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At least 19 records

Cumberland Falls chondritic inclusions - Mineralogy/petrology of a forsterite chondrite suite

The mineralogy and petrology of a suite of chondritic inclusions from the Cumberland Falls aubrite are investigated in order to clarify the relation of the inclusions to each other, forsterite chondrites, and the aubrites. Thin sections of nine chondritic inclusions and the achondritic matrix of Cumberland Falls were examined in reflected light, then analyzed for up to 12 elements by electron microprobe techniques. Minerals detected in abundant quantities include low-Ca pyroxene, olivine, plagioclase, kamacite, taenite, schreibersite, troilite, ferroan alabandite and daubreelite; diospide, oldhamite and a Ti-rich sulfide are found in one or two inclusions. The mineralogic compositions indicate similar degrees of reduction for the inclusions in the Cumberland Falls meteorites and in four meteorites identified as forsterite chondrites (Kakangari, Mt. Morris, Pontlyfni and Winona). The inclusions are found to be of a primitive composition, corresponding to petrological types 2 or 3, while the identification of jadeitic pyroxene in nearly all inclusions indicates a substantial degree of shock. The results suggest that the inclusions formed from nebular material that condensed and accreted over a broad redox range, and experienced tertiary shock in a collision with an enstatite meteorite in which the Cumberland Falls meteorite formed.

Neal, C. W.↗

Cumberland Falls chondritic inclusions. III - Consortium study of relationship to inclusions in Allan Hills 78113 aubrite

The contents of Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Sb, Se, Te, Tl, U, and Zn in large chondritic clasts from the Cumbersand Falls aubrite were determined by radiochemical neutron activation analysis, and the results, together with the results of a mineralogical investigation, were compared with respective data obtained for three primitive inclusions from the ALH A78113 aubrite. The results indicated that the clasts from both aubrite sources constitute a single chondritic suite. The analyses data, together with the results of thermoluminescence data for Cumberland Falls chondritic inclusions and achondritic host, indicate that inclusions in Cumberland Falls and in ALH A78113 aubrite represent a primitive chondrite sample suite whose properties were established during primary nebular accretion and condensation over a broad redox range.

Lipschutz, Michael E.↗

Role of Oxygen Fugacity on the Melting Properties of Enstatite Chondrites and Implications for Mercury’s Magmatic Evolution

Mercury, the innermost terrestrial planet, is the most reduced planet in our solar system. Insights from MESSENGER mission data revealed the presence of several distinct geochemical terranes, evidence of complex magmatic processes and collisional processes exposing subsurface materials. Surface chemical analysis indicated elevated S (~2-3 wt%) and low FeO (~1.5 wt%) concentrations. The high sulfur concentration indicates reduced conditions with an average of 5.4 log units below the Iron-Wüstite (IW) oxygen fugacity ( O 2 ) buffer (IW-5.4). Surface compositions also show a range in redox conditions during mantle melting and eruption, with inferred log f O 2 , ranging from IW-6.5 to IW-3.5. The effects of oxygen fugacity on magmatic differentiation are poorly constrained, despite their significance in our understanding of mantle-crust differentiation in the solar system. Enstatite High-Fe (EH) chondrites are very reduced undifferentiated meteorites with elevated concentrations of Fe and volatiles like S, Cl, Na, and K as compared to other chondrites. These characteristics suggest that EH chondrites are a potential analog for Mercury’s building blocks. However, the comparison of Mercury’s surface composition with melting products of EH chondrites is necessary to determine whether Mercury surface materials may be derived from EH chondrite- like materials. Here, we investigate the role of f O 2 on EH melting properties and its implications for Mercury’s accretion and differentiation.

