The Fate of Sulfur During Fluid-Present Melting of Subducting Basaltic Crust at Variable Oxygen Fugacity

International audienceTo constrain the effect of redox state on sulfur transport from subducting crust to mantle wedge during fluid-present melting and the stability of sulfur-bearing phases in the downgoing ocean crust, here we report high-pressure phase equilibria experiments on a H2O-saturated mid-ocean ridge basalt with 1 wt % S at variable oxygen fugacity (Graphic). Double-capsule experiments were conducted at 2*0 and 3*0 GPa and 950-1050°C, using Co-CoO, Ni-NiO, NixPd1-x-NiO, and Fe2O3-Fe3O4 external Graphic buffers. Sulfur content at sulfide saturation (SCSS) or sulfur content at sulfate saturation (SCAS) of experimental hydrous partial melts was measured by electron microprobe. All experiments were fluid-saturated and produced either pyrrhotite- or anhydrite-saturated assemblages of silicate glass, clinopyroxene, garnet, and rutile or titanomagnetite, ± amphibole ± quartz ± orthopyroxene. The silicate partial melt composition evolves from rhyolitic at 950°C to trachydacitic and trachyandesitic at 1050°C with increasing Graphic. At pyrrhotite saturation, melt S contents range from ∼30 ppm S at Graphic < FMQ - 1 to ∼500 ppm S at FMQ < Graphic ≤ FMQ + 1*1, whereas at anhydrite saturation (Graphic ≥ FMQ + 2*5) melt S concentrations range from ∼700 ppm S to 0*3 wt % S. Mass-balance calculations suggest that the aqueous fluid phase at equilibrium may contain as much as ∼15 wt % S at 1050°C at pyrrhotite saturation (Graphic ≤ FMQ + 1*1), in agreement with previous estimates, and up to 8 wt % S at anhydrite saturation. Our data also show that Graphic decreases markedly with increasing Graphic at pyrrhotite saturation, from several thousand at Graphic < FMQ - 1 to ∼ 200-400 at FMQ < Graphic ≤ FMQ + 1*1, owing to the increase of melt S content. At anhydrite saturation, Graphic is very low (<100) but increases with decreasing temperature, in an opposite way to previous observations at pyrrhotite saturation. As a consequence, at T ≤ 900°C, Graphic might be in the range 200 ± 100, irrespective of Graphic. The present study confirms that slab partial melts saturated with pyrrhotite are unable to efficiently transport S from slab to mantle wedge, and suggests that slab partial melts in equilibrium with anhydrite also have very limited power to enrich the mantle wedge in S. Importantly, slab-derived aqueous fluids appear to be efficient vectors for the transport of sulfur from slab to mantle wedge at all Graphic. Therefore, S transfer from ocean crust to wedge mantle is not Graphic dependent and could take place over a range of Graphic conditions, and oxidized slab conditions are not necessarily required to enrich the mantle wedge in S. Finally, depending on the initial amount of sulfur in the slab, the proportion of residual anhydrite and pyrrhotite in the dehydrated slab below the region of formation of arc magmas is likely to be significant and may efficiently be recycled into the deep mantle

A Multi-objective Perspective for Operator Scheduling using Fine-grained DVS Architecture

The stringent power budget of fine grained power managed digital integrated circuits have driven chip designers to optimize power at the cost of area and delay, which were the traditional cost criteria for circuit optimization. The emerging scenario motivates us to revisit the classical operator scheduling problem under the availability of DVFS enabled functional units that can trade-off cycles with power. We study the design space defined due to this trade-off and present a branch-and-bound(B/B) algorithm to explore this state space and report the pareto-optimal front with respect to area and power. The scheduling also aims at maximum resource sharing and is able to attain sufficient area and power gains for complex benchmarks when timing constraints are relaxed by sufficient amount. Experimental results show that the algorithm that operates without any user constraint(area/power) is able to solve the problem for most available benchmarks, and the use of power budget or area budget constraints leads to significant performance gain.Comment: 18 pages, 6 figures, International journal of VLSI design & Communication Systems (VLSICS

Effect of melt composition on crustal carbonate assimilation: Implications for the transition from calcite consumption to skarnification and associated CO2 degassing

