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At least 343 records · Page 19

Photochemistry and evolution of Mars' atmosphere - A Viking perspective

Viking measurements of the upper atmosphere of Mars have indicated thermospheric temperatures below 200 K, colder than those originally calculated by remote sensing experiments. It is suggested that dynamical coupling of the upper and lower regions of the Martian atmosphere may account for the variability in thermospheric temperature. The absorption of extreme ultraviolet solar radiation may account for observed ionospheric features, and may provide a source of fast N and O atoms escaping the planet's gravitational field. Measurements of the isotopic composition of O and N may be used to place constraints on models of the evolution of the Martian atmosphere. It is suggested that previous abundance of N2 may have exceeded that of CO2 in the present atmosphere, and that large sources of H2O may exist on the planet. The present degassing rate for nitrogen is felt to be less than the time-averaged degassing rate by at least a factor of 20.

Mcelroy, M. B.↗

The Martian polar caps: Stability and water transport at low obliquities

The seasonal cycle of water on Mars is regulated by the two polar caps. In the winter hemisphere, the seasonal CO2 deposits at a temperature near 150 K acts as a cold trap to remove water vapor from the atmosphere. When summer returns, water is pumped back into the atmosphere by a number of mechanisms, including release from the receding CO2 frost, diffusion from the polar regolith, and sublimation from a water-ice residual cap. These processes drive an exchange of water vapor between the polar caps that helps shape the Martian climate. Thus, understanding the behavior of the polar caps is important for interpreting the Martian climate both now and at other epochs. Mars' obliquity undergoes large variations over large time scales. As the obliquity decreases, the poles receive less solar energy so that more CO2 condenses from the atmosphere onto the poles. It has been suggested that permanent CO2 condenses from the atmosphere onto the poles. It has been suggested that permanent CO2 caps might form at the poles in response to a feedback mechanism existing between the polar cap albedo, the CO2 pressure, and the dust storm frequency. The year-round presence of the CO2 deposits would effectively dry out the atmosphere, while diffusion of water from the regolith would be the only source of water vapor to the atmosphere. We have reviewed the CO2 balance at low obliquity taking into account the asymmetries which make the north and south hemispheres different. Our analysis linked with a numerical model of the polar caps leads us to believe that one summertime cap will always lose its CO2 cover during a Martian year, although we cannot predict which cap this will be. We conclude that significant amounts of water vapor will sublime from the exposed cap during summer, and the Martian atmosphere will support an active water cycle even at low obliquity.

Henderson, B. G.↗

Risk Considerations of Transitioning CO2-EOR Field to CO2 storage Field: Case Study

In the United States (U.S.), carbon dioxide (CO2) injection wells at EOR sites are currently regulated as Class II wells under the U.S. Environmental Protection Agency’s (EPA) Underground Injection Control (UIC) program while dedicated geological CO2 storage (GCS) wells are considered Class VI wells. A CO2-EOR facility considering a transitioning from tertiary oil recovery to injecting CO2 for the primary purpose of long-term storage is required to obtain a Class VI permit where this transition poses an increased risk to underground sources of drinking water. This study considers how transitioning operations from CO2-EOR to storage can impact reservoir plume and pressure transient in the storage envelope, and how these changes could impact area of review and potential unwanted fluid migration. We developed a case study to assess subsurface response and leakage risks associated with a representative, hypothetical operation in a carbonate reservoir. This reservoir transitions from tertiary hydrocarbon recovery to dedicated GCS. Reservoir simulations were run for a set of credible CO2-EOR scenarios to estimate distributions of fluids phases and pressures throughout the model domain after CO2 flooding as well as forecasting the behavior of the reservoir after the transition to a dedicated storage phase. The evolutions from all simulated scenarios were used as the basis for leakage risk quantification using the National Risk Assessment Partnership’s Open-Source Integrated Assessment Model (NRAP-Open-IAM) with a novel reduced-order model to estimate time-dependent leakage of CO2, brine, and hydrocarbon fluids through potentially leaky wells. Results include a description of reservoir response, an estimate of the areal extent that could potentially be impacted by leakage to underground sources of drinking water, and estimates of the magnitude of potential leakage. Considerations for dedicated storage injection well selection, injectivity, and injection scheme performance and potential leakage risk are presented, with implications for risk assessment of well transition discussed. This study presents a risk-based workflow for the Class II to Class VI well transition. Integrating credible numerical simulation of viable CO2-EOR to dedicated CO2 storage with quantitative risk assessment tools, such as the NRAP-Open-IAM, will provide a valuable means to devise operational scenarios and inform decision-making related to storage benefit, leakage risk, and liability. Presented at the SPE/AAPG/SEG Carbon Capture Utilization and Storage Conference in Houston, TX, March 11-13, 2024.

