Mantle melting as a function of water content beneath back-arc basins

Subduction zone magmas are characterized by high concentrations of H_(2)O, presumably derived from the subducted plate and ultimately responsible for melting at this tectonic setting. Previous studies of the role of water during mantle melting beneath back-arc basins found positive correlations between the H_(2)O concentration of the mantle (H_(2)O_o ) and the extent of melting (F), in contrast to the negative correlations observed at mid-ocean ridges. Here we examine data compiled from six back-arc basins and three mid-ocean ridge regions. We use TiO_2 as a proxy for F, then use F to calculate H_(2)O_o from measured H_(2)O concentrations of submarine basalts. Back-arc basins record up to 0.5 wt % H_(2)O or more in their mantle sources and define positive, approximately linear correlations between H_(2)O_o and F that vary regionally in slope and intercept. Ridge-like mantle potential temperatures at back-arc basins, constrained from Na-Fe systematics (1350°–1500°C), correlate with variations in axial depth and wet melt productivity (∼30–80% F/wt % H_(2)O_o ). Water concentrations in back-arc mantle sources increase toward the trench, and back-arc spreading segments with the highest mean H_(2)O_o are at anomalously shallow water depths, consistent with increases in crustal thickness and total melt production resulting from high H_(2)O. These results contrast with those from ridges, which record low H_(2)O_o (<0.05 wt %) and broadly negative correlations between H_(2)O_o and F that result from purely passive melting and efficient melt focusing, where water and melt distribution are governed by the solid flow field. Back-arc basin spreading combines ridge-like adiabatic melting with nonadiabatic mantle melting paths that may be independent of the solid flow field and derive from the H_(2)O supply from the subducting plate. These factors combine significant quantitative and qualitative differences in the integrated influence of water on melting phenomena in back-arc basin and mid-ocean ridge settings

D/H of water released by stepped heating of Shergotty, Zagami, Chassigny, ALH 84001, and Nakhla

We report the yield and D/H of water released by stepped heating of bulk Shergotty, Zagami, Chassigny, and the newest martian meteorite, ALH 84001. For comparison, we also report data from Nakhla using the same procedure since the heating steps in this study are slightly different than our previously reported nakhlite analyses

Measurement of intact methane isotopologues, including ^(13)CH_3D

Methane (CH_4) is both a significant greenhouse gas and resource. Its present and past cycling can be studied through measurements of concentration and/or bulk isotopic ratios (^(13)C/^(12)C, D/H, and ^(14)C/^(12)C). Currently, isotope ratios are measured by mass spectrometric analysis of H_2 and CO_2 produced from CH_4, or by spectroscopy of CH_4. However, the interpretation of bulk isotopic variations of CH_4 are often equivocal, necessitating additional tracers

Effects of temperature and carbon source on the isotopic fractionations associated with O_2 respiration for ^(17)O/^(16)O and ^(18)O/^(16)O ratios in E. coli

^(18)O/^(16)O and ^(17)O/^(16)O ratios of atmospheric and dissolved oceanic O_2 are used as biogeochemical tracers of photosynthesis and respiration. Critical to this approach is a quantitative understanding of the isotopic fractionations associated with production, consumption, and transport of O_2 in the ocean both at the surface and at depth. We made measurements of isotopic fractionations associated with O_2 respiration by E. coli. Our study included wild-type strains and mutants with only a single respiratory O_2 reductase in their electron transport chains (either a heme-copper oxygen reductase or a bd oxygen reductase). We tested two common assumptions made in interpretations of O_2 isotope variations and in isotope-enabled models of the O_2 cycle: (i) laboratory-measured respiratory ^(18)O/^(16)O isotopic fractionation factors (^(18)α) of microorganisms are independent of environmental and experimental conditions including temperature, carbon source, and growth rate; And (ii) the respiratory ‘mass law’ exponent, θ, between ^(18)O/^(16)O and ^(17)O/^(16)O, ^(17)α = (^(18)α)^θ, is universal for aerobic respiration. Results demonstrated that experimental temperatures have an effect on both ^(18)α and θ for aerobic respiration. Specifically, lowering temperatures from 37 to 15 °C decreased the absolute magnitude of ^(18)α by 0.0025 (2.5‰), and caused the mass law slope to decrease by 0.005. We propose a possible biochemical basis for these variations using a model of O_2 reduction that incorporates two isotopically discriminating steps: the reversible binding and unbinding of O_2 to a terminal reductase, and the irreversible reduction of that O_2 to water. Finally, we cast our results in a one-dimensional isopycnal reaction-advection-diffusion model, which demonstrates that enigmatic δ^(18)O and Δ^(17)O variations of dissolved O_2 in the dark ocean can be understood by invoking the observed temperature dependence of these isotope effects

Survival of presolar silicon carbide grains during parent-body metamorphism: constraints on the composition of metamorphic fluids

