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At least 451 records · Page 25

Photochemistry of the stratosphere of Venus - Implications for atmospheric evolution

The photochemistry of the Venus stratosphere is modeled using an updated and expanded chemical scheme along with the results of recent observations and laboratory studies. Three models, with H2 mixing ratio equal to 2 x 10 to the -5th, 5 x 10 to the -7th, and 1 x 10 to the -13th, respectively, are examined. All three models are found to satisfactorily account for the observations of CO, O2, O2(1Delta), and SO2 in the stratosphere, but only the last one may be able to account for the diurnal behavior of mesospheric CO and the UV albedo. Oxygen, derived from CO2 photolysis, is mainly consumed by CO2 recombination and oxidation of SO2 to H2SO4. The photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen and free chlorine radicals, essential for the catalytic oxidation of CO. Oxidation of SO2 by O occurs in the lower stratosphere. The modeling reveals a number of interesting similarities, previously unsuspected between the chemistry of the stratosphere of Venus and that of the earth; photochemistry may have played a major role in the evolution of the atmosphere.

Yung, Y. L.↗

In situ results on the variation of neutral atmospheric hydrogen at Venus

The concentrations of neutral hydrogen, n(H), in the Venus atmosphere were derived from an ion and neutral charge exchange relationship involving O(+), H(+), O, and CO2, which were measured by OIMS and ONMS on board the Pioneer Venus for the period 1979-1980 covering three diurnal cycles of Venus. There was a persisting dawn bulge in the diurnal distribution of n(H), which peaked at levels near 5 x 10 to the 7th/cu cm at altitudes below 165 km. Large day-to-day variations of up to a factor of 5 in n(H) were frequently encountered, in addition to some local time variations in the bulge location. Although the appreciable short-term variability in n(H) makes precise assessment of the interannual variations difficult, no distinct evidence for interannual variation in n(H) was found. These results were confirmed by the facts that no significant interannual differences in n(H3) measured directly by ONMS were detected, and that only small (not more than 10 percent, decline) variations in the solar EUV flux were found in the 1979-1980 period.

Taylor, H. A., Jr.↗

Stable isotopes of carbon dioxide (CO2), dissolved inorganic carbon (DIC), water and concentrations of greenhouse gases in a mountainous watershed (Crested Butte, Colorado)

Temperature and precipitation variability in response to climate change affects water cycling of watersheds and can potentially impact water quality, water availability, elemental and molecular fluxes, and biogeochemical processes. Here we report the measurements of light stable isotopes and greenhouse gases analysis to a large multidisciplinary project addressing watershed function. Water hydrogen (H) and oxygen (O) stable isotopes of snow and water saturated soil were measured to constrain source contributions to groundwater and streamflow. In an effort to better constrain existing nitrogen and carbon cycling models in high-altitude ecosystems, carbon dioxide (CO2), nitrous oxide (N2O), methane (CH4) greenhouse gases concentrations and stable isotope signatures of CO2, dissolved inorganic carbon (DIC), and water were measured. This dataset includes one CSV file and one Excel file containing data including stable isotopes of carbon dioxide (CO2), dissolved inorganic carbon (DIC), water and concentrations of greenhouse gases. The CSV and Excel files contain the same information/data but have included both versions for accessibility.

54 ENVIRONMENTAL SCIENCES↗

LaNi x Fe 1–x O 3 as flexible oxygen or carbon carriers for tunable syngas production and CO 2 utilization

