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NASA NTRS1992

The effects of acid deposition on sulfate reduction and methane production in peatlands

Peatlands, as fens and bods, make up a large percentage of northern latitude terrestrial environments. They are organic rich and support an active community of anaerobic bacteria, such as methanogenic and sulfate-reducing bacteria. The end products of these microbial activities, methane and hydrogen sulfide, are important components in the global biogeochemical cycles of carbon and sulfur. Since these two bacterial groups compete for nutritional substrates, increases in sulfate deposition due to acid rain potentially can disrupt the balance between these processes leading to a decrease in methane production and emission. This is significant because methane is a potent greenhouse gas that effects the global heat balance. A section of Mire 239 in the Experimental Lakes Area, in Northwestern Ontario, was artificially acidified and rates of sulfate reduction and methane production were measured with depth. Preliminary results suggested that methane production was not affected immediately after acidification. However, concentrations of dissolved methane decreased and dissolved sulfide increased greatly after acidification and both took several days to recover. The exact mechanism for the decrease in methane was not determined. Analyses are under way which will be used to determine rates of sulfate reduction. These results will be available by Spring and will be discussed.

Murray, Georgia L.↗

NASA NTRS2002

Sulfur Saturation Limits in Silicate Melts and their Implications for Core Formation Scenarios for Terrestrial Planets

This study explores the controls of temperature, pressure, and silicate melt composition on S solubility in silicate liquids. The solubility of S in FeO-containing silicate melts in equilibrium with metal sulfide increases significantly with increasing temperature but decreases with increasing pressure. The silicate melt structure also exercises a control on S solubility. Increasing the degree of polymerization of the silicate melt structure lowers the S solubility in the silicate liquid. The new set of experimental data is used to expand the model of Mavrogenes and O'Neill(1999) for S solubility in silicate liquids by incorporating the influence of the silicate melt structure. The expected S solubility in the ascending magma is calculated using the expanded model. Because the negative pressure dependence of S solubility is more influential than the positive temperature dependence, decompression and adiabatic ascent of a formerly S-saturated silicate magma will lead to S undersaturation. A primitive magma that is S-saturated in its source region will, therefore, become S-undersaturated as it ascends to shallower depth. In order to precipitate magmatic sulfides, the magma must first cool and undergo fractional crystallization to reach S saturation. The S content in a metallic liquid that is in equilibrium with a magma ocean that contains approx. 200 ppm S (i.e., Earth's bulk mantle S content) ranges from 5.5 to 12 wt% S. This range of S values encompasses the amount of S (9 to 12 wt%) that would be present in the outer core if S is the light element. Thus, the Earth's proto-mantle could be in equilibrium (in terms of the preserved S abundance) with a core-forming metallic phase.

Holzheid, Astrid↗

NASA NTRS1988

Climatic changes resulting from mass extinctions at the K-T boundary (and other bio-events)

The mass extinctions at the Cretaceous-Tertiary (K-T) boundary include about 90 percent of marine calcareous nannoplankton (coccoliths), and carbon-isotope data show that marine primary productivity was drastically reduced for about 500,000 years after the boundary event, the so-called Strangelove Ocean effect. One result of the elimination of most marine phytoplankton would have been a severe reduction in production of dimethyl sulfide (DMS), a biogenic gas that is believed to be the major precursor of cloud condensation nuclei (CCN) over the oceans. A drastic reduction in marine CCN should lead to a cloud canopy with significantly lower reflectivity, and hence cause a significant warming at the earth's surface. Calculations suggest that, all other things being held constant, a reduction in CCN of more than 80 percent (a reasonable value for the K-T extinctions) could have produced a rapid global warming of 6 C or more. Oxygen-isotope analyses of marine sediments, and other kinds of paleoclimatic data, have provided for a marked warming, and a general instability of climate coincident with the killoff of marine plankton at the K-T boundary. Similar reductions in phytoplankton abundance at other boundaries, as indicated by marked shifts in carbon-isotope curves, suggest that severe temperature changes may have accompanied other mass extinctions, and raises the intriguing possibility that the extinction events themselves could have contributed to the climatic instabilities at critical bio-events in the geologic record.

