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18 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

Pyrite oxidation and reduction - Molecular orbital theory considerations

In this paper, molecular orbital theory is used to explain a heterogeneous reaction mechanism for both pyrite oxidation and reduction. The mechanism demonstrates that the oxidation of FeS2 by Fe(3+) may occur as a result of three important criteria: (1) the presence of a suitable oxidant having a vacant orbital (in case of liquid phase) or site (solid phase) to bind to the FeS2 via sulfur; (2) the initial formation of a persulfido (disulfide) bridge between FeS2 and the oxidant, and (3) an electron transfer from a pi(asterisk) orbital in S2(2-) to a pi or pi(asterisk) orbital of the oxidant.

Luther, George W., III↗
NASA NTRS1985

Laboratory infrared spectra of predicted condensates in carbon-rich stars

Laboratory spectra and mass absorption coefficients of MgS, CaS, FeS, SiS2, FeS2, Fe3C, and a commercial iron carbide are presented over the wavelength range 125-15 microns. These spectra confirm that MgS is the most likely source of the unidentified 30-micron emission in carbon-rich sources and that FeS, Fe3C, and 'iron carbide' cannot be responsible for this feature although they could contribute to the continuum in this region. CaS and FeS2 may contribute to the 30-micron feature; however, both higher resolution and higher precision astronomical observations are needed before their presence can be established. SiS2 has a peak near 22 microns and therefore cannot be a significant component of the dust in such regions.

Nuth, J. A.↗
DOE OSTI2025

Spatially resolved X-ray imaging and molecular characterisation of sulfur and iron in organic- and sulfur-rich hydrocarbon source mudstones

Sulfurisation of organic matter (OM) is a prominent preservation mechanism, however iron sulfide precipitation, particularly pyrite (FeS2), can counteract this mechanism. There is a dearth of high-resolution, spatially-resolved spectroscopic (redox) information on sulfur and iron inventories within organic-rich rocks that would improve our understanding of prevailing environmental conditions during deposition. Here, state-of-the-art synchrotron-based X-ray absorption and fluorescence analyses of key organic- and sulfur-rich mudstones demonstrate the potential of these techniques to non-destructively map and produce detailed spectroscopic information. Detailed high-resolution analyses (μm- to mm-scale) reveal the presence of widespread sulfurised OM in the Blackstone Band of the Kimmeridge Clay Formation, in line with a persistence of euxinia over a long temporal span and low reactive iron input, facilitating the preservation of OM through sulfurisation. In contrast, the presence of sulfurised OM was transitional in the Monterey Formation, consistent with fluctuating water column redox conditions, and is less significant in the Whitby Mudstone Formation, likely due to the high reactive iron concentrations outcompeting sulfurised OM formation. Analyses of sulfur species using model compounds further indicate that the Whitby Formation is strongly enriched in inorganic reduced sulfur minerals, while both the Kimmeridge Clay and Monterey Formations are dominated by organic sulfur species. These synchrotron-based observations improve our understanding of environmental conditions during the time of deposition of these mudstones and thus show great promise in the study of organic-rich sediments, especially in allowing their depositional settings to be more accurately reconstructed.

Kimmeridge Clay Formation↗
DOE OSTI2023

Microstructural diversity and digestion yields of select bituminous and subbituminous coals as raw material candidates for carbon fiber precursor production

