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At least 91 records · Page 5

Textural constraints on effusive silicic volcanism - Beyond the permeable foam model

The paper reports textural observations and presents isotopic evidence from active and recent silicic lava flows which show that at least some vesiculation occurs during surface advance of extrusions, after magma has reached the earth's surface. This view is in contrast to the widely promoted 'permeable foam' model, which states that all volatiles escape during ascent of the magma, and that all dense glassy material in lava flows forms from the collapse of pumiceous lava, i.e., that silicic lavas emerge as highly inflated foam flows. The permeable foam model also implies the unlikely requirement that explosive-to-effusive transitions be associated with an increase in the eruption rate. A more comprehensive model for the emplacement of silicic extrusions that allows for early gas loss during ascent, as well as late-stage vesiculation, is presented. The way in which the redistribution of volatiles during surface flow can increase explosive hazards from silicic lavas days, weeks, or months after the lava emerges from the event is discussed.

Fink, Jonathan H.↗

The unique radar scattering properties of silicic lava flows and domes

Silicic (silica-rich) lava flows, such as rhyolite, rhyodacite, and dacite, possess unique physical properties primarily because of the relatively high viscosity of the molten lava. Silicic flows tend to be thicker than basaltic flows, and the resulting large-scale morphology is typically a steep-sided dome or flow lobe, with aspect ratios (height/length) sometimes approaching unity. The upper surfaces of silicic domes and flows are normally emplaced as relatively cool, brittle slabs that fracture as they are extruded from the central vent areas, and are then rafted away toward the flow margin as a brittle carapace above a more ductile interior layer. This mode of emplacement results in a surface with unique roughness characteristics, which can be well-characterized by multiparameter synthetic aperture radar (SAR) observations. In this paper, we examine the scattering properties of several silicic domes in the Inyo volcanic chain in the Eastern Sierra of California, using AIRSAR and TOPSAR data. Field measurements of intermediate-scale (cm to tens of m) surface topography and block size are used to assess the mechanisms of the scattering process, and to quantify the unique roughness characteristics of the flow surfaces.

Plaut, Jeffrey J.↗

Annealing of Silicate Dust by Nebular Shocks at 10 AU

Silicate dust grains in the interstellar medium are known to be mostly amorphous, yet crystalline silicate grains have been observed in many long-period comets and in protoplanetary disks. Annealing of amorphous silicate grains into crystalline grains requires temperatures greater than or approximately equal to 1000 K, but exposure of dust grains in comets to such high temperatures is apparently incompatible with the generally low temperatures experienced by comets. This has led to the proposal of models in which dust grains were thermally processed near the protoSun, then underwent considerable radial transport until they reached the gas giant planet region where the long-period comets originated. We hypothesize instead that silicate dust grains were annealed in situ, by shock waves triggered by gravitational instabilities. We assume a shock speed of 5 km/s, a plausible value for shocks driven by gravitational instabilities. We calculate the peak temperatures of pyroxene grains under conditions typical in protoplanetary disks at 5-10 AU. We show that in situ annealing of micron-sized dust grains can occur, obviating the need for large-scale radial transport.

Harker, David E.↗

Structural Evolution and Mechanical Properties of PMR-15/Layered Silicate Nanocomposites

In the first year of this research, we successfully synthesized and characterized Polymer/ Layered Silicate nanocomposite using the polyimide PMR-15 as the polymer and several layered silicate nanoparticles. We have scaled up the process to allow fabrication of monoliths using these nanocomposites. The morphology of these systems was found to evolve during processing to an exfoliated structure for one system and intercalated for the rest. Correlation with Transmission Electron Microscopy studies is underway. Dynamic mechanical analysis (DMA) results showed a significant increase in the thermomechanical properties (E' and E'') of 2.5 wt.% clay loaded nanocomposites in comparison to the neat polyimide. Increasing the clay loading to 5 wt.% decreased these properties. Higher glass transition temperatures were observed for 2.5 wt.% nanocomposites compared to the neat polyimide. A lower coefficient of thermal expansion was observed only for the PGV/PMR-15 nanocomposite. An improvement in the flexural properties (modulus, strength and elongation) was observed for the 2.5 wt.% nanocomposite but not for the 5 wt.% nanocomposites. The improved barrier properties polymer/ silicate nanocomposites suggest that moisture uptake should be decreased for PMR-15 nanocomposites. The results of some recent experiments to examine delineate the ability of the silicate nanoparticles in improving the hydrolytic degradation of PMR-15 will be discussed.

Campbell, Sandi↗

Internal Rb-Sr Age and Initial Sr-87/Sr-86 of a Silicate Inclusion from the Campo Del Cielo Iron Meteorite

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.