The current study reports LaFe 1–x Ni x O 3–δ redox catalysts as flexible oxygen or carbon carriers for CO2 utilization and tunable production of syngas at relatively low temperatures (~700 °C), in the context of a hybrid redox process. Specifically, perovskite-structured LaFe 1–x Ni x O 3–δ with seven different compositions (x = 0.4–1) were prepared and investigated. Cyclic experiments under alternating methane and CO 2 flows indicated that all the samples exhibited favorable reactive performance: CH 4 and CO 2 conversions varied between 85% and 98% and 70–88%, respectively. While H 2 /CO ratio from Fe-rich redox catalysts was ~2.3:1 in the methane conversion step, Ni-rich catalysts produced a concentrated (~ 93.7 vol%) hydrogen stream via methane cracking. The flexibility of LaFe 1–x Ni x O 3–δ to produce syngas (or hydrogen) with tunable compositions was found to be governed by the iron/nickel (Fe/Ni) ratio. Redox catalysts with higher Fe contents act as a lattice oxygen carrier via chemical looping partial oxidation (CLPOx) of methane whereas those with higher Ni contents function as a carbon carrier via chemical looping methane cracking (CLMC) scheme. XRD analysis and temperature-programmed reactions revealed that both types of catalysts involve the formation of La 2 O 3 and Ni 0 /Ni-Fe phases under the methane environment. The ability to re-incorporate La 2 O 3 and Ni/Fe into a perovskite structure gives rise to oxygen-carrying capacity whereas stable Ni 0 or Ni/Fe phases would catalyze methane cracking without lattice oxygen exchange in the reaction cycles. Here, temperature programmed oxidation and Raman spectroscopy indicated the presence of graphitic and amorphous carbon species, which were effectively gasified by CO 2 to produce concentrated CO. Stability tests over LaFe 0.5 Ni 0.5 O 3 and LaNiO 3 revealed that the redox performance was stable over a span of 50 cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular-Level Overhaul of y-Aminopropyl Aminosilicone/Triethylene Glycol Post-Combustion CO2-Capture Solvents

Capturing carbon dioxide (CO2) from post-combustion gas streams is an energy-intensive process that is required prior to either converting or sequestering CO2. There are a few commercial offerings of 1st and 2nd generation aqueous amine technologies, however the cost of capturing CO2 with these technologies remains high. To decrease costs of capture, researchers are designing efficient solvent systems with the goal of being drop-in replacements for 1st and 2nd generation infrastructure. One approach has seen the development of water-lean solvents that aim to increase efficiency by reducing the water content in solution. Water-lean solvents such as GE’s GAP/TEG are promising technologies, with potential to halve the parasitic load to a coal-fired power plant, only if the intrinsically high solution viscosities and hydrolysis of the siloxane moieties could be mitigated. We present here, an integrated multidisciplinary approach to overhaul the GAP/TEG solvent system at the molecular level to mitigate hydrolysis while also reducing viscosity. We present molecular-level insights into chemical speciation of CO2-containing ions, showing that co-solvents and diluents have a negligible effect on reducing viscosity and are not needed. This finding allowed for the design of singlecomponent siloxane-free diamine derivatives with site-specific incorporation of selective chemical moieties for direct placement and orientation of hydrogen bonding to reduce viscosity. Ultimately, we present new single-component diamine formulations less susceptible to hydrolysis that exhibit up to a 98% reduction in viscosity compared to the initial GAP/TEG formulation.

Cantu Cantu, David↗

Carbon Dioxide Reduction Technology Trade Study

For long-term human missions, a closed-loop atmosphere revitalization system (ARS) is essential to minimize consumables. A carbon dioxide (CO2) reduction technology is used to reclaim oxygen (O2) from metabolic CO2 and is vital to reduce the delivery mass of metabolic O2. A key step in closing the loop for ARS will include a proper CO2 reduction subsystem that is reliable and with low equivalent system mass (ESM). Sabatier and Bosch CO2 reduction are two traditional CO2 reduction subsystems (CRS). Although a Sabatier CRS has been delivered to International Space Station (ISS) and is an important step toward closing the ISS ARS loop, it recovers only 50% of the available O2 in CO2. A Bosch CRS is able to reclaim all O2 in CO2. However, due to continuous carbon deposition on the catalyst surface, the penalties of replacing spent catalysts and reactors and crew time in a Bosch CRS are significant. Recently, technologies have been developed for recovering hydrogen (H2) from Sabatier-product methane (CH4). These include methane pyrolysis using a microwave plasma, catalytic thermal pyrolysis of CH4 and thermal pyrolysis of CH4. Further, development in Sabatier reactor designs based on microchannel and microlith technology could open up opportunities in reducing system mass and enhancing system control. Improvements in Bosch CRS conversion have also been reported. In addition, co-electrolysis of steam and CO2 is a new technology that integrates oxygen generation and CO2 reduction functions in a single system. A co-electrolysis unit followed by either a Sabatier or a carbon formation reactor based on Bosch chemistry could improve the overall competitiveness of an integrated O2 generation and CO2 reduction subsystem. This study evaluates all these CO2 reduction technologies, conducts water mass balances for required external supply of water for 1-, 5- and 10-yr missions, evaluates mass, volume, power, cooling and resupply requirements of various technologies. A system analysis and comparison among the technologies was made based on ESM, technology readiness level and reliability. Those technologies with potential were recommended for development.

