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NASA NTRS1991

Lunar sulfur

Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

Kuck, David L.↗

NASA NTRS1994

The production of 34S-depleted sulfide during bacterial disproportionation of elemental sulfur

Bacteria that disproportionate elemental sulfur fractionate sulfur isotopes such that sulfate is enriched in sulfur-34 by 12.6 to 15.3 per mil and sulfide is depleted in sulfur-34 by 7.3 to 8.6 per mil. Through a repeated cycle of sulfide oxidation to S0 and subsequent disproportionation, these bacteria can deplete sedimentary sulfides in sulfur-34. A prediction, borne out by observation, is that more extensive sulfide oxidation will lead to sulfides that are more depleted in sulfur-34. Thus, the oxidative part of the sulfur cycle creates circumstances by which sulfides become more depleted in sulfur-34 than would be possible with sulfate-reducing bacteria alone.

Non-NASA Center↗

DOE OSTI2026

Passivation‐Induced Species Dynamics and Microstructural Evolution in Solid‐State Lithium–Sulfur Cathodes

Solid-state lithium–sulfur (SSLS) batteries offer high theoretical energy density, yet their practical viability is hindered by poor sulfur utilization and limited rechargeability. At the core of this challenge lies the passivating nature of Li 2 S, which restricts ionic and electronic transport, suppresses interfacial activity, and severely impedes the reversibility of electrochemical reactions. In this study, we elucidate the mechanistic origins of these limitations by resolving how charge and discharge species form, grow, and spatially evolve within the cathode microstructure under varied current densities and electrode compositions. By resolving the species distribution at the particle scale and coupling it with Raman spectroscopy and X-ray diffraction, we demonstrate how Li 2 S formation induces localized surface passivation that progressively limits electrochemical accessibility within the cathode microstructure. Sulfur utilization is found to be strongly governed by the interplay between sulfur loading, residual porosity, and interfacial architecture. High sulfur contents result in buried, electrochemically isolated domains due to poor solid electrolyte (SE) percolation, while low sulfur contents trigger SE degradation via parasitic reactions. The resulting sulfur-porosity maps delineate the mechanistic boundaries between reversible and transport-limited regimes, offering actionable design guidance for SSLS cathodes with enhanced sulfur utilization.

electrode microstructure↗

DOE OSTI2025

Low-Cost Sulfur Thermal Storage for Solar Industrial Process Heat Applications

Industrial process heat (IPH) is one of the largest energy demands in U.S., representing about 10% of all domestic energy consumption. Fuel costs to generate this industrial process heat are generally a top three cost for industry, a major component in American manufacturing competitiveness. Roughly 60% of US IPH demand (about 6,500 TBtu annually) falls in the medium-temperature range of 100–250 °C. While concentrated solar thermal (CST) technologies can provide a cost-effective source of heat in this temperature range, solar intermittency limits their adoption in industries that operate 24/7. Element 16 Technologies, Inc. developed a low-cost sulfur thermal energy storage (TES) technology to bridge this gap by capturing excess solar heat during the day and dispatching it reliably during non-solar hours. The core innovation is the use of sulfur, an abundant, industrial waste byproduct that costs ten times less than molten salt used in commercial TES systems. The overall goal of the project was to advance the design and development of molten sulfur TES to a manufacturing-relevant prototype stage for solar industrial process heat applications, while establishing and validating a realistic pathway to commercial success. Key tasks included corrosion and mechanical durability testing to identify cost-effective materials, design investigations using physics-based simulation tools, techno-economic evaluations of system lifetime costs, and pilot-scale testing for performance verification. Corrosion testing of steel alloys under cyclic molten sulfur conditions showed that austenitic stainless steels in the 300 series performed particularly well, with no structural degradation of welds or joints. Thermal cyclic testing of pilot sulfur TES units up to 1.5 MWh quantified charge/discharge rates, heat losses, round-trip efficiency and validated the system's capability to operate effectively under intermittent charging conditions. A techno-economic model, informed by sulfur TES performance model validated using pilot test data, showed that hybrid solar+sulfur TES+NG boiler systems are economically competitive with incumbent natural gas boilers for multiple locations in the southwest US. In summary, this project established molten sulfur TES as a technically viable pathway to improve economic competitiveness of American manufacturing by lowering the cost of solar industrial process heat.