Liu, Guoxiang↗

An Electrochemically Mediated Amine Regeneration Process with a Mixed Absorbent for Postcombustion CO 2 Capture

Electrochemically mediated amine regeneration (EMAR) was recently developed to avoid the use of thermal means to release CO2 captured from postcombustion flue gas in the benchmark amine process. To address concerns related to the high vapor pressure of ethylenediamine (EDA) as the primary amine used in EMAR, a mixture of EDA and aminoethylethanolamine (AEEA) was investigated. The properties of the mixed amine systems, including the absorption rates, electrolyte pH and conductivity, and CO2 capacity, were evaluated in comparison with those of solely EDA. The mixed amine system had similar properties to that of EDA, indicating no significant changes would be necessary for the future implementation of the EMAR process with mixed amines as opposed to that with just EDA. The electrochemical performance of the mixed amines in terms of the cell voltage, gas desorption rate, electron utilization, and energetics was also investigated. A 50/50 mixture of EDA and AEEA displayed the lowest energetics: ~10% lower than that of 100% EDA. With this mixture, a continuous EMAR process, in which the absorption column was connected to the electrochemical cell as the desorption stage, was tested over 100 h. The cell voltage was very stable and there was a steady gas output close to theoretical values. The desorbed gas was further analyzed and found to be 100% CO2, confirming no evaporation of the amine. The mixed absorbent composition was also characterized using titration and nuclear magnetic resonance (NMR) spectroscopy, and the results showed no amine degradation. Furthermore, these findings that demonstrate a stable, low vapor pressure absorbent with improved energetics are promising and could be a guideline for the future development of EMAR for CO2 capture from flue gas and other sources.

54 ENVIRONMENTAL SCIENCES↗

Optical study of charge exchange collisions between He+ and CO2.

Helium ions were produced in an electron bombardment ion source and directed into a gas cell containing carbon dioxide. A Wien filter placed between the ion source and the gas cell insured that only singly charged helium ions reached the cell. The spectrum obtained for the bombardment of carbon dioxide with the helium ions at 1200 eV is shown in a graph. Prominent features of the lower spectrum are two atomic lines at 3889 and 4471 A.

Coplan, M. A.↗

Production of nitric oxide by lightning on Venus

The first measurements of the production of nitric oxide (NO) by a laboratory discharge in a simulated Venus atmosphere are presented. The average NO yield over a range of energies was found to be 3.7 + or - 0.7 x 10 to the 15th molecules/joule. Simultaneous measurements of carbon monoxide (CO) resulting from the lightning-induced dissociation of carbon dioxide (CO2) indicated a CO yield of about 4 x 10 to the 17th molecules/joule. These measurements suggest that at and below cloud level, a region where solar ultraviolet radiation cannot penetrate, the dissociation of CO2 by lightning may be a significant source of oxygen atoms. Depending on the assumed value for the total energy dissipated by lightning on Venus, the production of NO by lightning may be a significant sink of atmospheric nitrogen over the history of Venus.

