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At least 181 records · Page 10

Mass Spectrometric Study of Sulfur Vapor

It is well known that sulfur catenates and forms oligmers ranging from S2 to S20. The actual number of species present in the vapor depends on several factors and has been the subject of many studies (e.g.: ref. 1). The main problem associated with the mass spectrometric studies is the tendency of the sulfur vapor to depolymerize or break up into smaller units under the ion source conditions. Therefore, one has to employ lower electron impact energies to identify the true abundances of various species present in the sulfur vapor and the pathways of dissociation.

Sulfur Vapor↗

Effect of Sulfur on siderophile element partitioning between olivine and martian mantle primary melt

Ni and Co variations in primary martian magmas exhibit anomalous incompatible behavior, which has remained an unexplained conundrum. Because martian magmas are S-rich, and some trace metals are reported to have enhanced solubility in S-bearing magmas, we have carried out a series of experiments to evaluate the effect of high-S melts on the olivine/melt partitioning of Ni, Co, Mn, V, and Cr. Near-liquidus experiments on a synthetic primary martian mantle melt (Yamato-980459 [Y98]) were completed in a piston-cylinder apparatus at 0.75 GPa. Previous studies in S-free systems illustrate that the partition coefficients for these elements are dependent chiefly on D(Mg(Ol/melt)) (the partition coefficient defined as wt% Mg in olivine/wt% Mg in melt, a proxy for temperature), and were used to calibrate a predictive expression that includes the effects of temperature [i.e., D(Mg(Ol/melt))], melt composition, and oxygen fugacity. These predictive expressions are then used to isolate any effect in DM olivine/melt due to dissolved sulfur. The results show that S might have a small effect for Co, but not enough to change Co partitioning from compatible to incompatible in our experiments. The addition of a sulfur term to the D(Co) predictive expressions shows that nearly 8000 ppm of sulfur would be required in the melt (at liquidus temperature of Y98) for D(Co) to become <1. These S contents are two times higher than those of a sulfide-saturated melt at the P-T conditions of a martian mantle source region. Therefore, the anomalous incompatible behavior observed in these primary magma suites must be due to another mechanism. High temperature, oxygen fugacity, and diffusion are not viable mechanisms, but magma mixing, assimilation, or kinetic crystallization effects remain possibilities.

shergottite↗

Computationally Guided Development of Components for High Energy Density Solid-State Lithium-Sulfur Batteries

All electric vertical take-off and landing vehicles (eVTOL) for urban air mobility (UAM) concepts face numerous challenging technical barriers before their introduction into the consumer marketplace. The most challenging of these technical barriers to overcome is developing an energy storage system capable of meeting the rigorous aerospace safety and performance criteria1. The performance metrics for eVTOL craft, such as specific energy, specific power, and safety, exceed those of electric automobiles by a factor of two to four. Current state-of-the-art (SOA) lithium-ion batteries are incapable of meeting the key performance criteria of energy and safety for eVTOL. Therefore, next generation advanced chemistries and designs must be developed to meet required performance metrics for electric aviation2. Beyond lithium-ion chemistries, such as lithium-sulfur, show promise in their high energy, while limitations exist in their power and cyclability due to low electrical conductivity and high intermediate solubility in organic liquid electrolytes. Several strategies to overcome the low electrical conductivity involve the use of selenium as a dopant in the active sulfur material, along with the incorporation of 2-dimensional electron-conducting holey-graphene to improve the composite cathodes electronic conductivity. Furthermore, combining this chemistry with a solid-electrolyte avoids the components’ dissolution issues3. However, the development of composite solid-state cathodes is non-trivial as several components must be intimately mixed so that the active component has sufficient access to both electrons and lithium ions to undergo full electrochemical conversion. Mathematical modeling of battery components can assist experimental design through a robust and rigorous combination of computational modeling techniques covering multiple length scales. The objective is to leverage modern computational materials methods combined with battery multiphysics tools to develop radically advanced compatible cathode and electrolyte materials, build and test solid state lithium-sulfur cells and packs. A NASA-based cross-organizational team of high-powered experts combined integrated computational predictive modeling, fundamental chemistry analysis, advanced material science, and battery cell development to tackle this very challenging, multidisciplinary problem. This presentation will show a multiscale computational modeling approach that has produced a novel particle dynamics method called Solid Electrolyte Sphere Approximation Model (SESAM). SESAM modeling targets the 1-10 µm scale structures and provides electromechanical and grain interactions for predictive design guidelines for the manufacturing of solid-state components. Parameters such as particle size and volume fraction of the constituent materials were modeled and experimentally fabricated to optimize electrochemical performance through improved microstructure design. Experimental feedback was provided through ionic and electronic conductivity assessment and structural analysis of developed materials and cell components.

