Transport properties of carbonated silicate melt at high pressure

PubMed Central

Ghosh, Dipta B.; Karki, Bijaya B.

2017-01-01

Carbon dioxide, generally considered as the second most abundant volatile component in silicate magmas, is expected to significantly influence various melt properties. In particular, our knowledge about its dynamical effects is lacking over most of Earth’s mantle pressure regime. Here, we report the first-principles molecular dynamics results on the transport properties of carbonated MgSiO3 liquid under conditions of mantle relevance. They show that dissolved CO2 systematically enhances the diffusion rates of all elements and lowers the melt viscosity on average by factors of 1.5 to 3 over the pressure range considered. It is remarkable that CO2 has very little or no influence on the electrical conductivity of the silicate melt under most conditions. Simulations also predict anomalous dynamical behavior, increasing diffusivity and conductivity and decreasing viscosity with compression in the low-pressure regime. This anomaly and the concomitant increase of pressure and temperature with depth together make these transport coefficients vary modestly over extended portions of the mantle regime. It is possible that the melt electrical conductivity under conditions corresponding to the 410- and 660-km seismic discontinuities is at a detectable level by electromagnetic sounding observation. In addition, the low melt viscosity values of 0.2 to 0.5 Pa⋅s at these depths and near the core-mantle boundary may imply high mobility of possible melts in these regions. PMID:29226244

A Non-Arrhenian Viscosity Model for Natural Silicate Melts with Applications to Volcanology

NASA Astrophysics Data System (ADS)

Russell, J. K.; Giordano, D.; Dingwell, D. B.

2005-12-01

Silicate melt viscosity is the most important physical property in volcanic systems. It governs styles and rates of flow, velocity distributions in flowing magma, rates of vesiculation, and, ultimately, sets limits on coherent(vs. fragmented or disrupted) flow. The prediction of melt viscosity over the range of conditions found on terrestrial planets remains a challenge. However, the extraordinary increase in number and quality of published measurements of melt viscosity suggests the possibility of new models. Here we review the attributes of previous models for silicate melt viscosity and, then, present a new predictive model natural silicate melts. The importance of silicate melt viscosity was recognized early [1] and culminated in 2 models for predicting silicate melt viscosity [2,3]. These models used an Arrhenian T-dependence; they were limited by a limited experimental database dominated by high-T measurements. Subsequent models have aimed to: i) extend the compositional range of Arrhenian T-dependent models [4,5]; ii) to develop non-Arrhenian models for limited ranges of composition [6,7,8], iii) to develop new strategies for modelling the composition and T-dependence of viscosity [9,10,11], and, finally, to create chemical models for the non-Arrhenian T-dependence of natural melts [12]. We present a multicomponent model for the compositional and T dependence of silicate melt viscosity based on data spanning a wide range of anhydrous melt compositions. The experimental data include micropenetration and concentric cylinder viscometry measurements covering a viscosity range of 10-1 to 1012 Pa s and a T-range from 700 to 1650°C. These published data provide a high- quality database comprising ~ 800 experimental data on 44 well-characterized melt compositions. Our model uses the Adam-Gibbs equation to capture T-dependence: log η = A + B/[T · log (T/C)] where A, B, and C are adjustable parameters that vary for different melt compositions. We assume that all

Metal/Silicate Partitioning of P, Ga, and W at High Pressures and Temperatures: Dependence on Silicate Melt Composition

NASA Technical Reports Server (NTRS)

Bailey, Edward; Drake, Michael J.

2004-01-01

The distinctive pattern of element concentrations in the upper mantle provides essential evidence in our attempts to understand the accretion and differentiation of the Earth (e.g., Drake and Righter, 2002; Jones and Drake, 1986; Righter et al., 1997; Wanke 1981). Core formation is best investigated through use of metal/silicate partition coefficients for siderophile elements. The variables influencing partition coefficients are temperature, pressure, the major element compositions of the silicate and metal phases, and oxygen fugacity. Examples of studies investigating the effects of these variables on partitioning behavior are: composition of the metal phase by Capobianco et al. (1999) and Righter et al. (1997); silicate melt composition by Watson (1976), Walter and Thibault (1995), Hillgren et al. (1996), Jana and Walker (1997), and Jaeger and Drake (2000); and oxygen fugacity by Capobianco et al. (1999), and Walter and Thibault (1995). Here we address the relative influences of silicate melt composition, pressure and temperature.

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Choi, Y.; Pando, K.

2011-01-01

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo.

Partitioning of Mo, P and other siderophile elements (Cu, Ga, Sn, Ni, Co, Cr, Mn, V, and W) between metal and silicate melt as a function of temperature and silicate melt composition

NASA Astrophysics Data System (ADS)

Righter, K.; Pando, K. M.; Danielson, L.; Lee, Cin-Ty

2010-03-01

Metal-silicate partition coefficients can provide information about the earliest differentiation histories of terrestrial planets and asteroids. Systematic studies of the effects of key parameters such as temperature and melt composition are lacking for many elements. In particular, data for Mo is scarce, but given its refractory nature, is of great value in interpreting metal-silicate equilibrium. Two series of experiments have been carried out to study Mo and P partitioning between Fe metallic liquid and basaltic to peridotitic silicate melt, at 1 GPa and temperatures between 1500 and 1900 °C. Because the silicate melt utilized was natural basalt, there are also measurable quantities of 9 other siderophile elements (Ni, Co, W, Sn, Cu, Mn, V, Cr, Ga and Zn). The Ni and Co data can be used to assess consistency with previous studies. In addition, the new data also allow a first systematic look at the temperature dependence of Cu, Ga, Sn, Cr, Mn V and W for basaltic to peridotitic melts. Many elements exhibit an increase in siderophile behavior at higher temperature, contrary to popular belief, but consistent with predictions from thermodynamics. Using these new data we examine DMomet/sil and DPmet/sil in detail and show that increasing temperature causes a decrease in the former and an increase in the latter, whereas both increase with MgO content of the silicate melt. The depletions of Mo and P in the mantle of the Earth can be explained by metal-silicate equilibrium at magma ocean conditions — both elements are satisfied at PT conditions of an intermediate depth magma ocean for the Earth 22.5 GPa and 2400 °C.

Mg-perovskite/silicate melt and magnesiowuestite/silicate melt partition coefficients for KLB-1 at 250 Kbars

NASA Technical Reports Server (NTRS)

Drake, Michael J.; Rubie, David C.; Mcfarlane, Elisabeth A.

1992-01-01

The partitioning of elements amongst lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements was reported previously, and these results as well as interpretations based on them have generated controversy. Here we report what are to our knowledge only the second set of directly measured trace element partition coefficients for a natural system (KLB-1).

Sulfur Saturation Limits in Silicate Melts and their Implications for Core Formation Scenarios for Terrestrial Planets

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2002-01-01

This study explores the controls of temperature, pressure, and silicate melt composition on S solubility in silicate liquids. The solubility of S in FeO-containing silicate melts in equilibrium with metal sulfide increases significantly with increasing temperature but decreases with increasing pressure. The silicate melt structure also exercises a control on S solubility. Increasing the degree of polymerization of the silicate melt structure lowers the S solubility in the silicate liquid. The new set of experimental data is used to expand the model of Mavrogenes and O'Neill(1999) for S solubility in silicate liquids by incorporating the influence of the silicate melt structure. The expected S solubility in the ascending magma is calculated using the expanded model. Because the negative pressure dependence of S solubility is more influential than the positive temperature dependence, decompression and adiabatic ascent of a formerly S-saturated silicate magma will lead to S undersaturation. A primitive magma that is S-saturated in its source region will, therefore, become S-undersaturated as it ascends to shallower depth. In order to precipitate magmatic sulfides, the magma must first cool and undergo fractional crystallization to reach S saturation. The S content in a metallic liquid that is in equilibrium with a magma ocean that contains approx. 200 ppm S (i.e., Earth's bulk mantle S content) ranges from 5.5 to 12 wt% S. This range of S values encompasses the amount of S (9 to 12 wt%) that would be present in the outer core if S is the light element. Thus, the Earth's proto-mantle could be in equilibrium (in terms of the preserved S abundance) with a core-forming metallic phase.

Origin of silicic magmas along the Central American volcanic front: Genetic relationship to mafic melts

NASA Astrophysics Data System (ADS)

Vogel, Thomas A.; Patino, Lina C.; Eaton, Jonathon K.; Valley, John W.; Rose, William I.; Alvarado, Guillermo E.; Viray, Ela L.

2006-09-01

Silicic pyroclastic flows and related deposits are abundant along the Central American volcanic front. These silicic magmas erupted through both the non-continental Chorotega block to the southeast and the Paleozoic continental Chortis block to the northwest. The along-arc variations of the silicic deposits with respect to diagnostic trace element ratios (Ba/La, U/Th, Ce/Pb), oxygen isotopes, Nd and Sr isotope ratios mimic the along-arc variation in the basaltic and andesitic lavas. This variation in the lavas has been interpreted to indicate relative contributions from the slab and asthenosphere to the basaltic magmas [Carr, M.J., Feigenson, M.D., Bennett, E.A., 1990. Incompatible element and isotopic evidence for tectonic control of source mixing and melt extraction along the Central American arc. Contributions to Mineralogy and Petrology, 105, 369-380.; Patino, L.C., Carr, M.J. and Feigenson, M.D., 2000. Local and regional variations in Central American arc lavas controlled by variations in subducted sediment input. Contributions to Mineralogy and Petrology, 138 (3), 265-283.]. With respect to along-arc trends in basaltic lavas the largest contribution of slab fluids is in Nicaragua and the smallest input from the slab is in central Costa Rica — similar trends are observed in the silicic pyroclastic deposits. Data from melting experiments of primitive basalts and basaltic andesites demonstrate that it is difficult to produce high K 2O/Na 2O silicic magmas by fractional crystallization or partial melting of low-K 2O/Na 2O sources. However fractional crystallization or partial melting of medium- to high-K basalts can produce these silicic magmas. We interpret that the high-silica magmas associated Central America volcanic front are partial melts of penecontemporaneous, mantle-derived, evolved magmas that have ponded and crystallized in the mid-crust — or are melts extracted from these nearly completely crystallized magmas.

Partitioning of carbon between Fe-rich alloy melt and silicate melt in a magma ocean - Implications for the abundance and origin of volatiles in Earth, Mars, and the Moon

NASA Astrophysics Data System (ADS)

Chi, Han; Dasgupta, Rajdeep; Duncan, Megan S.; Shimizu, Nobumichi

2014-08-01

The budget and origin of carbon in Earth and other terrestrial planets are debated and one of the key unknowns is the fate of carbon during early planetary processes including accretion, core formation, and magma ocean (MO) crystallization. Here we determine, experimentally, the solubility of carbon in coexisting Fe-Ni alloy melt and basaltic silicate melt in shallow MO conditions, i.e., at 1-3 GPa, 1500-1800 °C. Oxygen fugacity of the experiments, estimated based on Fe (in metallic alloy melt)-FeO (in silicate melt) equilibrium, varied between ∼IW-0.4 and IW-1.0, where IW refers to the oxygen fugacity imposed by the coexistence of iron and wüstite. Four different starting mixes, each with 7:3 silicate:metal mass ratio and silicate melt NBO/T (estimated proportion of non-bridging oxygen with respect to tetrahedral cations; NBO/T=2×/total OT -4, where T = Si + Ti + Al + Cr + P) ranging from 0.81 to 1.54 were studied. Concentrations of carbon in the alloy melt were determined using electron microprobe whereas carbon contents of quenched basaltic glasses were determined using secondary ionization mass spectrometry (SIMS). Identification of carbon and hydrogen-bearing species in silicate glasses was performed using Raman and Fourier Transformed Infrared (FTIR) spectroscopy. Our results show that carbon in the metallic melt varies between 4.4 wt.% and 7.4 wt.% and increases with increasing temperature and modestly with increasing pressure but decreases with increasing Ni content of the alloy melt. Carbon concentration in the silicate melts, on the other hand, varies from 11 ± 1 ppm to 111 ± 7 ppm and is negatively correlated with pressure but positively correlated with temperature, the NBO/T, the oxygen fugacity and the water content of the silicate melts. Raman and FTIR results show that at our experimental conditions, carbon in silicate melt is dissolved both as hydrogenated species and CO32-. The calculated carbon partition coefficient DCmetal/silicate varies

Silicate melts: The “anomalous” pressure dependence of the viscosity

NASA Astrophysics Data System (ADS)

Bottinga, Y.; Richet, P.

1995-07-01

The decrease of the specific volume, when the extent of polymerization diminishes, is a cause of the pressure sensitivity of the viscosity of silicate melts. This effect can be explained by means of the Adam and Gibbs (1965) theory, taking into account the pressure dependence of the degree of polymerization of the melt and its influence on the configurational entropy. At temperatures close to their glass transitions, liquid silica and SiO2sbnd Na2O melts have configurational entropies that are probably due to the mixing of their bridging and nonbridging oxygen atoms.

Experimental investigations of influence of pressure on the solubility of sulfur in silicate melts.

NASA Astrophysics Data System (ADS)

Kostyuk, Anastasia; Gorbachev, Nikolay

2010-05-01

Sulfide-silicate demixing of silicate melts on immiscible silicate and sulfide liquids occurs at magma sulfur saturation. This type of liquation plays an important role in geochemistry of mantle magmas, in processes of magmatic differentiation, and in ore deposit formation. The major parameter defining sulfide-silicate stratification of silicate melts is solubility of sulfur in magmas. It is considered that «solubility of sulfur» is concentration of sulfur in silicate melts. The previous researches have established positive dependence of solubility of sulphur on temperature [1, 2], melt composition [3, 4], oxidation-reduction conditions [5, 6] and our experimental data confirm it. However, available data does not give a simple answer about dependence of solubility of sulfur from pressure in modelling and natural "dry" sulfide-saturated silicate melts. The reason of difference in experiments remains not clear and further work is needed on this topic. In this paper, we report our findings on the influence of pressure on the solubility of sulfur in hydrous magnesian melts. This melts are represent by olivine basalt - picrite, coexisting with Fe-Cu-Ni sulfide melt and harzburgite (Ol+Opx) and it was investigated in a temperature range from 1200 to 1350°С and a pressure range from 0.2 to 2.5 GPa. Experiments were carried out on the piston-cylinder at Р=1-2.5GPa and in an internal-heated pressure vessels at P=0.2-0.6 GPa by a quenching technique. Our findings disagree with all previous studies demonstrating the positive [7] or negative [8, 9] influence of pressure on the solubility of sulfur in silicate melts. Our researches have shown complicated influence of pressure. Concentration of sulfur in glasses increases with increase in pressure from 0.2 to 0.6 GPa in experiments where andesite was used as a starting material. The sulfur concentration increases from 0.09 wt.% at 0.2 GPa to 0.4 wt.% at 0.6 GPa and Т=1200°С. In hydrous magnesian basalts (12-18 % MgO), we

Copper Diffusion in Silicate Melts and Melt Inclusion Study on Volatiles in The Lunar Interior

NASA Astrophysics Data System (ADS)

Ni, Peng

This thesis focuses on the application of diffusion kinetics to both terrestrial and lunar geochemistry. In Chapters II and III, diffusivities of Cu in silicate melts were experimentally determined and used to discuss the role of Cu diffusion in formation of Cu ore deposits and also Cu isotope fractionation in tektites. In Chapters IV and V, lunar olivine-hosted melt inclusions are studied to understand their volatile loss during homogenization in lab, to estimate cooling rate for lunar Apollo sample 74220, and to estimate volatile abundance in the lunar mantle. Magmatic sulfide deposits and porphyry-type Cu deposits are two major types of Cu deposits that supply the world's Cu. In particular, porphyry-type Cu deposits provide ˜57% of the world's total discovered Cu. Recent studies suggest a potential role of diffusive transport of metals (e.g. Cu, Au, PGE, Mo) in the formation of magmatic sulfide deposits and porphyry-type deposits. Diffusivities of Cu in silicate melts, however, are poorly determined. In Chapters II and III of this thesis, Cu diffusion in basaltic melt and rhyolitic melts are studied by diffusion couple and chalcocite "dissolution" methods. Our results indicate high diffusivities of Cu and a general equation for Cu diffusion in silicate melts is obtained. The high diffusivity of Cu indicate that partition of Cu between the silicate phase and the sulfide or fluid phase can be assumed to be in equilibrium during the formation of magmatic sulfide deposits or porphyry-type deposits. In addition, our Cu diffusion data helps explain why Cu isotopes are more fractionated than Zn isotopes in tektites. Volatile abundances in the lunar mantle have profound implications for the origin of the Moon, which was thought to be bone-dry till about a decade ago, when trace amounts of H2O were detected in various types of lunar samples. In particular, high H2O concentrations comparable to mid-ocean ridge basalts were reported in lunar melt inclusions. There are

Metal/Silicate Partitioning of W, Ge, Ga and Ni: Dependence on Silicate Melt Composition

NASA Astrophysics Data System (ADS)

Singletary, S.; Drake, M. J.

2004-12-01

Metal/silicate partition coefficients (Dm/s) for siderophile elements are essential to investigations of core formation when used in conjunction with the pattern of elemental abundances in the Earth's mantle (Drake and Righter, 2002; Jones and Drake, 1986; Righter et al. 1997). The partitioning of siderophile elements is controlled by temperature, pressure, oxygen fugacity, and by the compositions of the metal and silicate phases. In this work, we investigate the role of silicate melt composition on the partitioning of the siderophile elements W, Ge, Ga and Ni between metallic and silicate liquid. Experiments were performed in the Experimental Geochemistry Laboratory at the University of Arizona utilizing a non-end loaded piston cylinder apparatus with a barium carbonate pressure medium. Starting materials were created by combining the mafic and silicic compositions of Jaeger and Drake (2000) with Fe powder (~25 wt% of the total mixture) to achieve metal saturation. Small amounts of W, Ge, Ga2O3 and NiO powder (less than 2 wt% each) were also added to the starting compositions. The experiments were contained in a graphite capsule and performed with temperature and pressure fixed at 1400ºC and 1.5 GPa. Experimental run products were analyzed with the University of Arizona Cameca SX50 electron microprobe with four wavelength dispersive spectrometers and a PAP ZAF correction program. All experiments in our set are saturated with metal and silicate liquid, indicating that oxygen fugacity is below IW. Several of the runs also contain a gallium-rich spinel as an additional saturating phase. Quench phases are also present in the silicate liquid in all runs. The experimentally produced liquids have nbo/t values (calculated using the method of Mills, 1993) that range from 1.10 to 2.97. These values are higher than those calculated for the liquids in the Jaeger and Drake (2000) study. The higher nbo/t values are due to uptake of Fe by the melt. The initial silicate

Metal/Silicate Partitioning, Melt Speciation, Accretion, and Core Formation in the Earth

NASA Astrophysics Data System (ADS)

Drake, M. J.; Hillgren, V. J.; Dearo, J. A.; Capobianco, C. J.

1993-07-01

Core formation in terrestrial planets was concomitant with accretion. Siderophile and chalcophile element signatures in the mantles of planets are the result of these processes. For Earth, abundances of most siderophile and chalcophile elements are elevated relative to predictions from simple metal/silicate equilibria at low pressures [1]. This observation has led to three hypotheses for how these abundances were established: heterogeneous accretion [2], inefficient core formation [3], and metal/silicate equilibria at magma ocean pressures and temperatures [4]. Knowledge of speciation of siderophile elements in silicate melts in equilibrium with metal may help distinguish between these hypotheses. But there is some uncertainty regarding speciation. For example, Ni and Co have been reported to be present as 1+ or zero valence species in silicate melts at redox states appropriate to planetary accretion, rather than the expected 2+ state [5-7]. Independent metal/silicate partitioning experiments by three members of this group using two different experimental designs on both synthetic and natural compositions do not show evidence for Ni and Co in valence states other than 2+ over a wide range of redox states. For example, solid metal/silicate melt partition coefficients for Ni at 1260 degrees C obtained by VJH from experiments investigating the partitioning of Ni, Co, Mo, W, and P are indistinguishable from those obtained by JAD in similar experiments investigating the partitioning of Ni, Ge, and Sn. Both datasets define a line with the equation: log D(Ni) = - 0.54log fO2 - 3.14 with r^2 > 0.995. (Note that fO2 was calculated in both studies from thermodynamic data and phase compositions. A small, systematic offset from the true fO2 as measured by a solid electrolyte cell affects both equations similarly, but does not diminish their close agreement.) The valence of Ni in the silicate melt is obtained by multiplying the slope of the line by -4, indicating divalent Ni in

Nanoscale Origin of the Dichotimous Viscosity-Pressure Behavior in Silicate Melts

NASA Astrophysics Data System (ADS)

Wang, Y.; Sakamaki, T.; Skiner, L.; Jing, Z.; Yu, T.; Kono, Y.; Park, C.; Shen, G.; Rivers, M. L.; Sutton, S. R.

2013-12-01

A defining characteristic of silicate melts is the degree of polymerization (tetrahedral connectivity), which dictates physical properties such as viscosity and density. While viscosity of depolymerized silicate melts increases with pressure consistent with free volume theory, isothermal viscosity of polymerized melts decreases with pressure up to ~3 - 5 GPa, above which it turns over to normal (positive) pressure dependence. We conducted high-pressure melt structure studies along the jadeite (Jd) - diopside (Di) join, using a Paris-Edinburgh Press at the HPCAT beamline 16-BM-B and measured Jd melt density using a DIA type apparatus based on x-ray absorption at GSECARS beamline 13-BM-D. Structures of polymerized (Jd and Jd50Di50) and depolymerized (Di) melts show distinct responses to pressure. For Jd melt, T-O, T-T bond lengths (where T denotes tetrahedrally coordinated Al and Si) and T-O-T angle all exhibit rapid, sometimes non-linear decrease with increasing pressure to ~3 GPa. For Di melt, these parameters vary linearly with pressure and change very little. Molecular dynamics calculations, constrained by the x-ray structural data, were employed to examine details of structural evolution in polymerized and depolymerized liquids. A structural model is developed to link structural evolution to changes in melt properties, such as density and viscosity, with pressure. We show that the pressure of the viscosity turnover corresponds to the tetrahedral packing limit, below which the structure is compressed through tightening of the inter-tetrahedral bond angle, resulting in continual breakup of tetrahedral connectivity and viscosity decrease. Above the turnover pressure, Si and Al coordination increases to allow further packing, with increasing viscosity. This structural response prescribes the distribution of melt viscosity and density with depth, and may be the main controlling factor for magma transport rates in terrestrial planetary interiors.

Silicate melts density, buoyancy relations and the dynamics of magmatic processes in the upper mantle

NASA Astrophysics Data System (ADS)

Sanchez-Valle, Carmen; Malfait, Wim J.

2016-04-01

Although silicate melts comprise only a minor volume fraction of the present day Earth, they play a critical role on the Earth's geochemical and geodynamical evolution. Their physical properties, namely the density, are a key control on many magmatic processes, including magma chamber dynamics and volcanic eruptions, melt extraction from residual rocks during partial melting, as well as crystal settling and melt migration. However, the quantitative modeling of these processes has been long limited by the scarcity of data on the density and compressibility of volatile-bearing silicate melts at relevant pressure and temperature conditions. In the last decade, new experimental designs namely combining large volume presses and synchrotron-based techniques have opened the possibility for determining in situ the density of a wide range of dry and volatile-bearing (H2O and CO2) silicate melt compositions at high pressure-high temperature conditions. In this contribution we will illustrate some of these progresses with focus on recent results on the density of dry and hydrous felsic and intermediate melt compositions (rhyolite, phonolite and andesite melts) at crustal and upper mantle conditions (up to 4 GPa and 2000 K). The new data on felsic-intermediate melts has been combined with in situ data on (ultra)mafic systems and ambient pressure dilatometry and sound velocity data to calibrate a continuous, predictive density model for hydrous and CO2-bearing silicate melts with applications to magmatic processes down to the conditions of the mantle transition zone (up to 2773 K and 22 GPa). The calibration dataset consist of more than 370 density measurements on high-pressure and/or water-and CO2-bearing melts and it is formulated in terms of the partial molar properties of the oxide components. The model predicts the density of volatile-bearing liquids to within 42 kg/m3 in the calibration interval and the model extrapolations up to 3000 K and 100 GPa are in good agreement

Core Formation: an Experimental Study of Metallic Melt-Silicate Segregation

NASA Astrophysics Data System (ADS)

Herpfer, M. A.; Larimer, J. W.

1993-07-01

To a large extent, the question of how metallic cores form reduces to the problem of understanding the surface tension between metallic melts and silicates [1]. This problem was addressed by performing experiments to determine the surface tensions between metallic melts with variable S contents and the silicate phases (olivine and orthopyroxene) expected in planetary mantles. The experiments were conducted in a piston-cylinder apparatus at P = 1GPa and T = 1250-1450 degrees C. Textural and chemical equilibration was confirmed in several ways: theoretical estimates were checked by conducting a series of experiments at progressively longer times (up to 72 hrs) until phase composition and dihedral angle ceased to change and the distribution of measured "apparent" angles matched the standard cumulative frequency curve. The dihedral "wetting" angles (theta) were measured from high resolution photomicrgraphs using a 10X optical protractor; 100-400 measurements were made for most experiments. The dihedral angle is related to the ratio of interfacial energies: gamma(sub)ss/gamma(sub)sl = 2 cos(theta/2), where gamma(sub)ss and gamma(sub)sl are the interfacial energies between solid-solid and liquid-solid. Since data exist for the pertinent solid-solid energies, the liquid-solid interfacial energies can be computed from measured theta values. However, the important relations are best expressed in terms of theta values. The extent to which a melt is interconnected along grain boundaries, and hence able to flow and segregate depends on the value of theta and the fraction of melt present. When theta < 60 degrees, the liquid can be interconnected at all melt fractions but when theta > 60 degrees, the melt fraction must be at least 1 vol% and increses as theta increases. Actually there is a predicted effect, analogous to a hysteresis effect, where for a given theta value the amount of melt that needs to be added for interconnection is greater than the amount left when the melt

The effect of melt composition on the partitioning of trace elements between titanite and silicate melt

NASA Astrophysics Data System (ADS)

Prowatke, S.; Klemme, S.

2003-04-01

The aim of this study is to systematically investigate the influence of melt composition on the partitioning of trace elements between titanite and different silicate melts. Titanite was chosen because of its important role as an accessory mineral, particularly with regard to intermediate to silicic alkaline and calc-alkaline magmas [e.g. 1] and of its relative constant mineral composition over a wide range of bulk compositions. Experiments at atmospheric pressure were performed at temperatures between 1150°C and 1050°C. Bulk compositions were chosen to represent a basaltic andesite (SH3 - 53% SiO2), a dacite (SH2 - 65 SiO2) and a rhyolite (SH1 - 71% SiO2). Furthermore, two additional experimental series were conducted to investigate the effect of Al-Na and the Na-K ratio of melts on partitioning. Starting materials consisted of glasses that were doped with 23 trace elements including some selected rare earth elements (La, Ce, Pr, Sm, Gd, Lu), high field strength elements (Zr, Hf, Nb, Ta) and large ion lithophile elements (Cs, Rb, Ba) and Th and U. The experimental run products were analysed for trace elements using secondary ion mass spectrometry at Heidelberg University. Preliminary results indicate a strong effect of melt composition on trace element partition coefficients. Partition coefficients for rare-earth elements uniformly show a convex-upward shape [2, 3], since titanite accommodates the middle rare-earth elements more readily than the light rare-earth elements or the heavy rare-earth elements. Partition coefficients for the rare-earth elements follow a parabolic trend when plotted against ionic radius. The shape of the parabola is very similar for all studied bulk compositions, the position of the parabola, however, is strongly dependent on bulk composition. For example, isothermal rare-earth element partition coefficients (such as La) are incompatible (D<1) in alkali-rich silicate melts and strongly compatible (D>>1) in alkali-poor melt compositions

Pt, Au, Pd and Ru Partitioning Between Mineral and Silicate Melts: The Role of Metal Nanonuggets

NASA Technical Reports Server (NTRS)

Malavergne, V.; Charon, E.; Jones, J.; Agranier, A.; Campbell, A.

2012-01-01

The partition coefficients of Pt and other Pt Group Elements (PGE) between metal and silicate D(sub Metal-Silicate) and also between silicate minerals and silicate melts D(sub Metal-Silicate) are among the most challenging coefficients to obtain precisely. The PGE are highly siderophile elements (HSE) with D(sub Metal-Silicate) >10(exp 3) due to the fact that their concentrations in silicates are very low (ppb to ppt range). Therefore, the analytical difficulty is increased by the possible presence of HSE-rich-nuggets in reduced silicate melts during experiments). These tiny HSE nuggets complicate the interpretation of measured HSE concentrations. If the HSE micro-nuggets are just sample artifacts, then their contributions should be removed before calculations of the final concentration. On the other hand, if they are produced during the quench, then they should be included in the analysis. We still don't understand the mechanism of nugget formation well. Are they formed during the quench by precipitation from precursor species dissolved homogeneously in the melts, or are they precipitated in situ at high temperature due to oversaturation? As these elements are important tracers of early planetary processes such as core formation, it is important to take up this analytical and experimental challenge. In the case of the Earth for example, chondritic relative abundances of the HSE in some mantle xenoliths have led to the concept of the "late veneer" as a source of volatiles (such as water) and siderophiles in the silicate Earth. Silicate crystal/liquid fractionation is responsible for most, if not all, the HSE variation in the martian meteorite suites (SNC) and Pt is the element least affected by these fractionations. Therefore, in terms of reconstructing mantle HSE abundances for Mars, Pt becomes a very important player. In the present study, we have performed high temperature experiments under various redox conditions in order to determine the abundances of Pt, Au

Experimental investigation on V isotope equilibrium fractionation factor between metal and silicate melt

NASA Astrophysics Data System (ADS)

Zhang, S.; Zhang, H.; Huang, F.

2017-12-01

Equilibrium fractionation factors of stable isotopes between metal and silicate melt are of vital importance for understanding the isotope variations within meteorites and planetary bodies. The V isotope composition (reported as δ51V = 1000 × [(51V/50Vsample/51V/50VAA)-1] ) of the bulk silicate Earth (BSE) has been estimated as δ51V = -0.7 ± 0.2‰ (2sd) [1], which is significantly heavier than most meteorites by 1‰ [2]. Such isotopic offset may provide insights for the core formation and core-mantle segregation. Therefore, it is important to understand V isotope equilibrium fractionation factor between silicate melt and metal. Nielsen et al. (2014) [2] had performed 3 experiments using starting materials of pure Fe metal and An50Di28Fo22 composition, revealing no resolvable V isotope fractionation. However, it is not clear whether chemical compositions in the melts can affect V isotope fractionations. Therefore, we experimentally calibrated equilibrium V isotope fractionation between Fe metallic and basaltic melt, with particular focus on the effect of Ni and other light elements. Experiments were performed at 1 GPa and 1600 oC using a 3/4″ end-loaded piston cylinder. The starting materials consisted of 1:1 mixture of pure Fe metal and basaltic composition [3]. The isotope equilibrium was assessed using time series experiments combined with the reverse reaction method. Carbon saturation and C-free experiments were achieved by using graphite and silica capsules, respectively. The Ni series experiments were doped with 6 wt% Ni into the starting Fe metal. The metal and silicate phases of samples were mechanically separated, V was purified using a chromatographic technique, and V isotope ratios were measured using MC-ICP-MS [4]. Carbon saturation, C-free experiments and Ni series experiment all show non-resolvable V isotope fractionation between metal and basaltic melt, which indicates that the presence of C and Ni could not affect V isotope fractionation

VOLATILECALC: A silicate melt-H2O-CO2 solution model written in Visual Basic for excel

USGS Publications Warehouse

Newman, S.; Lowenstern, J. B.

2002-01-01

We present solution models for the rhyolite-H2O-CO2 and basalt-H2O-CO2 systems at magmatic temperatures and pressures below ~ 5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within MicrosoftR Excel (Office'98 and 2000). The series of macros, entitled VOLATILECALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H2O and CO2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H2O and CO2 vapors at magmatic temperatures. The basalt-H2O-CO2 macros in VOLATILECALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar. ?? 2002 Elsevier Science Ltd. All rights reserved.

High-temperature apparatus for chaotic mixing of natural silicate melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morgavi, D.; Petrelli, M.; Vetere, F. P.

2015-10-15

A unique high-temperature apparatus was developed to trigger chaotic mixing at high-temperature (up to 1800 °C). This new apparatus, which we term Chaotic Magma Mixing Apparatus (COMMA), is designed to carry out experiments with high-temperature and high-viscosity (up to 10{sup 6} Pa s) natural silicate melts. This instrument allows us to follow in time and space the evolution of the mixing process and the associated modulation of chemical composition. This is essential to understand the dynamics of magma mixing and related chemical exchanges. The COMMA device is tested by mixing natural melts from Aeolian Islands (Italy). The experiment was performed atmore » 1180 °C using shoshonite and rhyolite melts, resulting in a viscosity ratio of more than three orders of magnitude. This viscosity ratio is close to the maximum possible ratio of viscosity between high-temperature natural silicate melts. Results indicate that the generated mixing structures are topologically identical to those observed in natural volcanic rocks highlighting the enormous potential of the COMMA to replicate, as a first approximation, the same mixing patterns observed in the natural environment. COMMA can be used to investigate in detail the space and time development of magma mixing providing information about this fundamental petrological and volcanological process that would be impossible to investigate by direct observations. Among the potentials of this new experimental device is the construction of empirical relationships relating the mixing time, obtained through experimental time series, and chemical exchanges between the melts to constrain the mixing-to-eruption time of volcanic systems, a fundamental topic in volcanic hazard assessment.« less

High-temperature apparatus for chaotic mixing of natural silicate melts.

PubMed

Morgavi, D; Petrelli, M; Vetere, F P; González-García, D; Perugini, D

2015-10-01

A unique high-temperature apparatus was developed to trigger chaotic mixing at high-temperature (up to 1800 °C). This new apparatus, which we term Chaotic Magma Mixing Apparatus (COMMA), is designed to carry out experiments with high-temperature and high-viscosity (up to 10(6) Pa s) natural silicate melts. This instrument allows us to follow in time and space the evolution of the mixing process and the associated modulation of chemical composition. This is essential to understand the dynamics of magma mixing and related chemical exchanges. The COMMA device is tested by mixing natural melts from Aeolian Islands (Italy). The experiment was performed at 1180 °C using shoshonite and rhyolite melts, resulting in a viscosity ratio of more than three orders of magnitude. This viscosity ratio is close to the maximum possible ratio of viscosity between high-temperature natural silicate melts. Results indicate that the generated mixing structures are topologically identical to those observed in natural volcanic rocks highlighting the enormous potential of the COMMA to replicate, as a first approximation, the same mixing patterns observed in the natural environment. COMMA can be used to investigate in detail the space and time development of magma mixing providing information about this fundamental petrological and volcanological process that would be impossible to investigate by direct observations. Among the potentials of this new experimental device is the construction of empirical relationships relating the mixing time, obtained through experimental time series, and chemical exchanges between the melts to constrain the mixing-to-eruption time of volcanic systems, a fundamental topic in volcanic hazard assessment.

Synchrotron X-ray spectroscopic investigations of an Nb-bearing silicate melt in contact with an aqueous fluid

NASA Astrophysics Data System (ADS)

Mayanovic, R. A.; Anderson, A. J.; Bassett, W. A.; Chou, I.

2006-05-01

Understanding the structural properties of trace elements in hydrous silicate melts in contact with a hydrothermal fluid is fundamentally important for a better assessment of the role of such elements in silicate melts being subjected to hydrothermal processes. We describe the use of synchrotron x-ray microprobe techniques and the modified hydrothermal diamond-anvil cell for in-situ spectroscopic analysis of individual phases of a silicate-melt/fluid system. Synchrotron X-ray fluorescence (XRF) and Nb K-edge X-ray absorption fine structure (XAFS) measurements were made on sectors ID20 and ID13 at the Advanced Photon Source, at the Argonne National Laboratory, on a Nb-bearing granitic glass in H2O and separately in a 1 M Na2CO3 aqueous solution at temperatures ranging from 25 to 880 °C and at up to 700 MPa of pressure. Individual phases of the Nb-glass/fluid system (at low temperatures) or the hydrous-silicate-melt/fluid system (at elevated temperatures) were probed using an X-ray beam focused to a diameter of 5 μm at the location of the sample. XRF analysis shows that the Nb partitions selectively from the hydrous silicate melt into the aqueous fluid at high temperatures in the Nb-glass/Na2CO3/H2O system but not so in the Nb-glass/H2O system. Analysis of XAFS spectra measured from the hydrous silicate melt phase of the Nb-glass/H2O sample in the 450 to 700 °C range shows that the first shell contains six oxygen atoms at a distance of ~1.98 Å. Our results suggest that reorganization of the silicate structure surrounding Nb occurs in the melt when compared to that of the starting glass. The X-ray absorption near edge structure (XANES) spectra show a pre-edge peak feature located at ~18995 eV that exhibits sharpening and becomes more intensified in the 450 to 700 °C range. Fitting of the Nb K-edge XANES spectra measured from the melt is accomplished using FEFF8.28 and an atomic model NbSi4O6-4(Na, K). The model is based on the structure of fresnoite (Ba2TiSi2O8

Partitioning of Moderately Siderophile Elements Among Olivine, Silicate Melt, and Sulfide Melt: Constraints on Core Formation in the Earth and Mars

NASA Technical Reports Server (NTRS)

Gaetani, Glenn A.; Grove, Timothy L.

1997-01-01

This study investigates the effects of Variations in the fugacities of oxygen and sulfur on the partitioning of first series transition metals (V, Cr, Mn, Fe, Co, Ni. and Cu) and W among coexisting sulfide melt, silicate melt, and olivine. Experiments were performed at 1 atm pressure, 1350 C, with the fugacities of oxygen and sulfur controlled by mixing CO2, CO, and SO2 gases. Starting compositions consisted of a CaO-MgO-Al2O3-SiO2-FeO-Na2O analog for a barred olivine chondrule from an ordinary chondrite and a synthetic komatiite. The f(sub O2)/f(sub S2), conditions ranged from log of f(sub O2) = -7.9 to - 10.6, with log of f(sub S2) values ranging from - 1.0 to -2.5. Our experimental results demonstrate that the f(sub O2)/f(sub S2) dependencies of sulfide melt/silicate melt partition coefficients for the first series transition metals arc proportional to their valence states. The f(sub O2)/f(sub S2) dependencies for the partitioning of Fe, Co, Ni, and Cu are weaker than predicted on the basis of their valence states. Variations in conditions have no significant effect on olivine/melt partitioning other than those resulting from f(sub O2)-induced changes in the valence state of a given element. The strong f(sub O2)/f(sub S2) dependence for the olivine/silicate melt partitioning of V is attributable to a change of valence state, from 4+ to 3+, with decreasing f(sub O2). Our experimentally determined partition coefficients are used to develop models for the segregation of sulfide and metal from the silicate portion of the early Earth and the Shergottite parent body (Mars). We find that the influence of S is not sufficient to explain the overabundance of siderophile and chalcophile elements that remained in the mantle of the Earth following core formation. Important constraints on core formation in Mars are provided by our experimental determination of the partitioning of Cu between silicate and sulfide melts. When combined with existing estimates for siderophile

Al Speciation in Silicate Melts: AlV a new Network Former?

NASA Astrophysics Data System (ADS)

Neuville, D. R.; Florian, P.; de Ligny, D.; Montouillout, V.; Massiot, D.

2009-05-01

The first human glasses were made 3500 BC. It was essentially sodo-lime silicate glass. To improve the chemical resistance, the thermal properties and increase the viscosity it is interesting to add aluminum in these silicates. But what is the speciation of the aluminum and how it varies according to the chemical composition and to the temperature? The aluminum appears essentially in four or five fold coordination in glasses and melts melted. The proportion of [5]Al varies according to the alkaline or to the earth-alkaline content and to the temperature. We shall present in a first part the influence of the network-modifier on the proportion of [5]Al and then we shall present some new results of absorption of high-temperature using NMR and XANES spectroscopy at the Al K-edge. Finally, from glass transition temperature measurements we propose to explain that [5]Al can be a new network former.

Partitioning of copper between olivine, orthopyroxene, clinopyroxene, spinel, garnet and silicate melts at upper mantle conditions

NASA Astrophysics Data System (ADS)

Liu, Xingcheng; Xiong, Xiaolin; Audétat, Andreas; Li, Yuan; Song, Maoshuang; Li, Li; Sun, Weidong; Ding, Xing

2014-01-01

Previously published Cu partition coefficients (DCu) between silicate minerals and melts cover a wide range and have resulted in large uncertainties in model calculations of Cu behavior during mantle melting. In order to obtain true DCumineral/melt values, this study used Pt95Cu05 alloy capsules as the source of Cu to experimentally determine the DCu between olivine (ol), orthopyroxene (opx), clinopyroxene (cpx), spinel (spl), garnet (grt) and hydrous silicate melts at upper mantle conditions. Three synthetic silicate compositions, a Komatiite, a MORB and a Di70An30, were used to produce these minerals and melts. The experiments were conducted in piston cylinder presses at 1.0-3.5 GPa, 1150-1300 °C and oxygen fugacities (fO2) of from ∼2 log units below to ∼5 log units above fayalite-magnetite-quartz (FMQ). The compositions of minerals and quenched melts in the run products were measured with EMP and LA-ICP-MS. Attainment of equilibrium is verified by reproducible DCu values obtained at similar experimental conditions but different durations. The results show that DCu for ol/, opx/, spl/ and possibly cpx/melt increase with increasing fO2 when fO2 > FMQ + 1.2, while DCu for cpx/ and spl/melt also increase with increasing Na2O in cpx and Fe2O3 in spinel, respectively. In the investigated P-T-fO2 conditions, the DCumineral/melt values are 0.04-0.14 for ol, 0.04-0.09 for opx, 0.02-0.23 for cpx, 0.19-0.77 for spl and 0.03-0.05 for grt. These results confirm that Cu is highly incompatible (DCu < ∼0.2) in all the silicate minerals and oxides of the upper mantle with the exception of the high-Fe spinel, in which Cu is moderately incompatible (DCu = 0.4-0.8) and thus Cu will be enriched in the derived melts during mantle partial melting and magmatic differentiation if sulfide is absent. These experimental DCu values are used to assess the controls on Cu behavior during mantle melting. The model results suggest that MORBs and most arc basalts must form by sulfide

Experimental study of the electrolysis of silicate melts

NASA Technical Reports Server (NTRS)

Keller, Rudolf

1992-01-01

Melting and electrolyzing lunar silicates yields oxygen gas and potentially can be practiced in situ to produce oxygen. With the present experiments conducted with simulant oxides at 1425-1480 C, it was ascertained that oxygen can be obtained anodically at feasible rates and current efficiencies. An electrolysis cell was operated with platinum anodes in a sealed vessel, and the production of gas was monitored. In these electrolysis experiments, stability of anodes remained a problem, and iron and silicon did not reduce readily into the liquid silver cathode.

Using MELTS to understand the evolution of silicic magmas: Challenges and successes in modeling the Highland Range Volcanic Sequence (NV)

NASA Astrophysics Data System (ADS)

Vaum, R. C.; Gualda, G. A.; Ghiorso, M. S.; Miller, C. F.; Colombini, L. L.

2009-12-01

The Highland Range near Searchlight, Nevada is comprised of mid-Miocene, intermediate to silicic volcanic rocks. This study focuses on the most silicic portion of the eruptive sequence (16.0-16.5 Ma). The first eruptions during this interval were effusive and produced trachydacite (66-70 wt% SiO2), but later the eruptive style shifted to explosive and compositions were more evolved (70-78 wt% SiO2). Glass compositions in rocks saturated in both quartz and sanidine align along the 150 MPa quartz+sanidine saturation surface, suggesting that the Highland Range magmas equilibrated in a single reservoir at that pressure. We are interested in better understanding this transition in eruptive style from effusive to eruptive, and our approach is based on modeling melt evolution using MELTS thermodynamic modeling software. We selected representative samples from key stratigraphic units, and focused on samples for which whole-rock and glass compositions, as well as mineral abundances, are available. This allows for direct comparison of simulation results with existing data. Initial simulations showed that MELTS predicts unrealistic paths of evolution when compared to the glass compositions and to the phase relations in the Qz-Ab-Or ternary. In particular, the stability field of quartz predicted by MELTS is much too small, causing melts to become exceedingly silicic (>80 wt% SiO2). Sanidine, on the other hand, has fairly sodic compositions and crystallizes too early in the sequence; therefore, simulated melt compositions are never as potassic as the analyzed glasses. Similar results are obtained when modeling the evolution of the Bishop and Campanian magmas, showing that these are systematic problems in MELTS calibration. Accordingly, we have adjusted the enthalpy of quartz and potassium end-member of the feldspar solid solution in MELTS so that the quartz-sanidine saturation surface is correctly predicted. We find that this modified version of MELTS much better models the

The solubility of gold in silicate melts: First results

NASA Technical Reports Server (NTRS)

Borisov, A.; Palme, H.; Spettel, B.

1993-01-01

The effects of oxygen fugacity and temperature on the solubility of Au in silicate melts were determined. Pd-Au alloys were equilibrated with silicate of anorthite-diopside eutectic composition at different T-fO2 conditions. The behavior of Au was found to be similar to that of Pd reported recently. Au solubilities for alloys with 30 to 40 at. percent Au decrease at 1400 C from 12 ppm in air to 160 ppb at a log fO2 = -8.7. The slope of the log(Me-solubility) vs. log(fO2) curve is close to 1/4 for Au and the simultaneously determined Pd suggesting a formal valence of Au and Pd of 1+. Near the IW buffer Pd and Au solubilities become even less dependent on fO2 perhaps reflecting the presence of some metallic Au and Pd.

Immiscible Transition from Carbonate-rich to Silicate-rich Melts in Eclogite+CO2 and Genesis of Ocean Island Melilitite

NASA Astrophysics Data System (ADS)

Dasgupta, R.; Stalker, K.; Hirschmann, M. M.

2004-12-01

Derivation of highly silica-undersaturated lavas such as olivine melilitites and melilite nephelinites from the mantle has been attributed to the effects of CO2. However, experimental studies have so far failed to demonstrate equilibrium of melilititic melts with a four-phase peridotite assemblage. Instead, the liquidus mineralogy of these silica-undersaturated magmas at high-pressures appears to be dominated by cpx1. Although, experimental partial melts from natural peridotite+CO2 span a continuum from carbonatite to alkali-basalts2, ocean-island melilitites have distinctly higher TiO2, FeO*, and CaO/(CaO+MgO)3,4 than compositions derived thus far from a carbonated lherzolite source. Partial melting experiments of a nominally anhydrous, natural eclogite with a small amount of added carbonate (SLEC1; 5 wt.% bulk CO2) were performed to investigate the transition between carbonate and silicate melts with increasing temperature. Experiments were conducted in a piston cylinder at 3 GPa from 1050 to 1400 ° C. Garnet and cpx appear in all the experiments and ilmenite is observed from 1075 to ˜1200 ° C. An Fe-bearing calcio-dolomitic melt is present from the solidus (1050-1075 ° C) up to 1375 ° C. Beginning at 1275 ° C, it coexists with a silica-poor silicate melt. Textural criteria indicate only a single CO2-rich silicate melt phase at 1400 ° C, coexisting with garnet and minor cpx. The liquidus temperature is estimated to be ˜1415 ° C from the melt fraction-temperature trend. With increasing temperature, the carbonate melt becomes richer in SiO2 ( ˜2 to 5 wt.%) and Al2O3 ( ˜0.75 to 2.25 wt.%) and poorer in CaO ( ˜30 to 25 wt.% from ˜1200 to 1375 ° C). Compositions of silicate partial melts change systematically with increasing temperature, increasing in SiO2 ( ˜36 to 41 wt.%), Al2O3 ( ˜4.5 to 9.5 wt.%), MgO ( ˜9.5 to 13 wt.%), CaO ( ˜8 to 14 wt.%) and decreasing in TiO2 ( ˜14 to 2.5 wt.%), FeO ( ˜20 to 13 wt.%), Na2O ( ˜3.3 to 1.7 wt.%). A wide

Experimental, in-situ carbon solution mechanisms and isotope fractionation in and between (C-O-H)-saturated silicate melt and silicate-saturated (C-O-H) fluid to upper mantle temperatures and pressures

NASA Astrophysics Data System (ADS)

Mysen, Bjorn

2017-02-01

Our understanding of materials transport processes in the Earth relies on characterizing the behavior of fluid and melt in silicate-(C-O-H) systems at high temperature and pressure. Here, Raman spectroscopy was employed to determine structure of and carbon isotope partitioning between melts and fluids in alkali aluminosilicate-C-O-H systems. The experimental data were recorded in-situ while the samples were at equilibrium in a hydrothermal diamond anvil cell at temperatures and pressures to 825 °C and >1300 MPa, respectively. The carbon solution equilibrium in both (C-O-H)-saturated melt and coexisting, silicate-saturated (C-O-H) fluid is 2CO3 + H2O + 2Qn + 1 = 2HCO3 + 2Qn. In the Qn-notation, the superscript, n, is the number of bridging oxygen in silicate structural units. At least one oxygen in CO3 and HCO3 groups likely is shared with silicate tetrahedra. The structural behavior of volatile components described with this equilibrium governs carbon isotope fractionation factors between melt and fluid. For example, the ΔH equals 3.2 ± 0.7 kJ/mol for the bulk 13C/12C exchange equilibrium between fluid and melt. From these experimental data, it is suggested that at deep crustal and upper mantle temperatures and pressures, the δ13C-differences between coexisting silicate-saturated (C-O-H) fluid and (C-O-H)-saturated silicate melts may change by more than 100‰ as a function of temperature in the range of magmatic processes. Absent information on temperature and pressure, the use of carbon isotopes of mantle-derived magma to derive isotopic composition of magma source regions in the Earth's interior, therefore, should be exercised with care.

V OLATILEC ALC: a silicate melt-H 2O-CO 2 solution model written in Visual Basic for excel

NASA Astrophysics Data System (ADS)

Newman, Sally; Lowenstern, Jacob B.

2002-06-01

We present solution models for the rhyolite-H 2O-CO 2 and basalt-H 2O-CO 2 systems at magmatic temperatures and pressures below ˜5000 bar. The models are coded as macros written in Visual Basic for Applications, for use within Microsoft ® Excel (Office'98 and 2000). The series of macros, entitled V OLATILEC ALC, can calculate the following: (1) Saturation pressures for silicate melt of known dissolved H 2O and CO 2 concentrations and the corresponding equilibrium vapor composition; (2) open- and closed-system degassing paths (melt and vapor composition) for depressurizing rhyolitic and basaltic melts; (3) isobaric solubility curves for rhyolitic and basaltic melts; (4) isoplethic solubility curves (constant vapor composition) for rhyolitic and basaltic melts; (5) polybaric solubility curves for the two end members and (6) end member fugacities of H 2O and CO 2 vapors at magmatic temperatures. The basalt-H 2O-CO 2 macros in V OLATILEC ALC are capable of calculating melt-vapor solubility over a range of silicate-melt compositions by using the relationships provided by Dixon (American Mineralogist 82 (1997) 368). The output agrees well with the published solution models and experimental data for silicate melt-vapor systems for pressures below 5000 bar.

The effect of melt composition on metal-silicate partitioning of siderophile elements and constraints on core formation in the angrite parent body

NASA Astrophysics Data System (ADS)

Steenstra, E. S.; Sitabi, A. B.; Lin, Y. H.; Rai, N.; Knibbe, J. S.; Berndt, J.; Matveev, S.; van Westrenen, W.

2017-09-01

We present 275 new metal-silicate partition coefficients for P, S, V, Cr, Mn, Co, Ni, Ge, Mo, and W obtained at moderate P (1.5 GPa) and high T (1683-1883 K). We investigate the effect of silicate melt composition using four end member silicate melt compositions. We identify possible silicate melt dependencies of the metal-silicate partitioning of lower valence elements Ni, Ge and V, elements that are usually assumed to remain unaffected by changes in silicate melt composition. Results for the other elements are consistent with the dependence of their metal-silicate partition coefficients on the individual major oxide components of the silicate melt composition suggested by recently reported parameterizations and theoretical considerations. Using multiple linear regression, we parameterize compiled metal-silicate partitioning results including our new data and report revised expressions that predict their metal-silicate partitioning behavior as a function of P-T-X-fO2. We apply these results to constrain the conditions that prevailed during core formation in the angrite parent body (APB). Our results suggest the siderophile element depletions in angrite meteorites are consistent with a CV bulk composition and constrain APB core formation to have occurred at mildly reducing conditions of 1.4 ± 0.5 log units below the iron-wüstite buffer (ΔIW), corresponding to a APB core mass of 18 ± 11%. The core mass range is constrained to 21 ± 8 mass% if light elements (S and/or C) are assumed to reside in the APB core. Incorporation of light elements in the APB core does not yield significantly different redox states for APB core-mantle differentiation. The inferred redox state is in excellent agreement with independent fO2 estimates recorded by pyroxene and olivine in angrites.

Partial Melting of the Indarch (EH4) Meteorite : A Textural, Chemical and Phase Relations View of Melting and Melt Migration

NASA Technical Reports Server (NTRS)

McCoy, Timothy J.; Dickinson, Tamara L.; Lofgren, Gary E.

2000-01-01

To Test whether Aubrites can be formed by melting of enstatite Chondrites and to understand igneous processes at very low oxygen fugacities, we have conducted partial melting experiments on the Indarch (EH4) chondrite at 1000-1500 C. Silicate melting begins at 1000 C. Substantial melt migration occurs at 1300-1400 C and metal migrates out of the silicate change at 1450 C and approx. 50% silicate partial melting. As a group, our experiments contain three immiscible metallic melts 9Si-, and C-rich), two immiscible sulfide melts(Fe-and FeMgMnCa-rich) and Silicate melt. Our partial melting experiments on the Indarch (EH4) enstatite Chondrite suggest that igneous processes at low fO2 exhibit serveral unique features. The complete melting of sulfides at 1000 C suggest that aubritic sulfides are not relicts. Aubritic oldhamite may have crystallized from Ca and S complexed in the silicate melt. Significant metal-sulfide melt migration might occur at relatively low degrees of silicate partial melting. Substantial elemental exchange occurred between different melts (e.g., between sulfide and silicate, Si between silicate and metal), a feature not observed during experiments at higher fO2. This exchange may help explain the formation of aubrites from known enstatite chondrites.

Anionic Pt in Silicate Melts at Low Oxygen Fugacity: Speciation, Partitioning and Implications for Core Formation Processes on Asteroids

NASA Technical Reports Server (NTRS)

Medard, E.; Martin, A. M.; Righter, K.; Malouta, A.; Lee, C.-T.

2017-01-01

Most siderophile element concentrations in planetary mantles can be explained by metal/ silicate equilibration at high temperature and pressure during core formation. Highly siderophile elements (HSE = Au, Re, and the Pt-group elements), however, usually have higher mantle abundances than predicted by partitioning models, suggesting that their concentrations have been set by late accretion of material that did not equilibrate with the core. The partitioning of HSE at the low oxygen fugacities relevant for core formation is however poorly constrained due to the lack of sufficient experimental constraints to describe the variations of partitioning with key variables like temperature, pressure, and oxygen fugacity. To better understand the relative roles of metal/silicate partitioning and late accretion, we performed a self-consistent set of experiments that parameterizes the influence of oxygen fugacity, temperature and melt composition on the partitioning of Pt, one of the HSE, between metal and silicate melts. The major outcome of this project is the fact that Pt dissolves in an anionic form in silicate melts, causing a dependence of partitioning on oxygen fugacity opposite to that reported in previous studies.

An Interconnected Network of Core-Forming Melts Produced by Shear Deformation

NASA Technical Reports Server (NTRS)

Bruhn, D.; Groebner, N.; Kohlstedt, D. L.

2000-01-01

The formation mechanism of terrestrial planetary is still poorly understood, and has been the subject of numerous experimental studies. Several mechanisms have been proposed by which metal-mainly iron with some nickel-could have been extracted from a silicate mantle to form the core. Most recent models involve gravitational sinking of molten metal or metal sulphide through a partially or fully molten mantle that is often referred to as a'magma ocean. Alternative models invoke percolation of molten metal along an interconnected network (that is, porous flow) through a solid silicate matrix. But experimental studies performed at high pressures have shown that, under hydrostatic conditions, these melts do not form an interconnected network, leading to the widespread assumption that formation of metallic cores requires a magma ocean. In contrast, here we present experiments which demonstrate that shear deformation to large strains can interconnect a significant fraction of initially isolated pockets of metal and metal sulphide melts in a solid matrix of polycrystalline olivine. Therefore, in a dynamic (nonhydrostatic) environment, percolation remains a viable mechanism for the segregation and migration of core-forming melts in a solid silicate mantle.

An interconnected network of core-forming melts produced by shear deformation

PubMed

Bruhn; Groebner; Kohlstedt

2000-02-24

The formation mechanism of terrestrial planetary cores is still poorly understood, and has been the subject of numerous experimental studies. Several mechanisms have been proposed by which metal--mainly iron with some nickel--could have been extracted from a silicate mantle to form the core. Most recent models involve gravitational sinking of molten metal or metal sulphide through a partially or fully molten mantle that is often referred to as a 'magma ocean'. Alternative models invoke percolation of molten metal along an interconnected network (that is, porous flow) through a solid silicate matrix. But experimental studies performed at high pressures have shown that, under hydrostatic conditions, these melts do not form an interconnected network, leading to the widespread assumption that formation of metallic cores requires a magma ocean. In contrast, here we present experiments which demonstrate that shear deformation to large strains can interconnect a significant fraction of initially isolated pockets of metal and metal sulphide melts in a solid matrix of polycrystalline olivine. Therefore, in a dynamic (non-hydrostatic) environment, percolation remains a viable mechanism for the segregation and migration of core-forming melts in a solid silicate mantle.

The solubility of carbon monoxide in silicate melts at high pressures and its effect on silicate phase relations. [in terrestrial and other planetary interiors

NASA Technical Reports Server (NTRS)

Eggler, D. H.; Mysen, B. O.; Hoering, T. C.; Holloway, J. R.

1979-01-01

Autoradiographic analysis and gas chromatography were used to measure the solubility in silicate melts of CO-CO2 vapors (30 to 40% CO by thermodynamic calculation) in equilibrium with graphite at temperatures up to 1700 deg C and pressures to 30 kbar. At near-liquidus temperatures CO-CO2 vapors were found to be slightly more soluble than CO2 alone. As a result of the apparently negative temperature dependence of CO solubility, the solubility of CO-CO2 at superliquidus temperatures is less than that of CO2. Melting points of two silicates were depressed more by CO than by CO2. Phase boundary orientations suggest that CO/CO + CO2 is greater in the liquid than in the vapor. The effect of the presence of CO on periodotite phase relations was investigated, and it was found that melts containing both CO and CO2 are nearly as polymerized as those containing only CO2. These results suggest that crystallization processes in planetary interiors can be expected to be about the same, whether the melts contain CO2 alone or CO2 and CO.

Veins in Silicates of IIE Iron Mont Dieu II: Melt Migration Caused by Impact?

NASA Astrophysics Data System (ADS)

Van Roosbroek, N.; Debaille, V.; Pittarello, L.; Hecht, L.; Claeys, Ph.

2014-09-01

Mont Dieu II is a ~450kg meteorite classified as IIE iron. The primitive silicate inclusions can be linked to the H-chondrites. Thick metal veins with angular clasts crosscut these inclusions and could point to an impact-melt migration formation.

In-situ determination of the oxidation state of iron in Fe-bearing silicate melts

NASA Astrophysics Data System (ADS)

Courtial, P.; Wilke, M.; Potuzak, M.; Dingwell, D. B.

2005-12-01

Terrestrial lavas commonly contain up to 10 wt% of iron. Furthermore, rocks returned from the Moon indicate lunar lava containing up to 25 wt% of iron and planetary scientists estimated that the martian mantle has about 18 wt% of iron. An experimental challenge in dealing with Fe-bearing silicate melts is that the oxidation state, controlling the proportions of ferric and ferrous iron, is a function of composition, oxygen fugacity and temperature and may vary significantly. Further complications concerning iron originate from its potential to be either four-, six- or even five-fold coordinated in both valence states. Therefore, the oxidation state of iron was determined in air for various Fe-bearing silicate melts. Investigated samples were Na-disilicate (NS), one atmosphere anorthite-diopside eutectic (AD) and haplogranitic (HPG8) melts containing up to 20, 20 and 10 wt% of iron, respectively. XANES spectra at the Fe K-edge were collected for all the melts at beamline A1, HASYLAB, Hamburg, using a Si(111) 4-crystal monochromator. Spectra were collected for temperatures up to 1573 K using a Pt-Rh loop as heating device. The Fe oxidation state was determined from the centroid position of the pre-edge feature using the calibration of Wilke et al. (2004). XANES results suggest that oxidation state of iron does not change within error for NS melts with addition of Fe, while AD and HPG8 melts become more oxidised with increasing iron content. Furthermore, NS melts are well more oxidised than AD and HPG8 melts that exhibit relatively similar oxidation states for identical iron contents. The oxidation state of iron for NS melts appears to be slightly temperature-dependent within the temperature range investigated (1073-1573 K). However, this trend is stronger for AD and HPG8 melts. Assuming that glass reflects a picture of the homogeneous equilibria of the melt, the present in-situ Fe-oxidation states determined for these melts were compared to those obtained on quenched

Thermodynamic controls on element partitioning between titanomagnetite and andesitic-dacitic silicate melts

NASA Astrophysics Data System (ADS)

Sievwright, R. H.; Wilkinson, J. J.; O'Neill, H. St. C.; Berry, A. J.

2017-08-01

Titanomagnetite-melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity ( fO2) and temperature ( T) in an andesitic-dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite-melt partitioning of the divalent cations (Mg2+, Mn2+, Co2+, Ni2+, Zn2+) and Cu2+/Cu+ with increasing fO2 between 0.2 and 3.7 log units above the fayalite-magnetite-quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral-melt partitioning of divalent cations, a more rigorous justification of magnetite-melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO2 implies a reciprocal relationship between a(Fe2+O) and a(Fe3+O1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite-melt partitioning of divalent cations with fO2 in magnetite-rich spinel. As a result of this, titanomagnetite-melt partitioning of divalent cations is indirectly sensitive to changes in fO2 in silicic, but less so in mafic bulk systems.

Copper solubility in a basaltic melt and sulfide liquid/silicate melt partition coefficients of Cu and Fe

NASA Astrophysics Data System (ADS)

Ripley, Edward M.; Brophy, James G.; Li, Chusi

2002-09-01

The solubility of copper in a sulfur-saturated basaltic melt has been determined at 1245°C as a function of fO 2 and fS 2. Copper solubilities at log fO 2 values between -8 and -11 fall into two distinct populations as a function of fS 2. At log fS 2 values < -1.65, sulfide liquid that coexists with the basaltic glass quenches to sulfur-poor bornite solid solution. At log fS 2 values in excess of -1.65, the sulfide liquid quenches to a complex intergrowth of sulfur-rich bornite and intermediate solid solution. Copper solubilities in the low-fS 2 population range from 594 to 1550 ppm, whereas those in the high-fS 2 population range from 80 to 768 ppm. Sulfide liquid/silicate liquid partition coefficients (D) for Cu and Fe range from 480 to 1303 and 0.7 to 13.6, respectively. Metal-sulfur complexing in the silicate liquid is shown to be insignificant relative to metal-oxide complexing for Fe but permissible for Cu at high fS 2 values. On log D Fe (sulfide-silicate) and log D Cu (sulfide-silicate) vs. 1/2 (log fS 2 - log fO 2) diagrams, both fS 2 populations show distinct but parallel trends. The observation of two D values for any fS 2/fO 2 ratio indicates nonideal mixing of species involved in the exchange reaction. The two distinct trends observed for both Cu and Fe are thought to be due to variations in activity coefficient ratios (e.g., γ FeO/γ FeS and γ CuO 0.5/γ CuS 0.5). Results of the experiments suggest that accurate assessments of fS 2/fO 2 ratios are required for the successful numerical modeling of processes such as the partial melting of sulfide-bearing mantle and the crystallization of sulfide-bearing magmas, as well as the interpretation of sulfide mineralogical zoning. In addition, the experiments provide evidence for oxide or oxy-sulfide complexing for Cu in silicate magmas and suggest that the introduction of externally derived sulfur to mafic magma may be an important process for the formation of Cu-rich disseminated magmatic sulfide ore

Mantle Mineral/Silicate Melt Partitioning

NASA Astrophysics Data System (ADS)

McFarlane, E. A.; Drake, M. J.

1992-07-01

Introduction: The partitioning of elements among mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. It has been proposed that the elevated Mg/Si ratio of the upper mantle of the Earth is a consequence of the flotation of olivine into the upper mantle (Agee and Walker, 1988). Agee and Walker (1988) have generated a model via mass balance by assuming average mineral compositions to generate upper mantle peridotite. This model determines that upper mantle peridotite could result from the addition of 32.7% olivine and 0.9% majorite garnet into the upper mantle, and subtraction of 27.6% perovskite from the upper mantle (Agee and Walker, 1988). The present contribution uses experimental data to examine the consequences of such multiple phase fractionations enabling an independent evaluation of the above mentioned model. Here we use Mg-perovskite/melt partition coefficients from both a synthetic and a natural system (KLB-1) obtained from this laboratory. Also used are partition coefficient values for majorite garnet/melt, beta spinel/melt and olivine/melt partitioning (McFarlane et al., 1991b; McFarlane et al., 1992). Multiple phase fractionations are examined using the equilibrium crystallization equation and partition coefficient values. The mineral proportions determined by Agee and Walker (1988) are converted into weight fractions and used to compute a bulk partition coefficient value. Discussion: There has been a significant debate concerning whether measured values of trace element partition coefficients permit large-scale fractionation of liquidus phases from an early terrestrial magma ocean (Kato et al., 1988a,b; Walker and Agee, 1989; Drake, 1989; Drake et al., 1991; McFarlane et al., 1990, 1991). It should be noted that it is unclear which, if any, numerical values of partition coefficients are appropriate for examining this question, and certainly the assumptions for the current model must be more fully

Melt segregation from silicic crystal mushes: a critical appraisal of possible mechanisms and their microstructural record

NASA Astrophysics Data System (ADS)

Holness, Marian B.

2018-06-01

One of the outstanding problems in understanding the behavior of intermediate-to-silicic magmatic systems is the mechanism(s) by which large volumes of crystal-poor rhyolite can be extracted from crystal-rich mushy storage zones in the mid-deep crust. The mechanisms commonly invoked are hindered settling, micro-settling, and compaction. The concept of micro-settling involves extraction of grains from a crystal framework during Ostwald ripening and has been shown to be non-viable in the metallic systems for which it was originally proposed. Micro-settling is also likely to be insignificant in silicic mushes, because ripening rates are slow for quartz and plagioclase, contact areas between grains in a crystal mush are likely to be large, and abundant low-angle grain boundaries promote grain coalescence rather than ripening. Published calculations of melt segregation rates by hindered settling (Stokes settling in a crystal-rich system) neglect all but fluid dynamical interactions between particles. Because tabular silicate minerals are likely to form open, mechanically coherent, frameworks at porosities as high as 75%, settling of single crystals is only likely in very melt-rich systems. Gravitationally-driven viscous compaction requires deformation of crystals by either dissolution-reprecipitation or dislocation creep. There is, as yet, no reported microstructural evidence of extensive, syn-magmatic, internally-generated, viscous deformation in fully solidified silicic plutonic rocks. If subsequent directed searches do not reveal clear evidence for internally-generated buoyancy-driven melt segregation processes, it is likely that other factors, such as rejuvenation by magma replenishment, gas filter-pressing, or externally-imposed stress during regional deformation, are required to segregate large volumes of crystal-poor rhyolitic liquids from crustal mushy zones.

