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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Atomic Layer Deposition for Enhanced Reactivity, Stability, and Sulfur Tolerance of Hydrogenation Catalysts

NREL is located in the beautiful scenic Colorado, but it has a dirty secret. It is among one the top 10 worst U.S. cities for hazardous air pollution, particularly in Denver. The Denver metro area has been out of compliance with EPA's limits on ozone pollution for decades and it's gotten so bad that at the end of last year the EPA moved our designation from moderate non-obtainment to serious non-obtainment. There's a lot of work that needs to be done in Denver and around the world to reduce air pollution in urban areas.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
NASA NTRS2013

Olivine Weathering aud Sulfate Formation Under Cryogenic Conditions

High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide‐spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playa‐like evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo‐concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0degC in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Mars‐like conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above ‐40degC. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial sulfur‐rich volcanism, and sulfur‐rich surface deposits also makes it very likely that sulfate aerosols have also been an important component of the martian atmosphere. Thus mixtures of ice, dust, and sulfate aerosols are likely to have been common on the martian surface. Given the fact that it is not difficult to achieve surface temperatures above ‐40degC on Mars throughout its history, it seems likely that sulfate formation on Mars is controlled by the availability of sulfate aerosols and not by the martian climate. The current polar regions of Mars and Earth provide interesting analogs. Large regions of sulfaterich material have been detected on and around the modern north polar region of Mars. The prevalence of ice‐dust mixtures in this region and the existence of sulfates within the ice cap itself are strong evidence for the origin of the sulfates from inside the ice deposits. In addition sulfates have been found in ice deposits in Greenland and Mount Fuji on Earth that have been attributed to forming within the ice deposit. These sulfates can form either through interaction with dust particles in the atmosphere or through weathering inside the ice itself.

Niles, Paul B.↗
NASA NTRS1985

Ecophysiology of phototrophic sulfur bacteria in lakes: Vertical distribution of planktonic populations

The study of purple and green sulfur bacterial populations in nature is of interest for the following reasons: (1) high quantities of biomass, with low species diversity can be collected; (2) study of planktonic life permits one to understand the mechanisms, structural as well as physiological, used to maintain their vertical position without sinking; and (3) they are capable of sulfur oxidations and reductions that act as important intermediates in the global sulfur cycle. Purple and green photosynthetic bacteria, moreover, may be responsible for certain geological deposits. Planktonic phototrophic sulfur bacteria were analyzed in relation to their vertical distribution in the water column. Factors, including competition for light, that determine their sedimentation rates and the numerical changes in species and populations were assessed.

Guerrero, R.↗
NASA NTRS1979

Formation and deposition of volcanic sulfate aerosols on Mars

The paper considers the formation and deposition of volcanic sulfate aerosols on Mars. The rate limiting step in sulfate aerosol formation on Mars is the gas phase oxidation of SO2 by chemical reactions with O, OH, and HO2; submicron aerosol particles would circuit Mars and then be removed from the atmosphere by gravitational forces, globally dispersed, and deposited over a range of equatorial and mid-latitudes. Volcanic sulfate aerosols on Mars consist of liquid droplets and slurries containing sulfuric acid; aerosol deposition on a global or hemispheric scale could account for the similar concentrations of sulfur within surficial soils at the two Viking lander sites.

Settle, M.↗
NASA NTRS1974

Io - A surface evaporite deposit

A model is suggested for Io's surface composition involving evaporite salt deposits, rich in sodium and sulfur. According to this model, these deposits were produced as a result of the migration of salt-saturated aqueous solutions to Io's surface from a warm or hot interior followed by loss of the water to space. This model satisfies cosmochemical constraints based on Io's initial composition, current density, and thermal history. Salt-rich assemblages are easily derivable from the leaching of carbonaceous chondritic material. The chemical and optical properties of such deposits, after modification by irradiation, can be used to explain Io's overall albedo and spectral reflectance, its dark reddish poles, and the observed sodium emission as well as or better than other currently suggested materials.

