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At least 19 records

New interaction potentials for alkaline earth silicate and borate glasses

New interaction potentials were developed for molecular dynamics simulations to study the role of Mg and Ca in modifying the structure and properties of alkaline earth silicates and borates. Competition between the depolymerization of the silica network and the formation of new bonds between oxygen atoms and modifiers leads to the enhancement of the elastic moduli with increasing modifier content in alkaline earth silicate glasses. Compared with calcium silicate, the higher elastic moduli of magnesium silicate result from a higher connectivity of the overall glass network due to the incorporation of fourfold coordinated magnesium and a more rigid connection between oxygen atoms and modifiers. In contrast to the silicates, the effect of modifier on the elastic moduli of alkaline earth borates is dominated by the formation of fourfold coordinated boron (N 4 ). Calcium borate with higher N 4 shows a more rigid network structure and higher elastic moduli.

36 MATERIALS SCIENCE↗

Corrosion resistant thermal barrier coating

A thermal barrier coating system for protecting metal surfaces at high temperature in normally corrosive environments is described. The thermal barrier coating system includes a metal alloy bond coating, the alloy containing nickel, cobalt, iron, or a combination of these metals. The system further includes a corrosion resistant thermal barrier oxide coating containing at least one alkaline earth silicate. The preferred oxides are calcium silicate, barium silicate, magnesium silicate, or combinations of these silicates.

Levine, S. R.↗

Aluminization Coatings and Glass Seals for High Temperature System: CRADA 536 [Abstract Only]

The proposed work will demonstrate the suitability of PNNL Reactive Air Aluminization (RAA) coatings (US Patent Numbers 10,577,694, 10,378,094, and 9,481,923) for use in high-temperature systems. In particular, the Participant and Contractor will explore applicability of these coatings in Participant’s high-temperature hydrogen reactors where they would be used to prepare the sealing surfaces of the reactor technology. Utility Global will also instruct PNNL regarding their needs relating to the further development of glass seal technologies that are suitable for use in their systems. This effort will entail alkaline earth-based silicate glass development and characterization; evaluation and characterization of reliability and compatibility of the coatings with glass seals, working environments, and substrates; performance demonstrations of representative cells and intermediate cells sealed using the glass seals and/or coatings of interest; and incorporation of the aluminization coatings and glass seals into the reactor for full-scale testing.

08 HYDROGEN↗

Aluminization Coatings and Glass Seals for High Temperature Systems - CRADA 536 (Final Report)

The objective of this project was to demonstrate the suitability of PNNL’s Reactive Air Aluminization (RAA) coatings (US Patent Numbers 10,577,694, 10,378,094, and 9,481,923) for use in high-temperature systems. In particular, PNNL and Utility Global undertook a collaborative effort to explore the applicability of these coatings in Utility Global’s high-temperature hydrogen reactors where they would be used to prepare the sealing surfaces of the reactor technology. Utility Global instructed PNNL regarding their needs relating to further development of glass seal technologies suitable for use in their systems. This effort entailed alkaline earth-based silicate glass development and characterization; evaluation and characterization of reliability and compatibility of the coatings with glass seals, working environments, and substrates; performance demonstrations of representative cells and intermediate cells sealed using the glass seals and/or coatings of interest; and incorporation of the aluminization coatings and glass seals into Utility Global reactors for testing.

36 MATERIALS SCIENCE↗

Carbonation and Sulfidation of Mg- and Ni-Containing Solutions: Implications for Carbon Mineralization and Critical Element Recovery