Levine, J. S.↗

Atmospheric Energy Limits on Subsurface Life on Mars

It has been suggested that the terrestrial biomass of subterranean organisms may equal or exceed that at the surface. Taken as a group, these organisms can live in heavily saline conditions at temperatures from 115 C to as low as -20 C. Such conditions might exist on Mars beneath the surface oxidant in an aquifer or hydrothermal system, where the surrounding rock would also protect against the solar ultraviolet radiation. The way that such systems could obtain energy and carbon is not completely clear, although it is believed that on Earth, energy flows from the interaction of highly reduced basalt with groundwater produce H2, while carbon is derived from CO2 dissolved in the groundwater. Another potential source is the Martian atmosphere, acting as a photochemical conduit of solar insolation.

Weiss, B. P.↗

Estimating CO2 Emissions Using Real and Simulated Total Column XCO2 Observations

Rising atmospheric CO2 concentrations necessitate deeper understanding of urban sources and sinks. Various sensor technologies and data assimilation strategies can be used to determine short- and long-term atmospheric trends. We seek to find the optimal synthesis of various measurement types in order to characterizing different types of sources in an urban environment.

Raheja, Garima↗

Biological methanogenesis and the CO2 greenhouse effect

It is well established that plants tend to increase net photosynthesis under increased carbon dioxide. It is also well established that a large fraction of atmospheric methane is produced by microbial metabolism of organic sediments in paddies and freshwater wetlands, where a major source of organic debris is local plant growth. As CO2 increases, it may lead to increased methane production and a resulting enhancement of the expected greenhouse warming. A rough estimate of the present rate of this biologically mediated feedback on the climate system indicates that it might account for as much as 30 percent of the observed methane increase and speed up the greenhouse forcing by as much as 15 percent.

Guthrie, P. D.↗

Mass transfer coefficients, kL, and air-CO2 ingassing rates in 3.4 m2 and 1-acre raceway ponds.

The US DOE 2016 Billion Ton Update (Langholtz 2016) projected that CO2 in flue-gas from power plants or similar sources would limit U.S. algal biofuel potential to under 5 billion gallons gasoline equivalent (gge) per year, due to lack of sufficient land, water and other requirements near such flue gas sources. 2nd generation carbon capture technologies are proposed to overcome this constraint (Davis 2017), and could expand this resource potential nearly 10-fold, assuming CO2 costs near the future, 2025 DOE NETL, goal of $40/metric ton CO2. An alternative pathway is the direct uptake of air CO2 into the algal ponds through an increase in the air-CO2 transfer rate resulting from the reaction of CO2 with hydroxide ions. However, such a ‘chemical enhancement’ in mass transfer depends on a high pH in the culture, and, by extension, the ability of microalgae to maintain high rates of carbon assimilation under such conditions. Abiotic experiments characterized the air-CO2 mass-transfer rate in 1-acre and 3.4 m2 raceway ponds as a function of pH, with rates approaching 10 g C/m2-day at pH 12 in the brackish water tested, equivalent to a biomass productivity potential of near 20 g AFDW/m2-day (@ 0.47 g C/g AFDW). The mass transfer rate was found to be nearly independent of the mass-transfer coefficient, indicating that at turbulence levels achievable in typical raceway ponds, the system is reaction rate, rather than diffusion limited. In biotic trials with an unknown green microalga, biomass productivity in ponds receiving CO2 from only direct surface air-CO2 exchange averaged 5 +/- 0.5 g AFDW/m2-day in August - September central California conditions, about half-that of experimental controls fertilized with supplemental CO2. pH in the air-only treatment reached a maximum of 10.5, supporting a model predicted air-CO2 ingassing rate between 2-3 g C/m2-day, consistent with the observed biomass carbon assimilation rate. Results suggest that unique alkaliphilic strains are required if reliant on direct in-pond air-CO2 transfer for algal inorganic carbon supply, and that reaching an economically viable biomass productivity will require strains that thrive at pH 11 and above.