Highly CO2-supersaturated melts in the Pannonian lithospheric mantle - A transient carbon reservoir?

NASA Astrophysics Data System (ADS)

Créon, Laura; Rouchon, Virgile; Youssef, Souhail; Rosenberg, Elisabeth; Delpech, Guillaume; Szabó, Csaba; Remusat, Laurent; Mostefaoui, Smail; Asimow, Paul D.; Antoshechkina, Paula M.; Ghiorso, Mark S.; Boller, Elodie; Guyot, François

2017-08-01

Subduction of carbonated crust is widely believed to generate a flux of carbon into the base of the continental lithospheric mantle, which in turn is the likely source of widespread volcanic and non-volcanic CO2 degassing in active tectonic intracontinental settings such as rifts, continental margin arcs and back-arc domains. However, the magnitude of the carbon flux through the lithosphere and the budget of stored carbon held within the lithospheric reservoir are both poorly known. We provide new constraints on the CO2 budget of the lithospheric mantle below the Pannonian Basin (Central Europe) through the study of a suite of xenoliths from the Bakony-Balaton Highland Volcanic Field. Trails of secondary fluid inclusions, silicate melt inclusions, networks of melt veins, and melt pockets with large and abundant vesicles provide numerous lines of evidence that mantle metasomatism affected the lithosphere beneath this region. We obtain a quantitative estimate of the CO2 budget of the mantle below the Pannonian Basin using a combination of innovative analytical and modeling approaches: (1) synchrotron X-ray microtomography, (2) NanoSIMS, Raman spectroscopy and microthermometry, and (3) thermodynamic models (Rhyolite-MELTS). The three-dimensional volumes reconstructed from synchrotron X-ray microtomography allow us to quantify the proportions of all petrographic phases in the samples and to visualize their textural relationships. The concentration of CO2 in glass veins and pockets ranges from 0.27 to 0.96 wt.%, higher than in typical arc magmas (0-0.25 wt.% CO2), whereas the H2O concentration ranges from 0.54 to 4.25 wt.%, on the low end for estimated primitive arc magmas (1.9-6.3 wt.% H2O). Trapping pressures for vesicles were determined by comparing CO2 concentrations in glass to CO2 saturation as a function of pressure in silicate melts, suggesting pressures between 0.69 to 1.78 GPa. These values are generally higher than trapping pressures for fluid inclusions

Redox equilibria and the structural role of iron in alumino-silicate melts

NASA Astrophysics Data System (ADS)

Dickenson, M. P.; Hess, P. C.

1982-01-01

The relationship between the redox ratio Fe+2/(Fe+2+Fe+3) and the K2O/(K2O + Al2O3) ratio (K2O*) were experimentally investigated in silicate melts with 78 mol% SiO2 in the system SiO2-Al2O3-K2O-FeO-Fe2O3, in air at 1,400° C. Quenched glass compositions were analyzed by electron microprobe and wet chemical microtitration techniques. Minimum values of the redox ratio were obtained at K2O*≈0.5. The redox ratio in peralkaline melts (K2O*>0.5) increases slightly with K2O* whereas this ratio increases dramatically in peraluminous melts (K2O*<0.5) as K2O is replaced by Al2O3. These data indicate that all Fe+3 (and Al+3) occur as tetrahedral species charge balanced with K+ in peralkaline melts. In peraluminous melts, Fe+3 (and Al+3) probably occur as both tetrahedral species using Fe+2 as a charge-balancing cation and as network-modifying cations associated with non-bridging oxygen.

Experimental calibration of a new oxybarometer for silicic magmas based on the partitioning of vanadium between magnetite and silicate melt

NASA Astrophysics Data System (ADS)

Arató, Róbert; Audétat, Andreas

2016-04-01

Oxygen fugacity is an important parameter in magmatic systems that affects the stability of mineral phases and fluid species. However, there is no well-established method to reconstruct the oxygen fugacity of slowly cooled magmas such as granite, for example, because existing oxybarometers (e.g., magnetite-ilmenite method) are susceptible to re-equilibration processes during slow cooling and thus lead to erroneous results when applied for granitic rocks. In this study, we aim at developing an oxybarometer that is based on the partitioning of vanadium (a redox-sensitive element) between magnetite inclusions and silicate melt inclusions preserved in quartz phenocrysts, where they were protected from subsolidus alteration and can be measured as entities by LA-ICP-MS. In the first - experimental - part of this study we investigated the effects of temperature (800-950 ° C), pressure (1-2 kbar), oxygen fugacity (from ΔFMQ+0.7 to ΔFMQ+4.0), magnetite composition, and melt composition on the partition coefficient of vanadium between magnetite and melt (DVmgt-melt). The experiments were carried out in cold-seal pressure vessels and the starting material was a mixture of V-doped haplogranite glasses or natural obsidian powder with variable aluminum saturation index (ASI), and synthetic, V-free magnetite of 10-20 μm grain size. The vanadium partition coefficient was found to depend strongly on oxygen fugacity, and to lesser (but still considerable) degrees on melt composition and temperature. A more than 1.5 log unit decrease in DVmgt-melt values with increasing oxygen fugacity can be explained by a change of the dominant valence state of V in the silicate melt. For a given oxygen fugacity buffer DVmgt-melt decreases with increasing temperature, but this reflects mostly the change in absolute fO2 values while the net temperature effect is in fact positive. DVmgt-melt depends significantly on melt composition, resulting in higher D-values with increasing aluminum

Planetesimal core formation with partial silicate melting using in-situ high P, high T, deformation x-ray microtomography

NASA Astrophysics Data System (ADS)

Anzures, B. A.; Watson, H. C.; Yu, T.; Wang, Y.

2017-12-01

Differentiation is a defining moment in formation of terrestrial planets and asteroids. Smaller planetesimals likely didn't reach high enough temperatures for widescale melting. However, we infer that core formation must have occurred within a few million years from Hf-W dating. In lieu of a global magma ocean, planetesimals likely formed through inefficient percolation. Here, we used in-situ high temperature, high pressure, x-ray microtomography to track the 3-D evolution of the sample at mantle conditions as it underwent shear deformation. Lattice-Boltzmann simulations for permeability were used to characterize the efficiency of melt percolation. Mixtures of KLB1 peridotite plus 6.0 to 12.0 vol% FeS were pre-sintered to achieve an initial equilibrium microstructure, and then imaged through several consecutive cycles of heating and deformation. The maximum calculated melt segregation velocity was found to be 0.37 cm/yr for 6 vol.% FeS and 0.61 cm/year for 12 vol.% FeS, both below the minimum velocity of 3.3 cm/year required for a 100km planetesimal to fully differentiate within 3 million years. However, permeability is also a function of grain size and thus the samples having smaller grains than predicted for small planetesimals could have contributed to low permeability and also low migration velocity. The two-phase (sulfide melt and silicate melt) flow at higher melt fractions (6 vol.% and 12 vol.% FeS) was an extension of a similar study1 containing only sulfide melt at lower melt fraction (4.5 vol.% FeS). Contrary to the previous study, deformation did result in increased permeability until the sample was sheared by twisting the opposing Drickamer anvils by 360 degrees. Also, the presence of silicate melt caused the FeS melt to coalesce into less connected pathways as the experiment with 6 vol.% FeS was found to be less permeable than the one with 4.5 vol.% FeS but without any partial melt. The preliminary data from this study suggests that impacts as well as

Reworking of Archean mantle in the NE Siberian craton by carbonatite and silicate melt metasomatism: Evidence from a carbonate-bearing, dunite-to-websterite xenolith suite from the Obnazhennaya kimberlite

NASA Astrophysics Data System (ADS)

Ionov, Dmitri A.; Doucet, Luc S.; Xu, Yigang; Golovin, Alexander V.; Oleinikov, Oleg B.

2018-03-01

The Obnazhennaya kimberlite in the NE Siberian craton hosts a most unusual cratonic xenolith suite, with common rocks rich in pyroxenes and garnet, and no sheared peridotites. We report petrographic and chemical data for whole rocks (WR) and minerals of 20 spinel and garnet peridotites from Obnazhennaya with Re-depletion Os isotope ages of 1.8-2.9 Ga (Ionov et al., 2015a) as well as 2 pyroxenites. The garnet-bearing rocks equilibrated at 1.6-2.8 GPa and 710-1050 °C. Some xenoliths contain vermicular spinel-pyroxene aggregates with REE patterns in clinopyroxene mimicking those of garnet. The peridotites show significant scatter of Mg# (0.888-0.924), Cr2O3 (0.2-1.4 wt.%) and high NiO (0.3-0.4 wt.%). None are pristine melting residues. Low-CaO-Al2O3 (≤0.9 wt.%) dunites and harzburgites are melt-channel materials. Peridotites with low to moderate Al2O3 (0.4-1.8 wt.%) usually have CaO > Al2O3, and some have pockets of calcite texturally equilibrated with olivine and garnet. Such carbonates, exceptional in mantle xenoliths and reported here for the first time for the Siberian mantle, provide direct evidence for modal makeover and Ca and LREE enrichments by ephemeral carbonate-rich melts. Peridotites rich in CaO and Al2O3 (2.7-8.0 wt.%) formed by reaction with silicate melts. We infer that the mantle lithosphere beneath Obnazhennaya, initially formed in the Mesoarchean, has been profoundly modified. Pervasive inter-granular percolation of highly mobile and reactive carbonate-rich liquids may have reduced the strength of the mantle lithosphere leading the way for reworking by silicate melts. The latest events before the kimberlite eruption were the formation of the carbonate-phlogopite pockets, fine-grained pyroxenite veins and spinel-pyroxene symplectites. The reworked lithospheric sections are preserved at Obnazhennaya, but similar processes could erode lithospheric roots in the SE Siberian craton (Tok) and the North China craton, where ancient melting residues and

Experimental Partitioning of Chalcophile Elements between Mantle Silicate Minerals and Basaltic Melt at High Pressures and Temperatures - Implications for Sulfur Geochemistry of Mantle and Crust

NASA Astrophysics Data System (ADS)

Dasgupta, R.; Jego, S.; Ding, S.; Li, Y.; Lee, C. T.

2015-12-01

The behavior of chalcophile elements during mantle melting, melt extraction, and basalt differentiation is critical for formation of ore deposits and geochemical model and evolution of crust-mantle system. While chalcophile elements are strongly partitioned into sulfides, their behavior with different extent of melting, in particular, in the absence of sulfides, can only be modeled with complete knowledge of the partitioning behavior of these elements between dominant mantle minerals and basaltic melt with or without dissolved sulfide (S2-). However, experimental data on mineral-melt partitioning are lacking for many chalcophile elements. Crystallization experiments were conducted at 3 GPa and 1450-1600 °C using a piston cylinder and synthetic silicate melt compositions similar to low-degree partial melt of peridotite. Starting silicate mixes doped with 100-300 ppm of each of various chalcophile elements were loaded into Pt/graphite double capsules. To test the effect of dissolved sulfur in silicate melt on mineral-melt partitioning of chalcophile elements, experiments were conducted on both sulfur-free and sulfur-bearing (1100-1400 ppm S in melt) systems. Experimental phases were analyzed by EPMA (for major elements and S) and LA-ICP-MS (for trace elements). All experiments produced an assemblage of cpx + melt ± garnet ± olivine ± spinel and yielded new partition coefficients (D) for Sn, Zn, Mo, Sb, Bi, Pb, and Se for cpx/melt, olivine/melt, and garnet/melt pairs. Derived Ds (mineral/basalt) reveal little effect of S2- in the melt on mineral-melt partition coefficients of the measured chalcophile elements, with Ds for Zn, Mo, Bi, Pb decreasing by less than a factor of 2 from S-free to S-bearing melt systems or remaining similar, within error, between S-free and S-bearing melt systems. By combining our data with existing partitioning data between sulfide phases and silicate melt we model the fractionation of these elements during mantle melting and basalt

Effect of water on the fluorine and chlorine partitioning behavior between olivine and silicate melt.

PubMed

Joachim, Bastian; Stechern, André; Ludwig, Thomas; Konzett, Jürgen; Pawley, Alison; Ruzié-Hamilton, Lorraine; Clay, Patricia L; Burgess, Ray; Ballentine, Christopher J

2017-01-01

Halogens show a range from moderate (F) to highly (Cl, Br, I) volatile and incompatible behavior, which makes them excellent tracers for volatile transport processes in the Earth's mantle. Experimentally determined fluorine and chlorine partitioning data between mantle minerals and silicate melt enable us to estimate Mid Ocean Ridge Basalt (MORB) and Ocean Island Basalt (OIB) source region concentrations for these elements. This study investigates the effect of varying small amounts of water on the fluorine and chlorine partitioning behavior at 1280 °C and 0.3 GPa between olivine and silicate melt in the Fe-free CMAS+F-Cl-Br-I-H 2 O model system. Results show that, within the uncertainty of the analyses, water has no effect on the chlorine partitioning behavior for bulk water contents ranging from 0.03 (2) wt% H 2 O (D Cl ol/melt = 1.6 ± 0.9 × 10 -4 ) to 0.33 (6) wt% H 2 O (D Cl ol/melt = 2.2 ± 1.1 × 10 -4 ). Consequently, with the effect of pressure being negligible in the uppermost mantle (Joachim et al. Chem Geol 416:65-78, 2015), temperature is the only parameter that needs to be considered for the determination of chlorine partition coefficients between olivine and melt at least in the simplified iron-free CMAS+F-Cl-Br-I-H 2 O system. In contrast, the fluorine partition coefficient increases linearly in this range and may be described at 1280 °C and 0.3 GPa with ( R 2  = 0.99): [Formula: see text]. The observed fluorine partitioning behavior supports the theory suggested by Crépisson et al. (Earth Planet Sci Lett 390:287-295, 2014) that fluorine and water are incorporated as clumped OH/F defects in the olivine structure. Results of this study further suggest that fluorine concentration estimates in OIB source regions are at least 10% lower than previously expected (Joachim et al. Chem Geol 416:65-78, 2015), implying that consideration of the effect of water on the fluorine partitioning behavior between Earth's mantle minerals and

Insights into Silicate and Oxide Melt Structure from Amorphous, Non-Glass-Forming Materials

NASA Astrophysics Data System (ADS)

Stebbins, J. F.

2015-12-01

Many silicate and oxide liquids of interest in the Earth sciences and in technology cannot readily be quenched to glasses, either because of low silica contents (and hence low viscosity at the melting point and accompanying liquid 'fragility') or because of liquid-liquid unmixing at high temperature. Although in-situ, high temperature structural tools have been in use for decades and are rapidly developing, many methods are still most informative for glass samples quenched to ambient pressure and temperature, e.g. high-resolution solid-state NMR. Amorphous oxides, including alumina and silicate compositions, have widespread technological applications. These are generally deposited by a variety of high-energy sputtering methods, as films of thicknesses of 10's to 100's of nm. Using Al-27, Si-29, and O-17 NMR, we have recently shown that for such films, very similar short-range structure is seen in materials made by very different kinetic pathways, such as sol-gel synthesis vs. ion-beam sputtering. This path-independent structure suggests that these materials pass through transient equilibrium states during their formation, probably that of deeply supercooled liquids just above glass transition temperatures. In the HfO2-SiO2 and ZrO2-SiO2 systems, for example, samples have well-resolved O-17 NMR spectra, allowing quantitation of O sites with only Hf(Zr) neighbors (so-called "free" oxide ions), with mixed Hf(Zr) and Si neighbors, and Si only. The observed oxygen speciation agrees well with a simple thermodynamic model of one of the most fundamental equilibria in silicate systems, namely the reaction of bridging (Si-O-Si) and "free" (e.g. OHf3 and OHf4) oxide ions to produce "non-bridging" oxygens (e.g. Si-OHf2). This new approach to sampling such structural equilibria in compositions far outside the range of normal glass-forming liquids may provide new insights into more geological compositions as well, as well as in more general models of silicate melt chemistry.

Velocity of a freely rising gas bubble in a soda-lime silicate glass melt

NASA Technical Reports Server (NTRS)

Hornyak, E. J.; Weinberg, M. C.

1984-01-01

A comparison is conducted between measured velocities for the buoyant rise of single bubbles of varying size and composition, in a soda-lime silicate glass melt, with the steady state velocities predicted by the Stokes and Hadamard-Rybczynski formulas. In all cases, the data are noted to fit the Hadamard-Rybczynski expression for steady state rise speed considerably better than the Stokes formula.

Eclogite-associated potassic silicate melts and chloride-rich fluids in the mantle: a possible connection

NASA Astrophysics Data System (ADS)

Safonov, O.; Butvina, V.

2009-04-01

Relics of potassium-rich (4-14 wt. % of K2O and K2O/Na2O > 1.0) melts are a specific features of some partially molten diamondiferous eclogite xenoliths in kimberlites worldwide [1, 2]. In addition, potassic silicic melt inclusions with up to 16 wt. % of K2O are associated with eclogite phases in kimberlitic diamonds (O. Navon, pers. comm.). According to available experimental data, no such potassium contents can be reached by "dry" and hydrous melting of eclogite. These data point to close connection between infiltration of essentially potassic fluids, partial melting and diamond formation in mantle eclogites [2]. Among specific components of these fluids, alkali chlorides, apparently, play an important role. This conclusion follows from assemblages of the melt relics with chlorine-bearing phases in eclogite xenoliths [1], findings of KCl-rich inclusions in diamonds from the xenoliths [3], and concentration of Cl up to 0.5-1.5 wt. % in the melt inclusions in diamonds. In this presentation, we review our experimental data on reactions of KCl melts and KCl-bearing fluids with model and natural eclogite-related minerals and assemblages. Experiments in the model system jadeite(±diopside)-KCl(±H2O) at 4-7 GPa showed that, being immiscible, chloride liquids provoke a strong K-Na exchange with silicates (jadeite). As a result, low-temperature ultrapotassic chlorine-bearing (up to 3 wt. % of Cl) aluminosilicate melts form. These melts is able to produce sanidine, which is characteristic phase in some partially molten eclogites. In addition, in presence of water Si-rich Cl-bearing mica (Al-celadonite-phlogopite) crystallizes in equilibrium with sanidine and/or potassic melt and immiscible chloride liquid. This mica is similar to that observed in some eclogitic diamonds bearing chloride-rich fluid inclusions [4], as well as in diamonds in partially molten eclogites [2]. Interaction of KCl melt with pyrope garnet also produce potassic aluminosilicate melt because of high

Evidence of denser MgSiO3 glass above 133 gigapascal (GPa) and implications for remnants of ultradense silicate melt from a deep magma ocean.

PubMed

Murakami, Motohiko; Bass, Jay D

2011-10-18

Ultralow velocity zones are the largest seismic anomalies in the mantle, with 10-30% seismic velocity reduction observed in thin layers less than 20-40 km thick, just above the Earth's core-mantle boundary (CMB). The presence of silicate melts, possibly a remnant of a deep magma ocean in the early Earth, have been proposed to explain ultralow velocity zones. It is, however, still an open question as to whether such silicate melts are gravitationally stable at the pressure conditions above the CMB. Fe enrichment is usually invoked to explain why melts would remain at the CMB, but this has not been substantiated experimentally. Here we report in situ high-pressure acoustic velocity measurements that suggest a new transformation to a denser structure of MgSiO(3) glass at pressures close to those of the CMB. The result suggests that MgSiO(3) melt is likely to become denser than crystalline MgSiO(3) above the CMB. The presence of negatively buoyant and gravitationally stable silicate melts at the bottom of the mantle, would provide a mechanism for observed ultralow seismic velocities above the CMB without enrichment of Fe in the melt. An ultradense melt phase and its geochemical inventory would be isolated from overlying convective flow over geologic time.

Magmatic infiltration and melting in the lower crust and upper mantle beneath the Cima volcanic field, California

USGS Publications Warehouse

Wilshire, H.G.; McGuire, A.V.

1996-01-01

Xenoliths of lower crustal and upper mantle rocks from the Cima volcanic field (CVF) commonly contain glass pockets, veins, and planar trains of glass and/or fluid inclusions in primary minerals. Glass pockets occupy spaces formerly occupied by primary minerals of the host rocks, but there is a general lack of correspondence between the composition of the glass and that of the replaced primary minerals. The melting is considered to have been induced by infiltration of basaltic magma and differentiates of basaltic magma from complex conduits formed by hydraulic fracturing of the mantle and crustal rocks, and to have occurred during the episode of CVF magmatism between ???7.5 Ma and present. Variable compositions of quenched melts resulted from mixing of introduced melts and products of melting of primary minerals, reaction with primary minerals, partial crystallization, and fractionation resulting from melt and volatile expulsion upon entrainment of the xenoliths. High silica melts (> ??? 60% SiO2) may result by mixing introduced melts with siliceous melts produced by reaction of orthopyroxene. Other quenched melt compositions range from those comparable to the host basalts to those with intermediate Si compositions and elevated Al, alkalis, Ti, P, and S; groundmass compositions of CVF basalts are consistent with infiltration of fractionates of those basalts, but near-solidus melting may also contribute to formation of glass with intermediate silica contents with infiltration only of volatile constituents.

Poly(ethylene glycol) layered silicate nanocomposites for retarded drug release prepared by hot-melt extrusion.

PubMed

Campbell, Kayleen; Craig, Duncan Q M; McNally, Tony

2008-11-03

Composites of paracetamol loaded poly(ethylene glycol) (PEG) with a naturally derived and partially synthetic layered silicate (nanoclay) were prepared using hot-melt extrusion. The extent of dispersion and distribution of the paracetamol and nanoclay in the PEG matrix was examined using a combination of field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and wide-angle X-ray diffraction (WAXD). The paracetamol polymorph was shown to be well dispersed in the PEG matrix and the nanocomposite to have a predominately intercalated and partially exfoliated morphology. The form 1 monoclinic polymorph of the paracetamol was unaltered after the melt mixing process. The crystalline behaviour of the PEG on addition of both paracetamol and nanoclay was investigated using differential scanning calorimetry (DSC) and polarised hot-stage optical microscopy. The crystalline content of PEG decreased by up to 20% when both drug and nanoclay were melt blended with PEG, but the average PEG spherulite size increased by a factor of 4. The time taken for 100% release of paracetamol from the PEG matrix and corresponding diffusion coefficients were significantly retarded on addition of low loadings of both naturally occurring and partially synthetic nanoclays. The dispersed layered silicate platelets encase the paracetamol molecules, retarding diffusion and altering the dissolution behaviour of the drug molecule in the PEG matrix.

An electrochemical series of redox couples in silicate melts - A review and applications to geochemistry

NASA Technical Reports Server (NTRS)

Schreiber, Henry D.

1987-01-01

An electrochemical series for redox couples in a glass-forming oxide melt is developed. This series is a quantitative numerical scale of reference reduction potentials of the redox couples in a silicate melt that is a model for basaltic magmas. The redox couples are ordered in terms of their reference reduction potentials; the order appears to be relatively independent of the exact melt composition and temperature. Thus, upon calibration to a desired composition, oxygen fugacity, and temperature, this electrochemical series can provide estimates of redox state proportions in basaltic magmas on different planetary bodies. The geochemical electrochemical series can also be used to understand the interrelationship of the redox state of the magma and the presence of volatile species such as oxygen, water, sulfur gases, and carbon gases.

Lattice thermal conductivity of silicate glasses at high pressures

NASA Astrophysics Data System (ADS)

Chang, Y. Y.; Hsieh, W. P.

2016-12-01

Knowledge of the thermodynamic and transport properties of magma holds the key to understanding the thermal evolution and chemical differentiation of Earth. The discovery of the remnant of a deep magma ocean above the core mantle boundary (CMB) from seismic observations suggest that the CMB heat flux would strongly depend on the thermal conductivity, including lattice (klat) and radiative (krad) components, of dense silicate melts and major constituent minerals around the region. Recent measurements on the krad of dense silicate glasses and lower-mantle minerals show that krad of dense silicate glasses could be significantly smaller than krad of the surrounding solid mantle phases, and therefore the dense silicate melts would act as a thermal insulator in deep lower mantle. This conclusion, however, remains uncertain due to the lack of direct measurements on the lattice thermal conductivity of silicate melts under relevant pressure-temperature conditions. Besides the CMB, magmas exist in different circumstances beneath the surface of the Earth. Chemical compositions of silicate melts vary with geological and geodynamic settings of the melts and have strong influences on their thermal properties. In order to have a better view of heat transport within the Earth, it is important to study compositional and pressure dependences of thermal properties of silicate melts. Here we report experimental results on lattice thermal conductivities of silicate glasses with basaltic and rhyolitic compositions up to Earth's lower mantle pressures using time-domain thermoreflectance coupled with diamond-anvil cell techniques. This study not only provides new data for the thermal conductivity of silicate melts in the Earth's deep interior, but is crucial for further understanding of the evolution of Earth's complex internal structure.

Equation of state of silicate liquids

NASA Astrophysics Data System (ADS)

Jing, Zhicheng

Equation of state of silicate liquids is crucial to our understanding of melting processes such as the generation and differentiation of silicate melts in Earth and hence to explore the geophysical and geochemical consequences of melting. A comparison of compressional properties reveals fundamental differences in compressional mechanisms between silicate liquids and solids. Due to a liquid's ability to change structures, the compression of liquids is largely controlled by the entropic contribution to the free energy in addition to the internal energy contribution that is available to solids. In order to account for the entropic contribution, a new equation of state of silicate liquids is proposed based on the theory of hard-sphere mixtures. The equation of state is calibrated for SiO2-Al 2O3-FeO-MgO-CaO liquids and other systems. The new equation of state provides a unified explanation for the experimental observations on compressional properties of liquids including the bulk moduli of silicate liquids as well as the pressure dependence of Gruneisen parameter. The effect of chemical composition on melt density can be studied by the equation of state. Results show that FeO and H2O are the most important components in melts that control the melt density at high pressure due to their very different mean atomic masses from other melt components. Adding SiO2 can make a melt more compressible at high pressure due to its continuous change of coordination from 4-fold to 6-fold. The effect of 1-120 on melt density is further investigated by high-pressure experiments at the conditions of 9 to 15 GPa (corresponding to the depths of 300-500 km in the Earth) and 1900 °C to 2200 °C. The density of three dry melts and four hydrous melts with 2-7 wt% H2O was determined. Density data are analyzed by both the Birch-Mumaghan equation of state and the hard sphere equation of state. The partial molar volume of H2O is determined to be 8.8 cm3/mol at 14 GPa and 2173 K. The hypothesis

Coordinated Hard Sphere Mixture (CHaSM): A fast approximate model for oxide and silicate melts at extreme conditions

NASA Astrophysics Data System (ADS)

Wolf, A. S.; Asimow, P. D.; Stevenson, D. J.

2015-12-01

Recent first-principles calculations (e.g. Stixrude, 2009; de Koker, 2013), shock-wave experiments (Mosenfelder, 2009), and diamond-anvil cell investigations (Sanloup, 2013) indicate that silicate melts undergo complex structural evolution at high pressure. The observed increase in cation-coordination (e.g. Karki, 2006; 2007) induces higher compressibilities and lower adiabatic thermal gradients in melts as compared with their solid counterparts. These properties are crucial for understanding the evolution of impact-generated magma oceans, which are dominated by the poorly understood behavior of silicates at mantle pressures and temperatures (e.g. Stixrude et al. 2009). Probing these conditions is difficult for both theory and experiment, especially given the large compositional space (MgO-SiO2-FeO-Al2O3-etc). We develop a new model to understand and predict the behavior of oxide and silicate melts at extreme P-T conditions (Wolf et al., 2015). The Coordinated Hard Sphere Mixture (CHaSM) extends the Hard Sphere mixture model, accounting for the range of coordination states for each cation in the liquid. Using approximate analytic expressions for the hard sphere model, this fast statistical method compliments classical and first-principles methods, providing accurate thermodynamic and structural property predictions for melts. This framework is applied to the MgO system, where model parameters are trained on a collection of crystal polymorphs, producing realistic predictions of coordination evolution and the equation of state of MgO melt over a wide P-T range. Typical Mg-coordination numbers are predicted to evolve continuously from 5.25 (0 GPa) to 8.5 (250 GPa), comparing favorably with first-principles Molecular Dynamics (MD) simulations. We begin extending the model to a simplified mantle chemistry using empirical potentials (generally accurate over moderate pressure ranges, <~30 GPa), yielding predictions rooted in statistical representations of melt structure

Evidence of denser MgSiO3 glass above 133 gigapascal (GPa) and implications for remnants of ultradense silicate melt from a deep magma ocean

PubMed Central

Murakami, Motohiko; Bass, Jay D.

2011-01-01

Ultralow velocity zones are the largest seismic anomalies in the mantle, with 10–30% seismic velocity reduction observed in thin layers less than 20–40 km thick, just above the Earth’s core-mantle boundary (CMB). The presence of silicate melts, possibly a remnant of a deep magma ocean in the early Earth, have been proposed to explain ultralow velocity zones. It is, however, still an open question as to whether such silicate melts are gravitationally stable at the pressure conditions above the CMB. Fe enrichment is usually invoked to explain why melts would remain at the CMB, but this has not been substantiated experimentally. Here we report in situ high-pressure acoustic velocity measurements that suggest a new transformation to a denser structure of MgSiO3 glass at pressures close to those of the CMB. The result suggests that MgSiO3 melt is likely to become denser than crystalline MgSiO3 above the CMB. The presence of negatively buoyant and gravitationally stable silicate melts at the bottom of the mantle, would provide a mechanism for observed ultralow seismic velocities above the CMB without enrichment of Fe in the melt. An ultradense melt phase and its geochemical inventory would be isolated from overlying convective flow over geologic time. PMID:21969547

Metal/sulfide-silicate intergrowth textures in EL3 meteorites: Origin by impact melting on the EL parent body

NASA Astrophysics Data System (ADS)

van Niekerk, Deon; Keil, Klaus

2011-10-01

We document the petrographic setting and textures of Fe,Ni metal, the mineralogy of metallic assemblages, and the modal mineral abundances in the EL3 meteorites Asuka (A-) 881314, A-882067, Allan Hills 85119, Elephant Moraine (EET) 90299/EET 90992, LaPaz Icefield 03930, MacAlpine Hills (MAC) 02635, MAC 02837/MAC 02839, MAC 88136, Northwest Africa (NWA) 3132, Pecora Escarpment 91020, Queen Alexandra Range (QUE) 93351/QUE 94321, QUE 94594, and higher petrologic type ELs Dar al Gani 1031 (EL4), Sayh al Uhaymir 188 (EL4), MAC 02747 (EL4), QUE 94368 (EL4), and NWA 1222 (EL5). Large metal assemblages (often containing schreibersite and graphite) only occur outside chondrules and are usually intergrown with silicate minerals (euhedral to subhedral enstatite, silica, and feldspar). Sulfides (troilite, daubréelite, and keilite) are also sometimes intergrown with silicates. Numerous authors have shown that metal in enstatite chondrites that are interpreted to have been impact melted contains euhedral crystals of enstatite. We argue that the metal/sulfide-silicate intergrowths in the ELs we studied were also formed during impact melting and that metal in EL3s thus does not retain primitive (i.e., nebular) textures. Likewise, the EL4s are also impact-melt breccias. Modal abundances of metal in the EL3s and EL4s range from approximately 7 to 30 wt%. These abundances overlap or exceed those of EL6s, and this is consistent either with pre-existing heterogeneity in the parent body or with redistribution of metal during impact processes.

The solubility of Pd and Au in hydrous intermediate silicate melts: The effect of oxygen fugacity and the addition of Cl and S

NASA Astrophysics Data System (ADS)

Sullivan, Neal A.; Zajacz, Zoltan; Brenan, James M.

2018-06-01

The solubilities of Pd and Au in a hydrous trachyandesitic melt were experimentally determined at 1000 °C and 200 MPa at oxygen fugacity (ƒO2) from 0.45 log units below to 6.55 log units above the Ni-NiO buffer (NNO). The effect of adding metal-binding ligands (i.e. Cl and S) to the silicate melt was also studied. The solubility of Au increases from 0.15 ± 0.1 to 3.85 ± 1.48 ppm in Cl- and S-free melts with ƒO2 increasing from NNO-0.45 to NNO+6.55 with a slope that suggests that it is present in 1+ oxidation state over the entire studied ƒO2 range. On the other hand, Pd solubility, shows a more moderate increase with ƒO2, especially in the lower half of the studied range, increasing from 2.66 ± 0.25 ppm at NNO-0.45 to only 3.62 ± 0.38 ppm at NNO+1.72 in Cl- and S-free melts. Overall, the variation in Pd solubility as a function of ƒO2 indicates Pd being dissolved in the silicate melt in both zero and 1+ oxidation state, with the former being dominant below NNO+4.5. At NNO-0.45 to +3.48, the addition of 3170-4060 ppm Cl to the silicate melt increased the solubility of Au by an average factor of 1.5, in comparison to Cl-free melts. However, at NNO+6.55, Au solubility increased by a factor of 2.5. The addition of Cl had a negligible effect on the solubility of Pd except for a large increase (factor of 2.4) at NNO+6.55. At reducing conditions (NNO-0.45), the addition of 170 ppm S to the silicate melt increased the solubility of Au by a factor of ∼4 but did not change the solubility of Pd in comparison to S-free melts. The observation that Pd is dominantly present as Pd0 at NNO < +4.5 may explain the lack of complexation with potential reduced sulfur-bearing and chloride ligands. As one may expect similar behavior in fluids degassing from magmas at depth, the lack of oxidized Pd species could be an important factor behind the scarcity of economically viable Pd-rich magmatic-hydrothermal deposits observed in nature.

Hydrogen-alkali exchange between silicate melts and two-phase aqueous mixtures: an experimental investigation

NASA Astrophysics Data System (ADS)

Williams, Thomas J.; Candela, Philip A.; Piccoli, Philip M.

Experiments were performed in the three-phase system high-silica rhyolite melt + low-salinity aqueous vapor + hydrosaline brine, to investigate the exchange equilibria for hydrogen, potassium, and sodium in magmatic-hydrothermal systems at 800 °C and 100 MPa, and 850 °C and 50 MPa. The Kaqm/meltH,Na and Kaqm/meltH,K for hydrogen-sodium exchange between a vapor + brine mixture and a silicate melt are inversely proportional to the total chloride concentration (ΣCl) in the vapor + brine mixture indicating that HCl/NaCl and HCl/KCl are higher in the low-salinity aqueous vapor relative to high-salinity brine. The equilibrium constants for vapor/melt and brine/melt exchange were extracted from regressions of Kaqm/meltH,Na and Kaqm/meltH,K versus the proportion of aqueous vapor relative to brine in the aqueous mixture (Faqv) at P and T, expressed as a function of ΣCl. No significant pressure effect on the empirically determined exchange constants was observed for the range of pressures investigated. Model equilibrium constants are: Kaqv/meltH,Na(vapor/melt)=26(+/-1.3) at 100 MPa (800 °C), and 19( +/- 7.0) at 50 MPa (850 °C) Kaqv/meltH,K=14(+/-1.1) at 100 MPa (800 °C), and 24(+/-12) at 50 MPa (850 °C) Kaqb/meltH,b(brine/melt)= 1.6(+/-0.7) at 100 MPa (800 °C), and 3.9(+/-2.3) at 50 MPa (850 °C) and Kaqb/meltH,K=2.7(+/-1.2) at 100 MPa (800 °C) and 3.8(+/-2.3) at 50 MPa (850 °C). Values for Kaqv/meltH,K and Kaqb/meltH,K were used to calculate KCl/HCl in the aqueous vapor and brine as a function of melt aluminum saturation index (ASI: molar Al2O3/(K2O+Na2O+CaO) and pressure. The model log KCl/HCl values show that a change in melt ASI from peraluminous (ASI = 1.04) to moderately metaluminous (ASI = 1.01) shifts the cooling pathway (in temperature-log KCl/HCl space) of the aqueous vapor toward the andalusite+muscovite+K-feldspar reaction point.

Reaction rim growth on olivine in silicic melts: Implications for magma mixing

USGS Publications Warehouse

Coombs, Michelle L.; Gardner, James E.

2004-01-01

Finely crystalline amphibole or pyroxene rims that form during reaction between silicic host melt and cognate olivine xenocrysts, newly introduced during magma mixing events, can provide information about the timing between mixing and volcanic eruptions. We investigated rim growth experimentally by placing forsteritic olivine in rhyolitic and rhyodacitic melts for times between 25 and 622 h at 50 and 150 MPa, H2O-saturated, at the Ni-NiO buffer. Rims of orthopyroxene microlites formed from high-silica rhyolite and rhyodacite melts at 885°C and 50 MPa, and in the rhyolite at 150 MPa and 885°C. Rims of amphibole with lesser orthopyroxene formed in the rhyolite at 150 MPa and 800°C and in the rhyodacite at 150 MPa and 885°C. Irregular, convolute olivine edges and mass balance between olivine, melt, and rim phases show that olivine partly dissolved at all conditions. Iron-rich zones at the exteriors of olivines, which increased in width parabolically with time, show that Fe-Mg interdiffusion occurring in olivines was not outpaced by olivine dissolution. Linear increases of the square of rim widths with time suggest that diffusion within the melt is the rate-controlling process for olivine dissolution and rim growth. Rims grew one-half to one order-of-magnitude faster when melt water contents were doubled, unless conditions were far above the liquidus. Rim growth rate in rhyolite increases from 0.055 ± 0.01 µm2/h at 885°C and 50 MPa to 0.64 ± 0.13 µm2/h at 800°C and 150 MPa. Melt composition has a lesser effect on rim growth rates, with growth rate increasing as melt SiO2 content decreases. Pyroxene rims on olivines in andesite erupted from Arenal volcano (Costa Rica) grew at a rate of 3.0 ± 0.2 µm2/h over an eleven-year period. This rate is faster than those of the experiments due to lower melt viscosity and higher temperatures, and suggests that a magma mixing event preceded the start of the eruption by days.

Experimental determination of activities of FeO and Fe 2O 3 components in hydrous silicic melts under oxidizing conditions

NASA Astrophysics Data System (ADS)

Gaillard, Fabrice; Pichavant, Michel; Scaillet, Bruno

2003-11-01

The critical role of iron on crystal-silicate liquid relationships and melt differentiation is mainly controlled by the redox conditions prevailing in magmas, but the presently available database merely constrains the thermodynamic properties of iron-bearing components in strongly reduced and anhydrous molten silicate where iron is in the ferrous form. This paper provides new standard states for pure ferrous (FeOliq) and ferric (Fe2O3liq) molten iron oxides and extends the experimental database towards oxidizing and water-bearing domains. Iron-iridium, iron-platinum alloys, magnetite or hematite were equilibrated with synthetic silicic liquids at high temperature and high pressure under controlled oxygen fugacity (fO2) to determine activity-composition relationships for FeOliq and Fe2O3liq. Between 1000 and 1300°C, the fO2 ranges from that in air to 3-log units below that of the nickel-nickel oxide buffer (NNO). Experiments were performed on both anhydrous and hydrous melts containing up to 6-wt.% water. Incorporation of water under reducing conditions increases the activity coefficient of FeOliq but has an opposite effect on Fe2O3liq. As calcium is added to system, the effect of water becomes weaker and is inverted for Fe2O3liq. Under oxidizing conditions, water has a negligible effect on both activities of FeOliq and Fe2O3liq. In contrast, changes in redox conditions dominate the activity coefficients of both FeOliq and Fe2O3liq, which increase significantly with increasing fO2. The present results combined with the previous work provide a specific database on the energetics of iron in silicate melts that cover most of the condition prevailing in natural magmas.

Structural environments of incompatible elements in silicate glass/melt systems: I. Zirconium at trace levels

NASA Astrophysics Data System (ADS)

Farges, Franã§Ois; Ponader, Carl W.; Brown, Gordon E., Jr.

1991-06-01

The structural environments of trace levels (2˜000 ppm) of Zr 4+ in several silicate glasses were examined as a function of melt composition and polymerization using Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Glass compositions investigated were albite (NaAlSi 3O 8: AB) and a peralkaline composition (Na 3.3AlSi 7O 17: PR)- Zirconium was added to the oxide-carbonate mix prior to melting in the form of ZrO 2 (baddeleyite). A second set of Zr-silicate glasses containing 2000 ppm Zr and 1.0 to 2.4 wt% halogens (F as NaF and Cl as NaCl) was also synthesized. These included the Zr-AB and Zr-PR base-glass compositions as well as Zr-sodium trisilicate composition (Na2Si 3O 7: TS). In all glasses studied, Zr is mainly 6-coordinated by oxygen atoms ( d[Zr-O] ˜2.07 ± 0.01 Å). In the most polymerized glass (AB), a small but significant amount of Zr was also found to occur in 8-coordinated sites ( d[Zr-O] ˜2.22 Å). No clear evidence for F or Cl complexes of Zr was observed in any of the halogen-containing glasses. The regularity of the Zr site increases in the series AB < TS ˜PR. We attribute this change to an increase in the number of non-bridging oxygens in the first-coordination sphere of Zr related to the depolymerizing effects of halogens and/or sodium. Minor but significant interactions of Zr with the tetrahedral network were observed ( d[Zr-{Si, Al}] ˜3.65-3.71 Å ± 0.03 Å), which are consistent with Zr-O-{Si, Al} angles close to 160-170°, as in catapleiite (Na 2ZrSi 3O 9 · 2H 2O). Intermediaterange order, as reflected by the presence and number of second-neighbor {Si, Al} around Zr, increases significantly with increasing melt polymerization. The local environment around Zr is more strongly influenced by bonding requirements than by the network topology of the melt. Stabilization of zirconium in 6-coordinated sites in relatively depolymerized melts should act to decrease the crystal-melt partition coefficients of Zr and may explain the

Experimental observations on noble metal nanonuggets and Fe-Ti oxides, and the transport of platinum group elements in silicate melts

NASA Astrophysics Data System (ADS)

Anenburg, Michael; Mavrogenes, John A.

2016-11-01

Platinum group element (PGE) nanonuggets are a nuisance in experimental studies designed to measure solubility or partitioning of noble metals in silicate melts. Instead of treating nanonuggets as experimental artifacts, we studied their behaviour motivated by recent discoveries of PGE nanonuggets in a variety of natural settings. We used an experimental setup consisting of AgPd, Pt or AuPd capsules and Fe(-Ti) oxide-saturated hydrous peralkaline silicate melts to maximise nanonugget production. TABS (Te, As, Bi, Sb, Sn) commonly occur in PGM (platinum group minerals), prompting addition of Bi to our experiments to investigate its properties as well. Three-dimensional optical examination by 100× objective and immersion oil reveals variable colour which correlates with nanonugget size and shape due to plasmon resonance effects. We observe two textural types: (1) intermediate-sized nanonuggets dispersed in the glass and adhering to oxides, and (2) abundant fine nanonuggets dispersed in the glass with coarse euhedral crystals in contact with oxides. Slow cooling removes dispersed nanonuggets and greatly coarsens existing oxide-associated metal crystals. Nanonugget-free halos are commonly observed around oxide grains. All metal phases are composed of major (Ag, Pd) and trace (Pt, Ir, Au) capsule material. Our results show reduction processes, imposed by growing oxides, causing local metal saturation in the oxide rich zones with preferential nucleation on smaller oxide grains. The redox gradient then blocks additional metals from diffusing into oxide rich zones, forming halos. As the entire experimental charge is reduced throughout the run, nanonuggets form in the distal glass. Bismuth contents of metal phases do not depend on Bi2O3 amounts dissolved in the melt. Further PGM crystallisation consumes nanonuggets as feedstock. We conclude that the appearance of metallic PGE phases happens in two stages: first as nanonuggets and then as larger PGM. Once formed

Kinetic D/H fractionation during hydration and dehydration of silicate glasses, melts and nominally anhydrous minerals

NASA Astrophysics Data System (ADS)

Roskosz, M.; Deloule, E.; Ingrin, J.; Depecker, C.; Laporte, D.; Merkel, S.; Remusat, L.; Leroux, H.

2018-07-01

The distribution of hydrogen isotopes during diffusion-driven aqueous processes in silicate glasses, melts and crystals was investigated. Hydration/dehydration experiments were performed on silica glasses at 1000 °C and 1 bar total pressure. Dehydration triggered by decompression-driven bubble nucleation and growth was performed on rhyolitic melts at 800 °C and a few hundred MPa. Hydrogen extraction from a nominally anhydrous mineral (grossular) single crystal was carried out at 800 °C and ambient pressure. After these three series of experiments, pronounced water (sensu lato) concentration profiles were observed in all recovered samples. In the grossular single-crystal, a large spatial variation in H isotopes (δD variation > 550‰) was measured across the sample. This isotopic distribution correlates with the hydrogen extraction profile. The fit to the data suggests an extreme decoupling between hydrogen and deuterium diffusion coefficients (DH and DD respectively), akin to the decoupling expected in a dilute ideal gas (DH/DD ≈ 1.41). Conversely, no measurable spatially- and time-resolved isotopic variations were measured in silicate glasses and melts. This contrasted behavior of hydrogen isotopes likely stands in the different water speciation and solution mechanisms in the three different materials. Glasses and melts contain essentially hydroxyl and molecular water groups but the mobile species is molecular water in both cases. Protonated defects make up most of the water accommodated in grossular and other nominally anhydrous minerals (NAM). These defects are also the mobile species that diffuse against polarons. These results are crucial to accurately model the degassing behavior of terrestrial and lunar magmas and to derive the initial D/H of water trapped in fluid inclusions commonly analyzed in mantle NAMs, which suffered complex geological histories.

Siderophile Element Partitioning between Sulfide- and Silicate melts.

NASA Astrophysics Data System (ADS)

Hackler, S.; Rohrbach, A.; Loroch, D. C.; Klemme, S.; Berndt, J.

2017-12-01

Different theories concerning the formation of the Earth are debated. Either Earth accreted mostly `dry' or volatile elements were delivered late after core formation was largely inactive [1, 2], or volatile rich material was accreted during the main stages of accretion and core formation [3, 4, 5]. The partitioning behavior of siderophile volatile elements (SVE; S, Se, Te, Tl, Ag, Au, Cd, Bi, Pb, Sn, Cu, Ge, and In) may provide first order constraints whether these element concentrations in Earth's mantle were established before or after core-mantle differentiation or perhaps during both periods by multi stage core formation [6]. A special interest is laid into chalcophile element behavior with respective to the possible formation and segregation of a hadean matte [7]. To examine the influence of sulfur on SVE partitioning between metal-silicate melts, we performed experiments simulating a magma ocean stage evolving from sulfur poor- (low fO2) to more oxidizing sulfur rich- (Fe, Ni)-S melts ( 20 wt% S) towards the end of accretion. We carried out partitioning experiments under various P-T-fO2 conditions with a Bristol type end loaded piston cylinder apparatus (<3 GPa) and a 1000 t walker-type multi-anvil press (3-20 GPa). Our results will be presented at the meeting. References: [1] Albarède F. (2009) Nature, 461, 1227-1233. [2] Ballhaus C. et al. (2013) EPSL, 362, 237-245. [3] Fischer-Gödde M. and Kleine T. (2017) Nature, 541, 525 527. [4] Wade J. and Wood B. J. (2005) EPSL, 236, 78-95. [5] Rubie D. et al. (2016) Science, 253, 1141-1144. [6] Rubie D. et al. (2011) EPSL, 301, 31-42. [7] O'Neill H. St. C. (1991) GCA, 55, 1159-1172.

The solvation radius of silicate melts based on the solubility of noble gases and scaled particle theory.

PubMed

Ottonello, Giulio; Richet, Pascal

2014-01-28

The existing solubility data on noble gases in high-temperature silicate melts have been analyzed in terms of Scaling Particle Theory coupled with an ab initio assessment of the electronic, dispersive, and repulsive energy terms based on the Polarized Continuum Model (PCM). After a preliminary analysis of the role of the contracted Gaussian basis sets and theory level in reproducing appropriate static dipole polarizabilities in a vacuum, we have shown that the procedure returns Henry's law constants consistent with the values experimentally observed in water and benzene at T = 25 °C and P = 1 bar for the first four elements of the series. The static dielectric constant (ɛ) of the investigated silicate melts and its optical counterpart (ɛ(∞)) were then resolved through the application of a modified form of the Clausius-Mossotti relation. Argon has been adopted as a probe to depict its high-T solubility in melts through an appropriate choice of the solvent diameter σs, along the guidelines already used in the past for simple media such as water or benzene. The σs obtained was consistent with a simple functional form based on the molecular volume of the solvent. The solubility calculations were then extended to He, Ne, and Kr, whose dispersive and repulsive coefficients are available from theory and we have shown that their ab initio Henry's constants at high T reproduce the observed increase with the static polarizability of the series element with reasonable accuracy. At room temperature (T = 25 °C) the calculated Henry's constants of He, Ne, Ar, and Kr in the various silicate media predict higher solubilities than simple extrapolations (i.e., Arrhenius plots) based on high-T experiments and give rise to smooth trends not appreciably affected by the static polarizabilities of the solutes. The present investigation opens new perspectives on a wider application of PCM theory which can be extended to materials of great industrial interest at the core of

Generation of Silicic Melts in the Early Izu-Bonin Arc Recorded by Detrital Zircons in Proximal Arc Volcaniclastic Rocks From the Philippine Sea

NASA Astrophysics Data System (ADS)

Barth, A. P.; Tani, K.; Meffre, S.; Wooden, J. L.; Coble, M. A.; Arculus, R. J.; Ishizuka, O.; Shukle, J. T.

2017-10-01

A 1.2 km thick Paleogene volcaniclastic section at International Ocean Discovery Program Site 351-U1438 preserves the deep-marine, proximal record of Izu-Bonin oceanic arc initiation, and volcano evolution along the Kyushu-Palau Ridge (KPR). Pb/U ages and trace element compositions of zircons recovered from volcaniclastic sandstones preserve a remarkable temporal record of juvenile island arc evolution. Pb/U ages ranging from 43 to 27 Ma are compatible with provenance in one or more active arc edifices of the northern KPR. The abundances of selected trace elements with high concentrations provide insight into the genesis of U1438 detrital zircon host melts, and represent useful indicators of both short and long-term variations in melt compositions in arc settings. The Site U1438 zircons span the compositional range between zircons from mid-ocean ridge gabbros and zircons from relatively enriched continental arcs, as predicted for melts in a primitive oceanic arc setting derived from a highly depleted mantle source. Melt zircon saturation temperatures and Ti-in-zircon thermometry suggest a provenance in relatively cool and silicic melts that evolved toward more Th and U-rich compositions with time. Th, U, and light rare earth element enrichments beginning about 35 Ma are consistent with detrital zircons recording development of regional arc asymmetry and selective trace element-enriched rear arc silicic melts as the juvenile Izu-Bonin arc evolved.

The Effect of fO2 on Partition Coefficients of U and Th between Garnet and Silicate Melt

NASA Astrophysics Data System (ADS)

Huang, F.; He, Z.; Schmidt, M. W.; Li, Q.

2014-12-01

Garnet is one of the most important minerals controlling partitioning of U and Th in the upper mantle. U is redox sensitive, while Th is tetra-valent at redox conditions of the silicate Earth. U-series disequilibria have provided a unique tool to constrain the time-scales and processes of magmatism at convergent margins. Variation of garnet/meltDU/Th with fO2 is critical to understand U-series disequilibria in arc lavas. However, there is still no systematic experimental study about the effect of fO2 on partitioning of U and Th between garnet and melt. Here we present experiments on partitioning of U, Th, Zr, Hf, Nb, Ta, and REE between garnet and silicate melts at various fO2. The starting material was hydrous haplo-basalt. The piston cylinder experiments were performed with Pt double capsules with C-CO, MnO-Mn3O4 (MM), and hematite-magnetite (HM) buffers at 3 GPa and 1185-1230 oC. The experiments produced garnets with diameters > 50μm and quenched melt. Major elements were measured by EMPA at ETH Zurich. Trace elements were determined using LA-ICP-MS at Northwestern University (Xi'an, China) and SIMS (Cameca1280 at the Institute of Geology and Geophysics, Beijing, China), producing consistent partition coefficient data for U and Th. With fO2 increasing from CCO to MM and HM, garnet/meltDU decreases from 0.041 to 0.005, while garnet/meltDTh ranges from 0.003 to 0.007 without correlation with fO2. Notably, garnet/meltDTh/U increases from 0.136 at CCO to 0.41 at HM. Our results indicate that U is still more compatible than Th in garnet even at the highest fO2 considered for the subarc mantle wedge (~NNO). Therefore, we predict that if garnet is the dominant phase controlling U-Th partitioning during melting of the mantle wedge, melts would still have 230Th excess over 238U. This explains why most young continental arc lavas have 230Th excess. If clinopyroxene is the dominant residual phase during mantle melting, U could be more incompatible than Th at high fO2

Dependence of Ru2O3 Activity on Composition of Silicate Melts: Using Statistical Correlations to Infer Thermodynamic Behavior in the Melt

NASA Technical Reports Server (NTRS)

Colson, R. O.; Malum, K. M.

2005-01-01

Understanding variations in activity with composition is an essential step in improving prediction of partition coefficients during magma evolution. Variations in activity with composition are complex and do not generally exhibit ideal behavior relative to a traditional melt-component set. Although deviations from component ideality can be modeled numerically by simply fitting to compositional variables (such as in a regular or subregular solution model), such models have not been particularly successful for describing variations in trace component activities. A better approach might be to try to identify components that do a better job of describing the behavior of the species in the melt. Electrochemical Measurement of Ru2O3 activities: Electrodes were inserted into silicate melt beads of various compositions (Table 1) suspended on Ptwire loops in a 1-atm gas mixing furnace. An electrical potential was imposed between the electrodes, the imposed potential increasing along a step ramp with a pulse imposed on each step (Fig. 1). Current flows between electrodes when electroactive species in the melt are oxidized or reduced at the electrodes. The resulting current was measured at the top and bottom of the voltage pulse, and the difference (the differential current) was plotted against potential. The peak of the resulting curve is related to the activity coefficient for the particular electroactive species (Ru2O3) in the melt [1, 2, 3]. A significant part of the nonideal contribution to activity is due not to intrinsic properties of the component in the melt, but to our ignorance about the state and mixing properties of the component in the melt.

Carbonate-silicate liquid immiscibility in the mantle propels kimberlite magma ascent

NASA Astrophysics Data System (ADS)

Kamenetsky, Vadim S.; Yaxley, Gregory M.

2015-06-01

Kimberlite is a rare volcanic rock renowned as the major host of diamonds and originated at the base of the subcontinental lithospheric mantle. Although kimberlite magmas are dense in crystals and deeply-derived rock fragments, they ascend to the surface extremely rapidly, enabling diamonds to survive. The unique physical properties of kimberlite magmas depend on the specific compositions of their parental melts that, in absence of historical eruptions and due to pervasive alteration of kimberlite rocks, remain highly debatable. We explain exceptionally rapid ascent of kimberlite magma from mantle depths by combining empirical data on the essentially carbonatite composition of the kimberlite primary melts and experimental evidence on interaction of the carbonate liquids with mantle minerals. Our experimental study shows that orthopyroxene is completely dissolved in a Na2CO3 melt at 2.0-5.0 GPa and 1000-1200 °C. The dissolution of orthopyroxene results in homogeneous silicate-carbonate melt at 5.0 GPa and 1200 °C, and is followed by unmixing of carbonate and carbonated silicate melts and formation of stable magmatic emulsion at lower pressures and temperatures. The dispersed silicate melt has a significant capacity for storing a carbonate component in the deep mantle (13 wt% CO2 at 2.0 GPa). We envisage that this component reaches saturation and is gradually released as CO2 bubbles, as the silicate melt globules are transported upwards through the lithosphere by the carbonatite magma. The globules of unmixed, CO2-rich silicate melt are continuously produced upon further reaction between the natrocarbonatite melt and mantle peridotite. On decompression the dispersed silicate melt phase ensures a continuous supply of CO2 bubbles that decrease density and increase buoyancy and promote rapid ascent of the magmatic emulsion.

Microscopic, Macroscopic, and Megascopic Melts: a simple model to synthesize simulation, spectroscopy, shock, and sink/float constraints on silicate melts and magma oceans

NASA Astrophysics Data System (ADS)

Asimow, P. D.; Thomas, C.; Wolf, A. S.

2012-12-01

Silicate melts are the essential agents of planetary differentiation and evolution. Their phase relations, element partitioning preferences, density, and transport properties determine the fates of heat and mass flow in the high-temperature interior of active planets. In the early Earth and in extrasolar super-Earth-mass terrestrial planets it is these properties at very high pressure (> 100 GPa) that control the evolution from possible magma oceans to solid-state convecting mantles. Yet these melts are complex, dynamic materials that present many challenges to experimental, theoretical, and computational understanding or prediction of their properties. There has been encouraging convergence among various approaches to understanding the structure and dynamics of silicate melts at multiple scales: nearest- and next-nearest neighbor structural information is derived from spectroscopic techniques such as high-resolution multinuclear NMR; first-principles molecular dynamics probe structure and dynamics at scales up to hundreds of atoms; Archimedean, ultrasonic, sink/float, and shock wave methods probe macroscopic properties (and occasionally dynamics); and deformation and diffusion experiments probe dynamics at macroscopic scale and various time scales. One challenge that remains to integrating all this information is a predictive model of silicate liquid structure that agrees with experiments and simulation both at microscopic and macroscopic scale. In addition to our efforts to collect macroscopic equation of state data using shock wave methods across ever-wider ranges of temperature, pressure, and composition space, we have introduced a simple model of coordination statistics around cations that can form the basis of a conceptual and predictive link across scales and methods. This idea is explored in this presentation specifically with regard to the temperature dependence of sound speed in ultramafic liquids. This is a highly uncertain quantity and yet it is key, in

Petrogenesis of Silicic Magmas in the Afro-Arabian Flood Volcanic Province in Yemen: A Melt Inclusion Study

NASA Astrophysics Data System (ADS)

Falkena, L. B.; Peate, D.; Ukstins Peate, I.

2009-05-01

The Oligocene (˜26-30 Ma) Afro-Arabian Flood Volcanic Province in Yemen and Ethiopia contains significant silicic material primarily deposited as large volume (>1,000 km 3 ) ignimbrites. These deposits have been correlated to tephra layers in ODP cores ˜2700 km SE of Yemen in the Indian Ocean. We are using melt inclusions (MI) in 4 ignimbrite units to model the petrogenesis and pre-eruptive volatile contents of the ignimbrites. Although quartz is a better MI host in silicic systems, these units only contain plagioclase that has the potential for degassing and leakage in cleavage planes. Through a series of experiments to investigate the rehomogenization temperature of the MI, we found inclusions were glassy at 1075 ° C after 24 hours. We also have compositional data from shorter duration runs (˜20 min.) at 1050 ° C. Reconnaissance MI data show a wide compositional variation compared to whole rock samples of the ignimbrites, and they provide a better estimate of true magmatic compositions compared to the heterogeneous whole rock samples. The inclusions are generally lower in Si (˜59-85 wt.%), yet significantly higher in Na and Al, which both decrease with increasing Si. We are currently modeling these variations to determine the petrogenesis of these silicic magmas. In terms of pre-eruptive volatiles, sulfur in the long duration experiments appears degassed (<5 ppm) yet is retained in the shorter duration runs (up to 500 ppm). Cl appears robust in the MI at ˜340 ppm and is consistent with modeled high halogen contents in such peralkaline melts. We will present estimates for the total S and Cl released during these large ignimbrite eruptions.

Electrical conductivity of basaltic and carbonatite melt-bearing peridotites at high pressures: Implications for melt distribution and melt fraction in the upper mantle

NASA Astrophysics Data System (ADS)

Yoshino, Takashi; Laumonier, Mickael; McIsaac, Elizabeth; Katsura, Tomoo

2010-07-01

Electrical impedance measurements were performed on two types of partial molten samples with basaltic and carbonatitic melts in a Kawai-type multi-anvil apparatus in order to investigate melt fraction-conductivity relationships and melt distribution of the partial molten mantle peridotite under high pressure. The silicate samples were composed of San Carlos olivine with various amounts of mid-ocean ridge basalt (MORB), and the carbonate samples were a mixture of San Carlos olivine with various amounts of carbonatite. High-pressure experiments on the silicate and carbonate systems were performed up to 1600 K at 1.5 GPa and up to at least 1650 K at 3 GPa, respectively. The sample conductivity increased with increasing melt fraction. Carbonatite-bearing samples show approximately one order of magnitude higher conductivity than basalt-bearing ones at the similar melt fraction. A linear relationship between log conductivity ( σbulk) and log melt fraction ( ϕ) can be expressed well by the Archie's law (Archie, 1942) ( σbulk/ σmelt = Cϕn) with parameters C = 0.68 and 0.97, n = 0.87 and 1.13 for silicate and carbonate systems, respectively. Comparison of the electrical conductivity data with theoretical predictions for melt distribution indicates that the model assuming that the grain boundary is completely wetted by melt is the most preferable melt geometry. The gradual change of conductivity with melt fraction suggests no permeability jump due to melt percolation at a certain melt fraction. The melt fraction of the partial molten region in the upper mantle can be estimated to be 1-3% and ˜ 0.3% for basaltic melt and carbonatite melt, respectively.

Phosphorus Equilibria Among Mafic Silicate Phases

NASA Technical Reports Server (NTRS)

Berlin, Jana; Xirouchakis, Dimitris

2002-01-01

Phosphorus incorporation in major rock-forming silicate minerals has the following implications: (1) Reactions between phosphorus-hosting major silicates and accessory phosphates, which are also major trace element carriers, may control the stability of the latter and thus may affect the amount of phosphorus and other trace elements released to the coexisting melt or fluid phase. (2) Less of a phosphate mineral is needed to account for the bulk phosphorus of planetaty mantles. (3) During partial melting of mantle mineral assemblages or equilibrium fractional crystallization of basaltic magmas, and in the absence or prior to saturation with a phosphate mineral, silicate melts may become enriched in phosphorus, especially in the geochemically important low melt fraction regime, Although the small differences in the ionic radii of IVp5+, IVSi4+, and IV Al3+ makes phosphoms incorporation into crystalline silicates perhaps unsurprising, isostructural silicate and phosphate crystalline solids do not readily form solutions, e.g., (Fe, Mg)2SiO4 vs. LiMgPO4, SiO)2 VS. AlPO4. Nonetheless, there are reports of, poorly characterized silico-phosphate phases in angrites , 2-4 wt% P2O5 in olivine and pyroxene grains in pallasites and reduced terestrial basalts which are little understood but potentially useful, and up to 17 wt% P2O5 in olivine from ancient slags. However, such enrichments are rare and only underscore the likelihood of phosphoms incorporation in silicate minerals. The mechanisms that allow phosphorus to enter major rock-forming silicate minerals (e.g., Oliv, Px, Gt) remain little understood and the relevant data base is limited. Nonetheless, old and new high-pressure (5-10 GPa) experimental data suggest that P2O5 wt% decreases from silica-poor to silica-rich compositions or from orthosilicate to chain silicate structures (garnet > olivine > orthopyroxene) which implies that phosphorus incorporation in silicates is perhaps more structure-than site-specific. The

The distribution of chromium among orthopyroxene, spinel and silicate liquid at atmospheric pressure

NASA Technical Reports Server (NTRS)

Barnes, S. J.

1986-01-01

The Cr distributions for a synthetic silicate melt equilibrated with bronzitic orthopyroxene and chromite spinel between 1334 and 1151 C over a range of oxygen fugacities between the nickel-nickel oxide and iron-wuestite buffers are studied. The occurrence, chemical composition, and structure of the orthopyroxene-silicate melt and the spinel-silicate melt are described. It is observed that the Cr content between bronzite and the melt increases with falling temperature along a given oxygen buffer and decreases with falling oxygen fugacity at a given temperature; however, the Cr content of the melt in equilibrium with spinel decreases with falling temperature and increases with lower oxygen fugacity.

Coordinated Hard Sphere Mixture (CHaSM): A simplified model for oxide and silicate melts at mantle pressures and temperatures

NASA Astrophysics Data System (ADS)

Wolf, Aaron S.; Asimow, Paul D.; Stevenson, David J.

2015-08-01

We develop a new model to understand and predict the behavior of oxide and silicate melts at extreme temperatures and pressures, including deep mantle conditions like those in the early Earth magma ocean. The Coordinated Hard Sphere Mixture (CHaSM) is based on an extension of the hard sphere mixture model, accounting for the range of coordination states available to each cation in the liquid. By utilizing approximate analytic expressions for the hard sphere model, this method is capable of predicting complex liquid structure and thermodynamics while remaining computationally efficient, requiring only minutes of calculation time on standard desktop computers. This modeling framework is applied to the MgO system, where model parameters are trained on a collection of crystal polymorphs, producing realistic predictions of coordination evolution and the equation of state of MgO melt over a wide range of pressures and temperatures. We find that the typical coordination number of the Mg cation evolves continuously upward from 5.25 at 0 GPa to 8.5 at 250 GPa. The results produced by CHaSM are evaluated by comparison with predictions from published first-principles molecular dynamics calculations, indicating that CHaSM is accurately capturing the dominant physics controlling the behavior of oxide melts at high pressure. Finally, we present a simple quantitative model to explain the universality of the increasing Grüneisen parameter trend for liquids, which directly reflects their progressive evolution toward more compact solid-like structures upon compression. This general behavior is opposite that of solid materials, and produces steep adiabatic thermal profiles for silicate melts, thus playing a crucial role in magma ocean evolution.

High chloride content calcium silicate glasses.

PubMed

Chen, Xiaojing; Karpukhina, Natalia; Brauer, Delia S; Hill, Robert G

2017-03-08

Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl 2 . The CaCl 2 has been added to the calcium metasilicate composition (CaO·SiO 2 ). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl 2 has been successfully incorporated into these silicate glasses without the occurrence of crystallization. 29 Si MAS-NMR spectra showed the silicon being present mainly as a Q 2 silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl 2 content, the T g reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl 2 content. However, both linear regressions revealed a breakpoint at a CaCl 2 content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl 2 crystallized to wollastonite, whilst the compositions with CaCl 2 content equal to or greater than 19.2 mol% are thought to crystallize to CaCl 2 . In practice, the crystallization of CaCl 2 could not occur until the crystallization temperature fell below the melting point of CaCl 2 . The implications of the results along with the high chloride retention are discussed.

Solubilities of nitrogen and noble gases in basalt melt

NASA Technical Reports Server (NTRS)

Miyazaki, A.; Hiyagon, H.; Sugiura, N.

1994-01-01

Nitrogen and noble gases are important tracers in geochemistry and chosmochemistry. Compared to noble gases, however, physicochemical properties of nitrogen, such as solubility in melt or melt/silicate partition, are not well known. Solubility of nitrogen in basalt melt depends on redox condition of the atmosphere. For example, solubility of nitrogen in E chondrite melt under reducing conditions is as high as 2 mol percent at 1500 C, suggesting that nitrogen is chemically dissolved in silicate melts, i.e., being dissolved as free anions or replacing oxygen sites in silicate network. However, the solubility and the dissolution mechanism of nitrogen under oxidizing conditions are not well investigated. To obtain nitrogen solubility in silicate melts under various redox conditions and to understand its mechanism, we are conducting experiments by using (15)N(15)N-labeled nitrogen gas. This makes it easy to distinguish dissolved nitrogen from later contamination of atmospheric nitrogen, and hence enables us to measure the nitrogen solubility accurately. As a preliminary experiment, we have measured solubility of nitrogen in basalt melt under the atmospheric oxygen pressure.