Carbonation of alkaline earth metals ( e.g. , magnesium (Mg)) and sulfidation of nickel (Ni) are promising methods to achieve concurrent carbon mineralization and selective Ni recovery. However, the coexistence of alkaline earth metals and Ni from silicate ores or mining wastewater complicates the carbonation and sulfidation owing to cation coprecipitation. To better understand simultaneous metal carbonation and Ni-sulfide formation, we used Mg- and Ni-containing solutions and systematically investigated the Mg and Ni coprecipitates’ phase transformation during sequential/concurrent carbonation and sulfidation. During a single carbonation process, hydromagnesite dehydrated and formed magnesite over time. Nickel bicarbonate formed and became a Mg–Ni carbonate solid solution because of their similar ionic radii. During a single sulfidation process, the pH did not affect Ni-sulfide formation, but it controlled Mg behavior. Specifically, at pH 9.6, brucite formed, while at pH 7.8, Mg 2+ remained in the solution. For the sequential carbonation–sulfidation process, Ni-carbonate formed during carbonation converted to Ni-sulfide because of the low Ni-sulfide K sp . For the sulfidation–carbonation process, Ni-sulfide remained the same even after carbonation and Mg-carbonate precipitates. For the concurrent carbonation and sulfidation process, Mg-carbonate and Ni-sulfide formed simultaneously. Finally, this study develops a scientific foundation of carbonation and sulfidation processes, benefiting coupled CO 2 storage and sulfide-enabled resource recovery.

54 ENVIRONMENTAL SCIENCES↗

Increasing Al-Pair Abundance in SSZ-13 Zeolite via Zeolite Synthesis in the Presence of Alkaline Earth Metal Hydroxide Produces Hydrothermally Stable Co-, Cu- and Pd-SSZ-13 Materials

Replacing alkaline for alkaline-earth metal hydroxide in the synthesis gel during the synthesis of siliceous SSZ-13 zeolite (Si/Al~10) yields SSZ-13 with novel, advantageous properties. Its NH 4 -form ion-exchanges higher amount of isolated divalent M(II) ions than the conventional one: this is the consequence of an increased number of Al pairs in the structure induced by the +2 charge of Sr(II) cations in the synthesis gel that force two charge-compensating AlO 4 – motives to reside closer together. We characterize the +2 state of Co(II) ions in these materials with infra-red spectroscopy and X-ray absorption spectroscopy measurements and show their utility for NOx pollutant adsorption from ambient air: the ones derived from SSZ-13 with higher Al pair content contain more isolated cobalt(II) and, thus, perform better as ambient-air NOx adsorbers. Notably, Co(II)/SSZ-13 with an increased number of Al pairs is significantly more hydrothermally stable than its NaOH-derived analogue. Loading Pd(II) into Co-SSZ-13(Sr) produces an active NOx adsorber (PNA) material that can be used for NOx adsorption from simulated diesel engine exhaust. The critical issue for these applications is hydrothermal stability of Pd-zeolites. Pd/SSZ-13 synthesized in the presence of Sr(OH) 2 does not lose its PNA capacity after extremely harsh aging at 850 and 900 °C (10 h in 10% H 2 O/air flow) and loses only ~55% capacity after hydrothermal aging at 930 °C. This can be extended to other divalent metals for catalytic applications, such as copper: we show that Cu/SSZ-13 catalyst can survive hydrothermal aging at 920 °C without losing its catalytic properties, metal dispersion and crystalline structure. Thus, we provide a new, simple, and scalable strategy for making remarkably (hydro)thermally stable metal-zeolite materials/catalysts with a number of useful applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self diffusion of alkaline-Earth in Ca-Mg-aluminosilicate melts: Experimental improvements on the determination of the self-diffusion coefficients

Experimental studies of self-diffusion isotopes in silicate melts often have quite large uncertainties when comparing one study to another. We designed an experiment in order to improve the precision of the results by simultaneously studying several elements (Mg, Ca, Sr, Ba) during the same experiment thereby greatly reducing the relative experimental uncertainties. Results show that the uncertainties on the diffusion coefficients can be reduced to 10 percent, allowing a more reliable comparison of differences of self-diffusion coefficients of the elements. This type of experiment permits us to study precisely and simultaneously several elements with no restriction on any element. We also designed an experiment to investigate the possible effects of multicomponent diffusion during Mg self-diffusion experiments by comparing cases where the concentrations of the elements and the isotopic compositions are different. The results suggest that there are differences between the effective means of transport. This approach should allow us to investigate the importance of multicomponent diffusion in silicate melts.

