Mitochondrial hydrogen sulfide supplementation improves health in the C. elegans Duchenne muscular dystrophy model
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Rebecca A. Ellwood↗
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Results for “hydrogen sulfide”
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Binding of the atomic cations hydrogen through argon to water and hydrogen sulfide
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Brent R. Westbrook↗
Ammonia - Did it have a role in chemical evolution
The significance of ammonia in the chemical evolution related to the origin of life is evaluated. A computer program was employed to calculate the time needed for the decomposition of ammonia by means of a photochemical reaction. Various possible protection mechanisms for ammonia are discussed, giving attention to hydrogen sulfide, hydrogen, ozone, and CO. It is concluded that in the absence of a sufficiently high pressure of hydrogen, any ammonia present in the primitive atmosphere would have been decomposed by photolysis in a million years.
Ferris, J. P.↗
An intercomparison of aircraft instrumentation for tropospheric measurements of sulfur dioxide
As part of the NASA Tropospheric Chemistry Program, a series of field intercomparisons have been conducted to evaluate the state-of-the art for measuring key tropospheric species. One of the objectives of the third intercomparison campaign in this series, Chemical Instrumentation Test and Evaluation 3 (CITE 3), was to evaluate instrumentation for making reliable tropospheric aircraft measurements of sulfur dioxide, dimethyl sulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide. This paper reports the results of the intercomparisons of five sulfur dioxide measurement methods ranging from filter techniques, in which samples collected in flight are returned to the laboratory for analyses (chemiluminescent or ion chromatographic), to near real-time, in-flight measurements via gas chromatographic, mass spectrometric, and chemiluminescent techniques. All techniques showed some tendency to track sizeable changes in ambient SO2 such as those associated with altitude changes. For SO2 mixing ratios in the range of 200 pptv to a few ppbv, agreement among the techniques varies from about 30% to several orders of magnitude, depending upon the pair of measurements intercompared. For SO2 mixing ratios less than 200 pptv, measurements from the techniques are uncorrelated. In general, observed differences in the measurement of standards do not account for the flight results. The CITE 3 results do not unambiguously identify one or more of the measurement techniques as providing valid or invalid SO2 measurements, but identify the range of 'potential' uncertainty in SO2 measurements reported by currently available instrumentation and as measured under realistic aircraft environments.
Gregory, Gerald L.↗
Prebiotic synthesis of 5-substituted uracils: a bridge between the RNA world and the DNA-protein world
Under prebiotic conditions, formaldehyde adds to uracil at the C-5 position to produce 5-hydroxymethyluracil with favorable rates and equilibria. Hydroxymethyluracil adds a variety of nucleophiles, such as ammonia, glycine, guanidine, hydrogen sulfide, hydrogen cyanide, imidazole, indole, and phenol, to give 5-substituted uracils with the side chains of most of the 20 amino acids in proteins. These reactions are sufficiently robust that, if uracil had been present on the primitive Earth, then these substituted uracils would also have been present. The ribozymes of the RNA world would have included many of the functional groups found in proteins today, and their catalytic activities may have been considerably greater than presently assumed.
NASA Program NSCORT↗
Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 Using FeS/H2S As a Reducing Agent
An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purities, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role In the origin of metabolism or the origin of life.
Keefe, Anthony D.↗
Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 using FeS/H2S as a Reducing Agent
An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purines, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role in the origin of metabolism or the origin of life.
Keefe, Anthony D.↗
Chemiluminescent reactions of cs sub 2, cos, and h sub 2 s with atomic oxygen.
Chemiluminescent reactions of carbon disulfide, carbonyl sulfide and hydrogen sulfide with atomic oxygen
CHEMILUMINESCENCE↗
Evaluation of volcano-style field ionization source and field emitting cathodes for mass spectrometry and applications
A volcano-style field ionization source was tested with eight different gases: hydrogen, helium, ammonia, methane, argon, neon, water vapor, and hydrogen sulfide. For ammonia, hydrogen sulfide, and water, the ionization efficiency of the field ionization source was determined as a function of the electrical potential difference between the ionizer and its counterelectrode. The ionization efficiencies for the other gases were too low to be measured in the present apparatus. The operating characteristics of a field emission cathode, were studied, in the presence of the same eight gases at pressures up to 0.00001 torr. The presence of the gases caused little or no significant change in the electron emission from the cathodes. Results indicate that the field emission cathode has advantages over electrically heated cathodes as a source of an electron beam in spacecraft mass spectrometers.