Rampino, Michael R.↗

NASA NTRS1995

Origin of condensation nuclei in the springtime polar stratosphere

An enhanced sulfate aerosol layer has been observed near 25 km accompanying springtime ozone depletion in the Antarctic stratosphere. We use a one-dimensional aerosol model that includes photochemistry, particle nucleation, condensational growth, coagulation, and sedimentation to study the origin of the layer. Annual cycles of sunlight, temperature, and ozone are incorporated into the model. Our results indicate that binary homogeneous nucleation leads to the formation of very small droplets of sulfuric acid and water under conditions of low temperature and production of H2SO4 following polar sunrise. Photodissociation of carbonyl sulfide (OCS) alone, however, cannot provide sufficient SO2 to create the observed condensation nuclei (CN) layer. When subsidence of SO2 from very high altitudes in the polar night vortex is incorporated into the model, the CN layer is reasonably reproduced. The model predictions, based on the subsidence in polar vortex, agree with in situ measurements of particle concentration, vertical distribution, and persistence during polar spring.

Zhao, Jingxia↗

NASA NTRS1995

Origin of Condensation Nuclei in the Springtime Polar Stratosphere

Zhao, Jingxia↗

NASA NTRS1976

Power Sources Symposium, 27th, Atlantic City, N.J., June 21-24, 1976, Proceedings

A lithium-chlorine rechargeable battery is considered along with an FeS electrode development for a secondary Li5Si-FeS battery, the sodium-sulfur battery, nickel battery systems for electric vehicles, reactions in lithium thionyl chloride cells, progress in the development of lithium inorganic batteries, a stable electrolyte for Li/SO2 reserve cells, and rechargeable lithium transition metal sulfide batteries. Attention is also given to thermal runaway tests on nickel-cadmium aircraft batteries, the development of nickel-zinc batteries for aircraft, an evaluation of sealed lead acid batteries for aircraft applications, the charging of sealed lead-acid batteries, hydrogen recombination in sealed nickel-cadmium cells, the characteristics of nickel-hydrogen flight cells, the lithium-iodine cell, low power methanol fuel cells, and a nuclear battery hybrid configuration study.

Source record↗

NASA NTRS1991

Evolution of ore deposits on terrestrial planets

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

Burns, R. G.↗

NASA NTRS2021

The Role of Hydrated Minerals and Space Weathering Products in the Bluing of Carbonaceous Asteroids

The surfaces of airless bodies such as lunar and S-type asteroids typically become spectrally redder in visible to near-infrared reflectance with longer exposures to space weathering. However, some carbonaceous asteroids instead become spectrally bluer. Space weathering experiments on carbonaceous meteorites have provided some clues as to the space weathering products that could produce spectral bluing. We applied these experimental results to our Hapke radiative transfer model, with which we modeled spectral data from the OSIRIS-REx mission in order to determine whether these space weathering products—specifically, nanophase and microphase metallic iron, troilite, and magnetite—could explain the globally blue spectrum of the carbonaceous asteroid (101955) Bennu. The model suggests that the surface of Bennu has microphase iron, nanophase magnetite, and nanophase and microphase troilite. Considering previous space weathering experiments together with our spectral modeling of Bennu, we posit that the presence of nanophase magnetite is what causes a carbonaceous asteroid to become spectrally bluer with exposure time. Nanophase magnetite can form on asteroids that have Fe-bearing hydrated minerals (phyllosilicates). On anhydrous carbonaceous asteroids, nanophase iron forms instead of magnetite, leading to spectral reddening. We therefore predict that samples returned by the OSIRIS-REx mission from Bennu will have more nanophase magnetite than nanophase iron with nanophase and microphase sulfides, whereas samples returned by the Hayabusa2 mission from the carbonaceous asteroid (162173) Ryugu, which is spectrally red, will contain nanophase and microphase sulfides as well as more nanophase iron than nanophase magnetite.

David Trang↗

NASA NTRS1952

Velocity of action of oxygen, hydrogen sulfide, and halogens on metals

This report discusses a method of determining the rate of surface oxidation of a metal by the change in the color of the surface film produced by reactions with oxygen, chlorine, or iodine. The metals studied included iron, nickel, copper, zinc, cadmium, tin, lead, cobalt, and manganese. Tables are given for surface film thickness versus color for various times.

TIN↗

NASA NTRS2004

Computed Tomography and its Application for the 3D Characterization of Coarse Grained Meteorites

With judicious selection of parameters, computed tomography can provide high precision density data. Such data can lead to a non-destructive determination of the phases and phase distribution within large solid objects. Of particular interest is the structure of the Mundrabilla meteorite, which has 25 volumes, percent of a sulfide within a metallic meteorite. 3D digital imaging has enabled a quantitative evaluation of the distribution and contiguity of the phases to be determined.