Fanale, F. P.↗
NASA NTRS1985

Planetary ecology; Proceedings of the Sixth International Symposium on Environmental Biogeochemistry, Santa Fe, NM, October 10-14, 1983

Topics presented include biological evolution and planetary chemistry; C-1 compounds; transport, deposition, and weathering; sulfur transformations; ground water; transformation processes for nitrogen oxides; and soils. Papers are presented on immunological studies on the organic matrix of recent and fossil invertebrate shells; biogenic gases in sediments deposited since Miocene times on the Walvis Ridge, South Atlantic Ocean; aspects of the biogeochemistry of Big Soda Lake, NV; mesophilic manganese-oxidizing bacteria from hydrothermal discharge areas at 21 deg North on the East Pacific Rise; and autotrophic growth and iron oxidation and inhibition kinetics of Leptospirillum ferrooxidans. Consideration is also given to thermophilic archaebacteria occurring in submarine hydrothermal areas; fate of sulfate in a soft-water, acidic lake; geochemical conditions in the ground water environment; microbial transformations as sources and sinks for nitrogen oxides; and the biogeochemistry of soil phosphorus.

Caldwell, D. E.↗
DOE OSTI2025

Microbial ecology of acidic, biogenic gypsum: community structure and distribution of extremophiles on freshly formed and relict sulfate deposits in a hydrogen sulfide-rich cave

Sulfate minerals are abundant on the Martian surface, and many of these evaporite deposits are thought to have precipitated from acidic fluids. On Earth, gypsum (CaSO 4 •2H 2 O) and other sulfates sometimes form under acidic conditions, so exploring the extremophilic life that occurs in these mineral environments can help evaluate the astrobiological potential of acid sulfate depositional settings. Here, we characterized the microbial communities associated with acidic gypsum deposits in a sulfuric acid cave, where sulfate precipitation is driven by sulfide-oxidizing bacteria and archaea. We used 16S rRNA gene sequencing and cell counts to characterize gypsum-associated microorganisms in freshly formed and relict deposits throughout the cave, to test how microbial community composition and abundance would vary with distance from the sulfidic water table and with the concentration of H 2 S(g) and other gases in the cave atmosphere. We found that actively forming gypsum in the lower cave levels was colonized by low-diversity communities that have few cells compared to other environments in the cave. The most abundant taxa were Acidithiobacillus, Metallibacterium, Mycobacteria, and three different Thermoplasmatales-group archaea, which occupied distinct niches based on proximity to sulfidic streams and the concentration of gases in the cave air. By contrast, deposits in older cave levels had more diverse communities that were distinct from those associated with freshly formed gypsum and likely represent a community reliant on different energy resources. These findings show that acidic sulfate deposits serve as habitats for extremophilic microorganisms and broaden our knowledge of the life associated with terrestrial sulfates.

58 GEOSCIENCES↗
NASA NTRS2014

Sulfur-Bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from approx.450 to 800 C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2(approx. 3-22 micro-mol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (approx.41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (approx.1-5 nmol) and CS2(approx.0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

evolved gas analysis↗
NASA NTRS2014

Sulfur-bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from ~450 to 800degC during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2 (~3-22 μmol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (~41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (~1-5nmol) and CS2 (~0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

Gale Crater↗
DOE OSTI2021

Exploring the Potential of Using Carbonyl Sulfide to Track the Urban Biosphere Signal

Abstract Cities are implementing additional urban green as a means to capture CO 2 and become more carbon neutral. However, cities are complex systems where anthropogenic and natural components of the CO 2 budget interact with each other, and the ability to measure the efficacy of such measures is still not properly addressed. There is still a high degree of uncertainty in determining the contribution of the vegetation signal, which furthermore confounds the use of CO 2 mole fraction measurements for inferring anthropogenic emissions of CO 2 . Carbonyl sulfide (OCS) is a tracer of photosynthesis which can aid in constraining the biosphere signal. This study explores the potential of using OCS to track the urban biosphere signal. We used the Sulfur Transport and dEposition Model (STEM) to simulate the OCS concentrations and the Carnegie Ames Stanford Approach ecosystem model to simulate global CO 2 fluxes over the Bay Area of San Francisco during March 2015. Two observation towers provided measurements of OCS and CO 2 : The Sutro tower in San Francisco (upwind from the area of study providing background observations), and a tower located at Sandia National Laboratories in Livermore (downwind of the highly urbanized San Francisco region). Our results show that the STEM model works better under stable marine influence, and that the boundary layer height and entrainment are driving the diurnal changes in OCS and CO 2 at the downwind Sandia site. However, the STEM model needs to better represent the transport and boundary layer variability, and improved estimates of gross primary productivity for characterizing the urban biosphere signal are needed.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1992

