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At least 559 records · Page 31

Solubility of Sulfur in Shergottitic Silicate Melts Up to 0.8 GPA: Implications for S Contents of Shergottites

Shergottites have high S contents (1300 to 4600 ppm; [1]), but it is unclear if they are sulfide saturated or under-saturated. This issue has fundamental implications for determining the long term S budget of the martian surface and atmosphere (from mantle degassing), as well as evolution of the highly siderophile elements (HSE) Au, Pd, Pt, Re, Rh, Ru, Ir, and Os, since concentrations of the latter are controlled by sulfide stability. Resolution of sulfide saturation depends upon temperature, pressure, oxygen fugacity (and FeO), and magma composition [2]. Expressions derived from experimental studies allow prediction of S contents, though so far they are not calibrated for shergottitic liquids [3-5]. We have carried out new experiments designed to test current S saturation models, and then show that existing calibrations are not suitable for high FeO and low Al2O3 compositions characteristic of shergottitic liquids. The new results show that existing models underpredict S contents of sulfide saturated shergottitic liquids by a factor of 2.

Righter, K.↗

Constraining the Depth of a Martian Magma Ocean through Metal-Silicate Partitioning Experiments: The Role of Different Datasets and the Range of Pressure and Temperature Conditions

Mars accretion is known to be fast compared to Earth. Basaltic samples provide a probe into the interior and allow reconstruction of siderophile element contents of the mantle. These estimates can be used to estimate conditions of core formation, as for Earth. Although many assume that Mars went through a magma ocean stage, and possibly even complete melting, the siderophile element content of Mars mantle is consistent with relatively low pressure and temperature (PT) conditions, implying only shallow melting, near 7 GPa and 2073 K. This is a pressure range where some have proposed a change in siderophile element partitioning behavior. We will examine the databases used for parameterization and split them into a low and higher pressure regime to see if the methods used to reach this conclusion agree for the two sets of data.

Righter, K.↗

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Ming, Douglas W.↗

High-Temperature, Perhaps Silicic, Volcanism on Mars Evidenced by Tridymite Detection in High-SiO2 Sedimentary Rock at Gale Crater, Mars

The Mars Science Laboratory (MSL) rover, Curiosity, has been exploring sedimentary rocks within Gale crater since landing in August, 2012. On the lower slopes of Aeolis Mons (a.k.a. Mount Sharp), drill powder was collected from a high-silica (74 wt% SiO2) outcrop named Buckskin (BK). It was a surprise to find that the Buckskin sample contained significant amounts of the relatively rare silica polymorph tridymite. We describe the setting of the Buckskin sample, the detection of tridymite by the MSL Chemistry and Mineralogy (CheMin) X-ray diffraction instrument, and detection implications. Geologic setting: The Buckskin outcrop is part of the Murray formation exposed in the Marias Pass area. The formation was previously studied by CheMin in the Pahrump Hills member [1] where three samples of drill fines were analyzed (Confidence Hills (CH), Mojave2 (MJ) and Telegraph Peak (TP) [2]). Assuming approximately horizontal bedding, the Buckskin outcrop is approx.15 m stratigraphically above the bottom of the Pahrump Hills member. Mudstone, generally characterized by fine lamination, is the dominant depositional facies [1]. Buckskin Mineralogical and Chemical Composition: The CheMin instrument and XRD pattern analysis procedures have been previously discussed [3-6]. The diffraction pattern used for quantitative XRD analysis (Fig. 1) is the sum of the first 4 of 45 diffraction images. The remaining images are all characterized by both on-ring and off-ring diffraction spots that we attributed to poor grain motion and particle clumping. Coincident with particle clumping was a significant decrease in the intensity of the tridymite diffraction peaks (Fig. 2a). The derived mineralogical composition of the crystalline component (derived from the first 4 diffraction images) is given in Table 1. The tridymite is well-crystalline and its pattern is refined as monoclinic tridymite (Fig 1). Mineral chemical compositions were derived from XRD unit cell parameters or obtained from stoichiometry. The XRD-calculated amorphous component was 50 +/- 15 wt%. We constrained the value to 60 wt% because it is the minimum value necessary to give a positive Al2O3 concentration for the amorphous component using APXS data for the post-sieve dump pile (Table 2). The amorphous component has high SiO2 (approx.77 wt%) and high anion (SO3+P2O5+Cl ~10 wt%) concentrations. Calculation shows that a cation-anion balance is achieved if the cations in the amorphous component except SiO2 and TiO2, which do not readily form salts, are assumed to be present as amorphous mixed-cation sulfates, phosphates, and chlorides (or perchlorates/ chlorates).