Here, this work investigates the use of coals as raw materials for carbon fiber precursor production as a new alternative to coal utilization. Coal being a highly complex and heterogeneous material with different macerals and minerals complicates this task. Extensive microstructural characterization as well as preliminary digestion studies are performed on three bituminous coals (Herrin and Springfield from the Illinois Basin and the Blue Gem from the Central Appalachians) and one subbituminous coal from the Powder River Basin (Monarch), as raw material candidates. The subbituminous coal was richer in oxygen, lower in sulfur, and had a higher volatile matter yield. Microstructural investigations were performed using X-ray diffraction, X-ray/neutron computed tomography, scanning electron microscopy with energy dispersive spectroscopy, and petrology. Mild solvent extraction studies were conducted using creosote and decant oil as solvents in microreactors. The extraction yield was sensitive to temperature and time (350 to 450 °C between 30 and 120 mins.) for both creosote and decant oil digestions. While the Blue Gem coal had more desirable microstructural properties with less mineral content and cleaner macerals, it had the lowest coal conversion to quinoline soluble ‘liquid’ (of the bituminous coals). The lower coal conversion yield was hypothesized to be connected to the lack of FeS2 which could act as a catalyst when Fe is liberated from the structure under solvent extraction conditions. The Herrin and Springfield coals revealed similar microstructures and coal conversion efficiencies (higher than Blue Gem). These coals were the most promising candidates for further examination from this first approximations study. The subbituminous Monarch coal, however, was deemed less suitable due to poor coal conversion and less desirable microstructures. Additionally, the presented results with combined microstructural data from multiple length scales established a framework necessary for a first approximations study in this new coal utilization approach.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

Evidence for autotrophic growth of purple sulfur bacteria using pyrite as electron and sulfur source

ABSTRACT Purple sulfur bacteria (PSB) are capable of anoxygenic photosynthesis via oxidizing reduced sulfur compounds and are considered key drivers of the sulfur cycle in a range of anoxic environments. In this study, we show that Allochromatium vinosum (a PSB species) is capable of autotrophic growth using pyrite as the electron and sulfur source. Comparative growth profile, substrate characterization, and transcriptomic sequencing data provided valuable insight into the molecular mechanisms underlying the bacterial utilization of pyrite and autotrophic growth. Specifically, the pyrite-supported cell cultures (“py”’) demonstrated robust but much slower growth rates and distinct patterns from their sodium sulfide-amended positive controls. Up to ~200-fold upregulation of genes encoding various c - and b -type cytochromes was observed in “py,” pointing to the high relevance of these molecules in scavenging and relaying electrons from pyrite to cytoplasmic metabolisms. Conversely, extensive downregulation of genes related to LH and RC complex components indicates that the electron source may have direct control over the bacterial cells’ photosynthetic activity. In terms of sulfur metabolism, genes encoding periplasmic or membrane-bound proteins (e.g., FccAB and SoxYZ) were largely upregulated, whereas those encoding cytoplasmic proteins (e.g., Dsr and Apr groups) are extensively suppressed. Other notable differentially expressed genes are related to flagella/fimbriae/pilin(+), metal efflux(+), ferrienterochelin(−), and [NiFe] hydrogenases(+). Characterization of the biologically reacted pyrite indicates the presence of polymeric sulfur. These results have, for the first time, put the interplay of PSB and transition metal sulfide chemistry under the spotlight, with the potential to advance multiple fields, including metal and sulfur biogeochemistry, bacterial extracellular electron transfer, and artificial photosynthesis. IMPORTANCE Microbial utilization of solid-phase substrates constitutes a critical area of focus in environmental microbiology, offering valuable insights into microbial metabolic processes and adaptability. Recent advancements in this field have profoundly deepened our knowledge of microbial physiology pertinent to these scenarios and spurred innovations in biosynthesis and energy production. Furthermore, research into interactions between microbes and solid-phase substrates has directly linked microbial activities to the surrounding mineralogical environments, thereby enhancing our understanding of the relevant biogeochemical cycles. Our study represents a significant step forward in this field by demonstrating, for the first time, the autotrophic growth of purple sulfur bacteria using insoluble pyrite (FeS2) as both the electron and sulfur source. The presented comparative growth profiles, substrate characterizations, and transcriptomic sequencing data shed light on the relationships between electron donor types, photosynthetic reaction center activities, and potential extracellular electron transfer in these organisms capable of anoxygenic photosynthesis. Furthermore, the findings of our study may provide new insights into early-Earth biogeochemical evolutions, offering valuable constraints for understanding the environmental conditions and microbial processes that shaped our planet’s history.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1981