Paillat, O.↗

Hydration and reaction mechanisms on sodium silicate glass surfaces from molecular dynamics simulations with reactive force fields

Recent development of reactive force fields have enabled molecular dynamics simulations of interactions between silicate glasses and water at the atomistic scale. While multicomponent silicate glasses encompass a wide variety of compositions and properties, one common structural feature in these glasses is the combination of the network structure that is made up of silica tetrahedra linked through corner sharing interspersed with network modifiers like alkali and alkaline-earth ions that break up the Si–O–Si linkages by forming nonbridging oxygen. In reactions with water, ion exchange between alkali ions in the glass and proton or hydronium in the solution, as well as hydrolysis reaction of the Si–O–Si linkages and subsequent silanol formation, is observed and well documented. Furthermore, we have used a set of recently developed reactive force field to investigate the reactions between water and the surfaces of silica and sodium silicate glasses of different compositions for reactions up to 8 nanoseconds. Our results indicate sodium leaching into water and diffusion of water molecules up to 25 Å into the glass surface. We examined the structural and compositional changes inside the glass and around the diffused ions and use these to explain the rates of silanol formation at the surface. We also observed proton transport in the glass which has an indirect influence on the silanol formation rates. While the surface of the glass was rough to start with, it undergoes further modification into a hydrated gel-like structure in the glass for up to 5 Å in the higher alkali containing glasses. It was found that the leached sodium ions remain close to the interface and that fragments of silicate network from the surface is capable of dislodging from the bulk glass and enter the aqueous solution. These simulations thus provide insights into the formation and structure of an alteration layers commonly observed in multicomponent silicate glasses corroded in aqueous solutions.

36 MATERIALS SCIENCE↗

Unlocking High Capacity and Reversible Alkaline Iron Redox Using Silicate-Sodium Hydroxide Hybrid Electrolytes

Alkaline iron (Fe) batteries are attractive due to the high abundance, low cost, and multiple valent states of Fe but show limited columbic efficiency and storage capacity when forming electrochemically inert Fe 3 O 4 on discharging and parasitic H 2 on charging. Herein, sodium silicate is found to promote Fe(OH) 2 /FeOOH against Fe(OH) 2 /Fe 3 O 4 conversions. Electrochemical experiments, operando X-ray characterization, and atomistic simulations reveal that improved Fe(OH) 2 /FeOOH conversion originates from (i) strong interaction between sodium silicate and iron oxide and (ii) silicate-induced strengthening of hydrogen-bond networks in electrolytes that inhibits water transport. Furthermore, the silicate additive suppresses hydrogen evolution by impairing energetics of water dissociation and hydroxyl de-sorption on iron surfaces. In conclusion, this new silicate-assisted redox chemistry mitigates H 2 and Fe 3 O 4 formation, improving storage capacity (199 mAh g -1 in half-cells) and coulombic efficiency (94 % after 400 full-cell cycles), paving a path to realizing green battery systems built from earth-abundant materials.

36 MATERIALS SCIENCE↗

Multilayer article having stabilized zirconia outer layer and chemical barrier layer

A multilayer article includes a substrate that includes at least one of a ceramic compound and a Si-containing metal alloy. An outer layer includes stabilized zirconia. Intermediate layers are located between the outer layer and the substrate and include a mullite-containing layer and a chemical barrier layer. The mullite-containing layer includes 1) mullite or 2) mullite and an alkaline earth metal aluminosilicate. The chemical barrier layer is located between the mullite-containing layer and the outer layer. The chemical barrier layer includes at least one of mullite, hafnia, hafnium silicate and rare earth silicate (e.g., at least one of RE.sub.2 SiO.sub.5 and RE.sub.2 Si.sub.2 O.sub.7 where RE is Sc or Yb). The multilayer article is characterized by the combination of the chemical barrier layer and by its lack of a layer consisting essentially of barium strontium aluminosilicate between the mullite-containing layer and the chemical barrier layer. Such a barium strontium aluminosilicate layer may undesirably lead to the formation of a low melting glass or unnecessarily increase the layer thickness with concomitant reduced durability of the multilayer article. In particular, the chemical barrier layer may include at least one of hafnia, hafnium silicate and rare earth silicate.