Systematic variations in the abundances of presolar grains of Sic and diamond with petrologic type in unequilibrated ordinary chondrites (UOCs) [1,2] probably reflect differences in P-T conditions and/or fluid composition during parent-body metamorphism. It may, therefore, be possible to constrain physical conditions during the metamorphism by determining the conditions under which presolar grains are destroyed

Sulfur speciation in lunar apatite

Apatite incorporates several volatile elements (including S, as SO_4 ^(2-)) and can provide a record of magmatic volatile evolution. Recent measurements of volatiles in apatite from Apollo sample 14053.241 revealed 300-450 ppm S. Although many lunar melts have sufficient S for sulfide saturation, the observed S content of lunar apatite is surprising because lunar samples (especially 14053) are highly reduced (≤ IW) and are thus expected to contain little SO_4 ^(2-). One possibility is that there are micro-environments in late-stage lunar melts that are more oxidized than one would infer from conditions recorded by other components of these rocks. Alternatively, it may be that S^(2-) substitutes for F+Cl+OH in lunar apatite: S^(2—)bearing apatite has been synthesized, but to our knowledge has not been observed in nature

Mantle Melting as a Function of Water Content beneath the Mariana Arc

Subduction zone magmas are characterized by high concentrations of pre-eruptive H_2O, presumably as a result of an H_2Oflux originating from the dehydrating, subducting slab. The extent of mantle melting increases as a function of increasing water content beneath back-arc basins and is predicted to increase in a similar manner beneath arc volcanoes. Here, we present new data for olivine-hosted, basaltic melt inclusions from the Mariana arc that reveal pre-eruptive H_2O contents of ~1•5-6•0 wt %, which are up to three times higher than concentrations reported for the Mariana Trough back-arc basin. Major element systematics of arc and back-arc basin basalts indicate that the back-arc basin melting regime does not simply mix with wet, arc-derived melts to produce the observed range of back-arc magmatic H_2O concentrations. Simple melting models reveal that the trend of increasing extents of melting with increasing H_2O concentrations of the mantle source identified in the Mariana Trough generally extends beneath the Mariana volcanic front to higher mantle water contents and higher extents of melting. In detail, however, each Mariana volcano may define a distinct relationship between extent of melting and the H_2O content of the mantle source. We develop a revised parameterization of hydrous melting, incorporating terms for variable pressure and mantle fertility, to describe the distinct relationships shown by each arc volcano. This model is used in combination with thermobarometry constraints to show that hydrous melts equilibrate at greater depths (34-87 km) and temperatures (>1300°C) beneath the Mariana arc than beneath the back-arc basin (21-37 km), although both magma types can form from a mantle of similar potential temperature (~1350°C).The difference lies in where the melts form and equilibrate. Arc melts are dominated by those that equilibrate within the hot core of the mantle wedge, whereas back-arc melts are dominated by those that equilibrate within the shallow zone of decompression melting beneath the spreading center. Despite higher absolute melting temperatures (>1300°C), Mariana arc melts reflect lower melt productivity as a result of wet melting conditions and a more refractory mantle source

Comparison of Experimental vs Theoretical Abundances of ¹³CH₃D and ¹²CH₂D₂ for Isotopically Equilibrated Systems from 1 to 500 °C

Methane is produced and consumed via numerous microbial and chemical reactions in atmospheric, hydrothermal, and magmatic reactions. The stable isotopic composition of methane has been used extensively for decades to constrain the source of methane in the environment. A recently introduced isotopic parameter used to study the formation temperature and formational conditions of methane is the measurement of molecules of methane with multiple rare, heavy isotopes (‘clumped’) such as ¹³CH₃D and ¹²CH₂D₂. In order to place methane clumped-isotope measurements into a thermodynamic reference frame that allows calculations of clumped-isotope based temperatures (geothermometry) and comparison between laboratories, all past studies have calibrated their measurements using a combination of experiment and theory based on the temperature dependence of clumped isotopologue distributions for isotopically equilibrated systems. These have previously been performed at relatively high temperatures (>150˚C). Given that many natural occurrences of methane form below these temperatures, previous calibrations require extrapolation when calculating clumped-isotope based temperatures outside of this calibration range. We provide a new experimental calibration of the relative equilibrium abundances of ¹³CH₃D and ¹²CH₂D₂ from 1–500˚C using a combination of γ-Al₂O₃ and Ni-based catalysts and compare them to new theoretical computations using Path Integral Monte Carlo (PIMC) methods and find 1:1 agreement (within ± 1 standard error) for the observed temperature dependence of clumping between experiment and theory over this range. This demonstrates that measurements, experiments, and theory agree from 1–500°C providing confidence in the overall approaches. Polynomial fits to PIMC computations, which are considered the most rigorous theoretical approach available, are given as follows (valid T ≥ 270 K): ∆¹³CH₃D≅1000×ln(K¹³CH₃D)= 1.47348×10¹⁹/T⁷ - 2.08648×10¹⁷/T⁶ + 1.19810×10¹⁵/T⁵ - 3.54757×10¹²/T⁴ +5.54476×10⁹/T³ – 3.49294×10⁶/T² + 8.89370×10₂/T ∆¹²CH₂D₂≅1000×ln(8/3×K¹²CH₂D₂)= -9.67634×10¹⁵/T⁶ + 1.71917×10¹⁴/T⁵ - 1.24819×10¹²/T⁴ + 4.30283×10⁹/T3 -4.48660×10⁶/T² + 1.86258×10³/T. We additionally compare PIMC computations to those performed utilizing traditional approaches that are the basis of most previous calibrations (Bigeleisen, Mayer, and Urey model, BMU) and discuss the potential sources of error in the BMU model relative to PIMC computations

Dynamic and physical clustering of gene expression during epidermal barrier formation in differentiating keratinocytes.