Infrared absorption spectra of metal carbides, nitrides and sulfides

The infrared absorption spectra of 12 kinds of metal carbides, 11 kinds of nitrides, and 7 kinds of sulfides, a total of 30 materials, were measured and the application of the infrared spectra of these materials to analytical chemistry was discussed. The measurements were done in the frequency (wave length) range of (1400 to 400/cm (7 to 25 mu). The carbides Al4C3, B4C, the nitrides AlN, BN, Si3N4, WB, and the sulfides Al2S3, FeS2, MnS, NiS and PbS were noted to have specific absorptions in the measured region. The sensitivity of Boron nitride was especially good and could be detected at 2 to 3 micrograms in 300 mg of potassium bromide.

Kammori, O.↗
NASA NTRS1989

A survey of advanced battery systems for space applications

The results of a survey on advanced secondary battery systems for space applications are presented. The objectives were: to identify advanced battery systems capable of meeting the requirements of various types of space missions, with significant advantages over currently available batteries, to obtain an accurate estimate of the anticipated improvements of these advanced systems, and to obtain a consensus for the selection of systems most likely to yield the desired improvements. Few advanced systems are likely to exceed a specific energy of 150 Wh/kg and meet the additional requirements of safety and reliability within the next 15 years. The few that have this potential are: (1) regenerative fuel cells, both alkaline and solid polymer electrolyte (SPE) types for large power systems; (2) lithium-intercalatable cathodes, particularly the metal ozides intercalatable cathodes (MnO2 or CoO2), with applications limited to small spacecrafts requiring limited cycle life and low power levels; (3) lithium molten salt systems (e.g., LiAl-FeS2); and (4) Na/beta Alumina/Sulfur or metal chlorides cells. Likely technological advances that would enhance the performance of all the above systems are also identified, in particular: improved bifunctional oxygen electrodes; improved manufacturing technology for thin film lithium electrodes in combination with polymeric electrolytes; improved seals for the lithium molten salt cells; and improved ceramics for sodium/solid electrolyte cells.

Attia, Alan I.↗
NASA NTRS1989

Advanced high-temperature batteries

The promise of very high specific energy and power was not yet achieved for practical battery systems. Some recent approaches are discussed for new approaches to achieving high performance for lithium/DeS2 cells and sodium/metal chloride cells. The main problems for the development of successful LiAl/FeS2 cells were the instability of the FeS2 electrode, which has resulted in rapidly declining capacity, the lack of an internal mechanism for accommodating overcharge of a cell, thus requiring the use of external charge control on each individual cell, and the lack of a suitable current collector for the positive electrode other than expensive molybdenum sheet material. Much progress was made in solving the first two problems. Reduction of the operating temperatures to 400 C by a change in electrolyte composition has increased the expected life to 1000 cycles. Also, a lithium shuttle mechanism was demonstrated for selected electrode compositions that permits sufficient overcharge tolerance to adjust for the normally expected cell-to-cell deviation in coulombic efficiency. Sodium/sulfur batteries and sodium/metal chloride batteries have demonstrated good reliability and long cycle life. For applications where very high power is desired, new electrolyte coinfigurations would be required. Design work was carried out for the sodium/metal chloride battery that demonstrates the feasibility of achieving high specific energy and high power for large battery cells having thin-walled high-surface area electrolytes.

Nelson, Paul A.↗
NASA NTRS1990

Iron-sulfur mineralogy of Mars - Magmatic evolution and chemical weathering products

Models are developed for the magmatic evolution and the oxidative weathering of sulfide minerals on Mars, based on petrogenetic associations among komatiitic rock types, Viking geochemical data, SNC meteorites, and terrestrial Fi-Ni deposits. The weathering model was tested by exposing komatiitic pyrrhotites and olivines to sulfuric acid solutions, with or without dissolved ferric iron, and identifying the reaction products by Moessbauer spectroscopy. The results suggest that, on Mars, acidic groundwater has induced oxidative weathering of pyrrhotite, yielding FeS2 and then FeOOH.