Skarns are residue of relatively low-temperature magma-induced decarbonation in the crust largely associated with silicic plutons. Mafic magmatic intrusions are also capable of releasing excess CO2 due to carbonate assimilation. However, the effect of mafic to silicic melt evolution on the decarbonation processes, in addition to temperature controls on carbonate-intrusive magmatic systems, particularly at continental arcs, remains unclear. In this study, experiments performed in a piston cylinder apparatus at midcrustal depth (0.5 GPa) at supersolidus temperatures (900–1200°C) document calcite interaction with andesite and dacite melts at equilibrium under closed-system conditions at calcite saturation in a 1:1 melt-calcite ratio by weight. With increasing silica content in the starting melt, at similar melt fractions and identical pressure, assimilation decreases drastically (≤65% andesite-calcite to ≤18% dacite-calcite). In conjunction, the CaO/SiO2 ratio in melts resulting from calcite assimilation in andesitic starting material is >1, but ≤0.3 in those formed from dacite-calcite interaction. With increasing silica-content in the starting melt skarn mineralogy, particularly wollastonite, increases in modal abundance while diopsidic clinopyroxene decreases slightly. More CO2 is released with andesite-calcite reaction (≤2.9 × 1011 g/y) than with more skarn-like dacite-calcite interaction (≤8.1 × 1010 g/y, at one volcano assuming respective calcite-free-superliquidus conditions and a magma flux of 1012 g/y). Our experimental results thus suggest that calcite assimilation in more mafic magmas may have first degassed a significant amount of crustal carbon before the melt evolves to more silicic compositions, producing skarn. Crustal decarbonation in long-lived magmatic systems may hence deliver significant albeit diminishing amounts of carbon to the atmosphere and contribute to long-term climate change

Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts

Volatile species such as H2O, CO2, F, and Cl have significant impact in generation and differentiation of basaltic melts. Thus far experimental work has primarily focused on the effect of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2] and the effects of halogens have received far less attention [3-4]. However, melts in the planetary interiors can have non-negligible chlorine and fluorine concentrations. Here, we explore the effects of fluorine on near-liquidus phase equilibria of basalt. We have conducted nominally anhydrous piston cylinder experiments using graphite capsules at 0.6 - 1.5 GPa on an Fe-rich model basalt composition. 1.75 wt% fluorine was added to the starting mix in the form of AgF2. Fluorine in the experimental glass was measured by SIMS and major elements of glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield a liquidus temperature from 1330 C at 0.8GPa to 1400 at 1.6GPa and an olivine(Fo72)-pyroxene(En68)-liquid multiple saturation point at 1.25 GPa and 1375 C. The F-bearing experiments yield a liquiudus temperature from 1260 C at 0.6GPa to 1305 at 1.5GPa and an ol(Fo66)-pyx(En64)-MSP at 1 GPa and 1260 C. This shows that F depresses the basalt liquidus, extends the pyroxene stability field to lower pressure, and forces the liquidus phases to be more Fe-rich. KD(Fe-Mg/mineral-melt) calculated for both pyroxenes and olivines show an increase with increasing F content of the melt. Therefore, we infer that F complexes with Mg in the melt and thus increases the melt s silica activity, depressing the liquidus and changing the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to the effect of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic fraction basis, the effect of F on liquidus depression of basalts is xxxx compared to the effect of H. Future studies on kimberlitic and subduction zone magmas, which could have significant amount of fluorine, will need to consider the combined effects of F, Cl, and H on their stability and chemical evolution

Carbon solution and partitioning between metallic and silicate melts in a shallow magma ocean: Implications for the origin and distribution of terrestrial carbon