Jeng, Frank F.↗

A study of LC-39 cryogenic systems. Part 1: A study of the vacuum insulated transfer lines at Kennedy Space Center. Part 2: Cooldown pressure surges

The vacuum liquid hydrogen and liquid oxygen transfer lines at Kennedy Space Center were studied to evaluate the feasibility of using a condensing gas such as CO2 inside the vacuum spaces to achieve a condensing-vacuum. The study indicates that at ambient temperature, a maximum vacuum hyphen space pressure of 4000 microns is acceptable for the LH2 transfer lines. In addition, the cooldown procedures for the 14-inch cross-country liquid oxygen line was studied using a simplified mathematical model. Preliminary cooldown times are presented for various heat leak rates to the line and for two vent configurations.

Ludtke, P. R.↗

Model calculations of the molecular composition of interstellar grain mantles

A chemical reaction scheme comprising gas phase as well as grain surface reactions is used for the numerical calculation of the chemical composition of mantles accreting on interstellar grains. The composition of the growing grain mantle is determined on the basis of the relative accretion rates of the gas phase molecules and diffusion-controlled surface reactions. Results show that grain mantles generally consist of the molecules H2O, H2CO, N2, O2, CO, CO2, H2O2, and NH3. A detailed examination of the formation of H2 on grain surfaces leads to the conclusion that it proceeds through hydrogen abstraction from such molecules as H2CO, H2S, N2H2, and N2H4. The IR characteristics of the calculated grain mantles are discussed with emphasis on the observed ice band at the 3250/cm wavelength.

Tielens, A. G. G. M.↗

Acetylene fuel from atmospheric CO2 on Mars

The Mars mission scenario proposed by Baker and Zubrin (1990) intended for an unmanned preliminary mission is extended to maximize the total impulse of fuel produced with a minimum mass of hydrogen from Earth. The hydrogen along with atmospheric carbon dioxide is processed into methane and oxygen by the exothermic reaction in an atmospheric processing module. Use of simple chemical reactions to produce acetylene/oxygen rocket fuel on Mars from hydrogen makes it possible to produce an amount of fuel that is nearly 100 times the mass of hydrogen brought from earth. If such a process produces the return propellant for a manned Mars mission, the required mission mass in LEO is significantly reduced over a system using all earth-derived propellants.

Landis, Geoffrey A.↗

Role of Intermolecular Interactions in Deep Eutectic Solvents for CO 2 Capture: Vibrational Spectroscopy and Quantum Chemical Studies

Recent research and reviews on CO 2 capture methods, along with advancements in industry, have highlighted high costs and energy-intensive nature as the primary limitations of conventional direct air capture and storage (DACS) methods. In response to these challenges, deep eutectic solvents (DESs) have emerged as promising absorbents due to their scalability, selectivity, and lower environmental impact compared to other absorbents. However, the molecular origins of their enhanced thermal stability and selectivity for DAC applications have not been explored before. Therefore, the current study focuses on a comprehensive investigation into the molecular interactions within an alkaline DES composed of potassium hydroxide (KOH) and ethylene glycol (EG). Combining Fourier transform infrared (FT-IR) and quantum chemical calculations, the study reports structural changes and intermolecular interactions induced in EG upon addition of KOH and its implications on CO 2 capture. Experimental and computational spectroscopic studies confirm the presence of noncovalent interactions (hydrogen bonds) within both EG and the KOH-EG system and point to the aggregation of ions at higher KOH concentrations. Additionally, molecular electrostatic potential (MESP) surface analysis, natural bond orbital (NBO) analysis, quantum theory of atoms-in-molecules (QTAIM) analysis, and reduced density gradient-noncovalent interaction (RDG-NCI) plot analysis elucidate changes in polarizability, charge distribution, hydrogen bond types, noncovalent interactions, and interaction strengths, respectively. Evaluation of explicit and hybrid models assesses their effectiveness in representing intermolecular interactions. This research enhances our understanding of molecular interactions in the KOH-EG system, which are essential for both the absorption and desorption of CO 2 . The study also aids in predicting and selecting DES components, optimizing their ratios with salts, and fine-tuning the properties of similar solvents and salts for enhanced CO 2 capture efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reformer Fuel Injector