Mercury↗

Non-Additive Voltametric Currents From a Mixture of Two, Three and Four Redox-Active Compounds and Electroanalytical Implications

We have published recently the effect of dissimilar diffusion coefficients on the size of the voltammetric waves from a mixture of two redox-active compounds. Similarly, at the potential range where three redox-active species, decamethylferrocene (dMeFc), ferrocene (Fc) and N-methylphenothiazine (MePTZ), are oxidized simultaneously with rates controlled by linear diffusion, electrogenerated radicals diffusing outwards from the electrode react with the original species diffusing towards the electrode from the bulk; thus, Fc(+) reacts with dMeFc producing Fc and dMeFc(+), while MePTZ(+) reacts both with dMeFc producing MePTZ and dMeFc(+), and with Fc producing MePTZ and Fc(+). These reactions replace dMeFc with Fc at the second plateau, and both dMeFc and Fc with MePTZ at the third plateau. Since the diffusion coefficients of the three species are not equal, the mass-transfer limited currents of the second and the third oxidation wave plateaus change by approx. 10%. Numerical simulations of the experimental voltamograms support this mechanism. Similar results were also obtained for a mixture of four redoxactive compounds. The implications of this non-additive nature of currents on: (a) the use of internal voltammetric standards for quantitative analysis of a mixture of redox-active compounds; and, (b) the half wave potentials (E1/2) of the 2nd, 3rd and 4th waves for qualitative analysis, will be discussed.

Dass, Amala↗

NASA Redox cell stack shunt current, pumping power, and cell performance tradeoffs

The NASA Redox energy storage system is under active technology development. The hardware undergoing laboratory testing is either 310 sq. cm. or 929 sq. cm. (0.33 sq. ft. or 1.0 sq. ft. per cell active area with up to 40 individual cells connected to make up a modular cell stack. This size of hardware allows rather accurate projections to be made of the shunt power/pump power tradeoffs. The modeling studies that were completed on the system concept are reviewed along with the approach of mapping the performance of Redox cells over a wide range of flow rates and depths of discharge of the Redox solutions. Methods are outlined for estimating the pumping and shunt current losses for any type of cell and stack combination. These methods are applicable to a variety of pumping options that are present with Redox systems. The results show that a fully developed Redox system has acceptable parasitic losses when using a fixed flow rate adequate to meet the worst conditions of current density and depth of discharge. These losses are reduced by about 65 percent if variable flow schedules are used. The exact value of the overall parasitics will depend on the specific system requirements of current density, voltage limits, charge, discharge time, etc.

Hagedorn, N.↗

Surveying Clay Mineral Diversity in the Murray Formation, Gale Crater, Mars

The CheMin XRD instrument aboard Mars Science Laboratory (MSL) has documented clay minerals in various drill samples during its traverse of Gale Crater's floor and ascent of Mt. Sharp. The most recent samples, named Marimba, Quela and Sebina were acquired from the Murray Formation in the Murray Buttes region of lower Mt. Sharp. Marimba and Quela come from a approx. 30 m package of finely laminated lacustrine mudstones. Sebina comes from an overlying package of heterolithic mudstone-sandstones. Clay minerals make up approx.15-25 wt.% of the bulk rock with similar contributions to XRD patterns in all three samples. Broad basal reflections at approx. 10deg 2(theta) CoK(alpha) indicate the presence of 2:1 group clay minerals. The 02(lambda) clay mineral band lies at approx. 22.9deg 2(theta), a region typically occupied by Fe-bearing dioctahedral 2:1 clay minerals like nontronite or Fe-illite. The low humidity within the CheMin instrument, which is open to the martian atmosphere, promotes loss of interlayer H2O and collapse of smectite interlayers making them difficult to distinguish from illites. However, based on the low K content of the bulk samples, it appears that smectitic clay minerals are dominant. Peak dehydroxylation of the Marimba sample measured by the SAM instrument on MSL occurred at 610C and 780C. Fe-bearing smectites are not consistent with these dehydroxylation temperatures. Thus, we suggest that a mixture of dioctahedral and trioctahedral smectite phases are present giving the appearance of intermediate octahedral occupancy in XRD. Dioctahedral smectites have not previously been reported in Gale Crater by MSL. Earlier in the mission, relatively clay mineral rich samples (approx. 20 wt.%) from lacustrine mudstones in Yellowknife Bay (YKB) were found to contain ferrian saponites. It is proposed that YKB saponites formed via isochemical aqueous alteration of detrital olivine close to the time of sediment deposition, under anoxic to poorly oxidizing conditions. In terrestrial settings where alteration sequences of basaltic rocks or sediments are observed, first-stage alteration clay minerals are typically trioctahedral smectite species, as reported from YKB. In later alteration stages trioctahedral clay minerals are replaced by dioctahedral clays as a result of removal and/or oxidation of Fe2+ and Mg. Observed changes in clay mineralogy between YKB and Murray Buttes samples correspond with differences in bulk mineralogy, including: 1) a transition from magnetite to hematite as the main Fe-oxide, 2) increasing abundances of Ca-sulfates and 3) a reduction in the quantity of reactive mafic minerals. This mineralogical change indicates an increasing degree of aqueous alteration and oxidation of mafic detritus in the upper part of the Murray Formation. These results broaden the spectrum of mineralogical facies documented by MSL. Together sedimentology and mineralogy indicate a long-lasting, dynamic fluvial-lacustrine system encompassing a range aqueous geochemical processes under varying redox conditions. Future work is needed to unravel the influence of global and local controls on the range of ancient conditions observed at Gale Crater.