Morris, R. V.↗

Space Weathering of Silicates Simulated by Successive Laser Irradiation: in Situ Reflectance Measurements of Fo90, Fo99+, and SiO2

Pulsed-laser irradiation causes the visible-near-infrared spectral slope of olivine (Fo90 and Fo99+) and SiO2 to increase (redden), while the olivine samples darken and the SiO2 samples brighten slightly. XPS analysis shows that irradiation of Fo90 produces metallic Fe. Analytical SEM and TEM measurements confirm that reddening in the Fo90 olivine samples correlates with the production of "nanophase" metallic Fe (npFe0) grains, 20-50 nm in size. The reddening observed in the SiO2 sample is consistent with the formation of SiO or other SiOx species that absorb in the visible. The weak spectral brightening induced by laser irradiation of SiO2 is consistent with a change in surface topography of the sample. The darkening observed in the olivine samples is likely caused by the formation of larger npFe0 particles, such as the 100-400 nm diameter npFe0 identified during our TEM analysis of Fo90 samples. The Fo90 reflectance spectra are qualitatively similar to those in previous experiments suggesting that in all cases formation of npFe0 is causing the spectral alteration. Finally, we find that the accumulation of successive laser pulses cause continued sample darkening in the Vis-NIR, which suggests that repeated surface impacts are an efficient way to darken airless body surfaces.

Airless planetary bodies↗

Distribution of Alkalis (Na, Cs, Rb) Between Silicate and Sulfide: Implications for Planetary Volatile Depletion

The abundances of volatile elements in the Earth's mantle are correlated with their temperatures of condensation. This depletion can be due to either incomplete condensation of the elements during the nebula condensation or evaporation processes during planetary growth. Elements that have affinities with metals (siderophile) and sulfides (chalcophile) are additionally depleted due to their segregation into the core. Therefore, study of lithophile elements could be useful to isolate processes of volatilization and their effect on the abundance of the elements in the Earth's mantle. However, the correlation of these lithophile elements including alkali elements, with their temperatures of condensation shows a significant scatter, which is difficult to reconcile with a depletion by vaporization or incomplete condensation alone.

Boujibar, A.↗

Corrigendum to "Mass Spectrometric Measurements of the Silica Activity in the Yb2O3-SiO2 System and Implications to Assess the Degradation of Silicate-Based Coatings in Combustion Environments"

The authors regret that errors appeared in the above manuscript.The corrections that need to be made are highlighted in yellow in the thermodynamic cycle of Table 2. The enthalpies in reactions 2, 5 and 6 are negative. Now that the enthalpies in reactions 2, 5 and 6 are negative, the correct enthalpy of formation of Yb2SiO5 is 2774 11 kJ mol-1. Also, the correct element in the formula Y2SiO5 on the right side of equation 2 is Yb instead Y.

Costa, Gustavo↗

Onset of long-lived silicic and alkaline magmatism in eastern North America preceded CAMP emplacement