The origin of bulk silicate Earth carbon inventory is unknown and the fate of carbon during the early Earth differentiation and core formation is a missing link in the evolution of the terrestrial carbon cycle. Here we present high pressure (P)–temperature (T) experiments that offer new constraints upon the partitioning of carbon between metallic and silicate melt in a shallow magma ocean. Experiments were performed at 1–5 GPa, 1600–2100 °C on mixtures of synthetic or natural silicates (tholeiitic basalt/alkali basalt/komatiite/fertile peridotite) and Fe–Ni–C ± Co ± S contained in graphite or MgO capsules. All the experiments produced immiscible Fe-rich metallic and silicate melts at oxygen fugacity (fO2) between ~IW-1.5 and IW- 1.9. Carbon and hydrogen concentrations of basaltic glasses and non-glassy quenched silicate melts were determined using secondary ionization mass spectrometry (SIMS) and speciation of dissolved C–O–H volatiles in silicate glasses was studied using Raman spectroscopy. Carbon contents of metallic melts were determined using both electron microprobe and SIMS. Our experiments indicate that at core-forming, reduced conditions, carbon in deep mafic–ultramafic magmas may dissolve primarily as various hydrogenated species but the total carbon storage capacity, although is significantly higher than solubility of CO2 under similar conditions, remains low (<500 ppm). The total carbon content in our reduced melts at graphite saturation increases with increasing melt depolymerization (NBO/T), consistent with recent spectroscopic studies, and modestly with increasing hydration. Carbon behaves as a metal-loving element during core-mantle separation and our experimental Dmetal=silicate C varies between ~4750 and P150 and increases with increasing pressure and decreases with increasing temperature and melt NBO/T. Our data suggest that if only a trace amount of carbon (~730 ppm C) was available during early Earth differentiation, most of it was partitioned to the core (with 0.20–0.25 wt.% C) and no more than ~10–30% of the present-day mantle carbon budget (50–200 ppm CO2) could be derived from a magma ocean residual to core formation. With equilibrium core formation removing most of the carbon initially retained in the terrestrial magma ocean, explanation of the modern bulk silicate Earth carbon inventory requires a later replenishment mechanism. Partial entrapment of metal melt in solid silicate matrix, carbon ingassing by magma ocean–atmosphere interaction, and carbon outgassing from the core aided by reaction of core metal and deeply subducted water are some of the viable mechanisms

Evidence for Dry Carbonatite Metasomatism in the Oceanic Lithosphere from Peridotite Xenoliths of Samoa and Lanzarote

Water in Earths mantle affects processes like magmatism and plate tectonics. Experiments show that CO2-rich fluids lower the water solubility in olivine, implying that CO2-rich melts/fluids may dehydrate the lithosphere during metasomatism. To test this hypothesis, we report water concentrations (by polarized FTIR) of olivines, orthopyroxenes (OPX) and clinopyroxenes (CPX) from Savaii (Samoa) and Lanzarote (Canary Islands) peridotite xenoliths with evidence of carbonatite metasomatism. Savaii peridotites are highly depleted harzburgites and dunites with spinel Cr# (Cr/(Cr+Al)) ranging from 0.4 to 0.76 (estimated degree of melting: 191.5%). Strong Light Rare Earth Element (LREE) enrichments with Ti and Zr depletions in OPX and CO2-rich fluid inclusions (via Raman spectroscopy) are consistent with carbonatite metasomatism. Olivine, OPX and reconstructed bulk rock water concentrations (0.67-3.8, 17-89 and 4-26 ppm H2O, respectively) are low and show no apparent relationship with extent of carbonatite metasomatism. Calculated water concentrations of melts in equilibrium with Savaii OPX (OPX/melt partitioning of water 0.0063 to 0.011) are, on average (0.540.32 wt% H2O), lower than host Samoan lavas (0.63 to 1.5 wt% H2O), despite the LREE enrichments in OPX. Lanzarote peridotites are also highly depleted (degree of melting from spinel Cr#: 171.8%).Water concentrations are low in olivines (1.7-5.3 ppm H2O) and variable in pyroxenes (OPX: 42-103 ppm H2O; CPX: 105-301 ppm H2O), and show no apparent correlation with indicators of carbonatite metasomatism. Both Savaii and Lanzarote peridotites show negative correlations between water and degree of melting (i.e. Mg/(Mg+Fe), Cr#), suggesting melt depletion rather than metasomatism may have influenced their water concentrations. Calculated water concentrations of melts in equilibrium with Lanzarote CPX (average 1.90.75 wt% H2O; CPX/melt partitioning of water 0.011 to 0.012) are similar to those for Western Canaries lavas (average 1.80.31 wt%; CPX/melt partitioning of water 0.016 to 0.021) inferred from their CPX phenocrysts. However, calculated Ce concentrations in such melts (352 to 378 ppm; CPX/melt partitioning of Ce 0.07) are an order of magnitude greater than the lavas, and similar to carbonatites. This leads to H2O/Ce to be an order of magnitude lower in the inferred melts (26 to 57) than estimates for Western Canary lavas (280150). These low H2O/Ce ratios may suggest H2O loss from CPX during ascent, but the lack of strong water diffusion gradients in Lanzarote minerals does not support this. Instead we hypothesize that carbonatite metasomatism resulted in greater enrichment of Ce over H2O. Assuming carbonatite magmas are water rich, this implies a lower partitioning of water between minerals and melts during metasomatism, as suggested by experiments. Our data suggests carbonatite metasomatism does not result in significant re-hydration of the lithosphere, in contrast to silicate metasomatism as previously observed in Hawaiian peridotites