09 BIOMASS FUELS↗

Experimental Constraints on the Stability of Clinopyroxene (+) Magnesite in Iron Bearing Planetary Mantles: Implications for Nakhlite Formation

Carbon is present in various forms in the Earth s upper mantle (carbonate- or diamond-bearing mantle xenoliths, carbonatite magmas, CO2 emissions from volcanoes...). Moreover, there is enough carbon in chondritic material to stabilize carbonates into the mantles of Mars or Venus as well as in the Earth. However, the interactions with iron have to be constrained, because Fe is commonly thought to buffer oxygen fugacity into planetary mantles. [1] and [2] show evidences of the stability of clinopyroxene Ca(Mg,Fe)Si2O6 + magnesite (Mg,Fe)CO3 in the Earth s mantle around 6GPa (about 180km). The stability of oxidized forms of carbon (like magnesite) depends on the oxygen fugacity of the system. In the Earth s mantle, the maximum carbon content is 10000 ppm [3]. The fO2 parameter varies vertically as a function of pressure, but also laterally because of geodynamic processes like subduction. Thus, carbonates, graphite, diamond, C-rich gases and melts are all stable forms of carbon in the Earth s mantle. [4] show that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. [5] inferred from thermodynamic calculations that the stable form of carbon in the source regions of the Martian basalts should be graphite (and/or diamond). After [6], a metasomatizing agent like a CO2-rich melt may infiltrate the mantle source of nakhlites. However, according to [7] and [8], the FeO wt% value in the Martian bulk mantle is more than twice that of the Earth s mantle (KLB-1 composition by [9]). As iron and carbon are two elements with various oxidation states, Fe/C interaction mechanisms must be considered.

Martin, Audrey M.↗

Rapid Cycle Amine (RCA 2.0) System Development

The Rapid Cycle Amine (RCA) system is a low power assembly capable of simultaneously removing carbon dioxide (CO2) and humidity from an influent air steam and subsequent regeneration when exposed to a vacuum source. Two solid amine sorbent beds are alternated between an uptake mode and a regeneration mode. During the uptake mode, the sorbent is exposed to an air steam (ventilation loop) to adsorb CO2 and water vapor, while during the regeneration mode, the sorbent rejects the adsorbed CO2 and water vapor to a vacuum source. The two beds operate such that while one bed is in the uptake mode, the other is in the regeneration mode, thus continuously providing an on-service sorbent bed by which CO2 and humidity may be removed. A novel valve assembly provides a simple means of diverting the process air flow through the uptake bed while simultaneously directing the vacuum source to the regeneration bed. Additionally, the valve assembly is designed to allow for switching between uptake and regeneration modes with only one moving part while minimizing gas volume losses to the vacuum source by means of an internal pressure equalization step during actuation. The process can be controlled by a compact, low power controller design with several modes of operation available to the user. Together with NASA, United Technologies Corporation Aerospace Systems has been developing RCA 2.0 based on performance and design feedback on several sorbent bed test articles and valve design concepts. A final design was selected in November 2011 and fabricated and assembled between March and August 2012, with delivery to NASA-JSC in September 2012. This paper will provide an overview on the RCA system design and results of pre-delivery testing.

Papale, William↗

Rapid Cycle Amine (RCA 2.0) System Development

The Rapid Cycle Amine (RCA) system is a low-power assembly capable of simultaneously removing carbon dioxide (CO2) and humidity from an influent air steam and subsequent regeneration when exposed to a vacuum source. Two solid amine sorbent beds are alternated between an uptake mode and a regeneration mode. During the uptake mode, the sorbent is exposed to an air steam (ventilation loop) to adsorb CO2 and water (H2O) vapor, whereas during the regeneration mode, the sorbent rejects the adsorbed CO2 and H2O vapor to a vacuum source. The two beds operate such that while one bed is in the uptake mode, the other is in the regeneration mode, thus continuously providing an on-service sorbent bed by which CO2 and humidity may be removed. A novel valve assembly provides a simple means of diverting the process air flow through the uptake bed while simultaneously directing the vacuum source to the regeneration bed. Additionally, the valve assembly is designed to allow for switching between uptake and regeneration modes with only one moving part while minimizing gas volume losses to the vacuum source by means of an internal pressure equalization step during actuation. The process can be controlled by a compact, low-power controller design with several modes of operation available to the user. Together with NASA Johnson Space Center, Hamilton Sundstrand Space Systems International, Inc. has been developing RCA 2.0 based on performance and design feedback on several sorbent bed test articles and valve design concepts. A final design of RCA 2.0 was selected in November 2011 and fabricated and assembled between March and August 2012, with delivery to NASA Johnson Space Center in September 2012. This paper provides an overview of the RCA system design and results of pre-delivery testing.