battery↗

A New Multi-Method Assessment of Stratospheric Sulfur Load From the Okmok II Caldera-Forming Eruption of 43 BCE

The 43 BCE eruption of Okmok Volcano has been proposed to have had a significant climate cooling impact in the Northern Hemisphere. In this study, we quantify the climate cooling potential of the Okmok II eruption by measuring sulfur concentration in melt inclusions (up to 1,606 ppm) and matrix glasses and estimate a total of 62 ± 16 Tg S released. The proportion reaching the stratosphere (2.5%–25%, i.e., 1.5–15.5 Tg S) was constrained by physical modeling of the caldera-collapse eruption. Using the NASA Goddard Institute for Space Studies E2.2 climate model we found a linear response between cooling and stratospheric sulfur load (0.05–0.08°C/Tg S). Thus, the 1–2°C of cooling derived from proxy records would require 16–32 Tg sulfur injection. This study underscores the importance of combining approaches to estimate stratospheric S load. For Okmok II, we find all methods are consistent with a range of 15–16 Tg S.

volcano-climate interaction↗

Statistical summary and trend evaluation of air quality data for Cleveland, Ohio in 1967 to 1971: Total suspended particulate, nitrogen dioxide, and sulfur dioxide

Air quality data for Cleveland, Ohio, for the period of 1967 to 1971 were collated and subjected to statistical analysis. The total suspended particulate component is lognormally distributed; while sulfur dioxide and nitrogen dioxide are reasonably approximated by lognormal distributions. Only sulfur dioxide, in some residential neighborhoods, meets Ohio air quality standards. Air quality has definitely improved in the industrial valley, while in the rest of the city, only sulfur dioxide has shown consistent improvement. A pollution index is introduced which displays directly the degree to which the environmental air conforms to mandated standards.

Neustadter, H. E.↗

Interaction of sulfur dioxide and carbon dioxide with clean silver in ultrahigh vacuum.

It is shown that when a clean polycrystalline silver surface is subjected to sulfur dioxide at a pressure of 1 nanotorr, sulfur is chemisorbed to the silver. Heating the contaminated silver leads to an estimation of the minimum heat of desorption of 59 kcal/mol. Sulfur Auger peak height and relative function measurements of the surface during exposure show that adsorption occurs during 6 microtorr/sec exposure at 1 nanotorr.

Lassiter, W. S.↗

Auger analysis of oxygen and sulfur interactions with various metals and the effect of sliding on these interactions

Various gases were adsorbed to copper, aluminum, and chromium surfaces. The gases included oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Chemisorption was conducted on static surfaces and during dynamic friction experiments. An Auger cyclindrical mirror analyzer was used to monitor surface films. The sulfur containing gases adsorbed readily to all surfaces. Exposures of as little as 0.000001 (torr)(sec) (1 langmuir) were sufficient to reduce friction. Sliding contact did not affect chemisorption of copper or aluminum but did affect chemisorption to chromium surfaces. Oxygen removed sulfur films from all surfaces at room temperature (23 C). Gaseous exposures were from 0.000001 to 0.01 (torr)(sec) (1 to 10,000 langmuirs).