Lee, Kang N.↗

Evaluating the carbon capture potential of industrial waste as a feedstock for enhanced weathering

Abstract Limiting anthropogenic global climate warming since the start of the industrial period to less than 2 °C will very likely require both deep and rapid reductions in anthropogenic greenhouse gas emissions and a range of approaches toward carbon dioxide removal (CDR). One prominent CDR approach is enhanced weathering (EW), in which crushed silicate rock is applied on land or in the open ocean to accelerate natural weathering processes that absorb carbon dioxide from Earth’s ocean–atmosphere system. However, in addition to a range of potential environmental, socioeconomic, and ethical issues associated with this pathway, bottlenecks in feedstock sourcing represent a key barrier for deployment of EW at scale. Here, we evaluate the potential of silicate wastes produced from industrial processes—such as steel slag and cement waste—as feedstocks for the EW process. An empirical model that links industrial alkaline waste production to gross domestic product at purchase power parity is developed to forecast waste production in the alternative futures described by the shared socioeconomic pathway (SSP) framework. By incorporating these results into an intermediate-complexity Earth system model, we also explore the impacts of EW using industrial waste on changes to global temperature, ocean pH, and ocean aragonite saturation state, while also quantifying overall CDR efficiency through the end of the century. We estimate a maximum cumulative end-of-century capture potential of ∼400 GtCO 2 for industrial waste, which could represent a significant fraction of the projected CDR requirement of many mitigation scenarios in the SSP framework. However, feedstock-dependent environmental impacts and the technoeconomics of feedstock redistribution may ultimately limit deployment scope.

Xu, Pengxiao (ORCID:0009000633724293)↗

Workshop on Oxygen in the Terrestrial Planets

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Source record↗

Exopaleontology and the search for a fossil record on Mars

Although present Martian surface conditions appear unfavorable for life as we know it, there is compelling geological evidence that the climate of early Mars was much more Earth-like, with a denser atmosphere and abundant surface water. The fact that life developed on the Earth within the first billion years of its history makes it quite plausible that life may have also developed on Mars. If life did develop on Mars, it is likely to have left behind a fossil record. This has led to the development of a new subdiscipline of paleontology, herein termed 'exopaleontology', which deals with the exploration for fossils on other planets. The most important factor enhancing microbial fossilization is the rapid entombment of microorganisms by fine-grained, stable mineral phases, such as silica, phosphate, or carbonate. The oldest body fossils on Earth are preserved in this way, occurring as permineralized cells in fine-grained siliceous sediments (cherts) associated with ancient volcanic terranes in Australia and South Africa. Modern terrestrial environments where minerals may precipitate in the presence of microorganisms include subaerial thermal springs and shallow hydrothermal systems, sub-lacustrine springs and evaporitic alkaline lakes, zones of mineralization within soils where 'hardpans' (e.g. calcretes, silcretes) form, and high latitude frozen soils or ground ice.

Farmer, Jack D.↗

Iodine Co-Precipitation with Calcium Carbonate in the Presence of Silica Ions - 20360