Burns, Roger G.↗
NASA NTRS1993

Venus mountain-top mineralogy: Misconceptions about pyrite as the high radar-reflecting phase

Altitude-dependent, high radar-reflectivity surfaces on Venus are observed on most mountainous volcanic terranes above a planetary radius of about 6054 km. However, high radar-reflectivity areas also occur at lower altitudes in some impact craters and plain terranes. Pyrite (FeS2) is commonly believed to be responsible for the high radar reflectivities at high elevations on Venus, on account of large dielectric constants measured for sulfide-bearing rocks that were erroneously attributed to pyrite instead of pyrrhotite. Pentlandite-pyrrhotite assemblages may be responsible for high reflectivities associated with impact craters on the Venusian surface, by analogy with Fe-Ni sulfide deposits occurring in terrestrial astroblemes. Mixed-valence Fe(2+)-Fe(3+) silicates, including oxyhornblende, oxybiotite, and ilvaite, may contribute to high radar reflecting surfaces on mountain-tops of Venus.

Burns, Roger G.↗
NASA NTRS1993

The rate of chemical weathering of pyrite on the surface of Venus

This abstract reports results of an experimental study of the chemical weathering of pyrite (FeS2) under Venus-like conditions. This work, which extends the earlier study by Fegley and Treiman, is part of a long range research program to experimentally measure the rates of thermochemical gas-solid reactions important in the atmospheric-lithospheric sulfur cycle on Venus. The objectives of this research are (1) to measure the kinetics of thermochemical gas-solid reactions responsible for both the production (e.g., anhydrite formation) and destruction (e.g., pyrrhotite oxidation) of sulfur-bearing minerals on the surface of Venus and (2) to incorporate these and other constraints into holistic models of the chemical interactions between the atmosphere and surface of Venus. Experiments were done with single crystal cubes of natural pyrite (Navajun, Logrono, Spain) that were cut and polished into slices of known weight and surface area. The slices were isothermally heated at atmospheric pressure in 99.99 percent CO2 (Coleman Instrument Grade) at either 412 C (685 K) or 465 C (738 K) for time periods up to 10 days. These two isotherms correspond to temperatures at about 6 km and 0 km altitude, respectively, on Venus. The reaction rate was determined by measuring the weight loss of the reacted slices after removal from the furnace. The reaction products were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy on the SEM.

Fegley, B., Jr.↗
NASA NTRS1995

The rate of pyrite decomposition on the surface of Venus

We report the results of a detailed experiment study of the kinetics and mechanism of pyrite (FeS2) chemical weathering under Venus surface conditions. Pyrite is thermodynamically unstable on the surface of Venus and will spontaneously decompose to pyrrhotite (Fe7S8) because the observed S2 partial pressure in the lower atmosphere of Venus is lower than the S2 vapor pressure over coexisting pyrite and pyrrhotite. Pyrite decomposition kinetics were studied in pure CO2 and CO2 gas mixtures along five isotherms in the temperature range 390-531 C. In all gas mixtures studied, pyrite thermally decomposes to pyrrhotite (Fe7S8), which on continued heating loses sulfur to form more Fe-rich pyrrhotites. During this process the pyrrhotites are also being oxidized to form magnetite (Fe3O4), which converts to maghemite (gamma-Fe2O3), and then to hematite (alpha-Fe2O3). The reaction rates for pyrite thermal decomposition to pyrrhotite were determined by measuring the weight loss. The thickness of the unreacted pyrite in the samples provided a second independent reaction rate measurement. Finally, Mossbauer spectra done on 42 of the 115 experimental samples provided a third set of independent reaction rate data. Pyrite decomposition follows zero-order kinetics and is independent of the amount of pyrite present. The rate of pyrite decomposition is apparently independent of the gas compositions used and of the CO2 number density over a range of a factor of 40. The derived activation energy of approximately 150 kJ/mole is the same in pure CO2, two different CO-CO2 mixtures, and a ternary CO-SO2-CO2 mixture. Based on data for a CO-CO2-SO2 gas mixture with a CO number density approximately 10 times higher than at the surface of Venus and a SO2 number density approximately equal to that at the surface of Venus, the rate of pyrite destruction on the surface of Venus varies from about 1225 +/- 238 days/cm at the top of Maxwell Montes (approximately 660 K) to about 233 +/- 133 days/cm in the plains of Venus (approximately 740 K). These lifetimes are very short on a geological time scale and show that pyrite cannot exist on the surface of Venus for any appreciable length of time.