Liu, Y.↗

C-O-H ratios of silicate melt inclusions in basalts from the Galapagos Spreading Center near 95 degrees W: a laser decrepitation mass spectrometry study

Volatile ratios (primarily of H2O and CO2) in individual silicate melt (glass) inclusions in minerals have been analyzed using laser volatilization and mass spectrometry. A Nd-glass laser was used to produce 50-micrometer diameter pits in silicate melt inclusions. Released volatiles were analyzed directly with a computer-controlled quadrupole mass spectrometer. The detection limits for CO2 and H2O were on the order of 3 x 10(-14) and 3 x 10(-13) moles, respectively. The reproducibility for CO2/H2O was better than +/- 9%. The total range of volatile ratios from vitreous silicate glass inclusions contained in a suite of Galapagos lavas were: 0.018 to 1.193 for CO2/H2O; 0.002 to 0.758 for CO/H2O; 0 to 0.454 for CH4/H2O; and 0 to 0.432 for Ar/H2O. The mean CO2/H2O from the propagating rift (0.245 +/- 0.068) silicate glass inclusions is significantly lower than that of the actively failing rift (0.641 +/- 0.241); this difference probably reflects different degrees of degassing during magmatic histories for the two regions. Relatively undifferentiated failing rift magmas must have relatively short crustal residence times prior to eruption and, therefore, have not undergone significant degassing of CO2, as would appear to be the case for the more highly fractionated propagating rift magmas. The laser-mass spectrometric system described herein has the ability to act as a point-source probing device that can differentiate between the various volatile sites in minerals and rocks (as well as synthetic materials) on a micrometer scale.

NASA Discipline Exobiology↗

How Deep and Hot was Earth's Magma Ocean? Combined Experimental Datasets for the Metal-silicate Partitioning of 11 Siderophile Elements - Ni, Co, Mo, W, P, Mn, V, Cr, Ga, Cu and Pd

Since approximately 1990 high pressure and temperature (PT) experiments on metal-silicate systems have showed that partition coefficients (D) for siderophile (iron-loving) elements are much different than those measured at low PT conditions. The high PT data have been used to argue for a magma ocean during growth of the early Earth. Initial conclusions were based on experiments and calculations for a small number of elements such as Ni and Co. However, for many elements only a limited number of experimental data were available then, and they only hinted at values of metal-silicate D's at high PT conditions. In the ensuing decades there have been hundreds of new experiments carried out and published on a wide range of siderophile elements. At the same time several different models have been advanced to explain the siderophile elements in the earth's mantle: a) intermediate depth magma ocean; 25-30 GPa, b) deep magma ocean; up to 50 GPa, and c) early reduced and later oxidized magma ocean. Some studies have drawn conclusions based on a small subset of siderophile elements, or a set of elements that provides little leverage on the big picture (like slightly siderophile elements), and no single study has attempted to quantitatively explain more than 5 elements at a time. The purpose of this abstract is to update the predictive expressions outlined by Righter et al. (1997) with new experimental data from the last decade, test the predictive ability of these expressions against independent datasets (there are more data now to do this properly), and to apply the resulting expressions to the siderophile element patterns in Earth's upper mantle. The predictive expressions have the form: lnD = alnfO2 + b/T + cP/T + d(1Xs) + e(1Xc) + SigmafiXi + g These expressions are guided by the thermodynamics of simple metal-oxide equilibria that control each element, include terms that mimic the activity coefficients of each element in the metal and silicate, and quantify the effect of variable oxygen fugacity. Preliminary results confirm that D(Ni) and D(Co) converge at pressures near 25-30 GPa and approximately 2200 K, and show that D(Pd) and D(Cu) become too low at the PT conditions of the deepest models. Furthermore, models which force fit V and Cr mantle concentrations by metal-silicate equilibrium overlook the fact that at early Earth mantle fO2, these elements will be more compatible in Mg-perovskite and (Fe,Mg)O than in metal. Thus an intermediate depth magma ocean, at 25-30 GPa, 2200 K, and at IW-2, can explain more mantle siderophile element concentrations than other models.

Righter, Kevin↗

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

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.