14 SOLAR ENERGY↗

DOE OSTI2024

NEXAFS spectroscopy of alkylated benzothienobenzothiophene thin films at the carbon and sulfur K-edges

Alkylated benzothienobenzothiophenes are an important class of organic semiconductors that exhibit high performance in solution-processed organic field-effect transistors. In this work, we study the near-edge x-ray absorption fine-structure (NEXAFS) spectra of 2,7-didecyl[1]benzothieno[3,2-b][1]benzothiophene (C 10 -BTBT) at both the carbon and sulfur K-edges. Angle-resolved experiments of thin films are performed to characterize the dichroism associated with molecular orientation. First-principles calculations using the density functional theory-based many-body x-ray absorption spectroscopy (MBXAS) method are also performed to correlate the peaks observed and their dichroism with transitions to specific antibonding molecular orbitals. Interestingly, the dichroism of the dominant, lowest energy peak is opposite at the carbon and sulfur K-edges. While the low-energy peak at the carbon K-edge is assigned to carbon 1s → π* transitions with transition dipole moment (TDM) perpendicular to the planar BTBT core, the dominant low energy peak at the sulfur K-edge is assigned to sulfur 1s → σ* transitions with TDM oriented along the long axis of the BTBT core. These differences at the sulfur and carbon K-edges are understood through the MBAXS simulations that find a reordering of the energy of the lowest energy π* and σ* transitions at the sulfur K-edge due to the strong localization of the σ* orbital over the sulfur atom. This work highlights differences in the NEXAFS spectra of organic semiconductors at carbon and sulfur K-edges and provides new insights into peak assignment and x-ray dichroism relevant for studying the molecular orientation of organic semiconductor films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1974

Sulfur abundances and distributions in the valley of Taurus-Littrow

Total sulfur abundances have been determined for 36 Apollo 17 soil, breccia and crystalline rock samples. Sulfur concentrations range from 550 to 1300 micrograms S/g for soil samples, with the orange soil containing the lowest amount of sulfur. Noritic breccias contain between 720 and 950 micrograms S/g, while the anorthositic rocks have sulfur contents of 270 and 368 micrograms S/g. The dunite 72415 contained the lowest sulfur content (44 micrograms S/g) of any Apollo 17 sample studied. Apollo 17 basalts have unusually high sulfur contents (1580-2770 micrograms S/g) as compared to Apollo 12 and 15 basalts and terrestrial basalts. Sulfur abundances for the Apollo 17 basalts are almost identical to those from Apollo 11 basalts. A negative correlation between percent metallic iron and total sulfur for the Apollo 17 and 15 basalts was found and suggests that a portion of the metallic iron in lunar basalts may result from desulfuration of the melt prior to crystallization from the lunar magma.

Gibson, E. K., Jr.↗

NASA NTRS1980

Are sulfur isotope ratios sufficient to determine the antiquity of sulfate reduction

Possible limitations on the use of sulfur isotope ratios in sedimentary sulfides to infer the evolution of microbial sulfate reduction are discussed. Current knowledge of the ways in which stable sulfur isotope ratios are altered by chemical and biological processes is examined, with attention given to the marine sulfur cycle involving various microbial populations, and sulfur reduction processes, and it is noted that satisfactory explanations of sulfur isotope ratios observed in live organisms and in sediments are not yet available. It is furthermore pointed out that all members of the same genus of sulfate reducing bacteria do not always fractionate sulfur to the same extent, that the extent of sulfur fractionation by many sulfate-reducing organisms has not yet been determined, and that inorganic processes can also affect sulfur isotope fractionation values. The information currently available is thus concluded to be insufficient to determine the time of initial appearance of biological sulfate reduction.