Buckley, D. H.↗

Cyclic octatomic sulfur - A possible infrared and visible chromophore in the clouds of Jupiter

Near-ultraviolet light is known to be an effective agent for the photoproduction of a variety of organic molecules from simulated primitive Earth and contemporary Jovian environments. The study discusses the infrared spectrum of a brown polymeric material produced under simulated Jovian conditions and its comparison with recent high-altitude infrared spectra of Jupiter. It is shown that this polymeric material is composed mainly of cyclic octatomic sulfur, even though a range of complex organic compounds is also present. The polymeric sulfur, produced from the ultraviolet photolysis of hydrogen sulfide, displays its strongest band at 465 reciprocal centimeters. This is in fair agreement with the frequency of the unidentified Jovian absorber recently reported by Houck et al. (1975). Polymeric octatomic sulfur may thus be an important constituent of Jovian clouds.

Khare, B. N.↗

Nature of the carbon and sulfur phases and inorganic gases in the Kenna ureilite

Abundances of carbon and sulfur in the Kenna ureilite are 2.219 plus or minus 0.060 wt. % C and 0.179 plus or minus 0.008 wt. % S. Secondary carbonates resulting from terrestrial weathering account for 0.25 plus or minus 0.02 wt. % C. No hydrocarbons were detected during gas release measurements. Most of the carbon is in graphite, diamond, or lonsdaleite. The sample of Kenna contained 0.95 plus or minus 0.05 wt.% H2O. Total carbon and sulfur measurements were made on three additional ureilites: Havero, Dingo Pup Donga, and North Haig. Ureilite carbon abundances are similar to those of C-2 chondrites, whereas sulfur abundances are a factor of 10 less than C-2 chondrites and ordinary chondrites. The elemental abundances, ratios, and phases present in the ureilites rule out a direct genetic relationship between the ureilites and the carbonaceous chondrites.

Gibson, E. K., Jr.↗

Sulfur in lunar mare basalts as a function of bulk composition

Sulfur abundances and metallic iron abundances in 18 Apollo 12 mare basalts were determined. No correlation between sulfur abundance and metallic iron content was detected; metallic iron abundances are not primarily caused by S loss. Sulfur abundances, directly related to the bulk composition of the rocks and especially to the TiO2 content, increase with increasing degrees of fractionation and appear to result from S concentration in the melts during fractionation. Unlike the Apollo 17 melts, the Apollo 12 melts were unsaturated with respect to sulfide. Composition appears to control S content for Apollo 17 basalts, and cumulus processes may cause Fe-FeS enrichment.

Gibson, E. K., Jr.↗

On matching the spectrum of Io - Variations in the photometric properties of sulfur-containing mixtures

The problem of comparing laboratory spectra of sulfur-containing binary mixtures with the spectrum of Io is discussed. For the satellite, the observable is the geometric albedo as a function of wavelength, whereas in the laboratory one often measures some other type of albedo. A previous paper demonstrated that for pure sulfur the multiplicative factor which converts the laboratory albedos to geometric albedos can be strongly wavelength dependent. The present paper demonstrates that this is also true for binary sulfur-containing mixtures. Furthermore, there is no universal conversion factor applicable to all binary mixtures, nor can the factor be interpolated for a particular mixture from the conversion factors of the two end members. The conversion factor is a function not only of the specific composition of a binary mixture but also of the relative particle size distributions of the two components, and must be measured specifically for each individual sample if a quantitative comparison between a laboratory sample and Io's surface is desired.

Veverka, J.↗

Sulfur volcanoes on Io

Widespread volcanism on Jupiter's satellite Io, if it occurred over the age of the solar system, would quickly reduce the inventory of most common volatiles needed to drive such volcanism. One exception is the volatile element sulfur. It is therefore postulated that sulfur is the driving volatile for Ionian volcanism. Its presence is consistent with a carbonaceous-chondrite-like bulk composition for the original material that formed Io 4.5 billion years ago. The ubiquity of sulfur on Io today demonstrates the importance of this element in the processes that formed its surface.