Iron metal production in silicate melts through the direct reduction of Fe/II/ by Ti/III/, Cr/II/, and Eu/II/. [in lunar basalts

NASA Technical Reports Server (NTRS)

Schreiber, H. D.; Balazs, G. B.; Shaffer, A. P.; Jamison, P. L.

1982-01-01

The production of metallic iron in silicate melts by chemical reactions of Ti(3+), Cr(2+), and Eu(2+) with Fe(2+) is demonstrated under experimental conditions in a simplified basaltic liquid. These reactions form a basis for interpreting the role of isochemical valency exchange models in explanations for the reduced nature of lunar basalts. The redox couples are individually investigated in the silicate melt to ascertain reference redox ratios that are independent of mutual interactions. These studies also provide calibrations of spectral absorptions of the Fe(2+) and Ti(2+) species in these glasses. Subsequent spectrophotometric analyses of Fe(2+) and Ti(2+) in glasses doped with both iron and titanium and of Fe(2+) in glasses doped with either iron and chromium or iron and europium ascertain the degree of mutual interactions in these dual-doped glasses.

XANES evidence for sulphur speciation in Mn-, Ni- and W-bearing silicate melts

NASA Astrophysics Data System (ADS)

Evans, K. A.; O'Neill, H. St. C.; Mavrogenes, J. A.; Keller, N. S.; Jang, L.-Y.; Lee, J.-F.

2009-11-01

S K-edge XANES and Mn-, W- and Ni-XANES and EXAFS spectra of silicate glasses synthesised at 1400 °C and 1 bar with compositions in the CaO-MgO-Al 2O 3-SiO 2-S plus MnO, NiO, or WO 3 systems were used to investigate sulphur speciation in silicate glasses. S K-edge spectra comprised a composite peak with an edge between 2470 and 2471.4 eV, which was attributed to S 2-, and a peak of variable height with an edge at 2480.2-2480.8 eV, which is consistent with the presence of S 6+. The latter peak was attributed to sample oxidation during sample storage. W-rich samples produced an additional lower energy peak at 2469.8 eV that is tentatively attributed to the existence of S 3p orbitals hybridised with the W 5d states. Deconvolution of the composite peak reveals that the composite peak for Mn-bearing samples fits well to a model that combines three Lorentzians at 2473.1, 2474.9 and 2476.2 eV with an arctan edge step. The composite peak for W-bearing samples fits well to the same combination plus an additional Lorentzian at 2469.8 eV. The ratio of the proportions of the signal accounted for by peaks at 2473.1 and 2476.2 eV correlates with Mn:Ca molar ratios, but not with W:Ca ratios. Spectra from Ni-bearing samples were qualitatively similar but S levels were too low to allow robust quantification of peak components. Some part of the signal accounted for by the 2473.1 eV peak was therefore taken to record the formation of Mn-S melt species, while the 2469.8 peak is interpreted to record the formation of W-S melt species. The 2474.9 and 2476.2 eV peaks were taken to be dominated by Ca-S and Mg-S interactions. However, a 1:1 relationship between peak components and specific energy transitions is not proposed. This interpretation is consistent with known features of the lower parts of the conduction band in monosulphide minerals and indicates a similarity between sulphur species in the melts and the monosulphides. S-XANES spectra cannot be reproduced by a combination of the

Occurrence of silicate melt, carbonate-rich melt and fluid during medium pressure anatexis of metapelitic gneisses (Oberpfalz, Bavaria) revealed by melt and fluid inclusions study

NASA Astrophysics Data System (ADS)

Ferrero, Silvio; O'Brien, Patrick; Hecht, Lutz; Wunder, Bernd

2014-05-01

of a silicate melt and a carbonate-rich melt during anatexis at relatively shallow crustal levels, but this hypothesis needs to be further tested through re-homogenization experiments by piston cylinder means. References Bartoli, O., Cesare, B., Poli, S., Bodnar, R.J., Acosta-Vigil, A., Frezzotti, M.L. & Meli, S., 2013. Recovering the composition of melt and the fluid regime at the onset of crustal anatexis and S-type granite formation. Geology, 41, 115-118. Cesare, B., Ferrero, S., Salvioli-Mariani, E., Pedron, D. & Cavallo, A., 2009. Nanogranite and glassy inclusions: the anatectic melt in migmatites and granulites. Geology, 37, 627-630. Ferrero, S., Bartoli, O., Cesare, B., Salvioli Mariani, E., Acosta-Vigil, A., Cavallo, A., Groppo, C. & Battiston, S., 2012. Microstructures of melt inclusions in anatectic metasedimentary rocks. Journal of Metamorphic Geology, 30, 303-322. Ferrero, S., Braga, R., Berkesi, M., Cesare, B. & Laridhi Ouazaa, N., 2014. Production of Metaluminous melt during fluid-present anatexis: an example from the Maghrebian basement, La Galite Archipelago, central Mediterranean. Journal of Metamorphic Geology, DOI:10.1111/jmg.12068. Tanner, D.C. & Behrmann, J.H., 1995. The Variscan tectonics of the Moldanubian gneisses, Oberpfalzer Wald: a compressional history. Neues Jahrbuch fur Geologie und Palaontologie. Abhandlungen, 197, 331-355. Touret, J.L.R., 2009. Mantle to lower-crust fluid/melt transfer through granulite metamorphism. Russian Geology and Geophysics, 50, 1052-1062.

The structural role and homogeneous redox equilibria of iron in peraluminous, metaluminous and peralkaline silicate melts

NASA Astrophysics Data System (ADS)

Dickenson, M. P.; Hess, P. C.

1986-02-01

The compositional dependence of the redox ratio (FeO/FeO1.5) has been experimentally determined in K2O-Al2O3-SiO2-Fe2O3-FeO (KASFF) and K2O-CaO-Al2O3-SiO2-Fe2O3-FeO (KCASFF) silicate melts. Compositions were equilibrated at 1,450° C in air, with 78 mol % SiO2. KASFF melts have from 1 to 5 mol % Fe2O3 and include both peraluminous (K2OAl2O3) compositions. KCASFF melts have 1 mol % Fe2O3 encompassing peraluminous, metaluminous (CaO+K2O>Al2O3) and peralkaline compositions. Peralkaline KASFF melts with 1 mol % Fe2O3 have low and constant values for the redox ratio, whereas in peraluminous melts the redox ratio increases with increasing (K2O/Al2O3). Increasing total iron concentration increases the redox ratio in peraluminous melts and slightly decreases the redox ratio in peralkaline melts. Substituting CaO for K2O at fixed total iron (1 mol %) increases the redox ratio in both peraluminous and metaluminous KCASFF melts; however, the redox ratio in peralkaline KCASFF melts is not affected by this exchange. These data indicate that Fe3+ is in four-fold coordination, with K+ or Ca2+ providing local charge balance. The tetrahedral ferric species is most stable in peralkaline melts and least stable in peraluminous melts, due to the competition between Al3+ and Fe3+ for charge balancing cations in the latter melt. Tetrahedral Fe3+ is also less stable when Ca2+ provides local charge balance. The data are consistent with a network modifying role for Fe2+ in the melt. The data are interpreted to reflect the effects of melt composition on the partitioning of K+ and Ca2+ and Fe3+ and Al3+ between various species in the melt. These relationships are discussed in terms of homogeneous equilibria between various iron-bearing and iron-free melt species. The results also reflect the effect of liquid composition on the exchange potentials μFe3+ Al-1 and μCa0.5K-1. The exchange potentials are relatively constant in peralkaline melts, but decrease in

P- T phase relations of silicic, alkaline, aluminous liquids: new results and applications to mantle melting and metasomatism

NASA Astrophysics Data System (ADS)

Draper, David S.; Green, Trevor H.

1999-07-01

We report new experimental results obtained under nominally anhydrous conditions at 1.0-1.5 GPa on a synthetic melt whose composition is typical of extreme-composition xenolith glasses. These results demonstrate that part of this extreme compositional range is in equilibrium with a lherzolitic assemblage (olivine, orthopyroxene, and clinopyroxene on the liquidus), extending our earlier findings [D.S. Draper, T.H. Green P- T phase relations of silicic, alkaline, aluminous mantle-xenolith glasses under anhydrous and C-O-H fluid-saturated conditions, J. Petrol. 38 (1997) 1187-1224] showing saturation with harzburgite minerals (olivine and orthopyroxene on the liquidus). The new results strengthen the view that such liquids can readily coexist with upper mantle rocks. Our results also bear on the current debate regarding the nature of low-degree mantle melts between proponents of the diamond-aggregate technique [who argue for comparatively silica- and alkali-rich low-degree melts; e.g., M.B. Baker, M.M. Hirschmann, M.S. Ghiorso, E.M. Stolper, Compositions of near-solidus peridotite melts from experiments and thermodynamic calculations, Nature 375 (1995) 308-311; M.B. Baker, M.M. Hirschmann, L.E. Wasylenki, E.M. Stolper, M.S. Ghiorso, Quest for low-degree mantle melts, Nature 381 (1996) 286] and those favoring the sandwich technique [who question the value of the diamond-aggregate work and argue that near-solidus melts must be nepheline- and olivine-normative; T.J. Falloon, D.H. Green, H.St.C. O'Neill, C.G. Ballhaus, Quest for low-degree mantle melts, Nature 381 (1996) 285; T.J. Falloon, D.H. Green, H.St.C. O'Neill, W.O. Hibberson, Experimental tests of low degree peridotite partial melt compositions: implications for the nature of anhydrous near-solidus peridotite melts at 1 GPa, Earth Planet. Sci. Lett. 152 (1997) 149-162]. Our results support aspects of both views. The sandwich-technique view is supported, for example, because all our liquids coexisting with mantle

Clinopyroxene-melt element partitioning during interaction between trachybasaltic magma and siliceous crust: Clues from quartzite enclaves at Mt. Etna volcano

NASA Astrophysics Data System (ADS)

Mollo, S.; Blundy, J. D.; Giacomoni, P.; Nazzari, M.; Scarlato, P.; Coltorti, M.; Langone, A.; Andronico, D.

2017-07-01

A peculiar characteristic of the paroxysmal sequence that occurred on March 16, 2013 at the New South East Crater of Mt. Etna volcano (eastern Sicily, Italy) was the eruption of siliceous crustal xenoliths representative of the sedimentary basement beneath the volcanic edifice. These xenoliths are quartzites that occur as subspherical bombs enclosed in a thin trachybasaltic lava envelope. At the quartzite-magma interface a reaction corona develops due to the interaction between the Etnean trachybasaltic magma and the partially melted quartzite. Three distinct domains are observed: (i) the trachybasaltic lava itself (Zone 1), including Al-rich clinopyroxene phenocrysts dispersed in a matrix glass, (ii) the hybrid melt (Zone 2), developing at the quartzite-magma interface and feeding the growth of newly-formed Al-poor clinopyroxenes, and (iii) the partially melted quartzite (Zone 3), producing abundant siliceous melt. These features makes it possible to quantify the effect of magma contamination by siliceous crust in terms of clinopyroxene-melt element partitioning. Major and trace element partition coefficients have been calculated using the compositions of clinopyroxene rims and glasses next to the crystal surface. Zone 1 and Zone 2 partition coefficients correspond to, respectively, the chemical analyses of Al-rich phenocrysts and matrix glasses, and the chemical analyses of newly-formed Al-poor crystals and hybrid glasses. For clinopyroxenes from both the hybrid layer and the lava flow expected relationships are observed between the partition coefficient, the valence of the element, and the ionic radius. However, with respect to Zone 1 partition coefficients, values of Zone 2 partition coefficients show a net decrease for transition metals (TE), high-field strength elements (HFSE) and rare earth elements including yttrium (REE + Y), and an increase for large ion lithophile elements (LILE). This variation is associated with coupled substitutions on the M1, M2 and

Silicate glasses and sulfide melts in the ICDP-USGS Eyreville B core, Chesapeake Bay impact structure, Virginia, USA

USGS Publications Warehouse

Belkin, H.E.; Horton, J. Wright

2009-01-01

Optical and electron-beam petrography of melt-rich suevite and melt-rock clasts from selected samples from the Eyreville B core, Chesapeake Bay impact structure, reveal a variety of silicate glasses and coexisting sulfur-rich melts, now quenched to various sulfi de minerals (??iron). The glasses show a wide variety of textures, fl ow banding, compositions, devitrifi cation, and hydration states. Electron-microprobe analyses yield a compositional range of glasses from high SiO2 (>90 wt%) through a range of lower SiO2 (55-75 wt%) with no relationship to depth of sample. Some samples show spherical globules of different composition with sharp menisci, suggesting immiscibility at the time of quenching. Isotropic globules of higher interfacial tension glass (64 wt% SiO2) are in sharp contact with lower-surface-tension, high-silica glass (95 wt% SiO2). Immiscible glass-pair composition relationships show that the immiscibility is not stable and probably represents incomplete mixing. Devitrifi cation varies and some low-silica, high-iron glasses appear to have formed Fe-rich smectite; other glass compositions have formed rapid quench textures of corundum, orthopyroxene, clinopyroxene, magnetite, K-feldspar, plagioclase, chrome-spinel, and hercynite. Hydration (H2O by difference) varies from ~10 wt% to essentially anhydrous; high-SiO2 glasses tend to contain less H2O. Petrographic relationships show decomposition of pyrite and melting of pyrrhotite through the transformation series; pyrite? pyrrhotite? troilite??? iron. Spheres (~1 to ~50 ??m) of quenched immiscible sulfi de melt in silicate glass show a range of compositions and include phases such as pentlandite, chalcopyrite, Ni-As, monosulfi de solid solution, troilite, and rare Ni-Fe. Other sulfi de spheres contain small blebs of pure iron and exhibit a continuum with increasing iron content to spheres that consist of pure iron with small, remnant blebs of Fe-sulfi de. The Ni-rich sulfi de phases can be explained by

Impact-melt hygrometer for Mars: The case of shergottite Elephant Moraine (EETA) 79001

NASA Astrophysics Data System (ADS)

Liu, Yang; Chen, Yang; Guan, Yunbin; Ma, Chi; Rossman, George R.; Eiler, John M.; Zhang, Youxue

2018-05-01

We report volatile concentrations and hydrogen isotope compositions of impact melts and minerals in EETA 79001. We observed chemical changes in pyroxene, maskelynite (or feldspathic glass), and merrillite in contact with or inside impact melts. All pyroxene grains analyzed here are inside or close to impact melt pockets and contain 10-41 ppm H2O and enriched in D (δD = + 1729 to + 3707 ‰), with the highest values found in a grain enclosed in an impact melt pocket. Maskelynite or feldspathic glass contains 6.3 to 98 ppm H2O with δD values of +1604 to + 3938 ‰. The high H2O and δD values were obtained in those enclosed inside or in contact with the impact melts, whereas low H2O content (4 ppm) and terrestrial-like D/H value (δD of - 90 ± 82 ‰) were found in one maskelynite grain away from impact melts contains. Rims of ∼5 μm thickness of merrillite grains next to impact melts display Na-depletion by ∼0.9 wt%, and the sides in contact with impact melts show Mg-enrichment by ∼0.5 wt%. However, the H2O and δD values of merrillite interiors (39-242 ppm H2O and δD of +1682 to + 3884 ‰) do not show correlation with their proximity to the impact melts. Rather, δD and 1/H2O of merrillite form a negative trend different from that of impact melt pockets and maskelynite, suggesting post-crystallization or late-crystallization interactions with the crustal fluids. The impact melt pockets in EETA 79001 contain 121-646 ppm H2O, 4.3-13 ppm F, 13-50 ppm Cl, 707-2702 ppm S, and the δD values of +3368 to + 4639 ‰. The correlations between H2O, F, Cl, P2O5, and δD values of impact melts and feldspathic glass are consistent with mixing between a volatile-rich and high δD (+3000 to + 5000 ‰) endmember and a volatile-poor and low δD endmember. The volatile-poor and low δD endmember is consistent with magmatic volatiles stored in silicates. The volatile-rich and high δD endmember represents pre-impact alteration materials by subsurface water. Alteration

CO2-rich phonolitic melt and carbonatite immiscibility in melt inclusions in nephelinite (Hanang volcano, North Tanzanian Divergence, East African Rift).

NASA Astrophysics Data System (ADS)

Baudouin, C.; Parat, F.

2016-12-01

Hanang is the southern volcano of the East branch of the East African Rift and represents volcanic activity at early stage rifting (0.9 Ma). Lavas are highly alkaline Mg-poor nephelinites (Mg#=24.4-35.2) with cpx, garnet, nepheline, titanite, and apatite and result from fractional crystallisation of primary melilitite magmas (Parat et al. AGU2016). In this study, we investigate glassy melt inclusions at the rim of nepheline phenocrysts to constrain the late stage of nephelinite evolution and the behaviour of volatiles (CO2, H2O, S, F, Cl) during magma storage and ascent. The melt inclusions have a green silicate glass, a microcrystalline carbonate phase and a shrinkage bubble free of gas phase (Raman analyses) suggesting that carbonatite-silicate liquid immiscibility (85:15) occurred during nephelinite differentiation. The silicate glasses have trachytic composition (Na+K/Al=1.6-7.2, SiO2=54-65.5 wt%) with high CO2 (0.43 wt% CO2, SIMS analyses), sulfur (0.21-0.92 wt% S) and halogens (0.28-0.84 wt% Cl; 0.35-2.54 wt% F) content and very low H2O content (<0.1wt%, Raman analyses). The carbonate phase is an anhydrous Ca-Na±S,K- carbonate with 33 wt% CaO, 20 wt% Na2O, 3 wt% K2O, and 3 wt% S. The pre-immiscible silicate liquid (e.g. silicate melt + carbonatite) in equilibrium with nepheline and cpx phenocrysts has CO2-rich phonolitic composition (Na+K/Al=6.2-6.9) with 6 ± 1.5 wt% CO2 at pressure of 700-1100 MPa. The entrapped melt in nepheline corresponds to evolved interstitial silicate melt after crystallisation of cpx (16.7%), nepheline (40%) garnet (6.5%) and apatite (1.7%) from Mg-nephelinite magma. The immiscibility process leading to glassy silicate melt and microcrystalline carbonatitic melt occurred in closed system during rapid ascent at crustal level at 200-230 MPa. The absence of gas phase in shrinkage bubble in melt inclusions suggests CO2-undersaturated conditions during quenching. The absence of carbonatite lavas at Hanang volcano is then explained by

Pyroxene-melt equilibria. [for lunar maria basalts

NASA Technical Reports Server (NTRS)

Nielsen, R. L.; Drake, M. J.

1979-01-01

A thermodynamic analysis of pyroxene-melt equilibria is performed through use of a literature survey of analyses of high-Ca pyroxene and coexisting silicate melt pairs and analyses of low-Ca pyroxene silicate melt pairs. Reference is made to a modified version of a model developed by Bottinga and Weill (1972) which more successfully accounts for variations in melt composition than does a model which considers the melt to be composed of simple oxides which mix ideally. By using a variety of pyroxene melt relations, several pyroxene-melt and low-Ca pyroxene-high-Ca pyroxene geothermometers are developed which have internally consistant precisions of approximately + or - 20 C. Finally, it is noted that these equations may have application in modeling the evolution of mineral compositions during differentiation of basaltic magmas.

Material transport in laser-heated diamond anvil cell melting experiments

NASA Technical Reports Server (NTRS)

Campbell, Andrew J.; Heinz, Dion L.; Davis, Andrew M.

1992-01-01

A previously undocumented effect in the laser-heated diamond anvil cell, namely, the transport of molten species through the sample chamber, over distances large compared to the laser beam diameter, is presented. This effect is exploited to determine the melting behavior of high-pressure silicate assemblages of olivine composition. At pressures where beta-spinel is the phase melted, relative strengths of partitioning can be estimated for the incompatible elements studied. Iron was found to partition into the melt from beta-spinel less strongly than calcium, and slightly more strongly than manganese. At higher pressures, where a silicate perovskite/magnesiowuestite assemblage is melted, it is determined that silicate perovskite is the liquidus phase, with iron-rich magnesiowuestite accumulating at the end of the laser-melted stripe.

Experimental constraints on the degree of melting beneath tectonic plates

NASA Astrophysics Data System (ADS)

Clark, A. N.; Lesher, C. E.

2017-12-01

Determining the volume and geometric distribution of silicate melts is fundamentally important to understand the current structure of the Earth as well as the dynamics of the Earth's interior. Regions in the upper mantle and crust that have lower velocities than the 1D global average are commonly attributed to the presence of silicate melts. Constraining melt fraction and distribution from seismic data requires a robust equation of state for silicate melts. Commonly, silicate melts are modeled at high pressure using equations of state developed for crystalline materials (e.g. the Birch-Murnaghan equation of state). However, amorphous silicates (glasses and melts), which lack long-range ordering, violate Birch's law at high pressures and high temperatures (Clark et al., 2016). We present a new model for seismic velocity reductions that accounts for the violation of Birch's law (anomalous compressibility) observed in amorphous silicates, rendering compressional wave velocities more sensitive to melt fraction and distribution than previous estimates. Forward modeling that combines our experimental data with the analytical solution of Takei (2002) predicts comparable velocity reductions for compressional and shear waves for partially molten mantle. Additionally, models that use crystalline equations of state to determine melt fraction at high pressure may overestimate melt fraction by 20% at pressures corresponding to the lithosphere-asthenosphere boundary (LAB) with the overestimation increasing with depth (e.g. a factor of 2 at the transition zone). By applying our results to recent seismic studies below the western Pacific plate that have reported low velocity regions associated with the lithosphere - asthenosphere boundary (LAB), we predict melt present at <5% distributed in near-textural equilibrium. These findings reconcile seismic observations for the LAB regionally and locally, and favor models of strong coupling across the LAB rather than melt channeling due

Melt segregation from partially molten source regions - The importance of melt density and source region size

NASA Technical Reports Server (NTRS)

Stolper, E.; Hager, B. H.; Walker, D.; Hays, J. F.

1981-01-01

An investigation is conducted regarding the changes expected in the density contrast between basic melts and peridotites with increasing pressure using the limited data available on the compressibilities of silicate melts and data on the densities of mantle minerals. It is concluded that since compressibilities of silicate melts are about an order of magnitude greater than those of mantle minerals, the density contrast between basic melts and mantle minerals must diminish significantly with increasing pressure. An earlier analysis regarding the migration of liquid in partially molten source regions conducted by Walker et al. (1978) is extended, giving particular attention to the influence of the diminished density contrast between melt and residual crystals with increasing source region depth and to the influence of source region size. This analysis leads to several generalizations concerning the factors influencing the depths at which magmas will segregate from their source regions and the degrees of partial melting that can be achieved in these source regions before melt segregation occurs.

Melt fracturing and healing: A mechanism for degassing and origin of silicic obsidian

USGS Publications Warehouse

Cabrera, A.; Weinberg, R.F.; Wright, H.M.N.; Zlotnik, S.; Cas, Ray A.F.

2011-01-01

We present water content transects across a healed fault in pyroclastic obsidian from Lami pumice cone, Lipari, Italy, using synchrotron Fourier transform infrared spectroscopy. Results indicate that rhyolite melt degassed through the fault surface. Transects define a trough of low water content coincident with the fault trace, surrounded on either side by high-water-content plateaus. Plateaus indicate that obsidian on either side of the fault equilibrated at different pressure-temperature (P-T) conditions before being juxtaposed. The curves into the troughs indicate disequilibrium and water loss through diffusion. If we assume constant T, melt equilibrated at pressures differing by 0.74 MPa before juxtaposition, and the fault acted as a low-P permeable path for H2O that diffused from the glass within time scales of 10 and 30 min. Assuming constant P instead, melt on either side could have equilibrated at temperatures differing by as much as 100 ??C, before being brought together. Water content on the fault trace is particularly sensitive to post-healing diffusion. Its preserved value indicates either higher temperature or lower pressure than the surroundings, indicative of shear heating and dynamic decompression. Our results reveal that water contents of obsidian on either side of the faults equilibrated under different P-T conditions and were out of equilibrium with each other when they were juxtaposed due to faulting immediately before the system was quenched. Degassing due to faulting could be linked to cyclical seismic activity and general degassing during silicic volcanic activity, and could be an efficient mechanism of producing low-water-content obsidian. ?? 2011 Geological Society of America.

Martian regolith in Elephant Moraine 79001 shock melts? Evidence from major element composition and sulfur speciation

NASA Astrophysics Data System (ADS)

Walton, E. L.; Jugo, P. J.; Herd, C. D. K.; Wilke, M.

2010-08-01

Shock veins and melt pockets in Lithology A of Martian meteorite Elephant Moraine (EETA) 79001 have been investigated using electron microprobe (EM) analysis, petrography and X-ray Absorption Near Edge Structure (XANES) spectroscopy to determine elemental abundances and sulfur speciation (S 2- versus S 6+). The results constrain the materials that melted to form the shock glasses and identify the source of their high sulfur abundances. The XANES spectra for EETA79001 glasses show a sharp peak at 2.471 keV characteristic of crystalline sulfides and a broad peak centered at 2.477 keV similar to that obtained for sulfide-saturated glass standards analyzed in this study. Sulfate peaks at 2.482 keV were not observed. Bulk compositions of EETA79001 shock melts were estimated by averaging defocused EM analyses. Vein and melt pocket glasses are enriched in Al, Ca, Na and S, and depleted in Fe, Mg and Cr compared to the whole rock. Petrographic observations show preferential melting and mobilization of plagioclase and pyrrhotite associated with melt pocket and vein margins, contributing to the enrichments. Estimates of shock melt bulk compositions obtained from glass analyses are biased towards Fe- and Mg- depletions because, in general, basaltic melts produced from groundmass minerals (plagioclase and clinopyroxene) will quench to a glass, whereas ultramafic melts produced from olivine and low-Ca pyroxene megacrysts crystallize during the quench. We also note that the bulk composition of the shock melt pocket cannot be determined from the average composition of the glass but must also include the crystals that grew from the melt - pyroxene (En 72-75Fs 20-21Wo 5-7) and olivine (Fo 75-80). Reconstruction of glass + crystal analyses gives a bulk composition for the melt pocket that approaches that of lithology A of the meteorite, reflecting bulk melting of everything except xenolith chromite. Our results show that EETA79001 shock veins and melt pockets represent local mineral

Shock recovery of a magnesium-silicate spinelloid

NASA Astrophysics Data System (ADS)

Tschauner, O. D.; Asimow, P. D.; Ahrens, T. J.; Kostandova, N.

2009-12-01

Previously it was believed that some high pressure polymorphs (e.g. of framework silicates) form under shock via growth from shock-induced precursor microscopic melt zones. Since diffusion in the melt was assumed to control crystallization rates, absence of shock recovery of any of those minerals was attributed to the short duration of laboratory shock (0.1 to 1 microsecond) experiments. In contrast to laboratory experiments, grains of high pressure polymorphs of 1 - 100 micrometer diameter have been found in melt veins of shocked meteorites and were widely believed to have formed via diffusion-controlled growth that occurred over seconds to minute time scales. Recently we reported formation of wadsleyite from a shock-generated melt in a laboratory shock experiment by analysis of the recovery products [1]. The growth rate of wadsleyite crystals at the experimental temperature of 2000 to 3000 K was estimated to be several m/s suggesting that diffusion was not the dominant factor in this ultra-rapid crystal growth. Consequently, S6 shock events in chondrites may not always be related to long shock duration and large impactors. Here we report formation of another high-pressure magnesium silicate polymorph in a shock experiment. The starting materials for this 30 GPa shot was single-crystal synthetic forsterite in a NIST 1157 tool-steel chamber. The recovered material was analyzed by micro-Raman spectroscopy and by synchrotron-based micro-X ray diffraction. Diffraction experiments were conducted in Gandolfi-geometry at station B2, CHESS, using a MAR345 image plate detector and a primary beam of 25 keV energy. Melted regions of the sample contained a spinelloid isotypic to a magnesium-gallium germanate spinelloid synthesized at ambient pressure [2]. As in the previous study [1] we observe oxidation of iron from melted metal of the recovery chamber wall entrained by the silicate melt while silicon is partially reduced. The new high-pressure silicate may have formed at

Dynamic crystallization of silicate melts

NASA Technical Reports Server (NTRS)

Russell, W. J.

1984-01-01

Two types of furnaces with differing temperature range capabilities were used to provide variations in melt temperatures and cooling rates in a study of the effects of heterogeneous nucleation on crystallization. Materials of chondrule composition were used to further understanding of how the disequilibrium features displayed by minerals in rocks are formed. Results show that the textures of natural chondrules were duplicated. It is concluded that the melt history is dominant over cooling rate and composition in controlling texture. The importance of nuclei, which are most readily derived from preexisting crystalline material, support an origin for natural chondrules based on remelting of crystalline material. This would be compatible with a simple, uniform chondrule forming process having only slight variations in thermal histories resulting in the wide range of textures.

A model that helps explain Sr-isotope disequilibrium between feldspar phenocrysts and melt in large-volume silicic magma systems

USGS Publications Warehouse

Duffield, W.A.; Ruiz, J.

1998-01-01

Feldspar phenocrysts of silicic volcanic rocks are commonly in Sr-isotopic disequilibrium with groundmass. In some cases the feldspar is more radiogenic, and in others it is less radiogenic. Several explanations have been published previously, but none of these is able to accommodate both senses of disequilibrium. We present a model by which either more- or less-radiogenic feldspar (or even both within a single eruptive unit) can originate. The model requires a magma body open to interaction with biotite- and feldspar-bearing wall rock. Magma is incrementally contaminated as wall rock melts incongruently. Biotite preferentially melts first, followed by feldspar. Such melting behavior, which is supported by both field and experimental studies, first contaminates magma with a relatively radiogenic addition, followed by a less-radiogenic addition. Feldspar phenocrysts lag behind melt (groundmass of volcanic rock) in incorporating the influx of contaminant, thus resulting in Sr-isotopic disequilibrium between the crystals and melt. The sense of disequilibrium recorded in a volcanic rock depends on when eruption quenches the contamination process. This model is testable by isotopic fingerprinting of individual feldspar crystals. For a given set of geologic boundary conditions, specific core-to-rim Sr-isotopic profiles are expectable. Moreover, phenocrysts that nucleate at different times during the contamination process should record different and predictable parts of the history. Initial results of Sr-isotopic fingerprinting of sanidine phenocrysts from the Taylor Creek Rhyolite are consistent with the model. More tests of the model are desirable.Feldspar phenocrysts of silicic volcanic rocks are commonly in Sr-isotopic disequilibrium with groundmass. In some cases the feldspar is more radiogenic, and in others it is less radiogenic. Several explanations have been published previously, but none of these is able to accommodate both senses of disequilibrium. We present a

Aubrite basalt vitrophyres: High sulfur silicate melts and a snapshot of aubrite formation. [Abstract only

NASA Technical Reports Server (NTRS)

Fogel, R. A.

1994-01-01

Two aubrite basalt vitrophyre clasts have been found within AMNH thin sections from the Parsa EH3 chondrite and the Khor Temiki aubrite. Polished sections of the Parsa Aubrite Inclusion (PAI) and the Khor Temiki Inclusion (KTI) were studied by optical, electron probe microanalysis (EPMA), and scanning electron microscopy (SEM) techniques with broad-beam and low absorbed EPMA currents used to minimize glass volatile loss. Some data have previously been reported for PAI and KTI may possibly correlate to a previously reported inclusion in Khor Tiimiki. In polished sections, PAI and KTI are approximately equal 4 mm in diameter and contain a large volume of glass. The clasts have similar textural characteristics and are akin to lunar vitrophyre textures. The glasses have high alkali rhyodacitic compositions Al-though PAI is peraluminous, KTI is significantly peralkaline. Additionally, the glasses have elevated sulfur concentrations that are extremely high by geochemical standards. SEM examination for beam overlap of microscopic CaS, FeS, and (Mg, Mn, Fe) S inclusions showed no such contamination. Furthermore, homogeneity of glass S content and low FeO contents help rule out contamination. Materials research data show that under reducing conditions alumino-silicate melts can dissolve up to several weight percent sulfur in the absence of Fe. The high S and alkali contents, the lack of associated high shock features, and the rationalized phase equilibria suggest that PAI and KTI are igneous melting products of an E-chondrite-like source material. Although large-scale impact melting cannot totally be ruled out, the above observations eliminate the possibility of in-situ shock melting.

In situ insights to Se (S) partitioning between silicate and metallic melts at extreme conditions

NASA Astrophysics Data System (ADS)

Borchert, M.; Petitgirard, S.; Appel, K.; Watenphul, A.; Morgenroth, W.

2012-12-01

The Earth's core mainly consists of a metallic Fe-Ni mixture. However, seismic observations show that the density is about 5-10% lower than expected for an Fe-Ni alloy under similar pressure and temperature conditions (e.g., [1,2]). This discovery initiated numerous studies to identify and quantify light elements in the Earth0s core. Among others, sulphur has been suggested to be a promisingly candidate to alloy with the metallic core because of its depletion in the crust and the mantle relative to other volatile elements by several orders of magnitude (e.g., [3-5]). In the last decades, several experimental studies have aimed to quantify the sulphur content in the Earth's core and to determine its influence on the physical properties (e.g., [6]). However, experimental data on sulphur partitioning between silicate and metallic liquids at pressures and temperatures relevant for core-mantle boundary conditions are missing. This lack is due to pressure and temperature limitations of conventional experimental approaches (up to 25 GPa and 2200 K). New developments, like laser-heated diamond-anvil cells (LDAC), allow studies at core-mantle boundary conditions, but in-situ chemical analysis of sulphur in LDACs is impossible due to the high absorption of S fluorescence in the diamonds. Instead of sulphur, selenium can be used to model sulphur partitioning between silicate and metallic melts at elevated PT conditions. This is based on the fact that sulphur and selenium can be considered as geochemical twins ([7,8]). The main advantage of this approach is the much higher excitation energy of selenium compared to sulphur, which enables in-situ XRF analysis in LDACs. Here, we present preliminary data on Se partitioning between silicate and metallic melt at extreme conditions. The experiments have been performed in double-sided laser-heated LDACs at the high pressure beamlines P02.2 (DESY, Germany) and ID27 (ESRF, France) as described in [9]. Micro-XRF mappings are used to

Impact-generated carbonate melts: evidence from the Haughton structure, Canada

NASA Astrophysics Data System (ADS)

Osinski, Gordon R.; Spray, John G.

2001-12-01

Evidence is presented for the melting of dolomite-rich target rocks during formation of the 24 km diameter, 23 Ma Haughton impact structure on Devon Island in the Canadian high Arctic. Field studies and analytical scanning electron microscopy reveal that the >200 m thick crater-fill deposit, which currently covers an ˜60 km2 area in the center of the structure, comprises fragmented target rocks set within a carbonate-silicate matrix. The silicate component of the matrix consists of Si-Al-Mg-rich glass. The carbonate component is microcrystalline calcite, containing up to a few wt% Si and Al. The calcite also forms spherules and globules within the silicate glass, with which it develops microtextures indicative of liquid immiscibility. Dolomite clasts exhibit evidence of assimilation and may show calcite and rare dolomite overgrowths. Some clasts are penetrated by calcite and silicate injections. Along with the carbonate-silicate glass textures, the presence of pigeonite and spinifex-textured diopside suggests that the matrix to the crater-fill deposit was originally molten and was rapidly cooled. This indicates that the impact event that generated Haughton caused fusion of the predominantly dolomitic target rocks. It appears that the Ca-Mg component of the dolomite may have dissociated, with Mg entering the silicate melt phase, while the Ca component formed a CaCO3-dominant melt. The silicates were derived by the fusion of Lower Paleozoic sandstones, siltstones, shales and impure dolomites. Evidence for melting is corroborated by a review of theoretical and experimental work, which shows that CaCO3 melts at >10 GPa and >2000 K, instead of dissociating to release CO2. This work indicates that carbonate-rich sedimentary targets may also undergo impact melting and that the volume of CO2 released into the atmosphere during such events may be considerably less than previously estimated.

Oceanic slab melting and mantle metasomatism.

PubMed

Scaillet, B; Prouteau, G

2001-01-01

Modern plate tectonic brings down oceanic crust along subduction zones where it either dehydrates or melts. Those hydrous fluids or melts migrate into the overlying mantle wedge trigerring its melting which produces arc magmas and thus additional continental crust. Nowadays, melting seems to be restricted to cases of young (< 50 Ma) subducted plates. Slab melts are silicic and strongly sodic (trondhjemitic). They are produced at low temperatures (< 1000 degrees C) and under water excess conditions. Their interaction with mantle peridotite produces hydrous metasomatic phases such as amphibole and phlogopite that can be more or less sodium rich. Upon interaction the slab melt becomes less silicic (dacitic to andesitic), and Mg, Ni and Cr richer. Virtually all exposed slab melts display geochemical evidence of ingestion of mantle material. Modern slab melts are thus unlike Archean Trondhjemite-Tonalite-Granodiorite rocks (TTG), which suggests that both types of magmas were generated via different petrogenetic pathways which may imply an Archean tectonic model of crust production different from that of the present-day, subduction-related, one.

Experimental correlation of melt structures, nucleation rates, and thermal histories of silicate melts

NASA Technical Reports Server (NTRS)

Boynton, W. V.; DRAKE; HILDEBRAND; JONES; LEWIS; TREIMAN; WARK

1987-01-01

The theory and measurement of the structure of liquids is an important aspect of modern metallurgy and igneous petrology. Liquid structure exerts strong controls on both the types of crystals that may precipitate from melts and on the chemical composition of those crystals. An interesting aspect of melt structure studies is the problem of melt memories; that is, a melt can retain a memory of previous thermal history. This memory can influence both nucleation behavior and crystal composition. This melt memory may be characterized quantitatively with techniques such as Raman, infrared and NMR spectroscopy to provide information on short-range structure. Melt structure studies at high temperature will take advantage of the microgravity conditions of the Space Station to perform containerless experiments. Melt structure determinations at high temperature (experiments that are greatly facilitated by containerless technology) will provide invaluable information for materials science, glass technology, and geochemistry. In conjunction with studies of nucleation behavior and nucleation rates, information relevant to nucleation in magma chambers in terrestrial planets will be acquired.

Inclusions of Sulphide Immiscible Melts in Primitive Olivine Phenocrysts from Mantle-Derived Magmas; Preliminary Results

NASA Astrophysics Data System (ADS)

Danyushevsky, L.; Ryan, C.; Kamenetsky, V.; Crawford, A.

2001-12-01

Sulphide inclusions have been identified in olivine phenocrysts (and in one case in a spinel phenocryst) in primitive volcanic rocks from mid- ocean ridges, subduction-related island arcs and backarc basins. These inclusions represent droplets of an immiscible sulphide melt and are trapped by olivine crystals growing from silicate melts. Sulphide melt is usually trapped as separate inclusions, however combined inclusions of sulphide and silicate melts have also been observed. Sulphide inclusions have rounded shapes and vary in size from several up to 100 microns in diameter. At room temperature sulphide inclusions consist of several phases. These phases are formed as a result of crystallisation of the sulphide melt after it was trapped. Crystallisation occurs due to decreasing temperature in the magma chamber after trapping and/or when magma ascents from the magma chamber during eruptions. In all studied sulphides three different phases can be identified: a high- Fe, low-Ni, low-Cu phase; a high-Fe, high-Ni, low-Cu phase; and high-Fe, low-Ni, high-Cu phase. Low-Cu phases appear to be monomineralic, whereas the high-Cu phase is usually composed of a fine intergrowth of high- and low-Cu phases, resembling the quench 'spinifex' structure. Fe, Ni and Cu are the major elements in all sulphides studied. The amount of Ni decreases with decreasing forsterite content of the host olivine phenocryst, which is an index of the degree of silicate magma fractionation. Since Ni content of the silicate magma is decreasing during fractionation, this indicates either that the immiscible sulfide melt remains in equilibrium with the silicate melt continuously changing its composition during fractionation, or that the sulfide melt is continuously separated from the silicate melt during fractionation, with later formed droplets having lower Ni content due to the lower Ni content of the evolved, stronger fractionated silicate melt. Trace element contents of the sulfide inclusions have

Evidence for a sulfur-undersaturated lunar interior from the solubility of sulfur in lunar melts and sulfide-silicate partitioning of siderophile elements

NASA Astrophysics Data System (ADS)

Steenstra, E. S.; Seegers, A. X.; Eising, J.; Tomassen, B. G. J.; Webers, F. P. F.; Berndt, J.; Klemme, S.; Matveev, S.; van Westrenen, W.

2018-06-01

Sulfur concentrations at sulfide saturation (SCSS) were determined for a range of low- to high-Ti lunar melt compositions (synthetic equivalents of Apollo 14 black and yellow glass, Apollo 15 green glass, Apollo 17 orange glass and a late-stage lunar magma ocean melt, containing between 0.2 and 25 wt.% TiO2) as a function of pressure (1-2.5 GPa) and temperature (1683-1883 K). For the same experiments, sulfide-silicate partition coefficients were derived for elements V, Cr, Mn, Co, Cu, Zn, Ga, Ge, As, Se, Mo, Sn, Sb, Te, W and Pb. The SCSS is a strong function of silicate melt composition, most notably FeO content. An increase in temperature increases the SCSS and an increase in pressure decreases the SCSS, both in agreement with previous work on terrestrial, lunar and martian compositions. Previously reported SCSS values for high-FeO melts were combined with the experimental data reported here to obtain a new predictive equation to calculate the SCSS for high-FeO lunar melt compositions. Calculated SCSS values, combined with previously estimated S contents of lunar low-Ti basalts and primitive pyroclastic glasses, suggest their source regions were not sulfide saturated. Even when correcting for the currently inferred maximum extent of S degassing during or after eruption, sample S abundances are still > 700 ppm lower than the calculated SCSS values for these compositions. To achieve sulfide saturation in the source regions of low-Ti basalts and lunar pyroclastic glasses, the extent of degassing of S in lunar magma would have to be orders of magnitude higher than currently thought, inconsistent with S isotopic and core-to-rim S diffusion profile data. The only lunar samples that could have experienced sulfide saturation are some of the more evolved A17 high-Ti basalts, if sulfides are Ni- and/or Cu rich. Sulfide saturation in the source regions of lunar melts is also inconsistent with the sulfide-silicate partitioning systematics of Ni, Co and Cu. Segregation of

Barrier Properties of Layered-Silicate Reinforced Ethylenepropylenediene Monomer/Chloroprene Rubber Nanorubbers.

PubMed

Wu, Chang Mou; Hsieh, Wen Yen; Cheng, Kuo Bin; Lai, Chiu-Chun; Lee, Kuei Chi

2018-05-09

The triacetin and nitroglycerin barrier properties of layered-silicate reinforced ethylenepropylenediene monomer/chloroprene rubber (EPDM/CR) nanorubbers were investigated as rocket-propellant inhibitors. EPDM/CR nanorubbers with intercalated structures were formulated and prepared by the melt-compounding method. The triacetin permeability and nitroglycerin absorption were observed to decrease with increasing layered-silicate content. The layered silicates also improved the flame retardancies of the nanorubbers by forming silicate reinforced carbonaceous chars. Layered-silicate reinforced EPDM/CR nanorubbers are potentially effective rocket propellant-inhibiting materials.

Microstructure and mechanical properties of stainless steel/calcium silicate composites manufactured by selective laser melting.

PubMed

Zheng, Zeng; Wang, Lianfeng; Jia, Min; Cheng, Lingyu; Yan, Biao

2017-02-01

Selective laser melting (SLM) is raised as one kind of additive manufacturing (AM) which is based on the discrete-stacking concept. This technique can fabricate advanced composites with desirable properties directly from 3D CAD data. In this research, 316L stainless steel (316L SS) and different fractions of calcium silicate (CaSiO 3 ) composites (weight fractions of calcium silicate are 0%, 5%,10% and 15%, respectively) were prepared by SLM technique with a purpose to develop biomedical metallic materials. The relative density, tensile, microhardness and elastic modulus of the composites were tested, their microstructures and fracture morphologies were observed using optical microscope (OM), scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was found that the addition of CaSiO 3 particles influenced the microstructure and mechanical properties of specimens significantly. The CaSiO 3 precipitates from the overlap of adjacent tracks and became the origin of the defects. The tensile strength of specimens range 320-722MPa. The microhardness and elastic modulus are around 250HV and 215GPa respectively. These composites were ductile materials and the fracture mode of the composites was mixed mode of ductile and brittle fracture. The 316L SS/CaSiO 3 composites can be a potential biomedical metallic materials in the medical field. Copyright © 2016. Published by Elsevier B.V.

(Energetics of silicate melts from thermal diffusion studies)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1989-01-01

Research during the past year has been concentrated in four major areas. We are continuing work initiated during the first two years on modelling thermal diffusion on multicomponent silicate liquids. We have derived appropriate relations for ternary and quaternary systems and reanalyzed experimental thermal diffusion data for the ternary system fayalite-leucite-silica. In our manuscript entitled Thermal Diffusion in Petrology'', to be published in Adv. in Phy. Geochem., we show that these model results independently recover the compositional extent and temperature of liquid immiscibility in this system. Such retrieval provides a rigorous test of our theoretical predictions and simplified treatment ofmore » complex silicate liquids reported in Geochimica Cosmochimica Acta in 1986. The usefulness of our Soret research in providing mixing energies of silicate liquids has been recently confirmed by Ghiorso (1987, Cont. Min. Pet.). This demonstration provides a strategy for incorporating Soret data into the calibration of phase equilibrium-based solution models such as the one developed by Ghiorso. During the past year we also have resumed our studies of thermal diffusion in borosilicate glasses which also exhibit liquid immiscibility. Our objectives in studying these systems are (1) to further test of our multicomponent thermal diffusion model and (2) to provide quantitative constraints on the mixing properties of these glass-forming systems which are important for evaluating their suitability for storage of high-level nuclear waste. 16 refs.« less

Experimentally determined sulfur isotope fractionation between metal and silicate and implications for planetary differentiation

NASA Astrophysics Data System (ADS)

Labidi, J.; Shahar, A.; Le Losq, C.; Hillgren, V. J.; Mysen, B. O.; Farquhar, J.

2016-02-01

The Earth's mantle displays a subchondritic 34S/32S ratio. Sulfur is a moderately siderophile element (i.e. iron-loving), and its partitioning into the Earth's core may have left such a distinctive isotope composition on the terrestrial mantle. In order to constrain the sulfur isotope fractionation occurring during core-mantle differentiation, high-pressure and temperature experiments were conducted with synthetic mixtures of metal and silicate melts. With the purpose to identify the mechanism(s) responsible for the S isotope fractionations, we performed our experiments in different capsules - namely, graphite and boron nitride capsules - and thus at different fO2, with varying major element chemistry of the silicate and metal fractions. The S isotope fractionations Δ34Smetal-silicate of equilibrated metal alloys versus silicate melts is +0.2 ± 0.1‰ in a boron-free and aluminum-poor system quenched at 1-1.5 GPa and 1650 °C. The isotope fractionation increases linearly with increasing boron and aluminum content, up to +1.4 ± 0.2‰, and is observed to be independent of the silicon abundance as well as of the fO2 over ∼3.5 log units of variations explored here. The isotope fractionations are also independent of the graphite or nitride saturation of the metal. Only the melt structural changes associated with aluminum and boron concentration in silicate melts have been observed to affect the strength of sulfur bonding. These results establish that the structure of silicate melts has a direct influence on the S2- average bonding strengths. These results can be interpreted in the context of planetary differentiation. Indeed, the structural environments of silicate evolve strongly with pressure. For example, the aluminum, iron or silicon coordination numbers increase under the effect of pressure. Consequently, based on our observations, the sulfur-bonding environment is likely to be affected. In this scheme, we tentatively hypothesize that S isotope fractionations

The solubility of platinum in silicate melt under reducing conditions: Results from experiments without metal inclusions

NASA Astrophysics Data System (ADS)

Bennett, N. R.; Brenan, J. M.; Koga, K. T.

2014-05-01

The solubility of Pt in silicate melt was investigated at conditions of 2073-2573 K, 2 GPa and ˜IW -1.5 to +3.5. These are the first measurements of Pt solubility under conditions more reducing than the iron-wüstite buffer (IW) which are demonstrably free from contamination by metal-inclusions. Pt solubility increases with increasing temperature and decreasing oxygen fugacity. The ability of carbon to enhance Pt solubility under reducing conditions (silicate partition coefficients calculated from our Pt solubility data show that, for core-mantle equilibrium at IW -2, Pt concentrations in the primitive upper mantle (PUM) can be satisfied if the temperature of equilibration is >3500 K. Under these conditions however, the estimated Pt/Os ratio is ˜40,000 times higher than that estimated for the PUM (Brandon et al., 2006). Instead, the PUM composition is generated most readily by metal-silicate equilibrium at more modest temperatures (˜3100 K), followed by a late accretion of chondritic material subsequent to core formation.

Barrier Properties of Layered-Silicate Reinforced Ethylenepropylenediene Monomer/Chloroprene Rubber Nanorubbers

PubMed Central

Hsieh, Wen Yen; Cheng, Kuo Bin; Lai, Chiu-Chun; Lee, Kuei Chi

2018-01-01

The triacetin and nitroglycerin barrier properties of layered-silicate reinforced ethylenepropylenediene monomer/chloroprene rubber (EPDM/CR) nanorubbers were investigated as rocket-propellant inhibitors. EPDM/CR nanorubbers with intercalated structures were formulated and prepared by the melt-compounding method. The triacetin permeability and nitroglycerin absorption were observed to decrease with increasing layered-silicate content. The layered silicates also improved the flame retardancies of the nanorubbers by forming silicate reinforced carbonaceous chars. Layered-silicate reinforced EPDM/CR nanorubbers are potentially effective rocket propellant-inhibiting materials. PMID:29747427

Iron K-edge X-ray absorption near-edge structure spectroscopy of aerodynamically levitated silicate melts and glasses

DOE PAGES

Alderman, O. L. G.; Wilding, M. C.; Tamalonis, A.; ...

2017-01-26

Here, the local structure about Fe(II) and Fe(III) in silicate melts was investigated in-situ using iron K-edge X-ray absorption near-edge structure (XANES) spectroscopy. An aerodynamic levitation and laser heating system was used to allow access to high temperatures without contamination, and was combined with a chamber and gas mixing system to allow the iron oxidation state, Fe 3+/ΣFe, to be varied by systematic control of the atmospheric oxygen fugacity. Eleven alkali-free, mostly iron-rich and depolymerized base compositions were chosen for the experiments, including pure oxide FeO, olivines (Fe,Mg) 2SiO 4, pyroxenes (Fe,Mg)SiO 3, calcic FeO-CaSiO 3, and a calcium aluminosilicatemore » composition, where total iron content is denoted by FeO for convenience. Melt temperatures varied between 1410 and 2160 K and oxygen fugacities between FMQ – 2.3(3) to FMQ + 9.1(3) log units (uncertainties in parentheses) relative to the fayalite-magnetite-β-quartz (FMQ) buffer.« less

Contrasting Effects of Carbon and Sulfur on Fe-Isotope Fractionation between Metal and Silicate Melt during Planetary Core Formation

NASA Astrophysics Data System (ADS)

Elardo, S. M.; Shahar, A.

2015-12-01

There are numerous studies that show well-resolved Fe isotope fractionations in igneous materials from different planetary bodies. Potential explanations for these fractionations include a non-chondritic bulk planetary Fe isotopic composition, and equilibrium fractionation between Fe-alloys or minerals and silicate melts during planetary differentiation, mantle melting, or fractional crystallization. This is further complicated by the fact that these processes are not mutually exclusive, making the interpretation of Fe isotope data a complex task. Here we present new experimental results investigating the effect of C on Fe isotope fractionation between molten peridotite and an Fe-alloy. Experiments were conducted at 1 GPa and 1850° C for 0.5 - 3 hours on a mixture of an 54Fe-spiked peridotite and Fe-metal with and without Ni metal in an end-loaded piston cylinder at the Geophysical Laboratory. Carbon saturation was achieved with a graphite capsule, and resulted in C contents of the Fe-alloy in our experiments ranging from 3.8 - 4.9 wt. %. The metal and silicate phases from half of each experiment were separated manually and dissolved in concentrated acids. Iron was separated from matrix elements by anion exchange chromatagraphy. Iron-isotopic compositions were determined with the Nu Plasma II MC-ICP-MS at GL. The other half of each experiment was used for quantitative microbeam analysis. Equilibrium was assessed with a time series and the three-isotope exchange method. The Ni-free experiments resulted in no resolvable Fe isotope fractionation between the Fe-C-alloy and molten silicate. This is in contrast to the results of Shahar et al. (2015) which showed a fractionation for Δ57Fe of ~0.18 ‰ between a peridotite and an Fe-alloy with a similar S abundance to C in these experiments. The one experiment thus far that contained Ni (~4 wt. % in the alloy) showed a resolvable fractionation between the Fe-Ni-C alloy and silicate of ~0.10 ‰. Shahar et al. found a

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus.

PubMed

Shellnutt, J Gregory

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra.

Derivation of intermediate to silicic magma from the basalt analyzed at the Vega 2 landing site, Venus

PubMed Central

2018-01-01

Geochemical modeling using the basalt composition analyzed at the Vega 2 landing site indicates that intermediate to silicic liquids can be generated by fractional crystallization and equilibrium partial melting. Fractional crystallization modeling using variable pressures (0.01 GPa to 0.5 GPa) and relative oxidation states (FMQ 0 and FMQ -1) of either a wet (H2O = 0.5 wt%) or dry (H2O = 0 wt%) parental magma can yield silicic (SiO2 > 60 wt%) compositions that are similar to terrestrial ferroan rhyolite. Hydrous (H2O = 0.5 wt%) partial melting can yield intermediate (trachyandesite to andesite) to silicic (trachydacite) compositions at all pressures but requires relatively high temperatures (≥ 950°C) to generate the initial melt at intermediate to low pressure whereas at high pressure (0.5 GPa) the first melts will be generated at much lower temperatures (< 800°C). Anhydrous partial melt modeling yielded mafic (basaltic andesite) and alkaline compositions (trachybasalt) but the temperature required to produce the first liquid is very high (≥ 1130°C). Consequently, anhydrous partial melting is an unlikely process to generate derivative liquids. The modeling results indicate that, under certain conditions, the Vega 2 composition can generate silicic liquids that produce granitic and rhyolitic rocks. The implication is that silicic igneous rocks may form a small but important component of the northeast Aphrodite Terra. PMID:29584745

Coordination chemistry of titanium (IV) in silicate glasses and melts: IV. XANES studies of synthetic and natural volcanic glasses and tektites at ambient temperature and pressure

NASA Astrophysics Data System (ADS)

Farges, François; Brown, Gordon E.

1997-05-01

The coordination environment of Ti(IV) in seven natural and synthetic glasses of basaltic, trachytic, rhyolitic composition as well as four tektites has been studied using high-resolution Ti K-edge x-ray absorption near edge structure (XANES) spectroscopy at ambient temperature and pressure. Pre-edge features of Ti K-edge XANES spectra for these glasses suggest that [5]Ti is the dominant Ti coordination in all volcanic glasses. However, in the less polymerized glasses studied (basaltic and trachytic), [6]Ti is also important (30-50% of the total Ti) but [4]Ti was not detected. In contrast, [4]Ti is important in the most polymerized glasses (rhyolites and tektites) (from 30 to 60% of the total Ti depending on NBO/T) with [6]Ti below the detection level (≈10 at%). The local structure around Ti in the natural volcanic glasses is similar to that observed in compositionally similar synthetic silicate glasses and also in Ti-bearing silicate glass and melts with simpler compositions. The presence of F, Cl, and H 2O does not appear to affect the coordination of Ti, based on Ti K-edge XANES measurements of natural glasses bearing these volatile components. In contrast, the presence of nonbridging oxygens (produced by network modifiers) favors [5]Ti in these glass/melts. In parallel, [4]Ti is important when nonbridging oxygens are at small concentrations (NBO/T < 0.1). [6]Ti is detected (i.e., when present >10% of the total Ti) when alkaline-earths are dominant over alkalis, in agreement with bond-valence predictions for Ti-bearing silicate glass/melts below TiO 2 saturation. The abundance of [5]Ti in these silicate glasses (and presumably their melts) is in sharp contrast with the rarity of this Ti coordination state in common rock-forming minerals. Titanium cannot readily enter the structure of most rock-forming minerals, because it is present dominantly as titanyl-bearing ( [5]TiO) units in most natural magmas. In contrast, [6]Ti and [4]Ti (present, respectively, in

The Effect of Pressure on Iron Speciation in Silicate Melts at a Fixed Oxygen Fugacity: The Possibility of a Redox Profile Through a Terrestrial Magma Ocean

NASA Astrophysics Data System (ADS)

Armstrong, K.; Frost, D. J.; McCammon, C. A.; Rubie, D. C.; Boffa Ballaran, T.

2017-12-01

As terrestrial planets accreted, mantle silicates equilibrated with core-forming metallic iron, which would have imposed a mantle oxygen fugacity below the iron-wüstite oxygen buffer. Throughout Earth's history, however, the oxygen fugacity of at least the accessible portions of the upper mantle has been 4-5 orders of magnitude higher. The process that caused the rapid increase in the redox state of the mantle soon after core formation is unclear. Here we test the possibility that pressure stabilises ferric iron in silicate melts, as has been observed in silicate minerals. A deep magma ocean, which would have likely existed towards the end of accretion, could then develop a gradient in oxygen fugacity for a fixed ferric-ferrous ratio as a result of pressure. We have equilibrated an andesitic melt with a Ru-RuO2 buffer in a multianvil press between 5 and 24 GPa. Further experiments were performed on the same melt in equilibrium with iron metal. The recovered melts were then analysed using Mössbauer spectroscopy to determine the ferric/ferrous ratio. The results show that for the Ru-RuO2 buffer at lower pressures, the ferric iron content decreases with pressure, due to a positive volume change of the reaction FeO + 1/4O2 = FeO1.5. Ferric iron content also appears to be sensitive to water content at lower pressures. However, above 15 GPa this trend apparently reverses and the ferric iron content increases with pressure. This reversal in pressure dependence would drive the oxygen fugacity of a deep magma ocean with a fixed ferric/ferrous ratio down with increasing depth. This would create a redox gradient, where the magma ocean could potentially be in equilibrium with metallic iron at its base but more oxidised in its shallower regions. Crystallisation of this magma ocean could render an upper mantle oxygen fugacity similar to that in the Earth's accessible mantle today.

Computational and experimental studies of iron-bearing carbonates and silicate glasses at lower mantle pressures

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Jackson, J. M.; Asimow, P. D.; Sturhahn, W.; Rossman, G. R.; Roskosz, M.

2017-12-01

Decomposition of carbonates may be responsible for creating silicate melts within the lower mantle by lowering the melting temperature of surrounding rock. Identifying and characterizing the stability of carbonates is therefore a necessary step towards understanding the transport of carbon in Earth's interior. Dolomite is one of the major mineral forms in which carbon is subducted into the Earth's mantle. Although iron-free dolomite is expected to break down upon compression, high-pressure polymorphs of iron-bearing dolomite may resist decomposition. Using a genetic algorithm that predicts crystal structures, we found a monoclinic phase with space group C2/c that has a lower energy than all previously reported dolomite structures at pressures above 15 GPa, where the substitution of iron for magnesium stabilizes monoclinic dolomite at certain pressures of the lower mantle. Thus, an iron-bearing dolomite polymorph may be an important carbon carrier in regions of Earth's lower mantle. The depth at which carbonates will decompose is dependent on the age, temperature and density of subducting slabs. Decarbonation reactions may lower the melting temperature of surrounding rocks to produce silicate melts. In regions of the mantle where silicate melts may exist, it is important to understand the physical properties and dynamic behavior of the melts because they affect the chemical and thermal evolution of its interior. Composition, degree of polymerization, and iron's spin state affect such properties. The behavior of iron in silicate melts is poorly understood but, in some cases, may be approximated by iron-bearing glasses. We measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to 120 GPa and 100 GPa, respectively, in a neon pressure medium using time-domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe2+-like sites with distinct quadrupole splittings, reflecting

Amphibole incongruent melting under Lithospheric Mantle conditions in spinel peridotites from Balaton area, Hungary

NASA Astrophysics Data System (ADS)

Ntaflos, Theodoros; Abart, Rainer; Bizimis, Michel

2017-04-01

Pliocene alkali basalts from the western Pannonian Basin carry mantle xenoliths comprising hydrous and anhydrous spinel peridotites. We studied coarse and fine grained fertile to depleted spinel lherzolites, spinel harzubrgites and dunites from Szentbékálla, Balaton, in detail, using XRF, EPMA and LA-ICP-MS and MC-ICP-MS techniques. Pliocene alkali basalts containing mantle xenoliths with three major types of textures are widespread in the studied area: fine-grained primary and secondary equigranular, coarse-grained protogranular and transitional between equigranular and protogranular textures. Melt pockets, are common in the studied xenoliths. The shape of several melt pockets resembles euhedral amphibole. Other samples have thin films of intergranular glass attributed to the host basalt infiltration. Calculations have shown that such xenoliths experienced an up to 2.4% host basalt infiltration. The bulk rock Al2O3 and CaO concentrations vary from 0.75 to 4.1 and from 0.9 to 3.6 wt% respectively, and represent residues after variable degrees of partial melting. Using bulk rock major element abundances, the estimated degree of partial melting ranges from 4 to 20%.. The Primitive Mantle normalized clinopyroxene trace element abundances reveal a complicated evolution of the Lithospheric mantle underneath Balaton, which range from partial melting to modal and cryptic metasomatism. Subduction-related melt/fluids and/or infiltration of percolating undersaturated melts could be account for the metasomatic processes. The radiogenic isotopes of Sr, Nd and Hf in clinopyroxene suggest that this metasomatism was a relatively recent event. Textural evidence suggests that the calcite filling up the vesicles in the melt pockets and in veinlets cross-cutting the constituent minerals is of epigenetic nature and not due to carbonatite metasomatism. Mass balance calculations have shown that the bulk composition of the melt pockets is identical to small amphibole relics found as

Slab-derived metasomatism in the Carpathian-Pannonian mantle revealed by investigations of mantle xenoliths from the Bakony-Balaton Highland Volcanic Field

NASA Astrophysics Data System (ADS)

Créon, Laura; Delpech, Guillaume; Rouchon, Virgile; Guyot, François

2017-08-01

A suite of fifteen peridotite xenoliths from the Bakony-Balaton Highland Volcanic Field (BBHVF, Pannonian Basin, Central Europe) that show abundant petrographic evidence of fluid and melt percolation were studied in order to decipher the formation of their melt pockets and veins. The suite mainly consists of "fertile" lherzolites (5.8-19.9 vol.% clinopyroxene) and a few harzburgites (1.9-5.4 vol.% clinopyroxene) from well-known localities (Szentbékkálla, Szigliget) and two previously unreported localities (Füzes-tó and Mindszentkálla). Major and trace element data indicate that most of the peridotites record variable degrees of partial melt extraction, up to > 15% for the harzburgites. Subsequently, the xenoliths experienced at least two stages of metasomatic modification. The first stage was associated with percolation of a volatile-bearing silicate melt and resulted in crystallization of amphibole, enrichment in the most incompatible trace elements (Ba, Th, U, Sr), and development of negative Nb-Ta anomalies in clinopyroxene. The second and last metasomatic event, widespread beneath the BBHVF, is associated with the formation of silicate melt pockets, physically connected to a network of melt veins, with large and abundant CO2 vesicles. The glass in these veins has sub-alkaline trachy-andesitic composition and displays an OIB-like trace element signature. Its composition attests to the migration through a supra-subduction zone mantle wedge of silicic melt highly enriched in volatiles (CO2, H2O, Cl, F), LILE, REE and HFSE and consistent with compositions of natural and experimental examples of slab melting-derived magma. In the present case, however, melt was likely derived from melting of oceanic crust and carbonated sediments under conditions where Nb-rich mineral phases were not stable in the residue. A likely scenario for the origin such melts involves melting after subduction ceased as the slab thermally equilibrated with the asthenosphere. Melt

Advances in Constraining Solubilities of H-O-C-S-Cl-bearing Fluids in Silicate Melts

NASA Astrophysics Data System (ADS)

Webster, J. D.

2009-12-01

Magmatic-hydrothermal fluids that are variably enriched in the volatile components H2O, CO2/CH4, H2S/SO2, Cl, F, ± B alter rock; dissolve, transport, and deposit ore metals, and drive volcanism. The efficacy of these processes varies directly with the compositions and quantities, and in particular, with the molar volumes of the fluids involved. Although natural hydrothermal fluids are geochemically diverse, experimental constraints on volatile solubilities in silicate melts are largely limited to two volatiles. Recent experimental research, however, has begun to address mutual solubility relationships of three and four volatiles in felsic to intermediate aluminosilicate melts at shallow crustal pressures. Following well-established correlations demonstrating that as little as a few hundred to thousand ppm CO2 or Cl reduce H2O solubility in melts, and hence enhance the tendency for magma to exsolve one or two fluid phases, recent work shows fundamentally important solubility relationships involving H2O, S, and Cl. Research on rhyodacitic (Botcharnikov et al., 2004) and phonolitic melts at 200 MPa reveals that hundreds to thousands of ppm S will reduce Cl solubility in these melts. Thus, S reduces Cl solubility, which in turn reduces H2O solubility in melts. Other investigations have determined that CaSO4 solubility in oxidizing hydrothermal fluids varies directly with the concentrations of NaCl ± KCl in these fluids (Newton and Manning, 2005; Webster et al., 2009). The CaSO4 contents in the most alkali chloride-enriched fluids exceed 60 wt.%. It follows that some mineralizing saline magmatic fluids are strongly enriched in Ca, Na, K, Cl, SO4, and reduced S species. Research on H2O-, CO2-, and Cl-bearing melts at 200 MPa also highlights critical reciprocal volatile solubility behavior. Work at 1200°C on andesitic melts saturated in two fluids determines that the presence of CO2 enlarges the immiscibility gap for vapor plus brine and increases the activities of H2O

Measurements of the Activity of dissolved H2O in an Andesite Melt

NASA Astrophysics Data System (ADS)

Moore, G. M.; Touran, J. P.; Pu, X.; Kelley, K. A.; Cottrell, E.; Ghiorso, M. S.

2016-12-01

The large effect of dissolved H2O on the physical and chemical nature of silicate melts, and its role in driving volcanism, is well known and underscores the importance of this volatile component. A complete understanding of the chemical behavior of dissolved H2O in silicate melts requires the quantification of its thermodynamic activity as a function of pressure, temperature, and melt composition, particularly at low H2O contents (i.e. at under-saturated conditions). Knowledge of the activity of H2O in silicate melts at H2O-undersaturated conditions will improve our understanding of hydrous phase equilibria, as well as our models of physical melt properties. Measurement of the activity of any silicate melt component, much less that of a volatile component such as H2O, is a difficult experimental task however. By using a modified double capsule design (Matjuschkin et al, 2015) to control oxygen fugacity in piston cylinder experiments, along with high precision X-ray absorption techniques (XANES) to measure iron oxidation state in silicate glasses (Cottrell et al, 2009), we are able to constrain the H2O activity in silicate melts at under-saturated conditions. Preliminary results on an andesite melt with low H2O content (3 wt%) have been shown (Moore et al, 2016) to match predicted H2O activity values calculated using the H2O equation of state of Duan and Zhang (1996) and the H2O solubility model of Ghiorso and Gualda (2015). More recent results on the same andesite melt containing approximately 5 wt% H2O however show a large negative deviation from the predicted values. Reversal experiments involving an oxidized starting material are ongoing, as well as further characterization of the samples to detect the presence of possible contaminants that would induce reduction of the melt beyond that related to the H2O activity (e.g. graphite contamination).