Papale, William↗

Laser Sounder for Global Measurement of CO2 Concentrations in the Troposphere from Space: Progress

We describe progress toward developing a laser-based technique for the remote measurement of the tropospheric CO2 concentrations from orbit. Our goal is to demonstrate a lidar technique and instrument technology that will permit measurements of the CO2 column abundance in the lower troposphere from aircraft at the few ppm level, with a capability of scaling to permit global CO2 measurements from orbit. Accurate measurements of the tropospheric CO2 mixing ratio from space are challenging due to the many potential error sources. These include possible interference from other trace gas species, the effects of temperature, clouds, aerosols & turbulence in the path, changes in surface reflectivity, and variability in dry air density caused by changes in atmospheric pressure, water vapor and topographic height. Some potential instrumental errors include frequency drifts in the transmitter, small transmission and sensitivity drifts in the instrument. High signal-to-noise ratios and measurement stability are needed for mixing ratio estimates at the few ppm level. We have been developing a laser sounder approach as a candidate for a future space mission. It utilizes multiple different laser transmitters to permit simultaneous measurement of CO2 and O2 extinction, and aerosol backscatter in the same measurement path. It directs the narrow co-aligned laser beams from the instrument's fiber lasers toward nadir, and measures the energy of the strong laser echoes reflected from the Earth's land and water surfaces. During the measurement its narrow linewidth lasers are rapidly tuned on- and off- selected CO2 line near 1572 nm and an O2 absorption line near 770 nm. The receiver measures the energies of the laser echoes from the surface and any clouds and aerosols in the path with photon counting detectors. Ratioing the on- to off-line echo pulse energies for each gas permits the column extinction and column densities of CO2 and O2 to be estimated simultaneously via the differential absorption lidar technique. For the on-line wavelengths, the side of the selected absorption lines are used, which due to pressure broadening, weights the measurements to the lower troposphere, where CO2 variations caused by surface sources and sinks are largest. Simultaneous measurements of O2 column abundance are made using an identical approach using an O2 line. The laser backscatter profiles from clouds and aerosols are measured with other lidar channels, which permits identifying measurements influenced by clouds and/or aerosol scattering in the path. For space use, our lidar would continuously measure at nadir in near polar circular orbit. Using dawn and dusk measurements made over the same region will make it possible to sample the diurnal variations in CO2 mixing ratios. A 1-m diameter telescope is used for the receiver for all wavelengths. When averaging over 50 seconds, our calculations show a SNR of approximately 1500 is achievable for each gas at each on- and off-line measurement. Measurements from such a mission can be used to generate monthly global maps of the lower tropospheric CO2 column abundance. Our calculations show global coverage with an accuracy of a few ppm with a spatial resolution of approximately 50,000 sq. km are achievable each month. We have demonstrated some key elements of the laser, detector and receiver approaches in the laboratory and with measurements over a 206 m horizontal path. These include stable measurements of CO2 line shapes in an absorption cell using a fiber laser amplifier seeded by a tunable diode laser, measurement of small amplitude changes at low optical signal levels with the PMT receiver, and comparison of the horizontal path measurements of CO2 against those from an in-situ instrument.