Ashendorf, D.↗

NASA NTRS1980

Stability of sulfur slopes on Io

The mechanical properties of elemental sulfur are such that the upper crust of Io cannot be primarily sulfur. For heat flows in the range 100-1000 ergs/sq cm sec sulfur becomes ductile within several hundred meters of the surface and would prevent the formation of calderas with depths greater than this. However, the one caldera for which precise depth data are available is 2 km deep, and this value may be typical. A study of the mechanical equilibrium of simple slopes shows that the depth to the zone of rapid ductile flow strongly controls the maximum heights for sulfur slopes. Sulfur scarps with heights greater than 1 km will fail for all heat flows greater than 180 ergs/sq cm sec and slope angles greater than 22.5 deg. The observed relief on Io is inconsistent with that anticipated for a predominantly sulfur crust. However, a silicate crust with several percent sulfur included satisfies both the mechanical constraints and the observed presence of sulfur on Io.

Clow, G. D.↗

NASA NTRS1985

Physics and chemistry of sulfur lakes on Io

Based on data from Loki and other hot spot regions, a model for a convecting sulfur lake that is heated from below is constructed. Temperature profiles and fluxes in the silicate and sulfur regions are consistent with the observed Loki highest-temperature component and excess flux. Evaporatin of sulfur sets a strong upper limit on the lake surface temperature, and the intermediate temperature in the Loki region is identified with sulfur vapor condensing primarily along lake shores. Simple models of sulfur vapor transport can be used to match the Voyager IRIS data, assuming sulfur vapor condensed on the shore radiates like a blackbody. The 1 - 100 year lifetime of such a lake in steady state implies that long-term earth-based observations interpreted with this model could detect variations in the Loki thermal output. The sodium-sulfur phase diagram is also presented and used to show that evaporated lakes may leave behind sodium-rich residue which could supply the torus with sodium. Finally, uncertainties in the model are assessed, including the lack of sulfur emission features in the Loki spectrum.

Lunine, J. I.↗

NASA NTRS1991

Effect of sulfur removal on Al2O3 scale adhesion

The effect of removing sulfur impurity on the adhesion of Al2O3 scale to NiCrAl was investigated in four experiments. It was found that removing sulfur to concentration less than 1 ppm per weight is sufficient to produce a very significant degree of alpha-Al2O3 scale adhesion to undoped NiCrAl alloys. Results of experiments show that repeated oxidation, and polishing after each oxidation cycle, of pure NiCrAl alloy lowered sulfur content from 10 to 2 ppm by weight (presumably by removing the segregated interfacial layer after each cycle); thinner samples became adherent after fewer oxidation-polishing cycles because of more limited supply of sulfur. It was found that spalling in subsequent cyclic oxidation tests was a direct function of the initial sulfur content. The transition between the adherent and nonadherent behavior was modeled in terms of sulfur flux, sulfur content, and sulfur segregation.

Smialek, James L.↗

NASA NTRS1993

A sulfur segregation study of PWA 1480, NiCrAl, and NiAl alloys

Some nickel based superalloys show reduced oxidation resistance from the lack of an adherent oxide layer during high temperature cyclic oxidation. The segregation of sulfur to the oxide-metal interface is believed to effect oxide adhesion, since low sulfur alloys exhibit enhanced adhesion. X ray Photoelectron Spectroscopy (XPS) was combined with an in situ sample heater to measure sulfur segregation in NiCrAl, PWA 1480, and NiAl alloys. The polished samples with a 1.5 to 2.5 nm (native) oxide were heated from 650 to 1100 C with hold times up to 6 hr. The sulfur concentration was plotted as a function of temperature versus time at temperature. One NiCrAl sulfur study was performed on the same casting used by Browning to establish a base line between previous Auger Electron Spectroscopy (AES) results and the XPS results of this study. Sulfur surface segregation was similar for PWA 1480 and NiCrAl and reached a maximum of 30 at% at 800 to 850 C. Above 900 C the sulfur surface concentration decreased to about 3 at% at 1100 C. These results are contrasted to the minimal segregation observed for low sulfur hydrogen annealed materials which exhibit improved scale adhesion.