Probing the atomic structure of basaltic melts generated by partial melting of upper mantle peridotite (KLB-1): Insights from high-resolution solid-state NMR study

NASA Astrophysics Data System (ADS)

Park, S. Y.; Lee, S. K.

2015-12-01

Probing the structural disorder in multi-component silicate glasses and melts with varying composition is essential to reveal the change of macroscopic properties in natural silicate melts. While a number of NMR studies for the structure of multi-component silicate glasses and melts including basaltic and andesitic glasses have been reported (e.g., Park and Lee, Geochim. Cosmochim. Acta, 2012, 80, 125; Park and Lee, Geochim. Cosmochim. Acta, 2014, 26, 42), many challenges still remain. The composition of multi-component basaltic melts vary with temperature, pressure, and melt fraction (Kushiro, Annu. Rev. Earth Planet. Sci., 2001, 71, 107). Especially, the eutectic point (the composition of first melt) of nepheline-forsterite-quartz (the simplest model of basaltic melts) moves with pressure from silica-saturated to highly undersaturated and alkaline melts. The composition of basaltic melts generated by partial melting of upper mantle peridotite (KLB-1, the xenolith from Kilbourne Hole) also vary with pressure. In this study we report experimental results for the effects of composition on the atomic structure of Na2O-MgO-Al2O3-SiO2 (NMAS) glasses in nepheline (NaAlSiO4)-forsterite (Mg2SiO4)-quartz (SiO2) eutectic composition and basaltic glasses generated by partial melting of upper mantle peridotite (KLB-1) using high-resolution multi-nuclear solid-state NMR. The Al-27 3QMAS (triple quantum magic angle spinning) NMR spectra of NMAS glasses in nepheline-forsterite-quartz eutectic composition show only [4]Al. The Al-27 3QMAS NMR spectra of KLB-1 basaltic glasses show mostly [4]Al and a non-negligible fraction of [5]Al. The fraction of [5]Al, the degree of configurational disorder, increases from 0 at XMgO [MgO/(MgO+Al2O3)]=0.55 to ~3% at XMgO=0.79 in KLB-1 basaltic glasses while only [4]Al are observed in nepheline-forsterite-quartz eutectic composition. The current experimental results provide that the fraction of [5]Al abruptly increases by the effect of

Thermodynamic Model of the Na-Al-Si-O-F Melts

NASA Astrophysics Data System (ADS)

Dolejs, D.; Baker, D. R.

2004-05-01

Fluorine is a common volatile element in magmatic-hydrothermal systems, but its solution mechanisms in highly polymerized silicate melts are poorly known. We have developed a thermodynamic model for fluorosilicate liquids which links experimentally determined phase equilibria and spectroscopic information on melt structure. The model is applicable to crystallization of fluoride minerals or fluoride-silicate immiscibility in natural felsic melts. Configurational properties of the liquid are defined by mixing of alkali fluoride, polyhedral aluminofluoride and silicofluoride species and non-bridging terminations of the silicate network. Abundances of individual structural species are described by a homogeneous equilibrium, representing melt depolymerization: F- (free) + O0 (bridging) = F0 (terminal) + O- (non-bridging), which is a replacement of one oxygen bridge, Si-O-Si, by two terminations, Si-F | Na-O-Si. In cryolite-bearing systems, the self-dissociation of octahedral aluminofluoride complexes: Na3[AlF6] = Na[AlF4] + 2 NaF, and the short-range order between (O,F)-corners and (Si,NaAl)-centers of tetrahedra: Si-O-Si + 2 [NaAl]-F = [NaAl]-O-[NaAl] + 2 Si-F, represent two additional interaction mechanisms. Portrayal of these equilibria in ternary Thompson reaction space allows to decrease the number of interaction mechanisms by linearly combining melt depolymerization with tetrahedral short-range order. In this formulation, the interaction parameters are incorporated directly in configurational properties, thus the complete melt speciation can be calculated, and the activities of any macroscopic species are readily derived. The model has been applied to subsystems of the Na2O-NaAlO2-SiO2-F2O-1 compositional space. Activity-composition relationships in the villiaumite-sodium silicate binaries require clustering of silicate tetrahedra in fluoride solvent. Phase-equilibria in cryolite-nepheline and cryolite-albite systems illustrate an overall increase of Na3AlF6 self

The density, compressibility and seismic velocity of hydrous melts at crustal and upper mantle conditions

NASA Astrophysics Data System (ADS)

Ueki, K.; Iwamori, H.

2015-12-01

Various processes of subduction zone magmatism, such as upward migration of partial melts and fractional crystallization depend on the density of the hydrous silicate melt. The density and the compressibility of the hydrous melt are key factors for the thermodynamic calculation of phase relation of the hydrous melt, and the geophysical inversion to predict physicochemical conditions of the melting region based on the seismic velocity. This study presents a new model for the calculations of the density of the hydrous silicate melts as a function of T, P, H2O content and melt composition. The Birch-Murnaghan equation is used for the equation of state. We compile the experimentally determined densities of various hydrous melts, and optimize the partial molar volume, compressibility, thermal expansibility and its pressure derivative, and K' of the H2O component in the silicate melt. P-T ranges of the calibration database are 0.48-4.29 GPa and 1033-2073 K. As such, this model covers the P-T ranges of the entire melting region of the subduction zone. Parameter set provided by Lange and Carmichael [1990] is used for the partial molar volume and KT value of the anhydrous silicate melt. K' of anhydrous melt is newly parameterized as a function of SiO2 content. The new model accurately reproduces the experimentally determined density variations of various hydrous melts from basalt to rhyolite. Our result shows that the hydrous melt is more compressive and less dense than the anhydrous melt; with the 5 wt% of H2O in melt, density and KT decrease by ~10% and ~30% from those of the anhydrous melt, respectively. For the application of the model, we calculated the P-wave velocity of the hydrous melt. With the 5 wt% of H2O, P-wave velocity of the silicate melt decreases by >10%. Based on the melt P-wave velocity, we demonstrate the effect of the melt H2O content on the seismic velocity of the partially molten zone of the subduction zone.

Genesis of IIICD Iron Meteorites: Evidence From Silicate Inclusions

NASA Astrophysics Data System (ADS)

McCoy, T. J.; Keil, K.; Scott, E. R. D.; Haack, H.

1992-07-01

The IAB and IIICD iron meteorite groups exhibit much larger ranges in siderophile concentrations than other groups and commonly contain silicate inclusions. Extensive studies of metal in both groups and silicates in IAB irons have led to a variety of ideas to explain the genesis of these groups. Wasson et al. (1980) envision each meteorite forming in a separate impact melt pool. Kracher (1982, 1985) suggested that the siderophile trends might result from fractional crystallization of both metal and troilite in a S-saturated magma. A role for oxidation-reduction in these groups has been proposed by Scott and Bild (1974). Similarities in siderophile elemental trends indicate that IIICD metal has a similar origin, although data on silicate inclusions in IIICD irons are scarce (Ramdohr, 1973; Scott and Bild, 1974; Kracher and Kurat, 1977; Prinz et al., 1982; Clayton et al., 1983). We report the first detailed study of silicate inclusions in IIICD iron meteorites in an attempt to elucidate their history. We have studied the only silicate-bearing IIICD irons - Carlton, Dayton, and the recently reported Maltahohe. Silicate-graphite-phosphate inclusions comprise at most a few percent of the bulk meteorite, and silicates comprise <25 vol% of the inclusion. Silicate mineralogy and chemistry vary systematically with increasing M content of the metal. Maltahohe (10.7 wt% Ni) and Carlton (13.0%) contain olivine, pyroxene, and plagioclase, whereas Dayton (17.0%) contains pyroxene, plagioclase, and SiO2. Pyroxene becomes more FeO-rich from Maltahohe (FS(sub)7.8) to Carlton (Fs(sub)9.7) to Dayton (Fs(sub)11.6). Inverse FeO zoning in silicates and lower Fa than Fs indicate reduction in all three meteorites. Plagioclase compositions in IIICD (An(sub)1.1-4.9) are lower than IAB (An(sub)9.2-2l.5) and uncorrelated with Ni content. The abundances of associated phases also vary. Graphite comprises ~25 vol% of Maltahohe silicate inclusions, but only a few percent in Carlton, and is absent

First-principles investigations of equilibrium Ca, Mg, Si and O isotope fractionations between silicate melts and minerals

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, X.; Kang, J.; He, L.

2017-12-01

Equilibrium isotope fractionation factors are essential for using stable isotope data to study many geosciences processes such as planetary differentiation and mantle evolution. The mass-dependent equilibrium isotope fractionation is primarily controlled by the difference in bond energies triggered by the isotope substitution. With the recent advances in computational capabilities, first-principles calculation has become a reliable tool to investigate equilibrium isotopic fractionations, greatly improving our understanding of the factors controlling isotope fractionations. It is important to understand the isotope fractionation between melts and minerals because magmatism is critical for creating and shaping the Earth. However, because isotope fractionation between melts and minerals is small at high temperature, it is difficult to experimentally calibrate such small signature. Due to the disordered and dynamic character of melts, calculations of equilibrium isotope fractionation of melts are more challenging than that for gaseous molecules or minerals. Here, we apply first-principles molecular dynamics method to calculate equilibrium Ca, Mg, Si, and O isotope fractionations between silicate melts and minerals. Our results show that equilibrium Mg, Si, and O isotope fractionations between olivine and pure Mg2SiO4 melt are close to zero at high temperature (e.g. δ26Mgmelt-ol = 0.03 ± 0.04‰, δ30Simelt-ol = -0.06 ± 0.07‰, δ18Omelt-ol = 0.07‰ ± 0.08 at 1500 K). Equilibrium Ca, Mg, Si, and O isotope fractionations between diopside and basalt melt (67% CaMgSi2O6 + 33% CaAl2Si2O8) are also negligible at high temperature (e.g. δ44/40Camelt-cpx = -0.01 ± 0.02‰, δ26Mgmelt-cpx = -0.05 ± 0.14‰, δ30Simelt-cpx = 0.04 ± 0.04‰, δ18Omelt-cpx = 0.03 ± 0.07‰ at 1500 K). These results are consistent with the observations in natural samples that there is no significant Ca, Mg, Si, and O isotope fractionation during mantle partial melting, demonstrating the

Evolution of melt-vapor surface tension in silicic volcanic systems: Experiments with hydrous melts

USGS Publications Warehouse

Mangan, M.; Sisson, T.

2005-01-01

We evaluate the melt-vapor surface tension (??) of natural, water-saturated dacite melt at 200 MPa, 950-1055??C, and 4.8-5.7 wt % H2O. We experimentally determine the critical supersaturation pressure for bubble nucleation as a function of dissolved water and then solve for ?? at those conditions using classical nucleation theory. The solutions obtained give dacite melt-vapor surface tensions that vary inversely with dissolved water from 0.042 (??0.003) J m-2 at 5.7 wt% H2O to 0.060 (??0.007) J m-2 at 5.2 wt% H2O to 0.073 (??0.003) J m-2 at 4.8 wt% H2O. Combining our dacite results with data from published hydrous haplogranite and high-silica rhyolite experiments reveals that melt-vapor surface tension also varies inversely with the concentration of mafic melt components (e.g., CaO, FeOtotal, MgO). We develop a thermodynamic context for these observations in which melt-vapor surface tension is represented by a balance of work terms controlled by melt structure. Overall, our results suggest that cooling, crystallization, and vapor exsolution cause systematic changes in ?? that should be considered in dynamic modeling of magmatic processes.

The Origin of Silicic Arc Crust - Insights from the Northern Pacific Volcanic Arcs through Space and Time

NASA Astrophysics Data System (ADS)

Straub, S. M.; Kelemen, P. B.

2016-12-01

The remarkable compositional similarities of andesitic crust at modern convergent margins and the continental crust has long evoked the hypothesis of similar origins. Key to understanding either genesis is understanding the mode of silica enrichment. Silicic crust cannot be directly extracted from the upper mantle. Hence, in modern arcs, numerous studies - observant of the pervasive and irrefutable evidence of melt mixing - proposed that arc andesites formed by mixing of mantle-derived basaltic melts and fusible silicic material from the overlying crust. Mass balance requires the amount of silicic crust in such hybrid andesites to be on the order to tens of percent, implying that their composition to be perceptibly influenced by the various crustal basements. In order to test this hypothesis, major and trace element compositions of mafic and silicic arc magmas with arc-typical low Ce/Pb< 10 of Northern Pacific arcs (Marianas through Mexico) were combined with Pb isotope ratios. Pb isotope ratios are considered highly sensitive to crustal contamination, and hence should reflect the variable composition of the oceanic and continental basement on which these arcs are constructed. In particular, in thick-crust continental arcs where the basement is isotopically different from the mantle and crustal assimilation thought to be most prevalent, silicic magmas must be expected to be distinct from those of the associated mafic melts. However, in a given arc, the Pb isotope ratios are constant with increasing melt silica regardless of the nature of the basement. This observation argues against a melt origin of silicic melts from the crustal basement and suggest them to be controlled by the same slab flux as their co-eval mafic counterparts. This inference is validated by the spatial and temporal pattern of arc Pb isotope ratios along the Northern Pacific margins and throughout the 50 million years of Cenozoic evolution of the Izu Bonin Mariana arc/trench system that are can

New poly(butylene succinate)/layered silicate nanocomposites: preparation and mechanical properties.

PubMed

Ray, Suprakas Sinha; Okamoto, Kazuaki; Maiti, Pralay; Okamoto, Masami

2002-04-01

New poly(butylene succinate) (PBS)/layered silicate nanocomposites have been successfully prepared by simple melt extrusion of PBS and octadecylammonium modified montmorillonite (C18-mmt) at 150 degrees C. The d-spacing of both C18-mmt and intercalated nanocomposites was investigated by wide-angle X-ray diffraction analysis. Bright-field transmission electron microscopic study showed several stacked silicate layers with random orientation in the PBS matrix. The intercalated nanocomposites exhibited remarkable improvement of mechanical properties in both solid and melt states as compared with that of PBS matrix without clay.

A pocket model for aluminum agglomeration in composite propellants

NASA Technical Reports Server (NTRS)

Cohen, N. S.

1981-01-01

This paper presents a model for the purpose of estimating the fraction of aluminum powder that will form agglomerates at the surface of deflagrating composite propellants. The basic idea is that the fraction agglomerated depends upon the amount of aluminum that melts within effective binder pocket volumes framed by oxidizer particles. The effective pocket depends upon the ability of ammonium perchlorate modals to encapsulate the aluminum and provide a local temperature sufficient to ignite the aluminum. Model results are discussed in the light of data showing effects of propellant formulation variables and pressure.

A thermodynamical model for the surface tension of silicate melts in contact with H2O gas

USGS Publications Warehouse

Colucci, Simone; Battaglia, Maurizio; Trigila, Raffaello

2016-01-01

Surface tension plays an important role in the nucleation of H2O gas bubbles in magmatic melts and in the time-dependent rheology of bubble-bearing magmas. Despite several experimental studies, a physics based model of the surface tension of magmatic melts in contact with H2O is lacking. This paper employs gradient theory to develop a thermodynamical model of equilibrium surface tension of silicate melts in contact with H2O gas at low to moderate pressures. In the last decades, this approach has been successfully applied in studies of industrial mixtures but never to magmatic systems. We calibrate and verify the model against literature experimental data, obtained by the pendant drop method, and by inverting bubble nucleation experiments using the Classical Nucleation Theory (CNT). Our model reproduces the systematic decrease in surface tension with increased H2O pressure observed in the experiments. On the other hand, the effect of temperature is confirmed by the experiments only at high pressure. At atmospheric pressure, the model shows a decrease of surface tension with temperature. This is in contrast with a number of experimental observations and could be related to microstructural effects that cannot be reproduced by our model. Finally, our analysis indicates that the surface tension measured inverting the CNT may be lower than the value measured by the pendant drop method, most likely because of changes in surface tension controlled by the supersaturation.

Silicate Inclusions in the Kodaikanal IIE Iron Meteorite

NASA Technical Reports Server (NTRS)

Kurat, G.; Varela, M. E.; Zinner, E.

2005-01-01

Silicate inclusions in iron meteorites display an astonishing chemical and mineralogical variety, ranging from chondritic to highly fractionated, silica- and alkali-rich assemblages. In spite of this, their origin is commonly considered to be a simple one: mixing of silicates, fractionated or unfractionated, with metal. The latter had to be liquid in order to accommodate the former in a pore-free way which all models accomplish by assuming shock melting. II-E iron meteorites are particularly interesting because they contain an exotic zoo of silicate inclusions, including some chemically strongly fractionated ones. They also pose a formidable conundrum: young silicates are enclosed by very old metal. This and many other incompatibilities between models and reality forced the formulation of an alternative genetic model for irons. Here we present preliminary findings in our study of Kodaikanal silicate inclusions.

Conductimetric determination of decomposition of silicate melts

NASA Technical Reports Server (NTRS)

Kroeger, C.; Lieck, K.

1986-01-01

A description of a procedure is given to detect decomposition of silicate systems in the liquid state by conductivity measurements. Onset of decomposition can be determined from the temperature curves of resistances measured on two pairs of electrodes, one above the other. Degree of decomposition can be estimated from temperature and concentration dependency of conductivity of phase boundaries. This procedure was tested with systems PbO-B2O3 and PbO-B2O3-SiO2.

Silicic melt evolution in the early Izu-Bonin arc recorded in detrital zircons: Zircon U-Pb geochronology and trace element geochemistry for Site U1438, Amami Sankaku Basin

NASA Astrophysics Data System (ADS)

Barth, A. P.; Tani, K.; Meffre, S.; Wooden, J. L.; Coble, M. A.

2016-12-01

Understanding the petrologic evolution of oceanic arc magmas through time is important because these arcs reveal the processes of formation and the early evolution of juvenile continental crust. The Izu-Bonin (IB) arc system has been targeted because it is one of several western Pacific intraoceanic arcs initiated at 50 Ma and because of its prominent spatial asymmetry, with widespread development of relatively enriched rear arc lavas. We examined Pb/U and trace element compositions in zircons recovered at IODP Site 351-U1438 and compared them to regional and global zircon suites. These new arc zircon data indicate that detrital zircons will yield new insights into the generation of IB silicic melts and form a set of useful geochemical proxies for interpreting ancient arc detrital zircon provenance. Project IBM drilling target IBM1 was explored by Expedition 351 at Site U1438, located in the proximal back-arc of the northern Kyushu-Palau Ridge (KPR) at 27.3°N. A 1.2 km thick section of Paleogene volcaniclastic rocks, increasingly lithified and hydrothermally altered with depth, constitutes a proximal rear arc sedimentary record of IB arc initiation and early arc evolution. The ages and compositions of U1438 zircons are compatible with provenance in one or more edifices of the northern KPR and are incompatible with drilling contamination. Melt zircon saturation temperatures and Ti-in-zircon thermometry suggest a provenance in relatively cool and silicic KPR melts. The abundances of selected trace elements with high native concentrations provide insight into the petrogenesis of U1438 detrital zircon host melts, and may be useful indicators of both short and long-term variations in melt compositions in arc settings. The U1438 zircons are slightly enriched in U and LREE and are depleted in Nb compared to zircons from mid-ocean ridges and the Parece-Vela Basin, as predicted for melts in a primitive oceanic arc setting with magmas derived from a highly depleted mantle

Impact-melt origin for the Simondium, Pinnaroo, and Hainholz mesosiderites: implicatiions for impact processes beyond the Earth--Moon system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Floran, R J; Caulfield, J B.D.; Harlow, G E

The Simondium, Pinnaroo, and Hainholz mesosiderites are interpreted to be clast-laden impact melts that crystallized from immiscible silicate, metallic (Fe-FeS) liquids. The existence of silicate melts is shown by intergranular basaltic textures. Metallic melts are inferred on the basis of smooth boundaries between metal and troilite and the occurrence of troilite as anastomosing areas that radiate outward into the silicate fractions. These relations suggest that troilite crystallized after silicates, concentrating as a late-stage residuum. Evidence for impact melting includes: diversity and abundance of clast types (mineral, metal, lithic) in various stages of recrystallization and assimilation; differences in mineral chemistries betweenmore » clasts and igneous-textured matrix silicates; unusual metal plus silicate bulk composition. Silicate clasts consist primarily of orthopyroxene and minor olivine with a range of Fe/Fe + Mg ratios, anorthitic plagioclase, and rare orthopyroxenite (diogenite) fragments. Substantial amounts of Fe-Ni metal were melted during the impact events and minor amounts were incorporated into the melts as clasts. The clast populations suggest that at least four rock types were melted and mixed: (a) diogenite, (b) a plagioclase-rich source, possibly cumulate eucrite, (c) dunite, and (d) metal. Most orthopyroxene appears to have been derived from fragmentation of diogenites. Orthopyroxene (En/sub 82-61/) and olivine (Fo/sub 86-67/) clasts include much material unsampled as individual meteorites and probably represent a variety of source rocks.« less

Melting in super-earths.

PubMed

Stixrude, Lars

2014-04-28

We examine the possible extent of melting in rock-iron super-earths, focusing on those in the habitable zone. We consider the energetics of accretion and core formation, the timescale of cooling and its dependence on viscosity and partial melting, thermal regulation via the temperature dependence of viscosity, and the melting curves of rock and iron components at the ultra-high pressures characteristic of super-earths. We find that the efficiency of kinetic energy deposition during accretion increases with planetary mass; considering the likely role of giant impacts and core formation, we find that super-earths probably complete their accretionary phase in an entirely molten state. Considerations of thermal regulation lead us to propose model temperature profiles of super-earths that are controlled by silicate melting. We estimate melting curves of iron and rock components up to the extreme pressures characteristic of super-earth interiors based on existing experimental and ab initio results and scaling laws. We construct super-earth thermal models by solving the equations of mass conservation and hydrostatic equilibrium, together with equations of state of rock and iron components. We set the potential temperature at the core-mantle boundary and at the surface to the local silicate melting temperature. We find that ancient (∼4 Gyr) super-earths may be partially molten at the top and bottom of their mantles, and that mantle convection is sufficiently vigorous to sustain dynamo action over the whole range of super-earth masses.

Carbon-bearing MgSiO3 melt at deep mantle conditions

NASA Astrophysics Data System (ADS)

Ghosh, D. B.; Bajgain, S. K.; Mookherjee, M.; Karki, B. B.

2016-12-01

Carbon di-oxide and water are two important volatiles that are often present in silicate magmas and volcanic eruptions. To address the influence of these volatiles in deep seated melts, their properties (e.g., structure, transport, thermodynamics) at relevant pressure-temperature (P-T) conditions along with compositional variance need to be explored. MgSiO3 being one of the major components of the mantle, the study of carbonated MgSiO3 melts is of great contextual relevance. In the present work we investigate the structure and thermodynamics of carbon bearing MgSiO3 melts under conditions of the entire mantle.Our first-principles molecular dynamics (MD) simulations of the MgSiO3-CO2 system show that pressure profoundly influences the behavior of carbon-bearing silicate melts. Our results encompassing from 5 - 30 wt.% CO2 in MgSiO3 demonstrate that: (1) carbon speciation consists of distinct molecular CO2 and carbonate ions ( (CO3)2-) below 15 GPa and interestingly almost all of the carbonate ions are bound to Mg polyhedra; (2) with compression they evolve to silicon-polyhedral bound carbonate (along with Mg polyhedra bound), CO4 , and di-carbonate species. Accordingly, carbon solubility in the silicate melt becomes nearly ideal and carbon remains completely miscible with increasing pressure. Carbon reduces the melt density modestly by 0.015 to 0.005 g cm-3 per wt.% CO2 between 15 and 140 GPa. These results imply that deep-seated silicate melts above and below the transition zone, and atop the core-mantle boundary may be able to sequester significant amounts of carbon without making melts gravitationally unstable.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.

2017-12-01

Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a

Properties of the Guin ungrouped iron meteorite - The origin of Guin and of group-IIE irons

NASA Astrophysics Data System (ADS)

Rubin, A. E.; Jerde, E. A.; Zong, P.; Wasson, J. T.; Westcott, J. W.; Mayeda, T. K.; Clayton, R. N.

1986-01-01

The composition and structure of the Guin ungrouped iron meteorite inclusions have been investigated experimentally. The structural characteristics of polished and etched slabs of the meteorite were studied microscopically in reflected light. Modal abundances of troilite nodules and silicate inclusions were determined by weighing paper traces. The bulk composition of the silicate inclusions was calculated by combining modal phase abundances and mineral compositions. It is found that the largest silicate inclusion (2 x 4 cm) consists mostly of a shock-melted plagioclase-rich matrix surrounding large, partly melted augite grains. The oxygen isotopic composition of the inclusion is near that of LL chondrites. The inclusion is found to be similar in composition to selected melt pocket glasses in ordinary chondrites produced in situ by preferential melting of plagioclase rock due to shock compression. It is suggested that the Guin assemblage was formed by impact melting on a chondritic parent body. Silicate inclusions in IIE irons share many of the compositional and petrological characteristics of the Guin inclusions, indicating that IIE irons also formed by impact-melting of chondritic materials. Black and white photomicrographs of the silicate inclusions are provided.

Chondritic Meteorites: Nebular and Parent-Body Formation Processes

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Lindstrom, David (Technical Monitor)

2002-01-01

It is important to identify features in chondrites that formed as a result of parent-body modification in order to disentangle nebular and asteroidal processes. However, this task is difficult because unmetamorphosed chondritic meteorites are mixtures of diverse components including various types of chondrules, chondrule fragments, refractory and mafic inclusions, metal-sulfide grains and fine-grained matrix material. Shocked chondrites can contain melt pockets, silicate-darkened material, metal veins, silicate melt veins, and impact-melt-rock clasts. This grant paid for several studies that went far in helping to distinguish primitive nebular features from those produced during asteroidal modification processes.

Residual Hydrochloride - Silicate Melt Associated With the Platinum-bearing Alaskan-type Galmoenan Intrusion (Koryak Highland, Russia)

NASA Astrophysics Data System (ADS)

Batanova, V.; Kamenetsky, D.; Pertsev, A.; Sobolev, A.

2005-12-01

Alaskan-type mafic-ultramafic complexes formed in subduction-related environments are considered to be a major source of platinum placer deposits [1]. A specific feature of these deposits is the dominant occurrence of Pt-Fe alloys (mainly isoferroplatinum) among PGE-bearing minerals [e.g. 2]. The PGE mineralization can be related to the high activity of chlorine in the parental magmas of Alaskan-type intrusions [3] and the potential of saline fluids to dissolve and transport Pt [4,5,6]. Fluxing of a refractory mantle wedge in a supra-subduction zone by chlorine-rich aqueous fluids was considered primarily responsible for the formation of PGE-enriched parental magmas [3]. Potential role of the saline magmatic fluids is further tackled by this study of melt/fluid inclusions in olivine from the Galmoenan pluton belonging to the Alaskan-type intrusive complex in the Kamchatka-Koryak province [7] and spatially associated with one of the most significant platinum placer deposits in Russia [8]. High-magnesian olivine (Fo 90.8) from the Galmoenan dunites hosts abundant hydrosaline chloride and hydrosaline chloride-silicate melt inclusions (5-30mkm). Inclusions trail fractures confined to individual olivine grains, and thus formed before re-crystallization completed. Heating stage experiments at 1 atm showed early melting within the inclusions at ~350C, however complete melting and homogenization was hampered by decrepitation at 650-750C. This suggests elevated pressures of trapping, at least 3-4 kb. The study of phase and chemical compositions of these inclusions by an electron probe, laser ablation ICP-MS and SIMS ion probe showed chlorides of Na, K, Ca, Fe and Ba, Fe-Cu-Ni sulfides and diopside among daughter phases; 2) high H2O abundances; 3) high abundances of alkali and alkali-earth elements (Na, K, Rb, Sr, Ba, Ca) and metals (Fe, Mn, Pb, Ni, Cu, Zn). Such compositions confirm the presence of metal-enriched hydrosaline melt at the latest stages of formation of the Pt

Smyer H-Chondrite Impact-Melt Breccia and Evidence for Sulfur Vaporization

NASA Technical Reports Server (NTRS)

Rubin, Alan E.

2002-01-01

Smyer is an H-chondrite impact-melt breccia containing approx.20 vol% 0.5- to 13-mm-thick silicate-rich melt veins surrounding unmelted subrounded chondritic clasts up to 7 cm in maximum dimension. At the interface between some of the melt veins and chondritic clasts, there are troilite-rich regions consisting of unmelted. crushed 0.2- to 140-micron-size angular silicate grains and chondrule fragments surrounded by troilite and transected by thin troilite veins. Troilite fills every available fracture in the silicates. including some as thin as 0.1 microns. Little metallic Fe-Ni is present in these regions: the FeS/Fe modal ratio ranges from -25: 1 to approx.500: 1, far higher than the eutectic weight ratio of 7.5: 1. The texture of these regions indicates that the sulfide formed from a fluid of very low viscosity. The moderately high viscosity (0.2 poise) and large surface tension of liquid FeS, its inability to wet silicate grain surfaces at low oxygen fugacities. and the supereutectic FeS/Fe ratios in the troilite-rich regions indicate that the fluid was a vapor. It seems likely that during the shock event that melted Smyer, many silicates adjacent to the melt veins were crushed. Upon release of shock pressure. some of the troilite evaporated and dissociated. Molecules of S2 were transported and condensed into fractures and around tiny silicate grains: there, they combined with Fe from small adjacent metallic Fe-Ni grains to form troilite. The Ni content at the edges of some of these metal grains increased significantly; Co from these Ni-rich grains diffused into nearby kamacite. Impact-induced S volatilization may have played a major role in depleting the surface of 433 Eros (and other chondritic asteroids) in S.

Crystal-chemical controls on the partitioning of Sr and Ba between plagioclase feldspar, silicate melts, and hydrothermal solutions

NASA Astrophysics Data System (ADS)

Blundy, Jonathan D.; Wood, Bernard J.

1991-01-01

The isothermal (750°C) experiments of LAGACHE and DUJON (1987) reveal that the partitioning of Sr between plagioclase feldspar and hydrothermal solutions is a funtion of the anorthite (An) content of the plagioclase, indicating that crystal chemistry may exert a powerful influence on trace element partitioning. In order to compare these results with those on trace element partitioning between plagioclase and silicate melts we have compiled from the literature a large dataset of experimental and volcanic distribution coefficients ( D's) for Sr (and Ba). These data, which span a compositional range from lunar basalt to high silica rhyolite and a temperature range of over 650°C, show a relationship between DSr (and DBa) and mole fraction An ( XAn) which is similar to that exhibited by the hydrothermal results obtained at constant temperature. Plots of In DSr and In DBa versus XAn are linear with negative slope, indicating that both elements are more compatible in albite than anorthite. In terms of molar distribution coefficients ( D Sr∗) the hydrothermal and silicate melt data display an identical linear relationship between RT In D Sr∗ (where T is the absolute temperature in K and R is the gas constant, 8.314 JK -1 mol -1) and XAn. We conclude therefore that crystal chemistry provides the dominant control on partitioning of Sr and Ba into plagioclase and that the effects of temperature, pressure, and fluid composition are minor. Apparent relationships between DSr (and DBa) and the reciprocal temperature (1/ T) are artefacts of the linear relationships between XAn and 1/ T in the experimental studies. By defining a Henry's law standard state for the silicate melts and hydrothermal solutions, and considering plagioclases to be ternary regular solutions, we are able to relate the observed relationships between RT In D i∗ (where i is Ba or Sr) and XAn to the excess free energies of the trace element partitioning reactions between plagioclase and melt or

Trace element diffusion and kinetic fractionation in wet rhyolitic melt

NASA Astrophysics Data System (ADS)

Holycross, Megan E.; Watson, E. Bruce

2018-07-01

Piston-cylinder experiments were run to determine the chemical diffusivities of 21 trace elements (Sc, V, Y, Zr, Nb, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Hf, Th and U) in hydrous rhyolitic melts at 1 GPa pressure and temperatures from 850 to 1250 °C. Diffusion couple glasses were doped with trace elements in low concentrations to characterize the diffusivities of all cations in a single experiment. Laser ablation ICP-MS was used to evaluate the trace element concentration gradients that developed in the silicate glasses. All calculated diffusion coefficients correspond to the temperature dependence D = D0exp(-Ea/RT). Rhyolite liquids contained either ∼4.1 wt% or ∼6.2 wt% dissolved H2O; separate Arrhenius relationships are produced for each melt composition. Trace element diffusivities in the melt with 6.2 wt% H2O are roughly two times higher than those in the less hydrous melt. Calculated trace element diffusion coefficients cover nearly two orders of magnitude at a given temperature. The high field strength elements are the slowest diffusers, followed by the transition metals and heavy rare earth elements. The light rare earth elements have the fastest diffusion rates in hydrous rhyolitic melt. The measured diffusion coefficients range down to values sufficiently low to preclude diffusive homogenization over geochemically realistic time scales in some cases. The substantial differences in the diffusivities of individual cations may result in fractionated trace element signatures in rhyolite melt pockets. A simple model is used to explore the potential for kinetic fractionation of REE during growth of an apatite crystal in a diffusive boundary layer locally saturated in P2O5. The faster-diffusing light REE are more efficiently transported away from the crystal interface than the slower-moving heavy REE. Diffusion effects will enrich the melt boundary layer in slow-moving HREE relative to the faster LREE. The kinetic fractionation of REE in the

Partial reactive crystallization of variable CO2-bearing siliceous MORB-eclogite-derived melt in fertile peridotite and genesis of alkalic basalts with signatures of crustal recycling

NASA Astrophysics Data System (ADS)

Mallik, A.; Dasgupta, R.

2013-12-01

The presence of heterogeneity in the form of recycled altered oceanic crust (MORB-eclogite) has been proposed in the source of HIMU ocean island basalts (OIBs) [1]. Partial melts of recycled oceanic crust, however, are siliceous and Mg-poor and thus do not resemble the major element compositions of alkalic OIBs that are silica-poor and Mg-rich. In an upwelling heterogenous mantle, MORB-eclogite undergoes melting deeper than volatile-free peridotite, hence, andesitic partial melt derived from eclogite will react with subsolidus peridotite. We have examined the effect of such a melt-rock reaction under volatile-free conditions at 1375 °C, 3 GPa by varying the melt-rock ratio from 8 to 50 wt.% [2]. We concluded that the reacted melts reproduce certain major element characteristics of oceanic basanites, but not nephelinites. Also, the melt-rock reaction produces olivine and garnet-bearing websteritic residue. Because presence of CO2 has been invoked in the source of many HIMU ocean islands, the effect of CO2 on such a melt-rock reaction needs to be evaluated. Accordingly, we performed reaction experiments on mixtures of 25% and 33% CO2-bearing andesitic partial melt and peridotite at 1375 °C, 3 GPa by varying the dissolved CO2 content of the reacting melts from 1 to 5 wt.% (bulk CO2 from 0.25 to 1.6 wt.%) [3, this study]. Owing to melt-rock reaction, with increasing CO2 in the bulk mixture, (a) modes of olivine and cpx decrease while melt, opx and garnet increase, (b) reacted melts evolve to greater degree of Si-undersaturation (from andesite through basanite to nephelinite), (c) enhanced crystallization of garnet take place with higher CO2 in the melt, reducing alumina content of the reacted melts, and (d) CaO and MgO content of the reacted melts increase, without affecting FeO* and Na2O contents (indicating greater propensity of Ca2+ and Mg2+ over Fe2+ and Na+ to enter silicate melt as carbonate). For a given melt-MgO, the CO2-bearing reacted melts are a better

Sulfide Melts and Chalcophile Element Behavior in High Temperature Systems

NASA Astrophysics Data System (ADS)

Wood, B. J.; Kiseeva, K.

2016-12-01

We recently found that partition coefficients (Di) of many weakly and moderately chalcophile elements (e.g., Cd, Zn, Co, Cr, Pb, Sb, In) between sulfide and silicate melts are simple functions of the FeO content of the silicate liquid: logDi A-Blog[FeO] where [FeO] is the FeO concentration in the silicate, A and B are constants and the latter is related to the valency of the element of interest. In contrast, some strongly chalcophile (e.g Cu, Ni, Ag) and lithophile elements (e.g Mn) show marked deviations from linearity on a plot of logDi vs log[FeO]. More recent experiments show that linear behavior is confined to elements whose affinities for S and O are similar to those of Fe. In the case of elements more strongly lithophile than Fe (Ti, U, REE, Zr, Nb, Ta, Mn) a plot of logDi versus log[FeO] describes a U-shape with the element partitioning strongly into the sulfide at very low FeO and again at very high FeO content of the silicate melt. In contrast, strongly chalcophile elements (Cu, Ni, Ag) describe an n-shape on the plot of logD vs log[FeO]. The result is that lithophile elements such as Nb become more "chalcophile" than Cu at very low and very high FeO contents of the silicate melt. The reasons for this surprising behavior are firstly that, at very low FeO contents the silicate melt dissolves substantial amounts of sulfur, which drives down the activity of FeO and, from mass-action "pulls" the lihophile element into the sulfide. At high FeO contents of the silicate the sulfide itself starts to dissolve substantial amounts of oxygen and lithophile elements follow the oxygen into the sulfide. Given the principles which we have established, we are able to describe the patterns of chalcophile element behavior during partial melting and fractional crystallisation on Earth and also on bodies such as Mercury and Mars which are, respectively, strongly reduced relative to Earth and more oxidised than Earth.

Apatite-Melt Partitioning at 1 Bar: An Assessment of Apatite-Melt Exchange Equilibria Resulting from Non-Ideal Mixing of F and Cl in Apatite

NASA Technical Reports Server (NTRS)

McCubbin, F. M.; Ustunisik, G.; Vander Kaaden, K. E.

2016-01-01

The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl

New findings for the equilibrated enstatite chondrite Grein 002

NASA Astrophysics Data System (ADS)

Patzer, Andrea; Schlüter, Jochen; Schultz, Ludolf; Tarkian, M.; Hill, Dolores H.; Boynton, William V.

2004-09-01

We report new petrographic and chemical data for the equilibrated EL chondrite Grein 002, including the occurrence of osbornite, metallic copper, abundant taenite, and abundant diopside. As inferred from low Si concentrations in kamacite, the presence of ferroan alabandite, textural deformation, chemical equilibration of mafic silicates, and a subsolar noble gas component, we concur with Grein 002's previous classification as an EL4-5 chondrite. Furthermore, the existence of pockets consisting of relatively coarse, euhedral enstatite crystals protruding large patches of Fe-Ni alloys suggests to us that this EL4-5 chondrite has been locally melted. We suspect impact induced shock to have triggered the formation of the melt pockets. Mineralogical evidence indicates that the localized melting of metal and adjacent enstatite must have happened relatively late in the meteorite's history. The deformation of chondrules, equilibration of mafic silicates, and generation of normal zoning in Fe, Zn-sulfides took place during thermal alteration before the melting event. Following parent body metamorphism, daubreelite was exsolved from troilite in response to a period of slow cooling at subsolidus temperatures. Exsolution of schreibersite from the coarse metal patches probably occurred during a similar period of slow cooling subsequent to the event that induced the formation of the melt pockets. Overall shock features other than localized melting correspond to stage S2 and were likely established by the final impact that excavated the Grein 002 meteoroid.

Evidence for the presence of carbonate melt during the formation of cumulates in the Colli Albani Volcanic District, Italy

NASA Astrophysics Data System (ADS)

Shaw, Cliff S. J.

2018-06-01

Fergusite and syenite xenoliths and mafic lapilli from two locations in the Villa Senni ignimbrite of the Colli Albani Volcanic District show evidence for fractionation of a silicate magma that led to exsolution of an immiscible carbonate melt. The fergusite xenoliths are divided into two groups on the basis of their clinopyroxene compositions. Group 1 clinopyroxene records the crystallisation of a silicate melt and enrichment of the melt in Al, Ti and Mn and depletion in Si as well as enrichment in incompatible trace elements. The second group of clinopyroxene compositions (group 2) comes mainly from Ba-F-phlogopite- and Ti-andradite-bearing fergusites. They have significantly higher Si and lower Al and Ti and, like the coexisting phlogopite and garnet are strongly enriched in Mn. The minerals in the fergusites containing group 2 clinopyroxene are enriched in Ba, Sr, Cs, V and Li all of which are expected to partition strongly into a carbonate melt phase relative to the coexisting silicate melt. The compositional data suggest that the group 1 fergusites record sidewall crystallisation of CO2-rich silicate melt and that once the melt reached a critical degree of fractionation, carbonate melt exsolved. The group 2 fergusites record continued crystallisation in this heterogeneous silicate - carbonate melt system. Composite xenoliths of fergusite and thermometamorphic skarn record contact times of hundreds to a few thousand years indicating that fractionation and assimilation was relatively rapid.

Effect of pressure on the short-range structure and speciation of carbon in alkali silicate and aluminosilicate glasses and melts at high pressure up to 8 GPa: 13C, 27Al, 17O and 29Si solid-state NMR study

NASA Astrophysics Data System (ADS)

Kim, Eun Jeong; Fei, Yingwei; Lee, Sung Keun

2018-03-01

Despite the pioneering efforts to explore the nature of carbon in carbon-bearing silicate melts under compression, experimental data for the speciation and the solubility of carbon in silicate melts above 4 GPa have not been reported. Here, we explore the speciation of carbon and pressure-induced changes in network structures of carbon-bearing silicate (Na2O-3SiO2, NS3) and sodium aluminosilicate (NaAlSi3O8, albite) glasses quenched from melts at high pressure up to 8 GPa using multi-nuclear solid-state NMR. The 27Al triple quantum (3Q) MAS NMR spectra for carbon-bearing albite melts revealed the pressure-induced increase in the topological disorder around 4 coordinated Al ([4]Al) without forming [5,6]Al. These structural changes are similar to those in volatile-free albite melts at high pressure, indicating that the addition of CO2 in silicate melts may not induce any additional increase in the topological disorder around Al at high pressure. 13C MAS NMR spectra for carbon-bearing albite melts show multiple carbonate species, including [4]Si(CO3)[4]Si, [4]Si(CO3)[4]Al, [4]Al(CO3)[4]Al, and free CO32-. The fraction of [4]Si(CO3)[4]Al increases with increasing pressure, while those of other bridging carbonate species decrease, indicating that the addition of CO2 may enhance mixing of Si and Al at high pressure. A noticeable change is not observed for 29Si NMR spectra for the carbon-bearing albite glasses with varying pressure at 1.5-6 GPa. These NMR results confirm that the densification mechanisms established for fluid-free, polymerized aluminosilicate melts can be applied to the carbon-bearing albite melts at high pressure. In contrast, the 29Si MAS NMR spectra for partially depolymerized, carbon-bearing NS3 glasses show that the fraction of [5,6]Si increases with increasing pressure at the expense of Q3 species ([4]Si species with one non-bridging oxygen as the nearest neighbor). The pressure-induced increase in topological disorder around Si is evident from an

Mg-perovskite/silicate melt partition coefficients in the CMS system at 2430 C and 226 Kbars

NASA Technical Reports Server (NTRS)

Mcfarlane, Elisabeth A.; Drake, Michael J.; Gasparik, Tibor

1992-01-01

The partitioning of elements among lower mantle phases and silicate melts is of interest in unraveling the early thermal history of the Earth. Because of the technical difficulty in carrying out such measurements, only one direct set of measurements has been reported, and these results as well as interpretations based on them have generated controversy. The first set of direct measurements on a synthetic system in the CaO-MgO-SiO2 (CMS) is reported. An experiment was conducted at Stony Brook, using the USSA-2000 split sphere anvil apparatus. An experiment in the CMS system doped with oxides of Al, Ti, Sc, and Sm and run at a nominal temperature of 2380 C and pressure of 226 kbars is reported. Nominal temperatures were measured with a W 3 percent Re/W 25 percent Re thermocouple. The hot spot temperature, where the liquidus is located, is estimated to be at 2430 C. A 10 mm MgO octahedron was used in concert with 4 mm truncation edge lengths on the WC cubes. The sample was contained in a Re capsule which was inserted into a LaCrO3 furnace. Pressure was calibrated at 2000 C. Run duration was approximately 3 minutes. The charge was mounted in epoxy and analyzed using a CAMECA SX-50 electron microprobe. Standard operating conditions were employed, although counting time for the less abundant elements was increased to improved counting statistics. The melt is unquenchable, and forms a dendritic intergrowth of quench crystals and residual melt. It was analyzed using a 30 micron raster. The structural identity of the Mg-perovskite phase was confirmed using x ray microdiffractometry. The results of the investigation are presented.

Melting Processes at the Base of the Mantle Wedge: Melt Compositions and Melting Reactions for the First Melts of Vapor-Saturated Lherzolite

NASA Astrophysics Data System (ADS)

Grove, T. L.; Till, C. B.

2014-12-01

Vapor-saturated melting experiments have been performed at pressures near the base of the mantle wedge (3.2 GPa). The starting composition is a metasomatized lherzolite containing 3 wt. % H2O. Near-solidus melts and coexisting mineral phases have been characterized in experiments that span 925 to 1100 oC with melt % varying from 6 to 9 wt. %. Olivine, orthopyroxene, clinopyroxene and garnet coexist with melt over the entire interval and rutile is also present at < 1000 oC. Melt is andesitic in composition and varies from 60 wt. % SiO2 at 950 oC to 52 wt. % at 1075 oC. The Al2O3 contents of the melt are 13 to 14 wt. %, and CaO contents range from 1 and 4 wt. %. Melting is peritectic with orthopyroxene + liquid produced by melting of garnet + olivine + high-Ca pyroxene. In addition to quenched melt, we observe a quenched silicate component that is rhyolitic (>72 % SiO2) that we interpret as a precipitate from the coexisting supercritical H2O-rich vapor. Extrapolation of the measured compositional variation toward the solidus suggests that the first melt may be very SiO2 rich (i.e., granitic). We suggest that these granitic melts are the first melts of the mantle near the slab-wedge interface. As these SiO2-rich melts ascend into shallower, hotter overlying mantle, they continue to interact with the surrounding mantle and evolve in composition. These first melts may elucidate the geochemical and physical processes that accompany the beginnings of H2O flux melting.

An observational and thermodynamic investigation of carbonate partial melting

NASA Astrophysics Data System (ADS)

Floess, David; Baumgartner, Lukas P.; Vonlanthen, Pierre

2015-01-01

Melting experiments available in the literature show that carbonates and pelites melt at similar conditions in the crust. While partial melting of pelitic rocks is common and well-documented, reports of partial melting in carbonates are rare and ambiguous, mainly because of intensive recrystallization and the resulting lack of criteria for unequivocal identification of melting. Here we present microstructural, textural, and geochemical evidence for partial melting of calcareous dolomite marbles in the contact aureole of the Tertiary Adamello Batholith. Petrographic observations and X-ray micro-computed tomography (X-ray μCT) show that calcite crystallized either in cm- to dm-scale melt pockets, or as an interstitial phase forming an interconnected network between dolomite grains. Calcite-dolomite thermometry yields a temperature of at least 670 °C, which is well above the minimum melting temperature of ∼600 °C reported for the CaO-MgO-CO2-H2O system. Rare-earth element (REE) partition coefficients (KDcc/do) range between 9-35 for adjacent calcite-dolomite pairs. These KD values are 3-10 times higher than equilibrium values between dolomite and calcite reported in the literature. They suggest partitioning of incompatible elements into a melt phase. The δ18O and δ13C isotopic values of calcite and dolomite support this interpretation. Crystallographic orientations measured by electron backscattered diffraction (EBSD) show a clustering of c-axes for dolomite and interstitial calcite normal to the foliation plane, a typical feature for compressional deformation, whereas calcite crystallized in pockets shows a strong clustering of c-axes parallel to the pocket walls, suggesting that it crystallized after deformation had stopped. All this together suggests the formation of partial melts in these carbonates. A Schreinemaker analysis of the experimental data for a CO2-H2O fluid-saturated system indeed predicts formation of calcite-rich melt between 650-880 °C, in

Identification of Gravity-Related Effects on Crystal Growth From Melts With an Immiscibility Gap

NASA Technical Reports Server (NTRS)

Kassemi, M.; Sayir, A.; Farmer, S.

1999-01-01

This work involves an experimental-numerical approach to study the effects of natural and Marangoni convections on solidification of single crystals from a silicate melt with a liquid-liquid immiscibility gap. Industrial use of crystals grown from silicate melts is becoming increasingly important in electronic, optical, and high temperature structural applications. Even the simplest silicate systems like Al203-SiO2 have had, and will continue to have, a significant role in the development of traditional and advanced ceramics. A unique feature of crystals grown from the silicate systems is their outstanding linear electro-optic properties. They also exhibit exceptionally high optical rotativity. As a result, these crystals are attractive materials for dielectric, optical, and microwave applications. Experimental work in our laboratory has indicated that directional solidification of a single crystal mullite appears to be preceded by liquid-liquid phase separation in the melt. Disruption of the immiscible state results in crystallization of a two phase structure. There is also evidence that mixing in the melt caused by density-driven convection can significantly affect the stability of the immiscible liquid layers and result in poly-crystalline growth. On earth, the immiscible state has only been observed for small diameter crystals grown in float zone systems where natural convection is almost negligible. Therefore, it is anticipated that growth of large single crystals from silicate melts would benefit from microgravity conditions because of the reduction of the natural convective mixing. The main objective of this research is to determine the effects of transport processes on the phase separation in the melt during growth of a single crystal while addressing the following issues: (1) When do the immiscible layers form and are they real?; (2) What are the main physical characteristics of the immiscible liquids?; and (3) How mixing by natural or Marangoni convection

The viscosity of magmatic silicate liquids: A model for calculation

NASA Technical Reports Server (NTRS)

Bottinga, Y.; Weill, D. F.

1971-01-01

A simple model has been designed to allow reasonably accurate calculations of viscosity as a function of temperature and composition. The problem of predicting viscosities of anhydrous silicate liquids has been investigated since such viscosity numbers are applicable to many extrusive melts and to nearly dry magmatic liquids in general. The fluidizing action of water dissolved in silicate melts is well recognized and it is now possible to predict the effect of water content on viscosity in a semiquantitative way. Water was not incorporated directly into the model. Viscosities of anhydrous compositions were calculated, and, where necessary, the effect of added water and estimated. The model can be easily modified to incorporate the effect of water whenever sufficient additional data are accumulated.

Concentrations and behavior of oxygen and oxide ion in melts of composition CaO.MgO.xSiO2

NASA Technical Reports Server (NTRS)

Semkow, K. W.; Haskin, L. A.

1985-01-01

The behavior of oxygen and oxide ion in silicate melts was investigated through their electrochemical reactions at a platinum electrode. Values are given for the diffusion coefficient for molecular oxygen in diopside melt and the activation energy of diffusion. It is shown that molecular oxygen dissociates prior to undergoing reduction and that oxide ion reacts quickly with silicate polymers when it is produced. The concentration of oxide ion is kept low by a buffering effect of the silicate, the exact level being dependent on the silicate composition. Data on the kinetics of reaction of the dissociation of molecular oxygen and on the buffering reactions are provided. It is demonstrated that the data on oxygen in these silicate melts are consistent with those for solid buffers.

Spade: An H Chondrite Impact-melt Breccia that Experienced Post-shock Annealing

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Jones, Rhian H.

2006-01-01

The low modal abundances of relict chondrules (1.8 Vol%) and of coarse (i.e. >= 2200 micron-size) isolated mafic silicate grains (1.8 Vol%) in Spade relative to mean H6 chondrites (11.4 and 9.8 vol%, respectively) show Spade to be a rock that has experienced a significant degree of melting. Various petrographic features (e.g., chromite-plagioclase assemblages, chromite veinlets, silicate darkening) indicate that melting was caused by shock. Plagioclase was melted during the shock event and flowed so that it partially to completely surrounded nearby mafic silicate grains. During crystallization, plagioclase developed igneous zoning. Low-Ca pyroxene that crystallized from the melt (or equilibrated with the melt at high temperatures) acquired relatively high amounts of CaO. Metallic Fe-Ni cooled rapidly below the Fe-Ni solws and transformed into martensite. Subsequent reheating of the rock caused transformation of martensite into abundant duplex plessite. Ambiguities exist in the shock stage assignment of Spade. The extensive silicate darkening, the occurrence of chromite-plagioclase assemblages, and the impact-melted characteristics of Spade are consistent with shock stage S6. Low shock (stage S2) is indicated by the undulose extinction and lack of planar fractures in olivine. This suggests that Spade reached a maximum prior shock level equivalent to stage S6 and then experienced post-shock annealing (probably to stage Sl). These events were followed by a less intense impact that produced the undulose extinction in the olivine, characteristic of shock stage S2. Annealing could have occurred if Spade were emplaced near impact melts beneath the crater floor or deposited in close proximity to hot debris within an ejecta blanket. Spade firmly establishes the case for post-shock annealing. This may have been a common process on ordinary chondrites (OC) asteroids.

Transport and thermodynamic properties of hydrous melts in the system An-Di.

NASA Astrophysics Data System (ADS)

Giordano, D.; Potuzak, M.; Romano, C.; Russell, J. K.; Nowak, M.; Dingwell, D. B.

2006-12-01

The thermodynamic and transport properties hydrous silicate melts are of fundamental importance for characterization of the dynamics and energetics associated with silicate melts in the Earth. The literature concerning the transport and calorimetric properties of hydrous silicate melts remains scarce. With few exceptions little has been effectively done in order to provide chemical models that bridge the gap between the description of both complex and simple systems. The An-Di system is of general interest to geochemists as well as petrologists because it serves as a simple analogue for basaltic compositions. It was chosen here due to the combination of its simple chemical description and the presence of an extensive database of published experimental data on both its transport and thermodynamic properties. We have measured the viscosity (η)), the glass transition temperatures (Tg) and the heat capacity (Cp) of silicate melts in the An-Di system containing up to 3 wt.% of dissolved H2O. Viscosity data were obtained by using the dilatometric method of micropenetration, whereas a differential scanning calorimeter (DSC) was employed to determine the glass transition temperatures and the heat capacities. In order to characterize the well-known cooling/heating rate dependence of the glass transition temperatures the calorimetric measurements were performed at heating/cooling rate of 5, 10, 15 and 20 K/min. These results together with those of previous experimental studies have been used to provide a compositional model capable of calculating the Newtonian viscosity of melts as well as the Tg and Cp values for the An- Di+H2O system. The non-Arrhenian T-dependence of viscosity is accounted for by the Vogel-Fulcher- Tammann (VFT) and the Adam Gibbs (AG) equations. Our optimizations assume a common, high-T limit (A) for silicate melt viscosity, consistent with values provided by both theoretical and experimental studies. In particular, we also show that glass transition

Microstructural evidence of melting in crustal rocks (Invited)

NASA Astrophysics Data System (ADS)

Holness, M. B.; Cesare, B.; Sawyer, E. W.

2010-12-01

The signature of the former presence of melt on a microscopic scale is highly variable, subject to modification both during the melting event and during its subsequent history. Static pyrometamorphism results in melt films on grain boundaries between reactant phases. If a volume increase is involved, melting results in hydrofracture. On a longer timescale, as demonstrated by fragments of the crustal source in lava flows at El Hoyazo (SE Spain), melt occurs throughout the rock. These examples are highly unusual: the great majority of rocks that underwent melting cooled more slowly, permitting microstructural modification driven by a combination of textural equilibration, reaction and deformation. In the absence of deformation, and at constant temperature, melt-bearing rocks approach textural equilibrium, characterised by uniform grain size, smoothly curved grain boundaries and the establishment at all three-grain junctions of the equilibrium dihedral angle. The dihedral angle controls melt connectivity, with consequences for melt mobility and rock rheology. However, deformation is the rule rather than the exception in regional metamorphic terrains with profound effects on melt distribution. If deformation occurs predominantly by diffusive processes, textural equilibration can keep pace. At higher deformation rates melt is squeezed into planar pockets aligned parallel to the shearing direction or perpendicular to the extensional stress. Microstructures formed during solidification are controlled by cooling rate, H2O, and the size of the melt pockets. Large pockets solidify to look like igneous rocks. In small pores the supersaturation required for crystal growth is high and melt persist to lower temperatures, even being preserved as tiny glassy inclusions (“nanogranites”) in regional terranes. The pore size effect changes crystallization order, resulting in small, highly cuspate grains on grain boundaries with low dihedral angles. Crystallisation microstructures

The stability of hibonite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1993-01-01

Phase fields in which hibonite (Hib) and silicate melt coexist with spinel (Sp), CaAl4O7 (CA2), gehlenitic melilite (Mel), anorthite (An), or corundum (Cor) in the system CaO-MgO-Al203-SiO2-TiO2 (CMAST) were determined and activity models developed for Mel and Hib solid solutions. Experimentally determined partition coefficients for Ti between Hib and coexisting melt, D sub t, vary from 0.8 to 2.1 and generally decrease with increasing TiO2 content in the liquid (L). Based on Ti partioning between Hib and melt, bulk inclusion compositions and Hib-saturated liquid use phase diagrams, the Hib in Fluffy Type A inclusions (FTA's) from Allende and at least some of the Hib from Hib-rich inclusions is relict; much of the Hib from Hib-glass spherules probably crystallized from a melt under nonequilibrium conditions. Bulk compositions for all of these Ca-Al-rich inclusions (CAI's) are consistent with an origin as Mel + Hib + Sp + perovskite (Pv) proto-inclusions in which Mel was partially altered. In some cases, the proto-inclusion was partially or completely melted with vaporization occurring over a period of time sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. If equilibration temperatures based on Hib-bearing CAI's reflect condensation in a cooling gas of solar composition, then Hib + Cor condensed at approximately 1260 C (referenced to 10 exp -3 atm) and Hib + Sp + Mel at approximately 1215 +/- 10 C. Simple thermochemical models for the substitution of trace elements into the Ca-site of meteoritic Hib suggest that virtually all Eu is divalent in early condensate Hibs but that Eu(2+)/Eu(3+) decreases by a factor of 20 or more during the course of condensation, primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phases condense. The relative sizes of Eu and Yb anomalies in meteoritic Hibs and CAI's may be influenced by

Investigating the Importance of the Pocket-estimation Method in Pocket-based Approaches: An Illustration Using Pocket-ligand Classification.

PubMed

Caumes, Géraldine; Borrel, Alexandre; Abi Hussein, Hiba; Camproux, Anne-Claude; Regad, Leslie

2017-09-01

Small molecules interact with their protein target on surface cavities known as binding pockets. Pocket-based approaches are very useful in all of the phases of drug design. Their first step is estimating the binding pocket based on protein structure. The available pocket-estimation methods produce different pockets for the same target. The aim of this work is to investigate the effects of different pocket-estimation methods on the results of pocket-based approaches. We focused on the effect of three pocket-estimation methods on a pocket-ligand (PL) classification. This pocket-based approach is useful for understanding the correspondence between the pocket and ligand spaces and to develop pharmacological profiling models. We found pocket-estimation methods yield different binding pockets in terms of boundaries and properties. These differences are responsible for the variation in the PL classification results that can have an impact on the detected correspondence between pocket and ligand profiles. Thus, we highlighted the importance of the pocket-estimation method choice in pocket-based approaches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diffusion of major and trace elements in natural silicate melts as a tool to investigate timescales in magma mixing

NASA Astrophysics Data System (ADS)

González-García, Diego; Zezza, Angela; Behrens, Harald; Vetere, Francesco; Petrelli, Maurizio; Morgavi, Daniele; Perugini, Diego

2016-04-01

New melt injection into a shallow magma chamber is regarded as one of the potential triggers for explosive volcanic eruptions. Chemical diffusion occurring between the two mixing melts is a time-dependent process, and thus has the potential to shed light on the timescales involved in magma mixing events leading to an eruption. In order to achieve this, a complete database of diffusion coefficients in natural melts is a necessary prerequisite. We have carried out a set of 12 diffusion couple experiments in order to determine diffusion coefficients (D) of major and trace elements in two natural silicate melts. Two end-members from the Vulcano island (Aeolian archipelago, Italy) have been chosen for the experiments: a shoshonite (Vulcanello lava platform) and a rhyolitic obsidian (Pietre Cotte lava flow, La Fossa cone). Glasses from each end-member with added water contents of 0 wt%, 1 wt% and 2 wt% were produced in an Internally Heated Pressure Vessel (IHPV). Two glass cylinders with similar water content but different base composition are inserted in Au-Pd capsules and experiments are run in the IHPV at 1200° C with pressure from 0.5 to 3 kbar. Experiment capsules are rapidly quenched and analyzed by FTIR, EPMA and LA-ICP-MS for H2O, major and trace elements, respectively, along 2 mm linear profiles extending across the interface. A Boltzmann-Matano approach is used to obtain concentration-dependent diffusivities. The obtained concentration-distance profiles are asymmetric and extend deeper into the shoshonite relative to the rhyolite, indicating that diffusion is slower in the latter. Results show that diffusivities are notably accelerated by the presence of H2O in the melt. Experiments performed by using water-free glass show diffusivities one order of magnitude lower compared to glasses containing up to 2 wt% H2O. The effect of pressure, in the investigated range, is negligible and falls within measurement error. Among major elements, Si and Ti are the slowest

Behaviour of niobium during early Earth’s differentiation: insights from its local structure and oxidation state in silicate melts at high pressure

NASA Astrophysics Data System (ADS)

Sanloup, C.; Cochain, B.; de Grouchy, C.; Glazyrin, K.; Konôpkova, Z.; Liermann, H.-P.; Kantor, I.; Torchio, R.; Mathon, O.; Irifune, T.

2018-02-01

Niobium (Nb) is one of the key trace elements used to understand Earth’s formation and differentiation, and is remarkable for its deficiency relative to tantalum in terrestrial rocks compared to the building chondritic blocks. In this context, the local environment of Nb in silica-rich melts and glasses is studied by in situ x-ray absorption spectroscopy (XAS) at high pressure (P) up to 9.3 GPa and 1350 K using resistive-heating diamond-anvil cells. Nb is slightly less oxidized in the melt (intermediate valence between  +4 and  +5) than in the glass (+5), an effect evidenced from the shift of the Nb-edge towards lower energies. Changes in the pre-edge features are also observed between melt and glass states, consistently with the observed changes in oxidation state although likely enhanced by temperature (T) effects. The oxidation state of Nb is not affected by pressure neither in the molten nor glassy states, and remains constant in the investigated P-range. The Nb-O coordination number is constant and equal to 6.3+/-0.4 below 5 GPa, and only progressively increases up to 7.1+/-0.4 at 9.3 GPa, the maximum P investigated. If these findings were to similarly apply to basaltic melts, that would rule out the hypothesis of Nb/Ta fractionation during early silicate Earth’s differentiation, thus reinforcing the alternative hypothesis of fractionation during core formation on reduced pre-planetary bodies.

Melt inclusions: Chapter 6

USGS Publications Warehouse

,; Lowenstern, J. B.

2014-01-01

Melt inclusions are small droplets of silicate melt that are trapped in minerals during their growth in a magma. Once formed, they commonly retain much of their initial composition (with some exceptions) unless they are re-opened at some later stage. Melt inclusions thus offer several key advantages over whole rock samples: (i) they record pristine concentrations of volatiles and metals that are usually lost during magma solidification and degassing, (ii) they are snapshots in time whereas whole rocks are the time-integrated end products, thus allowing a more detailed, time-resolved view into magmatic processes (iii) they are largely unaffected by subsolidus alteration. Due to these characteristics, melt inclusions are an ideal tool to study the evolution of mineralized magma systems. This chapter first discusses general aspects of melt inclusions formation and methods for their investigation, before reviewing studies performed on mineralized magma systems.

Simulating the behavior of volatiles belonging to the C-O-H-S system in silicate melts under magmatic conditions with the software D-Compress

NASA Astrophysics Data System (ADS)

Burgisser, Alain; Alletti, Marina; Scaillet, Bruno

2015-06-01

Modeling magmatic degassing, or how the volatile distribution between gas and melt changes at pressure varies, is a complex task that involves a large number of thermodynamical relationships and that requires dedicated software. This article presents the software D-Compress, which computes the gas and melt volatile composition of five element sets in magmatic systems (O-H, S-O-H, C-S-O-H, C-S-O-H-Fe, and C-O-H). It has been calibrated so as to simulate the volatiles coexisting with three common types of silicate melts (basalt, phonolite, and rhyolite). Operational temperatures depend on melt composition and range from 790 to 1400 °C. A specificity of D-Compress is the calculation of volatile composition as pressure varies along a (de)compression path between atmospheric and 3000 bars. This software was prepared so as to maximize versatility by proposing different sets of input parameters. In particular, whenever new solubility laws on specific melt compositions are available, the model parameters can be easily tuned to run the code on that composition. Parameter gaps were minimized by including sets of chemical species for which calibration data were available over a wide range of pressure, temperature, and melt composition. A brief description of the model rationale is followed by the presentation of the software capabilities. Examples of use are then presented with outputs comparisons between D-Compress and other currently available thermodynamical models. The compiled software and the source code are available as electronic supplementary materials.

Density Measurement for MORB Melts by X-ray Absorption Method

NASA Astrophysics Data System (ADS)

Sakamaki, T.; Urakawa, S.; Suzuki, A.; Ohtani, E.; Katayama, Y.

2006-12-01

Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the top anvil sizes of 6 mm and 4 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 5 GPa, from 300 to 2000 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

Density Measurement for MORB Melts by X-ray Absorption Method

NASA Astrophysics Data System (ADS)

Sakamaki, T.; Urakawa, S.; Ohtani, E.; Suzuki, A.; Katayama, Y.

2005-12-01

Density of silicate melts at high pressure is one of the most important properties to understand magma migration in the planetary interior and the differentiation of the terrestrial planets. The density measurements of silicate melts have been carried out by several methods (shock compression experiments and sink-float method in static experiments, etc.). However, since these methods have difficulties in acquisition of data at a desired pressure and temperature, the density of the silicate melt have been measured under only a few conditions. Recently a new density measurement was developed by the X-ray absorption method. Advantage of this method is to measure density of liquids at a desired pressure and temperature. In the present study we measured the density of MORB melt by X-ray absorption method. Experiments were carried out at the BL22XU beamline at SPring-8. A DIA-type cubic anvil apparatus was used for generation of high pressure and temperature. We used tungsten carbide anvils with the edge-length of 6 mm. The energy of monochromateized X-ray beam was 23 keV. The intensities of incident and transmitted X-ray were measured by ion chambers. The density of the melt was calculated on the basis of Beer-Lambert law. The starting material was a glass with the MORB composition. Experiments were made from 1 atm to 4 GPa, from 300 to 2200 K. We compared the density of MORB melt with the compression curve of the melt in previous works. The density measured by this study is lower than that expected from the compression curve determined at higher pressures by the sink-float method. Structural change of the MORB melt with increasing pressure might be attributed to this discrepancy.

Differentiation of Asteroid 4 Vesta: Core Formation by Iron Rain in a Silicate Magma Ocean

NASA Technical Reports Server (NTRS)

Kiefer, Walter S.; Mittlefehldt, David W.

2017-01-01

Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft while orbiting asteroid 4 Vesta, suggest that Vesta resembles H chondrites in bulk chemical composition, possible with about 25 percent of a CM-chondrite like composition added in. For this model, the core is 15 percent by mass (or 8 percent by volume) of the asteroid, with a composition of 73.7 percent by weight Fe, 16.0 percent by weight S, and 10.3 percent by weight Ni. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite solidification. The combination of the melting phase relationships for the silicate and metal phases, together with the moderately siderophile element concentrations together require that complete melting of the metal phase occurred (temperature is greater than1350 degrees Centigrade), along with substantial (greater than 40 percent) melting of the silicate material. Thus, core formation on Vesta occurs as iron rain sinking through a silicate magma ocean.

Shock melting and vaporization of lunar rocks and minerals.