MSL↗

The expanding network of mineral chemistry throughout earth history reveals global shifts in crustal chemistry during the Proterozoic.

Earth surface redox conditions are intimately linked to the co-evolution of the geosphere and biosphere. Minerals provide a record of Earth’s evolving surface and interior chemistry in geologic time due to many diferent processes (e.g. tectonic, volcanic, sedimentary, oxidative, etc.). Here, we show how the bipartite network of minerals and their shared constituent elements expanded and evolved over geologic time. To further investigate network expansion over time, we derive and apply a novel metric (weighted mineral element electronegativity coefcient of variation; wMEECV) to quantify intra-mineral electronegativity variation with respect to redox. We fnd that element electronegativity and hard soft acid base (HSAB) properties are central factors in mineral redox chemistry under a wide range of conditions. Global shifts in mineral element electronegativity and HSAB associations represented by wMEECV changes at 1.8 and 0.6 billion years ago align with decreased continental elevation followed by the transition from the intermediate ocean and glaciation eras to postglaciation, increased atmospheric oxygen in the Phanerozoic, and enhanced continental weathering. Consequently, network analysis of mineral element electronegativity and HSAB properties reveal that orogenic activity, evolving redox state of the mantle, planetary oxygenation, and climatic transitions directly impacted the evolving chemical complexity of Earth’s crust.

Eli K. Moore↗

Chromium Oxidation State in Planetary Basalts: Oxygen Fugacity Indicator and Critical Variable for Cr-Spinel Stability

Cr is a ubiquitous and relatively abundant minor element in basaltic, planetary magmas. At the reduced oxidation states (<FMQ) of many planetary basalts Cr is present in melts as both divalent and trivalent forms. The ratio of trivalent to divalent Cr present in the melt has many consequences for the stability and Cr concentration of magmatic phases such as spinel, clinopyroxene, and olivine. However, understanding the Cr valence in quenched melts has historically been plagued with analytical issues, and only recently has reliable methodology for quantifying Cr valence in quenched melts been developed. Despite this substantial difficulty, the pioneering works of Hanson and Jones and Berry and O'Neill provided important insights into the oxidation state of Cr in in silicate melts. Here we present a series of 1-bar gas mixing experiments performed with a Fe-rich basaltic melt in which have determined the Cr redox ratio of the melt at over a range of fO2 values by measuring this quantity in olivine with X-ray Absorption Near Edge Spectroscopy (XANES). The measured Cr redox ratio of the olivine phenocrysts can be readily converted to the ratio present in the conjugate melt via the ratio of crystal-liquid partition coefficients for Cr3+ and Cr2+. We have applied these results to modeling Cr spinel stability and Cr redox ratios in a primitive, iron-rich martian basalt.

Bell, A. S.↗

The Role of (Delta)C-13 in the Search for Reduced Organics on the Surface of Mars