Black Carbon (Soot) Aerosol in the Lower Stratosphere and Upper Troposphere

We have used two approaches to measure BCA in the stratosphere. The first method consists of collecting aerosols by impaction on quartz rods, upon which are mounted strips of polystyrene filter material. Each 25 mm by 0.5 mm filter strip is alternately masked and exposed in 5 mm long sections. After sampling, the optical density of the exposed sections is measured and compared with the optical density of the masked (unexposed) sections. The filter strip is a Lambertian collector, the scattering property of which is not affected by the deposition of liquid sulfuric acid droplets which dominate the stratospheric aerosol. Hence, all attenuation greater in the exposed than in the non-exposed sections is due to absorption by BCA or rare opaque materials such as meteoritic iron. In a second approach we expose carbon-coated gold or palladium wires to air outside the aircraft boundary layer [Farlow et al., 1979; Pueschel et al., 1989]. With a field emission scanning electron microscope we are able to characterize BCA particles in addition to the dominant sulfuric acid droplets. Typically, soot is comprised of 20 nm diameter spheres linked together as branching chains or loosely packed aggregates (Figure 1a). The microscope has a lateral image resolution of 1.5 nm and can clearly resolve individual spheres making up BCA aggregates. Their morphology is uniquely different from that of the liquid sulfuric acid-water aerosol (Figure 1b). We approximate the size of each BCA particle by that of a sphere of equivalent volume and fit a lognormal size distribution to both the BCA and H2SO4/H2O aerosols. Both sampler types have been mounted on NASA's ER-2 high-altitude research aircraft (altitude ceiling of 70,000 feet), and on NASA's DC-8 (40,000 feet ceiling) aircraft to sample aerosols from a significant portion of the atmosphere.

Pueschel, R. F.↗
DOE OSTI2024

Tailoring-Orientated Deposition of Li 2 S for Extreme Fast-Charging Lithium–Sulfur Batteries

Precipitation/dissolution of insulating Li 2 S has long been recognized as the rate-determining step in lithium-sulfur (Li-S) batteries, which dramatically undermines sulfur utilization at elevated charging rates. Herein, we present an orientated Li 2 S deposition strategy to achieve extreme fast charging (XFC, ≤15 min) through synergistic control of porosity, electronic conductivity, and anchoring sites of electrode substrate. Via magnesiothermic reduction of a zeolitic imidazolate framework, a nitrogen-doped and hierarchical porous carbon with highly graphitic phase was developed. This design effectively reduces interfacial resistance and ensures efficient sequestration of polysulfides during deposition, leading to (110)-preferred growth of Li 2 S nanocrystalline between (002)-dominated graphitic layers. Our approach directs an alternative Li 2 S deposition pathway to the commonly reported lateral growth and 3D thickening growth mode, ameliorating the electrode passivation. Therefore, a Li-S cell capable of charging/discharging at 5C (12 min) while maintaining excellent cycling stability (82% capacity retention) for 1000 cycles is demonstrated. In conclusion, even under high S loading (8.3 mg cm -2 ) and low electrolyte/sulfur ratio (3.8 mL mg -1 ), the sulfur cathode still delivers a high areal capacity of >7 mAh cm -2 for 80 cycles.

