The effect of phosphorus on the iron redox ratio, viscosity, and density of an evolved ferro-basalt

Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO2. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P2O5 is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P2O5 on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P2O5 results in a relatively small change in viscosity, while further addition of P2O5 results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm3/mol for P2O5 in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm3/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P2O5 on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully

Influence of limestone grain size on glass homogeneity

International audienceThe lack of homogeneity in a glass is characterized by the occurrence of layers of different chemical compositions and densities. When starting materials relevant for the synthesis of soda-lime silicate glasses are melted in a crucible, silica- and calcium-enrichments are observed at the top and at the bottom of the melt respectively. This behaviour may be due to the occurrence of several reaction pathways. In this respect, an interesting observation is that the grain size of limestone is found to be an important parameter influencing the level of glass homogeneity. The reasons for this have been studied here using systematic differential thermal analysis and thermogravimetric analysis. The experiments showed that, in presence of limestone of small grain size (< 200 micrometers), sodium carbonate disappears before the temperature at which it is observed to interact with silica in the CaO - free system. We infer that this is most probably due to production of a mixed carbonate liquid, which subsequently reacts with silica to spontaneously yield a homogeneous silicate melt. A characteristic of this probable mixed carbonate (assumed to be close to the composition CaNa2(CO3)2) is its density of 2.54g/cm3, close to that of the silicates and of silica itself. On the contrary, coarse limestone decomposes to CaO (and CO2), which is slowly incorporated in the sodium silicate liquid formed when sodium carbonate interacts with silica. The much higher density of CaO (3.35 g/cm3) and of calcium silicates could explain the tendency for CaO concentrations to be greatest towards the base of melting crucibles

The effect of phosphorus on the iron redox ratio, viscosity, and density of an evolved ferro-basalt

Despite the abundant evidence for the enrichment of phosphorus during the petrogenesis of natural ferro-basalts, the effect of phosphorus on the physical properties of these melts is poorly understood. The effects of phosphorus on the viscosity, density and redox ratio of a ferro-basaltic melt have been determined experimentally. The viscosity measurements were obtained using the concentric cylinder method on a ferro-basaltic melt above its liquidus, at 1 atm, in equilibrium with air and with CO2. The density measurements were performed using the double Pt-bob Archimedean method at superliquidus conditions under 1 atm of air. The redox ratio was obtained by wet chemical analysis of samples collected during physical property measurements. Phosphorus pentoxide reduces ferric iron in ferro-basaltic melt. The reduction due to P2O5 is much larger than that for most other oxide components in basaltic melts. A coefficient for the reduction of ferric iron has been generated for inclusion in calculation schemes. The effect of P2O5 on the viscosity is shown to be complex. The initial reduction of ferric iron with the addition of P2O5 results in a relatively small change in viscosity, while further addition of P2O5 results in a strong increase. The addition of phosphorus to a ferro-basaltic melt also reduces the density. A partial molar volume of 64.5±0.7 cm3/mol for P2O5 in this melt has been obtained at 1300° C, yielding a volume of 12.9 cm3/mol per oxygen, consistent with a tetrahedral coordination for this high field strength cation. The effects of P2O5 on redox state, density and viscosity provide constraints on the structural role of phosphorus in these melts. The results suggest a complex interaction of phosphorus with the aluminosilicate network, and tetrahedral ferric iron. In light of the significant effects of phosphorus on the physical and chemical properties of ferro-basaltic liquids, and the extreme enrichments possible in these liquids in nature, the role of phosphorus in these melts should, in future, be considered more carefully

In-situ synchrotron microtomography reveals multiple reaction pathways during soda-lime glass synthesis

Ultrafast synchrotron microtomography has been used to study in-situ and in real time the initial stages of silicate glass melt formation from crystalline granular raw materials. Significant and unexpected rearrangements of grains occur below the nominal eutectic temperature, and several drastically different solid-state reactions are observed to take place at different types of intergranular contacts. These reactions have a profound influence on the formation and the composition of the liquids produced, and control the formation of defects.Comment: 4 pages, 4 figure

Clinopyroxene microtextures reveal incompletely extracted melts in abyssal peridotites.