Historical releases of I-129 to the subsurface at the U.S. Department of Energy Hanford Site have resulted in large dilute plumes that cover an area of over 50 km{sup 2}. The most concentrated I-129 plume is associated with the 200 West Area in the 200-UP-1 operable unit of the Hanford Central Plateau, where peak concentrations have been measured up to 30 times the drinking water standard of 1 pCi/L. The mobility of iodine depends on many factors, including chemical speciation, pH, redox conditions, as well as the presence of organic matter, calcium carbonate minerals and microbial activities. Speciation measurements estimate that the majority of the iodine (∼76%) in Hanford groundwater exists as iodate. Information on processes that affect iodate mobility in the Hanford subsurface support evaluation of environmental management options for the I-129 plumes. Iodate can be incorporated into calcium carbonate, which is a potential mechanism of naturally attenuating radioiodine in groundwater. However, the silica content in porewater may impact the contaminant-calcium carbonate incorporation process. Silica is one of the most abundant elements in nature and can have an impact on chemical weathering of alkaline-earth carbonates in the environment. Hence, this research aims to advances knowledge of the iodine co-precipitation process with calcium carbonate in the presence of silica. This information supports the technical basis evaluation of natural attenuation for I-129. Samples for these studies were prepared using calcium carbonate-forming solutions that included certified grade sodium meta-silicate nonahydrate (Na{sub 2}SiO{sub 3}), calcium chloride dehydrate (CaCl{sub 2}.2H{sub 2}O), sodium carbonate (NaCO{sub 2}), and sodium hydroxide (NaOH) solutions for pH adjustments. Triplicate samples were prepared with silica concentrations in the solution of 0 mM, 0.5 mM and 20 mM, mixed with an iodate standard (1000 ppm of IO{sub 3}{sup -} in H{sub 2}O) and sampled over a one-week period. Preliminary data analyses suggest that less iodine remains in solution in the presence of silica (average remaining aqueous fraction 0.23±0.03 at 20 mM of Si) relative to samples without silica (0.52±0.06); an indication that more iodine has been sorbed or incorporated into precipitates. However, the mechanisms for this behavior are still under investigation and need to be interpreted relative to pore water compositions that are representative of Hanford site-specific conditions. Scanning electron microscope equipped with energy dispersive spectroscopy (SEM-EDS) analyses were performed to observe the solid phase morphology in these experiments and showed rhombohedral calcite crystals covered with amorphous Si floccules. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Unraveling the Effects of Melt–Mantle Interactions on the Gold Fertility of Magmas

The oxidation state of the Earth’s mantle and its partial melting products exert a key control on the behavior and distribution of sulfur and chalcophile and siderophile elements between the mantle and crust, underpinning models of ore deposit formation. Whether the oxidized nature of magmas is inherited from the asthenospheric mantle source or acquired during ascent and differentiation is vigorously debated, limiting our understanding of the mechanisms of extraction of sulfur and metals from the mantle. Here, we focused on the redox-sensitive behavior of sulfur in apatite crystallized from quenched alkaline basaltic melts preserved within a peridotite xenolith from the El Deseado Massif auriferous province in southern Patagonia. We took advantage of this unique setting to elucidate the redox evolution of melts during their ascent through the subcontinental lithospheric mantle (SCLM) and grasp the inner workings of the Earth’s mantle during gold metallogenesis. Our data reveal that an initially reduced silicate melt (ΔFMQ -2.2 to -1.2) was oxidized to ΔFMQ between 0 and 1.2 during percolation and interaction with the surrounding peridotite wall-rock (ΔFMQ 0 to +0.8). This process triggered changes in sulfur speciation and solubility in the silicate melt, boosting the potential of the melt to scavenge ore metals such as gold. We suggest that large redox gradients resulting from the interaction between ascending melts and the surrounding mantle can potentially modify the oxidation state of primitive melts and enhance their metallogenic fertility. Among other factors including an enriched metal source and favorable geodynamic conditions, redox gradients in the mantle may exert a first-order control on the global-scale localization of crustal provinces endowed with gold deposits.