Today's form of jet engine power comes from what is called a gas turbine engine. This engine is on average 14% efficient and emits great quantities of green house gas carbon dioxide and air pollutants, Le. nitrogen oxides and sulfur oxides. The alternate method being researched involves a reformer and a solid oxide fuel cell (SOFC). Reformers are becoming a popular area of research within the industry scale. NASA Glenn Research Center's approach is based on modifying the large aspects of industry reforming processes into a smaller jet fuel reformer. This process must not only be scaled down in size, but also decrease in weight and increase in efficiency. In comparison to today's method, the Jet A fuel reformer will be more efficient as well as reduce the amount of air pollutants discharged. The intent is to develop a 10kW process that can be used to satisfy the needs of commercial jet engines. Presently, commercial jets use Jet-A fuel, which is a kerosene based hydrocarbon fuel. Hydrocarbon fuels cannot be directly fed into a SOFC for the reason that the high temperature causes it to decompose into solid carbon and Hz. A reforming process converts fuel into hydrogen and supplies it to a fuel cell for power, as well as eliminating sulfur compounds. The SOFC produces electricity by converting H2 and CO2. The reformer contains a catalyst which is used to speed up the reaction rate and overall conversion. An outside company will perform a catalyst screening with our baseline Jet-A fuel to determine the most durable catalyst for this application. Our project team is focusing on the overall research of the reforming process. Eventually we will do a component evaluation on the different reformer designs and catalysts. The current status of the project is the completion of buildup in the test rig and check outs on all equipment and electronic signals to our data system. The objective is to test various reformer designs and catalysts in our test rig to determine the most efficient configuration to incorporate into the specific compact jet he1 reformer test rig. Additional information is included in the original extended abstract.

Suder, Jennifer L.↗

Increased Oxygen Recovery from Sabatier Systems Using Plasma Pyrolysis Technology and Metal Hydride Separation

State-of-the-art life support carbon dioxide (CO2) reduction technology is based on the Sabatier reaction where less than 50% of the oxygen required for the crew is recovered from metabolic CO2. The reaction produces water as the primary product and methane as a byproduct. Oxygen recovery is constrained by the limited availability of reactant hydrogen. This is further exacerbated when Sabatier methane (CH4) is vented as a waste product resulting in a continuous loss of reactant hydrogen. Post-processing methane with the Plasma Pyrolysis Assembly (PPA) to recover hydrogen has the potential to dramatically increase oxygen recovery and thus drastically reduce the logistical challenges associated with oxygen resupply. The PPA decomposes methane into predominantly hydrogen and acetylene. Due to the highly unstable nature of acetylene, a separation system is necessary to purify hydrogen before it is recycled back to the Sabatier reactor. Testing and evaluation of a full-scale Third Generation PPA is reported and investigations into metal hydride hydrogen separation technology is discussed.