Flux of carbonate melt from deeply subducted pelitic sediments: Geophysical and geochemical implications for the source of Central American volcanic arc

[1] We determined the fluid-present and fluid-absent near-solidus melting of an Al-poor carbonated pelite at 3–7 GPa, to constrain the possible influence of sediment melt in subduction zones. Hydrous silicate melt is produced at the solidi at 3–4 GPa whereas Na-K-rich carbonatite is produced at the solidi at ≥5 GPa for both starting compositions. At ≥5 GPa and 1050°C, immiscible carbonate and silicate melts appear with carbonate melt forming isolated pockets embedded in silicate melt. Application of our data to Nicaraguan slab suggests that sediment melting may not occur at sub-arc depth (∼170 km) but carbonatite production can occur atop slab or by diapiric rise of carbonated-silicate mélange zone to the mantle wedge at ∼200–250 km depth. Flux of carbonatite to shallower arc-source can explain the geochemistry of Nicaraguan primary magma (low SiO2and high CaO, Ba/La). Comparison of carbonate-silicate melt immiscibility field with mantle wedge thermal structure suggests that carbonatite might temporally be trapped in viscous silicate melt, and contribute to seismic low-velocity zone at deep mantle wedge of Nicaragua

The speciation of carbon, nitrogen, and water in magma oceans and its effect on volatile partitioning between major reservoirs of the Solar System rocky bodies

The composition of atmospheres and the resulting potential for planetary habitability in the rocky bodies of our Solar System and beyond is strongly controlled by the volatile exchange between their silicate reservoirs and exospheres. The initial budget and speciation of major volatiles, like carbon (C), nitrogen (N) and water (H2O), in the silicate reservoirs and atmospheres was set during the formation stages of rocky bodies. However, the speciation of these major volatiles in reduced silicate melts prevalent during the differentiation stages of rocky bodies and its effect on the partitioning of volatiles between major rocky body reservoirs is poorly known. Here we present SIMS and vibrational spectroscopy (FTIR and Raman) data, determining C solubility, H content, and speciation of mixed C-O-N-H volatiles in graphite saturated silicate glasses from high P (1–7 GPa)-T (1500–2200 °C) experiments reported in Grewal et al., 2019a, Grewal et al., 2019b. The experiments recorded oxygen fugacity (log fO2) between IW–4.3 and IW–0.8. C-O-N-H speciation varied systematically as function of fO2 at any given P-T. We find out that C-N−, , N2, and OH− are the dominant species in the oxidized range (>IW–1.5), along with some contributions from C-H, N-H, and C-O bearing species. Between IW–3.0 and IW–1.5, C is bonded as C-O either in the form of isolated C-O molecules or Fe-carbonyl complexes, or as C-H in hydrocarbons, or as combination of both in esters, while almost all of the H is bonded with the dominant N species, i.e., NH2− or . At the most reduced conditions (<IW–3.0), C is present mostly in the form of C-H bearing species, while anhydrous N3− followed by N-H bearing molecules are the dominant N bearing species. Magma oceans (MOs) in highly reduced bodies like Mercury would contain most of their C as graphite if MO is carbon saturated and the dissolved C and N would be chemically bonded with the silicate network either in the form of anhydrous C4− and N3−, or hydrogenated C-H and N-H bearing species depending on H content of the silicate melts. MOs relevant for Mars, the Moon, Vesta, and angrite parent body would contain C and N mostly in the form of C-O and N-H bearing species, respectively. If the composition of Earth’s accreting material evolved from reduced to oxidized, then initially a significant amount of the C and N budget would be locked in the silicate reservoirs, which would subsequently be released to the proto-atmosphere(s) at later stages. The retention of proto-atmosphere(s) formed by MO degassing on Earth could have provided important precursors for prebiotic chemistry which possibly led to the eventual habitability of our planet. Additionally, based on the dominant speciation of N versus C in silicate melt as a function of fO2, we also predict that is unaffected by fH2 under highly reduced conditions (<IW–3), while is affected. Therefore, caution must be taken during the application of experimentally determined and to nominally anhydrous MOs