Danielson, L. R.↗

Formation and Processing of Amorphous Silicates in Primitive Carbonaceous Chondrites and Cometary Dust

Chondritic-porous interplanetary dust particles (CP IDPs) exhibit strongly heterogeneous and unequilibrated mineralogy at sub-micron scales, are enriched in carbon, nitrogen and volatile trace elements, and contain abundant presolar materials [1-4]. These observations suggest that CP IDPs have largely escaped the thermal processing and water-rock interactions that have severely modified or destroyed the original mineralogy of primitive meteorites. CP IDPs are believed to represent direct samples of the building blocks of the Solar System - a complex mixture of nebular and presolar materials largely unperturbed by secondary processing. The chemical and isotopic properties of CP IDPs and their atmospheric entry velocities are also consistent with cometary origins. GEMS (glass with embedded metal and sulfides) grains are a major silicate component of CP IDPs. GEMS grains are < 0.5 microns in diameter objects that consist of numerous 10 to 50 nm-sized Fe-Ni metal and Fe-Ni sulfide grains dispersed in a Mg-Si-Al-Fe amorphous silicate matrix [2, 5]. Based on their chemistry and isotopic compositions, most GEMS appear to be non-equilibrium condensates from the early solar nebula [2]. If GEMS grains are a common nebular product, then they should also be abundant in the matrices of the most physically primitive chondritic meteorites. Although amorphous silicates are common in the most primitive meteorites [6-9], their relationship to GEMS grains and the extent to which their compositions and microstructure have been affected by parent body processing (oxidation and aqueous alteration) is poorly constrained. Here we compare and contrast the chemical, microstructural and isotopic properties of amorphous silicates in primitive carbonaceous chondrites to GEMS grains in IDPs.

Keller, Lindsay P.↗

Core Formation on Asteroid 4 Vesta: Iron Rain in a Silicate Magma Ocean

Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA's Dawn spacecraft, suggest that Vesta resembles H chondrites in bulk chemical composition, possibly with about 25% of a CM-chondrite like composition added in. For this model, the core is 15% by mass (or 8 volume %) of the asteroid. 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. Melting in the Fe-Ni-S system begins at a cotectic temperature of ~940 deg. C. Only about 40% of the total metal phase, or 3-4 volume % of Vesta, melts prior to the onset of silicate melting. Liquid iron in solid silicate initially forms isolated pockets of melt; connected melt channels, which are necessary if the metal is to segregate from the silicate, are only possible when the metal phase exceeds about 5 volume %. Thus, metal segregation to form a core does not occur prior to the onset of silicate melting.

Kiefer, Walter S.↗

Thermodynamics of the Lu2O3 – SiO2 system and comparison to other Rare Earth Silicates

Environmental barrier coatings are necessary to protect SiC based ceramics and composites from water vapor degradation in harsh engine environments. Currently, rare earth (RE) silicates are the most promising systems to protect SiC based ceramics and composites. This protection is largely based on reduced silica activity in these rare earth silicates which results in a lowered reactivity with water vapor. To that end, previous Knudsen effusion mass spectrometry (KEMS) studies have explored RE = Yb, Y silicates to measure the reduced silica activity and subsequent water vapor reactivity. Similarly, this work employs the KEMS technique to measure the SiO(g) vapor pressure in Lu containing RE silicates to calculate the activity of silica within the monosilicate [log(a(SiO2)) = -2351.1*1/T-1.6731] and the disilicate (log(a(SiO2)) = -4884.0*1/T + 2.2208) as a function of temperature. The enthalpies of formation for Lu monosilicate from the oxides and the elements were calculated to be -45±3 kJ/mol at 1550 K and -2831.1±12 kJ/mol at 298 K, respectively. The measured enthalpy of formation and those found in literature are compared to modeled values from density functional theory and those estimated using electronegativity.

Knudesen Effusion Mass Spectrometry↗

Machine Learning Applications to Metal-Silicate Equilibria and their Insights into Core Formation

An extensive number of studies have experimentally investigated how elements distribute between metal and silicate phases, to better constrain core-mantle chemical equilibrium. Here, we present a new database compiling all (to our knowledge) experimental data on liquid metal-silicate partitioning from 118 peer-reviewed publications. We applied various machine learning techniques to gain further insights into these partitioning equilibria and their dependencies. We performed a network analysis to investigate the relationship between experiments and partition coefficients, which enables visualizing gaps in the experimental dataset and biases related to varying experimental conditions and analytical setup. In addition, semi-empirical thermodynamic models are commonly used to extrapolate these chemical reactions to the wide range of pressure, temperature and compositional conditions of planetary differentiation. These models are based on linear regressions that assume continuous relationship between partition coefficients and experimental variables. Here, we considered random forest regressions, which are algorithms based on ensembles of decision trees and does not consider continuous effects of each variable. The application of this regression significantly improves the prediction of metal-silicate partitioning for several elements including Ni, Si and Cr. We will show how this new approach improves our understanding of elemental exchange between metal and silicate and their implications for the Earth’s core formation.

siderophile element↗

Oxygen Isotopes in AMMS and IDPS: Universality of Oxygen Isotope Systematics Of Crystalline Silicates in Comets

It has been suggested that the major source of crystalline silicates in comets is CR chondrule-like materials along with minor sources including O, R, CH-CB chondrite chondrule-like materials based on the comparisons of oxygen isotope systematics between cometary silicates and chondrules from various types of primitive chondrites [1-3]. However, cometary silicates used for these studies are from only two comets: Wild2 and a parent comet of U2-20GCA. It is uncertain that the oxygen isotope systematics represent that of crystalline silicates in all comets.