NASA Technical Reports Server (NTRS)

Ahrens, T. J.; O'Keefe, J. D.

1972-01-01

The entropy associated with the thermodynamic states produced by hypervelocity meteoroid impacts at various velocities are calculated for a series of lunar rocks and minerals and compared with the entropy values required for melting and vaporization. Taking into account shock-induced phase changes in the silicates, we calculate that iron meteorites impacting at speeds varying from 4 to 6 km/sec will produce shock melting in quartz, plagioclase, olivine, and pyroxene. Although calculated with less certainty, impact speeds required for incipient vaporization vary from 7 to 11 km/sec for the range of minerals going from quartz to periclase for aluminum (silicate-like) projectiles. The impact velocities, which are required to induce melting in a soil, are calculated to be in the range of 3 to 4 km/sec, provided thermal equilibrium is achieved in the shock state.

Degassing-induced crystallization in silicate melt inclusion: evaluating the role of post-entrapment changes in melt inclusion from the SW volcanic flows of Deccan Large Igneous Province (Deccan LIP) lava.

NASA Astrophysics Data System (ADS)

Rani Choudhary, Babita

2017-04-01

Melt inclusions represent sampling of magma during their growth in magma chambers and during ascent to the surface. Several studies of melt inclusions in Large Igneous Provinces (LIPs) in different parts of the world have been documented in the literature (Sobolev et al. 2011; Kamenetsky et al. 2012). Melt inclusions study from Deccan LIP can provide new insights into the physio-chemical conditions and evolution of this important LIP. The Deccan LIP was fissure eruption mainly emplaced over a very short duration at 66 Ma (Schoene et al. 2015). To better characterize and explain the diversity in geochemical composition, petrogenesis and volatile degassing, melt inclusions studies have been carried out in clinopyroxene and plagioclase feldspar from a suite of samples in the Western Ghats section. Samples were obtained from the upper three formations (the Wai subgroup). The inclusions are primary and range in shape and size varies from a few microns, up to 100 microns. The inclusions are crystalline, and contain daughter phases. Some are glassy, with or without a shrinkage bubble. The melt inclusions show substantial variations in major element composition. Inclusions are significantly enriched in TiO2 (3.68 to 0.08 wt%) and FeO (18.3 to 2.63 wt%). SiO2 ranges from 43.4-66.8 wt% and classification diagrams of total alkali (Na2O+K2O) Vs. silica melt inclusions show that most inclusions are of sub-alkaline to mildly alkaline composition. Al2O3 ranges from 9.7- 22.4wt % and MgO 18.3-1.6. EPMA measurements demonstrated the presence of daughter crystals, such as magnetite and titanomagnetite, and high FeO, TiO2 and CaO within melt inclusions among the silicate daughter crystal clusters. Volatiles are determined have wide range in composition in both plagioclase- and pyroxene-hosted melt inclusions by using FTIR technique, values up to 2wt% H2Ototal and 1808 ppm CO2. Moreover the variability in composition and volatiles the melt from the samples in a single flow suggests

Volatile Element Behavior During Melting and Vaporisation on Earth and Protoplanets.

NASA Astrophysics Data System (ADS)

Wood, B. J.; Norris, C. A.

2017-12-01

During accretion the Earth and many of the smaller bodies which were added to it, underwent periods of partial melting, vaporisation and re-condensation. This resulted in patterns of volatile element depletion relative to CI chondrite which are difficult to interpret. The behavior of moderately volatile elements (Pb, Cd, Zn,Cu, In,Tl etc) during these melting, vaporisation and condensation processes is usually approximated by the temperature of condensation from a gas of solar composition. Thus, Tl and In have low condensation temperatures and are regarded as the most volatile of this group. In order to test this volatility approximation we have studied the vaporisation behavior of 13 elements (Ag,Bi,Cd,Cr,Cu,Ga,Ge,In,Pb,Sb,Sn,Tl,Zn) from molten basalt at 1 atm pressure and oxygen fugacities between Ni-NiO and 2 log units below Fe-FeO. The relative volatilities of the elements turn out to be only weakly correlated with condensation temperature, indicating that the latter is a poor proxy for volatility on molten bodies. Cu, Zn and In for example all have similar volatility in the oxygen fugacity range of concern, despite the condensation temperature of Cu (1037K at 10-4bar) being 500K greater than that of In. The oxygen fugacity dependence of volatility indicates that the volatile species are, for all elements more reduced than the melt species. We addressed the differences between condensation temperature and relative volatility in 2 steps. Firstly we used metal-silicate partitioning experiments to estimate the activity coefficients of the trace element oxides in silicate melts. We then used available thermodynamic data to compute the vapor pressures of the stable species of these 13 elements over the silicate melt at oxygen fugacities ranging from Ni-NiO to about 6 log units below Fe-FeO, which approximates the solar gas. Thus we find that presence of Cl and S in the solar gas and the stable Cl and S species of In,Tl Ga Ge Cd and Sn are important contributing

The effect of oxygen fugacity on the partitioning of nickel and cobalt between olivine, silicate melt, and metal

NASA Technical Reports Server (NTRS)

Ehlers, Karin; Grove, Timothy L.; Sisson, Thomas W.; Recca, Steven I.; Zervas, Deborah A.

1992-01-01

The effect of oxygen fugacity, f(O2), on the partitioning behavior of Ni and Co between olivine, silicate melt, and metal was investigated in the CaO-MgO-Al2O3-SiO2-FeO-Na2O system, an analogue of a chondrule composition from an ordinary chondrite. The conditions were 1350 C and 1 atm, with values of f(O2) varying between 10 exp -5.5 and 10 exp -12.6 atm (i.e., the f(O2) range relevant for crystal/liquid processes in terrestrial planets and meteorite parent bodies). Results of chemical analysis showed that the values of the Ni and Co partitioning coefficients begin to decrease at values of f(O2) that are about 3.9 log units below the nickel-nickel oxide and cobalt-cobalt oxide buffers, respectively, near the metal saturation for the chondrule analogue composition.

Grain-scale alignment of melt in sheared partially molten rocks: implications for viscous anisotropy

NASA Astrophysics Data System (ADS)

Pec, Matej; Quintanilla-Terminel, Alejandra; Holtzman, Benjamin; Zimmerman, Mark; Kohlstedt, David

2016-04-01

Presence of melt significantly influences rheological properties of partially molten rocks by providing fast diffusional pathways. Under stress, melt aligns at the grain scale and this alignment induces viscous anisotropy in the deforming aggregate. One of the consequences of viscous anisotropy is melt segregation into melt-rich sheets oriented at low angle to the shear plane on much larger scales than the grain scale. The magnitude and orientation of viscous anisotropy with respect to the applied stress are important parameters for constitutive models (Takei and Holtzman 2009) that must be constrained by experimental studies. In this contribution, we analyze the shape preferred orientation (SPO) of individual grain-scale melt pockets in deformed partially molten mantle rocks. The starting materials were obtained by isostatically hot-pressing olivine + basalt and olivine + chromite + basalt powders. These partially molten rocks were deformed in general shear or torsion at a confining pressure, Pc = 300 MPa, temperature, T = 1200° - 1250° C, and strain rates of 10-3 - 10-5 s-1to finite shear strains, γ, of 0.5 - 5. After the experiment, high resolution backscattered electron images were obtained using a SEM equipped with a field emission gun. Individual melt pockets were segmented and their SPO analyzed using the paror and surfor methods and Fourier transforms (Heilbronner and Barret 2014). Melt segregation into melt-rich sheets inclined at 15° -20° antithetic with respect to the shear plane occurs in three-phase system (olivine + chromite + basalt) and in two-phase systems (olivine + basalt) twisted to high strain. The SPO of individual melt pockets within the melt-rich bands is moderately strong (b/a ≈ 0.8) and is always steeper (20° -40°) than the average melt-rich band orientation. In the two-phase system (olivine + basalt) sheared to lower strains, no distinct melt-rich sheets are observed. Individual grain-scale melt pockets are oriented at 45° -55�

Ar and K partitioning between clinopyroxene and silicate melt to 8 GPa

NASA Astrophysics Data System (ADS)

Chamorro, E. M.; Brooker, R. A.; Wartho, J.-A.; Wood, B. J.; Kelley, S. P.; Blundy, J. D.

2002-02-01

The relative incompatibility of Ar and K are fundamental parameters in understanding the degassing history of the mantle. Clinopyroxene is the main host for K in most of the upper mantle, playing an important role in controlling the K/Ar ratio of residual mantle and the subsequent time-integrated evolution of 40Ar/36Ar ratios. Clinopyroxene also contributes to the bulk Ar partition coefficient that controls the Ar degassing rate during mantle melting. The partitioning of Ar and K between clinopyroxene and quenched silicate melt has been experimentally determined from 1 to 8 GPa for the bulk compositions Ab80Di20 (80 mol% albite-20 mol% diopside) and Ab20Di80 with an ultraviolet laser ablation microprobe (UVLAMP) technique for Ar analysis and the ion microprobe for K. Data for Kr (UVLAMP) and Rb (ion probe) have also been determined to evaluate the role of crystal lattice sites in controlling partitioning. By excluding crystal analyses that show evidence of glass contamination, we find relatively constant Ar partition coefficients (DAr) of 2.6 × 10-4 to 3.9 × 10-4 for the Ab80Di20 system at pressures from 2 to 8 GPa. In the Ab20Di80 system, DAr shows similar low values of 7.0 × 10-5 and 3.0 × 10-4 at 1 to 3 GPa. All these values are several orders of magnitude lower than previous measurements on separated crystal-glass pairs. DK is 10 to 50 times greater than DRb for all experiments, and both elements follow parallel trends with increasing pressure, although these trends are significantly different in each system studied. The DK values for clinopyroxene are at least an order of magnitude greater than DAr under all conditions investigated here, but DAr appears to show more consistent behavior between the two systems than K or Rb. The partitioning behavior of K and Rb can be explained in terms of combined pressure, temperature, and crystal chemistry effects that result in changes for the size of the clinopyroxene M2 site. In the Ab20Di80 system, where

Experimental modeling of the interaction of subducted carbonates and sulfur with mantle silicates

NASA Astrophysics Data System (ADS)

Bataleva, Yu. V.; Palyanov, Yu. N.; Borzdov, Yu. M.; Zdrokov, E. V.; Sobolev, N. V.

2016-09-01

Experimental studies in the system Fe,Ni-olivine-carbonate-S ( P = 6.3 GPa, T = 1050-1550°C, t = 40-60 h) aimed at modeling of the interaction of subducted carbonates and sulfur with rocks of the silicate mantle and at investigation of the likely mechanism of the formation of mantle sulfides were performed. It is shown that an association of olivine + orthopyroxene + magnesite + pyrite coexisting with a sulfur melt/fluid with dissolved Fe, Ni, and O is formed at T ≤ 1250°C. An association of low-Fe olivine, orthopyroxene, and magnesite and two immiscible melts of the carbonate and S-Fe-Ni-O compositions are formed at T ≥ 1350°C. It is shown that the reduced S-bearing fluids may transform silicates and carbonates, extract metals from the solid-phase matrix, and provide conditions for generation of sulfide melts.

Modifying Silicates for Better Dispersion in Nanocomposites

NASA Technical Reports Server (NTRS)

Campbell, Sandi

2005-01-01

, the co-ion exchange strengthens the polymer/silicate interface and ensures irreversible separation of the silicate layers. One way in which it does this is to essentially tether one amine of each diamine molecule to a silicate surface, leaving the second amine free for reaction with monomers during the synthesis of a polymer. In addition, the incorporation of alkyl ammonium ions into the galleries at low concentration helps to keep low the melt viscosity of the oligomer formed during synthesis of the polymer and associated processing - a consideration that is particularly important in the case of a highly cross-linked, thermosetting polymer. Because of the chemical bonding between the surface-modifying amines and the monomers, even when the alkyl ammonium ions become degraded at high processing temperature, the silicate layers do not aggregate and, hence, nanometer-level dispersion is maintained.

Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

NASA Technical Reports Server (NTRS)

King, C.; Righter, K.; Danielson, L.; Pando, K.; Lee, C.

2010-01-01

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

Experimental Determination of Spinel/Melt, Olivine/Melt, and Pyroxene/Melt Partition Coefficients for Re, Ru, Pd, Au, and Pt

NASA Technical Reports Server (NTRS)

Righter, K.; Campbell, A. J.; Humayun, M.

2003-01-01

Experimental studies have identified spinels as important hosts phases for many of the highly siderophile elements (HSE). Yet experimental studies involving chromite or Cr-rich spinel have been lacking. Experimental studies of partitioning of HSEs between silicate, oxides and silicate melt are plagued by low solubilities and the presence of small metallic nuggets at oxygen fugacities relevant to magmas, which interfere with analysis of the phases of interest. We have circumvented these problems in two ways: 1) performing experiments at oxidized conditions, which are still relevant to natural systems but in which nuggets are not observed, and 2) analysis of run products with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), allowing a combination of high sensitivity and good spatial resolution.

Ahrensite, γ-Fe2SiO4, a new shock-metamorphic mineral from the Tissint meteorite: Implications for the Tissint shock event on Mars

NASA Astrophysics Data System (ADS)

Ma, Chi; Tschauner, Oliver; Beckett, John R.; Liu, Yang; Rossman, George R.; Sinogeikin, Stanislav V.; Smith, Jesse S.; Taylor, Lawrence A.

2016-07-01

Ahrensite (IMA 2013-028), γ-Fe2SiO4, is the natural Fe-analog of the silicate-spinel ringwoodite (γ-Mg2SiO4). It occurs in the Tissint Martian meteorite, where it forms through the transformation of the fayalite-rich rims of olivine megacrysts or Fe-rich microphenocrysts in contact with shock melt pockets. The typical sequence of phase assemblages traversing across a Tissint melt pocket into olivine is: quenched melt or fayalite-pigeonite intergrowth ⇒ bridgmanite + wüstite ⇒ ahrensite and/or ringwoodite ⇒ highly-deformed olivine + nanocrystalline ringwoodite ⇒ deformed olivine. We report the first comprehensive set of crystallographic, spectroscopic, and quantitative chemical analysis of type ahrensite, and show that concentrations of ferric iron and inversion in the type material of this newly approved mineral are negligible. We also report the occurrence of nanocrystalline ringwoodite in strained olivine and establish correlations between grain size and distance from melt pockets. The ahrensite and ringwoodite crystals show no preferred orientation, consistent with random nucleation and incoherent growth within a highly strained matrix of olivine. Grain sizes of ahrensite immediately adjacent to melt pockets are consistent with growth during a shock of moderate duration (1-10 ms).

Ahrensite, γ-Fe 2SiO 4, a new shock-metamorphic mineral from the Tissint meteorite: Implications for the Tissint shock event on Mars

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Chi; Tschauner, Oliver; Beckett, John R.

Ahrensite (IMA 2013-028), gamma-Fe 2SiO 4, is the natural Fe-analog of the silicate-spinel ringwoodite (gamma-Mg 2SiO 4). It occurs in the Tissint Martian meteorite, where it forms through the transformation of the fayalite-rich rims of olivine megacrysts or Ferich microphenocrysts in contact with shock melt pockets. The typical sequence of phase assemblages traversing across a Tissint melt pocket into olivine is: quenched melt or fayalite-pigeonite intergrowth → bridgmanite + wustite → ahrensite and/or ringwoodite double right arrow highly-deformed olivine + nanocrystalline ringwoodite → deformed olivine. We report the first comprehensive set of crystallographic, spectroscopic, and quantitative chemical analysis of typemore » ahrensite, and show that concentrations of ferric iron and inversion in the type material of this newly approved mineral are negligible. We also report the occurrence of nanocrystalline ringwoodite in strained olivine and establish correlations between grain size and distance from melt pockets. The ahrensite and ringwoodite crystals show no preferred orientation, consistent with random nucleation and incoherent growth within a highly strained matrix of olivine. As a result, grain sizes of ahrensite immediately adjacent to melt pockets are consistent with growth during a shock of moderate duration (1-10 ms).« less

Ahrensite, γ-Fe 2SiO 4, a new shock-metamorphic mineral from the Tissint meteorite: Implications for the Tissint shock event on Mars

DOE PAGES

Ma, Chi; Tschauner, Oliver; Beckett, John R.; ...

2016-04-27

Ahrensite (IMA 2013-028), gamma-Fe 2SiO 4, is the natural Fe-analog of the silicate-spinel ringwoodite (gamma-Mg 2SiO 4). It occurs in the Tissint Martian meteorite, where it forms through the transformation of the fayalite-rich rims of olivine megacrysts or Ferich microphenocrysts in contact with shock melt pockets. The typical sequence of phase assemblages traversing across a Tissint melt pocket into olivine is: quenched melt or fayalite-pigeonite intergrowth → bridgmanite + wustite → ahrensite and/or ringwoodite double right arrow highly-deformed olivine + nanocrystalline ringwoodite → deformed olivine. We report the first comprehensive set of crystallographic, spectroscopic, and quantitative chemical analysis of typemore » ahrensite, and show that concentrations of ferric iron and inversion in the type material of this newly approved mineral are negligible. We also report the occurrence of nanocrystalline ringwoodite in strained olivine and establish correlations between grain size and distance from melt pockets. The ahrensite and ringwoodite crystals show no preferred orientation, consistent with random nucleation and incoherent growth within a highly strained matrix of olivine. As a result, grain sizes of ahrensite immediately adjacent to melt pockets are consistent with growth during a shock of moderate duration (1-10 ms).« less

A Tale of Two Melt Rocks: Equilibration and Metal/Sulfide-Silicate Segregation in the L7 Chondrites PAT 91501 and LEW 88663

NASA Astrophysics Data System (ADS)

Harvey, R. P.

1993-07-01

Type 7 ordinary chondrites have experienced temperatures near or beyond those necessary for partial melting. Two recently collected Antarctic specimens, PAT91501 (PAT) and LEW88663 (LEW), have been tentatively identified as L7 chondrites based on mineral and oxygen isotope compositions [1,2]. The petrology and mineralogy of these meteorites suggests that they have undergone significant metal/sulfide-silicate segregation, with implications for meteorite parent bodies. PAT consists of an equigranular contact-framework of nearly euhedral olivine grains, with interstitial spaces filled by plagioclase, pyroxenes, and several minor phases. Ortho- and clinopyroxene occur in an exsolution relationship. Olivine and pyroxene are highly equilibrated, varying <<1% in Fe-endmember content. Pyroxene equilibration temperatures calculated for PAT using the methods of [3] are self-consistent at about 1180 degrees C. In thin section, PAT contains only traces of metal, as tiny isolated blebs in sulfide grains; large (>1 cm) globular sulfide inclusions are seen in hand-sample [1], but are not present in the section examined. LEW was originally classified as an achondrite with olivine and pyroxene compositions similar to those in L chondrites [2]. Metal is absent in LEW, although the specimen is small and heavily rusted, making it impossible to gauge the original metal content. Olivine grains are commonly rounded in shape and seldom in contact with more than a few other grains. LEW olivine and pyroxene are also highly equilibrated. Veins of Ni-bearing metal oxides and sulfides are common. Both low- and high-Ca pyroxene occur as discrete grains, orthopyroxene often poikilitically enclosing olivine. Pyroxene equilibration temperatures for LEW are more variable than those for PAT and consistently lower, with an average around 900 degrees C. The various textural and compositional characteristics of PAT and LEW suggest they have experienced partial melting to varying degrees. Both visually

Calcium isotopic fractionation in mantle peridotites by melting and metasomatism and Ca isotope composition of the Bulk Silicate Earth

NASA Astrophysics Data System (ADS)

Kang, Jin-Ting; Ionov, Dmitri A.; Liu, Fang; Zhang, Chen-Lei; Golovin, Alexander V.; Qin, Li-Ping; Zhang, Zhao-Feng; Huang, Fang

2017-09-01

To better constrain the Ca isotopic composition of the Bulk Silicate Earth (BSE) and explore the Ca isotope fractionation in the mantle, we determined the Ca isotopic composition of 28 peridotite xenoliths from Mongolia, southern Siberia and the Siberian craton. The samples are divided in three chemical groups: (1) fertile, unmetasomatized lherzolites (3.7-4.7 wt.% Al2O3); (2) moderately melt-depleted peridotites (1.3-3.0 wt.% Al2O3) with no or very limited metasomatism (LREE-depleted cpx); (3) strongly metasomatized peridotites (LREE-enriched cpx and bulk rock) further divided in subgroups 3a (harzburgites, 0.1-1.0% Al2O3) and 3b (fertile lherzolites, 3.9-4.3% Al2O3). In Group 1, δ44/40Ca of fertile spinel and garnet peridotites, which experienced little or no melting and metasomatism, show a limited variation from 0.90 to 0.99‰ (relative to SRM 915a) and an average of 0.94 ± 0.05‰ (2SD, n = 14), which defines the Ca isotopic composition of the BSE. In Group 2, the δ44/40Ca is the highest for three rocks with the lowest Al2O3, i.e. the greatest melt extraction degrees (average 1.06 ± 0.04 ‰, i.e. ∼0.1‰ heavier than the BSE estimate). Simple modeling of modal melting shows that partial melting of the BSE with 103 ln ⁡αperidotite-melt ranging from 0.10 to 0.25 can explain the Group 2 data. By contrast, δ44/40Ca in eight out of nine metasomatized Group 3 peridotites are lower than the BSE estimate. The Group 3a harzburgites show the greatest δ44/40Ca variation range (0.25-0.96‰), with δ44/40Ca positively correlated with CaO and negatively correlated with Ce/Eu. Chemical evidence suggests that the residual, melt-depleted, low-Ca protoliths of the Group 3a harzburgites were metasomatized, likely by carbonate-rich melts/fluids. We argue that such fluids may have low (≤0.25‰) δ44/40Ca either because they contain recycled crustal components or because Ca isotopes, similar to trace elements and their ratios, may be fractionated by kinetic and

X-ray Raman scattering study of MgSiO3 glass at high pressure: Implication for triclustered MgSiO3 melt in Earth's mantle

PubMed Central

Lee, Sung Keun; Lin, Jung-Fu; Cai, Yong Q.; Hiraoka, Nozomu; Eng, Peter J.; Okuchi, Takuo; Mao, Ho-kwang; Meng, Yue; Hu, Michael Y.; Chow, Paul; Shu, Jinfu; Li, Baosheng; Fukui, Hiroshi; Lee, Bum Han; Kim, Hyun Na; Yoo, Choong-Shik

2008-01-01

Silicate melts at the top of the transition zone and the core-mantle boundary have significant influences on the dynamics and properties of Earth's interior. MgSiO3-rich silicate melts were among the primary components of the magma ocean and thus played essential roles in the chemical differentiation of the early Earth. Diverse macroscopic properties of silicate melts in Earth's interior, such as density, viscosity, and crystal-melt partitioning, depend on their electronic and short-range local structures at high pressures and temperatures. Despite essential roles of silicate melts in many geophysical and geodynamic problems, little is known about their nature under the conditions of Earth's interior, including the densification mechanisms and the atomistic origins of the macroscopic properties at high pressures. Here, we have probed local electronic structures of MgSiO3 glass (as a precursor to Mg-silicate melts), using high-pressure x-ray Raman spectroscopy up to 39 GPa, in which high-pressure oxygen K-edge features suggest the formation of tricluster oxygens (oxygen coordinated with three Si frameworks; [3]O) between 12 and 20 GPa. Our results indicate that the densification in MgSiO3 melt is thus likely to be accompanied with the formation of triculster, in addition to a reduction in nonbridging oxygens. The pressure-induced increase in the fraction of oxygen triclusters >20 GPa would result in enhanced density, viscosity, and crystal-melt partitioning, and reduced element diffusivity in the MgSiO3 melt toward deeper part of the Earth's lower mantle. PMID:18535140

Effect of Sulfur on Siderophile Element Partitioning Between Olivine and Martian Primary Melt

NASA Technical Reports Server (NTRS)

Usui, T.; Shearer, C. K.; Righter, K.; Jones, J. H.

2011-01-01

Since olivine is a common early crystallizing phase in basaltic magmas that have produced planetary and asteroidal crusts, a number of experimental studies have investigated elemental partitioning between olivine and silicate melt [e.g., 1, 2, 3]. In particular, olivine/melt partition coefficients of Ni and Co (DNi and DCo) have been intensively studied because these elements are preferentially partitioned into olivine and thus provide a uniquely useful insight into the basalt petrogenesis [e.g., 4, 5]. However, none of these experimental studies are consistent with incompatible signatures of Co [e.g., 6, 7, 8] and Ni [7] in olivines from Martian meteorites. Chemical analyses of undegassed MORB samples suggest that S dissolved in silicate melts can reduce DNi up to 50 % compared to S-free experimental systems [9]. High S solubility (up to 4000 ppm) for primitive shergottite melts [10] implies that S might have significantly influenced the Ni and Co partitioning into shergottite olivines. This study conducts melting experiments on Martian magmatic conditions to investigate the effect of S on the partitioning of siderophile elements between olivine and Martian primary melt.

Mutual interactions of redox couples via electron exchange in silicate melts - Models for geochemical melt systems

NASA Technical Reports Server (NTRS)

Schreiber, Henry D.; Merkel, Robert C., Jr.; Schreiber, V. Lea; Balazs, G. Bryan

1987-01-01

The mutual interactions via electron exchange of redox couples in glass-forming melts were investigated both theoretically and experimentally. A thermodynamic approach for considering the mutual interactions leads to conclusion that the degree of mutual interaction in the melt should be proportional in part to the difference in relative reduction potentials of the interacting redox couples. Experimental studies verify this conclusion for numerous redox couples in several composition/temperature/oxygen fugacity regimes. Geochemical systems simultaneously possess many potentially multivalent elements; the stabilized redox states in the resulting magmas can be explained in part by mutual interactions and by redox buffering through the central Fe(III)- Fe(II) couples in the melts. The significance of these results for basaltic magmas of the earth, moon, and meteorites is addressed.

High-performance polymer/layered silicate nanocomposites

NASA Astrophysics Data System (ADS)

Heidecker, Matthew J.

High-performance layered-silicate nanocomposites of Polycarbonate (PC), poly(ethylene terephthalate) (PET), and their blends were produced via conventional melt-blending techniques. The focus of this thesis was on the fundamentals of dispersion, control of thermal stability, maintenance of melt-blending processing conditions, and on optimization of the composites' mechanical properties via the design of controlled and thermodynamically favorable nano-filler dispersions within the polymer matrices. PET and PC require high temperatures for melt-processing, rendering impractical the use of conventional/commercial organically-modified layered-silicates, since the thermal degradation temperatures of their ammonium surfactants lies below the typical processing temperatures. Thus, different surfactant chemistries must be employed in order to develop melt-processable nanocomposites, also accounting for polymer matrix degradation due to water (PET) or amine compounds (PC). Novel high thermal-stability surfactants were developed and employed in montmorillonite nanocomposites of PET, PC, and PC/PET blends, and were compared to the respective nanocomposites based on conventional quaternary-ammonium modified montmorillonites. Favorable dispersion was achieved in all cases, however, the overall material behavior -- i.e., the combination of crystallization, mechanical properties, and thermal degradation -- was better for the nanocomposites based on the thermally-stable surfactant fillers. Studies were also done to trace, and ultimately limit, the matrix degradation of Polycarbonate/montmorillonite nanocomposites, through varying the montmorillonite surfactant chemistry, processing conditions, and processing additives. Molecular weight degradation was, maybe surprisingly, better controlled in the conventional quaternary ammonium based nanocomposites -- even though the thermal stability of the organically modified montmorillonites was in most cases the lowest. Dependence of the

Rutile solubility and titanium coordination in silicate melts

NASA Astrophysics Data System (ADS)

Dickinson, James E., Jr.; Hess, Paul C.

1985-11-01

The solubility of rutile has been determined in a series of compositions in the K 2O-Al 2O 3-SiO 2 system ( K ∗ = K 2O /(K 2O + Al 2O 3) = 0.38-0.90), and the CaO-Al 2O 3-SiO 2 system ( C ∗ = CaO/(CaO + Al 2O 3) = 0.47-0.59 ). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the K ∗ ratio. For example, at 1475°C the amount of TiO 2 required for rutile saturation varies from 9.5 wt% ( K ∗ = 0.38 ) to 11.5 wt% ( K ∗ = 0.48 ) to 41.2 wt% ( K ∗ = 0.90 ). In the CAS system at 1475°C, rutile solubility is not a strong function of C ∗. The amount of TiO 2 required for saturation varies from 14 wt% ( C ∗ = 0.48 ) to 16.2 wt% ( C ∗ = 0.59 ). The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K + in excess of that needed to charge balance Al 3+. The suggested stoichiometry of this complex is K 2Ti 2O 5 or K 2Ti 3O 7. In CAS melts, the data suggest that Ca 2+ in excess of A1 3+ is not as effective at complexing with Ti as is K +. The greater solubility of rutile in CAS melts when C ∗ is less than 0.54 compared to KAS melts of equal K ∗ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K). TiK β x-ray emission spectra of KAS glasses ( K ∗ = 0.43-0.60 ) with 7 mole% added TiO 2, rutile, and Ba 2TiO 4, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba 2TiO 4, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.

Seismic evidence for silicate melt atop the 410-km mantle discontinuity

USGS Publications Warehouse

Revenaugh, Justin; Sipkin, S.A.

1994-01-01

LABORATORY results demonstrating that basic to ultrabasic melts become denser than olivine-rich mantle at pressures above 6 GPa (refs 1-3) have important implications for basalt petrogenesis, mantle differentiation and the storage of volatiles deep in the Earth. A density cross-over between melt and solid in the extensively molten Archaean mantle has been inferred from komatiitic volcanism and major-element mass balances, but present-day evidence of dense melt below the seismic low-velocity zone is lacking. Here we present mantle shear-wave impedance profiles obtained from multiple-ScS reverberation mapping for corridors connecting western Pacific subduction zone earthquakes with digital seismograph stations in eastern China, imaging a ~5.8% impedance decrease roughly 330 km beneath the Sea of Japan, Yellow Sea and easternmost Asia. We propose that this represents the upper surface of a layer of negatively buoyant melt lying on top of the olivine ??? ??- phase transition (the 410-km seismic discontinuity). Volatile-rich fluids expelled from the partial melt zone as it freezes may migrate upwards, acting as metasomatic agents and perhaps as the deep 'proto-source' of kimberlites. The remaining, dense, crystalline fraction would then concentrate above 410 km, producing a garnet-rich layer that may flush into the transition zone.

First finding of impact melt in the IIE Netschaëvo meteorite

NASA Astrophysics Data System (ADS)

Roosbroek, N.; Pittarello, L.; Greshake, A.; Debaille, V.; Claeys, P.

2016-02-01

About half of the IIE nonmagmatic iron meteorites contain silicate inclusions with a primitive to differentiated nature. The presence of preserved chondrules has been reported for two IIE meteorites so far, Netschaëvo and Mont Dieu, which represent the most primitive silicate material within this group. In this study, silicate inclusions from two samples of Netschaëvo were examined. Both silicate inclusions are characterized by a porphyritic texture dominated by clusters of coarse-grained olivine and pyroxene, set in a fine-grained groundmass that consists of new crystals of olivine and a glassy appearing matrix. This texture does not correspond to the description of the previously examined pieces of Netschaëvo, which consist of primitive chondrule-bearing angular clasts. Detailed petrographic observations and geochemical analyses suggest that the investigated samples of Netschaëvo consist of quenched impact melt. This implies that Netschaëvo is a breccia containing metamorphosed and impact-melt rock (IMR) clasts and that collisions played a major role in the formation of the IIE group.

Carbonate-silicate melt immiscibility, REE mineralising fluids, and the evolution of the Lofdal Intrusive Suite, Namibia

NASA Astrophysics Data System (ADS)

Bodeving, Sarah; Williams-Jones, Anthony E.; Swinden, Scott

2017-01-01

The Lofdal Intrusive Suite, Namibia, consists of calcio-carbonatite and silica-undersaturated alkaline intrusive rocks ranging in composition from phono-tephrite to phonolite (and nepheline syenite). The most primitive of these rocks is the phono-tephrite, which, on the basis of its Y/Ho and Nb/Ta ratios, is interpreted to have formed by partial melting of the mantle. Roughly linear trends in major and trace element contents from phono-tephrite to phonolite and nepheline syenite indicate that the latter two rock types evolved from the phono-tephrite by fractional crystallisation. The nepheline syenite, however, has a lower rare earth element (REE) content than the phonolite. The carbonatite has a primitive mantle-normalised REE profile roughly parallel to that of the silica-undersaturated alkaline igneous rocks, although the absolute REE concentrations are higher. Like the phono-tephrite, it also has a mantle Y/Ho ratio. However, the Nb/Ta and Zr/Hf ratios are significantly higher. Moreover, the carbonatite displays strong negative Ta, Zr and Hf anomalies on spidergrams, whereas the silicate rocks display positive anomalies for these elements. Significantly, this behaviour is predicted by the corresponding carbonatite-silicate melt partition coefficients, as is the behaviour of the REE. Based on these observations, we interpret the carbonatite to represent an immiscible liquid that exsolved from the phono-tephrite or possibly the phonolite melt. The result was a calcio-carbonatite that is enriched in the heavy REE (HREE) relative to most other carbonatites. Fluids released from the corresponding magma are interpreted to have been the source of the REE mineralisation that is currently the target of exploration. 2. The composition of feldspar in nepheline syenite, fenite, calcio-carbonatite and phonolite plotted on the feldspar ternary classification diagram modified after Schairer (1950) in terms of the components albite (Ab), orthoclase (Or) and anorthite (An

Density of jadeite melt under upper mantle conditions from in-situ X-ray micro-tomography measurements

NASA Astrophysics Data System (ADS)

Jing, Z.; Xu, M.; Jiang, P.; Yu, T.; Wang, Y.

2017-12-01

Knowledge of the density of silicate melts under high pressure conditions is important to our understanding of the stability and migration of melt layers in the Earth's deep mantle. A wide range of silicate melts have been studied at high pressures using the sink/float technique (e.g., Agee and Walker, 1988) and the X-ray absorption technique (e.g., Sakamaki et al, 2009). However, the effect of the Na2O component on high-pressure melt density has not been fully quantified, despite its likely presence in mantle melts. This is partly due to the experimental challenges that the Na-bearing melts often have relatively low density but high viscosity, both of which make it difficult to study using the above-mentioned techniques. In this study, we have developed a new technique based on X-ray micro-tomography to determine the density of melts at high pressures. In this technique, the volume of a melt is directly measured from the reconstructed 3-D images of the sample using computed X-ray micro-tomography. If the mass of the sample is measured using a balance or estimated from a reference density, then the density of the melt at high pressures can be calculated. Using this technique, we determined the density of jadeite melt (NaAlSi2O6) at high pressures up to 4 GPa in a Paris-Edinburg cell that can be rotated for 180 degrees under pressure. Results show that the Na2O component significantly decreases both the density and bulk modulus of silicate melts at high pressures. These data can be incorporated into a hard-sphere equation of state (Jing and Karato, 2011) to model the effect of the Na2O component on the potential density crossovers between melts produced in the mantle and the residual solid.

The role of liquid-liquid immiscibility and crystal fractionation in the genesis of carbonatite magmas: insights from Kerimasi melt inclusions

NASA Astrophysics Data System (ADS)

Guzmics, Tibor; Zajacz, Zoltán; Mitchell, Roger H.; Szabó, Csaba; Wälle, Markus

2015-02-01

We have reconstructed the compositional evolution of the silicate and carbonate melt, and various crystalline phases in the subvolcanic reservoir of Kerimasi Volcano in the East African Rift. Trace element concentrations of silicate and carbonate melt inclusions trapped in nepheline, apatite and magnetite from plutonic afrikandite (clinopyroxene-nepheline-perovskite-magnetite-melilite rock) and calciocarbonatite (calcite-apatite-magnetite-perovskite-monticellite-phlogopite rock) show that liquid immiscibility occurred during the generation of carbonatite magmas from a CO2-rich melilite-nephelinite magma formed at relatively high temperatures (1,100 °C). This carbonatite magma is notably more calcic and less alkaline than that occurring at Oldoinyo Lengai. The CaO-rich (32-41 wt%) nature and alkali-"poor" (at least 7-10 wt% Na2O + K2O) nature of these high-temperature (>1,000 °C) carbonate melts result from strong partitioning of Ca (relative to Mg, Fe and Mn) in the immiscible carbonate and the CaO-rich nature (12-17 wt%) of its silicate parent (e.g., melilite-nephelinite). Evolution of the Kerimasi carbonate magma can result in the formation of natrocarbonatite melts with similar composition to those of Oldoinyo Lengai, but with pronounced depletion in REE and HFSE elements. We suggest that this compositional difference results from the different initial parental magmas, e.g., melilite-nephelinite at Kerimasi and a nephelinite at Oldoinyo Lengai. The difference in parental magma composition led to a significant difference in the fractionating mineral phase assemblage and the element partitioning systematics upon silicate-carbonate melt immiscibility. LA-ICP-MS analysis of coeval silicate and carbonate melt inclusions provides an opportunity to infer carbonate melt/silicate melt partition coefficients for a wide range of elements. These data show that Li, Na, Pb, Ca, Sr, Ba, B, all REE (except Sc), U, V, Nb, Ta, P, Mo, W and S are partitioned into the carbonate

Contribution of early impact events to metal-silicate separation, thermal annealing, and volatile redistribution: Evidence in the Pułtusk H chondrite

NASA Astrophysics Data System (ADS)

Krzesińska, Agata M.

2017-11-01

Three-dimensional X-ray tomographic reconstructions and petrologic studies reveal voluminous accumulations of metal in Pułtusk H chondrite. At the contact of these accumulations, the chondritic rock is enriched in troilite. The rock contains plagioclase-rich bands, with textures suggesting crystallization from melt. Unusually large phosphates are associated with the plagioclase and consist of assemblages of merrillite, and fluorapatite and chlorapatite. The metal accumulations were formed by impact melting, rapid segregation of metal-sulfide melt and the incorporation of this melt into the fractured crater basement. The impact most likely occurred in the early evolution of the H chondrite parent body, when post-impact heat overlapped with radiogenic heat. This enabled slow cooling and separation of the metallic melt into metal-rich and sulfide-rich fractions. This led to recrystallization of chondritic rock in contact with the metal accumulations and the crystallization of shock melts. Phosphorus was liberated from the metal and subsumed by the silicate shock melt, owing to oxidative conditions upon slow cooling. The melt was also a host for volatiles. Upon further cooling, phosphorus reacted with silicates leading to the formation of merrillite, while volatiles partitioned into the residual halogen-rich, dry fluid. In the late stages, the fluid altered merrillite to patchy Cl/F-apatite. The above sequence of alterations demonstrates that impact during the early evolution of chondritic parent bodies might have contributed to local metal segregation and silicate melting. In addition, postshock conditions supported secondary processes: compositional/textural equilibration, redistribution of volatiles, and fluid alterations.

Core formation in the early solar system through percolation: 4-D in-situ visualization of melt migration

NASA Astrophysics Data System (ADS)

Bromiley, G.; Berg, M.; Le Godec, Y.; Mezouar, N.; Atwood, R. C.; Phillipe, J.

2015-12-01

Although core formation was a key stage in the evolution of terrestrial planets, the physical processes which resulted in segregation of iron and silicate remain poorly understood. Formation of a silicate magma oceans provides an obvious mechanism for segregation of core-forming liquids, although recent work has strengthened arguments for a complex, multi-stage model of core formation. Extreme pressure1 and the effects of deformation2 have both been shown to promote percolation of Fe-rich melts in a solid silicate matrix, providing mechanisms for early, low temperature core-formation. However, the efficiency of these processes remains untested and we lack meaningful experimental data on resulting melt segregation velocities. Arguments regarding the efficiency of core formation through percolation of Fe-rich melts in solid silicate are based on simple, empirical models. Here, we review textural evidence from recent experiments which supports early core formation driven by deformation-aided percolation of Fe-rich melts. We then present results of novel in-situ synchrotron studies designed to provide time-resolved 3-D microimaging of percolating melt in model systems under extreme conditions. Under low strain rates characteristic of deformation-aided core formation, segregation of metallic (core-forming) melts by percolation is driven by stress gradients. This is expected to ultimately result in channelization and efficient segregation of melts noted in high-strain, low pressure experiments3. In-situ visualization also demonstrates that percolation of viscous metallic melts is surprisingly rapid. A combination of melt channelization and hydraulic fracture results in rapid, episodic melt migration, even over the limited time scale of experiments. The efficiency of this process depends strongly on the geometry of the melt network and is scaled to grain size in the matrix. We use both in-situ visualization and high-resolution ex-situ analysis to provide accurate

Fe-Ti-oxide textures and microstructures in shear zones from oceanic gabbros at Atlantis Bank, Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Till, Jessica; Morales, Luiz F. G.; Rybacki, Erik

2016-04-01

Ocean drilling expeditions at several oceanic core complexes formed at slow- and ultra-slow-spreading ridges have recovered cores containing numerous zones of oxide-rich gabbros containing ilmenite and magnetite. In these cores, high modal concentrations of Fe-Ti-oxides are systematically associated with high-temperature plastic deformation features in silicates. We present observations of Fe-Ti-oxide mineral structures and textural characteristics from a series of oxide-rich shear zones from Atlantis Bank (ODP Site 735B) on the Southwest Indian Ridge aimed at determining how oxide mineral abundances relate to strain localization. Fe-Ti-oxide minerals in undeformed oxide gabbros and in highly deformed samples from natural shear zones generally have morphologies characteristic of crystallized melt, including highly cuspate grains and low dihedral angles. Anisotropy of magnetic susceptibility in oxide-rich shear zones is very strong, with fabrics mainly characterized by strong magnetic foliations parallel to the macroscopic foliation. Crystallographic preferred orientations (CPO) in magnetite are generally weak, with occasionally well-defined textures. Ilmenite typically displays well-developed CPOs, however, the melt-like ilmenite grain shapes indicate that at least part of the crystallographic texture results from oriented ilmenite growth during post-deformation crystallization. The oxides are hypothesized to have initially been present as isolated pockets of trapped melt (intercumulus liquid) in a load-bearing silicate framework. Progressive plastic deformation of silicate phases at high-temperature mainly produced two features: (i) elongated melt pockets, which crystallized to form strings of opaque minerals and (ii), interconnected networks of melt regions. The latter lead to intense strain localization of the rock, which appears as oxide-rich mylonites in the samples. In some samples, abundant low-angle grain boundaries in both magnetite and ilmenite suggest

Constraints on Ureilite Petrogenesis and Carbon-Metal-Silicate Equilibria on the UPB

NASA Astrophysics Data System (ADS)

Goodrich, C. A.; Holloway, J. R.

1992-07-01

The most important constraints on models of ureilite petrogenesis are 1) Ureilites have lost a basaltic complement (they are ultramafic, extremely depleted in plagiophile elements, enriched in HREE, and have negative Eu anomalies and superchondritic Ca/Al ratios). 2) Ureilites experienced long equilibration times at high T (indicated by coarse grain size, extreme homogeneity of core crystals, correlations between olivine and pyroxene compositions, and metamorphic-like textures), followed by rapid cooling (indicated by structural features of pyroxene and narrow reduction rims on olivine). 3) Ureilites are probably residues (based on mass balance) but partly crystallized from melts. 4) Ureilites are derived from a minimum of six reservoirs that were distinct in oxygen isotopic composition and did not equilibrate with one another (this is consistent with the observation that olivine and pyroxene cores do not show correlations of mg with MnO, Cr2O3, Sm/Eu or Lu/Eu). 5) There is a correlation between oxygen isotopic composition and mg ratio in ureilites. Similar correlations are observed for Allende chondrules and group means of H3-L3-LL3 chondrites (Fig. 1), and are argued to result from nebular processes [1]. 6) If graphite-metal-silicate-CO/CO2 equilibrium was established during melting, then mg ratios of ureilites were determined by depth because CCO redox reactions are strongly pressure-dependent. Cohenite-bearing metallic spherule inclusions in the silicates and euhedral shapes of large graphite crystals in low-shock ureilites have been taken as evidence of equilibrium. Olivine reduction rims, highly variable interstitial metal compositions, and a lack of correlation between mg and metal content argue against equilibrium. 7) Ureilites either lost a low melting-T metal fraction or gained a refractory-rich metal component. (they have high abundances of siderophile elements but show fractionation between [Os, Ir, W, Re] and [Ni, Ga, Ge, Au]). 8) Primordial noble

Shock compression of stishovite and melting of silica at planetary interior conditions

NASA Astrophysics Data System (ADS)

Millot, M.; Dubrovinskaia, N.; Černok, A.; Blaha, S.; Dubrovinsky, L.; Braun, D. G.; Celliers, P. M.; Collins, G. W.; Eggert, J. H.; Jeanloz, R.

2015-01-01

Deep inside planets, extreme density, pressure, and temperature strongly modify the properties of the constituent materials. In particular, how much heat solids can sustain before melting under pressure is key to determining a planet’s internal structure and evolution. We report laser-driven shock experiments on fused silica, α-quartz, and stishovite yielding equation-of-state and electronic conductivity data at unprecedented conditions and showing that the melting temperature of SiO2 rises to 8300 K at a pressure of 500 gigapascals, comparable to the core-mantle boundary conditions for a 5-Earth mass super-Earth. We show that mantle silicates and core metal have comparable melting temperatures above 500 to 700 gigapascals, which could favor long-lived magma oceans for large terrestrial planets with implications for planetary magnetic-field generation in silicate magma layers deep inside such planets.

Residual stresses and phase transformations in Ytterbium silicate environmental barrier coatings

NASA Astrophysics Data System (ADS)

Stolzenburg, Fabian

Due to their high melting temperature, low density, and good thermomechanical stability, silicon-based ceramics (SiC, Si3N4) are some of the most promising materials systems for high temperature structural applications in gas turbine engines. However, their silica surface layer reacts with water vapor contained in combustion environments. The resulting hydroxide layer volatilizes, leading to component recession. Environmental barrier coatings (EBCs) have been developed to shield the substrate from degradation. Next generation coatings for silicon-based ceramics based on ytterbium silicates have shown a promising combination of very low and good thermomechanical properties. The focus of this thesis is threefold: In the first part, phase transformations in plasma sprayed ytterbium silicates were investigated. Plasma sprayed materials are known to contain large amounts of amorphous material. Phase changes during the conversion from amorphous to crystalline materials were investigated as they have been known to lead to failure in many coatings. The second part of this work focused on measuring residual stresses in multilayer EBCs using synchrotron X-ray diffraction (XRD). Strains were resolved spatially, with probe sizes as small as 20 um. Stresses were calculated using mechanical properties of ytterbium silicates, determined with in-situ loading and heating experiments. In-situ and ex-situ heating experiments allowed for the study of changes in stress states that occur in these EBC materials during heating and cooling cycles. Lastly, the interaction of ytterbium silicates with low-melting environmental calcium-magnesium-aluminosilicate (CMAS) glasses was studied. Synchrotron XRD was used to study the influence of CMAS on the stress state in the coating, X-ray computed tomography was used to provide 3D images of coatings, and EDS and TEM analysis were used to study the interactions at the CMAS/ytterbium silicate interface in detail.

Sulfide in the core and the composition of the silicate Earth

NASA Astrophysics Data System (ADS)

Burton, K. W.

2015-12-01

The chemical composition of the Earth is traditionally explained in terms of evolution from a solar-like composition, similar to that found in primitive 'chondritic' meteorites. It now appears, however, that the silicate Earth is not 'chondritic', but depleted in incompatible elements, including refractory lithophile and heat-producing elements. Either Earth lost material during planet-building due to collisional erosion or else internal differentiation processes produced a hidden reservoir deep in the early Earth. Sulfide in the core may provide a reservoir capable of balancing the composition of the silicate Earth. Recent experimental work suggests that the core contains a significant proportion of sulfide, added during the final stages of accretion and new data suggests that at high pressures sulfide can incorporate a substantial amount of refractory lithophile and heat-producing elements [1]. Pioneering work using the short-lived 146Sm-142Nd system strongly suggests that Earth's silicate mantle is non-chondritic [e.g. 2]. The drawback of such radiogenic isotope systems is that it is not possible to distinguish the fractionation of Sm/Nd that occurs during silicate melting from that occurring during the segregation of a sulfide-melt to form the core. Neodymium stable isotopes have the potential to provide just such a tracer of sulfide segregation, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Preliminary data indicate that mantle rocks do indeed possess heavier 146Nd/144Nd values than chondritic meteorites, consistent with the removal of light Nd into sulfide in the core, driving the residual mantle to heavy values. Overall, our isotope and elemental data indicate that the rare earths and other incompatible elements are substantially incorporated into sulfide. While Nd Stable isotope

Melt densities in the CaO-FeO-Fe 2O 3-SiO 2 system and the compositional dependence of the partial molar volume of ferric iron in silicate melts

NASA Astrophysics Data System (ADS)

Dingwell, Donald B.; Brearley, Mark

1988-12-01

temperature, composition and redox state, are sufficient to describe the above observations. The presence of more than one coordination geometry for Fe 3+ in low pressure silicate melts has several implications for igneous petrogenesis. The possible effects on compressibility, the pressure dependence of the redox ratio, and redox enthalpy are briefly noted.

Float processing of high-temperature complex silicate glasses and float baths used for same

NASA Technical Reports Server (NTRS)

Cooper, Reid Franklin (Inventor); Cook, Glen Bennett (Inventor)

2000-01-01

A float glass process for production of high melting temperature glasses utilizes a binary metal alloy bath having the combined properties of a low melting point, low reactivity with oxygen, low vapor pressure, and minimal reactivity with the silicate glasses being formed. The metal alloy of the float medium is exothermic with a solvent metal that does not readily form an oxide. The vapor pressure of both components in the alloy is low enough to prevent deleterious vapor deposition, and there is minimal chemical and interdiffusive interaction of either component with silicate glasses under the float processing conditions. Alloys having the desired combination of properties include compositions in which gold, silver or copper is the solvent metal and silicon, germanium or tin is the solute, preferably in eutectic or near-eutectic compositions.

Silicate Crystal Formation in the Disk of an Erupting Star Artist Concept

NASA Image and Video Library

2009-05-13

This artist's concept illustrates how silicate crystals like those found in comets can be created by an outburst from a growing star. The image shows a young sun-like star encircled by its planet-forming disk of gas and dust. The silicate that makes up most of the dust would have begun as non-crystallized, amorphous particles. Streams of material are seen spiraling from the disk onto the star increasing its mass and causing the star to brighten and heat up dramatically. The outburst causes temperatures to rise in the star's surrounding disk. The animation (figure 1) zooms into the disk to show close-ups of silicate particles. When the disk warms from the star's outburst, the amorphous particles of silicate melt. As they cool off, they transform into forsterite (figure 2), a type of silicate crystal often found in comets in our solar system. In April 2008, NASA's Spitzer Space Telescope detected evidence of this process taking place on the disk of a young sun-like star called EX Lupi. http://photojournal.jpl.nasa.gov/catalog/PIA12008

The Extent of Disorder among Charge-balancing Cations in Silicate Glasses and Melts: Spectroscopic Analysis and ab initio Molecular Orbital Calculations

NASA Astrophysics Data System (ADS)

Lee, S.; Doyle, C. S.; Stebbins, J. F.

2001-12-01

Aluminosilicate melts are one of the dominant components in upper mantle and crust. Essential to the thermodynamic and transport properties of these systems is the full understanding on the atomic arrangements and the extent of disorder. Recent quantification of the extent of disorder among 'framework cations' in silicate melts using NMR provided improved prospects on the atomic structure of the glasses and melt and their corresponding properties and allowed the degree of randomness to be evaluated in terms of the degree of Al-avoidance (Q) and degree of phase separations (P) (Lee and Stebbins, J. Phys. Chem. B 104, 4091; Lee and Stebbins, GCA in press). Quantitative estimation of the extent of disorder among 'charge-balancing cations' including Na in aluminosilicate glasses, however, has remained an unsolved problem and these cations have often been assumed to be randomly distributed. Here, we explore the intermediate range order around Na in charge-balanced aluminosilicate glasses using Na-23 NMR and Near-edge X-ray absorption fine structure (NEXAFS) with full multiple scattering (FMS) simulations combined with ab initio molecular orbital calculations. We also quantify the extent of disorder in charge balancing cations as a function of Na-O bond length (d(Na-O)) distribution with composition and present a structural model favoring ordered Na distributions. Peak position in Na-23 magic angle spinning (MAS) spectra of aluminosilicate glasses with varying R (Si/Al) at 14.1 T varies from -10.28 ppm (R = 0.7) to -19.98 ppm (R = 6). These results suggest that average d(Na-O) increases with increasing R, which is confirmed by Na-23 multiple quantum MAS spectra where the chemical shift moves toward lower frequency with increasing Si and shows the individual Gaussian components of Na-O distributions such as Na-(Al-O-Al), Na-(Si-O-Al) and Na-(Si-O-Si). Calculated d(Na-(Al-O-Al)) of 2.57 Å is shorter than d(Na-(Si-O-Si)) of 2.88 Å. Strong compositional dependence is

Experimental Constraints on Fe Isotope Fractionation in Carbonatite Melt Systems

NASA Astrophysics Data System (ADS)

Stuff, M.; Schuessler, J. A.; Wilke, M.

2015-12-01

Iron isotope data from carbonatite rocks show the largest variability found in igneous rocks to date [1]. Thus, stable Fe isotopes are promising tracers for the interaction of carbonate and silicate magmas in the mantle, particularly because their fractionation is controlled by oxidation state and bonding environment. The interpretation of Fe isotope data from carbonatite rocks remains hampered, since Fe isotope fractionation factors between silicate and carbonate melts are unknown and inter-mineral fractionation can currently only be assessed by theoretical calculations [1;2]. We present results from equilibration experiments in three natrocarbonatite systems between immiscible silicate and carbonate melts, performed at 1200°C and 0.7 GPa in an internally heated gas pressure vessel at intrinsic redox conditions. The Fe isotope compositions of the silicate melt (sil.m.), quenched to a glass, and the carbonate melt (carb.m.), forming fine-grained quench crystals, were analysed by solution MC-ICP-MS. Our first data indicate a remarkable fractionation of Δ56Fesil.m.‒carb.m.= 0.29 ±0.07 ‰ near equilibrium. At short run durations, even stronger fractionation up to Δ56Fesil.m.‒carb.m. = 0.41 ±0.07 ‰ occurs, due to kinetic effects. Additionally, Δ56Fesil.m.‒carb.m. changes with bulk chemical composition, likely reflecting considerable differences between the studied systems in terms of the Fe3+/Fe2+-ratios in the two immiscible liquids. Our findings provide experimental support for a carbonatite genesis model, in which extremely negative δ56Fe values in carbonatites result from differentiation processes, such as liquid immiscibility [1]. This effect can be enhanced by disequilibrium during fast ascent of carbonatite magmas. Their sensitivity to chemical and redox composition makes Fe isotopes a potential tool for constraining the original compositions of carbonatite magmas. [1] Johnson et al. (2010) Miner. Petrol. 98, 91-110. [2] Polyakov & Mineev (2000

Fractionation products of basaltic komatiite magmas at lower crustal pressures: implications for genesis of silicic magmas in the Archean

NASA Astrophysics Data System (ADS)

Mandler, B. E.; Grove, T. L.

2015-12-01

Hypotheses for the origin of crustal silicic magmas include both partial melting of basalts and fractional crystallization of mantle-derived melts[1]. Both are recognized as important processes in modern environments. When it comes to Archean rocks, however, partial melting hypotheses dominate the literature. Tonalite-trondhjemite-granodiorite (TTG)-type silicic magmas, ubiquitous in the Archean, are widely thought to be produced by partial melting of subducted, delaminated or otherwise deeply buried hydrated basalts[2]. The potential for a fractional crystallization origin for TTG-type magmas remains largely unexplored. To rectify this asymmetry in approaches to modern vs. ancient rocks, we have performed experiments at high pressures and temperatures to closely simulate fractional crystallization of a basaltic komatiite magma in the lowermost crust. These represent the first experimental determinations of the fractionation products of komatiite-type magmas at elevated pressures. The aim is to test the possibility of a genetic link between basaltic komatiites and TTGs, which are both magmas found predominantly in Archean terranes and less so in modern environments. We will present the 12-kbar fractionation paths of both Al-depleted and Al-undepleted basaltic komatiite magmas, and discuss their implications for the relative importance of magmatic fractionation vs. partial melting in producing more evolved, silicic magmas in the Archean. [1] Annen et al., J. Petrol., 47, 505-539, 2006. [2] Moyen J-F. & Martin H., Lithos, 148, 312-336, 2012.

In Situ XANES of U and Th in Silicate Liquids at High Pressure and Temperature

NASA Astrophysics Data System (ADS)

Mallmann, G.; Wykes, J.; Berry, A.; O'Neill, H. S.; Cline, C. J., II; Turner, S.; Rushmer, T. A.

2016-12-01

Although the chemical environments of elements in silicate melts at specific conditions of temperature, pressure and oxygen fugacity (fO2) are often inferred from measurements after quenching the melts to glasses, it is widely recognized that changes may occur during the quenching process, making measurements in situ at high pressure and temperature highly desirable. A case of importance in geochemistry is the speciation of uranium in silicate melts as a function of pressure. Evidence from mineral-melt partitioning and XANES (X-ray Absorption Near-Edge Structure) spectroscopy of glasses suggests that U5+ may be stable at low pressures in the Earth's crust (along with U4+ or U6+, depending on fO2) where basaltic liquids crystallize, but not in the Earth's upper mantle where peridotite partially melts to produce such liquids. To test these observations we recorded in situ transmission U and Th L3-edge XANES spectra of U and Th-doped silicate liquids at 1.6 GPa and 1350°C using the D-DIA apparatus at the X-ray Absorption Spectroscopy Beamline of the Australian Synchrotron. Data for thorium, which occurs exclusively as a tetravalent cation under terrestrial fO2 conditions, were collected as a `control' to monitor for changes in coordination. The cell assembly consisted of a boron-epoxy cube as pressure medium, alumina sleeve and cylindrical graphite heater. The starting mix, a powdered synthetic average MORB silicate glass doped with 2 wt.% of U and Th, was loaded into San Carlos olivine capsules along with solid oxygen buffers (either Re-ReO2 or Ru-RuO2) in a sandwich arrangement. The capsule was then placed inside the graphite heater and insulated with crushable MgO powder. Temperature was monitored using a type D thermocouple. U and Th L3-edge XANES spectra were recorded throughout the heating/compression cycle and then after quenching. Our preliminary assessment indicates that the U-XANES spectra recorded for the liquid in situ at high pressure and temperature and

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions.

PubMed

Bennett, Neil R; Brenan, James M; Fei, Yingwei

2015-06-13

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied.

Metal-silicate Partitioning at High Pressure and Temperature: Experimental Methods and a Protocol to Suppress Highly Siderophile Element Inclusions

PubMed Central

Bennett, Neil R.; Brenan, James M.; Fei, Yingwei

2015-01-01

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the piston-cylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied. PMID:26132380

PockDrug: A Model for Predicting Pocket Druggability That Overcomes Pocket Estimation Uncertainties.

PubMed

Borrel, Alexandre; Regad, Leslie; Xhaard, Henri; Petitjean, Michel; Camproux, Anne-Claude

2015-04-27

Predicting protein druggability is a key interest in the target identification phase of drug discovery. Here, we assess the pocket estimation methods' influence on druggability predictions by comparing statistical models constructed from pockets estimated using different pocket estimation methods: a proximity of either 4 or 5.5 Å to a cocrystallized ligand or DoGSite and fpocket estimation methods. We developed PockDrug, a robust pocket druggability model that copes with uncertainties in pocket boundaries. It is based on a linear discriminant analysis from a pool of 52 descriptors combined with a selection of the most stable and efficient models using different pocket estimation methods. PockDrug retains the best combinations of three pocket properties which impact druggability: geometry, hydrophobicity, and aromaticity. It results in an average accuracy of 87.9% ± 4.7% using a test set and exhibits higher accuracy (∼5-10%) than previous studies that used an identical apo set. In conclusion, this study confirms the influence of pocket estimation on pocket druggability prediction and proposes PockDrug as a new model that overcomes pocket estimation variability.

Polymer Layered Silicate Nanocomposites: A Review

PubMed Central

Mittal, Vikas

2009-01-01

This review aims to present recent advances in the synthesis and structure characterization as well as the properties of polymer layered silicate nanocomposites. The advent of polymer layered silicate nanocomposites has revolutionized research into polymer composite materials. Nanocomposites are organic-inorganic hybrid materials in which at least one dimension of the filler is less than 100 nm. A number of synthesis routes have been developed in the recent years to prepare these materials, which include intercalation of polymers or pre-polymers from solution, in-situ polymerization, melt intercalation etc. The nanocomposites where the filler platelets can be dispersed in the polymer at the nanometer scale owing to the specific filler surface modifications, exhibit significant improvement in the composite properties, which include enhanced mechanical strength, gas barrier, thermal stability, flame retardancy etc. Only a small amount of filler is generally required for the enhancement in the properties, which helps the composite materials retain transparency and low density.

Evaporation and Accompanying Isotopic Fractionation of Sulfur from FE-S Melt During Shock Wave Heating

NASA Technical Reports Server (NTRS)

Tachibana, S.; Huss, G. R.; Miura, H.; Nakamoto, T.

2004-01-01

Chondrules probably formed by melting and subsequent cooling of solid precursors. Evaporation during chondrule melting may have resulted in depletion of volatile elements in chondrules. It is known that kinetic evaporation, especially evaporation from a melt, often leads to enrichment of heavy isotopes in an evaporation residue. However, no evidence for a large degree of heavy-isotope enrichment has been reported in chondrules for K, Mg, Si, and Fe (as FeO). The lack of isotopic fractionation has also been found for sulfur in troilites (FeS) within Bishunpur (LL3.1) and Semarkona (LL3.0) chondrules by an ion microprobe study. The largest fractionation, found in only one grain, was 2.7 +/- 1.4 %/amu, while all other troilite grains showed isotopic fractionations of <1 %/amu. The suppressed isotopic fractionation has been interpreted as results of (i) rapid heating of precursors at temperatures below the silicate solidus and (ii) diffusion-controlled evaporation through a surrounding silicate melt at temperatures above the silicate solidus. The kinetic evaporation model suggests that a rapid heating rate of >10(exp 4)-10(exp 6) K/h for a temperature range of 1000-1300 C is required to explain observed isotopic fractionations. Such a rapid heating rate seems to be difficult to be achieved in the X-wind model, but can be achieved in shock wave heating models. In this study, we have applied the sulfur evaporation model to the shock wave heating conditions of to evaluate evaporation of sulfur and accompanying isotopic fractionation during shock wave heating at temperatures below the silicate solidus.

Syntectic Reactions involving Limestones and Limestone-Derived Carbonatitic Melts in the Generation of some Peralkalic Magmas: Reflections on Reginald Daly's Insights 100 Years Later

NASA Astrophysics Data System (ADS)

Lentz, D.

2017-12-01

The theoretical analysis of how sedimentary limestones and marbles could melt as a result of infiltrative contact metasomatism associated with silicate magmas, enables reconsideration of the limestone syntectic (assimilation) hypothesis for the origin of some peralkalic rocks. Reginald Daly's syntectic model published in detail in early 1918 fell out of favor because experimental evidence from the early 1960's suggested; 1) that limestone assimilation would increase P(CO2) and cause solidification of the silicate intrusion, 2) that there is a thermal barrier between silica-saturated and undersaturated magmas that would inhibit extensive desilication of the magma, and 3) the endothermic decarbonation reactions would require heat via magmatic crystallization of near-solidus magmas. However, these concerns were not as critical for high-T mafic melts relative to more low-T silicic melts, although most subsequent researchers dismissed syntexis as isotopic arguments also seemed robust. However, skarn-related limestone melts can interact much more easily with silicate magma, resulting in calc-silicate-forming (endoskarn-like) limestone syntectic (desilication - calcification-magnesification processes) decarbonation reactions with compositional evolution into the silica-undersaturated field. If mafic in composition originally when syntectically modified, then the CO2-bearing derivative peralkalic melt may subsequently react with the dominant volume magma or fractionate separately into a more evolved composition. As well, an increase in P(CO2) within the modified silicate fraction coupled with compositional evolution to more silica-undersaturated compositions enhances the stability of the immiscible, extremely low viscosity carbonate melt fraction. In addition, dynamic interaction of these co-existing immiscible melts (analogous to the current hypothesis) would partition elements, as well as isotopic signatures, such that they would be virtually unrecognizable as having a

Seismic perspectives from the western U.S. on the evolution of magma reservoirs underlying major silicic eruptions

NASA Astrophysics Data System (ADS)

Schmandt, B.; Huang, H. H.; Farrell, J.; Hansen, S. M.; Jiang, C.

2017-12-01

The western U.S. Cordillera has hosted widespread magmatic activity since the Eocene including ≥1,000 km3 silicic eruptions since 1 Ma. A review of recent seismic constraints on relatively young (≤1.1 Ma) and old (Oligocene) magmatic systems provides insight into the heterogeneity among these systems and their temporal evolution. Local seismic data vary widely but all of these systems are covered by the USArray's 70-km spacing. Among 3 young systems with ≥300 km3 silicic eruptions (Yellowstone - 0.64 Ma; Long Valley - 0.76 Ma; Valles - 1.1 Ma) only Yellowstone shows sufficiently low seismic velocities to require partial melt in the upper crust at scales visible with USArray data. Finer-scale arrays refine the shape of large (>1,000 km3) partially molten volumes in the upper and lower crust at Yellowstone, and similar studies at Long Valley and Valles indicate much smaller volumes of partial melt. Notably, Long Valley Caldera is seismically active in the upper and lower crust, has a high flux of CO2 degassing, and multi-year geodetic transients consistent with an inflating upper crustal reservoir of 2-4 km radius (compared to 20x50x5 km at Yellowstone). Upper mantle seismic imaging finds strong low velocity anomalies that require some partial melt beneath Yellowstone and Long Valley, but more ambiguous results beneath Valles. Thus, the structures of the three young large-volume silicic systems are highly variable suggesting that large reservoirs of melt in the upper crust are short-lived with respect to the ≤1.1 Ma since the last major eruption, consistent with recent inferences from geochemically constrained thermal histories of erupted crystals. Among long-extinct silicic systems, most were severely overprinted by extensional deformation. The San Juan and Mogollon Datil are exceptions with only modest deformation. These systems show low-to-average velocity crust down to a sharp Moho and relatively thin crust for their elevations. Both are consistent with a

Early metal-silicate differentiation during planetesimal formation revealed by acapulcoite and lodranite meteorites

NASA Astrophysics Data System (ADS)

Dhaliwal, Jasmeet K.; Day, James M. D.; Corder, Christopher A.; Tait, Kim T.; Marti, Kurt; Assayag, Nelly; Cartigny, Pierre; Rumble, Doug; Taylor, Lawrence A.