Buttrill, S. E., Jr.↗
Qualitative Headspace GCMS Analysis of Lunar Regolith and Volatile Simulant Mixtures
Introduction: Future Artemis missions aim to return the volatile-bearing samples collected near lunar polar craters. We, as advanced curation scientists, are responsible for developing techniques and methodologies for preserving the integrity of returned samples and the science value those samples contain. The extent to which that preservation is possible, and the trade-offs preservation requires (e.g. monetary costs, sample volume limitations) all must be considered. Even less-than pristine volatile-bearing samples will be of tremendous value to the scientific community seeking to unravel the history of lunar surface volatiles and, more broadly, volatiles in the solar system. A sample collected on the lunar surface will experience at least five distinctive periods during which any changes here referred to as “alteration” will certainly occur at some scale: collection on the lunar surface; transportation back to Earth; long-term storage; curatorial processing; and allocation/distribution. The Planetary Exploration and Astromaterials Research Lab (PEARL) seeks to understand temperature and pressure effects on returned volatile samples by working with high-fidelity volatile-containing regolith simulants, setting the foundation for the future of cold curation. This abstract is focused on gas-surface interactions between LCROSS volatiles and readily available lunar regolith simulants. Experiments involved analyzing differences in headspace gas composition for various combinations of volatile and regolith simulants using gas chromatography/mass spectrometry (GC/MS). Experimental Procedure: The volatile simulants were chosen based on the molecules detected during the LCROSS mission.1 Stock solutions of condensed lunar volatile analytes were: methanol, 7 N ammonia in methanol, and 0.4% hydrogen sulfide in water. The regolith simulants used were primarily JSC-1A and NU-LHT-4M. Additional regolith simulant control studies were conducted with <150 μm sieved sand and KBr. A nested vial sample preparation approach separated the liquid stock solutions from the regolith, eliminating potential matrix effects between liquid and solid phases. Fifteen microliter aliquots of liquid volatile simulants were added to a 2 mL liquid GC vial and capped in atmosphere. An 18G needle punctured the 2 mL GC vial immediately before being transferred and sealed in a 20 mL GC vial containing 0-0.3 g of regolith simulant, see Figure 1. Separating the analytes ensures any changes observed in the total headspace gases is a result of gas-surface and/or gas-gas interactions. Equipment and Method: Initial GC/MS method development for the separation and identification of relevant headspace gases can be found in Amick, et al. 2023.2 The only hardware change is a different column: a TG-1701MS 30 m × 0.25 mm × 1.00 μm column. The vials were sampled at 10°C, room temperature (~25°C) and 50°C. Low temperature samples were kept in a chilled autosampler stage for at least 1 hour prior to sampling. High temperature samples were agitated at 50°C for 5 minutes immediately prior to injection onto the column. Headspace chromatograms were collected for each combination of temperature, regolith, and volatile simulant, including controls without one or both types of analytes, in triplicate. The chromatogram elution window for each analyte or significant atmospheric gas was identified using the peak mass spectrum cross-referenced with Figure 1.Picture of the nested vial set-up. a NIST MS library search. Each analyte peak was integrated after filtering the mass spectrum trace for the parent or most unique mass-to-charge ratio. For example, the mass-to-charge ratio used to identify, filter for, and integrate the carbon dioxide peak was centered around 44 m/z. Results: Figure 2 shows the integrated peak area for hydrogen sulfide in all combinations of regolith simulants, temperatures, and the addition of ammonia in methanol solution. Multiple repeat experiments with H2S and regolith simulants have confirmed hydrogen sulfide is removed from the headspace within 1 hour when exposed to JSC-1A, NU-LHT-4M and sand (not pictured). The consumption of H2S by lunar regolith simulants at different temperatures indicates surface chemistry will be an integral component in sample integrity and preservation. It is important to note that while the effect of surface chemistry on gaseous hydrogen sulfide is intriguing, further investigation into more chemically accurate regolith simulants is necessary and ongoing. The sulfur in hydrogen sulfide is in its most reduced state while off-the-shelf, terrestrially sourced JSC-1A and NU-LHT-4M are more oxidized than most lunar materials,3which likely leads to different oxidation-reduction reactions than would be expected in lunar regolith. Figure 3 shows the integrated peak area of carbon dioxide for each sample combination that contained ammonia in methanol solution. The addition of ammonia to the GC vials results in a consistent and reproducible decrease in carbon dioxide gas, even at 50°C. The effect became more pronounced when JSC-1A or NU-LHT-4M were present. This set of experiments demonstrated that the sample composition will affect the chemical and physical state of each component present. Future