Gillies, Donald C.↗

NASA NTRS2024

Exposure Limits for Hydrogen Sulfide in Spaceflight

Hydrogen sulfide (H 2 S) has not historically been detected in spacecraft, but the possible evolution of volatile components from polar ice on the lunar surface is a potential concern for NASA’s planned Artemis missions. Numerous case reports and occupational epidemiological studies document that exposure to H 2 S at high concentrations has effects on the respiratory system, potentially leading to unconsciousness followed by debilitating neurological effects. Studies in rodents demonstrate sensitivity of the respiratory system to lower concentrations of H 2 S. Adverse respiratory effects have also been indicated in workers chronically exposed to H 2 S. The objective of the present publication is to develop Spacecraft Maximum Allowable Concentrations (SMACs) for H 2 S for all current standard durations of exposure for spaceflight (1-hour, 24-hours, 7-days, 30-days, 180-days, and 1000-days). Summary sources and literature review were used to identify relevant studies to inform SMAC development. Space flight mission specific activities and most probable exposure scenarios were used to determine the relevant toxicity endpoints and supporting studies. SMACs were established for hydrogen sulfide of 5 ppm for 1-hour, 1.3 ppm for 24-hours, 1.3 ppm for 7-days, 1.3 ppm for 30-days, and 0.3 ppm for 180-days. Data are not sufficient currently to establish a 1000-day SMAC value. SMACs for H 2 S will support development of handling protocols and proper containment for lunar sample collection.

hydrogen sulfide↗

NASA NTRS1997

Global Troposphere Experiment Project

For the Global Troposphere Experiment project Pacific Exploratory Measurements West B (PEM West B), we made determinations of sulfur dioxide (SO2) and dimethyl sulfide (DMS) using gas chromatography-mass spectrometry with isotopically labelled internal standards. This technique provides measurements with precision of 1 part-per-trillion by volume below 20 pptv and 1% above 20 pptv. Measurement of DMS and SO2 were performed with a time cycle of 5-6 minutes with intermittent zero checks. The detection limits were about 1 pptv for SO2 and 2 pptv for DMS. Over 700 measurements of each compound were made in flight. Volcanic impacts on the upper troposphere were again found as a result of deep convection in the tropics. Extensive emission of SO2 from the Pacific Rim land masses were primarily observed in the lower well-mixed part of the boundary layer but also in the upper part of the boundary layer. Analyses of the SO2 data with aerosol sulfate, beryllium-7, and lead-210 indicated that SO2, contributed to half or more of the observed total oxidized sulfur (SO2 plus aerosol sulfate) in free tropospheric air. Cloud processing and rain appeared to be responsible for lower SO2 levels between 3 and 8.5 km than above or below this region. During both phases of PEM-West, dimethyl sulfide did not appear to be a major source of sulfur dioxide in the upper free troposphere over the western Pacific Ocean. In 1991 the sources Of SO2 at high altitude appeared to be both anthropogenic and volcanic with an estimated 1% being solely from DMS. The primary difference for the increase in the DMS source was the very low concentration of SO2 at high altitude. In the midlatitude region near the Asian land masses, DMS in the mixed layer was lower than in the tropical region of the western Pacific. Convective cloud systems near volcanoes in the tropical convergence in the western Pacific troposphere were a major source of SO2 at high altitudes during PEM-West B. High levels of SO2 were observed in several instances with large number concentrations of ultrafine CN above 9 km in the tropical convergence zone. Conversion of SO2, by OH to SO3 and subsequently to sulfuric acid may have been enhanced by lightning-produced NO levels exceeding 1 part per billion. Coupling of strong convection and volcanic sources of SO2 apparently is an important source of new particle formation at high altitude in the tropical convergence zone.

Bandy, Alan R.↗

NASA NTRS2002

Uses of Computed Tomography in the NASA Materials Science Program

Computed Tomography (CT) has proved to be of inestimable use in providing a rapid evaluation of a variety of samples from Mechanics of Granular Materials (MGM) to electronic materials (Ge-Si alloys) to space grown materials such as meteorites. The system at Kennedy Space Center (KSC), because of its convenient geographical location, is ideal for examining samples immediately after returning to Earth. It also has the advantage of the choice of fluxes, and in particular the use of a radioactive cobalt source, which is basically monochromatic. This permits a reasonable measurement of density to be made from which chemical composition can be determined. Due to the current dearth of long duration space grown materials, the CT instrument has been used to characterize materials in preparation for flight, to determine thermal expansion values, and to examine long duration space grown materials, i.e. meteorites. The work will first describe the establishment of the protocol for obtaining the optimum density readings for any material. This will include both the effects of the hardware or instrumental parameters that can be controlled, and the techniques used to process the CT data. Examples will be given of the compositional variation along single crystals of germanium-silicon alloys. Density variation with temperature has been measured in preparation for future materials science experiments; this involved the fabrication and installation of a single zone furnace incorporating a heat pipe to ensure of high temperature uniformity. At the time of writing the thermal expansion of lead has been measured from room temperature to 900 C. Three methods are available. Digital radiography enable length changes to be determined. Prior to melting the sample is small than the container and the diameter change can be measured. Most critical, however, is the density change in solid, through the melting region, and in the liquid state. These data are needed for engineering purposes to aid in the design of containment cartridges, and for enabling fluid flow calculations. A second sample, with the lead alloyed with antimony is ready for scanning. This corresponds to the planned composition of Dr. Poirier's flight experiment. Finally, three-dimensional results will be shown of the structure of a two-phase metallic meteorite of metal and sulfide, in which the iron-nickel phase has coarsened during slow cooling over hundreds of millions of years.