2017-11-01

In order to establish the role and expression of silicate-metal fractionation in early planetesimal bodies, we have conducted a highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundance and 187Re-187Os study of acapulcoite-lodranite meteorites. These data are reported with new petrography, mineral chemistry, bulk-rock major and trace element geochemistry, and oxygen isotopes for Acapulco, Allan Hills (ALHA) 81187, Meteorite Hills (MET) 01195, Northwest Africa (NWA) 2871, NWA 4833, NWA 4875, NWA 7474 and two examples of transitional acapulcoite-lodranites, Elephant Moraine (EET) 84302 and Graves Nunataks (GRA) 95209. These data support previous studies that indicate that these meteorites are linked to the same parent body and exhibit limited degrees (<2-7%) of silicate melt removal. New HSE and osmium isotope data demonstrate broadly chondritic relative and absolute abundances of these elements in acapulcoites, lower absolute abundances in lodranites and elevated (>2 × CI chondrite) HSE abundances in transitional acapulcoite-lodranite meteorites (EET 84302, GRA 95209). All of the meteorites have chondritic Re/Os with measured 187Os/188Os ratios of 0.1271 ± 0.0040 (2 St. Dev.). These geochemical characteristics imply that the precursor material of the acapulcoites and lodranites was broadly chondritic in composition, and were then heated and subject to melting of metal and sulfide in the Fe-Ni-S system. This resulted in metallic melt removal and accumulation to form lodranites and transitional acapulcoite-lodranites. There is considerable variation in the absolute abundances of the HSE, both among samples and between aliquots of the same sample, consistent with both inhomogeneous distribution of HSE-rich metal, and of heterogeneous melting and incomplete mixing of silicate material within the acapulcoite-lodranite parent body. Oxygen isotope data for acapulcoite-lodranites are also consistent with inhomogeneous melting and mixing of accreted components

Carbonatite and silicate melt metasomatism of the mantle surrounding the Hawaiian plume: Evidence from volatiles, trace elements, and radiogenic isotopes in rejuvenated-stage lavas from Niihau, Hawaii

NASA Astrophysics Data System (ADS)

Dixon, Jacqueline; Clague, David A.; Cousens, Brian; Monsalve, Maria Luisa; Uhl, Jessika

2008-09-01

We present new volatile, trace element, and radiogenic isotopic compositions for rejuvenated-stage lavas erupted on Niihau and its submarine northwest flank. Niihau rejuvenated-stage Kiekie Basalt lavas are mildly alkalic and are isotopically similar to, though shifted to higher 87Sr/86Sr and lower 206Pb/204Pb than, rejuvenated-stage lavas erupted on other islands and marginal seafloor settings. Kiekie lavas display trace element heterogeneity greater than that of other rejuvenated-stage lavas, with enrichments in Ba, Sr, and light-rare earth elements resulting in high and highly variable Ba/Th and Sr/Ce. The high Ba/Th lavas are among the least silica-undersaturated of the rejuvenated-stage suite, implying that the greatest enrichments are associated with the largest extents of melting. Kiekie lavas also have high and variable H2O/Ce and Cl/La, up to 620 and 39, respectively. We model the trace element concentrations of most rejuvenated-stage lavas by small degrees (˜1% to 9%) of melting of depleted peridotite recently metasomatized by a few percent of an enriched incipient melt (0.5% melting) of the Hawaiian plume. Kiekie lavas are best explained by 4% to 13% partial melting of a peridotite source metasomatized by up to 0.2% carbonatite, similar in composition to oceanic carbonatites from the Canary and Cape Verde Islands, with lower proportion of incipient melt than that for other rejuvenated-stage lavas. Primary H2O and Cl of the carbonatite component must be high, but variability in the volatile data may be caused by heterogeneity in the carbonatite composition and/or interaction with seawater. Our model is consistent with predictions based on carbonated eclogite and peridotite melting experiments in which (1) carbonated eclogite and peridotite within the Hawaiian plume are the first to melt during plume ascent; (2) carbonatite melt metasomatizes plume and surrounding depleted peridotite; (3) as the plume rises, silica-undersaturated silicate melts are also

Silicate Inclusions in IAB Irons: Correlations Between Metal Composition and Inclusion Properties, and Inferences for Their Origin

NASA Astrophysics Data System (ADS)

Benedix, G. K.; McCoy, T. J.; Keil, K.

1995-09-01

IAB irons are the largest group of iron meteorites, exhibit a large range of siderophile element concentrations in their metal, and commonly contain silicate inclusions with roughly chondritic composition. They are closely related to IIICD irons [1,2] and their inclusions resemble winonaites [3]. It has been suggested that IAB's and IIICD's formed in individual impact melt pools [4,2] on a common parent body. However, it has also been suggested that fractional crystallization [5,6] of a S-saturated core could produce the observed siderophile element trends. Metal composition is correlated with silicate inclusion mineralogy in IIICD's [1], indicating reactions between solid silicates and the metallic magma in a core. These trends observed in IIICD's differ from those in IAB's, suggesting different parent bodies. A bi-modal grouping, based primarily on mineralogy and mineral abundances, was suggested for IAB inclusions [7]. However, recent recoveries of several new silicate-bearing IAB's, along with the emergence of new ideas on their origins, prompted a comprehensive study to document more fully the range of inclusions within IAB irons, to examine possible correlations between the compositions of the metallic host and the silicate inclusions, and to elucidate the origin of IAB irons. We are studying troilite-graphite-silicate inclusions in 24 IAB irons with Ni concentrations ranging from 6.6-25.0%. These include Odessa and Copiapo types [7], newly recovered meteorites (e.g., Lueders [8]) and meteorites with extreme Ni contents (e.g., Jenny's Creek, 6.8%; San Cristobal, 25.0% [9]). The inclusions exhibit a range of textures from recrystallized to partial melts (e.g., Caddo County [10]). Rigorous classification [7] is hampered by heterogeneities between group meteorites, between different samples of distinct meteorites, and within individual inclusions. While intergroup heterogeneities make comparisons between the suite of IAB's somewhat difficult, some general trends

Quaternary silicic pyroclastic deposits of Atitlán Caldera, Guatemala

USGS Publications Warehouse

Rose, William I.; Newhall, Christopher G.; Bornhorst, Theodore J.; Self, Stephen

1987-01-01

Atitlán caldera has been the site of several silicic eruptions within the last 150,000 years, following a period of basalt/andesite volcanism. The silicic volcanism began with 5–10 km3 of rhyodacites, erupted as plinian fall and pyroclastic flows, about 126,000 yr. B.P. At 85,000 yr. B.P. 270–280 km3 of compositionally distinct rhyolite was erupted in the Los Chocoyos event which produced widely dispersed, plinian fall deposits and widespread, mobile pyroclastic flows. In the latter parts of this eruption rhyodacite and minor dacite were erupted which compositionally resembled the earliest silicic magmas of the Atitlán center. As a result of this major eruption, the modern Atitlán (III) caldera formed. Following this event, rhyodacites were again erupted in smaller (5–13 km3) volumes, partly through the lake, and mafic volcanism resumed, forming three composite volcanoes within the caldera. The bimodal mafic/silicic Atitlán volcanism is similar to that which has occurred elsewhere in the Guatemalan Highlands, but is significantly more voluminous. Mafic lavas are thought to originate in the mantle, but rise, intrude and underplate the lower crust and partly escape to the surface. Eventually, silicic melts form in the crust, possibly partly derived from underplated basaltic material, rise, crystallize and erupt. The renewed mafic volcanism could reflect either regional magmato-tectonic adjustment after the large silicic eruption or the onset of a new cycle.

Chemical Zoning of Feldspars in Lunar Granitoids: Implications for the Origins of Lunar Silicic Magmas

NASA Technical Reports Server (NTRS)

Mills, R. D; Simon, J. I.; Alexander, C.M. O'D.; Wang, J.; Christoffersen, R.; Rahman, Z..

2014-01-01

Fine-scale chemical and textural measurements of alkali and plagioclase feldspars in the Apollo granitoids (ex. Fig. 1) can be used to address their petrologic origin(s). Recent findings suggest that these granitoids may hold clues of global importance, rather than of only local significance for small-scale fractionation. Observations of morphological features that resemble silicic domes on the unsampled portion of the Moon suggest that local, sizable net-works of high-silica melt (>65 wt % SiO2) were present during crust-formation. Remote sensing data from these regions suggest high concentrations of Si and heat-producing elements (K, U, and Th). To help under-stand the role of high-silica melts in the chemical differentiation of the Moon, three questions must be answered: (1) when were these magmas generated?, (2) what was the source material?, and (3) were these magmas produced from internal differentiation. or impact melting and crystallization? Here we focus on #3. It is difficult to produce high-silica melts solely by fractional crystallization. Partial melting of preexisting crust may therefore also have been important and pos-sibly the primary mechanism that produced the silicic magmas on the Moon. Experimental studies demonstrate that partial melting of gabbroic rock under mildly hydrated conditions can produce high-silica compositions and it has been suggested by that partial melting by basaltic underplating is the mechanism by which high-silica melts were produced on the Moon. TEM and SIMS analyses, coordinated with isotopic dating and tracer studies, can help test whether the minerals in the Apollo granitoids formed in a plutonic setting or were the result of impact-induced partial melting. We analyzed granitoid clasts from 3 Apollo samples: polymict breccia 12013,141, crystalline-matrix breccia 14303,353, and breccia 15405,78

Primary melt and fluid inclusions in regenerated crystals and phenocrysts of olivine from kimberlites of the Udachnaya-East Pipe, Yakutia: The problem of the kimberlite melt

NASA Astrophysics Data System (ADS)

Tomilenko, A. A.; Kuzmin, D. V.; Bul'bak, T. A.; Sobolev, N. V.

2017-08-01

The primary melt and fluid inclusions in regenerated zonal crystals of olivine and homogeneous phenocrysts of olivine from kimberlites of the Udachnaya-East pipe, were first studied by means of microthermometry, optic and scanning electron microscopy, electron and ion microprobe analysis (SIMS), inductively coupled plasma mass-spectrometry (ICP MSC), and Raman spectroscopy. It was established that olivine crystals were regenerated from silicate-carbonate melts at a temperature of 1100°C.

Shock-Induced Phase Transitions in the Martian Meteorite Tissint: Mechanisms and Constraints on Shock Pressure

NASA Astrophysics Data System (ADS)

Sharp, T. G.; Hu, J.; Walton, E. L.

2013-12-01

Martian meteorites are important samples for understanding the origin and age of the Martian crust. All of these samples have been shocked to some degree during their ejection from Mars or earlier. Tissint, a picritic shergottite, has many high-pressure phases that have been used to constrain shock conditions and suggest a deep crustal origin [1] and to argue for multiple impact events [2]. Here we investigate the products and mechanisms of various olivine transformation reactions. Olivine in and adjacent to shock-melt veins and pockets is transformed into high-pressure minerals. In the hottest parts of the sample, olivine dissociated into 50-nm crystals of magnesiowüstite intergrown with either a pyroxene-composition glass or with low-Ca clinopyroxene. In both cases, the olivine is inferred to have transformed to silicate perovskite + magnesiowüstite during shock with subsequent breakdown of the perovskite after pressure release. Olivine along the margins of shock veins transformed into ringwoodite. Polycrystalline ringwoodite formed at the olivine-melt interface wheras coherent ringwoodite lamellae formed farther from the melt. These ringwoodite lamellae have the same topotaxial relationship to olivine as seen in static high-pressure experiments [3] and shocked meteorites [4]: (100)Ol || {111}Rw and [011]Ol || <110>Rw. The various olivine reactions can be explained by a single shock to above 24 GPa where only the highest temperatures allowed the dissociation of olivine to silicate-perovskite plus magnesiowüstite. The silicate perovskite in the melt pocket transformed to pyroxene because the melt pocket remained very hot after pressure release. At lower temperatures, the kinetically easier polymorphic transformation of olivine to metastable ringwoodite occurred. At the lowest temperatures, this reaction was facilitated by nucleation of ringwoodite lamellae on stacking faults in olivine. The variation in assemblages that we see are consistent with a single shock

Preparations of PbSe quantum dots in silicate glasses by a melt-annealing technique

NASA Astrophysics Data System (ADS)

Ma, D. W.; Cheng, C.; Zhang, Y. N.; Xu, Z. S.

2014-11-01

Silicate glass containing PbSe quantum dots (QDs) has important prospective applications in near infra-red optoelectronic devices. In this study, single-stage and double-stage heat-treatment methods were used respectively to prepare PbSe QDs in silicate glasses. Investigation results show that the double-stage heat-treatment is a favorable method to synthesize PbSe QDs with strong photoluminescence (PL) intensity and narrow full weight at half maximum (FWHM) in PL peak. Therefore, the method to prepare PbSe QDs was emphasized on the double-stage heat-treatment. Transmission electron microscopy measurements show that the standard deviations of the average QD sizes from the samples heat-treated at the development temperature of 550 °C fluctuate slightly in the range of 0.6-0.8 nm, while this deviation increases up to 1.2 nm for the sample with the development temperature of 600 °C. In addition, the linear relationship between the QD size and holding time indicates that the crystallization behavior of PbSe QDs in silicate glasses is interface-controlled growth in early stage of crystallization. The growth rates of PbSe QDs are determined to be 0.24 nm/h at 550 °C and 0.72 nm/h at 600 °C. In short, the double-stage heat-treatment at 450 °C for 20 h followed by heat-treatment at 550 °C for 5 h is a preferred process for the crystallization of PbSe QDs in silicate glass. Through this treatment, PbSe QDs with a narrow size dispersion of 5.0 ± 0.6 nm can be obtained, the PL peak from this sample is highest in intensity and narrowest in FWHM among all samples, and the peak is centered on 1575 nm, very close to the most common wavelength of 1550 nm in fiber-optic communication systems.

Thermochemistry of amorphous and crystalline zirconium and hafnium silicates.

NASA Astrophysics Data System (ADS)

Ushakov, S.; Brown, C. E.; Navrotsky, Alexandra; Boatner, L. A.; Demkov, A. A.; Wang, C.; Nguyen, B.-Y.

2003-03-01

Calorimetric investigation of amorphous and crystalline zirconium and hafnium silicates was performed as part of a research program on thermochemistry of alternative gate dielectrics. Amorphous hafnium and zirconium silicates with varying SiO2 content were synthesized by a sol-gel process. Crystalline zirconium and hafnium silicates (zircon and hafnon) were synthesized by solid state reaction at 1450 °C from amorphous gels and grown as single crystals from flux. High temperature oxide melt solution calorimetry in lead borate (2PbO.B2O3) solvent at 800 oC was used to measure drop solution enthalpies for amorphous and crystalline zirconium and hafnium silicates and corresponding oxides. Applying appropriate thermochemical cycles, formation enthalpy of crystalline ZrSiO4 (zircon) from binary oxides (baddeleite and quartz) at 298 K was calculated as -23 +/-2 kJ/mol and enthalpy difference between amorphous and crystalline zirconium silicate (vitrification enthalpy) was found to be 61 +/-3 kJ/mol. Crystallization onset temperatures of amorphous zirconium and hafnium silicates, as measured by differential scanning calorimetry (DSC), increased with silica content. The resulting crystalline phases, as characterized by X-ray diffraction (XRD), were tetragonal HfO2 and ZrO2. Critical crystallite size for tetragonal to monoclinic transformation of HfO2 in the gel was estimated as 6 +/-2 nm from XRD data Crystallization enthalpies per mole of hafnia and zirconia in gels decrease slightly together with crystallite size with increasing silica content, for example from -22 to -15 +/-1 kJ per mol of HfO2 crystallized at 740 and 1006 °C from silicates with 10 and 70 mol Applications of thermal analyses and solution calorimetry techniques together with first-principles density functional calculations to estimate interface and surface energies are discussed.

Local structural variation with oxygen fugacity in Fe 2SiO 4+x fayalitic iron silicate melts

DOE PAGES

Alderman, O.L.G.; Lazareva, L.; Wilding, M. C.; ...

2017-01-07

Here, the structure of molten Fe 2SiO 4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe 3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature ( T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and –5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K andmore » –2.1(3) < ΔFMQ < +4.4(3) log units. Fe 3+ contents, x = Fe 3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe–O coordination numbers, n FeO, close to 5 for all Fe 3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < n FeO < 4.7(1). There is limited evidence for a linear trend n FeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe–O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean r FeO lie close to 2.06 Å, consistent with n FeO close to 5. These observations suggest that Fe 2+ is less efficient at stabilizing tetrahedral Fe 3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe 3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts

Local structural variation with oxygen fugacity in Fe2SiO4+x fayalitic iron silicate melts

NASA Astrophysics Data System (ADS)

Alderman, O. L. G.; Lazareva, L.; Wilding, M. C.; Benmore, C. J.; Heald, S. M.; Johnson, C. E.; Johnson, J. A.; Hah, H.-Y.; Sendelbach, S.; Tamalonis, A.; Skinner, L. B.; Parise, J. B.; Weber, J. K. R.

2017-04-01

The structure of molten Fe2SiO4+x has been studied using both high-energy X-ray diffraction and Fe K-edge X-ray absorption near-edge structure (XANES) spectroscopy, combined with aerodynamic levitation and laser beam heating. A wide range of Fe3+ contents were accessed by varying the levitation and atmospheric gas composition. Diffraction measurements were made in the temperature (T) and oxygen partial pressure ranges 1624(21) < T < 2183(94) K (uncertainties in parentheses) and -5.6(3) < ΔFMQ < +2.8(5) log units (relative to the Fayalite-Magnetite-Quartz buffer). Iron K-edge XANES measurements covered the ranges 1557(33) < T < 1994(36) K and -2.1(3) < ΔFMQ < +4.4(3) log units. Fe3+ contents, x = Fe3+/ΣFe, estimated directly from the pre-edge peaks of the XANES spectra varied between 0.15(1) and 0.40(2). While these agree in some cases with semi-empirical models, notable discrepancies are discussed in the context of the redox kinetics and the limitations in both the models and in the calibrations used to derive oxidation state from XANES spectra. XANES pre-edge peak areas imply average Fe-O coordination numbers, nFeO, close to 5 for all Fe3+/ΣFe. Diffraction measurements yielded values of 4.4(2) < nFeO < 4.7(1). There is limited evidence for a linear trend nFeO(x) = 4.46(3) + 0.4(1)x. Asymmetric Fe-O bond length distributions peak at around 1.96 Å and have a shoulder arising from longer interatomic distances. Mean rFeO lie close to 2.06 Å, consistent with nFeO close to 5. These observations suggest that Fe2+ is less efficient at stabilizing tetrahedral Fe3+ compared to large monovalent alkali cations. Comparison of in-situ XANES estimates of Fe3+/ΣFe in the melts to those of the quenched solids obtained from XANES as well as Mössbauer spectroscopy indicate rapid oxidation during cooling, enabled by stirring of the melt by the levitation gas flow. As such, the oxidation state of hot komatiitic and other highly fluid melts may not be retained, even during

A geochemical study of the winonaites: Evidence for limited partial melting and constraints on the precursor composition

NASA Astrophysics Data System (ADS)

Hunt, Alison C.; Benedix, Gretchen K.; Hammond, Samantha J.; Bland, Philip A.; Rehkämper, Mark; Kreissig, Katharina; Strekopytov, Stanislav

2017-02-01

The winonaites are primitive achondrites which are associated with the IAB iron meteorites. Textural evidence implies heating to at least the Fe, Ni-FeS cotectic, but previous geochemical studies are ambiguous about the extent of silicate melting in these samples. Oxygen isotope evidence indicates that the precursor material may be related to the carbonaceous chondrites. Here we analysed a suite of winonaites for modal mineralogy and bulk major- and trace-element chemistry in order to assess the extent of thermal processing as well as constrain the precursor composition of the winonaite-IAB parent asteroid. Modal mineralogy and geochemical data are presented for eight winonaites. Textural analysis reveals that, for our sub-set of samples, all except the most primitive winonaite (Northwest Africa 1463) reached the Fe, Ni-FeS cotectic. However, only one (Tierra Blanca) shows geochemical evidence for silicate melting processes. Tierra Blanca is interpreted as a residue of small-degree silicate melting. Our sample of Winona shows geochemical evidence for extensive terrestrial weathering. All other winonaites studied here (Fortuna, Queen Alexander Range 94535, Hammadah al Hamra 193, Pontlyfni and NWA 1463) have chondritic major-element ratios and flat CI-normalised bulk rare-earth element patterns, suggesting that most of the winonaites did not reach the silicate melting temperature. The majority of winonaites were therefore heated to a narrow temperature range of between ∼1220 (the Fe, Ni-FeS cotectic temperature) and ∼1370 K (the basaltic partial melting temperature). Silicate inclusions in the IAB irons demonstrate partial melting did occur in some parts of the parent body (Ruzicka and Hutson, 2010), thereby implying heterogeneous heat distribution within this asteroid. Together, this indicates that melting was the result of internal heating by short-lived radionuclides. The brecciated nature of the winonaites suggests that the parent body was later disrupted by

Deep-Earth Equilibration between Molten Iron and Solid Silicates

NASA Astrophysics Data System (ADS)

Brennan, M.; Zurkowski, C. C.; Chidester, B.; Campbell, A.

2017-12-01

Elemental partitioning between iron-rich metals and silicate minerals influences the properties of Earth's deep interior, and is ultimately responsible for the nature of the core-mantle boundary. These interactions between molten iron and solid silicates were influential during planetary accretion, and persist today between the mantle and liquid outer core. Here we report the results of diamond anvil cell experiments at lower mantle conditions (40 GPa, >2500 K) aimed at examining systems containing a mixture of metals (iron or Fe-16Si alloy) and silicates (peridotite). The experiments were conducted at pressure-temperature conditions above the metallic liquidus but below the silicate solidus, and the recovered samples were analyzed by FIB/SEM with EDS to record the compositions of the coexisting phases. Each sample formed a three-phase equilibrium between bridgmanite, Fe-rich metallic melt, and an oxide. In one experiment, using pure Fe, the quenched metal contained 6 weight percent O, and the coexisting oxide was ferropericlase. The second experiment, using Fe-Si alloy, was highly reducing; its metal contained 10 wt% Si, and the coexisting mineral was stishovite. The distinct mineralogies of the two experiments derived from their different starting metals. These results imply that metallic composition is an important factor in determining the products of mixed phase iron-silicate reactions. The properties of deep-Earth interfaces such as the core-mantle boundary could be strongly affected by their metallic components.

XANES study on Fe, U and Th in hydrous melts at high temperature and pressure

NASA Astrophysics Data System (ADS)

Wilke, M.; Schmidt, C.; Farges, F.; Borchert, M.; Simionovici, A.; Hahn, M.

2005-12-01

Insight to the structural units of melts is an important key to model properties of magmas. The effect of water and pressure on the local structure around minor to trace elements in silicate melts was investigated at in-situ conditions. The study was performed using XANES spectroscopy and a diamond anvil-cell. This was done to characterize spurious effects observed on glasses that are potentially invoked by quenching [1] and to understand better the processes occurring during the quench. We present results of in-situ XANES measurements on iron, uranium and thorium in hydrous silicate melt up to 1 GPa and 700° C. In-situ XANES spectra were recorded at the ESRF (Grenoble, France), beamline ID 22, using a hydrothermal diamond anvil cell with a design optimized for such measurements [2], i.e. recesses on the front and the back-side of one of the diamond anvils that provide the possibility to collect spectra at relatively low energies (down to 7 keV) and relatively low concentrations (0.1-1 wt%). In-situ Fe K-edge XANES spectra of Fe(II) in hydrous haplogranitic melt at 700° C and 500 MPa suggests that the local structure around Fe in hydrous glass observed previously is probably due to ordering during the quench. Additionally, the XANES is very similar to in-situ spectra taken on Fe(II) in anhydrous haplogranitic melt at 1150° C and ambient pressure. This indicates that the combined effect of water and pressure (0-500 MPa range) does not influence drastically the local structure of Fe in this type of melt composition. In-situ LIII-edge XANES of U in hydrous haplogranitic melt (1 wt% U) at 700° C and 620 MPa show that, upon reduction, U precipitated as uraninite. This suggests a low amount of NBO's (to which tetravalent actinides preferentially bond [3]) in this water-saturated melt. In contrast, U-bearing (1000 ppm) hydrous sodium-tri-silicate melt shows the presence of U(IV) dissolved in the melt as 6-7 coordinated species, as in dry glasses [3]. Similar

Experimental Constraints on the Partitioning Behavior of F, Cl, and OH Between Apatite and Basaltic Melt

NASA Technical Reports Server (NTRS)

McCubbin, Francis M.; Barnes, Jessica J.; Vander Kaaden, Kathleen E.; Boyce, Jeremy W.; Ustunisik, Gokce; Whitson, Eric S.

2017-01-01

The mineral apatite is present in a wide range of planetary materials. The presence of volatiles (F, Cl, and OH) within its crystal structure (X-site) have motivated numerous studies to investigate the partitioning behavior of F, Cl, and OH between apatite and silicate melt with the end goal of using apatite to constrain the volatile contents of planetary magmas and mantle sources. A number of recent experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in magmatic systems. Apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, the partitioning behavior is likely to change as a function of temperature, pressure, oxygen fugacity, apatite composition, and melt composition. In the present study, we have conducted experiments to assess the partitioning behavior of F, Cl, and OH between apatite and silicate melt over a pressure range of 0-6 gigapascals, a temperature range of 950-1500 degrees Centigrade, and a wide range of apatite ternary compositions. All of the experiments were conducted between iron-wustite oxidation potentials IW minus 1 and IW plus 2 in a basaltic melt composition. The experimental run products were analyzed by a combination of electron probe microanalysis and secondary ion mass spectrometry (NanoSIMS). Temperature, apatite crystal chemistry, and pressure all play important roles in the partitioning behavior of F, Cl, and OH between apatite and silicate melt. In portions of apatite ternary space that undergo ideal mixing of F, Cl, and OH, exchange coefficients remain constant at constant temperature and pressure. However, exchange coefficients vary at constant temperature (T) and pressure (P) in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. The variation in exchange coefficients exhibited by apatite that does not undergo ideal mixing far exceeds the variations

Effect of water on the composition of partial melts of greenstone and amphibolite

NASA Technical Reports Server (NTRS)

Beard, James S.; Lofgren, Gary E.

1989-01-01

Closed-system partial melts of hydrated, metamorphosed arc basalts and andesites (greenstones and amphibolites), where only water structurally bound in metamorphic minerals is available for melting (dehydration melting), are generally water-undersaturated, coexist with plagioclase-rich, anhydrous restites, and have compositions like island arc tonalites. In contrast, water-saturated melting at water pressures of 3 kilobars yields strongly peraluminous, low iron melts that coexist with an amphibole-bearing, plagioclase-poor restite. These melt compositions are unlike those of most natural silicic rocks. Thus, dehydration melting over a range of pressures in the crust of island arcs is a plausible mechanism for the petrogenesis of islands arc tonalite, whereas water-saturated melting at pressure of 3 kilobars and above is not.

Composition of Impact Melt Debris from the Eltanin Impact Strewn Field, Bellingshausen Sea

NASA Technical Reports Server (NTRS)

Kyte, Frank T.

2002-01-01

The impact of the km-sized Eltanin asteroid into the Bellingshausen Sea produced mm- to cm-sized vesicular impact melt-rock particles found in sediment cores across a large area of the ocean floor. These particles are composed mainly of olivine and glass with minor chromite and traces of NiFe-sulfides. Some particles have inclusions of unmelted mineral and rock fragments from the precursor asteroid. Although all samples of melt rock examined have experienced significant alteration since their deposition in the late Pliocene, a significant portion of these particles have interiors that remain pristine and can be used to estimate the bulk composition of the impact melt. The bulk composition of the melt-rock particles is similar to the composition of basaltic meteorites such as howardites or mesosiderite silicates, with a contribution from seawater salts and a siderophile-rich component. There is no evidence that the Eltanin impact melt contains a significant terrestrial silicate component that might have been incorporated by mixing of the projectile with oceanic crust. If terrestrial silicates were incorporated into the melt, then their contribution must be much less than 10 wt%. Since excess K, Na, and CI are not present in seawater proportions, uptake of these elements into the melt must have been greatest for K and least for CI, producing a K/CI ratio about 4 times that in seawater. After correcting for the seawater component, the bulk composition of the Eltanin impact melt provides the best estimate of the bulk composition of the Eltanin asteroid. Excess Fe in the impact melt, relative to that in howardites, must be from a significant metal phase in the parent asteroid. Although the estimated Fe:Ni:Ir ratios (8:1:4 x 10(exp -5)) are similar to those in mesosiderite metal nodules (10:1:6 x 10(exp -5), excess Co and Au by factors of about 2 and 10 times, respectively, imply a metal component distinct from that in typical mesosiderites. An alternative interpretation

Planetary science. Shock compression of stishovite and melting of silica at planetary interior conditions.

PubMed

Millot, M; Dubrovinskaia, N; Černok, A; Blaha, S; Dubrovinsky, L; Braun, D G; Celliers, P M; Collins, G W; Eggert, J H; Jeanloz, R

2015-01-23

Deep inside planets, extreme density, pressure, and temperature strongly modify the properties of the constituent materials. In particular, how much heat solids can sustain before melting under pressure is key to determining a planet's internal structure and evolution. We report laser-driven shock experiments on fused silica, α-quartz, and stishovite yielding equation-of-state and electronic conductivity data at unprecedented conditions and showing that the melting temperature of SiO2 rises to 8300 K at a pressure of 500 gigapascals, comparable to the core-mantle boundary conditions for a 5-Earth mass super-Earth. We show that mantle silicates and core metal have comparable melting temperatures above 500 to 700 gigapascals, which could favor long-lived magma oceans for large terrestrial planets with implications for planetary magnetic-field generation in silicate magma layers deep inside such planets. Copyright © 2015, American Association for the Advancement of Science.

Intraplate mantle oxidation by volatile-rich silicic magmas

NASA Astrophysics Data System (ADS)

Martin, Audrey M.; Médard, Etienne; Righter, Kevin; Lanzirotti, Antonio

2017-11-01

The upper subcontinental lithospheric mantle below the French Massif Central is more oxidized than the average continental lithosphere, although the origin of this anomaly remains unknown. Using iron oxidation analysis in clinopyroxene, oxybarometry, and melt inclusions in mantle xenoliths, we show that widespread infiltration of volatile (HCSO)-rich silicic melts played a major role in this oxidation. We propose the first comprehensive model of magmatism and mantle oxidation at an intraplate setting. Two oxidizing events occurred: (1) a 365-286 Ma old magmatic episode that produced alkaline vaugnerites, potassic lamprophyres, and K-rich calc-alkaline granitoids, related to the N-S Rhenohercynian subduction, and (2) < 30 Ma old magmatism related to W-E extension, producing carbonatites and hydrous potassic trachytes. These melts were capable of locally increasing the subcontinental lithospheric mantle fO2 to FMQ + 2.4. Both events originate from the melting of a metasomatized lithosphere containing carbonate + phlogopite ± amphibole. The persistence of this volatile-rich lithospheric source implies the potential for new episodes of volatile-rich magmatism. Similarities with worldwide magmatism also show that the importance of volatiles and the oxidation of the mantle in intraplate regions is underestimated.

30Ar-40Ar Ages of Silicates from IIE Iron Meteorites

NASA Astrophysics Data System (ADS)

Garrison, D. H.; Bogard, D. D.

1995-09-01

early in parent body history. The ^39Ar-^40Ar age for Miles, however, appears slightly younger and is similar to Rb-Sr ages for Weekeroo Station of ^-4.28-4.39 Ga [8, 9]. Young isotopic ages do not obviously correlate with the degree of melting and silicate fractionation, except that three of four dated IIEs showing significant fractionation give older ages. Totally unrelated events may have melted and fractionated similar silicates to produce comparable mixtures with IIE metal at both ^-4.5 and ^-3.7 Ga ago. This requires at least the younger event to have been an impact, possibly related to impact chronometer resetting observed in lunar highland rocks and HED meteorites near this time. However, petrologic data suggest that IIE meteorites may also represent a suite of samples that responded in different degrees to a single, early mixing event [1]. This explanation suggests that isotopic ages of Watson, Netschaevo, and Kodaikanal were reset by strong impact heating, possibly involving melting of individual silicate clasts, in one or more events long after their initial formation. Impacts may also explain the apparent younger ages observed for Miles and Weekeroo Station. A problem for the origin of IIEs in a single, early event is the apparent requirement from initial ^87Sr/^86Sr of Kodaikanal that the Rb/Sr ratio was increased significantly at a time near 3.7 Ga [2]. Whether such fractionation could occur within or across shock-melted silicate inclusions [10] deserves further consideration. References: [1] McCoy, this volume. [2] Burnett and Wasserburg (1967) EPSL, 2, 397. [3] Gopel et al. (1985) Nature, 317, 341. [4] Bogard et al. (1969) EPSL, 5, 273. [5] Niemeyer (1980) GCA, 44, 33. [6] Olsen et al. (1994) Meteoritics, 29, 200. [7] Sanz et al. (1970) GCA, 34, 1227. [8] Burnett and Wasserburg (1967) EPSL, 2, 397. [9] Evensen et al. (1979) LPS X, 376. [10] Bence and Burnett (1969) GCA, 33, 387.

Deformation of a crystalline olivine aggregate containing two immiscible liquids: Implications for early core-mantle differentiation

NASA Astrophysics Data System (ADS)

Cerantola, V.; Walte, N. P.; Rubie, D. C.

2015-05-01

Deformation-assisted segregation of metallic and sulphidic liquid from a solid peridotitic matrix is a process that may contribute to the early differentiation of small planetesimals into a metallic core and a silicate mantle. Here we present results of an experimental study using a simplified system consisting of a polycrystalline Fo90-olivine matrix containing a small percentage of iron sulphide and a synthetic primitive MORB melt, in order to investigate whether the silicate melt enhances the interconnection and segregation of FeS liquid under deformation conditions at varying strain rates. The experiments have been performed at 2 GPa, 1450 °C and strain rates between 1 ×10-3s-1 to 1 ×10-5s-1. Our results show that the presence of silicate melt actually hinders the migration and segregation of sulphide liquid by reducing its interconnectivity. At low to moderate strain rates the sulphide liquid pockets preserved a roundish shape, showing the liquid behavior is governed mainly by surface tension rather than by differential stress. Even at the highest strain rates, insignificant FeS segregation and interconnection were observed. On the other hand the basaltic melt was very mobile during deformation, accommodating part of the strain, which led to its segregation from the matrix at high bulk strains leaving the sulphide liquid stranded in the olivine matrix. Hence, we conclude that deformation-induced percolation of sulphide liquid does not contribute to the formation of planetary cores after the silicate solidus is overstepped. A possible early deformation enhanced core-mantle differentiation after overstepping the Fe-S solidus is not possible between the initial formation of silicate melt and the formation of a widespread magma ocean.

In situ study at high pressure and temperature of the environment of water in hydrous Na and Ca aluminosilicate melts and coexisting aqueous fluids

NASA Astrophysics Data System (ADS)

Le Losq, Charles; Dalou, Célia; Mysen, Bjorn O.

2017-07-01

The bonding and speciation of water dissolved in Na silicate and Na and Ca aluminosilicate melts were inferred from in situ Raman spectroscopy of the samples, in hydrothermal diamond anvil cells, while at crustal temperature and pressure conditions. Raman data were also acquired on Na silicate and Na and Ca aluminosilicate glasses, quenched from hydrous melts equilibrated at high temperature and pressure in a piston cylinder apparatus. In the hydrous melts, temperature strongly influences O-H stretching ν(O-H) signals, reflecting its control on the bonding of protons between different molecular complexes. Pressure and melt composition effects are much smaller and difficult to discriminate with the present data. However, the chemical composition of the melt + fluid system influences the differences between the ν(O-H) signals from the melts and the fluids and, hence, between their hydrogen partition functions. Quenching modifies the O-H stretching signals: strong hydrogen bonds form in the glasses below the glass transition temperature Tg, and this phenomenon depends on glass composition. Therefore, glasses do not necessarily record the O-H stretching signal shape in melts near Tg. The melt hydrogen partition function thus cannot be assessed with certainty using O-H stretching vibration data from glasses. From the present results, the ratio of the hydrogen partition functions of hydrous silicate melts and aqueous fluids mostly depends on temperature and the bulk melt + fluid system chemical composition. This implies that the fractionation of hydrogen isotopes between magmas and aqueous fluids in water-saturated magmatic systems with differences in temperature and bulk chemical composition will be different.

Melt transport - a personal cashing-up

NASA Astrophysics Data System (ADS)

Renner, J.

2005-12-01

The flow of fluids through rocks transports heat and material and changes bulk composition. The large-scale chemical differentiation of the Earth is related to flow of partial melts. From the perspective of current understanding of tectonic processes, prominent examples of such transport processes are the formation of oceanic crust from ascending basic melts at mid-ocean ridges, melt segregation involved in the solidification of the Earth's core, and dissolution-precipitation creep in subduction channels. Transport and deformation cannot be separated for partially molten aggregates. Permeability is only defined as an instantaneous parameter in the sense that Darcy's law is assumed to be valid; it is not an explicit parameter in the fundamental mechanical conservation laws but can be derived from them in certain circumstances as a result of averaging schemes. The governing, explicit physical properties in the mechanical equations are the shear and bulk viscosities of the solid framework and the fluid viscosity and compressibility. Constraints on the magnitude of these properties are available today from experiments at specific loading configurations, i.e., more or less well constrained initial and boundary conditions. The melt pressure remains the least controlled parameter. While the fluid viscosity is often much lower than the solid's the two-phase aggregate may exhibit considerable strength owing to the difficulty of moving the fluid through the branched pore network. The extremes in behavior depend on the time scale of loading, as known from daily live experiences (spounge, Danish coffee-pot, human tissue between neighboring bones). Several theoretical approaches attempted to formulate mechanical constitutive equations for two-phase aggregates. An important issue is the handling of internal variables in these equations. At experimental conditions, grain size, melt pocket orientation and crystallographic orientation -prime candidates for internal variables

Effects of water, depth and temperature on partial melting of mantle-wedge fluxed by hydrous sediment-melt in subduction zones

NASA Astrophysics Data System (ADS)

Mallik, Ananya; Dasgupta, Rajdeep; Tsuno, Kyusei; Nelson, Jared

2016-12-01

This study investigates the partial melting of variable bulk H2O-bearing parcels of mantle-wedge hybridized by partial melt derived from subducted metapelites, at pressure-temperature (P-T) conditions applicable to the hotter core of the mantle beneath volcanic arcs. Experiments are performed on mixtures of 25% sediment-melt and 75% fertile peridotite, from 1200 to 1300 °C, at 2 and 3 GPa, with bulk H2O concentrations of 4 and 6 wt.%. Combining the results from these experiments with previous experiments containing 2 wt.% bulk H2O (Mallik et al., 2015), it is observed that all melt compositions, except those produced in the lowest bulk H2O experiments at 3 GPa, are saturated with olivine and orthopyroxene. Also, higher bulk H2O concentration increases melt fraction at the same P-T condition, and causes exhaustion of garnet, phlogopite and clinopyroxene at lower temperatures, for a given pressure. The activity coefficient of silica (ϒSiO2) for olivine-orthopyroxene saturated melt compositions (where the activity of silica, aSiO2 , is buffered by the reaction olivine + SiO2 = orthopyroxene) from this study and from mantle melting studies in the literature are calculated. In melt compositions generated at 2 GPa or shallower, with increasing H2O concentration, ϒSiO2 increases from <1 to ∼1, indicating a transition from non-ideal mixing as OH- in the melt (ϒSiO2 <1) to ideal mixing as molecular H2O (ϒSiO2 ∼1). At pressures >2 GPa, ϒSiO2 >1 at higher H2O concentrations in the melt, indicate requirement of excess energy to incorporate molecular H2O in the silicate melt structure, along with a preference for bridging species and polyhedral edge decorations. With vapor saturation in the presence of melt, ϒSiO2 decreases indicating approach towards ideal mixing of H2O in silicate melt. For similar H2O concentrations in the melt, ϒSiO2 for olivine-orthopyroxene saturated melts at 3 GPa is higher than melts at 2 GPa or shallower. This results in melts generated at

Thermodynamic modeling of melts in the system Na 2O-NaAlO 2-SiO 2-F 2O -1

NASA Astrophysics Data System (ADS)

Dolejš, David; Baker, Don R.

2005-12-01

Fluorine is a common volatile element in magmatic-hydrothermal systems, but its solution mechanisms and thermodynamic description in highly polymerized silicate melts are poorly known. We have developed a thermodynamic model for fluorosilicate liquids that links experimentally determined phase equilibria and spectroscopic information on melt structure. The model is applicable to crystallization of fluoride minerals, fluoride-silicate immiscibility in natural felsic melts, and metallurgical processes. Configurational properties of fluorosilicate melts are described by mixing on three site levels (sublattices): (1) alkali fluoride, polyhedral aluminofluoride and silicofluoride species and nonbridging terminations of the aluminosilicate network, (2) alkali-aluminate and silicate tetrahedra within the network and (3) bridging oxygen, nonbridging oxygen and terminal fluorine atoms on tetrahedral apices of the network. Abundances of individual chemical species are described by a homogeneous equilibrium representing melt depolymerization: F - (free) + O 0 (bridging) = F 0 (terminal) + O - (nonbridging) which corresponds to a replacement of an oxygen bridging two tetrahedra by a pair of terminations, one with F and the other with an O and a charge-balancing Na. In cryolite-bearing systems two additional interaction mechanisms occur: (1) the self-dissociation of octahedral aluminofluoride complexes: [AlF 6] = [AlF 4] + 2 [F], and (2) the short-range order between (O,F)-corners and (Si,NaAl)-centers of tetrahedra: Si-O-Si + 2 [NaAl]-F = [NaAl]-O-[NaAl] + 2 Si-F. Portrayal of these equilibria in ternary Thompson reaction space allows for the decrease in the number of interaction mechanisms by linearly combining melt depolymerization with tetrahedral short-range order. In this formulation, the nonideal thermodynamic properties are represented by reaction energies of homogeneous equilibria, thus defining directly individual chemical species concentrations and configurational

Bursting the bubble of melt inclusions

USGS Publications Warehouse

Lowenstern, Jacob B.

2015-01-01

Most silicate melt inclusions (MI) contain bubbles, whose significance has been alternately calculated, pondered, and ignored, but rarely if ever directly explored. Moore et al. (2015) analyze the bubbles, as well as their host glasses, and conclude that they often hold the preponderance of CO2 in the MI. Their findings entreat future researchers to account for the presence of bubbles in MI when calculating volatile budgets, saturation pressures, and eruptive flux.

High temperature calorimetric studies of heat of solution of NiO, CuO, La2O3, TiO2, HfO2 in sodium silicate liquids

NASA Astrophysics Data System (ADS)

Linard, Yannick; Wilding, Martin C.; Navrotsky, Alexandra

2008-01-01

The enthalpies of solution of La2O3, TiO2, HfO2, NiO and CuO were measured in sodium silicate melts at high temperature. When the heat of fusion was available, we derived the corresponding liquid-liquid enthalpies of mixing. These data, combined with previously published work, provide insight into the speciation reactions in sodium silicate melts. The heat of solution of La2O3 in these silicate solvents is strongly exothermic and varies little with La2O3 concentration. The variation of heat of solution with composition of the liquid reflects the ability of La(III) to perturb the transient silicate framework and compete with other cations for oxygen. The enthalpy of solution of TiO2 is temperature-dependent and indicates that the formation of Na-O-Si species is favored over Na-O-Ti at low temperature. The speciation reactions can be interpreted in terms of recent spectroscopic studies of titanium-bearing melts which identify a dual role of Ti4+ as both a network-former end network-modifier. The heats of solution of oxides of transition elements (Ni and Cu) are endothermic, concentration-dependent and reach a maximum with concentration. These indicate a charge balanced substitution which diminishes the network modifying role of Na+ by addition of Ni2+ or Cu2+. The transition metal is believed to be in tetrahedral coordination, charge balanced by the sodium cation in the melts.

Intraplate mantle oxidation by volatile-rich silicic magmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martin, Audrey M.; Médard, Etienne; Righter, Kevin

The upper subcontinental lithospheric mantle below the French Massif Central is more oxidized than the average continental lithosphere, although the origin of this anomaly remains unknown. Using iron oxidation analysis in clinopyroxene, oxybarometry, and melt inclusions in mantle xenoliths, we show that widespread infiltration of volatile (HCSO)-rich silicic melts played a major role in this oxidation. We propose the first comprehensive model of magmatism and mantle oxidation at an intraplate setting. Two oxidizing events occurred: (1) a 365–286 Ma old magmatic episode that produced alkaline vaugnerites, potassic lamprophyres, and K-rich calc-alkaline granitoids, related to the N–S Rhenohercynian subduction, and (2)more » < 30 Ma old magmatism related to W–E extension, producing carbonatites and hydrous potassic trachytes. These melts were capable of locally increasing the subcontinental lithospheric mantle fO2 to FMQ + 2.4. Both events originate from the melting of a metasomatized lithosphere containing carbonate + phlogopite ± amphibole. The persistence of this volatile-rich lithospheric source implies the potential for new episodes of volatile-rich magmatism. Similarities with worldwide magmatism also show that the importance of volatiles and the oxidation of the mantle in intraplate regions is underestimated.« less

Predicting major element mineral/melt equilibria - A statistical approach

NASA Technical Reports Server (NTRS)

Hostetler, C. J.; Drake, M. J.

1980-01-01

Empirical equations have been developed for calculating the mole fractions of NaO0.5, MgO, AlO1.5, SiO2, KO0.5, CaO, TiO2, and FeO in a solid phase of initially unknown identity given only the composition of the coexisting silicate melt. The approach involves a linear multivariate regression analysis in which solid composition is expressed as a Taylor series expansion of the liquid compositions. An internally consistent precision of approximately 0.94 is obtained, that is, the nature of the liquidus phase in the input data set can be correctly predicted for approximately 94% of the entries. The composition of the liquidus phase may be calculated to better than 5 mol % absolute. An important feature of this 'generalized solid' model is its reversibility; that is, the dependent and independent variables in the linear multivariate regression may be inverted to permit prediction of the composition of a silicate liquid produced by equilibrium partial melting of a polymineralic source assemblage.

A IAB-Complex Iron Meteorite Containing Low-Ca Clinopyroxene: Northwest Africa 468 and its Relationship to Iodranites and Formation by Impact Melting

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.

2002-01-01

Northwest Africa 468 (NWA 468) is a new ungrouped, silicate-rich member of the IAB complex of nonmagmatic iron meteorites. The silicates contain relatively coarse (approximately 300 micron-size) grains of low-Ca clinopyroxene with polysynthetic twinning and inclined extinction. Low-Ca clinopyroxene is indicative of quenching from high temperatures (either from protoenstatite in a few seconds or high-temperature clinoenstatite in a few hours). It seems likely that NWA 468 formed by impact melting followed by rapid cooling to less than or equal to 660 C. After the loss of a metal-sulfide melt from the silicates, sulfide was reintroduced, either from impact-mobilized FeS or as an S2 vapor that combined with metallic Fe to produce FeS. The O-isotopic composition (delta O-17 = -1.39 %) indicates that the precursor material of NWA 468 was a metal-rich (e.g., CR) carbonaceous chondrite. Lodranites are similar in bulk chemical and O-isotopic composition to the silicates in NWA 468; the MAC 88177 lodranite (which also contains low-Ca clinopyroxene) is close in bulk chemical composition. Both NWA 468 and MAC 88177 have relatively low abundances of REE (rare earth elements) and plagiophile elements. Siderophiles in the metal-rich areas of NWA 468 are similar to those in the MAC 88177 whole rock; both samples contain low Ir and relatively high Fe, Cu and Se. Most unweathered lodranites contain approximately 20 - 38 wt. % metallic Fe-Ni. These rocks may have formed in an analogous manner to NWA 468 (i.e., by impact melting of metal-rich carbonaceous-chondrite precursors) but with less separation of metal-rich melts from silicates.

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Beckett, J. R.; Stolper, E.

1994-01-01

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that

Discovery of Ahrensite γ-Fe2SiO4 and Tissintite (Ca,Na,[])AlSi2O6, Two New Shock-induced Minerals from the Tissint Martian Meteorite: a Nanomineralogy Investigation

NASA Astrophysics Data System (ADS)

Ma, C.; Tschauner, O. D.; Liu, Y.; Sinogeikin, S. V.; Zhuravlev, K. K.; Prakapenka, V.; Dera, P. K.; Taylor, L. A.

2013-12-01

The recent Martian meteorite fall, Tissint, is a fresh olivine-phyric shergottite, with strong shock features. During our nano-mineralogy investigation of the Tissint meteorite with a combined analytical scanning electron microscope and synchrotron diffraction approach, two new shock-induced minerals have been discovered; these provide new insights into understanding shock conditions and impact processes on Mars. Ahrensite (IMA 2013-028), the Fe-analogue (γ-Fe2SiO4) of ringwoodite, is a new high-pressure mineral identified in Tissint. Both ahrensite and ringwoodite occur in Tissint as fine-grained polycrystalline aggregates in the rims of olivines around some shock-melt pockets. The morphology and texture of these silicate-spinels suggest formation by a solid-state transformation from Fe-rich olivine. Associated with the ahrensite and ringwoodite, inside melt pockets, often resides a thin layer of vitrified silicate-perovskite and magnesio-wüstite or wüstite. Such transitions represent a unique pressure and temperature gradient. Tissintite (IMA 2013-027), (Ca,Na,[])AlSi2O6 with the C2/c clinopyroxene structure, is a new jadeite-like mineral in Tissint. It appears as fine-grained aggregates within plagioclase glass, inside many shock-melt pockets. Both ahrensite and tissintite are high-pressure minerals formed by shock during the impact event(s) on Mars that excavated and ejected the rock off Mars. We will discuss the path of structure analysis for both new-mineral cases. Such novel methodology be utilized for many cases of mineralogical phase identification or structure analysis; this demonstrates how nano-mineralogy can be addressed and how it may play a unique role in meteorite and Mars rock research, in general.

Dynamic observations of vesiculation reveal the role of silicate crystals in bubble nucleation and growth in andesitic magmas

NASA Astrophysics Data System (ADS)

Pleše, P.; Higgins, M. D.; Mancini, L.; Lanzafame, G.; Brun, F.; Fife, J. L.; Casselman, J.; Baker, D. R.

2018-01-01

Bubble nucleation and growth control the explosivity of volcanic eruptions, and the kinetics of these processes are generally determined from examinations of natural samples and quenched experimental run products. These samples, however, only provide a view of the final state, from which the initial conditions of a time-evolving magmatic system are then inferred. The interpretations that follow are inexact due to the inability of determining the exact conditions of nucleation and the potential detachment of bubbles from their nucleation sites, an uncertainty that can obscure their nucleation location - either homogeneously within the melt or heterogeneously at the interface between crystals and melts. We present results of a series of dynamic, real-time 4D X-ray tomographic microscopy experiments where we observed the development of bubbles in crystal bearing silicate magmas. Experimentally synthesized andesitic glasses with 0.25-0.5 wt% H2O and seed silicate crystals were heated at 1 atm to induce bubble nucleation and track bubble growth and movement. In contrast to previous studies on natural and experimentally produced samples, we found that bubbles readily nucleated on plagioclase and clinopyroxene crystals, that their contact angle changes during growth and that they can grow to sizes many times that of the silicate on whose surface they originated. The rapid heterogeneous nucleation of bubbles at low degrees of supersaturation in the presence of silicate crystals demonstrates that silicates can affect when vesiculation ensues, influencing subsequent permeability development and effusive vs. explosive transition in volcanic eruptions.

Characterizing Amorphous Silicates in Extraterrestrial Materials

NASA Astrophysics Data System (ADS)

Fu, X.; Wang, A.; Krawczynski, M. J.

2015-12-01

Amorphous silicates are common in extraterrestrial materials. They are seen in the matrix of carbonaceous chondrites as well as in planetary materials. Tagish Lake is one of the most primitive carbonaceous meteorites in which TEM and XRD analyses found evidence for poorly crystalline phyllosilicate-like species; Raman spectra revealed amorphous silicates with variable degree of polymerization and low crystallinity. On Mars, CheMin discovered amorphous phases in all analyzed samples, and poorly crystalline smectite in mudstone samples. These discoveries pose questions on the crystallinity of phyllosilicates found by remote sensing on Mars, which is directly relevant to aqueous alteration during geologic history of Mars. Our goal is to use spectroscopy to better characterize amorphous silicates. We use three approaches: (1) using silicate glasses synthesized with controlled chemistry to study the effects of silicate polymerization and (2) using phyllosilicates synthesized with controlled hydrothermal treatment to study the effect of crystallinity on vibrational spectroscopy, finally (3) to use the developed correlations in above two steps to study amorphous phases in meteorites, and those found in future missions to Mars. In the 1st step, silicate glasses were synthesized from pure oxides in a range of NBO/T ratios (from 0 to 4). Depending on the targeted NBO/T and composition of mixed oxides, temperatures for each experiment fell in a range from 1260 to 1520 °C, run for ~ 4 hrs. The melt was quenched in liquid N2 or water. Homogeneity of glass was checked under optical microscopy. Raman spectra were taken over 100 spots on small chips free of bubbles and crystals. We have observed that accompanying an increase of NBO/T, there is a strengthening and a position shift of the Raman peak near 1000 cm-1 (Si-Onon-bridging stretching mode), and the weakening of broad Raman peaks near 500 cm-1 (ring breathing mode) and 700cm-1 (Si-Obridging-Si mode). We are building the

Experimental Constraints on Silicic Slab Melt and Depleted Mantle Reaction in the Presence of CO2-H2O: Implications for the Origin of Mid Lithospheric Discontinuity

NASA Astrophysics Data System (ADS)

Saha, S.; Dasgupta, R.; Tsuno, K.

2016-12-01

Seismic shear wave velocity, VS drop (upto 24% and mostly 2-7%) observed globally beneath continents at depths of 60-160 km, known as the Mid Lithospheric Discontinuity (MLD) [e.g., 1], is an enigmatic feature of cratons whose origin is highly debated [e.g., 2, 3]. One of the mechanisms that can explain the MLD is the presence of volatile bearing phases such as partial melts and/or hydrous or carbonate minerals at depths. However, the compositional vector and geodynamic scenario required for their formation and the proportion and composition of infiltrating melt or fluid that may lead to their stability is poorly known at present. We performed high P-T experiments equilibrating a depleted peridotite (Mg# 92) with variable proportion of a H2O-CO2 bearing silicic melt, interaction that could occur during the formation of continents by imbrication of slabs. The first set of experiments were performed with 10 wt.% melt (0.9 wt.% H2O and 0.5 wt.% CO2 in the bulk) at 950-1175 °C at 3 GPa using a piston cylinder and 950-1150 °C at 4 GPa using a multi anvil apparatus. Olivine, opx, cpx, garnet/spinel and phlogopite (5-6%) are present in all runs. Amphibole (3.5-9.5%) is present at 3 GPa and ≤1050 °C. Magnesite ( 1%) is present at ≤1000 °C at 3 and ≤1050 °C at 4 GPa. Trace melt is observed along the grain boundaries above 1000 °C at 3 GPa and 1050 ° C at 4 GPa, respectively. Mineral modes obtained by mass balance calculations, ignoring the presence of melts, were used to calculate VS of the resulting assemblages [4]. The calculated drops in VS at 3 GPa (3.8-4.5%) and 4 GPa (1.6-3.2%) are well within the range of velocity drops for MLDs observed globally. Further experiments on different melt-rock ratios are underway and will constrain how modal proportion of hydrous and carbonate minerals varies as a function of melt:rock ratio and bulk volatile contents. [1] Abt et al., 2010, JGR; [2] Rader et al., 2015, G3; [3] Karato et al., 2015, NatGeo [4] Abers & Hacker

Role of crystallizational differention in the origin of island-arc andesitic melts: evidence from data on melt inclusions and oxygen isotopes

NASA Astrophysics Data System (ADS)

Krasheninnikov, S. P.; Portnyagin, M.; Bindeman, I. N.; Bazanova, L. I.

2012-12-01

Several recent studies of melt inclusions in island-arc rocks revealed a strong bimodality of the melt compositions at the predominance of basic and silicic melts and the scarcity of intermediate melts with SiO2=59-66 wt% (e.g. [1]). These observations were used to interpret the origin of island-arc andesites by magma mingling, crustal assimilation and crystal accumulation rather than by fractional crystallization of basaltic magmas. In this work we addressed the question about the scarcity of andesitic melts in island-arc setting by systematic study of bulk compositions, melt inclusions and oxygen isotopes in minerals from Avachinskiy volcano in Kamchatka. We studied ~500 melt inclusions in 6 different mineral phases (Ol, Cpx, Opx, Pl, Amph, Mt), and concentrated on rapidly-quenched tephra samples from 40 Holocene eruptions of andesites and basaltic andesites. The melt inclusions span a large range of compositions from basalts to rhyolites. In comparison with host bulk tephra samples, melt inclusions tend to have more silicic compositions (up to 10 wt% of SiO2), and this disparity tend to increase with increasing SiO2 content in the host rocks. Both melt inclusion and host rock compositions form trends along the line dividing low- and middle-K island-arc series, and variations of major elements are continuous, without apparent bimodality, which is observed in data set from [1]. The MI statistical distribution is rather three-modal with maxima at ~56-58, ~66 and 74 wt% of SiO2. Much of the major element variability in MI can be explained by fractional crystallization from parental basaltic melts using numerical modeling of crystallization path. Magnetite crystallization starts at ~58 wt% of SiO2 and affects significantly on the evolutional path of melts. Abundant crystallization of magnetite lead to formation of more silica rich coexistent melts and change of crystallizing assemblage occurred at ~60 wt% of SiO2, when Opx replaced Ol, and Amph and Ap become stable

Petrogenesis of Western Cascades Silicic Volcanics Near Sweet Home, Oregon

NASA Astrophysics Data System (ADS)

Cook, G. W.; White, C. M.

2002-12-01

scenario involves some combination of fractional crystallization and assimilation of partial melts of silicic crust.

Water diffusion in silicate glasses: the effect of glass structure

NASA Astrophysics Data System (ADS)

Kuroda, M.; Tachibana, S.

2016-12-01

Water diffusion in silicate melts (glasses) is one of the main controlling factors of magmatism in a volcanic system. Water diffusivity in silicate glasses depends on its own concentration. However, the mechanism causing those dependences has not been fully understood yet. In order to construct a general model for water diffusion in various silicate glasses, we performed water diffusion experiments in silica glass and proposed a new water diffusion model [Kuroda et al., 2015]. In the model, water diffusivity is controlled by the concentration of both main diffusion species (i.e. molecular water) and diffusion pathways, which are determined by the concentrations of hydroxyl groups and network modifier cations. The model well explains the water diffusivity in various silicate glasses from silica glass to basalt glass. However, pre-exponential factors of water diffusivity in various glasses show five orders of magnitude variations although the pre-exponential factor should ideally represent the jump frequency and the jump distance of molecular water and show a much smaller variation. Here, we attribute the large variation of pre-exponential factors to a glass structure dependence of activation energy for molecular water diffusion. It has been known that the activation energy depends on the water concentration [Nowak and Behrens, 1997]. The concentration of hydroxyls, which cut Si-O-Si network in the glass structure, increases with water concentration, resulting in lowering the activation energy for water diffusion probably due to more fragmented structure. Network modifier cations are likely to play the same role as water. With taking the effect of glass structure into account, we found that the variation of pre-exponential factors of water diffusivity in silicate glasses can be much smaller than the five orders of magnitude, implying that the diffusion of molecular water in silicate glasses is controlled by the same atomic process.

Low-(18)O Silicic Magmas: Why Are They So Rare?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balsley, S.D.; Gregory, R.T.

1998-10-15

LOW-180 silicic magmas are reported from only a small number of localities (e.g., Yellowstone and Iceland), yet petrologic evidence points to upper crustal assimilation coupled with fractional crystallization (AFC) during magma genesis for nearly all silicic magmas. The rarity of 10W-l `O magmas in intracontinental caldera settings is remarkable given the evidence of intense 10W-l*O meteoric hydrothermal alteration in the subvolcanic remnants of larger caldera systems. In the Platoro caldera complex, regional ignimbrites (150-1000 km3) have plagioclase 6180 values of 6.8 + 0.1%., whereas the Middle Tuff, a small-volume (est. 50-100 km3) post-caldera collapse pyroclastic sequence, has plagioclase 8]80 valuesmore » between 5.5 and 6.8%o. On average, the plagioclase phenocrysts from the Middle Tuff are depleted by only 0.3%0 relative to those in the regional tuffs. At Yellowstone, small-volume post-caldera collapse intracaldera rhyolites are up to 5.5%o depleted relative to the regional ignimbrites. Two important differences between the Middle Tuff and the Yellowstone 10W-180 rhyolites elucidate the problem. Middle Tuff magmas reached water saturation and erupted explosively, whereas most of the 10W-l 80 Yellowstone rhyolites erupted effusively as domes or flows, and are nearly devoid of hydrous phenocrysts. Comparing the two eruptive types indicates that assimilation of 10W-180 material, combined with fractional crystallization, drives silicic melts to water oversaturation. Water saturated magmas either erupt explosively or quench as subsurface porphyrins bejiire the magmatic 180 can be dramatically lowered. Partial melting of low- 180 subvolcanic rocks by near-anhydrous magmas at Yellowstone produced small- volume, 10W-180 magmas directly, thereby circumventing the water saturation barrier encountered through normal AFC processes.« less

Termochemical Models For Slags and Silicate Melts, Review and Perspectives

NASA Astrophysics Data System (ADS)

Ottonello, G.

Thermochemical models devoted to the comprehension of reactive and mixing properties of silicate melts and slags may be roughly grouped into four main classes: 1) fictive chemical; 2) quasi chemical; 3) fictive structural; 4) polymeric. In the first class we may group the fictive regular mixture approach of Ghiorso and Carmichael [1,2]and its extensions [3-5]and the subregular model of Berman and Brown [6]. To the second class belong the modified quasi chemical approach of Pelton and coworkers [7,8] , and the Kapoor - Froberg cellular model and its extensions [9-11]. The third class has much to share with the second one (and indeed the cellular model could be ascribed to this class as well). To this class belong the "central surround model" of Sastri and Lahiri [12] , the associated solution models of Bjorkman [13], Hastie and coworkers [14]and Goel and coworkers [15], the two sublattice model of Hillert and coworkers [16]and the polynomial expansions of Hoch and Arpshofen [17] . The fourth class encompasses the models of Masson[18-20] , Toop-Samis [21,22]and its extensions [23-25] . The phylosophy beyond each one of the four classes is basically different. Benefits and drawbacks are present in any of them, and applications are often limited to simple systems (or to sufficiently complex systems, in the case of arbitrary deconvolutions of type 1) and to limited P-T ranges. The crucial aspects of the various models will be outlined to some extent. It will be shown that, often, model conflictuality is only appartent and that, in some cases, model failure is unperceived by acritical utilizers. New perspectives in the future research devoted to the comprehension of melt reactivity in compositionally complex systems, with special enphasis on the solubility of gaseous components and unmixing, will be finally discussed. References: [1] Ghiorso M.S. and Carmichael I.S.E. (1980) Contrib. Mineral. Petrol., 71, 323-342. [2] Ghiorso M.S., Carmichael I.S.E., Rivers M.L. and Sack

Melting of the Primitive Mercurian Mantle, Insights into the Origin of Its Surface Composition

NASA Technical Reports Server (NTRS)

Boujibar, A.; Righter, K.; Rapp, J. F.; Ross, D. K.; Pando, K. M.; Danielson, L. R.; Fontaine, E.

2016-01-01

Recent findings of the MESSENGER mission on Mercury have brought new evidence for its reducing nature, widespread volcanism and surface compositional heteregeneity. MESSENGER also provided major elemental ratios of its surface that can be used to infer large-scale differentiation processes and the thermal history of the planet. Mercury is known as being very reduced, with very low Fe-content and high S and alkali contents on its surface. Its bulk composition is therefore likely close to EH enstatite chondrites. In order to elucidate the origin of the chemical diversity of Mercury's surface, we determined the melting properties of EH enstatite chondrites, at pressures between 1 bar and 3 GPa and oxygen fugacity of IW-3 to IW-5, using piston-cylinder experiments, combined with a previous study on EH4 melting at 1 bar. We found that the presence of Ca-rich sulfide melts induces significant decrease of Ca-content in silicate melts at low pressure and low degree of melting (F). Also at pressures lower than 3 GPa, the SiO2-content decreases with F, while it increases at 3 GPa. This is likely due to the chemical composition of the bulk silicate which has a (Mg+Fe+Ca)/Si ratio very close to 1 and to the change from incongruent to congruent melting of enstatite. We then tested whether the various chemical compositions of Mercury's surface can result from mixing between two melting products of EH chondrites. We found that the majority of the geochemical provinces of Mercury's surface can be explained by mixing of two melts, with the exception of the High-Al plains that require an Al-rich source. Our findings indicate that Mercury's surface could have been produced by polybaric melting of a relatively primitive mantle.

The stable Cr isotopic compositions of chondrites and silicate planetary reservoirs

NASA Astrophysics Data System (ADS)

Schoenberg, Ronny; Merdian, Alexandra; Holmden, Chris; Kleinhanns, Ilka C.; Haßler, Kathrin; Wille, Martin; Reitter, Elmar

2016-06-01

The depletion of chromium in Earth's mantle (∼2700 ppm) in comparison to chondrites (∼4400 ppm) indicates significant incorporation of chromium into the core during our planet's metal-silicate differentiation, assuming that there was no significant escape of the moderately volatile element chromium during the accretionary phase of Earth. Stable Cr isotope compositions - expressed as the ‰-difference in 53Cr/52Cr from the terrestrial reference material SRM979 (δ53/52CrSRM979 values) - of planetary silicate reservoirs might thus yield information about the conditions of planetary metal segregation processes when compared to chondrites. The stable Cr isotopic compositions of 7 carbonaceous chondrites, 11 ordinary chondrites, 5 HED achondrites and 2 martian meteorites determined by a double spike MC-ICP-MS method are within uncertainties indistinguishable from each other and from the previously determined δ53/52CrSRM979 value of -0.124 ± 0.101‰ for the igneous silicate Earth. Extensive quality tests support the accuracy of the stable Cr isotope determinations of various meteorites and terrestrial silicates reported here. The uniformity in stable Cr isotope compositions of samples from planetary silicate mantles and undifferentiated meteorites indicates that metal-silicate differentiation of Earth, Mars and the HED parent body did not cause measurable stable Cr isotope fractionation between these two reservoirs. Our results also imply that the accretionary disc, at least in the inner solar system, was homogeneous in its stable Cr isotopic composition and that potential volatility loss of chromium during accretion of the terrestrial planets was not accompanied by measurable stable isotopic fractionation. Small but reproducible variations in δ53/52CrSRM979 values of terrestrial magmatic rocks point to natural stable Cr isotope variations within Earth's silicate reservoirs. Further and more detailed studies are required to investigate whether silicate

New approach on volatile contents determination in silicate melt inclusions: A coupling X-ray microtomography and geochemical approach in Los Humeros caldera complex (Eastern Mexican Volcanic Belt)

NASA Astrophysics Data System (ADS)

Creon, L.; Levresse, G.; Carrasco Nuñez, G.

2016-12-01

Volatile contents and magma degassing behavior are known to affect the style, frequency, and intensity of near-surface magmatic processes. For this reason, much effort have been devoted to characterize the volatile evolution of shallow magmatic systems to better constrain volcanic history. Silicate melt inclusions (SMI) represent samples of melt that were isolated from the bulk magma at depth, thus preserving the PTX conditions of the pre-eruptive material. SMI are often affected by the formation of a bubble after trapping; this is a natural consequence of the PVTX properties of crystal-melt-volatile systems. Previous workers have recognized that bubble formation is an obstacle, which affects the interpretation of SMI trapping conditions based only on analysis of the glass phase. Indeed, they explained that bubbles can contain a significant percentage of the volatiles, particularly for those with low solubility in the melt (e.g. CO2). In this study, we propose to define the pre-eruptive PTX conditions of Los Humeros magma chamber using SMI from the various eruption events within 460 and 30 Ka. An innovative analytical coupling has been used in order to determine: (1) the volume of the SMI glass and bubble, using high resolution 3D X-ray microtomography; (2) the density and composition of the bubbles, using Raman spectroscopy; (3) the volatile element contents in glass, using NanoSIMS; and, (4) the major elements composition of the glass, using EPMA. The recalculated volatile concentrations of the total SMI (glass + bubble), illustrate clearly that the volatile content determinations using only the glass phase, underestimate drastically the total volatile content and therefore induce significant error on the determination of the pre-eruptive volcanic budget and on the constrain on the volcanic and thermal history. This study had moreover highlighted the complex evolution of Los Humeros composite magma chamber and, gave constrains for geothermal exploration purpose.