D Nakashima↗

Thermochemistry of Silicates

The thermodynamic properties of vapor and condensed phases of silicates are crucial in many fields of science. These quantities address fundamental questions on the formation, stability, transformation, and physical properties of silicate minerals and silicate coating compositions. Here the thermodynamic activities of silica and other species in solid solution have been measured by the analysis of the corresponding high temperature vapors using Knudsen Effusion Mass Spectrometry (KEMS). In first set of experiments KEMS has been used to examine the volatility sequence of species (Fe, SiO, Mg, O2 and O) present in the vapor phase during heating of fosterite-rich olivine (Fo93Fa7) up to 2400 C and to measure the Fe, SiO and Mg activities in its solid solution. The data of fosterite-rich olivine are essential for thermochemical equilibrium models to predict the atmospheric and surface composition of hot, rocky exoplanets (Lava Planets). In the second set of experiments the measured thermodynamic activities of the silica in Y2O3-SiO2 and Yb2O3-SiO2 systems are used to assess their reactivity and degradation recession as environmental barrier coatings (EBCs) in combustion environments (e.g. non-moveable parts of gas turbine engine).

Silicates↗

Discrimination of basic silicate rocks by recognition maps processed from aerial infrared data.

A method is presented which can be used to map silicate rock-type from aerial infrared data. The method has been partially tested over a sand quarry at Mill Creek, Oklahoma, in which highly siliceous targets were discriminated from nonsilicates in the scene. The technique is currently being tested experimentally on basic silicates. On the basis of the Mill Creek results and theoretical considerations, percent SiO2 differences as small as 14% should be detectable with the University of Michigan's currently available detectors.

Vincent, R. K.↗

Spectral compositional imaging of silicate rocks.

A technique is presented for the broad-scale mapping of gross compositional differences in silicate rocks from three medium-width (2 to 3 microns) spectral channels of thermal infrared scanner data. Ratios of radiances in two of the channels as measured by a two-element Hg:Cd:Te detector from an altitude of 1000 meters are calculated for 25 silicate rocks. The ratios are shown to be nearly linearly correlated with the position of the centers of gravity of the reststrahlen spectral emissivity features, as measured in the laboratory. Further, the ratios are shown to be generally correlated with SiO2 content of silicate rocks. A third channel is proposed for correction of temperature variations across the scene.

Vincent, R. K.↗

Redox equilibria of multivalent ions in silicate glasses

Experimental studies were made on the compositional dependence of the redox equilibrium of Eu in synthetic silicate liquids, together with an empirical model describing the observed compositional dependence. Electron paramagnetic resonance (EPR) was used to measure the concentration ratio of Eu(2+) to Eu(3+) in various glasses formed by rapidly quenching silicate liquids. The compositional field studied comprised mixtures of SiO2, TiO2, Al2O3, CaO, MgO, and Na2O. The proposed model describes the Eu(2+)/Eu(3+) ratio over the entire compositional field in terms of parameters easily related to each glass composition. The general applicability and utility of the model is further demonstrated by its application to the Fe(2+)-Fe(3+), Ce(3+)-Ce(4+), and Cr(3+)-Cr(6+) redox reactions in binary alkali oxide silicate glasses of Li, Na, and K.

Lauer, H. V., Jr.↗

I-Xe dating of silicate and troilite from IAB iron meteorites

Silicate and troilite inclusions from IAB iron meteorites were dated by the I-Xe technique. Silicate samples from inclusions in the Copiapo, Landes, Woodbine, Pitts and Mundrabilla meteorites and troilite samples from Pitts and Mundrabilla were subjected to neutron irradiation and the xenon isotope ratios produced were determined. Well-defined I-Xe ages were obtained for Woodbine, Copiapo, Landes and Mundrabilla and are found to be within 3.7 million years of the Bjurbole meteorite, suggesting a close relationship to the stone chondrites. The analysis of troilite from Pitts suggests an age of 17 million years older than Bjurbole, while Mundrabilla troilite is observed to predate Mundrabilla silicate. The abundances of Ga, Ge and Ni are found to be correlated with I-Xe ages, supporting the validity of the I-Xe dating method. The results are considered to favor a nebular model of meteorite formation.

Niemeyer, S.↗