Engel, H. Peter↗

NASA NTRS2006

Sulfates on Mars: Indicators of Aqueous Processes

Recent analyses by MER instruments at Meridiani Planum and Gusev crater and the OMEGA instrument on Mars Express have provided detailed information about the presence of sulfates on Mars [1,2,3]. We are evaluating these recent data in an integrated multi-disciplinary study of visible-near-infrared, mid-IR and Mossbauer spectra of several sulfate minerals and sulfate-rich analog sites. Our analyses suggest that hydrated iron sulfates may account for features observed in Mossbauer and mid-IR spectra of Martian soils [4]. The sulfate minerals kieserite, gypsum and other hydrated sulfates have been identified in OMEGA spectra in the layered terrains in Valles Marineris and Terra Meridiani [2]. These recent discoveries emphasize the importance of studying sulfate minerals as tracers of aqueous processes. The sulfate-rich rock outcrops observed in Meridiani Planum may have formed in an acidic environment similar to acid rock drainage environments on Earth [5]. Because microorganisms typically are involved in the oxidation of sulfides to sulfates in terrestrial sites, sulfate-rich rock outcrops on Mars may be a good location to search for evidence of past life on that planet. Whether or not life evolved on Mars, following the trail of sulfate minerals will lead to a better understanding of aqueous processes and chemical weathering.

Bishop, Janice L.↗

NASA NTRS2015

Petrology and Cosmochemistry of a Suite of R Chondrites

Chondrites are among the most primitive surviving materials from the early solar system. They are divided into groups based on chemical types defined by mineralogy, bulk composition, and oxygen isotope compositions. Chondrites range in petrographic grade from type 1 to type 7. Type 3 chondrites are the most primitive and are little changed from the nebular solids accreted to form asteroids. They are composed of chondrules, fine-grained matrix, metal and sulfide, plus or minus Ca-Al-rich inclusions. With increasing aqueous alteration at low temperatures, members of some chondrite classes transformed from type 3 towards type 1. With increasing thermal metamorphism and low fluid content, members of other classes changed from type 3 towards type 7. Rumuruti (R) chondrites are a rare group (0.1% of falls) similar to ordinary chondrites in some properties but different in others. They are characterized by low chondrule/matrix modal abundance ratios, high oxidation state, small mean chondrule size, abundant sulfides and low metal contents. R chondrites vary in petrologic type from 3 to 6. They are important objects to study because some of them have undergone metamorphism at high temperatures in the presence of aqueous fluids. In contrast, CM and CI chondrites were heated to low temperatures in the presence of aqueous fluids leading to alteration; they contain low-T hydrous phases (phyllosilicates) and little or no remaining metal. Ordinary chondrites were heated to high temperatures in a low-fluid environment resulting in anhydrous metamorphic rocks. R6 chondrites are highly metamorphosed and some contain the high-T hydrous phases mica and amphibole. R chondrites are thus unique and give us an opportunity to examine whether there are compositional effects caused by high-T, highfluid metamorphism of nebular materials.

Torrano, Z. A.↗

NASA NTRS1983

Low temperature hot corrosion

The reaction of Co-Cr, Ni-Cr, Co-Cr-Al, and Ni-Cr-Al alloys with Na2SO4 in the presence of SO3 at temperatures between 700 and 750 C leads to the formation of liquid CoSO4-Na2SO4 or NiSO4-Na2SO4 deposits on the alloy surface. The formation of Cr2O3 and/or Al2O3 below this deposit results in a locally low P(O2) and a higher P(S2) and P(SO2). It is noted that these conditions can prevent protective oxide formation either by sulfide formation in the alloy, which localizes the Cr and/or Al in discrete particles, or by acid fluxing involving a reaction between Al2O3 or Cr2O3 and SO2 to form a salt-soluble species and subsequent reprecipitation as porous oxides in regions of higher P(O2). These processes may occur simultaneously, although a given alloy generally exhibits features of predominantly one type. Here, the Ni-Cr and Ni-Cr-Al alloys, and to some extent the Co-Cr alloys, exhibit features indicative of the sulfidation mechanism, whereas the morphology for the Co-Cr-Al alloy is more consistent with a predominant acid fluxing mechanism.