Consolmagno, G. J.↗

The solubility of sulfur in high-TiO2 mare basalts

The present paper deals with an experimental investigation of the solubility of sulfur of the high-TiO2 mare basalt 74275 at 1 atm, 1250 C. The data indicate that at saturation, 74275 is capable of dissolving 3400 ppm sulfur at 10 to 15 degrees below its liquidus. The analyzed samples of 74275 show sulfur contents of 1650 ppm S, which indicates that 74275 was 50% undersaturated at the time of eruption.

Danckwerth, P. A.↗

Total carbon and sulfur abundances in Antarctic meteorites

Total carbon and sulfur abundances have been measured in five Antarctic meteorites. Two C2 carbonaceous chondrites Yamato 74662 and Allan Hills 77306 have sulfur abundances (3.490 plus or minus .040% and 3.863 plus or minus 0.050% respectively) similar to other C2 chondrites but their carbon abundances (1.514 plus or minus 0.050% and 1.324 plus or minus .040% respectively) are lower than previously measured C2 chondrites. The decreased carbon abundances may reflect the effects of weathering in cold environments. Carbon and sulfur abundances for one C4 carbonaceous chondrite, one E4 enstatite chondrite and one ureilite are similar to values reported previously for meteorites of the same petrologic grades.

Gibson, E. K., Jr.↗

Stratospheric hydroxyl radical concentrations - New limitations suggested by observations of gaseous and particulate sulfur

A one-dimensional aerosol model is employed in investigating the sensitivity of the stratospheric distributions of gaseous sulfur compounds and sulfate aerosol particles to changes in OH and CS2 concentrations, in eddy diffusion coefficients, and in important chemical rate constants. By comparing model predictions with recent observational data for SO2, OCS, and particulates, it is found that, with regard to atmospheric sulfur, CS2 is only a secondary source of sulfur for the stratosphere relative to OCS and that background tropospheric CS2 concentrations by volume are likely to be less than 70 parts per trillion. It is also established that under stratospheric conditions the rate coefficients for the reactions of OH with OCS and CS2 may be substantially smaller than the room temperature laboratory values of Kurylo (1978).

Turco, R. P.↗

Interstellar sulfur chemistry

The results of a chemical model of SO, CS, and OCS chemistry in dense clouds are summarized. The results are obtained from a theoretical study of sulfur chemistry in dense interstellar clouds using a large-scale time-dependent model of gas-phase chemistry. Among the results are the following: (1) owing to activation energy, the reaction of CS with O atoms is efficient as a loss mechanism of CS during the early phases of cloud evolution or in hot and oxygen-rich sources such as the KL nebula; (2) if sulfur is not abnormally depleted in dense clouds, then the observed abundances of SO, SO2, H2S, CS, OCS, H2CS, and SiS indicate that sulfur is mostly atomic in dense clouds; and (3) OCS is stable against reactions with neutral atoms and radicals in dense clouds.

Prasad, S. S.↗

A New Use for High-Sulfur Coal

New process recovers some of economic value of high-sulfur coal. Although high-sulfur content is undesirable in most coal-utilization schemes (such as simple burning), proposed process prefers high-sulfur coal to produce electrical power or hydrogen. Potential exists for widespread application in energy industry.

Lawson, D. D.↗

Sighting of El Chichon sulfur dioxide clouds with the Nimbus 7 total ozone mapping spectrometer

The eruptions of El Chichon volcano on March 28 and April 3 and 4, 1982 were observed by the Nimbus 7 total ozone mapping spectrometer due to strong absorption by volcanic gases at the shortest wavelengths of the spectrometer (312.5 and 317.5 nm). These ultraviolet pictures permit a measurement of the volume, dispersion, and drift of volcanic gas clouds. The tropospheric clouds were rapidly dispersed in westerly winds while persistent stratospheric clouds drifted in easterly winds at speeds up to 13 m/sec. The spectral reflectance is consistent with sulfur dioxide absorption and rules out carbon disulfide as a major constituent. A preliminary estimate of the mass of sulfur dioxide deposited in the stratosphere by the large eruptions on April 3 and 4 is 3.3 million tons. Prior estimates of volcanic cloud volume were based on extrapolation of locally measured sulfur dioxide concentrations.

Krueger, A. J.↗