25 ENERGY STORAGE↗
NASA NTRS1981

The effects of organosulfur compounds upon the storage stability of Jet A fuel

This study examined the effect of sulfur-containing compounds on the storage stability of Jet A turbine fuel. It was found that alkyl sulfides and disulfides increased the fuel's stability while all thiols and thiophene derivatives tested decreased fuel stability (increased deposit formation) at temperatures and sulfur concentrations selected. Linear Arrhenius plots of sulfur-spiked fuel samples demonstrated that deposit formation decreased with increased slope for all alkyl sulfides, alkyl disulfides, thiols, and thiophene derivatives. A plot of insoluble deposit vs. concentration of added alkyl sulfide produces a negative slope. It appears that the inhibiting mechanism for alkyl sulfides is a result of the compound's reactivity with intermediate soluble precursors to deposit in the fuel. A method of approximating the relative basicity of weak organosulfur bases was developed via measurement of their resonance chemical shifts in proton NMR. Linear plots of log gm. deposit vs. change in chemical shift (shift differences between sulfur bases neat and complexed with I2) were found for alkyl sulfides and alkyl thiols. This suggests the possibility that increased deposit formation is due to base catalysis with these compound classes.

Heneman, F. C.↗
DOE OSTI2022

Early diagenetic processes in an iron-dominated marine depositional system

The early diagenetic interplay between reactive iron, sulfur, and organic matter in the bathymetrically isolated Santa Monica Basin (SMB) sediments are investigated in this study. Here, we explore solid-phase and porewater profiles from the basin, supplemented with a transect from 71 to 907 m water depth that includes oxygenated (>60 μM O 2 ) bottom waters near the coast and oxygen-deficient waters (~4 µM O 2 ) in the basin. The geochemical data of the basin sediments are further scrutinized by means of reactive transport modeling. The results show that the basin sediments do not follow the traditional geochemical signatures of oxygen-deficient settings. A lack of dissolved sulfide accumulation and sulfurized iron persists despite the sediments being deposited under reducing conditions (without bioturbation/bioirrigation), strong organic carbon input (TOC up to 5.0 wt%), and active dissimilatory sulfate reduction. Not only did we find an exceptional enrichment in highly reactive Fe in the surface sediments (~45 % of total Fe), but the enrichment of reactive Fe, including ferrihydrite, persists downcore and coexists with high levels of dissolved Fe. The enhanced preservation of Fe oxides and lack of iron-sulfide precipitation is in part explained by detection via Mössbauer spectra of iron oxides bounded to organic matter (Fe[III]-OM coprecipitates). The modeled Fe budget shows that most of the Fe oxides in the surface sediments are internally recycled by upward diffusion and subsequent oxidation of Fe 2+ . Sulfide oxidation coupled to Fe reduction effectively precludes sulfide accumulation while enhancing build-up of dissolved Fe, fueling the Fe cycle within the first 5 cm depth. Continuous reoxidation of Fe 2+ enhances the formation of Fe(III)-OM coprecipitates, limiting the amount of reactive organic matter. In the unavailability of labile organic matter, other than within the uppermost layers, the organic-rich sediment profiles are dominated by Fe cycling that limits the production and preservation of sulfides and enhances the preservation of Fe oxides and organic carbon. Finally, this study highlights key local controls on Fe availability in marginal basins and describes an intricate biogeochemical C-Fe-S cycling in modern and possibly ancient marine systems with important implications for Fe availability in the marine realm.

58 GEOSCIENCES↗
NASA NTRS2000

Segregation Behavior of Sulfur and Other Impurities Onto the Free Surfaces of ED-Ni Deposits

Most researchers attribute grain boundary embrittlement in electro-deposited Nickel (ED-Ni) to the presence of small quantities of Sulfur as an impurity. It occurs in a highly mobile form that segregates to the grain boundaries. Evaluation of Sulfur segregation requires that a sample be fractured through the grain boundaries. However, this action may not always be possible. ED-Ni is inherently tough at ambient temperature, especially if a low level of Sulfur was intentionally maintained. A new method was developed to study Sulfur and other migrant species to the grain boundaries, which also migrate to free surfaces. A test specimen is heated by a quartz lamp within the sample preparation chamber, allowing the mobile species to migrate to polished free surfaces. There the mobile species are analyzed using X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA).