The capabilities of the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to detect trace amounts of organic carbon compounds are unprecedented, and MSL may be the first mission to reveal the presence of organic carbon on Mars. The search for reduced organic carbon on Mars is inextricably tied to: a) the preservation potential of the environment from which we take a solid sample, and b) the evolved gas analysis (EGA) techniques used by SAM to release volatiles from this solid sample. Several prospective targets have been identified for sample analysis at Gale Crater. Stratigraphic sequences of phyllosilicates and sulfates at Gale are thought to represent a period of global climate transition from a moderate pH lacustrine environment to an evaporitic environment, both of which could sequester organic carbon (Thomson et al. 2011). The sediment mound in Gale Crater contains a range of lithologies suggesting changes in redox conditions, and evidence of both lacustrine and fluvial depositional processes, which may have transported organic carbon from the layer in which it formed and resulted in its preservation elsewhere within the crater (Anderson and Bell, 2010). Inverted channel fills suggest erosion resistant material that could serve to preserve organics originally deposited in a low energy aqueous environment. The lithology sampled will affect not only the preservation of organics, but also our ability to detect organics during our evolved gas analysis, based on the sample matrix. For example, reduced organics may be trapped in the mineral structure, and thermal evolution of these organics will occur during thermal decomposition of the host mineral. If organics are occluded in minerals that have very high thermal decomposition temperatures, they may be, in effect, "too well preserved," and difficult to detect during EGA. Alternatively, the possible presence of perchlorate, or other strong oxidants in surface regolith, may result in destruction of structural information identifying organic molecules before reaching the QMS on SAM via oxidation to C02 during heating. If this is the case, the stable carbon isotopic composition (delta 13C) of the C02 evolved and measured by the Tunable Laser Spectrometer (TLS) on SAM may help identify the presence of organics. On Earth, biological activity can cause large fractionations of 13C/12C, which can preserved in sedimentary deposits and distinguish the organic products of biotic processes from inorganic atmospheric and geological reservoirs. It is plausible that similar fractionations could occur on Mars and be preserved in reduced organic matter in sediments. Bulk delta 13C measurements alone may not reveal a signature of trace organic carbon that may be present along with inorganic carbon. If both organic and inorganic carbon compounds are present, it may be possible to detect the organic carbon by comparing the 013C of pyrolysis and combustion experiments. The TLS on SAM is capable of obtaining high precision measurements of delta13C from C02 evolved during pyrolysis and combustion of solid regolith samples. Because carbonates are expected to be present at abundances of 0.1-1 % in Martian soil, and organics in the ppb range (Webster and Mahaffy, 2011), analog samples must represent this mix of reduced organic carbon and carbonate. The work presented here will examine the use of delta13C of C02 produced during combustion of bulk Mars analog samples as a proxy for detection of reduced organic carbon.

Stern, J. C.↗

Stable light isotope biogeochemistry of hydrothermal systems

The stable isotopic composition of the elements O, H, S and C in minerals and other chemical species can indicate the existence, extent, conditions and the processes (including biological activity) of hydrothermal systems. Hydrothermal alteration of the 18O/16O and D/H values of minerals can be used to detect fossil systems and delineate their areal extent. Water-rock interactions create isotopic signatures which indicate fluid composition, temperature, water-rock ratios, etc. The 18O/16O values of silica and carbonate deposits tend to increase with declining temperature and thus help to map thermal gradients. Measurements of D/H values can help to decipher the origin(s) of hydrothermal fluids. The 34S/32S and 13C/12C values of fluids and minerals reflect the origin of the S and C as well as oxygen fugacities and key redox processes. For example, a wide range of 34S/32S values which are consistent with equilibration below 100 degrees C between sulfide and sulfate can be attributed to sulfur metabolizing bacteria. Depending on its magnitude, the difference in the 13C/12C value of CO2 and carbonates versus organic carbon might be attributed either to equilibrium at hydrothermal temperatures or, if the difference exceeds 1% (10/1000), to organic biosynthesis. Along the thermal gradients of thermal spring outflows, the 13C/12C value of carbonates and 13C-depleted microbial organic carbon increases, principally due to the outgassing of relatively 13C-depleted CO2.

Review, Tutorial↗

Iron Redox Systematics of Shergottites and Martian Magmas

Martian meteorites record a range of oxygen fugacities from near the IW buffer to above FMQ buffer [1]. In terrestrial magmas, Fe(3+)/ SigmaFe for this fO2 range are between 0 and 0.25 [2]. Such variation will affect the stability of oxides, pyroxenes, and how the melt equilibrates with volatile species. An understanding of the variation of Fe(3+)/SigmaFe for martian magmas is lacking, and previous work has been on FeO-poor and Al2O3-rich terrestrial basalts. We have initiated a study of the iron redox systematics of martian magmas to better understand FeO and Fe2O3 stability, the stability of magnetite, and the low Ca/high Ca pyroxene [3] ratios observed at the surface.