Redox dependent behaviour of molybdenum during magmatic processes in the terrestrial and lunar mantle: Implications for the Mo/W of the bulk silicate Moon

NASA Astrophysics Data System (ADS)

Leitzke, F. P.; Fonseca, R. O. C.; Sprung, P.; Mallmann, G.; Lagos, M.; Michely, L. T.; Münker, C.

2017-09-01

We present results of high-temperature olivine-melt, pyroxene-melt and plagioclase-melt partitioning experiments aimed at investigating the redox transition of Mo in silicate systems. Data for a series of other minor and trace elements (Sc, Ba, Sr, Cr, REE, Y, HFSE, U, Th and W) were also acquired to constrain the incorporation of Mo in silicate minerals. All experiments were carried out in vertical tube furnaces at 1 bar and temperatures ranging from ca. 1220 to 1300 °C. Oxygen fugacity was controlled via CO-CO2 gas mixtures and varied systematically from 5.5 log units below to 1.9 log units above the fayalite-magnetite-quartz (FMQ) redox buffer thereby covering the range in oxygen fugacities of terrestrial and lunar basalt genesis. Molybdenum is shown to be volatile at oxygen fugacities above FMQ and that its compatibility in pyroxene and olivine increases three orders of magnitude towards the more reducing conditions covered in this study. The partitioning results show that Mo is dominantly tetravalent at redox conditions below FMQ-4 and dominantly hexavalent at redox conditions above FMQ. Given the differences in oxidation states of the terrestrial (oxidized) and lunar (reduced) mantles, molybdenum will behave significantly differently during basalt genesis in the Earth (i.e. highly incompatible; average DMoperidotite/melt ∼ 0.008) and Moon (i.e. moderately incompatible/compatible; average DMoperidotite/melt ∼ 0.6). Thus, it is expected that Mo will strongly fractionate from W during partial melting in the lunar mantle, given that W is broadly incompatible at FMQ-5. Moreover, the depletion of Mo and the Mo/W range in lunar samples can be reproduced by simply assuming a primitive Earth-like Mo/W for the bulk silicate Moon. Such a lunar composition is in striking agreement with the Moon being derived from the primitive terrestrial mantle after core formation on Earth.

Experimental and geochemical evidence for derivation of the El Capitan Granite, California, by partial melting of hydrous gabbroic lower crust

USGS Publications Warehouse

Ratajeski, K.; Sisson, T.W.; Glazner, A.F.

2005-01-01

Partial melting of mafic intrusions recently emplaced into the lower crust can produce voluminous silicic magmas with isotopic ratios similar to their mafic sources. Low-temperature (825 and 850??C) partial melts synthesized at 700 MPa in biotite-hornblende gabbros from the central Sierra Nevada batholith (Sisson et al. in Contrib Mineral Petrol 148:635-661, 2005) have major-element and modeled trace-element (REE, Rb, Ba, Sr, Th, U) compositions matching those of the Cretaceous El Capitan Granite, a prominent granite and silicic granodiorite pluton in the central part of the Sierra Nevada batholith (Yosemite, CA, USA) locally mingled with coeval, isotopically similar quartz diorite through gabbro intrusions (Ratajeski et al. in Geol Soc Am Bull 113:1486-1502, 2001). These results are evidence that the El Capitan Granite, and perhaps similar intrusions in the Sierra Nevada batholith with lithospheric-mantle-like isotopic values, were extracted from LILE-enriched, hydrous (hornblende-bearing) gabbroic rocks in the Sierran lower crust. Granitic partial melts derived by this process may also be silicic end members for mixing events leading to large-volume intermediate composition Sierran plutons such as the Cretaceous Lamarck Granodiorite. Voluminous gabbroic residues of partial melting may be lost to the mantle by their conversion to garnet-pyroxene assemblages during batholithic magmatic crustal thickening. ?? Springer-Verlag 2005.

Metal and polymer melt jet formation by the high-power laser ablation

NASA Astrophysics Data System (ADS)

Yoh, Jack J.; Gojani, Ardian B.

2010-02-01

The laser-induced metal and polymer melt jets are studied experimentally. Two classes of physical phenomena of interest are: first, the process of explosive phase change of laser induced surface ablation and second, the hydrodynamic jetting of liquid melts ejected from a beamed spot. We focus on the dynamic link between these two distinct physical phenomena in a framework of forming and patterning of metallic and polymer jets using a high-power Nd:YAG laser. The microexplosion of ablative spot on a target first forms a pocket of hot liquid melt and then it is followed by a sudden volume change of gas-liquid mixture leading to a pressure-induced spray jet ejection into surrounding medium.

Melt inclusions in veins: linking magmas and porphyry Cu deposits.

PubMed

Harris, Anthony C; Kamenetsky, Vadim S; White, Noel C; van Achterbergh, Esmé; Ryan, Chris G

2003-12-19

At a porphyry copper-gold deposit in Bajo de la Alumbrera, Argentina, silicate-melt inclusions coexist with hypersaline liquid- and vapor-rich inclusions in the earliest magmatic-hydrothermal quartz veins. Copper concentrations of the hypersaline liquid and vapor inclusions reached maxima of 10.0 weight % (wt %) and 4.5 wt %, respectively. These unusually copper-rich inclusions are considered to be the most primitive ore fluid found thus far. Their preservation with coexisting melt allows for the direct quantification of important oreforming processes, including determination of bulk partition coefficients of metals from magma into ore-forming magmatic volatile phases.

Chloride-bearing liquids and partial melting of mantle eclogites: experimental study and application to the diamond-forming processes.

NASA Astrophysics Data System (ADS)

Safonov, Oleg

2010-05-01

Recent studies prove that the partial melting in some eclogite xenoliths in kimberlites is closely related to formation of diamonds in these rocks at 4-6 GPa and 1150-12500C [e.g. 1, 2]. Along with specific mineral assemblages, the products of the eclogite partial melting commonly include relics of potassium-rich silicic melts (45-65 wt. % of SiO2, 4-14 wt. % of K2O and K2O/Na2O > 1.0) [1, 2]. Available experimental data, however, demonstrate that such melts can not be produced by 'dry' or hydrous melting of a common eclogite. It implies that partial melting and conjugate diamond formation in mantle eclogites was triggered by infiltration of potassic fluids/melts. Assemblages of Cl-bearing phases and carbonates in eclogite xenoliths [1], and eclogitic diamonds [3-6] suggest that these agents were chloride-carbonate-H2O melts or/and chloride-H2O-CO2 fluids. In order to characterize interaction of both types of liquids with eclogites and their minerals, experiments in the eclogite-related systems with participation of CaCO3-Na2CO3-KCl-H2O or H2O-CO2-KCl are reviewed. Melting relations in the system eclogite-CaCO3-Na2CO3-KCl-H2O follow the general scheme proposed earlier for chloride-carbonate-silicate systems [7]. Below 12000C, Grt, Cpx and phlogopite (Phl) coexist with LCC only. Formation of Phl and Ca-rich Grt after Cpx indicate active reactions of Cpx with LCC accompanied by CO2 degassing and depletion of the clinopyroxene in jadeite. Subsequent dissolution of silicates in LCC at >1200OC results in formation of potassic silica-undersaturated carbonate and Cl-bearing melt (LCS) (37-40 wt. % of SiO2, 10-12 wt. % of K2O, ~3.5 wt. % of Cl) immiscible with the LCC. Compositional feature of this melt is very comparable to those of low-Mg carbonate-silicate melt inclusions in diamonds [6]. However, it is not relevant to the melt relics preserved in the partially molten eclogite xenoliths. Melting of eclogites with participation of the H2O-CO2-KCl fluid at 5 GPa at 1200

Vapor pressure and vapor fractionation of silicate melts of tektite composition

USGS Publications Warehouse

Walter, Louis S.; Carron, M.K.

1964-01-01

The total vapor pressure of Philippine tektite melts of approximately 70 per cent silica has been determined at temperatures ranging from 1500 to 2100??C. This pressure is 190 ?? 40 mm Hg at 1500??C, 450 ?? 50 mm at 1800??C and 850 ?? 70 mm at 2100?? C. Determinations were made by visually observing the temperature at which bubbles began to form at a constant low ambient pressure. By varying the ambient pressure, a boiling point curve was constructed. This curve differs from the equilibrium vapor pressure curve due to surface tension effects. This difference was evaluated by determining the equilibrium bubble size in the melt and calculating the pressure due to surface tension, assuming the latter to be 380 dyn/cm. The relative volatility from tektite melts of the oxides of Na, K, Fe, Al and Si has been determined as a function of temperature, total pressure arid roughly, of oxygen fugacity. The volatility of SiO2 is decreased and that of Na2O and K2O is increased in an oxygen-poor environment. Preliminary results indicate that volatilization at 2100??C under atmospheric pressure caused little or no change in the percentage Na2O and K2O. The ratio Fe3 Fe2 of the tektite is increased in ambient air at a pressure of 9 ?? 10-4 mm Hg (= 106.5 atm O2, partial pressure) at 2000??C. This suggests that tektites were formed either at lower oxygen pressures or that they are a product of incomplete oxidation of parent material with a still lower ferricferrous ratio. ?? 1964.

Composition of primary fluid and melt inclusions in regenerated olivines from hypabyssal kimberlites of the Malokuonapskaya pipe (Yakutia)

NASA Astrophysics Data System (ADS)

Tomilenko, A. A.; Kuzmin, D. V.; Bulbak, T. A.; Timina, T. Yu.; Sobolev, N. V.

2015-11-01

The primary fluid and melt inclusions in regenerated zonal crystals of olivine from kimberlites of the Malokuonapskaya pipe were first examined by means of microthermometry, optic and scanning electron microscopy, and Raman spectroscopy. The high-pressure genesis of homogenous central parts of the olivines was revealed, probably under intense metasomatism at early hypogene stages with subsequent regeneration in the kimberlitic melt. The olivine crystals were regenerated from silicate-carbonate melts at about 1100°C. The composition of the kimberlitic melt was changed by way of an increase in the calcium content.

MELTS_Excel: A Microsoft Excel-based MELTS interface for research and teaching of magma properties and evolution

NASA Astrophysics Data System (ADS)

Gualda, Guilherme A. R.; Ghiorso, Mark S.

2015-01-01

thermodynamic modeling software MELTS is a powerful tool for investigating crystallization and melting in natural magmatic systems. Rhyolite-MELTS is a recalibration of MELTS that better captures the evolution of silicic magmas in the upper crust. The current interface of rhyolite-MELTS, while flexible, can be somewhat cumbersome for the novice. We present a new interface that uses web services consumed by a VBA backend in Microsoft Excel©. The interface is contained within a macro-enabled workbook, where the user can insert the model input information and initiate computations that are executed on a central server at OFM Research. Results of simple calculations are shown immediately within the interface itself. It is also possible to combine a sequence of calculations into an evolutionary path; the user can input starting and ending temperatures and pressures, temperature and pressure steps, and the prevailing oxidation conditions. The program shows partial updates at every step of the computations; at the conclusion of the calculations, a series of data sheets and diagrams are created in a separate workbook, which can be saved independently of the interface. Additionally, the user can specify a grid of temperatures and pressures and calculate a phase diagram showing the conditions at which different phases are present. The interface can be used to apply the rhyolite-MELTS geobarometer. We demonstrate applications of the interface using an example early-erupted Bishop Tuff composition. The interface is simple to use and flexible, but it requires an internet connection. The interface is distributed for free from http://melts.ofm-research.org.

On the formation of continental silicic melts in thermochemical mantle convection models: implications for early Earth

NASA Astrophysics Data System (ADS)

van Thienen, P.; van den Berg, A. P.; Vlaar, N. J.

2004-12-01

Important constituents of Archean cratons, formed in the early and hot history of the Earth, are Tonalite-Trondhjemite-Granodiorite (TTG) plutons and greenstone belts. The formation of these granite-greenstone terrains is often ascribed to plate-tectonic processes. Buoyancy considerations, however, do not allow plate tectonics to take place in a significantly hotter Earth. We therefore propose an alternative mechanism for the coeval and proximate production of TTG plutons and greenstone-like crustal successions. That is, when a locally anomalously thick basaltic crust has been produced by continued addition of extrusive or intrusive basalts due to partial melting of the underlying convecting mantle, the transition of a sufficient amount of basalt in the lower crust to eclogite may trigger a resurfacing event, in which a complete crustal section of over 1000 km long sinks into the mantle in less than 2 million years. Pressure release partial melting in the complementary upwelling mantle produces large volumes of basaltic material replacing the original crust. Partial melting at the base of this newly produced crust may generate felsic melts which are added as intrusives and/or extrusives to the generally mafic crustal succession, adding to what resembles a greenstone belt. Partial melting of metabasalt in the sinking crustal section produces a significant volume of TTG melt which is added to the crust directly above the location of 'subduction', presumably in the form of a pluton. This scenario is self-consistently produced by numerical thermochemical mantle convection models, presented in this paper, including partial melting of mantle peridotite and crustal (meta)basalt. The metamorphic p, T conditions under which partial melting of metabasalt takes place in this scenario are consistent with geochemical trace element data for TTGs, which indicate melting under amphibolite rather than eclogite facies. Other geodynamical settings which we have also investigated

Hydrophobic pocket targeting probes for enteroviruses

NASA Astrophysics Data System (ADS)

Martikainen, Mari; Salorinne, Kirsi; Lahtinen, Tanja; Malola, Sami; Permi, Perttu; Häkkinen, Hannu; Marjomäki, Varpu

2015-10-01

Visualization and tracking of viruses without compromising their functionality is crucial in order to understand virus targeting to cells and tissues, and to understand the subsequent subcellular steps leading to virus uncoating and replication. Enteroviruses are important human pathogens causing a vast number of acute infections, and are also suggested to contribute to the development of chronic diseases like type I diabetes. Here, we demonstrate a novel method to target site-specifically the hydrophobic pocket of enteroviruses. A probe, a derivative of Pleconaril, was developed and conjugated to various labels that enabled the visualization of enteroviruses under light and electron microscopes. The probe mildly stabilized the virus particle by increasing the melting temperature by 1-3 degrees, and caused a delay in the uncoating of the virus in the cellular endosomes, but could not however inhibit the receptor binding, cellular entry or infectivity of the virus. The hydrophobic pocket binding moiety of the probe was shown to bind to echovirus 1 particle by STD and tr-NOESY NMR methods. Furthermore, binding to echovirus 1 and Coxsackievirus A9, and to a lesser extent to Coxsackie virus B3 was verified by using a gold nanocluster labeled probe by TEM analysis. Molecular modelling suggested that the probe fits the hydrophobic pockets of EV1 and CVA9, but not of CVB3 as expected, correlating well with the variations in the infectivity and stability of the virus particles. EV1 conjugated to the fluorescent dye labeled probe was efficiently internalized into the cells. The virus-fluorescent probe conjugate accumulated in the cytoplasmic endosomes and caused infection starting from 6 hours onwards. Remarkably, before and during the time of replication, the fluorescent probe was seen to leak from the virus-positive endosomes and thus separate from the capsid proteins that were left in the endosomes. These results suggest that, like the physiological hydrophobic content

The distribution of H2O between silicate melt and nominally anhydrous peridotite and the onset of hydrous melting in the deep upper mantle

NASA Astrophysics Data System (ADS)

Novella, Davide; Frost, Daniel J.; Hauri, Erik H.; Bureau, Helene; Raepsaet, Caroline; Roberge, Mathilde

2014-08-01

The partitioning of H2O between a mantle peridotite assemblage and low degree hydrous melt has been investigated at 6 GPa (corresponding to ∼180 km depth) at a temperature of 1400 °C. Peridotite mineral phases were analysed from 6 melting experiments performed in a natural chemical system. The experiments contained ∼80 wt% of a low degree hydrous melt that was obtained through a series of experiments where the melt composition was iteratively adjusted until saturation with the appropriate peridotite assemblage was achieved. The melt is fluid-undersaturated at the conditions of the experiment. Ion microprobe measurements of the mineral phases indicate olivine H2O concentrations of 434±61 ppm wt and average clinopyroxene (cpx) concentrations of 1268±173 ppm wt H2O. Orthopyroxene (opx) and garnet contain 700±46 ppm wt and 347±83 ppm wt H2O, respectively. The H2O content of the hydrous melts was determined by mass balance to be 11±0.5 wt% H2O. H2O partition coefficients between minerals and melt (DH2Omin/melt=XH2Omin/XH2Omelt) are 0.0040±0.0006 for olivine, 0.0064±0.0004 for opx, 0.0115±0.0016 for cpx and 0.0032±0.0008 for garnet. Using the determined H2O partition coefficients the onset and extent of melting at conditions equivalent to 180 km below mid-ocean ridges was determined as a function of mantle H2O content. Current estimates for the H2O content of the depleted mantle (50-200 ppm wt H2O) are insufficient to induce mantle melting at this depth, which requires ∼700 ppm wt H2O to produce 0.1% melting and 1600 ppm wt H2O for 1% melting, along an adiabat with a potential temperature of 1327 °C. Melting can occur at these conditions within the mantle source of ocean island basalts, which are estimated to contain up to 900 ppm wt H2O. If adiabatic temperatures are 200 °C higher within such plume related sources, then melt fractions of over 1% can be reached at 180 km depth. In addition, a model for the distribution of H2O between peridotite mineral

Sulfide in the core and the Nd isotopic composition of the silicate Earth

NASA Astrophysics Data System (ADS)

McCoy-West, A.; Millet, M. A.; Nowell, G. M.; Wohlers, A.; Wood, B. J.; Burton, K. W.

2016-12-01

The chemical composition of the Earth is traditionally explained in terms of evolution from a solar-like composition, similar to that found in primitive chondritic meteorites. It now appears, however, that the silicate Earth is not chondritic, but depleted in incompatible elements and a resovable 20 ppm excess is observed in 142Nd relative to chondirtes [1, 2]. This anomaly requires a process that occurred within 30 Myr of solar system formation and has been variably ascribed to: a complementary enriched reservoir in the deep Earth [1]; loss to space through collisional erosion [3]; or the inhertence of nucleosynthetic anomalies [4]. Sulfide in the core may provide a reservoir capable of balancing the composition of the silicate Earth. Recent experimental work suggests that the core contains a significant proportion of sulfide, added during the final stages of accretion and new data suggests that at high pressures sulfide can incorporate a substantial amount of refractory lithophile and heat-producing elements [5]. The drawback of the short-lived 146Sm-142Nd radiogenic isotope system is that it is not possible to distinguish between fractionations of Sm/Nd that occurs during silicate melting or segregation of a sulfide-melt. Neodymium stable isotopes have the potential to provide just such a tracer of sulfide segregation, because there is a significant contrast in bonding environment between sulfide and silicate, where heavy isotopes should be preferentially incorporated into high force-constant bonds involving REE3+ (i.e. the silicate mantle). Preliminary data indicate that mantle rocks do indeed possess heavier 146Nd/144Nd values than chondritic meteorites by 0.3 ‰, consistent with the removal of light Nd into sulfide in the core, driving the residual mantle to heavier values. Overall, our isotope and elemental data indicate that the rare earths and other incompatible elements are substantially incorporated into sulfide. While Nd stable isotope data for

The opportunity of silicate product manufacturing with simultaneous pig iron reduction from slag technogenic formations

NASA Astrophysics Data System (ADS)

Sheshukov, O. Yu.; Lobanov, D. A.; Mikheenkov, M. A.; Nekrasov, I. V.; Egiazaryan, D. K.

2017-09-01

There are two main kinds of slag in modern steelmaking industry: the electric arc furnace slag (EAF slag) and ladle furnace slag (LF slag). The all known slag processing schemes provide the iron-containing component reduction while silicate component stays unprocessed. On the contrary, the silicate processing schemes doesn't provide the utilization of the iron-containing component. The present-day situation doesn't solve the problem of total slag utilization. The aim of this work is to investigate the opportunity of silicate product obtaining with simultaneous pig iron reduction from EAF and LF slags. The tests are conducted by the method of simplex-lattice design. The test samples are heated and melted under reductive conditions, slowly cooled and then analyzed by XRD methods. The experiment results prove the opportunity: the Portland clinker and pig iron can be simultaneously produced on the basis of these slags with a limestone addition.

Mixing Silicate Melts with High Viscosity Contrast by Chaotic Dynamics: Results from a New Experimental Device

NASA Astrophysics Data System (ADS)

de Campos, Cristina; Perugini, Diego; Ertel-Ingrisch, Werner; Dingwell, Donald B.; Poli, Giampiero

2010-05-01

A new experimental device has been developed to perform chaotic mixing between high viscosity melts under controlled fluid-dynamic conditions. The apparatus is based on the Journal Bearing System (JBS). It consists of an outer cylinder hosting the melts of interest and an inner cylinder, which is eccentrically located. Both cylinders can be independently moved to generate chaotic streamlines in the mixing system. Two experiments were performed using as end-members different proportions of a peralkaline haplogranite and a mafic melt, corresponding to the 1 atm eutectic composition in the An-Di binary system. The two melts were stirred together in the JBS for ca. two hours, at 1,400° C and under laminar fluid dynamic condition (Re of the order of 10-7). The viscosity ratio between the two melts, at the beginning of the experiment, was of the order of 103. Optical analyses of experimental samples revealed, at short length scale (of the order of μm), a complex pattern of mixed structures. These consisted of an intimate distribution of filaments; a complex inter-fingering of the two melts. Such features are typically observed in rocks thought to be produced by magma mixing processes. Stretching and folding dynamics between the melts induced chaotic flow fields and generated wide compositional interfaces. In this way, chemical diffusion processes become more efficient, producing melts with highly heterogeneous compositions. A remarkable modulation of compositional fields has been obtained by performing short time-scale experiments and using melts with a high viscosity ratio. This indicates that chaotic mixing of magmas can be a very efficient process in modulating compositional variability in igneous systems, especially under high viscosity ratios and laminar fluid-dynamic regimes. Our experimental device may replicate magma mixing features, observed in natural rocks, and therefore open new frontiers in the study of this important petrologic and volcanological process.

Valence State Partitioning of Cr and V Between Olivine-Melt and Pyroxene-Melt in Experimental Basalts of a Eucritic Composition

NASA Technical Reports Server (NTRS)

Karner, J. M.; Jones, J. H.; Le, L.

2017-01-01

The partitioning of multivalent elements in basaltic systems can elucidate the oxygen fugacity (fO2) conditions under which basalts formed on planetary bodies (Earth, Moon, Mars, asteroids). Chromium and V are minor and trace elements in basaltic melts, partition into several minerals that crystallize from basaltic melts, exist in multiple valence states at differing fO2 conditions, and can therefore be used as oxybarometers for basaltic melts. Chromium is mostly 3+ in terrestrial basaltic melts at relatively high fO2 values (= IW+3.5), and mostly 2+ in melts at low fO2 values (= IW-1), such as those on the Moon and some asteroids. At intermediate fO2s, (i.e., IW-1 to IW+3.5), basaltic melts contain both Cr3+ and Cr2+. Vanadium in basaltic melts is mostly 4+ at high fO2, mostly 3+ at low fO2, and a mix of V3+ and V4+ at intermediate fO2 con-ditions. Understanding the partitioning of Cr and V into silicate phases with changing fO2 is therefore critical to the employment of Cr and V oxybarometers. In this abstract we examine the equilibrium partitioning of Cr and V between olivine/melt and pyroxene/melt in experimental charges of a eucritic composition produced at differing fO2 conditions. This study will add to the experimental data on DCr and DV (i.e., olivine/melt, pyroxene/melt) at differing fO2, and in turn these D values will be used to assess the fO2 of eucrite basalts and perhaps other compositionally similar planetary basalts.

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten

2013-10-01

Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to <1400 °C, while variable Fe-oxide contents were used to vary oxygen fugacity in graphite and MgO capsules. Isotopic analyses were performed using a double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

Study of diffusion and local structure of sodium-silicate liquid: the molecular dynamic simulation

NASA Astrophysics Data System (ADS)

Hung, Pham Khac; Noritake, Fumiya; San, Luyen Thi; Van, To Ba; Vinh, Le The

2017-10-01

A systematic analysis on sodium-silicate melt with various silica contents was carried out. The simulation revealed two diffusion mechanisms occurred in the melt: the bond-breaking and hopping between sites. The local structure was analyzed through T-simplexes. It was revealed that T-clusters have a non-spherical shape and represent the diffusion channel, in which Na atoms are dominant, but no any O atoms are located. The SiO2-poor melt acquires a long channel. In contrast, the SiO2-rich melt consists of unconnected short channels. The simulation also revealed the immobile and mobile regions which differ in local structure and constituent composition. We propose a new CL-function to characterizing the spatial distribution of different atom component. The spatial distribution of mobile and immobile atoms is found quite different. In particular, the immobile atoms are concentrated in high-density regions possessing very large density of immobile atoms. The spatial distribution of mobile atoms in contrast is more homogeneous.

Clinopyroxene dissolution in basaltic melt

NASA Astrophysics Data System (ADS)

Chen, Yang; Zhang, Youxue

2009-10-01

The history of magmatic systems may be inferred from reactions between mantle xenoliths and host basalt if the thermodynamics and kinetics of the reactions are quantified. To study diffusive and convective clinopyroxene dissolution in silicate melts, diffusive clinopyroxene dissolution experiments were conducted at 0.47-1.90 GPa and 1509-1790 K in a piston-cylinder apparatus. Clinopyroxene saturation is found to be roughly determined by MgO and CaO content. The effective binary diffusivities, DMgO and DCaO, and the interface melt saturation condition, C0MgO×C0CaO, are extracted from the experiments. DMgO and DCaO show Arrhenian dependence on temperature. The pressure dependence is small and not resolved within 0.47-1.90 GPa. C0MgO×C0CaO in the interface melt increases with increasing temperature, but decreases with increasing pressure. Convective clinopyroxene dissolution, where the convection is driven by the density difference between the crystal and melt, is modeled using the diffusivities and interface melt saturation condition. Previous studies showed that the convective dissolution rate depends on the thermodynamics, kinetics and fluid dynamics of the system. Comparing our results for clinopyroxene dissolution to results from a previous study on convective olivine dissolution shows that the kinetic and fluid dynamic aspects of the two minerals are quite similar. However, the thermodynamics of clinopyroxene dissolution depends more strongly on the degree of superheating and composition of the host melt than that of olivine dissolution. The models for clinopyroxene and olivine dissolution are tested against literature experiments on mineral-melt interaction. They are then applied to previously proposed reactions between Hawaii basalts and mantle minerals, mid-ocean ridge basalts and mantle minerals, and xenoliths digestion in a basalt at Kuandian, Northeast China.

The geometry and volume of melt beneath Ethiopia

NASA Astrophysics Data System (ADS)

Kendall, J. M.; Hammond, J. O. S.

2016-12-01

A range of seismic measurements can be used to map melt distribution in the crust and uppermost mantle. These include seismic P- and S-wave velocities derived from surface- and body-wave tomography, Vp/Vs ratios obtained from receiver functions, and estimates of seismic anisotropy and attenuation. The most obvious melt parameter that seismic data might be sensitive to is volume fraction. However, such data are more sensitive to the aspect ratio of melt inclusions, which is controlled by the melt wetting angle or in other words the shape of the melt inclusion. To better understand this we perform numerical modelling, varying the shape and amount of melt, to show how various seismic phases are effected by melt. To consider the effects on seismic anisotropy we assume that the melt can be stored in pockets of melt that are either horizontally or vertically aligned (e.g., sills versus dykes). We then consider a range of seismic observations from the rifting environment of Ethiopia. Recent studies of P- and S-wave tomography, Rayleigh and Love waves, and Pn or wide angle P-wave refractions provide provide complimentary constraints on melt volume, orientation and inclusion aspect ratio. Furthermore, receiver functions and shear-wave splitting in body waves show strong anisotropy in this region and can be used to constrain the strike of vertically-aligned partial melt. We show that melt in the mantle beneath Ethiopia is likely stored in low aspect ratio disk-like inclusions, suggesting melt is not in textural equilibrium. We estimate that 2-7% vertically aligned melt is stored beneath the Main Ethiopian Rift, >6% horizontally and vertically aligned melt is stored beneath the Afar-region of the Red Sea Rift and 1-6% horizontally aligned melt is stored beneath the Danakil microplate. This supports ideas of strong shear-derived segregation of melt in narrow parts of the rift and large volumes of melt beneath Afar.

Making Earth's earliest continental crust - an analogue from voluminous Neogene silicic volcanism in NE-Iceland

NASA Astrophysics Data System (ADS)

Berg, Sylvia E.; Troll, Valentin R.; Burchardt, Steffi; Riishuus, Morten S.; Deegan, Frances M.; Harris, Chris; Whitehouse, Martin J.; Gústafsson, Ludvik E.

2014-05-01

Borgarfjörður Eystri in NE-Iceland represents the second-most voluminous exposure of silicic eruptive rocks in Iceland and is a superb example of bimodal volcanism (Bunsen-Daly gap), which represents a long-standing controversy that touches on the problem of crustal growth in early Earth. The silicic rocks in NE-Iceland approach 25 % of the exposed rock mass in the region (Gústafsson et al., 1989), thus they significantly exceed the usual ≤ 12 % in Iceland as a whole (e.g. Walker, 1966; Jonasson, 2007). The origin, significance, and duration of the voluminous (> 300 km3) and dominantly explosive silicic activity in Borgarfjörður Eystri is not yet constrained (c.f. Gústafsson, 1992), leaving us unclear as to what causes silicic volcanism in otherwise basaltic provinces. Here we report SIMS zircon U-Pb ages and δ18O values from the region, which record the commencement of silicic igneous activity with rhyolite lavas at 13.5 to 12.8 Ma, closely followed by large caldera-forming ignimbrite eruptions from the Breiðavik and Dyrfjöll central volcanoes (12.4 Ma). Silicic activity ended abruptly with dacite lava at 12.1 Ma, defining a ≤ 1 Myr long window of silicic volcanism. Magma δ18O values estimated from zircon range from 3.1 to 5.5 (± 0.3; n = 170) and indicate up to 45 % assimilation of a low-δ18O component (e.g. typically δ18O = 0 ‰, Bindeman et al., 2012). A Neogene rift relocation (Martin et al., 2011) or the birth of an off-rift zone to the east of the mature rift associated with a thermal/chemical pulse in the Iceland plume (Óskarsson & Riishuus, 2013), likely brought mantle-derived magma into contact with fertile hydrothermally-altered basaltic crust. The resulting interaction triggered large-scale crustal melting and generated mixed-origin silicic melts. Such rapid formation of silicic magmas from sustained basaltic volcanism may serve as an analogue for generating continental crust in a subduction-free early Earth (e.g. ≥ 3 Ga, Kamber et

Characterization of layered silicate-reinforced blends of thermoplastic starch (TPS) and poly(butylene adipate-co-terephthalate).

PubMed

Lendvai, László; Apostolov, Anton; Karger-Kocsis, József

2017-10-01

A two-step melt blending procedure was used to produce binary systems composed of thermoplastic starch (TPS) and poly(butylene adipate-co-terephthalate) (PBAT). To improve the properties of the blends, two different layered silicates, viz. bentonite (BT) and organically modified montmorillonite (oMMT) were incorporated. First, TPS and its layered silicate nanocomposites were prepared via extrusion compounding during which starch was plasticized with glycerol and water. In the second step, PBAT was added to TPS/layered silicate to produce blends in a batch-type mixer. Mechanical and thermal properties were determined. The blends showed acceptable ductility over 50wt.% PBAT content, although at the cost of strength and stiffness. By contrast to oMMT the BT became intercalated in TPS and TPS/PBAT blends. The reinforcing effect of BT and oMMT was most prominent for the glassy states of both TPS and TPS/PBAT blends. Thermal, and thermooxidative properties were not significantly affected by the presence of layered silicates. Copyright © 2017 Elsevier Ltd. All rights reserved.

Loss of iron to gold capsules in rock-melting experiments

USGS Publications Warehouse

Ratajeski, K.; Sisson, T.W.

1999-01-01

Gold is used widely for capsules in high-temperature rock-melting studies because it is generally thought to absorb negligible Fe from silicate samples. However, we observed significant losses of Fe from fluid-absent melting experiments on hornblende gabbros at 800-975 ??C and 8 kbar, using standard piston-cylinder techniques. The extent of Fe loss from the sample is dependent on the relative masses of the sample and the capsule. Low sample to capsule mass ratios (~0.04) lead to the highest Fe losses (32-49% relative). Concentrations of Fe in silicate melt and used gold capsules define an apparent equilibrium constant (K') that follows a linear 1n K' vs. 1/T relation (at an estimated log f(O)(2) of QFM-1). The apparent equilibrium constant is used to make limiting upper estimates on the amount of Fe that could be lost during rock-melting experiments for a range of f(O)(2) and sample to capsule mass ratios. At high f(O)(2) (NNO + 2), loss of Fe to gold is negligible (<2% relative) for a wide range of sample to capsule mass ratios. At an f(O)(2) of NNO, Fe loss can be kept to <10% relative by using a sample to capsule mass ratio of 0.2 or greater. At low f(O)(2) (QFM-1), presaturating the Au with Fe would be necessary to ensure that Fe losses remained <10% relative. Fe loss can compromise experimental results for small samples run at low f(O)(2) conditions, be they buffered, imposed by the pressure media, or produced by intrinsically reduced (graphitic) starting materials.

Experimental determination of the partitioning of gallium between solid iron metal and synthetic basaltic melt Electron and ion microprobe study

NASA Technical Reports Server (NTRS)

Drake, M. J.; Newsom, H. E.; Reed, S. J. B.; Enright, M. C.

1984-01-01

The distribution of Ga between solid Fe metal and synthetic basaltic melt is investigated experimentally at temperatures of 1190 and 1330 C, and over a narrow range of oxygen fugacities. Metal-silicate reversal experiments were conducted, indicating a close approach to equilibrium. The analysis of the partitioned products was performed using electron and ion microprobes. At one bar total pressure, the solid metal/silicate melt partition coefficient D(Ga) is used to evaluate metal-silicate fractionation processes in the earth, moon, and Eucrite Parent Body (EPB). It is found that the depletion of Ga abundances in the EPB is due to the extraction of Ga into a metallic core. Likewise, the depletion of Ga in the lunar mantle is consistent with the extraction of Ga into a smaller lunar core if Ga was originally present in a subchondritic concentration. The relatively high Ga abundances in the earth's mantle are discussed, with reference to several theoretical models.

Investigation of the noble gas solubility in H 2O-CO 2 bearing silicate liquids at moderate pressure II: the extended ionic porosity (EIP) model

NASA Astrophysics Data System (ADS)

Nuccio, P. M.; Paonita, A.

2000-12-01

A semi-theoretical model is proposed to predict partitioning of noble gases between any silicate liquid and a H 2O-CO 2 gas phase with noble gas as a minor component, in a large range of pressures (at least up to 300 MPa). The model is based on the relationship between the concentration of dissolved noble gas and ionic porosity of the melt, found by Carroll and Stolper [Geochim. Cosmochim. Acta 57 (1993) 5039-5051] for H 2O-CO 2 free melts. It evaluates the effect of dissolved H 2O and CO 2 on the melt ionic porosity and, consequently on Henry's constants of noble gases. The fugacities of the noble gases in the H 2O-CO 2-noble gas mixtures are also considered in our equilibrium calculations of dissolved gas by using a modified Redlich-Kwong equation of state for the H 2O-CO 2-noble gas system. The formulated model (referred to as the extended ionic porosity model) clearly predicts a positive dependence of noble gas solubility on dissolved H 2O in melt, which becomes negligible when water concentration is higher than 3 wt%. Oppositely, noble gas solubility decreases as a consequence of increasing CO 2 in both basaltic and rhyolitic melts. The increase of noble gas solubility as a consequence of H 2O addition to the melt grows exponentially with the increase of the noble gas atomic size. As a result, although xenon solubility is much lower than the helium solubility in anhydrous melts, they become almost comparable at several percent of dissolved H 2O in the melt. On this basis, an exponential augmentation of the number of large free spaces in silicate liquid can be inferred in relation to increasing dissolved H 2O. Comparison between our predicted values and available experimental data [A. Paonita et al., Earth Planet. Sci. Lett. 181 (2000) 595-604] shows good agreement. At present, the EIP model is the unique tool which predicts how the main volatiles in magmatic systems affect the noble gas solubility in silicate melts, therefore it should be taken into account

Pressure-induced coordination changes in alkali-germanate melts - An in situ spectroscopic investigation

NASA Technical Reports Server (NTRS)

Farber, Danial L.; Williams, Quentin

1992-01-01

The structure of liquid Na2Ge2O5-H2O, a silicate melt analog, has been studied with Raman spectroscopy to pressures of 2.2 gigapascals. Upon compression, a peak near more than 240 wavenumbers associated with octahedral GeO6 groups grows relative to a peak near 500 wavenumbers associated with tetrahedral GeO4 groups. This change corresponds to an increase in octahedral germanium in the liquid from near 0 percent at ambient pressures to more than 50 percent at a pressure of 2.2 gigapascals. Silicate liquids pausibly undergo similar coordination changes at depth in the earth. Such structural changes may generate decreases in the fusion slopes of silicates at high pressures as well as neutrally buoyant magmas within the transition zone of the earth's mantle.

Visualizing electron pockets in cuprate superconductors

NASA Astrophysics Data System (ADS)

Das, Tanmoy; Markiewicz, R. S.; Bansil, A.; Balatsky, A. V.

2012-06-01

Fingerprints of the electron pocket in cuprates have been obtained only in numerous magnetotransport measurements, but its absence in spectroscopic observations poses a long-standing mystery. We develop a theoretical tool to provide ways to detect electron pockets via spectroscopies including scanning tunneling microscopy (STM) spectra, inelastic neutron scattering (INS), and angle-resolved photoemission spectroscopy (ARPES). We show that the quasiparticle-interference (QPI) pattern, measured by STM, shows an additional seven q vectors associated with the scattering on the electron pocket than that on the hole pocket. Furthermore, the Bogolyubov quasiparticle scatterings of the electron pocket lead to a second magnetic resonance mode in the INS spectra at a higher resonance energy. Finally, we reanalyze some STM, INS, and ARPES experimental data of several cuprates which dictates the direct fingerprints of electron pockets in these systems.

Solubility of tungsten in a haplobasaltic melt as a function of temperature and oxygen fugacity

NASA Astrophysics Data System (ADS)

Ertel, W.; O'Neill, H. St. C.; Dingwell, D. B.; Spettel, B.

1996-04-01

The solubility of tungsten (W) in a haplobasaltic melt has been determined as a function of oxygen fugacity in the temperature range 1300-1500°C using the mechanically assisted equilibrium technique of Dingwell et al. (1994), and at 1600-1700°C by the wire loop method. Quenched samples were analysed for W by using ICP-AES as well as INAA, and sample major element compositions were checked by electron microprobe. W concentrations ranged from 20 ppm to 17 wt%, and the solution of WO 2 in the melt may be described by Henry's Law up to remarkably high concentrations (e.g., 14 wt% at 1500°C). W dissolves in the melt with a quadrivalent (4+) formal oxidation state over the entire range of oxygen fugacity and temperature investigated. The solubility of W decreases strongly with increasing temperature at constant oxygen fugacity. The solubility data have been used to calculate trace distribution coefficients for W between Fe-rich metal and silicate melt, using literature values for the activity coefficient of W in liquid Fe. Comparison of our data with the distribution coefficients for Mo calculated from the analogous Mo solubility data of Holzheid et al. (1994) shows that the ratio of the metal-silicate distribution coefficient DMomet/sil/ DWmet/sil remains very high (~10 3) at all T-fO 2 conditions. However, in the Earth's mantle, Mo is relatively more depleted than W only by a factor of three. The relative abundances of W and Mo in the Earth's mantle cannot, therefore, be explained by core formation from a homogeneously accreted Earth whatever the temperature at which metal/silicate equilibrium may have ocurred might have been. Their abundances may be quantitatively accounted for by a heterogeneous accretion model such as that of O'Neill (1991).

Hydrophobic pocket targeting probes for enteroviruses.

PubMed

Martikainen, Mari; Salorinne, Kirsi; Lahtinen, Tanja; Malola, Sami; Permi, Perttu; Häkkinen, Hannu; Marjomäki, Varpu

2015-11-07

Visualization and tracking of viruses without compromising their functionality is crucial in order to understand virus targeting to cells and tissues, and to understand the subsequent subcellular steps leading to virus uncoating and replication. Enteroviruses are important human pathogens causing a vast number of acute infections, and are also suggested to contribute to the development of chronic diseases like type I diabetes. Here, we demonstrate a novel method to target site-specifically the hydrophobic pocket of enteroviruses. A probe, a derivative of Pleconaril, was developed and conjugated to various labels that enabled the visualization of enteroviruses under light and electron microscopes. The probe mildly stabilized the virus particle by increasing the melting temperature by 1-3 degrees, and caused a delay in the uncoating of the virus in the cellular endosomes, but could not however inhibit the receptor binding, cellular entry or infectivity of the virus. The hydrophobic pocket binding moiety of the probe was shown to bind to echovirus 1 particle by STD and tr-NOESY NMR methods. Furthermore, binding to echovirus 1 and Coxsackievirus A9, and to a lesser extent to Coxsackie virus B3 was verified by using a gold nanocluster labeled probe by TEM analysis. Molecular modelling suggested that the probe fits the hydrophobic pockets of EV1 and CVA9, but not of CVB3 as expected, correlating well with the variations in the infectivity and stability of the virus particles. EV1 conjugated to the fluorescent dye labeled probe was efficiently internalized into the cells. The virus-fluorescent probe conjugate accumulated in the cytoplasmic endosomes and caused infection starting from 6 hours onwards. Remarkably, before and during the time of replication, the fluorescent probe was seen to leak from the virus-positive endosomes and thus separate from the capsid proteins that were left in the endosomes. These results suggest that, like the physiological hydrophobic content

Chronology and Petrology of Silicates From IIE Iron Meteorites: Evidence of a Complex Parent Body Evolution

NASA Technical Reports Server (NTRS)

Bogard, Donald D.; Garrison, Daniel H.; McCoy, Timothy J.

1999-01-01

IIE iron meteorites contain silicate inclusions whose characteristics suggest a parent body similar to that of H-chondrites. However, these silicates show a wide range of alteration, ranging from Netschadvo and Techado, whose inclusions are little altered. to highly differentiated silicates like-those in Kodaikanal, Weekeroo Station and Colomera, which have lost metal and sulfur and are enriched in feldspar. We find these inclusions to show varying degrees of shock alteration. Because only a limited amount of data on - isotopic ages of HE silicates were available, we made Ar-39 - Ar-40 age determinations of Watson, Techado, miles Colomera, and Sombrerete. Watson has an Ar-Ar age of 3.653 +/- 0.012 Gyr, similar to previously reported ages for Kodaikanal and Netschadvo. We suggest that the various determined radiometric ages of these three meteorites were probably reset by a common impact event. The space exposure ages for these three meteorites are also similar to each other and are considerably younger than exposure ages of other IIEs. Ar-39 - Ar-40 ages inferred for the other four meteorites analyzed are considerably older than Watson and are: Techado =4.49 +/- 0.01 Gyr, Miles =4.412 +/- 0.016 Gyr, Colomera =4.469 +/- 0.012 Gyr, and Sombrerete =4.535 +/- 0.005 Gyr. These ages are in fair agreement with previously reported Rb-Sr isochron ages for Colomera and Weekeroo Station. Although several mechanisms to form HE meteorites previously were suggested, it is not obvious that a single mechanism could produce a suite of meteorites with very different degrees of silicate differentiation and with isotopic ages that differ by >0.8 Gyr. We suggest that those IIEs with older isotopic ages are a product of partial melting and differentiation within the parent body, followed by mixing of silicate and metal while both were relatively hot. Netschadvo and Watson may have formed by this same process or by impact mixing about 4.5 Gyr ago, but their isotopic ages were

Laboratory plant study on the melting process of asbestos waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakai, Shinichi; Terazono, Atsushi; Takatsuki, Hiroshi

The melting process was studied as a method of changing asbestos into non-hazardous waste and recovering it as a reusable resource. In an initial effort, the thermal behaviors of asbestos waste in terms of physical and chemical structure have been studied. Then, 10 kg/h-scale laboratory plant experiments were carried out. By X-ray diffraction analysis, the thermal behaviors of sprayed-on asbestos waste revealed that chrysotile asbestos waste change in crystal structure at around 800 C, and becomes melted slag, mainly composed of magnesium silicate, at around 1,500 C. Laboratory plant experiments on the melting process of sprayed-on asbestos have shown thatmore » melted slag can be obtained. X-ray diffraction analysis of the melted slag revealed crystal structure change, and SEM analysis showed the slag to have a non-fibrous form. And more, TEM analysis proved the very high treatment efficiency of the process, that is, reduction of the asbestos content to 1/10{sup 6} as a weight basis. These analytical results indicate the effectiveness of the melting process for asbestos waste treatment.« less

Origins of ultralow velocity zones through slab-derived metallic melt

PubMed Central

Liu, Jiachao; Li, Jie; Smith, Jesse S.

2016-01-01

Understanding the ultralow velocity zones (ULVZs) places constraints on the chemical composition and thermal structure of deep Earth and provides critical information on the dynamics of large-scale mantle convection, but their origin has remained enigmatic for decades. Recent studies suggest that metallic iron and carbon are produced in subducted slabs when they sink beyond a depth of 250 km. Here we show that the eutectic melting curve of the iron−carbon system crosses the current geotherm near Earth’s core−mantle boundary, suggesting that dense metallic melt may form in the lowermost mantle. If concentrated into isolated patches, such melt could produce the seismically observed density and velocity features of ULVZs. Depending on the wetting behavior of the metallic melt, the resultant ULVZs may be short-lived domains that are replenished or regenerated through subduction, or long-lasting regions containing both metallic and silicate melts. Slab-derived metallic melt may produce another type of ULVZ that escapes core sequestration by reacting with the mantle to form iron-rich postbridgmanite or ferropericlase. The hypotheses connect peculiar features near Earth's core−mantle boundary to subduction of the oceanic lithosphere through the deep carbon cycle. PMID:27143719

Metal-silicate partitioning of U: Implications for the heat budget of the core and evidence for reduced U in the mantle

NASA Astrophysics Data System (ADS)

Chidester, Bethany A.; Rahman, Zia; Righter, Kevin; Campbell, Andrew J.

2017-02-01

Earth's core might require an internal heat source, such as radioactive decay, to explain the presence of the magnetic field through geologic time. To investigate whether U would be an important heat source in the core, we performed metal-silicate partitioning experiments of U at P-T (up to 67 GPa and 5400 K) conditions more relevant to a magma ocean scenario than has previously been reported. This study finds the partitioning of U to be strongly dependent on ƒO2, temperature, the S content of the metal and the SiO2 content of the silicate during core-mantle differentiation. Differentiation at mean conditions of 42-58 GPa and 3900-4200 K would put 1.4-3.5 ppb U (2-8 wt% S) in the core, amounting to a maximum of 1.4 (+1/-0.7) TW of heat 4.5 billion years ago. This is likely not enough heat to mitigate early widespread mantle melting. It was also found that U likely exists in the 2+ oxidation state in silicate melts in the deep Earth, a state which has not been previously observed in nature.

Aluminum enrichment in silicate melts by fractional crystallization: some mineralogic and petrographic constraints.

USGS Publications Warehouse

Zen, E.

1986-01-01

The degree of Al saturation of an igneous rock may be given by its aluminium saturation index (ASI), defined as the molar ratio Al2O3/(CaO+K2O+Na2O). One suggested origin for mildly peraluminous granites (ASI 1-1.1) is fractional crystallization of subaluminous magmas (ASI 1. For hornblende to effectively cause a melt to evolve into a peraluminous composition, it must be able to coexist with peraluminous magmas; e.g. at = or <5 kbar hornblende can coexist with strongly peraluminous melts (ASI approx 1.5). Potentials and problems of using coarse-grained granitic rocks to prove courses of magmatic evolution are illustrated by a suite of samples from the Grayling Lake pluton, SW Montana. Such rocks generally contain a large cumulate component and should not be used as a primary test for the occurrence or efficacy of a fractionation process that might lead to peraluminous melts. The process is unlikely to give rise to peraluminous plutons of batholithic dimensions. A differential equation is presented which allows the direct use of mineral chemistry and modal abundance to predict the path of incremental evolution of a given magma.-R.A.H.

Preparation, characterization and properties of polymer-layered silicate nanocomposites

NASA Astrophysics Data System (ADS)

Fonseca, Claudia Alencar

Nanocomposites are a relatively new class of composites, that in the polymer area typically consist of particle-filled polymers where at least one dimension of the dispersed particles is in the nanometer range. Amongst all potential nanocomposite precursors, those based on clay and layered silicates have been more widely investigated. These nanocomposites exhibit markedly improved mechanical, thermal, optical and physico-chemical properties when compared to conventional (microscale) composites. In the present work, properties of nanocomposites of Ethylene Methacrylic Acid copolymers and organically modified Montmorillonite formed from the melt was investigated. Nanocomposites of Poly(vinyl alcohol) and Montmorillonite formed from solution was also studied.

An Overview of the Origin of A-type Silicic Magmatism Along the Snake River Plain-Yellowstone Hotspot Track

NASA Astrophysics Data System (ADS)

Christiansen, E. H.; Bindeman, I. N.; Leishman, J. R.

2015-12-01

Disparate models have been proposed for the origin of A-type rhyolites--a volumetrically minor part of modern terrestrial magmatism. But understanding the origin of A-type granites and rhyolites has significance for understanding the formation of the Earth's first silicic crust and for planetary magmatism--small volumes of such granitic materials have been found in lunar rocks, martian and asteroidal meteorites, and have been speculated to have formed on Venus. On other planets, vertical tectonics and plume-like mantle convection dominate, not the recycling of wet, oxidized plates of lithosphere as on Earth. Thus, understanding the origins of A-type silicic magma is important on multiple levels. Voluminous A-type rhyolite were produced on the Snake River Plain-Yellowstone hotspot track and provide the opportunity to better understand these important silicic magmas. Detailed petrologic studies suggest that most Snake River Plain rhyolites ultimately formed by partially melting of previously emplaced basaltic intrusions rather than by fractional crystallization of basalt or melting of Archean crust. This hypothesis is favored because of the bimodal association of rhyolite and basalt without linking intermediate compositions. In addition, incompatible element ratios (e.g., La/Nb, Pb/Ce), a lack of old zircon antecrysts, low-U inherited zircon, high ɛNd and ɛHf values, high eruption temperatures (1050°C to 850°C), low fO2 (near QFM), and H2O (as low as 1.5%), link the rhyolites to a plume-derived basaltic parent through partial melting with lesser incorporation of the Archean to Mesozoic crust that underlies the plain. Moreover, the contrast with wetter, lower temperature rhyolites that must have formed by direct crustal melting (e.g., Arbon Valley Tuff) strengthens this interpretation. Many of the rhyolites also have low δ18O values that must be produced in two stages: first by partial melting of already hydrothermally altered basalt, and subsequently in single

The evolution of magma during continental rifting: New constraints from the isotopic and trace element signatures of silicic magmas from Ethiopian volcanoes

NASA Astrophysics Data System (ADS)

Hutchison, William; Mather, Tamsin A.; Pyle, David M.; Boyce, Adrian J.; Gleeson, Matthew L. M.; Yirgu, Gezahegn; Blundy, Jon D.; Ferguson, David J.; Vye-Brown, Charlotte; Millar, Ian L.; Sims, Kenneth W. W.; Finch, Adrian A.

2018-05-01

Magma plays a vital role in the break-up of continental lithosphere. However, significant uncertainty remains about how magma-crust interactions and melt evolution vary during the development of a rift system. Ethiopia captures the transition from continental rifting to incipient sea-floor spreading and has witnessed the eruption of large volumes of silicic volcanic rocks across the region over ∼45 Ma. The petrogenesis of these silicic rocks sheds light on the role of magmatism in rift development, by providing information on crustal interactions, melt fluxes and magmatic differentiation. We report new trace element and Sr-Nd-O isotopic data for volcanic rocks, glasses and minerals along and across active segments of the Main Ethiopian (MER) and Afar Rifts. Most δ18 O data for mineral and glass separates from these active rift zones fall within the bounds of modelled fractional crystallization trajectories from basaltic parent magmas (i.e., 5.5-6.5‰) with scant evidence for assimilation of Pan-African Precambrian crustal material (δ18 O of 7-18‰). Radiogenic isotopes (εNd = 0.92- 6.52; 87Sr/86Sr = 0.7037-0.7072) and incompatible trace element ratios (Rb/Nb <1.5) are consistent with δ18 O data and emphasize limited interaction with Pan-African crust. However, there are important regional variations in melt evolution revealed by incompatible elements (e.g., Th and Zr) and peralkalinity (molar Na2 O +K2 O /Al2O3). The most chemically-evolved peralkaline compositions are associated with the MER volcanoes (Aluto, Gedemsa and Kone) and an off-axis volcano of the Afar Rift (Badi). On-axis silicic volcanoes of the Afar Rift (e.g., Dabbahu) generate less-evolved melts. While at Erta Ale, the most mature rift setting, peralkaline magmas are rare. We find that melt evolution is enhanced in less mature continental rifts (where parental magmas are of transitional rather than tholeiitic composition) and regions of low magma flux (due to reduced mantle melt productivity

Aqueous Silicate Polymers: An Alternative to `Supercritical' Fluids as Transport Agents in Subduction Zones

NASA Astrophysics Data System (ADS)

Mannig, C. E.

2005-12-01

The chemistry of subduction-zone fluids is complicated by melt-vapor miscibility and the existence of critical end-points in rock-H2O systems. It is commonly assumed that fluids in subduction zones attain properties intermediate in composition between hydrous silicate liquid and H2O, and that such fluids possess enhanced material transport capabilities. However, the relevance of supercritical, intermediate fluids to subduction zones presents four problems. (1) Albite-H2O is typically used as an analogue system, but the favorable position of its critical curve is not representative; critical curves for polymineralic subduction-zone lithologies lie at substantially higher P. (2) Even if albite-H2O is relevant, jadeite may interfere because of its different solubility and the positive clapeyron slope of its solidus, which points to liquid-structure changes that could cause reappearance of the liquid+vapor field. (3) Critical curves are features of very H2O-rich compositions; low-porosity, H2O-poor natural systems will coexist with intermediate fluids only over a narrow PT interval. (4) Intermediate fluids are expected only over short length scales because their migration will likely result in compositional shifts via reaction and mineral precipitation in the mantle wedge. Although supercritical, intermediate fluids are probably relatively unimportant in subduction zones, they reflect a chemical process that may hold the key to understanding high- P mass transfer. Miscibility in melt-vapor systems is a consequence of polymerization of dissolved components, primarily Si ± Al, Na and Ca. This behavior yields, e.g., aqueous Si-Si, Si-Al, Si-Na-Al, and Si-Ca oxide dimers and other multimers of varying stoichiometry (silicate polymers), even in subcritical, dilute, H2O-rich vapor. Silicate polymers in subcritical aqueous solutions have been inferred from high- P mineral-solubility experiments. The abundance of these species at high P shows that the chemistry of aqueous

Calculation of Oxygen Fugacity in High Pressure Metal-Silicate Experiments and Comparison to Standard Approaches

NASA Technical Reports Server (NTRS)

Righter, K.; Ghiorso, M.

2009-01-01

Calculation of oxygen fugacity in high pressure and temperature experiments in metal-silicate systems is usually approximated by the ratio of Fe in the metal and FeO in the silicate melt: (Delta)IW=2*log(X(sub Fe)/X(sub FeO)), where IW is the iron-wustite reference oxygen buffer. Although this is a quick and easy calculation to make, it has been applied to a huge variety of metallic (Fe- Ni-S-C-O-Si systems) and silicate liquids (SiO2, Al2O3, TiO2, FeO, MgO, CaO, Na2O, K2O systems). This approach has surely led to values that have little meaning, yet are applied with great confidence, for example, to a terrestrial mantle at "IW-2". Although fO2 can be circumvented in some cases by consideration of Fe-M distribution coefficient, these do not eliminate the effects of alloy or silicate liquid compositional variation, or the specific chemical effects of S in the silicate liquid, for example. In order to address the issue of what the actual value of fO2 is in any given experiment, we have calculated fO2 from the equilibria 2Fe (metal) + SiO2 (liq) + O2 = Fe2SiO4 (liq).

Partial melting of carbonated pelite at 3-7 GPa and deep cycling of CO2 and H2O in subduction zones

NASA Astrophysics Data System (ADS)

Tsuno, K.; Dasgupta, R.; Danielson, L. R.; Righter, K.

2011-12-01

The exchange of water and carbon dioxide between the Earth's crustal rocks and the interior is important for understanding geochemical and geophysical evolution of the planet on geologic timescale. Subduction of pelitic sediments is a key mechanism for volatile introduction to the mantle but the high-pressure behavior of H2O+ CO2 bearing sediments is only constrained for alumina-rich, low-Mg# bulk compositions [1, 2]. However, the ocean-floor sediments for many subduction zones that contain both water and CO2 are alumina-poor and have higher Mg#. To constrain the melting behavior of a model alumina poor carbonated pelite, we performed new experiments. Piston cylinder (3 GPa) and multianvil (5 and 7 GPa) experiments were conducted between 800 and 1150 °C, using a model sediment composition containing 1 wt.% H2O and 5 wt.% CO2 (trace vapor-present at subsolidus conditions). The choice of the bulk composition was aimed to model the loss of siliceous hydrous fluid during the shallow part of subduction. We determined the solidus temperatures between 800 and 850 °C at 3 GPa, 900 and 950 °C at 5 GPa, and <1000 °C at 7 GPa. The subsolidus phases include cpx, garnet, coesite, rutile, phengite, and calcitess at 3 GPa, and kyanite comes in at 5 GPa. Hydrous rhyolitic silicate melt was observed at 3 GPa and up to 1150 °C. The near-solidus melt at 5-7 GPa was K-rich and calcio-carbonatitic, in contrast to the previous experimental results in alumina-rich and low Mg# bulk composition [1, 2], which showed the stability of Al-rich trachyitic silicate melt at near-solidus temperatures up to 5 GPa, and replaced by carbonate melt only at ≥5.5 GPa. Carbonate-silicate melt immiscibility was observed at 5 GPa, 1100 °C in our study. The phengite-out boundary is located between 850 and 900 °C at 3 GPa, between 1000 and 1100 °C at 5 GPa, and <1000 °C at 7 GPa. The crystalline carbonate-out boundary is between 950 and 1000 °C at 3 and 5 GPa, and <1000 °C at 7 GPa. Comparison of

A Study of Melt Inclusions in Tin-Mineralized Granites From Zinnwald, Germany

NASA Astrophysics Data System (ADS)

Sookdeo, C. A.; Webster, J. D.; Eschen, M. L.; Tappen, C. M.

2001-12-01

We have analyzed silicate melt inclusions from drill core samples from the eastern Erzgebirge region, Germany, to investigate magmatic-hydrothermal and mineralizing processes in compositionally evolved, tin-bearing granitic magmas. Silicate melt inclusions are small blebs of glass that are trapped or locked within phenocrysts and may contain high concentrations of volatiles that usually leave magma via degassing. Quartz phenocrysts were carefully hand picked from crushed samples of albite-, zinnwaldite- +/- lepidolite-bearing granitic dikes from Zinnwald and soaked in cold dilute HF to remove any attached groundmass. The cleaned phenocrysts were loaded into precious metal capsules with several drops of immersion oil to create a reducing environment at high temperature. The quartz-bearing capsules were inserted into quartz glass tubes, loaded into a furnace for heating at temperatures of 1025\\deg and 1050\\deg C (1atm) for periods of 20 to 30 hours, and subsequently the inclusions were quenched to glass. The inclusions were analyzed for major and minor elements (including F, Cl, and P) by electron microprobe and for H2O, trace elements, and ore elements by ion microprobe. The melt inclusion compositions are similar to that of the whole-rock sample from which the quartz separates were extracted. The average melt inclusion and whole-rock compositions are peraluminous, high in silica and rare alkalis, and low in MgO, CaO, FeO, MnO, and P2O5. Unlike the whole-rock sample, the melt inclusions contain from 0.5 to more than 4 wt.% F. The Cl contents of the inclusions are variable and range from hundreds of ppm to several thousand ppm. The variable and strong enrichments in F of the melt inclusions may correlate with (Na2O/Na2O+K2O) in the inclusions which is consistent with crystal fractionation of feldspars which drives the residual melt to increasing Na contents. Overall, the compositions of these melt inclusions are different from melt inclusions extracted from the

Carbonatitic and granitic melts produced under conditions of primary immiscibility during anatexis in the lower crust

NASA Astrophysics Data System (ADS)

Ferrero, Silvio; Wunder, Bernd; Ziemann, Martin A.; Wälle, Markus; O'Brien, Patrick J.

2016-11-01

Carbonatites are peculiar magmatic rocks with mantle-related genesis, commonly interpreted as the products of melting of CO2-bearing peridotites, or resulting from the chemical evolution of mantle-derived magmas, either through extreme differentiation or secondary immiscibility. Here we report the first finding of anatectic carbonatites of crustal origin, preserved as calcite-rich polycrystalline inclusions in garnet from low-to-medium pressure migmatites of the Oberpfalz area, SW Bohemian Massif (Central Europe). These inclusions originally trapped a melt of calciocarbonatitic composition with a characteristic enrichment in Ba, Sr and LREE. This interpretation is supported by the results of a detailed microstructural and microchemical investigation, as well as re-melting experiments using a piston cylinder apparatus. Carbonatitic inclusions coexist in the same cluster with crystallized silicate melt inclusions (nanogranites) and COH fluid inclusions, suggesting conditions of primary immiscibility between two melts and a fluid during anatexis. The production of both carbonatitic and granitic melts during the same anatectic event requires a suitable heterogeneous protolith. This may be represented by a sedimentary sequence containing marble lenses of limited extension, similar to the one still visible in the adjacent central Moldanubian Zone. The presence of CO2-rich fluid inclusions suggests furthermore that high CO2 activity during anatexis may be required to stabilize a carbonate-rich melt in a silica-dominated system. This natural occurrence displays a remarkable similarity with experiments on carbonate-silicate melt immiscibility, where CO2 saturation is a condition commonly imposed. In conclusion, this study shows how the investigation of partial melting through melt inclusion studies may unveil unexpected processes whose evidence, while preserved in stiff minerals such as garnet, is completely obliterated in the rest of the rock due to metamorphic re

Observations of impact-induced molten metal-silicate partitioning

NASA Technical Reports Server (NTRS)

Rowan, Linda R.; Ahrens, Thomas J.

1994-01-01

Observations of molten mid-ocean ridge basalt (MORB)-molybdenum (Mo) interactions produced by shock experiments provide insight into impact and differentiation processes involving metal-silicate partitioning. Analysis of fragments recovered from experiments (achieving MORB liquid shock pressures from 0.8 to 6 GPa) revealed significant changes in the composition of the MORB and Mo due to reaction of the silicate and metal liquids on a short time scale (less than 13 s). The FeO concentration of the shocked liquid decreases systematically with increasing pressure. In fact, the most highly shocked liquid (6 GPa) contains only 0.1 wt% FeO compared to an initial concentration of 9 wt% in the MORB. We infer from the presence of micrometer-sized Fe-, Si- and Mo-rich metallic spheres in the shocked glass that the Fe and Si oxides in the MORB were reduced in an estimated oxygen fugacity of 10(exp -17) bar and subsequently alloyed with the Mo. The in-situ reduction of FeO in the shocked molten basalt implies that shock-induced reduction of impact melt should be considered a viable mechanism for the formation of metallic phases. Similar metallic phases may form during impact accretion of planets and in impacted material found on the lunar surface and near terrestrial impact craters. In particular, the minute, isolated Fe particles found in lunar soils may have formed by such a process. Furthermore, the metallic spheres within the shocked glass have a globular texture similar to the textures of metallic spheroids from lunar samples and the estimated, slow cooling rate of less than or equal to 140 C/s for our spheres is consistent with the interpretation that the lunar spheroids formed by slow cooling within a melted target.

Metal/silicate partitioning of Pt and the origin of the "late veneer"

NASA Astrophysics Data System (ADS)

Ertel, W.; Walter, M. J.; Drake, M. J.; Sylvester, P. J.

2002-12-01

the melting point of the 1 atm, AnDi system and the melting point of the Pt capsule material. Over 150 piston cylinder and 12 multi anvil experiments have been performed. Pt solubility is only slightly dependent on temperature, decreasing between 1800 and 1400°C by less than an order of magnitude. In consequence, the partitioning behavior of Pt is mostly determined by its oxygen fugacity dependence, which has only been determined in 1 atm experiments. At 10 kbar, metal/silicate partition coefficients (D's) decrease by about 3 orders of magnitude. The reason for this is not understood, but might be attributed to a first order phase transition as found for, e.g., SiO2 or H2O. Above 10 kbar any increase in pressure does not lead to any further significant decrease in partition coefficients. Solubilities stay roughly constant up to 140 kbar. Abundances of moderately siderophile elements were possibly established by metal/silicate equilibrium in a magma ocean. These results for Pt suggest that the abundances of HSEs were most probably established by the accretion of a chondritic veneer following core formation, as metal/silicate partition coefficients are too high to be consistent with metal/silicate equilibrium in a magma ocean.

Origins of ultralow velocity zones through slab-derived metallic melt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Jiachao; Li, Jie; Hrubiak, Rostislav

2016-05-03

Understanding the ultralow velocity zones (ULVZs) places constraints on the chemical composition and thermal structure of deep Earth and provides critical information on the dynamics of large-scale mantle convection, but their origin has remained enigmatic for decades. Recent studies suggest that metallic iron and carbon are produced in subducted slabs when they sink beyond a depth of 250 km. Here we show that the eutectic melting curve of the iron-carbon system crosses the current geotherm near Earth’s core-mantle boundary, suggesting that dense metallic melt may form in the lowermost mantle. If concentrated into isolated patches, such melt could produce themore » seismically observed density and velocity features of ULVZs. Depending on the wetting behavior of the metallic melt, the resultant ULVZs may be short-lived domains that are replenished or regenerated through subduction, or long-lasting regions containing both metallic and silicate melts. Slab-derived metallic melt may produce another type of ULVZ that escapes core sequestration by reacting with the mantle to form iron-rich post-bridgmanite or ferropericlase. The hypotheses connect peculiar features near Earth’s core-mantle boundary to subduction of the oceanic lithosphere through the deep carbon cycle.« less

Pocket Guide to Transportation 2017

DOT National Transportation Integrated Search

2017-05-01

The BTS Pocket Guide to Transportation is a quick reference guide to significant transportation statistics. All the previous seven sections plus a new Major Trends section are included. This year marks the 20th anniversary of the Pocket Guide, which ...

Melt inclusions come of age: Volatiles, volcanoes, and sorby's legacy

USGS Publications Warehouse

Lowenstern, J. B.