spectroscopic and microscopy experiments will be geared towards identifying the cause for the CO2(g) concentration decrease and the consumption of hydrogen sulfide. As cold and volatile curation scientists, this information provides necessary insight on how to appropriately handle and analyze volatile bearing returned samples, as well as predict the effect chemical composition has on the various sample phases we will analyze upon return to Earth. Unlike traditional curation of geologic materials, the molecules in a sample cannot be identified or processed using the naked eye or even an optical microscope. Volatile curation will require a combination of analytical techniques, including but not limited to highly sensitive gas and solid/condensed phase spectroscopy. This set of experiments has demonstrated the need for more detailed studies of volatile mixtures with mineralogically and geochemically analogous lunar regolith simulants to prepare for the curation of volatile-rich lunar samples from the south polar region of the Moon. References: [1] Colaprete, A., et al. (2010) Science, 330, (463-468). [2] Amick, C. L., et al.(2023) Houston, Texas, [3] Heiken, G. H., et al.(1991) (778-778)
Cecilia L Amick↗
Oxidation of CS2 and COS - sources for atmospheric SO2
The oxidation of COS and CS2 by reaction with hydroxyl radicals is investigated as a possible source of atmospheric SO2 in remote marine regions. Calculations of the vertical profiles of SO2 were performed based on a one-dimensional photochemical model of the formation and destruction of SO2 by various processes for observed O3, CO, CH4 and H2O profiles at 15 deg S. Variations in the rate of SO2 destruction, the chosen deposition velocity and the loss due to aerosols are shown to lead to similar SO2 profiles, which indicate higher mixing ratios at high altitude, while the oxidation of dimethyl sulfide or hydrogen sulfide can not account for the profiles observed. Possible diffuse sources of CS2 and COS are indicated, and it is concluded that the oxidation of COS and possibly CS2 may provide an explanation for the existence of a uniform background level of SO2.
Logan, J. A.↗
Photochemistry and clouds of Jupiter, Saturn and Uranus
Photochemistry of ammonia, methane, phosphine, hydrogen sulfide, methylamine, hydrogen cyanide and carbon monoxide in the atmospheres of Jupiter, Saturn and Uranus is discussed. Condensation of ammonia, ammonium hydrosulfide, water, methane, ethane and acetylene below and near the tropopause of these planets is formulated. Whenever necessary, new calculations are included. Candidates for the upper atmospheric hazes, and the reddish-brown chromosphore in the clouds of Jupiter and Saturn are discussed.
Atreya, S. K.↗
Hydrogen Embrittlement
Hydrogen embrittlement (HE) is a process resulting in a decrease in the fracture toughness or ductility of a metal due to the presence of atomic hydrogen. In addition to pure hydrogen gas as a direct source for the absorption of atomic hydrogen, the damaging effect can manifest itself from other hydrogen-containing gas species such as hydrogen sulfide (H2S), hydrogen chloride (HCl), and hydrogen bromide (HBr) environments. It has been known that H2S environment may result in a much more severe condition of embrittlement than pure hydrogen gas (H2) for certain types of alloys at similar conditions of stress and gas pressure. The reduction of fracture loads can occur at levels well below the yield strength of the material. Hydrogen embrittlement is usually manifest in terms of singular sharp cracks, in contrast to the extensive branching observed for stress corrosion cracking. The initial crack openings and the local deformation associated with crack propagation may be so small that they are difficult to detect except in special nondestructive examinations. Cracks due to HE can grow rapidly with little macroscopic evidence of mechanical deformation in materials that are normally quite ductile. This Technical Memorandum presents a comprehensive review of experimental data for the effects of gaseous Hydrogen Environment Embrittlement (HEE) for several types of metallic materials. Common material screening methods are used to rate the hydrogen degradation of mechanical properties that occur while the material is under an applied stress and exposed to gaseous hydrogen as compared to air or helium, under slow strain rates (SSR) testing. Due to the simplicity and accelerated nature of these tests, the results expressed in terms of HEE index are not intended to necessarily represent true hydrogen service environment for long-term exposure, but rather to provide a practical approach for material screening, which is a useful concept to qualitatively evaluate the severity of hydrogen embrittlement. The effects of hydrogen gas on mechanical properties such as tensile strength, ductility, fracture, low and high cycle fatigue, crack growth rate, and creep rupture are analyzed with respect to the general trends established from the HEE index values. It is observed that the severity of HE effects is also influenced by environmental factors such as pressure, temperature, and hydrogen gas purity. The severity of HE effects is also influenced by material factors such as surface finish, heat treatment, and product forms, compositions, grain direction, and crystal orientations.