Abshire, J. B.↗

Combustion of Metals in Reduced-Gravity and Extraterrestrial Environments

As a result of the ongoing exploration of Mars and the several unmanned and possibly manned missions planned for the near future, increased attention has been given to the use of the natural resources of the planet for rocket propellant production and energy generation. Since the atmosphere of Mars consists of approximately 95% carbon dioxide (CO2), this gas is the resource of choice to be employed for these purposes. Since many metals burn vigorously with CO2, these may be used as an energy source or as propellants for a research vehicle on the surface of Mars. Shafirovich and Goldshleger conducted experiments with spherical particles up to 2.5 mm in diameter and found that the burning process was controlled by diffusion and that the particles exhibited pulsating combustion due to superheating of the Mg vapor trapped inside a protective oxide shell. They also proposed a reaction mechanism based on the gas-phase reaction, Mg + CO2 yields MgO + CO and the heterogeneous reaction Mg + CO yields MgO + C occurring on the sample surface. In all the above studies with large Mg particles, the burning process is invariably influenced by strong convective currents that accelerate the combustion reaction and shorten the burning times. Although these currents are nearly absent in the burning of small particles, the high emissivity of the flames, rapid reaction, and small length scales make the gathering of any useful information on burning rates and flame structure very difficult. The goal of this investigation is to provide a detailed study of flame structure by taking advantage of large, free-floating spherical metal samples and their corresponding long burning times available in a weightless environment. The use of reduced gravity is essential to eliminate the intrusive buoyant flows that plague high temperature metal reactions, to remove the destructive effect of gravity on the shape of molten metal samples, and to study the combustion behavior of metals in the presence of solid oxides undisturbed by natural convection. This work presents the most complete modeling of metal particle burning to date for Mg with CO2 and O2.

Branch, M. C.↗

CO/d-3 Delta sub i to X-1 Sigma +/ fluorescence from photodissociation of CO2 by 923 A photons

Measurements of vacuum ultraviolet fluorescence from the photodissociation of CO2 by photons from a N IV line emission source at a wavelength of 923 A have revealed a second CO band system in addition to the expected emission bands. Spectra with time resolution were obtained and the fluorescence lifetime and the dependence of fluorescence intensity on CO2 pressure were measured. An analysis of this data has permitted the second band system to be identified as originating from CO(d-3 Delta sub i to X-1 Sigma +) transitions.

Phillips, E.↗

Mid-infrared trace gas detection using continuous-wave difference frequency generation in periodically poled RbTiOAsO4

A tunable mid-infrared continuous-wave (cw) spectroscopic source in the 3.4-4.5 micrometers region is reported, based on difference frequency generation (DFG) in a quasi-phase-matched periodically poled RbTiOAsO4 (PPRTA) crystal. DFG power levels of 10 microW were generated at approximately 4 micrometers in a 20-mm long PPRTA crystal by mixing two cw single-frequency Ti:Al2O3 lasers operating near 713 nm and 871 nm, respectively, using a laser pump power of 300 mW. A quasi-phase-matched infrared wavelength-tuning bandwidth (FWHM) of ~ 12 cm-1 and a temperature tuning rate of 1.02 cm-1/degree C were achieved. Experimental details regarding the feasibility of trace gas detection based on absorption spectroscopy of CO2 in ambient air using this DFG radiation source are also described.

NASA Discipline Life Sciences Technologies↗

Sublimation rates of carbon monoxide and carbon dioxide from comets at large heliocentric distances

Using a simple model for outgassing from a small flat surface area, the sublimation rates of carbon monoxide and carbon dioxide, two species more volatile than water ice that are known to be present in comets, are calculated for a suddenly activated discrete source on the rotating nucleus. The instantaneous sublimation rate depends upon the comet's heliocentric distance and the Sun's zenith angle at the location of the source. The values are derived for the constants of CO and CO2 in an expression that yields the local rotation-averaged sublimation rate as a function of the comet's spin parameters and the source's cometocentric latitude.

Sekanina, Zdenek↗