Jayne, D. T.↗

NASA NTRS1997

The Effect of Hydrogen Annealing and Sulfur Content on the Oxidation Resistance of PWA 1480

For many decades the dramatic effect of trace amounts of reactive elements on alumina and chromia scale adhesion has been recognized and widely studied. Although various theories have been used to account for such behavior, the connection between scale adhesion and sulfur segregation was initially reported by Smeggil et al. This study found strong surface segregation of sulfur from very low levels in the bulk which could then be curtailed by the addition of reactive elements. It was assumed that the reactive elements, which are strong sulfide formers, acted by getting sulfur in the bulk thus precluding sulfur segregation and weakening of the oxide-metal bond. Subsequent studies confirmed that adhesion could be produced by reducing the sulfur impurity level, without reactive elements. The understanding of this phenomenon has been applied to modern single crystal superalloys, where the addition of Y, although very effective, is problematic. Also problematic is definition of the level of sulfur that is acceptable and below which no further adhesion benefit is reached. Published works have indicated a broad transition defined by various materials and oxidation tests. The present study describes the oxidation behavior of one superalloy (PWA 1480) as a function of various sulfur contents produced by hydrogen annealing for various temperatures, times, and sample thicknesses. The purpose is to define more precisely a criterion for adhesion based on total sulfur reservoir and segregation potential.

Smialek, James L.↗

NASA NTRS1999

Measurements of Nucleation-Mode Particle Size Distributions in Aircraft Plumes during SULFUR 6

This report summarizes the participation of the University of Denver in an airborne measurement program, SULFUR 6, which was undertaken in late September and early October of 1998 by the Deutsches Zentrum fur Luft und Raumfahrt (DLR). Scientific findings from two papers that have been published or accepted and from one manuscript that is in preparation are presented. The SULFUR 6 experiment was designed to investigate the emissions from subsonic aircraft to constrain calculations of possible atmospheric chemical and climatic effects. The University of Denver effort contributed toward the following SULFUR 6 goals: (1) To investigate the relationship between fuel sulfur content (FSC--mass of sulfur per mass of fuel) and particle number and mass emission index (El--quantity emitted per kg of fuel burned); (2) To provide upper and lower limits for the mass conversion efficiency (nu) of fuel sulfur to gaseous and particulate sulfuric acid; (3) To constrain models of volatile particle nucleation and growth by measuring the particle size distribution between 3 and 100 nm at aircraft plume ages ranging from 10(exp -1) to 10(exp 3) s; (4) To determine microphysical and optical properties and bulk chemical composition of soot particles in aircraft exhaust; and (5) To investigate the differences in particle properties between aircraft plumes in contrail and non-contrail situations. The experiment focused on emissions from the ATTAS research aircraft (a well characterized, but older technology turbojet) and from an in-service Boeing 737-300 aircraft provided by Lufthansa, with modem, high-bypass turbofan engines. Measurements were made from the DLR Dassault Falcon 900 aircraft, a modified business jet. The Atmospheric Effects of Aviation Program (AEAP) provided funding to operate an instrument, the nucleation-mode aerosol size spectrometer (N-MASS), during the SULFUR 6 campaign and to analyze the data. The N-MASS was developed at the University of Denver with the support of NOAA's Office of Global Programs and NASA's AEAP and measures particle size distributions in the 4-100 nm range.

Brock, Charles A.↗

NASA NTRS2000

Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?

Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard properties of organic sulfur gases. However, a number of the properties for aqueous organic sulfur compounds have not been experimentally determined. Furthermore, most of thermodynamic data that are available are for 25 C and 1 bar. In order to determine reaction properties to temperatures and pressures appropriate to the hydrothermal conditions in which thermophilic organisms actually live, we use equations of state developed by Helgeson and co-workers (Helgeson et al., 1981, AJS 281, 1249). A key piece of information needed to go up in temperature is the partial molal heat capacity, which is one of the properties for which experimental data are unavailable for nearly all organic sulfur compounds. We have used correlation methods to determine the partial molal heat capacities and volumes of many organic solutes. These estimates allow us to asses the role of organic sulfur compounds during the reduction of carbon in hydrothermal settings. We will present these data, along with examples of the thermodynamic properties of reactions involving aqueous organic sulfur compounds.