Chiang, K. T.↗

NASA NTRS2006

Non-nebular Origin of Dark Mantles Around Chondrules and Inclusions in CM Chondrites

Our examination of nine CM chondrites that span the aqueous alteration sequence leads us to conclude that compact dark fine mantles surrounding chondrules and inclusions in CM chondrites are not discrete fine-grained rims acquired in the solar nebula as modeled by Metzler et al. [Accretionary dust mantles in CM chondrites: evidence for solar nebula processes. Geochim. Cosmochim. Acta 56, 1992, 2873-28971. Nebular processes that lead to agglomeration produce materials with porosities far higher than those in the dark mantles. We infer that the mantles were produced from porous nebular materials on the CM parent asteroid by impact-compaction (a process that produces the lowest porosity adjacent to chondrules and inclusions). Compaction was followed by aqueous alteration that formed tochilinite, serpentine, Ni-bearing sulfide, and other secondary products in voids in the interchondrule regions. Metzler et al. reported a correlation between mantle thickness and the radius of the enclosed object. In Yamato 791 198 we find no correlation when all sizes of central objects and dark lumps are included but a significant correlation (r(sup 2) = 0.44) if we limit consideration to central objects with radii >35 microns; a moderate correlation is also found in QUE 97990. We suggest that impact-induced shear of a plum-pudding-like precursor produced the observed "mantles"; these were shielded from comminution during impact events by the adjacent stronger chondrules and inclusions. Some mantles in CM chondrites with low degrees of alteration show distinct layers that may largely reflect differences in porosity. Typically, a gray, uniform inner layer is surrounded by an outer layer consisting of darker silicates with BSE-bright speckles. The CM-chondrite objects characterized as "primary accretionary rocks" by Metzler et al. did not form in the nebula, but rather on the parent body. The absence of solar-flare particle tracks and solar-wind-implanted rare gases in these clasts reflect their lithified nature and low surface/volume ratios during the period when they resided in the regolith and were subject to irradiation by solar particles. The clasts are analogous to the light-colored metamorphosed clasts in ordinary-chondrite regolith breccias (which also lack solar-flare particle tracks and solar-wind gas).

Trigo-Rodriquez, Josep M.↗

NASA NTRS2000

Analysis of Siderite Thermal Decomposition by Differential Scanning Calorimetry

Characterization of carbonate devolitilization has important implications for atmospheric interactions and climatic effects related to large meteorite impacts in platform sediments. On a smaller scale, meteorites contain carbonates which have witnessed shock metamorphic events and may record pressure/temperature histories of impact(s). ALH84001 meteorite contains zoned Ca-Mg-Fe-carbonates which formed on Mars. Magnetite crystals are found in the rims and cores of these carbonates and some are associated with void spaces leading to the suggestion by Brearley et al. that the crystals were produced by thermal decomposition of the carbonate at high temperature, possibly by incipient shock melting or devolitilization. Golden et al. recently synthesized spherical Mg-Fe-Ca-carbonates from solution under mild hydrothermal conditions that have similar carbonate compositional zoning to those of ALH84001. They have shown experimental evidence that the carbonate-sulfide-magnetite assemblage in ALH84001 can result from a multistep inorganic process involving heating possibly due to shock events. Experimental shock studies on calcium carbonate prove its stability to approx. 60 GPa, well in excess of the approx. 45 GPa peak pressures indicated by other shock features in ALH84001. In addition, Raman spectroscopy of carbonate globules in ALH84001 indicates no presence of CaO and MgO. Such oxide phases should be found associated with the magnetites in voids if these magnetites are high temperature shock products, the voids resulting from devolitilization of CO2 from calcium or magnesium carbonate. However, if the starting material was siderite (FeCO3), thermal breakdown of the ALH84001 carbonate at 470 C would produce iron oxide + CO2. As no documentation of shock effects in siderite exists, we have begun shock experiments to determine whether or not magnetite is produced by the decomposition of siderite within the < 45GPa pressure window and by the resultant thermal pulse to approx. 600 C experienced by ALH84001. Here, we report thermal and compositional characterization of unshocked siderite and its transition to magnetite. Additional information is contained in the original extended abstract.

Bell, M. S.↗