Nonstoichiometry and growth of some Fe carbides

Iron carbides containing from 31 to 17 atomic % carbon, with cohenite XRD structure and optical properties, were grown in experiments in Fe-Ni-S-C, Fe-Ni-C, and in Fe-C at 1, 6, and 7 GPa. X-ray cell volumes increase with C content. Compositions listed above vary considerably outside the nominal (Fe,Ni)3C stoichiometry of cohenite/cementite. Cohenites coexisting with Fe-C liquid are carbon-poor. The Eckstrom-Adcock carbide, nominally Fe7C3, was found to show compositions from 29 to 36 atomic % C at 7 GPa in Fe-C. Both these materials are better regarded as solutions than as stoichiometric compounds, and their properties such as volume have compositional dependencies, as do the iron oxides, sulfides, silicides, and hydrides. The fraction of C dissolved in cohenite-saturated alloy is found to become smaller between 1 and 7 GPa. If this trend continues at higher pressures, the deep mantle should be easier to saturate with carbide than the shallow mantle, whether or not carbide is metastable as at ambient pressure. At temperatures below the cohenite-graphite peritectic, cohenite may grow as a compositionally zoned layer between Fe and graphite. The Eckstrom-Adcock carbide joins the assemblage at 7 GPa. Phases appear between Fe and C in an order consistent with metasomatic interface growth between chemically incompatible feed stocks. Diffusion across the carbide layer is not the growth-rate-limiting step. Carbon transport along the grain boundaries of solid Fe source stock at 1 GPa, to form Csaturated Fe alloy, is observed to be orders of magnitude faster than the cohenite layer growth. Growth stagnates too rapidly to be consistent with diffusion control. Furthermore lateral variations in carbide layer thickness, convoluted inert marker horizons, and variable compositional profiles within the layers suggest that there are local transport complexities not covered by one-dimensional diffusive metasomatic growth. In contrast to many transport phenomena which slow with pressure, at 7 GPa and 1162 °C, carbide growth without open grain boundaries is faster than at 1 GPa with fast grain boundary channels, again suggesting C transport is less of a constraint on growth than C supply. C supply at 7 GPa is enhanced by graphite metastability and the absence of fast grain boundary channels to divert C into the Fe instead of growing carbide. At both 1 and 7 GPa, the growth rate of carbide is found to systematically vary depending on which of two stock pieces of graphite are used to form the growth couple, suggesting that some property of each specific graphite, like C-release rate, possibly from amorphous binder material, may influence the cohenite growth process. At temperatures near and above the cohenite-graphite peritectic at 1-1.5 GPa, complex intergrowths involving Fe-C liquids and extensive thermal migration transport were encountered, eroding the organized spatial resolution and the range of cohenite compositions found grown below this peritectic from growth couples of crystalline Fe and graphite. The migration of graphite to a position in the metasomatic sequence between liquid and cohenite demonstrates that the solubility of graphite in liquid increases with temperature above the peritectic, whereas the solubility of graphite in cohenite below the peritectic decreases with temperature. The variable solubility of graphite in cohenite, shown by thermal migration, emphasizes that cohenite does have compositional variations

Internal or external magma oceans in the earliest protoplanets -- perspectives from nitrogen and carbon fractionation

When the extent of protoplanetary melting approached magma ocean (MO)-like conditions, alloy melts efficiently segregated from the silicates to form metallic cores. The nature of the MO of a differentiating protoplanet, i.e., internal or external MO (IMO or EMO), not only determines the abundances of life-essential volatiles like nitrogen (N) and carbon (C) in its core and mantle reservoirs but also the timing and mechanism of volatile loss. Whether the earliest formed protoplanets had IMOs or EMOs is, however, poorly understood. Here we model equilibrium N and C partitioning between alloy and silicate melts in the absence (IMO) or presence (EMO) of vapor degassed atmospheres. Bulk N and C inventories of the protoplanets during core formation are constrained for IMOs and EMOs by comparing the predicted N and C abundances in the alloy melts from both scenarios with N and C concentrations in the parent cores of magmatic iron meteorites. Our results show that in comparison to EMOs, protoplanets having IMOs satisfy N and C contents of the parent cores with substantially lower amounts of bulk N and C present in the parent body during core formation. As the required bulk N and C contents for IMOs and EMOs are in the sub-chondritic and chondritic range, respectively, N and C fractionation models alone cannot be used to distinguish the prevalence of these two end-member differentiation regimes. A comparison of N and C abundances in chondrites with their peak metamorphic temperatures suggests that protoplanetary interiors could lose a substantial portion of their N and C inventories with increasing degrees of thermal metamorphism.Comment: 19 pages, 8 figures, 1 tabl