58 GEOSCIENCES↗

Evolution of ore deposits on terrestrial planets

Ore deposits on terrestrial planets materialized after core formation, mantle evolution, crustal development, interactions of surface rocks with the hydrosphere and atmosphere, and, where life exists on a planet, the involvement of biological activity. Core formation removed most of the siderophilic and chalcophilic elements, leaving mantles depleted in many of the strategic and noble metals relative to their chondritic abundances. Basaltic magma derived from partial melting of the mantle transported to the surface several metals contained in immiscible silicate and sulfide melts. Magmatic ore deposits were formed during cooling, fractional crystallization and density stratification from the basaltic melts. Such ore deposits found in earth's Archean rocks were probably generated during early histories of all terrestrial planets and may be the only types of igneous ores on Mars. Where plate tectonic activity was prevalent on a terrestrial planet, temporal evolution of ore deposits took place. Repetitive episodes of subduction modified the chemical compositions of the crust and upper mantles, leading to porphyry copper and molybdenum ores in calc-alkaline igneous rocks and granite-hosted tin and tungsten deposits. Such plate tectonic-induced mineralization in relatively young igneous rocks on earth may also have produced hydrothermal ore deposits on Venus in addition to the massive sulfide and cumulate chromite ores associated with Venusian mafic igneous rock. Sedimentary ore deposits resulting from mechanical and chemical weathering in reducing atmospheres in Archean earth included placer deposits (e.g., uraninite, gold, pyrite ores). Chromite, ilmenite, and other dense unreactive minerals could also be present on channel floors and in valley networks on Mars, while banded iron formations might underlie the Martian northern plains regions. As oxygen evolved in earth's atmosphere, so too did oxide ores. By analogy, gossans above sulfide ores probably occur on Mars, but not submarine ferromanganese nodules and crusts which have precipitated in oxygenated seawater on earth.

Burns, R. G.↗

Constraints on the Composition and Petrogenesis of the Martian Crust

Spectral interpretation that silicic rocks are widespread on Mars implies that Earth's differentiated crust is not unique. Evaluation of observations bearing on the composition of the Martian crust (Martian meteorite petrology and a possible crustal assimilant, analysis of Mars Pathfinder rocks, composition of Martian fines, interpretation of spacecraft thermal emission spectra, and inferred crustal densities) indicates that the crust can be either basalt plus andesite or basalt plus weathering products. New calculated chemical compositions for Thermal Emission Spectrometer (TES) global surface units indicate that surface type 1 has basaltic andesite composition and surface type 2 has the composition of andesite. If these materials represent volcanic rocks, their calc-alkaline compositions on a FeO*/MgO versus silica diagram suggest formation by hydrous melting and fractional crystallization. On Earth, this petrogenesis requires subduction, and it may suggest an early period of plate tectonics on Mars. However, anorogenic production of andesite might have been possible if the primitive Martian mantle was wet. Alternatively, chemical weathering diagrams suggest that surface type 2 materials could have formed by partial weathering of surface type 1 rocks, leading to depletion in soluble cations and mobility of silica. A weathered crust model is consistent with the occurrence of surface type 2 materials as sediments in a depocenter and with the alpha proton X-ray spectrometer (APXS) analysis of excess oxygen suggesting weathering rinds on Pathfinder rocks. If surface type 1 materials are also weathered or mixed with weathered materials, this might eliminate the need for hydrous melting, consistent with a relatively dry Martian mantle without tectonics.

McSween, Harry Y., Jr.↗

Calcium nitrate: A chemical admixture to inhibit aggregate dissolution and mitigate expansion caused by alkali-silica reaction

Alkali-silica reaction (ASR) is a significant cause of the degradation of concrete structures. ASR results from the dissolution of reactive silicate aggregates and the subsequent formation of damaging, expansive ASR gels. Despite the prevalence of ASR, so far only lithium-based chemical admixtures have been shown to be successful in mitigating its deleterious effects. Herein, dissolved calcium nitrate (Ca(NO 3 ) 2 : CN) is demonstrated to reduce ASR-induced expansion caused by the use of sodium borosilicate (NBS) glass as a model reactive aggregate. The significance of reductions of NBS-glass dissolution and mortar-bar expansion rates is discussed, with special focus on highlighting the mechanism by which calcium nitrate mitigates ASR, i.e., by the inhibition of aggregate dissolution. This study reveals a new and cost-effective pathway to suppress aggregate dissolution and ASR in concrete based on the dosage of soluble alkaline-earth additives.

36 MATERIALS SCIENCE↗