Zachary W Greenwood↗

CO2 Sorption in Ionic Liquid Crystals

Ionic liquid crystals (ILCs) have an affinity for certain polarizable gases such as CO2, due to their similarity to ionic liquids. We investigated three ILCs in the [1-alkyl-3-methylimidazolium+] family: n=12,14 with [BF4-] and [PF6-]: liquid crystalline analogues to ionic liquids with moderate (e.g., 1-2 mol%) CO2 solubility at atmospheric conditions: [1-butyl-3-methylimidazolium+] with [BF4-] and [PF6-]. While ionic liquids show high CO2 solubility, regenerating the CO2 is a high-energy process. Liquid crystals show low CO2 solubility but have a much lower regeneration energy requirement. Will ionic liquid crystals uptake CO2? What are the energy requirements of regenerating CO2? Conclusions: 1. C12mim BF4- shows the highest sorption at 0.12 wt% CO2 in the isotropic phase vs. C14mim BF4- with 0.097 wt% in the smectic phase. We hypothesize that the increase in chain length affects the free volume of the smectic vs. isotropic phase of C14mim BF4-, increasing the latter. 2. The change in anion from BF4- to PF6- decreased the sorption to an insignificant level more analogous to a physical adsorption onto the material in all phases. We hypothesize that the change in anion to the larger, less charge dense PF6- decreased the attractive forces between CO2 and the anion. 3. 0.12 wt% of CO2 in C12mim BF4- is small but significant. This in combination with the room temperature release of CO2 after only requiring refrigeration temperatures to occlude the CO2, making ionic liquid crystals promising materials for future.

carbon dioxide sorption↗

Theoretical emergent Lyman alpha intensities from Mars.

The behavior of the Lyman alpha 1216-A intensity on Mars is presented for a range of atomic hydrogen density distributions below 200 km. Two sets of radiative transfer calculations have been performed. The first is based on spherical geometry and includes the effect of pure absorption of the resonance photons by CO2. The second set is based on the simpler plane parallel geometry and includes the effects of both pure absorption and a varying Doppler width associated with the planetary Lyman alpha line. From the plane parallel solutions, we are able to estimate and account for the effect of a varying Doppler width on our spherical model results. When pure absorption and a varying Doppler width are incorporated in the theory, the maximum change in the Lyman alpha disc intensity is a factor of about 2 over the range of hydrogen density models considered.

Strickland, D. J.↗

Mars - Chemical weathering as a massive volatile sink

The amounts of volatiles incorporated in the Martian regolith by photostimulated oxidation weathering of Fe(2+)-bearing minerals are estimated. The process of photostimulated oxidation weathering is described, and it is noted that all the necessary constituents for this process are present on Mars. The rates at which oxygen and hydrogen are irreversibly removed from the Martian atmosphere by the present process are determined, irreversible and reversible water losses are considered, and the loss of CO2 by carbonate formation is shown to be irreversible. The results suggest that photostimulated oxidation weathering has irreversibly consumed 100 to 100,000 g/sq cm of H2O and 10 to 10,000 g/sq cm of CO2, assuming a uniform rate over geologic time. It is concluded that if the amounts of H2O and CO2 actually removed by photostimulated oxidation are close to the upper limits of the present estimates, then that process may have had a major effect in limiting the amount of H2O and CO2 trapped in the regolith and polar caps.

Huguenin, R. L.↗

Hydrogen Isotopic Composition of Water in the Martian Atmosphere and Released from Rocknest Fines

The Mars Science Laboratory Curiosity rover sampled the aeolian bedform called Rocknest as its first solid samples to be analyzed by the analytical instruments CheMin and SAM. The instruments ingested aliquots from a sieved sample of less than 150 micrometer grains. As discussed in other reports at this conference [e.g., 1], CheMin discovered many crystalline phases, almost all of which are igneous minerals, plus some 10s of percent of x-ray amorphous material. The SAM instrument is focused on understanding volatiles and possible organics in the fines, performing evolved gas analysis (EGA) with the SAM quadrapole mass spectrometer (QMS), isotope measurements using both the QMS and the tunable laser spectrometer (TLS), which is sensitive to CO2, water and methane, and organics with the gas chromatograph mass spectrometer (GCMS). As discussed in the abstract by Franz et al. [2] and others, EGA of Rocknest fines revealed the presence of significant amounts of H2O as well as O-, C- and S-bearing materials. SAM has also tasted the martian atmosphere several times, analyzing the volatiles in both the TLS and QMS [e.g., 3,4]. This abstract will focus on presentation of initial hydrogen isotopic data from the TLS for Rocknest soils and the atmosphere, and their interpretation. Data for CO2 isotopes and O isotopes in water are still being reduced, but should be available by at the conference.

Leshin, L. A.↗