Panda, Binayak↗
NASA NTRS2001

Segregation Behavior of Sulfur and Other Impurities onto the Free Surfaces of ED-NI Deposits

Most researchers attribute grain boundary embrittlement in electro-deposited nickel (ED-Ni) to the presence of small quantities of sulfur as an impurity. It occurs in a highly mobile form that segregates to the grain boundaries. Evaluation of sulfur segregation requires that a sample be fractured through the grain boundaries. However, this action may not always be possible. ED-Ni is inherently tough at ambient temperature, especially if a low level of sulfur was intentionally maintained. A new method was developed to study sulfur and other migrant species to the grain boundaries, which also migrate to free surfaces. A test specimen is heated by a quartz lamp within the sample preparation chamber, allowing the mobile species to migrate to polished free surfaces. There the mobile species are analyzed using X-ray photoelectron spectroscopy (XPS) also known as Electron Spectroscopy for Chemical Analysis (ESCA).

Panda, B.↗
DOE OSTI2022

Stable all-solid-state sodium-sulfur batteries for low-temperature operation enabled by sodium alloy anode and confined sulfur cathode

All-solid-state sodium-sulfur (Na-S) batteries are promising for stationary energy storage devices because of their low operating temperatures (less than 100 °C), improved safety, and low-cost fabrication. Using Na alloy instead of Na metal as an anode in Na-S batteries can prevent dendrite growth and improve interfacial stability between the anode and solid electrolytes to achieve long-cycling stability. A high-sulfur content cathode possessing high sulfur utilization is also important to enable an energy-dense Na-S battery. In this work, we studied Na-Sb and Na- Sn alloy anodes and demonstrated the superiority of Na 3 Sb alloy undergoing a stable Na alloying/dealloying process at 0.04 mA cm -2 for over 500 hours. Combining the optimized Na3Sb alloy anode with sulfur-carbon composites prepared by the vapor deposition approach, the full cell shows a high sulfur specific capacity and improved rate performance. Moreover, the all-solid-state Na alloy-S battery can deliver a high initial discharge specific capacity of 1377 mAh g -1 and maintain good capacity retention of 70 % after 180 cycles at 60 °C. Further, post-cycle characterizations show that both the anode and cathode perform a reversible discharge/charge process after the 1st cycle, and the cathode undergoes significantly rearranged distributions of carbon and solid-state electrolytes after 180 cycles due to severe volume change induced by repeated sodiation/desodiation process.

25 ENERGY STORAGE↗
NASA NTRS2013

Historical and Future Black Carbon Deposition on the Three Ice Caps: Ice Core Measurements and Model Simulations from 1850 to 2100

Ice core measurements in conjunction with climate model simulations are of tremendous value when examining anthropogenic and natural aerosol loads and their role in past and future climates. Refractory black carbon (BC) records from the Arctic, the Antarctic, and the Himalayas are analyzed using three transient climate simulations performed with the Goddard Institute for Space Studies ModelE. Simulations differ in aerosol schemes (bulk aerosols vs. aerosol microphysics) and ocean couplings (fully coupled vs. prescribed ocean). Regional analyses for past (1850-2005) and future (2005-2100) carbonaceous aerosol simulations focus on the Antarctic, Greenland, and the Himalayas. Measurements from locations in the Antarctic show clean conditions with no detectable trend over the past 150 years. Historical atmospheric deposition of BC and sulfur in Greenland shows strong trends and is primarily influenced by emissions from early twentieth century agricultural and domestic practices. Models fail to reproduce observations of a sharp eightfold BC increase in Greenland at the beginning of the twentieth century that could be due to the only threefold increase in the North American emission inventory. BC deposition in Greenland is about 10 times greater than in Antarctica and 10 times less than in Tibet. The Himalayas show the most complicated transport patterns, due to the complex terrain and dynamical regimes of this region. Projections of future climate based on the four CMIP5 Representative Concentration Pathways indicate further dramatic advances of pollution to the Tibetan Plateau along with decreasing BC deposition fluxes in Greenland and the Antarctic.

Antarctic Regions↗