Righter, Kevin↗

Design Flexibility of Redox Flow Systems

The characteristics inherent in Redox flow systems permit considerable latitude in designing systems for specific storage applications. The first of these characteristics is the absence of plating/deplating reactions with their attendant morphology changes at the electrodes. This permits a given Redox system to operate over a wide range of depths of discharge and charge/discharge rates. The second characteristic is the separation of power generating components (stacks) from the energy storage components (tanks). This results in cost effective system design, ease of system growth via modularization, and freedom from sizing restraints so that the whole spectrum of applications, from utilities down to single residence can be considered. The final characteristic is the commonality of the reactant fluids which assures that all cells at all times are receiving reactants at the same state of charge. Since no cell can be out of balance with respect to any other cell, it is possible for some cells to be charged while others are discharging, in effect creating a DC to DC transformer. It is also possible for various groups of cells to be connected to separate loads, thus supplying a range of output voltages. Also, trim cells can be used to maintain constant bus voltage as the load is changed or as the depth of discharge increases. The commonality of reactant fluids also permits any corrective measures such as rebalancing to occur at the system level instead of at the single cell level.

Hagedorn, N. H.↗

Voltammetric studies of porous molybdenum electrodes for the alkali metal thermoelectric converter

Voltammetry of partially oxidized porous molybdenum alkali metal thermoelectric converter (AMTEC) electrodes from about 600 to 1000 K revealed a series of redox processes within the AMTEC operational voltage range which can be used to establish the electronic and ionic conductivities of these electrodes. Improved estimates of the free energies of formation of Na2Mo3O6, NaMoO2, and Na3MoO4 are obtained. Evidence is provided for the slow corrosive attack by Na2MoO4 on molybdenum. The ionic conductivity of Na2MoO4 is found to be sufficiently large at temperatures of greater than 700 K to explain the observed electrochemical phenomena in addition to the enhanced sodium transport in AMTEC electrodes below the freezing point of Na2MoO4.

Williams, R. M.↗

Metal-silicate thermochemistry at high temperature - Magma oceans and the 'excess siderophile element' problem of the earth's upper mantle

Low-temperature metal-silicate partition coefficients are extrapolated to magma ocean temperatures. If the low-temperature chemistry data is found to be applicable at high temperatures, an important assumption, then the results indicate that high temperature alone cannot account for the excess siderophile element problem of the upper mantle. For most elements, a rise in temperature will result in a modest increase in siderophile behavior if an iron-wuestite redox buffer is paralleled. However, long-range extrapolation of experimental data is hazardous when the data contains even modest experimental errors. For a given element, extrapolated high-temperature partition coefficients can differ by orders of magnitude, even when data from independent studies is consistent within quoted errors. In order to accurately assess siderophile element behavior in a magma ocean, it will be necessary to obtain direct experimental measurements for at least some of the siderophile elements.

Capobianco, Christopher J.↗

Evolved Gas Analyses of Sedimentary Rocks from the Glen Torridon Clay-Bearing Unit, Gale Crater, Mars: Results From the Mars Science Laboratory Sample Analysis at Mars Instrument Suite

Evolved gas analysis (EGA) data from the Sample Analysis at Mars (SAM) instrument suite indicated Fe-rich smectite, carbonate, oxidized organics, Fe/Mg sulfate, and chloride in sedimentary rocks from the Glen Torridon (GT) region of Gale crater that displayed phyllosilicate spectral signatures from orbit. SAM evolved H2O data indicated that the primary phyllosilicate in all GT samples was an Fe-rich dioctahedral smectite (e.g., nontronite) with lesser amounts of a phyllosilicate such as mixed layer talc-serpentine or greenalite-minnesotaite. CO(2) data supported the identification of siderite in several samples, and CO(2) and CO data was also consistent with trace oxidized organic compounds such as oxalate salts. SO(2) data indicated trace and/or amorphous Fe sulfates in all samples and one sample may contain Fe sulfides. SO(2) data points to significant Mg sulfates in two samples, and lesser amounts in several other samples. A lack of evolved O(2) indicated the absence of oxychlorine salts and Mn3+/Mn4+ oxides. The lack of, or very minor, evolved NO revealed absent or very trace nitrate/nitrite salts. HCl data suggested chloride salts in GT samples. Constraints from EGA data on mineralogy and chemistry indicated that the environmental history of GT involved alteration with fluids of variable redox potential, chemistry and pH under a range of fluid-to-rock ratio conditions. Several of the fluid episodes could have provided habitable environmental conditions and carbon would have been available to any past microbes though the lack of significant N could have been a limiting factor for microbial habitability in the GT region.