Fegley, B., Jr.↗
NASA NTRS1998

Polymerization on the rocks: beta-amino acids and arginine

We have studied the accumulation of long oligomers of beta-amino acids on the surface of minerals using the 'polymerization on the rocks' protocol. We find that long oligopeptides of beta-glutamic acid which cannot be formed in homogeneous aqueous solution are accumulated efficiently on the surface of hydroxylapatite using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as condensing agent. The EDAC-induced oligomerization of aspartic acid on hydroxylapatite proceeds even more efficiently. Hydroxylapatite can also facilitate the ligation of the tripeptide (glu)3. The 'polymerization on the rocks' scenario is not restricted to negatively-charged amino acids. Oligoarginines are accumulated on the surface of illite using carbonyldiimidizole (CDI) as condensing agent. We find that FeS2 catalyzes the CDI-induced oligomerization of arginine, although it does not adsorb oligoarginines. These results are relevant to the formation of polypeptides on the primitive earth.

NASA Discipline Exobiology↗
NASA NTRS2008

Solid-State High-Temperature Power Cells

All-solid-state electrochemical power cells have been fabricated and tested in a continuing effort to develop batteries for instruments for use in environments as hot as 500 C. Batteries of this type are needed for exploration of Venus, and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal and oil wells, processing furnaces, and combustion engines. In the state-of-the-art predecessors of the present solid-state power cells, fully packaged molten eutectic salts are used as electrolytes. The molten-salt-based cells can be susceptible to significant amounts of self-discharge and corrosion when used for extended times at elevated temperatures. In contrast, all-solid-state cells such as the present ones are expected to be capable of operating for many days at temperatures up to 500 C, without significant self-discharge. The solid-state cell described here includes a cathode made of FeS2, an electrolyte consisting of a crystalline solid solution of equimolar amounts of Li3PO4 and Li4SiO4, and an anode made of an alloy of Li and Si (see figure). The starting material for making the solid electrolyte is a stoichiometric mixture of Li3PO4, SiO2, and Li3CO2. This mixture is ball-milled, then calcined for two hours at a temperature of 1,100 C, then placed in a die atop the cathode material. Next, the layers in the die are squeezed together at a pressure between 60 and 120 MPa for one hour at a temperature of 600 C to form a unitary structure comprising the solid electrolyte and cathode bonded together. Finally, the lithium-alloy anode is pressure-bonded to the solid electrolyte layer, using an intermediate layer of pure lithium. In one test of a cell of this type, a discharge rate of about 1 mA per gram of cathode material was sustained for 72 hours at a temperature of about 460 C. This is about three times the discharge rate required to support some of the longer duration Venus-exploration mission scenarios.

Whitacre, Jay↗
NASA NTRS2009

NiF2/NaF:CaF2/Ca Solid-State High-Temperature Battery Cells

Experiments and theoretical study have demonstrated the promise of all-solid-state, high-temperature electrochemical battery cells based on NiF2 as the active cathode material, CaF2 doped with NaF as the electrolyte material, and Ca as the active anode material. These and other all-solid-state cells have been investigated in a continuing effort to develop batteries for instruments that must operate in environments much hotter than can be withstood by ordinary commercially available batteries. Batteries of this type are needed for exploration of Venus (where the mean surface temperature is about 450 C), and could be used on Earth for such applications as measuring physical and chemical conditions in geothermal wells and oil wells. All-solid-state high-temperature power cells are sought as alternatives to other high-temperature power cells based, variously, on molten anodes and cathodes or molten eutectic salt electrolytes. Among the all-solid-state predecessors of the present NiF2/NaF:CaF2/Ca cells are those described in "Solid-State High-Temperature Power Cells" (NPO-44396), NASA Tech Briefs, Vol. 32, No. 5 (May 2008), page 40. In those cells, the active cathode material is FeS2, the electrolyte material is a crystalline solid solution of equimolar amounts of Li3PO4 and LiSiO4, and the active anode material is Li contained within an alloy that remains solid in the intended high operational temperature range.