The mammalian epidermis is a continually renewing structure that provides the interface between the organism and an innately hostile environment. The keratinocyte is its principal cell. Keratinocyte proteins form a physical epithelial barrier, protect against microbial damage, and prepare immune responses to danger. Epithelial immunity is disordered in many common diseases and disordered epithelial differentiation underlies many cancers. In order to identify the genes that mediate epithelial development we used a tissue model of the skin derived from primary human keratinocytes. We measured global gene expression in triplicate at five times over the ten days that the keratinocytes took to fully differentiate. We identified 1282 gene transcripts that significantly changed during differentiation (false discovery rate <0.01%). We robustly grouped these transcripts by K-means clustering into modules with distinct temporal expression patterns, shared regulatory motifs, and biological functions. We found a striking cluster of late expressed genes that form the structural and innate immune defences of the epithelial barrier. Gene Ontology analyses showed that undifferentiated keratinocytes were characterised by genes for motility and the adaptive immune response. We systematically identified calcium-binding genes, which may operate with the epidermal calcium gradient to control keratinocyte division during skin repair. The results provide multiple novel insights into keratinocyte biology, in particular providing a comprehensive list of known and previously unrecognised major components of the epidermal barrier. The findings provide a reference for subsequent understanding of how the barrier functions in health and disease

Zonation of H_(2)O and F Concentrations around Melt Inclusions in Olivines

Studies of both naturally quenched and experimentally reheated melt inclusions have established that they can lose or gain H_(2)O after entrapment in their host mineral, before or during eruption. Here we report nanoSIMS analyses of H2O, Cl and F in olivine around melt inclusions from two natural basaltic samples: one from the Sommata cinder cone on Vulcano Island in the Aeolian arc and the other from the Jorullo cinder cone in the Trans-Mexican Volcanic Belt. Our results constrain olivine/basaltic melt partition coefficients and allow assessment of mechanisms of volatile loss from melt inclusions in natural samples. Cl contents in olivine from both samples are mostly below detection limits (≤0·03 ± 0·01 ppm), with no detectable variation close to the melt inclusions. Assuming a maximum Cl content of 0·03 ppm for all olivines, maximum estimates for Cl partition coefficients between olivine and glass are 0·00002 ± 0·00002. Olivines from the two localities display contrasting H_(2)O and F compositions: Sommata olivines contain 27 ± 11 ppm H_(2)O and 0·28 ± 0·07 ppm F, whereas Jorullo olivines have lower and proportionately more variable H_(2)O and F (11 ± 12 ppm and 0·12 ± 0·09 ppm, respectively; uncertainties are two standard deviations for the entire population). The variations of H_(2)O and F contents in the olivines exhibit clear zonation patterns, increasing with proximity to melt inclusions. This pattern was most probably generated during transfer of volatiles out of the inclusions through the host olivine. H_(2)O concentration gradients surrounding melt inclusions are roughly concentric, but significantly elongated parallel to the crystallographic a-axis of olivine. Because of this preferential crystallographic orientation, this pattern is consistent with H_(2)O loss that is rate-limited by the ‘proton–polaron’ mechanism of H diffusion in olivine. Partition coefficients based on olivine compositions immediately adjacent to melt inclusions are 0·0007 ± 0·0003 for H_(2)O and 0·0005 ± 0·0003 for F. The H_(2)O and F diffusion profiles most probably formed in response to a decrease in the respective fugacities in the external melt, owing to either degassing or mixing with volatile-poor melt. Volatile transport out of inclusions might also have been driven in part by increases in the fugacity within the inclusion owing to post-entrapment crystallization. In the case of F, because of the lack of data on F diffusion in olivine, any interpretation of the measured F gradients is speculative. In the case of H_(2)O, we model the concentration gradients using a numerical model of three-dimensional anisotropic diffusion of H, where initial conditions include both H2O decrease in the external melt and post-entrapment enrichment of H_(2)O in the inclusions. The model confirms that external degassing is the dominant driving force, showing that the orientation of the anisotropy in H diffusion is consistent with the proton–polaron diffusion mechanism in olivine. The model also yields an estimate of the initial H_(2)O content of the Sommata melt inclusions before diffusive loss of 6 wt % H_(2)O. The findings provide new insights on rapid H_(2)O loss during magma ascent and improve our ability to assess the fidelity of the H_(2)O record from melt inclusions