A. C. McAdam↗

Diffusion of Redox-Sensitive Elements in Basalt at Different Oxygen Fugacities

The terrestrial planets and moons of our solar system have differentiated over a range of oxygen fugacity conditions. Basalts formed from magmas on the Earth cover a range of more oxidized states (from approximately IW (iron wustite) plus 2 to approximately FMQ (fayalite-magnetite-quartz) plus 3) than crustal rocks from Mars (IW to approximately IW plus 3), and basalts from the Moon are more reduced than both, ranging from IW to IW minus 2. The small body Vesta differentiated around IW minus 4. Characterization of redox sensitive elements' diffusivities will offer insight into behavior of these elements as a function of f (fugacity of) O2 for these planetary bodies. Here, we report a systematic study of the diffusion of redox-sensitive elements in basaltic melts with varying oxygen fugacities (fO2) for trace elements, V, Nb, W, Mo, La, Ce, Pr, Sm, Eu, Gd, Ta, and W. Since fO2 is an intensive variable that is different for the reservoirs of various planets and moons in our solar system, it is important to characterize how changes in redox states will affect diffusion. We conducted experiments in a piston cylinder device at 1300 degrees Centigrade and 1 gigapascal, at the University of Rochester and NASA Johnson Space Center. We buffered some experiments at Ru-RuO2 (FMQ plus 6.00), and conducted other experiments within either a graphite or Mo capsule, which corresponds to fO2s of either FMQ minus1.2, or FMQ minus 3.00, respectively. Characterizing the diffusivities of redox sensitive elements at different fO2s is important because some elements, like Eu, have varying valence states, such as Eu (sup 2 plus) and Eu (sup 3 plus). Differences in charge and ion radii may lead to differences in diffusivities within silicate melts. This could, lead to formation of a Eu anomaly by diffusion, the magnitude of which may be controlled by the fO2. Characterization of trace element diffusion is also important in understanding trace element fractionation. We found, during the course of our investigation, that not only did the diffusivities of the redox sensitive elements change with fO2, but that the diffusivities of all other analyzed elements also changed. This indicates that not only do changes in valence influence trace elements diffusivities but that the structure of melt may have changed with varying oxygen fugacity, probably due to changes in the speciation of the major element Fe.

Szumila, I.↗

Study to establish cost projections for production of Redox chemicals

A cost study of four proposed manufacturing processes for redox chemicals for the NASA REDOX Energy Storage System yielded favorable selling prices in the range $0.99 to $1.91/kg of chromic chloride, anhydrous basis, including ferrous chloride. The prices corresponded to specific energy storage costs from under $9 to $17/kWh. A refined and expanded cost analysis of the most favored process yielded a price estimate corresponding to a storage cost of $11/kWh. The findings supported the potential economic viability of the NASA REDOX system.

Walther, J. F.↗

Redox storage systems for solar applications

It is noted that the worldwide development of solar photovoltaic and wind turbine systems to meet a range of terrestrial electrical energy requirements has underscored the need for inexpensive and reliable electrical energy storage. The NASA Redox Energy Storage System, based on soluble aqueous iron and chromium chloride redox couples, has exhibited many system-related features which for the most part are unique to this storage system. The technology advances required in the two elements (electrodes and membranes), which are the key to its technological feasibility, have been attained and system development has begun. The design, construction, and testing of a 1-kW system integrated with a solar photovoltaic array is underway to provide early demonstration of the attractive system-related features of the NASA Redox Storage System. Also demonstrated will be its versatility and compatibility with a terrestrial solar photovoltaic electric power system.

Hagedorn, N. H.↗