The White Mountain Magma Series (WMMS) is the largest Mesozoic felsic igneous province on the Eastern North American Margin (ENAM). Existing geochronology has suggested that magmatism occurred over 50 Myr with published ages for the oldest units apparently coeval with the ca. 201 Ma Central Atlantic Magmatic Province (CAMP), the flood basalt province associated with the end-Triassic mass extinction and the opening of the Atlantic Ocean. We use zircon U-Pb geochronology to show that emplacement of WMMS plutons was already underway at 207.5 Ma. The largest volcanic-plutonic complex, the White Mountain Batholith, was emplaced episodically from ca. 198.5 Ma to ca. 180 Ma, ca. 25 Myr older than published ages suggest, and all samples we dated from the Moat Volcanics are between ca. 185 to 180 Ma. This result shows that the Moat Volcanics and the White Mountain Batholith are broadly comagmatic, and it also constrains the age of a key Jurassic paleomagnetic pole. Our data suggest that a regional mantle thermal anomaly in eastern North America developed at least ca. 5 Myr prior to the main stage of CAMP flood basalt volcanism and suggests a geodynamic link between the WMMS and the CAMP.

Sean T. Kinney↗

Simulating the Diffusion of Hydrogen in Amorphous Silicates: A ‘Jumping’ Migration Process and its Implications for Solar Wind Implanted Lunar Volatiles

We use molecular dynamics (MD) simulations to better explain the movement of atomic hydrogen in amorphous silica and quantify the planetary science implications of these findings. Previous MD simulations had a large range of predicted values and did not agree well with experiment. Our simulations sample atomic motion for a longer duration and consider a wider range of temperatures than previous simulations. In contrast to constant atomic motion, the hydrogen atoms were shown to undergo random intermittent jumps from one oxygen atom to another, the number of which increase with temperature. Predicted diffusion coefficients had a better agreement to experimental values than previous MD simulations, suggesting the importance of longer simulation durations for better statistics. The low activation energy and jumps observed at lunar temperatures do not support the theory of diurnal variations in OH content for an undamaged amorphous silica surface. Instead, we conclude that energetic solar wind impacts can induce two competing atomic hydrogen motion processes in the exposed surface: A prompt effect that induces jumps in the temperature spike volume, but also a long term effect of damage in the structure that traps atomic hydrogen. We then use SDTrimSP to quantify the damage created during exposure and MD to demonstrate the H retention and trapping near these defects. Damage was shown to be dependent on impact energy, with defects easily retaining implanted hydrogen. MD results like those presented herein on unweathered surfaces are therefore most relevant to magnetic anomalies. As a result, we demonstrate the importance of lunar volatile models to account for the damage state of the substrate when modelling hydrogen diffusion, retention, and subsequent OH/water production.

Liam S. Morrissey↗

Estimates of Permeability of Water in Rare Earth Silicates Using the Modified Theory of Deal and Grove

The salient elements of the theory of oxide growth under an environmental barrier are reviewed. In addition, the results from steam oxidation tests recently conducted on environmental barrier coated specimens are reported. The oxide thickness between the coating and substrate are reported as a function of time. Also, the results from previously conducted steam oxidation tests are reviewed. An approach to estimate the permeability of water through the various coating systems using the oxide thickness versus time measurements and the theory of oxide growth is demonstrated. Although the steam oxidation tests may have been performed under disparate conditions, the approach allows one to rank the protection efficiency of the various coating systems against substrate oxidation on an equivalent basis.

environmental barrier coatings↗

An Ensemble Neural Network Model for Predicting Rare-Earth Oxide and Silicate Heat Capacities at High Temperature

In this work, a neural network model was developed to predict the constant pressure heat capacity for materials in the rare-earth oxide—silica material space. Several model architectures were trained and tested on heat capacity data generated from first-principles density functional theory calculations. Hyperparameter optimization was performed, and the optimal model was selected for heat capacity predictions. The optimal model architecture was found to have a root-mean-squared error of 5.12 ± 3.37 J/mol-K. The optimal model architecture was then used in a bagging ensemble model trained using the leave-one-group-out method to provide error estimates for model predictions. The out-of-bag score for the ensemble model was 0.997. The predicted heat capacities agree well with the DFT and experimental results and were computed orders of magnitude faster than DFT simulations. Machine learning shows the potential to provide a suitable surrogate model for thermochemical property predictions for candidate environmental barrier coating materials but refining of input material features and model architectures could further improve accuracy for these models.

environmental barrier coatings↗