2003-01-01

Despite nearly forty years of modern research on silicate melt inclusions (MI), only within the past 10-15 years have volcanologists and petrologists come to regularly accept their utility for characterizing magmatic systems. Their relatively slow acceptance was likely due to a number of factors including: 1) Lack of reliable analytical techniques, 2) Concern that MI represent anomalous boundary-layer melts or are altered by leakage or post-entrapment crystallization, 3) Data sets indicative of heterogeneous melts and, 4) Homogenization temperatures greater than those calculated by other techniques. With improvements in analytical methods and careful studies of MI systematics, workers are increasingly convinced of the utility of these features to unravel the complexities of volcanic systems: melt inclusions have "come of age." Recent studies provide compelling evidence for the compositions of dissolved and exsolved volatiles in magma reservoirs. Evidence for immiscibility of gases, hydrosaline brines and pegmatitic fluids demonstrate that magmatic phase relations are often more complicated than can be inferred by inspection of crystalline phases alone. ?? 2003 Elsevier B.V. All rights reserved.

187Os/188Os in Spinel Peridotites from Borée, Massif Central, France: Seeing through the Effects of Melt Infiltration in the Sub-continental Lithospheric Mantle

NASA Astrophysics Data System (ADS)

Barnett, C. J.; Harvey, J.

2015-12-01

The Re-Os isotope system can be used to model the timing of melt extraction in peridotites, although secondary metasomatic processes can obscure primary melt depletion signatures, implying that bulk-rock Os model ages should be treated with caution.1Spinel peridotites from the volcanic Maar de Borée (French Massif Central) have equigranular to protogranular and occasionally poikilitic textures. Their bulk-rock chemistry are consistent with moderate degrees of partial melting, but elevated incompatible trace element ratios (e.g. La/YbN) are indicative of subsequent secondary processes. Petrographic observation reveals no infiltration of host basalt, but melt infiltration unrelated to the host basalt has occurred, most likely within the sub-continental lithospheric mantle prior to entrainment as xenoliths. The peridotites have a mean [Os] concentration of 2.35 ng g-1 and 187Os/188Os values from 0.12081 ± 16 to 0.12639 ± 14 (cf. PUM = 0.1296 ± 00082), with rhenium depletion model ages (TRD) ranging from 0.48 to 1.30 Ga. Silicate melt contains up to 2 orders of magnitude less Os than peridotites3 but the 187Os/188Os of melt infiltrated peridotite can be skewed by the precipitation of immiscible sulfide when an infiltrating melt reaches S-saturation4. The Borée peridotites retain an unradiogenic Os-isotope signature despite silicate melt infiltration; this may be due to primary base metal sulfides enclosed in silicate minerals and therefore protected from interaction with infiltrating melts. TRD of enclosed sulphides should therefore be able to 'see through' any secondary metasomatic events and reveal melt depletion ages significantly older than those obtained from bulk-rock analyses (cf. 4). 1. Rudnick & Walker (2009) Lithos 112S, 1083-1095. 2. Meisel et al. (2001) Geochim Cosmochim Ac 65, 1311-1323. 3. Day, J.M.D. (2013) Chem Geol 341, 50-74. 4. Harvey et al. (2010) Geochim Cosmochim Acta 74, 293-320.

Partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulfide phases and hydrous basanite melt at upper mantle conditions

NASA Astrophysics Data System (ADS)

Li, Yuan; Audétat, Andreas

2012-11-01

The partitioning of 15 major to trace metals between monosulfide solid solution (MSS), sulfide liquid (SL) and mafic silicate melt (SM) was determined in piston-cylinder experiments performed at 1175-1300 °C, 1.5-3.0 GPa and oxygen fugacities ranging from 3.1 log units below to 1.0 log units above the quartz-fayalite-magnetite fO2 buffer, which conditions are representative of partial melting in the upper mantle in different tectonic settings. The silicate melt was produced by partial melting of a natural, amphibole-rich mantle source rock, resulting in hydrous (˜5 wt% H2O) basanitic melts similar to low-degree partial melts of metasomatized mantle, whereas the major element composition of the starting sulfide (˜52 wt% Fe; 39 wt% S; 7 wt% Ni; 2 wt% Cu) was similar to the average composition of sulfides in this environment. SL/SM partition coefficients are high (≥100) for Au, Ni, Cu, Ag, Bi, intermediate (1-100) for Co, Pb, Sn, Sb (±As, Mo), and low (≤1) for the remaining elements. MSS/SM partition coefficients are generally lower than SL/SM partition coefficients and are high (≥100) for Ni, Cu, Au, intermediate (1-100) for Co, Ag (±Bi, Mo), and low (≤1) for the remaining elements. Most sulfide-silicate melt partition coefficients vary as a function of fO2, with Mo, Bi, As (±W) varying by a factor >10 over the investigated fO2 range, Sb, Ag, Sn (±V) varying by a factor of 3-10, and Pb, Cu, Ni, Co, Au, Zn, Mn varying by a factor of 3-10. The partitioning data were used to model the behavior of Cu, Au, Ag, and Bi during partial melting of upper mantle and during fractional crystallization of primitive MORB and arc magmas. Sulfide phase relationships and comparison of the modeling results with reported Cu, Au, Ag, and Bi concentrations from MORB and arc magmas suggest that: (i) MSS is the dominant sulfide in the source region of arc magmas, and thus that Au/Cu ratios in the silicate melt and residual sulfides may decrease with increasing degree of

Partial melting of metagreywackes, Part II. Compositions of minerals and melts

NASA Astrophysics Data System (ADS)

Montel, Jean-Marc; Vielzeuf, Daniel

A series of experiments on the fluid-absent melting of a quartz-rich aluminous metagreywacke has been carried out. In this paper, we report the chemical composition of the phases present in the experimental charges as determined by electron microprobe. This analytical work includes biotite, plagioclase, orthopyroxene, garnet, cordierite, hercynite, staurolite, gedrite, oxide, and glass, over the range 100-1000MPa, 780-1025°C. Biotites are Na- and Mg-rich, with Ti contents increasing with temperature. The compositions of plagioclase range from An17 to An35, with a significant orthoclase component, and are always different from the starting minerals. At high temperature, plagioclase crystals correspond to ternary feldspars with Or contents in the range 11-20 mol%. Garnets are almandine pyrope grossular spessartine solid solutions, with a regular and significant increase of the grossular content with pressure. All glasses are silicic (SiO2=67.6-74.4 wt%), peraluminous, and leucocratic (FeO+MgO=0.9-2.9 wt%), with a bulk composition close to that of peraluminous leucogranites, even for degrees of melting as high as 60 vol.%. With increasing pressure, SiO2 contents decrease while K2O increases. At any pressure, the melt compositions are more potassic than the water-saturated granitic minima. The H2O contents estimated by mass balance are in the range 2.5-5.6 wt%. These values are higher than those predicted by thermodynamic models. Modal compositions were estimated by mass balance calculations and by image processing of the SEM photographs. The positions of the 20 to 70% isotects (curves of equal proportion of melt) have been located in the pressure-temperature space between 100MPa and 1000MPa. With increasing pressure, the isotects shift toward lower temperature between 100 and 200MPa, then bend back toward higher temperature. The melting interval increases with pressure; the difference in temperature between the 20% and the 70% isotects is 40°C at 100MPa, and 150�

Carbon substitution for oxygen in silicates in planetary interiors

PubMed Central

Sen, Sabyasachi; Widgeon, Scarlett J.; Navrotsky, Alexandra; Mera, Gabriela; Tavakoli, Amir; Ionescu, Emanuel; Riedel, Ralf

2013-01-01

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiOxC4-x tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiOxC4-x tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10–100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle. PMID:24043830

Carbon substitution for oxygen in silicates in planetary interiors.

PubMed

Sen, Sabyasachi; Widgeon, Scarlett J; Navrotsky, Alexandra; Mera, Gabriela; Tavakoli, Amir; Ionescu, Emanuel; Riedel, Ralf

2013-10-01

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiO(x)C(4-x) tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiO(x)C(4-x) tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10-100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle.

Cubic zirconia in >2370 °C impact melt records Earth's hottest crust

NASA Astrophysics Data System (ADS)

Timms, Nicholas E.; Erickson, Timmons M.; Zanetti, Michael R.; Pearce, Mark A.; Cayron, Cyril; Cavosie, Aaron J.; Reddy, Steven M.; Wittmann, Axel; Carpenter, Paul K.

2017-11-01

Bolide impacts influence primordial evolution of planetary bodies because they can cause instantaneous melting and vaporization of both crust and impactors. Temperatures reached by impact-generated silicate melts are unknown because meteorite impacts are ephemeral, and established mineral and rock thermometers have limited temperature ranges. Consequently, impact melt temperatures in global bombardment models of the early Earth and Moon are poorly constrained, and may not accurately predict the survival, stabilization, geochemical evolution and cooling of early crustal materials. Here we show geological evidence for the transformation of zircon to cubic zirconia plus silica in impact melt from the 28 km diameter Mistastin Lake crater, Canada, which requires super-heating in excess of 2370 °C. This new temperature determination is the highest recorded from any crustal rock. Our phase heritage approach extends the thermometry range for impact melts by several hundred degrees, more closely bridging the gap between nature and theory. Profusion of >2370 °C superheated impact melt during high intensity bombardment of Hadean Earth likely facilitated consumption of early-formed crustal rocks and minerals, widespread volatilization of various species, including hydrates, and formation of dry, rigid, refractory crust.

Lead recovery from waste CRT funnel glass by high-temperature melting process.

PubMed

Hu, Biao; Hui, Wenlong

2018-02-05

In this research, a novel and effective process for waste CRT funnel glass treatment was developed. The key to this process is removal of lead from the CRT funnel glass by high-temperature melting process. Sodium carbonate powder was used as a fusion agent, sodium sulfide serves as a catalytic agent and carbon powder acts as reducing agent. Experimental results showed that lead recovery rate increased with an increase in the amount of added sodium carbonate, sodium sulfide, carbonate, temperature and holding time initially, and then reached a stable value. The maximum lead recovery rate was approximately 94%, when the optimum adding amount of sodium carbonate, sodium sulfide, carbonate, temperature and holding time were 25%, 8%, 3.6%, 1200°C and 120min, respectively. In the high-temperature melting process, lead silicate in the funnel glass was firstly reduced, and then removed. The glass slag can be made into sodium and potassium silicate by hydrolysis process. This study proposed a practical and economical process for recovery of lead and utilization of waste glass slag. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental and Theoretical Studies on the Viscosity-Structure Correlation for High Alumina-Silicate Melts

NASA Astrophysics Data System (ADS)

Talapaneni, Trinath; Yedla, Natraj; Pal, Snehanshu; Sarkar, Smarajit

2017-06-01

Blast furnaces are encountering high Alumina (Al2O3 > 25 pct) in the final slag due to the charging of low-grade ores. To study the viscosity behavior of such high alumina slags, synthetic slags are prepared in the laboratory scale by maintaining a chemical composition of Al2O3 (25 to 30 wt pct) CaO/SiO2 ratio (0.8 to 1.6) and MgO (8 to 16 wt pct). A chemical thermodynamic software FactSage 7.0 is used to predict liquidus temperature and viscosity of the above slags. Experimental viscosity measurements are performed above the liquidus temperature in the range of 1748 K to 1848 K (1475 °C to 1575 °C). The viscosity values obtained from FactSage closely fit with the experimental values. The viscosity and the slag structure properties are intent by Fourier Transform Infrared (FTIR) and Raman spectroscopy. It is observed that increase in CaO/SiO2 ratio and MgO content in the slag depolymerizes the silicate structure. This leads to decrease in viscosity and activation energy (167 to 149 kJ/mol) of the slag. Also, an addition of Al2O3 content increases the viscosity of slag by polymerization of alumino-silicate structure and activation energy from 154 to 161 kJ/mol. It is witnessed that the activation energy values obtained from experiment closely fit with the Shankar model based on Arrhenius equation.

Configurational Heat Capacity of Na- and Ca-bearing Aluminosilicate Melts

NASA Astrophysics Data System (ADS)

Webb, S. L.

2006-12-01

The Na2O-Al2O3-SiO2 and CaO-Al2O3-SiO2 systems are used as analogs for the more complex natural magmatic systems of the Earth in studies of the physical properties, structure and flow mechanisms of silicate melts. Although the description of flow in binary alkali-silicate melts is clear; that for multi-oxide compositions quickly becomes very complex. The addition of aluminium to melts creates the need for a charge-balancing cation for the tetrahedrally co-ordinated Al3+. With the presence of both mono- and di-valent ions there are questions about which atom is preferred as the charge balancer and which will create non-bridging oxygens. This study addresses the structure of peraluminous and peralkaline/metaluminous Na2O-CaO-Al2O3-SiO2 melts and the change in structure with composition via determination of their shear viscosity and heat capacity. Viscosity has been determined using the micropenetration technique and the heat capacity and configurational heat capacity have been determined by differential scanning calorimetry. While the viscosity of these melts indicates structural changes at the condition where there are no longer enough Na+ or Ca2+ to charge balance all of the Al3+ in tetrahedral co-ordination, it is the heat capacity data which provides more information about the energy required for flow to occur in the melts as the structure changes due to changing composition. The configurational heat capacity can be determined from the difference between the liquid (cpl) and the glass (cpg) heat capacity at the glass transition temperature. To a first approximation cpg can be calculated from a linear summation of the cps of the oxide components. Similarly, if there are no anomalous changes in melt structure upon heating through Tg, the cpl will be a linear sum of the contributions of the component oxides. Configurational entropy Sconf(Tg) has been calculated from the viscosity data using the Adam-Gibbs equation for viscosity as a function of configurational

Final report on the safety assessment of potassium silicate, sodium metasilicate, and sodium silicate.

PubMed

Elmore, Amy R

2005-01-01

Potassium Silicate, Sodium Metasilicate, and Sodium Silicate combine metal cations with silica to form inorganic salts used as corrosion inhibitors in cosmetics. Sodium Metasilicate also functions as a chelating agent and Sodium Silicate as a buffering and pH adjuster. Sodium Metasilicate is currently used in 168 formulations at concentrations ranging from 13% to 18%. Sodium Silicate is currently used in 24 formulations at concentrations ranging from 0.3% to 55%. Potassium Silicate and Sodium Silicate have been reported as being used in industrial cleaners and detergents. Sodium Metasilicate is a GRAS (generally regarded as safe) food ingredient. Aqueous solutions of Sodium Silicate species are a part of a chemical continuum of silicates based on an equilibrium of alkali, water, and silica. pH determines the solubility of silica and, together with concentration, determines the degree of polymerization. Sodium Silicate administered orally is readily absorbed from the alimentary canal and excreted in the urine. The toxicity of these silicates has been related to the molar ratio of SiO2/Na2O and the concentration being used. The Sodium Metasilicate acute oral LD50 ranged from 847 mg/kg in male rats to 1349.3 mg/kg in female rats and from 770 mg/kg in female mice to 820 mg/kg in male mice. Gross lesions of variable severity were found in the oral cavity, pharynx, esophagus, stomach, larynx, lungs, and kidneys of dogs receiving 0.25 g/kg or more of a commercial detergent containing Sodium Metasilicate; similar lesions were also seen in pigs administered the same detergent and dose. Male rats orally administered 464 mg/kg of a 20% solution containing either 2.0 or 2.4 to 1.0 ratio of sodium oxide showed no signs of toxicity, whereas doses of 1000 and 2150 mg/kg produced gasping, dypsnea, and acute depression. Dogs fed 2.4 g/kg/day of Sodium Silicate for 4 weeks had gross renal lesions but no impairment of renal function. Dermal irritation of Potassium Silicate, Sodium

Self-diffusion of magnesium in spinel and in equilibrium melts - Constraints on flash heating of silicates

NASA Technical Reports Server (NTRS)

Sheng, Y. J.; Wasserburg, G. J.; Hutcheon, I. D.

1992-01-01

An isotopic tracer is used to measure Mg self-diffusion in spinel and coexisting melt at bulk chemical equilibrium. The diffusion coefficients were calculated from the measured isotope profiles using a model that includes the complementary diffusion of Mg-24, Mg-25, and Mg-26 in both phases with the constraint that the Mg content of each phase is constant. The activation energy and preexponential factor for Mg self-diffusion in spinel are, respectively, 384 +/- 7 kJ and 74.6 +/- 1.1 sq cm/s. These data indicate Mg diffusion in spinel is much slower than previous estimates. The activation energy for Mg self-diffusion in coexisting melt is 343 +/- 25 kJ and the preexponential factor is 7791.9 +/- 1.3 sq cm/s. These results are used to evaluate cooling rates of plagioclase-olivine inclusions (POIs) in the Allende meteorite. Given a maximum melting temperature for POIs of about 1500 C, these results show that a 1-micron radius spinel would equilibrate isotopically with a melt within about 60 min.

Vacuum melting and mechanical testing of simulated lunar glasses

NASA Technical Reports Server (NTRS)

Carsley, J. E.; Blacic, J. D.; Pletka, B. J.

1992-01-01

Lunar silicate glasses may possess superior mechanical properties compared to terrestrial glasses because the anhydrous lunar environment should prevent hydrolytic weakening of the strong Si-O bonds. This hypothesis was tested by melting, solidifying, and determining the fracture toughness of simulated mare and highlands composition glasses in a high vacuum chamber. The fracture toughness, K(IC), of the resulting glasses was obtained via microindentation techniques. K(IC) increased as the testing environment was changed from air to a vacuum of 10 exp -7 torr. However, this increase in toughness may not result solely from a reduction in the hydrolytic weakening effect; the vacuum-melting process produced both the formation of spinel crystallites on the surfaces of the glass samples and significant changes in the compositions which may have contributed to the improved K(IC).

Form and deformity: the trouble with Victorian pockets.

PubMed

Matthews, Christopher Todd

2010-01-01

This essay explores the Victorian debate about the place of pockets in men's and women's clothing. By studying the representation of men as naturally pocketed creatures and the general denial of useful pockets to middle-class women, the essay demonstrates the tenacious cultural logic by which men's and women's pockets were imagined to correspond to sexual differences and to index access, or lack thereof, to public mobility and financial agency. Interconnected readings of visual art, essays, and novels show how the common sense about gendered pockets was utilized and promulgated in Victorian narratives. The question of who gets pockets is thus positioned as part of the history of gendered bodies in public space.

Electrical Conductivity Measurements on Hydrous Carbonate Melts at Mantle Pressure

NASA Astrophysics Data System (ADS)

Sifre, D.; Gaillard, F.

2012-04-01

Electromagnetic methods image mantle regions in the asthenosphere with elevated conductivity (0.1 to 1 S.m-1), which constrasts with the conductivity of dry olivine (10-2 to 10-3 S.m-1). A correct interpretation of the petrological nature of the conductive mantle is critical for our understanding of mantle geodynamics because such conductive regions indicate mantle rocks with physical and chemical properties that importantly deviates from the canonical peridotites. For decades, such anomalously high mantle conductivities have been attributed to mineralogical defects associated to few tens of ppm water incorporated in olivine. Most recent experimental surveys, however, refute this hydrous olivine model. Conductive mantle regions could then reflect partial melting. The presence of melts in the Earth's mantle has long been proved by geochemical observations and experimental petrology on peridotite rocks. The requirement for melting in the asthenospheric mantle is the presence of volatile species (water, carbon dioxide, halogens). Small melt fractions are then produced by small volatile contents and they are the first liquids produced by melting magma. This study reports electrical conductivity measurements on such melts at mantle pressure and temperature. We investigated on melt chemical compositions produced by melting of peridotite that would interact with CO2-H2O and Cl. Such melts are carbonatite melts, carbonated silicate melts, hydrous carbonate melts, hydrous basalts. A new system allowing in situ electrical conductivity measurements in piston cylinder has been deployed. This design has been specifically adapted to perfom measurements on liquid samples with elevated electrical conductivities. The chemical compositions investigated are pure liquid CaCO3 and CaMg(CO3)2, to which, cloride (as salts), silicate (as basalts) and water (as brucite) have been added. Experiments have been realized at 1.5 and 2.7 GPa pressure and temperature of 1000-1700° C. Impedance

First in-situ monitoring of CO2 delivery to the mantle followed by compression melting, using synchrotron generated X-ray diffraction.

NASA Astrophysics Data System (ADS)

Hammouda, Tahar; Chantel, Julien; Manthilake, Geeth; Guignard, Jérémy; Crichton, Wilson; Gaillard, Fabrice

2014-05-01

Melting of peridotite + CO2 upon compression has been directly monitored in situ, for the first time. We have combined high pressure experiments in the multianvil apparatus with synchrotron-generated X-ray diffraction, in order to monitor sample decarbonation upon heating, followed by melting upon compression. Experiments were performed in the model system CaO-MgO-SiO2+CO2, using dolomite and silicates contained in graphite capsules as starting material. Save Al, starting composition was aimed at reproducing peridotitic system. The sample was first compressed at room temperature, then heated. Decarbonation was observed at 2.2 GPa and 1100°C. After further heating to 1300°C, pressure was increased. Melting was observed at 2.7 GPa, while temperature was kept at 1300°C. All transformations were followed using X-ray diffraction. Starting with silicate + carbonate mixtures, we were thus able to keep CO2 fluid in the experimental sample at high P and T, up to the solidus. Concerning carbon recycling at subduction zones, it is known that CO2 is a non-wetting fluid in silicate aggregates. Therefore, any CO2 resulting from carbonate breakdown likely remains trapped at grain corners either in the subducted lithosphere or in the mantle wedge before eventually being trapped in mantle minerals as fluid inclusions, due to dynamic recrystallization. In this way, CO2 released from the slab may be spread laterally due to mantle convection. Entrainment to further depths by deep subduction or in convection cells induces CO2 introduction to depth wherein the solidus can be crossed, due to pressure increase. The solidus corresponds to the so-called carbonate ledge, beyond which carbonatitic melts are produced. Therefore, compression melting of CO2-bearing lithologies is a way to produce carbonatitic melts at depths corresponding to about 80 km. This mechanism is a viable explanation for the observed geophysical anomalies, such as those revealed by electrical conductivity

Structure of carbonate melts at high pressure

NASA Astrophysics Data System (ADS)

Hudspeth, J.; Sanloup, C.; Cochain, B.; Konopkova, Z.; Afonina, V.; Morgenroth, W.

2015-12-01

Carbonate melts are rare magmas with only a single active volcano (Oldoinyo Lengai,Tanzania [1]). They are of fundamental interest for their role in the Earth's deep carbon cycle and are of immense economic importance due to their affinity for REE strategic metals (niobium, uranium, tantalum, etc). They have remarkable physical properties such as very low viscosity [2] and magmatic temperatures for alkaline carbonate lavas [3] and it has been predicted that their compressibility could be significantly higher than that of silicate melts [4,5]. Despite the atomic structure of carbonate melts being fundamental for controlling their physical and chemical behavior in natural systems, very few structural studies have been reported and these have been largely computational. Here we present initial structural investigations of carbonate melts at mantle pressures using in situ x-ray diffraction in diamond anvil cells. The structure factor S(Q) is transformed to obtain the real space pair distribution function G(R) which describes the local and intermediate range atomic ordering allowing bond length and coordination number changes with pressure to be determined. [1] Krafft and Keller, Science 245:168-170, 1989 [2] Yono et al., Nat. Commun. 5:5091, 2014 [3] Dobson et al., Earth Planet. Sci. Lett. 143:207-215, 1996 [4] Genge et al., Earth Planet. Sci. Lett. 131:225-238, 1995 [5] Jones et al., Rev. Mineral. Geochem. 75:289-322, 2013

Constraints on cosmic silicates

NASA Astrophysics Data System (ADS)

Ossenkopf, V.; Henning, Th.; Mathis, J. S.

1992-08-01

Observational determinations of opacities of circumstellar silicates, relative to the peak value near 10 microns, are used to estimate the optical constants n and k, the real and imaginary parts of the index of refraction. Circumstellar dust is modified by processing within the interstellar medium. This leads to higher band strengths and a somewhat larger ratio of the opacities at the 18 and 10-micron peaks, compared with circumstellar silicates. By using an effective-medium theory, we calculate the effects of small spherical inclusions of various materials (various oxides, sulfides, carbides, amorphous carbon, and metallic iron) upon silicate opacities. Some of these can increase the absorption coefficient k in the 2-8 micron region appreciably, as is needed to reconcile laboratory silicate opacities with observations of both the interstellar medium and envelopes around late-type stars. We give tables of two sets of optical constants for warm oxygen-deficient and cool oxygen-rich silicates, representative for circumstellar and interstellar silicates. The required opacity in the 2-8 micron region is provided by iron and magnetite.

Multidiffusion mechanisms for noble gases (He, Ne, Ar) in silicate glasses and melts in the transition temperature domain: Implications for glass polymerization

NASA Astrophysics Data System (ADS)

Amalberti, Julien; Burnard, Pete; Laporte, Didier; Tissandier, Laurent; Neuville, Daniel R.

2016-01-01

Noble gases are ideal probes to study the structure of silicate glasses and melts as the modifications of the silicate network induced by the incorporation of noble gases are negligible. In addition, there are systematic variations in noble gas atomic radii and several noble gas isotopes with which the influence of the network itself on diffusion may be investigated. Noble gases are therefore ideally suited to constrain the time scales of magma degassing and cooling. In order to document noble gas diffusion behavior in silicate glass, we measured the diffusivities of three noble gases (4He, 20Ne and 40Ar) and the isotopic diffusivities of two Ar isotopes (36Ar and 40Ar) in two synthetic basaltic glasses (G1 and G2; 20Ne and 36Ar were only measured in sample G1). These new diffusion results are used to re-interpret time scales of the acquisition of fractionated atmospheric noble gas signatures in pumices. The noble gas bearing glasses were synthesized by exposing the liquids to high noble gas partial pressures at high temperature and pressure (1750-1770 K and 1.2 GPa) in a piston-cylinder apparatus. Diffusivities were measured by step heating the glasses between 423 and 1198 K and measuring the fraction of gas released at each temperature step by noble gas mass spectrometry. In addition we measured the viscosity of G1 between 996 and 1072 K in order to determine the precise glass transition temperature and to estimate network relaxation time scales. The results indicate that, to a first order, that the smaller the size of the diffusing atom, the greater its diffusivity at a given temperature: D(He) > D(Ne) > D(Ar) at constant T. Significantly, the diffusivities of the noble gases in the glasses investigated do not display simple Arrhenian behavior: there are well-defined departures from Arrhenian behavior which occur at lower temperatures for He than for Ne or Ar. We propose that the non-Arrhenian behavior of noble gases can be explained by structural modifications

Some physical aspects of fluid-fluxed melting

NASA Astrophysics Data System (ADS)

Patiño Douce, A.

2012-04-01

surprising result that fluid infiltration produces more melt during fractional melting than during batch melting. This behavior, which is opposite to that of decompression melting of a dry solid, arises because the melting point depression effect of the added fluid is greater during fractional melting than during batch melting, which results in a greater release of enthalpy and, therefore, greater melt production for fractional melting than for batch melting, for the same total amount of fluid added. The difference may be considerable. As an example, suppose that 0.1 mols of H2O infiltrate 1 mol or silicate rock. Depending on the rock composition this may corresponds to ˜ 1 wt% H2O. For a given choice of model parameters (initial temperature, heat capacity and entropy of fusion), about 28% of the rock melts during fractional melting, versus some 23 % during batch melting. Fluid fluxing is a robust process of melt generation, without which magmatism at Earth's convergent plate margins would be impossible.

Melt inclusions in alluvial sapphires from Montana, USA: Formation of sapphires as a restitic component of lower crustal melting?

NASA Astrophysics Data System (ADS)

Palke, Aaron C.; Renfro, Nathan D.; Berg, Richard B.

2017-05-01

We report here compositions of glassy melt inclusions hosted in sapphires (gem quality corundum) from three alluvial deposits in Montana, USA including the Rock Creek, Dry Cottonwood Creek, and Missouri River deposits. While it is likely that sapphires in these deposits were transported to the surface by Eocene age volcanic events, their ultimate origin is still controversial with many models suggesting the sapphires are xenocrysts with a metamorphic or metasomatic genesis. Melt inclusions are trachytic, dacitic, and rhyolitic in composition. Microscopic observations allow separation between primary and secondary melt inclusions. The primary melt inclusions represent the silicate liquid that was present at the time of sapphire formation and are enriched in volatile components (8-14 wt.%). Secondary melt inclusions analyzed here for Dry Cottonwood Creek and Rock Creek sapphires are relatively volatile depleted and represent the magma that carried the sapphires to the surface. We propose that alluvial Montana sapphires from these deposits formed through a peritectic melting reaction during partial melting of a hydrated plagioclase-rich protolith (e.g. an anorthosite). The heat needed to drive this reaction was likely derived from the intrusion of mantle-derived mafic magmas near the base of the continental lithosphere during rollback of the Farallon slab around 50 Ma. These mafic magmas may have ended up as the ultimate carrier of the sapphires to the surface as evidenced by the French Bar trachybasalt near the Missouri River deposit. Alternatively, the trachytic, rhyolitic, and dacitic secondary melt inclusions at Rock Creek and Dry Cottonwood Creek suggests that the same magmas produced during the partial melting event that generated the sapphires may have also transported them to the surface. Determining the genesis of these deposits will further our understanding of sapphire deposits around the world and may help guide future sapphire prospecting techniques. This

Entropy and structure of silicate glasses and melts

USGS Publications Warehouse

Richet, P.; Robie, R.A.; Hemingway, B.S.

1993-01-01

Low-temperature adiabatic Cp measurements have been made on NaAlSi2O6, MgSiO3, Ca3Al2Si3O12 and Ca1.5Mg1.5Al2Si3O12 glasses. Above about 50 K, these and previous data show that the heat capacity is an additive function of composition to within ??1% throughout the investigated glassforming part of the system CaO-MgO-Al2O3-SiO2. In view of the determining role of oxygen coordination polyhedra on the low-temperature entropy, this is interpreted as indicating that Si and Al are tetrahedrally coordinated in all these glasses, in agreement with structural data; whereas Ca and Mg remain octahedrally coordinated. In contrast, heat capacities and entropies are not additive functions of composition for alkali aluminosilicates, indicating increases in the coordination numbers of alkali elements from about six to nine when alumina is introduced. A thermochemical consequence of additivity of vibrational entropies of glasses is that entropies of mixing are essentially configurational for calcium and magnesium aluminosilicate melts. For alkali-bearing liquids, it is probable that vibrational entropies contribute significantly to entropies of mixing. At very low temperatures, the additive nature of the heat capacity with composition is less well followed, likely as a result of specific differences in medium-range order. ?? 1993.

Calcio-carbonatite melts and metasomatism in the mantle beneath Mt. Vulture (Southern Italy)

NASA Astrophysics Data System (ADS)

Rosatelli, Gianluigi; Wall, Frances; Stoppa, Francesco

2007-12-01

At Mt. Vulture volcano (Basilicata, Italy) calcite globules (5-150 μm) are hosted by silicate glass pools or veins cross-cutting amphibole-bearing, or more common spinel-bearing mantle xenoliths and xenocrysts. The carbonate globules are rounded or elongated and are composed of a mosaic of 2-20 μm crystals, with varying optical orientation. These features are consistent with formation from a quenched calciocarbonatite melt. Where in contact with carbonate amphibole has reacted to form fassaitic pyroxene. Some of these globules contain liquid/gaseous CO 2 bubbles and sulphide inclusions, and are pierced by quench microphenocrysts of silicate phases. The carbonate composition varies from calcite to Mg-calcite (3.8-5.0 wt.% MgO) both within the carbonate globules and from globule to globule. Trace element contents of the carbonate, determined by LAICPMS, are similar to those of carbonatites worldwide including ΣREE up to 123 ppm. The Sr-Nd isotope ratios of the xenolith carbonate are similar to the extrusive carbonatite and silicate rocks of Mt. Vulture testifying to derivation from the same mantle source. Formation of immiscibile silicate-carbonatite liquids within mantle xenoliths occurred via disequilibrium immiscibility during their exhumation.

Apatite-hosted melt inclusions in Damiao massif anorthosite complex, North China

NASA Astrophysics Data System (ADS)

Wang, M.; Veksler, I. V.; Zhang, Z.

2014-12-01

silicate melt. We propose that the inclusions at Damiao record a trend of intercumulus melt evolution, which was strongly affected by separation of a hydrothermal fluid phase and the losses of alkali and Ca silicate components from the melt into the fluid.

Spin-polarized Molecular Dynamics simulations of liquid iron silicate at high pressures.

NASA Astrophysics Data System (ADS)

Munoz Ramo, David; Stixrude, Lars

2010-05-01

Liquid iron silicate (Fe2SiO4) is an important component of natural silicate liquids appearing in Earth's interior. The effect of iron in the properties of these melts is a crucial issue, as it displays a high-spin to low-spin transition at high pressures which is accompanied by volume reduction and changes in the optical absorption spectrum. This phenomenon has a major influence on properties like the buoyancy or the thermal conductivity of the melt, and ultimately on the chemical and thermal evolution of our planet. Computer simulations using ab initio methods have proven to be a powerful approach to the study of liquid silicate systems[1,2], although not yet including Fe. In this paper, we report ab initio molecular dynamics studies of liquid iron silicate at high pressure (up to 400 GPa) and high temperatures (from 3000K to 6000K) that allow us to predict different properties of the system. We use the spin-polarized formalism and the GGA+U density functional for a better treatment of the iron magnetic moments in the system. Previous studies in the solid phase have shown that GGA predicts fayalite as a metal, while the introduction of U leads to a correct description of the band gap and the magnetic ordering of the system. We extend this analysis to the liquid phase. By means of these simulations we predict the liquid structure and thermodynamic properties of the liquid. We compute the theoretical Hugoniot for the system and find good agreement with values obtained from shock experiments [3]. Our calculations show large differences in the magnitude and orientation of the magnetic moments depending on the choice of functional; the GGA+U functional consistently provides larger values of the individual moments (about 1 unit larger) and of the total magnetization of the system. The high-spin to low-spin transition is predicted to take place at pressures from around 260GPa at 3000K to around 280GPa at 6000K in this iron-rich system. [1] N. P. de Koker, L. Stixrude, B

The variable influence of P 2O 5 on the viscosity of melts of differing alkali/aluminium ratio: Implications for the structural role of phosphorus in silicate melts

NASA Astrophysics Data System (ADS)

Toplis, M. J.; Dingwell, D. B.

1996-11-01

The shear viscosities of forty melts in the system Na 2OAl 2O 3SiO 2P 2O 5 have been determined in the temperature range 1652-1052°C using the concentric cylinder method. Six P-free compositions containing ˜67 mol% SiO 2 varying in molar Na/(Na + Al) from 0.70 (peralkaline) to 0.44 (peraluminous) were studied, to each of which successive additions of up to 7 mol% (13 wt%) P 2O 5 were made. At a fixed temperature, viscosities in the P-free system show a maximum, not at the 'charge-balanced' metaluminous composition ( Na/(Na + Al) = 0.50 ), but at Na/(Na + Al) = 0.47 . Addition of P to peralkaline melts results in an increase in viscosity. With progressive additions of P to mildly peralkaline melts ( Na/(Na + Al) < 0.60 ), there is a maximum in melt viscosity that occurs at lower P content as the peralkalinity of the melt decreases. In contrast, the addition of P to the metaluminous and peraluminous melts causes a decrease in melt viscosity. The magnitude of this decrease is identical for the metaluminous, and mildly peraluminous ( Na/(Na + Al) = 0.47 ) compositions, but smaller for the most peraluminous melt ( Na/(Na + Al) = 0.44 ). The following inferences are made from the present viscosity data, together with spectroscopic data from the literature: (1) At the metaluminous join in the P-free system, not all the Al is present as a charge-balanced network-former. Between the metaluminous join and the viscosity maximum the incorporation of a small proportion of Al (3% relative) in a charge-balancing role (for Al IV) could explain the observations. (2) The addition of P to peralkaline melts results in the formation of Na phosphate complexes which, upon exhaustion of excess Na, have the stoichiometry of extended metaphosphate chains with Na/P ratios that tend to 1 as the metaluminous ioin is approached. (3) Estimates of the relative effects of Na and Al phosphate melt complexes on viscosity are consistent with the formation of both NaPO 3 and AlPO 4 melt

Petrology and geochemistry of the Tasse mantle xenoliths of the Canadian Cordillera: A record of Archean to Quaternary mantle growth, metasomatism, removal, and melting

NASA Astrophysics Data System (ADS)

Polat, Ali; Frei, Robert; Longstaffe, Fred J.; Thorkelson, Derek J.; Friedman, Eyal

2018-07-01

Mantle xenoliths hosted by the Quaternary Tasse alkaline basalts in the Canadian Cordillera, southeastern British Columbia, are mostly spinel lherzolite originating from subcontinental lithospheric mantle. The xenoliths contain abundant feldspar veins, melt pockets and spongy clinopyroxene, recording extensive alkaline metasomatism and partial melting. Feldspar occurs as veins and interstitial crystal in melt pockets. Melt pockets occur mainly at triple junctions, along grain boundaries, and consist mainly of olivine, cpx, opx and spinel surrounded by interstitial feldspar. The Nd, Sr and Pb isotopic compositions of the xenoliths indicate that their sources are characterized by variable mixtures of depleted MORB mantle and EM1 and EM2 mantle components. Large variations in εNd values (-8.2 to +9.6) and Nd depleted mantle model ages (TDM = 66 to 3380 Ma) are consistent with multiple sources and melt extraction events, and long-term (>3300 Ma) isolation of some source regions from the convecting mantle. Samples with Archean and Paleoproterozoic Nd model ages are interpreted as either have been derived from relict Laurentian mantle pieces beneath the Cordillera or have been eroded from the root of the Laurentian craton to the east and transported to the base of the Cordilleran lithosphere by edge-driven convection currents. The oxygen isotope compositions of the xenoliths (average δ18O = +5.1 ± 0.5‰) are similar to those of depleted mantle. The average δ18O values of olivine (+5.0 ± 0.2‰), opx (+5.9 ± 0.6‰), cpx (+6.0 ± 0.6‰) and spinel (+4.5 ± 0.2‰) are similar to mantle values. Large fractionations for olivine-opx, olivine-cpx and opx-cpx pairs, however, reflect disequilibrium stemming from metasomatism and partial melting. Whole-rock trace element, Nd, Sr, Pb and O isotope compositions of the xenoliths and host alkaline basalts indicate different mantle sources for these two suites of rocks. The xenoliths were derived from shallow lithospheric

A pocket of variability in Pinus rigida

Treesearch

F. Thomas Ledig; John H. Fryer

1971-01-01

Steady state gene frequencies around a pocket of differential fitness have been formulated by Hanson (1966) in a generalization of the work of Haldane (1948). A pocket of differential fitness would result in a pocket-of-variability, assuming that the radius of the area of contrasting fitness was large in relation to the vagility of the organism. Conversely, the absence...

Heterogeneously entrapped, vapor-rich melt inclusions record pre-eruptive magmatic volatile contents

NASA Astrophysics Data System (ADS)

Steele-MacInnis, Matthew; Esposito, Rosario; Moore, Lowell R.; Hartley, Margaret E.

2017-04-01

Silicate melt inclusions (MI) commonly provide the best record of pre-eruptive H2O and CO2 contents of subvolcanic melts, but the concentrations of CO2 and H2O in the melt (glass) phase within MI can be modified by partitioning into a vapor bubble after trapping. Melt inclusions may also enclose vapor bubbles together with the melt (i.e., heterogeneous entrapment), affecting the bulk volatile composition of the MI, and its post-entrapment evolution. In this study, we use numerical modeling to examine the systematics of post-entrapment volatile evolution within MI containing various proportions of trapped vapor from zero to 95 volume percent. Modeling indicates that inclusions that trap only a vapor-saturated melt exhibit significant decrease in CO2 and moderate increase in H2O concentrations in the melt upon nucleation and growth of a vapor bubble. In contrast, inclusions that trap melt plus vapor exhibit subdued CO2 depletion at equivalent conditions. In the extreme case of inclusions that trap mostly the vapor phase (i.e., CO2-H2O fluid inclusions containing trapped melt), degassing of CO2 from the melt is negligible. In the latter scenario, the large fraction of vapor enclosed in the MI during trapping essentially serves as a buffer, preventing post-entrapment modification of volatile concentrations in the melt. Hence, the glass phase within such heterogeneously entrapped, vapor-rich MI records the volatile concentrations of the melt at the time of trapping. These numerical modeling results suggest that heterogeneously entrapped MI containing large vapor bubbles represent amenable samples for constraining pre-eruptive volatile concentrations of subvolcanic melts.

Ag-doped Lithium alumino silicate photostructurable glass for microdevice fabrication

NASA Astrophysics Data System (ADS)

Mishra, Richa; Goswami, Madhumita; Krishnan, Madangopal

2018-04-01

Ag-doped LAS glass of composition (wt.%):74SiO2-6Al2O3-15Li2O-5X (X=other additives) were prepared by melt-quench technique and characterized for thermal and optical properties using DTA and UV-Visible spectrometer. XRD technique was used for phase identification in the heat treated glasses. Glass samples were exposed to UV-light for conversion of Ce3+ to Ce4+ state and Ag+ into Ago metallic state. DTA shows a lower crystallization temperature (Tp) at around 605°C for exposed samples as compared to unexposed base glass which is at around 625°C. UV-Visible spectra shows a broad band at around 305nm which indicates Ce3+ in base glass whereas in case of UV-exposed sample the reduced peak intensity indicates conversion of Ce3+ to Ce4+ ions, which also confirm formation of Ago in glass samples. Ag agglomeration was also confirmed from the band position at 430nm in heat treated sample, found responsible for early growth of meta-silicate phase in exposed sample. The meta-silicate phase was selectively etched for fabrication of micro-devices.

Shock compression of preheated silicate liquids: 30 years of progress

NASA Astrophysics Data System (ADS)

Asimow, Paul

2011-06-01

Tom Ahrens and his students pioneered, beginning around 1981, the technique of determining silicate liquid equations of state for geophysical applications using shock compression of pre-heated, encapsulated samples. In the last decade, we have ported this technique to the Caltech two-stage light gas gun and extended several pre-heated liquid Hugoniots to over 125 GPa. We now have enough compositions studied to perform several tests of the theory of linear mixing or, assuming linear mixing, to describe any liquid in the five-component CaO-MgO-FeO-Al2O3-SiO2 system. This data allows us to identify liquid compositions likely to be negatively or neutrally buoyant in the lower mantle and to form a preliminary description of the dynamics of partial melting of solid lower mantle or initial crystallization of a deep mantle magma ocean. The most robust and surprising feature of all studied liquids, which places very strong constraints on microscopic models for silicate liquid compression behavior, is anomalous increase of the Grüneisen parameter upon compression, with remarkably consistent q = dln γ/dlnV = -1.75 +/- 0.25. Thanks to long-term support by the National Science Foundation.

The partitioning behavior of silver in a vapor brine rhyolite melt assemblage

NASA Astrophysics Data System (ADS)

Simon, Adam C.; Pettke, Thomas; Candela, Philip A.; Piccoli, Philip M.

2008-03-01

The partitioning of silver in a sulfur-free rhyolite melt-vapor-brine assemblage has been quantified at 800 °C, pressures of 100 and 140 MPa and f≈NNO (nickel-nickel oxide). Silver solubility (±2 σ) in rhyolite increases 5-fold from 105 ± 21 to 675 ± 98 μg/g as pressure increases from 100 to 140 MPa. Nernst-type partition coefficients (DAgi,j±2σ) describing the mass transfer of silver at 100 MPa between vapor and melt, brine and melt and vapor and brine are 32 ± 30, 1151 ± 238 and 0.026 ± 0.004, respectively. At 140 MPa, values for DAgi,j(±2σ) for vapor and melt, brine and melt, and vapor and brine are 32 ± 10, 413 ± 172 and 0.06 ± 0.03, respectively. Apparent equilibrium constant values (±2 σ) describing the exchange of silver and sodium between vapor and melt, KAg,Nav/m, at 100 and 140 MPa are 105 ± 68 and 14 ± 6. The average values (±2 σ) for silver and sodium exchange between brine and melt, KAg,Nab/m, at 100 and 140 MPa are 313 ± 288 and 65 ± 12. These data indicate that the mass transfer of silver from rhyolite melt to an exsolved volatile phase(s) is enhanced at 100 MPa relative to 140 MPa, suggesting that decompression increases the silver ore-generative potential of an evolving silicate magma. Model calculations using the new data suggest that the evolution of low-density, aqueous fluid (i.e., vapor) may be responsible for the the silver tonnage of many porphyry-type and perhaps epithermal-type ore deposits. For example, Halter et al. (Halter W. E., Pettke T. and Heinrich C. A. (2002) The origin of Cu/Au ratios in porphyry-type ore deposits. Science296, 1842-1844) used detailed silicate and sulfide melt inclusion and vapor and brine fluid inclusions analyses to estimate a melt volume on the order of 15 km 3 to satisfy the copper budget at the Bajo de la Alumbrera copper-, gold-, silver-ore deposit. Using their melt volume estimate with the data presented here, model calculations for a 15-km 3 felsic melt, saturated with pyrrhotite

Internal Rb-Sr Age and Initial Sr-87/Sr-86 of a Silicate Inclusion from the Campo Del Cielo Iron Meteorite

NASA Technical Reports Server (NTRS)

Liu, Y.; Nyquist, L.; Wiesmann, H.; Shih, C.; Schwandt, C.; Takeda, H.

2003-01-01

The largest group of iron meteorites, IAB, is distinguished by the presence of diverse silicate inclusions. In principle, Rb-Sr and Sm-Nd radiometric dating of these silicate inclusions by internal isochron techniques can determine both the times of melting and parent/daughter ratios in the precursor materials via initial Sr-87/Sr-86 and Nd-143/Nd-144 ratios. The Sr-87/Sr-86 and Nd-143/Nd-144 ratios could distinguish chondritic precursors from already differentiated silicates. We reported Rb-Sr and Sm-Nd internal ischron ages of 4.52+/-0.03 Ga and 4.50+/-0.04 Ga, respectively, for plagioclase-diopside-rich material in the Caddo County IAB iron meteorite. These results are essentially identical to literature values of its Ar-Ar age of 4.520+/-0.005 Ga and its Sm-Nd age of 4.53+/-0.02 Ga. The purpose of this study is to evaluate the formation and evolution of silicate inclusions in IAB iron meteorites by determination of their initial Sr-87/Sr-86 ratios combined with higher-resolution chronology and mineralogical and geochemical studies.

Sulfur in Hydrous, Oxidized Basaltic Magmas: Phase Equilibria and Melt Solubilities

NASA Astrophysics Data System (ADS)

Pichavant, M.; Scaillet, B.; di Carlo, I.; Rotolo, S.; Metrich, N.

2006-05-01

Basaltic magmas from subduction zone settings are typically S-rich and may be the ultimate source of sulfur in vapor phases emitted during eruptions of more silicic systems. To understand processes of sulfur recycling in subduction zones, the behaviour of S in hydrous, oxidized, mafic arc magmas must be known. Although experimental data on S-bearing basaltic melts are available for dry conditions, and under both reduced and oxidized fO2, no study has yet examined the effect of S in hydrous mafic melts. In this work, 3 starting compositions were investigated, a basaltic andesite, a K basalt and a picritic basalt. For each composition, experimental data for S-added (1 wt % elemental sulfur) and S-free charges were obtained under similar P-T- H2O-fO2. All experiments were performed at 4 kbar and at either 950 ° C (basaltic andesite), 1100 ° C (K basalt) or 1150 ° C (picritic basalt). These were carried out in an internally heated vessel pressurized with Ar-H2 mixtures and fitted with a drop-quench device, and lasted for between 15 and 99 h. Either Au (950 ° C) or AuPd alloys (1100 and 1150 ° C) were used as containers. These latter perform satisfactorily under strongly oxidizing conditions, i.e., for fO2 above NNO+1 at 1100 and 1150 ° C. Below NNO+1, Pd- Au-S-Fe phases appear in the charges, suggesting extensive interaction between S and the capsule material. Experimental redox conditions, determined from Ni-Pd-O sensors, ranged between NNO+1.3 to +4.1 (basaltic andesite), +0.6 to +2.0 (K basalt), and +0.3 to +3.6 (picritic basalt). H2O concentrations in melt ranged from 8.2 wt % (basaltic andesite), decreasing to 2.2-3.9 wt % (K basalt) and 2.5-5.0 wt % (picritic basalt). All 3 compositions studied crystallize anhydrite and Fe-Ni-S-O sulphide as saturating S-bearing phases, anhydrite at high fO2 and sulphide at lower fO2, although melt composition also influences their stability. Anhydrite is present at a fO2 as low as NNO+1.5 in the K basalt. In the picritic

Partitioning of Ni, Co and V between Spinel-Structured Oxides and Silicate Melts: Importance of Spinel Composition

NASA Technical Reports Server (NTRS)

Righter, K.; Leeman, W. P.; Hervig, R. L.

2006-01-01

Partitioning of Ni, Co and V between Cr-rich spinels and basaltic melt has been studied experimentally between 1150 and 1325 C, and at controlled oxygen fugacity from the Co-CoO buffer to slightly above the hematite magnetite buffer. These new results, together with new Ni, Co and V analyses of experimental run products from Leeman [Leeman, W.P., 1974. Experimental determination of the partitioning of divalent cations between olivine and basaltic liquid, Pt. II. PhD thesis, Univ. Oregon, 231 - 337.], show that experimentally determined spinel melt partition coefficients (D) are dependent upon temperature (T), oxygen fugacity (fO2) and spinel composition. In particular, partition coefficients determined on doped systems are higher than those in natural (undoped) systems, perhaps due to changing activity coefficients over the composition range defined by the experimental data. Using our new results and published runs (n =85), we obtain a multilinear regression equation that predicts experimental D(V) values as a function of T, fO2, concentration of V in melt and spinel composition. This equation allows prediction of D(V) spinel/melt values for natural mafic liquids at relevant crystallization conditions. Similarly, D(Ni) and D(Co) values can be inferred from our experiments at redox conditions approaching the QFM buffer, temperatures of 1150 to 1250 C and spinel composition (early Cr-bearing and later Ti-magnetite) appropriate for basic magma differentiation. When coupled with major element modelling of liquid lines of descent, these values (D(Ni) sp/melt=10 and D(Co) sp/melt=5) closely reproduce the compositional variation observed in komatiite, mid-ocean ridge basalt (MORB), ocean island basalt (OIB) and basalt to rhyolite suites.

The Role of CO2 on Silica Undersaturated Melt Structure: Implication for Melt Physical Properties

NASA Astrophysics Data System (ADS)

Scaillet, B.; Morizet, Y.; Paris, M.; Gaillard, F.

2012-12-01

Silica undersaturated melts such as nephelinite and melilitite are very peculiar magmatic materials. Their occurrence on the Earth surface is often associated with carbonatites melts. These low-silica melts can dissolve a large quantity of CO2 issued from mantle fluid metasomatism. However, the melt structure, the way CO2 dissolves into these melts and the effect of different alkalis element are poorly constrained. We present preliminary experimental results on the melt structure of synthetic nephelinite (NBO/T = 1.25) and Ca-melilitite (NBO/T = 2.50) synthesized in the NKCMAS system and equilibrated at high-pressure (200-300 MPa), high-temperature (1250°C) with an excess C-O-H fluid phase. The nephelinite glasses were synthesized with varying K2O / K2O+Na2O (0-10 mol.% K2O) ratio so as to investigate the differential effect of those two cations. All experiments were conducted under oxidizing conditions (ΔNNO+5) resulting in binary fluid phase composition with CO2 and H2O species. The silicate melt structure, CO2 solubility and speciation were investigated using Micro-Raman and Solid State NMR spectroscopies for 13C, 1H, 29Si, 27Al and 23Na nuclei. The replacement of Na by K does not change the nephelinite melt structure for volatile-free sample suggesting that the basicity of these glasses is not dramatically affected by the presence of mixed alkali. Within 5 mol.% K2O, the CO2 solubility (measured in relative to Raman signature of the melt structure) is only slightly affected with an increasing CO2 solubility with increasing K2O content. As a function of pressure, we observe an increase in CO2 solubility consistent with previous studies. The 13C NMR investigation of the CO2 speciation show three different carbonates environments for CO2 in nephelinite melts attributed to non-network carbonates: 1) 170 ppm shift assigned to NBO-carb. Na or K; 2) 169 ppm assigned to NBO-carb. Ca; and 3) 165 ppm assigned to isolated Na+..CO32- carbonates. As K2O is increased into

Conduction mechanism in bismuth silicate glasses containing titanium

NASA Astrophysics Data System (ADS)

Dult, Meenakshi; Kundu, R. S.; Murugavel, S.; Punia, R.; Kishore, N.

2014-11-01

Bismuth silicate glasses mixed with different concentrations of titanium dioxide having compositions xTiO2-(60-x)Bi2O3-40SiO2 with x=0, 5, 10, 15 and 20 were prepared by the normal melt quench technique. The frequency dependence of the ac electrical conductivity of different compositions of titanium bismuth silicate glasses has been studied in the frequency range 10-1 Hz to 10 MHz and in the temperature range 623-703 K. The temperature and frequency dependent conductivity is found to obey Jonscher's universal power law for all the compositions of titanium bismuth silicate glass system. The dc conductivity (σdc), so called crossover frequency (ωH), and frequency exponent (s) have been estimated from the fitting of experimental data of ac conductivity with Jonscher's universal power law. Enthalpy to dissociate the cation from its original site next to a charge compensating center (Hf) and enthalpy of migration (Hm) have also been estimated. The conductivity data have been analyzed in terms of different theoretical models to determine the possible conduction mechanism. Analysis of the conductivity data and the frequency exponent shows that the correlated barrier hopping of electrons between Ti3+ and Ti4+ ions in the glasses is the most favorable mechanism for ac conduction. The temperature dependent dc conductivity has been analyzed in the framework of theoretical variable range hopping model (VRH) proposed by Mott which describe the hopping conduction in disordered semiconducting systems. The various polaron hopping parameters have also been deduced. Mott's VRH model is found to be in good agreement with experimental data and the values of inverse localization length of s-like wave function (α) obtained by this model with modifications suggested by Punia et al. are close to the ones reported for a number of oxide glasses.

A Physical Model for Three-Phase Compaction in Silicic Magma Reservoirs

NASA Astrophysics Data System (ADS)

Huber, Christian; Parmigiani, Andrea

2018-04-01

We develop a model for phase separation in magma reservoirs containing a mixture of silicate melt, crystals, and fluids (exsolved volatiles). The interplay between the three phases controls the dynamics of phase separation and consequently the chemical and physical evolution of magma reservoirs. The model we propose is based on the two-phase damage theory approach of Bercovici et al. (2001, https://doi.org/10.1029/2000JB900430) and Bercovici and Ricard (2003, https://doi.org/10.1046/j.1365-246X.2003.01854.x) because it offers the leverage of considering interface (in the macroscopic limit) between phases that can deform depending on the mechanical work and phase changes taking place locally in the magma. Damage models also offer the advantage that pressure is defined uniquely to each phase and does not need to be equal among phases, which will enable us to consider, in future studies, the large capillary pressure at which fluids are mobilized in mature, crystal-rich, magma bodies. In this first analysis of three-phase compaction, we solve the three-phase compaction equations numerically for a simple 1-D problem where we focus on the effect of fluids on the efficiency of melt-crystal separation considering the competition between viscous and buoyancy stresses only. We contrast three sets of simulations to explore the behavior of three-phase compaction, a melt-crystal reference compaction scenario (two-phase compaction), a three-phase scenario without phase changes, and finally a three-phase scenario with a parameterized second boiling (crystallization-induced exsolution). The simulations show a dramatic difference between two-phase (melt crystals) and three-phase (melt-crystals-exsolved volatiles) compaction-driven phase separation. We find that the presence of a lighter, significantly less viscous fluid hinders melt-crystal separation.

Bismuth silicate glass containing heavy metal oxide as a promising radiation shielding material

NASA Astrophysics Data System (ADS)

Elalaily, Nagia A.; Abou-Hussien, Eman M.; Saad, Ebtisam A.

2016-12-01

Optical and FTIR spectroscopic measurements and electron paramagnetic resonance (EPR) properties have been utilized to investigate and characterize the given compositions of binary bismuth silicate glasses. In this work, it is aimed to study the possibility of using the prepared bismuth silicate glasses as a good shielding material for γ-rays in which adding bismuth oxide to silicate glasses causes distinguish increase in its density by an order of magnitude ranging from one to two more than mono divalent oxides. The good thermal stability and high density of the bismuth-based silicate glass encourage many studies to be undertaken to understand its radiation shielding efficiency. For this purpose a glass containing 20% bismuth oxide and 80% SiO2 was prepared using the melting-annealing technique. In addition the effects of adding some alkali heavy metal oxides to this glass, such as PbO, BaO or SrO, were also studied. EPR measurements show that the prepared glasses have good stability when exposed to γ-irradiation. The changes in the FTIR spectra due to the presence of metal oxides were referred to the different housing positions and physical properties of the respective divalent Sr2+, Ba2+ and Pb2+ ions. Calculations of optical band gap energies were presented for some selected glasses from the UV data to support the probability of using these glasses as a gamma radiation shielding material. The results showed stability of both optical and magnetic spectra of the studied glasses toward gamma irradiation, which validates their irradiation shielding behavior and suitability as the radiation shielding candidate materials.

Dynamics of the Axial Melt Lens/Dike transition at fast spreading ridges: assimilation and hydrous partial melting

NASA Astrophysics Data System (ADS)

France, L.; Ildefonse, B.; Koepke, J.

2009-04-01

Recent detailed field studies performed in the Oman ophiolite on the gabbro/sheeted dike transition, compared to corresponding rocks from the EPR drilled by IODP (Site 1256), constrain a general model for the dynamics of the axial melt lens (AML) present at fast spreading ridges (France et al., 2008). This model implies that the AML/dike transition is a dynamic interface migrating up- and downward, and that the isotropic gabbro horizon on top of the igneous section represents its fossilization. It is also proposed that upward migrations are associated to reheating of the base of the sheeted dike complex and to assimilation processes. Plagiogranitic lithologies are observed close to the truncated base of the dikes and are interpreted to represent frozen melts generated by partial melting of previously hydrothermalized sheeted dikes. Relicts of previously hydrothermalized lithologies are also observed in the fossil melt lens, and are associated to lithologies that have crystallized under high water activities, with clinopyroxene crystallizing before plagioclase, and An-rich plagioclase. To better understand our field data, we performed hydrous partial melting experiments at shallow pressures (0.1 GPa) under slightly oxidizing conditions (NNO oxygen buffer) and water saturated conditions on hydrothermalized sheeted dike sample from the Oman ophiolite. These experiments have been performed between 850°C and 1030°C; two additional experiments in the subsolidus regime were also conducted (750°C and 800°C). Clinopyroxenes formed during incongruent melting at low temperature (<910°C) have compositions that match those from the corresponding natural rocks (reheated base of the sheeted dike and relicts of assimilated lithologies). In particular, the characteristic low TiO2 and Al2O3 contents are reproduced. The experimental melts produced at low temperatures correspond to compositions of typical natural plagiogranites. In natural settings, these silicic liquids would be

Flow, melt and fossil seismic anisotropy beneath Ethiopia

NASA Astrophysics Data System (ADS)

Hammond, James; Kendall, J.-Michael; Wookey, James; Stuart, Graham; Keir, Derek; Ayele, Atalay

2014-05-01

Ethiopia is a region where continental rifting gives way to oceanic spreading. Yet the role that pre-existing lithospheric structure, melt, mantle flow or active upwellings may play in this process is debated. Measurements of seismic anisotropy are often used to attempt to understand the contribution that these mechanisms may play. In this study we use new data in Afar, Ethiopia along with legacy data across Ethiopia, Djibouti and Yemen to obtain estimates of mantle anisotropy using SKS-wave splitting. We show that two layers of anisotropy exist, and use shear-wave splitting tomography to invert for these. We show that fossil anisotropy with fast directions oriented northeast-southwest may be preserved in the lithosphere away from the rift. Beneath the Main Ethiopian Rift and parts of Afar, anisotropy due aligned melt due to sharp changes in lithospheric thickness dominate the shear-wave splitting signal in the mantle. Beneath Afar, away from lithospheric topography, melt pockets associated with the crustal magma storage dominate the signal and little anisotropy is seen in the uppermost mantle suggesting melt retains no preferential alignment, possibly due to a lack of mantle lithosphere. These results show the important role melt plays in weakening the lithosphere and imply that as rifting evolves passive upwelling sustains extension. A dominant northeast-southwest anisotropic fast direction is observed in a deeper layer across all of Ethiopia. This suggests that a conduit like plume is absent beneath Afar today, rather a broad flow from the southwest dominates in the upper mantle.

Convective melting in a magma chamber: theory and numerical experiment.

NASA Astrophysics Data System (ADS)

Simakin, A.

2012-04-01

We present results of the numerical modeling of convective melting in a magma chamber in 2D. Model was pointed on the silicic system approximated with Qz-Fsp binary undersaturated with water. Viscosity was calculated as a function of the melt composition, temperature and crystal content and comprises for the pure melt 104.5-105.5 Pas. Lower boundary was taken thermally insulated in majority of the runs. Size of FEM (bilinear elements) grid for velocity is 25x25 cm and for the integration of the density term 8x8 cm. Melting of the chamber roof proceeds with the heat supply due to the chaotic thermo-compositional convection and conductive heat loose into melted substrate. We compare our numerical data with existing semi-analytical models. Theoretical studies of the assimilation rates in the magma chambers usually use theoretical semi-analytical model by Huppert and Sparks (1988) (e.g., Snyder, 2000). We find that this model has strong points: 1) Independence of the melting rate on the sill thickness (Ra>>Rac) 2) Independence of the convective heat transfer on the roof temperature 3) Determination of the exponential thermal boundary layer ahead of the melting front and weak points: 1) Ignoring the possibility of the crystallization without melting regime for narrow sills and dykes. 2)Neglecting of two-phase character of convection. 3)Ignoring of the strong viscosity variation near the melting front. Independence of convective flux from the sill size (at Ra>>Rac) allows reducing of computational domain to the geologically small size (10-15 m). Concept of exponential thermal boundary layer is also rather important. Length scale (L0) of this layer is related to the melting rate and thermal diffusivity coefficient kT as L0=kT/um and at the melting rate 10 m/yr becomes about 2 m. Such small scale implies that convective melting is very effective (small conductive heat loss) and part of the numerical domain filled with roof rocks can be taken small. In the H&S model

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Calcium silicate. 172.410 Section 172.410 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely...

A scaling relationship for impact-induced melt volume

NASA Astrophysics Data System (ADS)

Nakajima, M.; Rubie, D. C.; Melosh, H., IV; Jacobson, S. A.; Golabek, G.; Nimmo, F.; Morbidelli, A.

2016-12-01

During the late stages of planetary accretion, protoplanets experience a number of giant impacts and extensive mantle melting. The impactor's core sinks through the molten part of the target mantle (magma ocean) and experiences metal-silicate partitioning (e.g., Stevenson, 1990). For understanding the chemical evolution of the planetary mantle and core, we need to determine the impact-induced melt volume because the partitioning strongly depends on the ranges of the pressures and temperatures within the magma ocean. Previous studies have investigated the effects of small impacts (i.e. impact cratering) on melt volume, but those for giant impacts are not well understood yet. Here, we perform giant impact simulations to derive a scaling law for melt volume as a function of impact velocity, impact angle, and impactor-to-target mass ratio. We use two different numerical codes, namely smoothed particle hydrodynamics we developed (SPH, a particle method) and the code iSALE (a grid-based method) to compare their outcomes. Our simulations show that these two codes generally agree as long as the same equation of state is used. We also find that some of the previous studies developed for small impacts (e.g., Abramov et al., 2012) overestimate giant impact melt volume by orders of magnitudes partly because these models do not consider self-gravity of the impacting bodies. Therefore, these models may not be extrapolated to large impacts. Our simulations also show that melt volume can be scaled by the total mass of the system. In this presentation, we further discuss geochemical implications for giant impacts on planets, including Earth and Mars.

21 CFR 172.410 - Calcium silicate.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Calcium silicate. 172.410 Section 172.410 Food and... PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Anticaking Agents § 172.410 Calcium silicate. Calcium silicate, including synthetic calcium silicate, may be safely used in food in accordance with the...

Experimental determination of carbon solubility in Fe-Ni-S melts

NASA Astrophysics Data System (ADS)

Zhang, Zhou; Hastings, Patrick; Von der Handt, Anette; Hirschmann, Marc M.

2018-03-01

To investigate the effect of metal/sulfide and Ni/Fe ratio on the C storage capacity of sulfide melts, we determine carbon solubility in Fe-Ni-S melts with various (Fe + Ni)/S and Ni/Fe via graphite-saturated high-pressure experiments from 2-7 GPa and 1200-1600 °C. Consistent with previous results, C solubility is high (4-6 wt.%) in metal-rich sulfide melts and diminishes with increasing S content. Melts with near M/S = 1 (XS > 0.4) have <0.5 wt.% C in equilibrium with graphite. C solubility is diminished modestly with increased Ni/Fe ratio, but the effect is most pronounced for S-poor melts, and becomes negligible in near-monosulfide compositions. Immiscibility between S-rich and C-rich melts is observed in Ni-poor compositions, but above ∼18 wt.% Ni there is complete miscibility. Because mantle sulfide compositions are expected to have high Ni concentrations, sulfide-carbide immiscibility is unlikely in natural mantle melts. An empirical parameterization of C solubility in Ni-Fe-S melts as a function of S and Ni contents allows estimation of the C storage capacity of sulfide in the mantle. Importantly, as the metal/sulfide (M/S) ratio of the melt increases, C storage increases both because C solubility increases and because the mass fraction of melt is enhanced by addition of metal from surrounding silicates. Under comparatively oxidized conditions where melts are near M/S = 1, as prevails at <250 km depth, bulk C storage is <3 ppm. In the deeper, more reduced mantle where M/S increases, up to 200 ppm C in typical mantle with 200 ± 100 ppm S can be stored in Fe-Ni-S melts. Thus, metal-rich sulfide melts are the principal host of carbon in the deep upper mantle and below. Residual carbon is present either as diamond or, if conditions are highly reduced and total C concentrations are low, solid alloy.

Melt/mantle interaction and melt evolution in the Sartohay high-Al chromite deposits of the Dalabute ophiolite (NW China)

NASA Astrophysics Data System (ADS)

Zhou, M.-F.; Robinson, P. T.; Malpas, J.; Aitchison, J.; Sun, M.; Bai, W.-J.; Hu, X.-F.; Yang, J.-S.

2001-06-01

The Sartohay block of the Dalabute ophiolite consists chiefly of mantle harzburgite and lherzolite with minor dunite. These rocks host voluminous chromite deposits with lenticular or vein-like shapes. The podiform chromitites are associated with, and cross-cut by, numerous troctolite dykes. Chromite in the chromitites has Al 2O 3 (23-31 wt%), TiO 2 (0.29-0.44 wt%), and Cr 2O 3 contents (<45 wt%) with Cr#s [100Cr/(Cr+Al)] (<60), typical of high-Al chromite deposits. The host peridotites in Sartohay have been texturally and geochemically modified by magmas from which the high-Al chromitites and mafic dykes formed. Dunites commonly envelop the podiform chromite bodies and show transitional contacts with the peridotites. Some of the peridotites and chromitites contain plagioclase that crystallized from impregnated melts. The dunite locally grades into troctolite with increasing plagioclase contents. As a result of melt impregnation, peridotites and dunites show variable Ca and Al contents and LREE enrichment. The parental magma of the chromitites was likely tholeiitic in composition, derived from partial melting of the asthenospheric mantle in a rising diapir. The interaction between this magma and pre-existing lithospheric mantle, composed of depleted lherzolite, would have formed a more silicic, tholeiitic magma from which high-Al chromitites crystallized. During this interaction, harzburgite and dunite were depleted in modal pyroxene and enriched in some incompatible elements (such as Al, Ca and LREE) due to melt impregnation.