation) is interpreted to have occurred at depths ranging from 600 to 300 m below the lunar surface based on the pressure necessary to explain the C content of the orange glass beads. The gas volume (70%) required to fragment the ascending magma at this depth is a factor of ~5 greater than the volume determined for closed-system degassing of an orange glass magma at 500 m, strongly implying that the gas was produced by open-system degassing as the magma ascended from greater depths. Formation of the dike carrying the magma up from the ~550 km deep source is considered to occur by a crack propagation mechanism ( Wilson and Head 2003 , 2017 ). The rapid dike-propagation process facilitates gas collection by open-system degassing in the upper part of the dike. This is necessary to achieve the gas volumes required for magma fragmentation at 600 m depths, and the magma-ascent velocities to explain the wide areal distribution of the bead deposit. The explosive nature of the picritic orange glass eruption, and the homogeneity of the bead compositions, are consistent with this gas-assisted eruption scenario, as is the evidence of a Fe-metal forming reduction event during Stage 2 followed by a Stage 3 oxidation event in the ascending magma.

Description: The chlorine isotope composition of Earth’s interior can place strong constraints on deep-Earth cycling of halogens and the origin of mantle chemical heterogeneity. However, all mantle-derived volcanic samples studied for Cl isotopes thus far originate from submarine volcanic systems, where the influence of seawater-derived Cl is pervasive. Here, we present Cl isotope data from subglacial volcanic glasses from Iceland, where the mid-ocean ridge system emerges above sea level and is free of seawater influence. The Iceland data display significant variability in 37 Cl values, from –1.8 to +1.4, and are devoid of regional controls. The absence of correlations between Cl and O isotope ratios and the lack of evidence for seawater-derived enrichments in Cl indicate that the variation in 37 Cl values in Icelandic basalts can be solely attributed to mantle heterogeneity. Indeed, positive correlations are evident between 37 Cl values and incompatible trace element ratios (e.g., La/Y), and long-lived radiogenic Pb isotope ratios. The data are consistent with the incorporation of altered lithosphere, including the uppermost sedimentary package, subducted into the Iceland mantle plume source, resulting in notable halogen enrichments in Icelandic basalts relative to lavas from adjacent mid-ocean ridges.

Description: The sources and nature of organic carbon on Mars have been a subject of intense research. Steele et al. (2012) showed that 10 martian meteorites contain macromolecular carbon phases contained within pyroxene- and olivine-hosted melt inclusions. Here, we show that martian meteorites Tissint, Nakhla, and NWA 1950 have an inventory of organic carbon species associated with fluid-mineral reactions that are remarkably consistent with those detected by the Mars Science Laboratory (MSL) mission. We advance the hypothesis that interactions among spinel-group minerals, sulfides, and a brine enable the electrochemical reduction of aqueous CO 2 to organic molecules. Although documented here in martian samples, a similar process likely occurs wherever igneous rocks containing spinel-group minerals and/or sulfides encounter brines.