ABSTRACT Textural evidence is interpreted to suggest that in regions where upwelling rates of the mantle are slow to very slow, a small amount (ϳ2%) of melt was present when plagioclasefree abyssal peridotites entered the conductive regime at the base of the oceanic lithosphere. Upon crystallization, this melt appears to have been undersaturated in orthopyroxene, but precipitated clinopyroxene, Al-rich and Ti-poor spinel, and sulfides. Furthermore, the primary clinopyroxene grains have rare earth element patterns typical of residues of fractional melting, suggesting that the interstitial liquids were incremental partial melts rather than having mid-oceanic-ridge basalt compositions

Nickel isotope fractionation during metal-silicate differentiation of planetesimals: Experimental petrology and ab initio calculations

Metal-silicate fractionation of nickel isotopes has been experimentally quantified at 1623 K, with oxygen fugacities varying from 10−8.2 to 10−9.9 atm and for run durations from 0.5 to 1 h. Both kinetic and equilibrium fractionations have been studied. A wire loop set-up was used in which the metal reservoir is a pure nickel wire holding a silicate melt droplet of anorthite-diopside eutectic composition. During the course of the experiment, diffusion of nickel from the wire to the silicate occurred. The timescale to reach chemical equilibrium was fO2 dependent and decreased from 17 to 1 hour, as conditions became more reducing. The isotopic composition of each reservoir was determined by Multicollector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICPMS) after Ni purification. The isotopic composition was found to be constant in the metallic wire, which therefore behaved as an infinite reservoir. On the contrary, strong kinetic fractionation was observed in the silicate melt (δNi down to −0.98‰.amu−1 relative to the standard). Isotopic equilibrium was typically reached after 24 hours. For equilibrated samples at 1623 K, no metal-silicate fractionation was observed within uncertainty (2SD), with ΔNiMetal-Silicate = 0.02 ± 0.04‰.amu−1. Theoretical calculations of metal-silicate isotope fractionation at equilibrium were also performed on different metal-silicate systems. These calculations confirm (1) the absence of fractionation at high temperature and (2) a weak temperature dependence for Ni isotopic fractionation for the metal-olivine and metal-pyroxene pairs with the metal being slightly lighter isotopically. Our experimental data were finally compared with natural samples. Some mesosiderites (stony-iron meteorites) show a ΔNiMetal-Silicate close to experimental values at equilibrium, whereas others exhibit positive metal-silicate fractionation that could reflect kinetic processes. Conversely, pallasites display a strong negative metal-silicate fractionation. This most likely results from kinetic processes with Ni diffusion from the silicate to the metal phase due to a change of Ni partition coefficient during cooling. In this respect we note that in these pallasites, iron isotopes show metal-silicate fractionation that is opposite direction to Ni, supporting the idea of kinetic isotope fractionation, associated with Fe-Ni interdiffusion

Chemical Mapping of Vesta and Ceres

Following successful science operations at Vesta, the Dawn spacecraft is headed for an encounter with Ceres in 2015. What have we learned at Vesta? And, what do we expect to learn by comparing Vesta and Ceres? We will address these questions from the standpoint of geochemistry. Dawn's Gamma Ray and Neutron Detector (GRaND) is sensitive to the elemental composition of surface materials to depths of a few decimeters [1]. Gamma rays and neutrons, produced by the steady bombardment of galactic cosmic rays and by the decay of naturally ]occurring radioisotopes (K, Th, U), provide a chemical fingerprint of the regolith. Analysis of planetary radiation emissions enables mapping of specific elements (such as Fe, Mg, Si, Cl, and H) and compositional parameters (such as average atomic mass), which provide information about processes that shaped the planet1s surface and interior. Dawn has exceeded operational goals for GRaND at Vesta, accumulating an abundance of nadir-pointed data during five months in a 210 km, low altitude mapping orbit around Vesta (265-km mean radius). Chemical information from gamma ray and neutron measurements was used to test the connection between Vesta and the howardite, eucrite, and diogenite (HED) meteorites [2]. Additionally, GRaND searched for evolved, igneous lithologies [3], mantle and upper crustal materials exposed in large impact basins, mesosiderite compositions, and hydrogen in Vesta1s bulk regolith. Results of our analyses and their implications for thermal evolution and regolith-processes will be presented. The possibility of a subcrustal ocean [4, 5] and lack of cerean meteorites makes water-rich Ceres a compelling target of exploration [6]. If Ceres underwent aqueous differentiation, then crustal overturn or gas driven volcanism may have significantly modified its primitive surface; and products of aqueous alteration (e.g. [7]) would detectable by GRaND [1]. For example, the presence of Cl in salts, associated with liquid-water-processes, would have a profound effect on the thermal neutron leakage flux. GRaND is sensitive to H and H-layering, which may be in the form of endogenic water ice or hydrous minerals on Ceres. Ammonia ice (e.g., from recent cryovolcanism) would produce a distinctly different neutron signature than water ice [1]. Prospective results for GRaND at Ceres will be presented in the context of what we have learned about Vesta