West, William↗
NASA NTRS2015

Preliminary Analysis of Pyrite Reactivity Under Venusian Temperature and Atmosphere

Measurements of Venus surface chemistry suggest a basaltic composition with a predominantly CO2 atmosphere. In order to understand the reactivity of certain possible mineral species on the surface, previous simulation chambers conduct experiments at 1 atmosphere with a simplified CO2 atmosphere. Following this procedure, pyrite (FeS2) samples are used to estimate the reactivity of sulfide minerals under a Venusian atmosphere and climate. Sulfurous gas species have been identified and quantified in the Venusian atmosphere, and sulfurous gas and mineral species are known to be created through volcanism, which is suggested to still occur on the surface of Venus. This experimentation is necessary to constrain reactions that could occur between the surface and atmosphere of Venus to understand terrestrial geology in a thick and hot greenhouse atmosphere. Quantifying this reaction can lead to approximations necessary for further experimentation in more complex environments such as those in the GEER chamber at Glenn Research Center that can simulate pressure along with temperature and a more inclusive and representative Venusian atmosphere.

Venus surface↗
DOE OSTI2022

Autogenous acid production using a regulated bio-oxidation method for economical recovery of REEs and critical metals from coal-based resources

Acid is a necessary component for the successful leaching of minerals containing REEs (rare earth elements) and other sources. Pyrite (FeS2), which is present in REE containing minerals, can be used to produce acid. Pyrite is utilized as a source to create ferric sulfate and sulfuric acid in the presence of A. Ferroxidans. Such microorganism-based bio-oxidation necessitates the establishment of optimal conditions for continual acid production. For efficient acid generation, additional optimization was done by varying residence time, solid percentage, and airflow rate. A step-by-step analysis and associated details are offered in this work, which used pyrite to create acid for leaching. For the bio-oxidation of pyrite with varying purity, an automated bioreactor was used. Scanning electron microscopy with energy-dispersive X-ray spectroscopy was used to examine the morphology and elemental content of bioleaching sediments. Eh and pH measurements were continuously done to ensure healthy operation of the bioreactors. The analysis suggested that, the Eh value in the range of ∼ 640–680 mV, pH range of ∼ 1.3–1.5 and residence time of 4–6 days with 6% solid feed are favorable conditions of operation.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2022

Benchmarking Solid-State Batteries Containing Sulfide Separators: Effects of Electrode Composition and Stack Pressure

Integrating sulfide separators into solid-state batteries (SSBs) containing high energy cathodes typically requires one or more materials and engineering solutions including: (i) applying interfacial coatings to mitigate electrolyte decomposition, (ii) applying high stack pressures to form robust solid-solid contacts, and (iii) using alloying anodes to avoid Li dendrite formation. Despite the promise of these approaches, a lack of standardized testing protocols makes it difficult to directly compare results among different studies. To address this problem, the present work benchmarks the performance of SSBs containing β-Li 3 PS 4 (LPS) separators and composite cathodes. By systematically varying the anode/cathode composition and stack pressure, this work demonstrates that cathode design is a major bottleneck for solid-state cells cycled at low rates (<100 µA cm -2 ). Operando stack pressure measurements show that, while mechanical confinement generally promotes higher active material utilization and cycling stability, this strategy alone does not address interfacial reactivity between LPS and high voltage cathodes. Here, these results also demonstrate that stress evolution during cycling is dominated by volume changes at the Li metal anode. Finally, we show that FeS 2 cathodes with moderate operating voltages (<3 V vs Li/Li + ) exhibit superior cycling performance compared to high voltage cathodes by facilitating formation of stable cathode/electrolyte interfaces.

25 ENERGY STORAGE↗