Jonathan A. Lee↗
Membranes for gas separation
Membranes, methods of making the membranes, and methods of using the membranes are described herein. The membranes can comprise a support layer, and a selective polymer layer disposed on the support layer. The selective polymer layer can comprise a selective polymer matrix and carbon nanotubes dispersed within the selective polymer matrix. The carbon nanotubes can comprise multi-walled carbon nanotubes wrapped in a hydrophilic polymer, such as polyvinylpyrrolidone or a copolymer thereof, such as poly(1-vinylpyrrolidone-co-vinyl acetate). The membranes can exhibit selective permeability to gases. As such, the membranes can be for the selective removal of carbon dioxide and/or hydrogen sulfide from hydrogen and/or nitrogen.
Ho, W. S. Winston↗
Membranes for gas separation
Membranes, methods of making the membranes, and methods of using the membranes are described herein. The membranes can comprise a support layer, and a selective polymer layer disposed on the support layer. In some cases, the support layer can comprise a gas permeable polymer and hydrophilic additive dispersed within the gas permeable polymer. In some cases, the selective polymer layer can comprise a selective polymer matrix and carbon nanotubes dispersed within the selective polymer matrix. The membranes can exhibit selective permeability to gases. As such, the membranes can be for the selective removal of carbon dioxide and/or hydrogen sulfide from hydrogen and/or nitrogen.
Ho, W. S. Winston↗
Concentrations of carbonyl sulfide and hydrogen cyanide in the free upper troposphere and lower stratosphere deduced from ATMOS/Spacelab 3 infrared solar occultation spectra
This paper presents the results on the volume mixing ratio profiles of carbonyl sulfide and hydrogen cyanide, deduced from the spectroscopic analysis of IR solar absorption spectra obtained in the occultation mode with the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument during its mission aboard Spacelab 3. A comparison of the ATMOS measurements for both northern and southern latitudes with previous field investigations at low midlatitudes shows a relatively good agreement. Southern Hemisphere volume mixing ratio profiles for both molecules were obtained for the first time, as were the profiles for the Northern Hemisphere covering the upper troposphere and the lower stratosphere simultaneously.
Zander, R.↗
Simple thermal vapor deposition process for and characterization of n-type indium oxysulfide thin films
The search continues for alternative nontoxic n-type electron transport layers in optoelectronic thin-film devices. Indium oxysulfide, In 2 (O,S) 3 , represents one promising material for this application, especially when paired with chalcogenide absorber layers. The ternary nature of the composition allows for electrical conductivity and optical bandgap tuning by tailoring the sulfur to oxygen ratio in the oxysulfide alloy. However, thin films of In 2 (O,S) 3 are typically deposited only by chemical bath deposition or plasma-enhanced atomic layer deposition. Here we report deposition of thin films of In 2 (O,S) 3 in a custom-built thermal reactor using only water vapor and hydrogen sulfide as the coreactants. This advance is enabled by the use of a recently reported, highly reactive indium formamidinate precursor. As shown by x-ray photoelectron spectroscopy, the composition can be tuned from pure In 2 (O,S) 3 to pure In 2 S 3 by varying the ratio of cycles employing water or hydrogen sulfide. The oxygen to the sulfur ratio in the film can be controlled by altering the dose sequence, although films typically contain more sulfur than would be expected naively from the percentage of hydrogen sulfide doses in the deposition recipe. Rutherford backscattering spectrometry confirms the composition is sulfur-rich relative to the dosing ratio. Structural characterization indicates films are relatively amorphous in nature. Electrically, these films offer reasonably constant electron mobility at different O:S ratios, with an electron concentration tunable over 4 orders of magnitude. These oxysulfide films possess a higher indirect bandgap than their oxygen-free indium sulfide counterparts, indicating higher transmittance to blue light. These indium oxysulfide films may be suitable candidates for electron transport layers in thin-film solar cells where their wider bandgap might result in higher optical transparency and thus short circuit current density, while the tunability of their conduction band offset with an absorber layer may result in higher open circuit voltage.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Oxygen and sulfur interactions with a clean iron surface and the effect of rubbing contact on these interactions
An investigation was conducted to determine the nature of the chemical interactions of oxygen and sulfur with iron when surfaces are stationary and also during sliding in a vacuum environment. Various gases that contained sulfur, oxygen, or both were adsorbed to iron at 23 C. The gases included oxygen, hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Friction experiments were conducted with a hemispherical rider sliding on a rotating disk. An Auger cylindrical mirror analyzer was used to monitor the iron surface chemistry. The results of this study indicate that oxygen will completely displace sulfide films from iron surfaces. Organic thiols containing sulfur, such as methyl mercaptan, adsorb to an iron surface dissociatively. Only sulfur is detected on the iron surface. Sliding inhibits the formation of sulfide films on iron with the adsorption of hydrogen sulfide and methyl mercaptan. With oxygen and sulfur dioxide, the sliding process does not affect adsorption behavior.
Buckley, D. H.↗