Submarine back-arc lava with arc signature : Fonualei Spreading Center, northeast Lau Basin, Tonga

Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): B08S07, doi:10.1029/2007JB005451.We present major, volatile, and trace elements for quenched glasses from the Fonualei Spreading Center, a nascent spreading system situated very close to the Tofua Volcanic Arc (20 km at the closest), in the northeast Lau Basin. The glasses are basalts and basaltic andesites and are inferred to have originated from a relatively hot and depleted mantle wedge. The Fonualei Spreading Center shows island arc basalt (IAB) affinities, indistinguishable from the Tofua Arc. Within the Fonualei Spreading Center no geochemical trends can be seen with depth to the slab and/or distance to the arc, despite a difference in depth to the slab of >50 km. Therefore we infer that all the subduction-related magmatism is captured by the back arc as the adjacent arc is shut off. There is a sharp contrast between the main spreading area of the Fonualei Spreading Center (FSC) and its northernmost termination, the Mangatolu Triple Junction (MTJ). The MTJ samples are characteristic back-arc basin basalts (BABB). We propose that the MTJ and FSC have different mantle sources, reflecting different mantle origins and/or different melting processes. We also document a decrease in mantle depletion from the south of the FSC to the MTJ, which is the opposite to what has been documented for the rest of the Lau Basin where depletion generally increases from south to north. We attribute this reverse trend to the influx of less depleted mantle through the tear between the Australian and the Pacific plates, at the northern boundary of the Lau Basin.NSK acknowledges the support of an A.E. Ringwood Scholarship from the RSES

Transient HCl in the atmosphere of Mars

A major quest in Mars’ exploration has been the hunt for atmospheric gases, potentially unveiling ongoing activity of geophysical or biological origin. Here, we report the first detection of a halogen gas, HCl, which could, in theory, originate from contemporary volcanic degassing or chlorine released from gas-solid reactions. Our detections made at ~3.2 to 3.8 μm with the Atmospheric Chemistry Suite and confirmed with Nadir and Occultation for Mars Discovery instruments onboard the ExoMars Trace Gas Orbiter, reveal widely distributed HCl in the 1- to 4-ppbv range, 20 times greater than previously reported upper limits. HCl increased during the 2018 global dust storm and declined soon after its end, pointing to the exchange between the dust and the atmosphere. Understanding the origin and variability of HCl shall constitute a major advance in our appraisal of martian geo- and photochemistry

The SuperCam Instrument Suite on the Mars 2020 Rover: Science Objectives and Mast-Unit Description

On the NASA 2020 rover mission to Jezero crater, the remote determination of the texture, mineralogy and chemistry of rocks is essential to quickly and thoroughly characterize an area and to optimize the selection of samples for return to Earth. As part of the Perseverance payload, SuperCam is a suite of five techniques that provide critical and complementary observations via Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), visible and near-infrared spectroscopy (VISIR), high-resolution color imaging (RMI), and acoustic recording (MIC). SuperCam operates at remote distances, primarily 2-7 m, while providing data at sub-mm to mm scales. We report on SuperCam's science objectives in the context of the Mars 2020 mission goals and ways the different techniques can address these questions. The instrument is made up of three separate subsystems: the Mast Unit is designed and built in France; the Body Unit is provided by the United States; the calibration target holder is contributed by Spain, and the targets themselves by the entire science team. This publication focuses on the design, development, and tests of the Mast Unit; companion papers describe the other units. The goal of this work is to provide an understanding of the technical choices made, the constraints that were imposed, and ultimately the validated performance of the flight model as it leaves Earth, and it will serve as the foundation for Mars operations and future processing of the data.In France was provided by the Centre National d'Etudes Spatiales (CNES). Human resources were provided in part by the Centre National de la Recherche Scientifique (CNRS) and universities. Funding was provided in the US by NASA's Mars Exploration Program. Some funding of data analyses at Los Alamos National Laboratory (LANL) was provided by laboratory-directed research and development funds