Schulte, Mitchell↗

DOE OSTI2025

Electrolyte Design and Optimization for Alkali Metal‐Sulfur Batteries

Alkali metal-sulfur batteries, including lithium-sulfur (Li-S), sodium-sulfur (Na-S), and potassium-sulfur (K-S) systems, have garnered significant attention as promising electrochemical energy storage (EES) technologies. Among them, Li-S batteries stand out as strong contenders for next-generation energy storage, owing to their high energy density and the cost-effectiveness of sulfur-based cathodes. However, with the rapid technological advances and the escalating energy demand, lithium resources are becoming increasingly scarce, making it imperative to explore alternative metal anodes to replace lithium. Therefore, Na-S and K-S batteries, serving as counterparts to Li-S systems, are emerging as formidable contenders for next-generation energy storage technologies due to the abundant and cost-effective nature of sodium and potassium. Although Na-S and K-S batteries possess considerable potential in the energy sector, their development is still in its infancy, with performance constrained by the nascent state of electrolyte design and optimization. This review article provides a comprehensive overview of recent advancements and developments in liquid electrolytes for alkali metal-sulfur batteries. Additionally, it identifies key challenges and proposes future research directions aimed at enhancing electrolyte stability, optimizing interfacial compatibility, and improving the overall performance of alkali metal-sulfur batteries.

25 ENERGY STORAGE↗

NASA NTRS1976

Extralunar sulfur in Apollo 16 and 17 lunar fines

An evaluation of Apollo 16 and 17 lunar fines data by the use of mixing models demonstrates evidence of extralunar sulfur in the fines. Fines are enriched in sulfur with respect to their component rocks. The enrichment of sulfur in 25 Apollo 16 and 17 fines samples shows a positive correlation with a CC-1 like meteoritic component as estimated from siderophilic element concentrations. Mixing models were calculated with variations in mare basalt sulfur concentration values to account for possible variability in mare basalt contribution due to reduction and sulfur loss during flow implacement. Implantation of sulfur by meteoritic processes provides a source for sulfur during regolith maturation and a mechanism for exposure related enrichment in S-34.

Cripe, J. D.↗

NASA NTRS1984

Sulfur volcanoes on Io?

The unusual rheological properties of sulfur are discussed in order to determine the distinctive volcanic flow morphologies which indicate the presence of sulfur volcanoes on the Saturnian satellite Io. An analysis of high resolution Voyager imagery reveals three features which are considered to be possible sulfur volcanoes: Atar Patera, Daedalus Patera, and Kibero Patera. All three features are distinguished by circular-to-oval central masses surrounded by irregular widespread flows. The central zones of the features are interpreted to be domes formed of high temperature sulfur. To confirm the interpretations of the satellite data, molten sulfur was extruded in the laboratory at a temperature of 210 C on a flat surface sloping 0.5 deg to the left. At this temperature, the sulfur formed a viscous domelike mass over the event. As parts of the mass cooled to 170 C the viscosity decreased to a runny stage, forming breakout flows. It is concluded that a case can be made for sulfur volcanoes on Io sufficient to warrant further study, and it is recommended that the upcoming Galileo mission examine these phenomena.

Greeley, R.↗

NASA NTRS1985

Aerobic sulfur-oxidizing bacteria: Environmental selection and diversification

Sulfur-oxidizing bacteria oxidize reduced inorganic compounds to sulfuric acid. Lithotrophic sulfur oxidizer use the energy obtained from oxidation for microbial growth. Heterotrophic sulfur oxidizers obtain energy from the oxidation of organic compounds. In sulfur-oxidizing mixotrophs energy are derived either from the oxidation of inorganic or organic compounds. Sulfur-oxidizing bacteria are usually located within the sulfide/oxygen interfaces of springs, sediments, soil microenvironments, and the hypolimnion. Colonization of the interface is necessary since sulfide auto-oxidizes and because both oxygen and sulfide are needed for growth. The environmental stresses associated with the colonization of these interfaces resulted in the evolution of morphologically diverse and unique aerobic sulfur oxidizers.

Caldwell, D.↗