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At least 289 records · Page 16

Monochromatic calculations of atmospheric radiative transfer due to molecular line absorption

Sensitivity studies related to the effects of line cutoff, spectral resolution, and temperature and pressure interpolations in radiative transfer have been performed so that a data set of absorption coefficients for water vapor, CO2, and O3 may be created efficiently. Results show that computations of absorption coefficients are affected only slightly by cutting a line off at a wave number 190 times the Lorentz half width from the center, or equivalently, cutting off 0.33 percent of the line intensity from the wings. To achieve a relative cooling rate error smaller than 2 percent, it is sufficient to precompute the absorption coefficient at three temperatures (210, 250, and 290 K) and 19 pressures with Delta (log 10 p) = 0.2. The absorption coefficient at other conditions can be interpolated linearly with pressure and exponentially with a quadratic in temperature. For the spectral resolution the absorption coefficients can be adequately computed at 0.01, 0.002, 0.005, and 0.025/cm intervals in the thermal water vapor, the CO2 and O3 bands, and the solar water vapor bands, respectively, which limits the error to only a few percent in the cooling and heating rates. Using the precomputed absorption coefficients, repeated monochromatic calculations of atmospheric heating/cooling rates for radiation model developments and for comparison with less detailed calculations are no longer difficult.

Chou, M.-D.↗

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

Measurements of tropospheric CO2 abundance with global-coverage, a few hundred km spatial and monthly temporal resolution are needed to quantify processes that regulate CO2 storage by the land and oceans. The Orbiting Carbon Observatory (OCO) is the first space mission focused on atmospheric CO2 for measuring total column CO, and O2 by detecting the spectral absorption in reflected sunlight. The OCO mission is an essential step, and will yield important new information about atmospheric CO2 distributions. However there are unavoidable limitations imposed by its measurement approach. These include best accuracy only during daytime at moderate to high sun angles, interference by cloud and aerosol scattering, and limited signal from CO2 variability in the lower tropospheric CO2 column. We have been developing a new laser-based technique for the remote measurement of the tropospheric CO2 concentrations from orbit. Our initial 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. Our final goal is to develop a space instrument and mission approach for active measurements of the CO2 mixing ratio at the 1-2 ppmv level. Our technique is much less sensitive to cloud and atmospheric scattering conditions and would allow continuous measurements of CO2 mixing ratio in the lower troposphere from orbit over land and ocean surfaces during day and night. Our approach is to use the 1570nm CO2 band and a 3-channel laser absorption spectrometer (i.e. lidar used an altimeter mode), which continuously measures at nadir from a near polar circular orbit. The approach directs the narrow co-aligned laser beams from the instrument's lasers toward nadir, and measures the energy of the laser echoes reflected from land and water surfaces. It uses several tunable fiber laser transmitters which allowing measurement of the extinction from a single selected CO2 absorption line in the 1570 nm band. This band is free from interference from other gases and has temperature insensitive absorption lines. During the measurement the lasers are tuned on- and off- a selected CO2 line near 1572 nm and a selected O2 line near 768 nm in the Oxygen A band at kHz rates. The lasers use tunable diode seed lasers followed by fiber amplifiers, and have spectral widths much narrower than the gas absorption lines. The receiver uses a 1-m diameter telescope and photon counting detectors and measures the background light and energies of the laser echoes from the surface. The extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on and offline surface echo via the differential optical absorption technique. Our technique rapidly alternates between several on-line wavelengths set to the sides of the selected gas absorption lines. It exploits the atmospheric pressure broadening of the lines to weight the measurement sensitivity to the atmospheric column below 5 km. This maximizes sensitivity to CO2 in the boundary layer, where variations caused by surface sources and sinks are largest. Simultaneous measurements of O2 column will use an identical approach with an O2 line. Thee laser frequencies are tunable and have narrow (MHz) line widths. In combination with sensitive photon counting detectors these enables much higher spectral resolution and precision than is possible with passive spectrometer. 1aser backscatter profiles are also measured, which permits identifying measurements made to cloud tops and through aerosol layers. The measurement approach using lasers in common-nadir-zenith path allows retrieving CO2 column mixing ratios in the lower troposphere irrespective of sun angle. Pulsed laser signals, time gated receiver and a narrow receiver field-of-view are used to isolate the surface laser echo signals and to exclude photons scattered from clouds and aerosols. Nonetheless, the optical absorption change due to a change of a few ppO2 is small, <1 % which makes achieving the needed measurement sensitivities and stabilities quite challenging. Measurement SNRs and stabilities of >600:1 are needed to estimate CO2 mixing ratio at the 1-2 ppm level. We have calculated characteristics of the technique and have demonstrated aspects of the laser, detector and receiver approaches in th e laboratory We have also measured O2 in an absorption cell, and made C02 measurements over a 400 m long (one way) horizontal path using a sensor breadboard. We will describe these and more details of our approach in the paper.

Abshire, James B.↗

L 98-59: A Benchmark System of Small Planets for Future Atmospheric Characterization

The M3V dwarf star L 98-59 hosts three small (R < 1.6 Rꚛ) planets. The host star is bright (K = 7.1) and nearby (10.6 pc), making the system a prime target for follow-up characterization with the Hubble Space Telescope (HST) and the upcoming James Webb Space Telescope (JWST). Herein, we use simulated transmission spectroscopy to evaluate the detectability of spectral features with HST and JWST assuming diverse atmospheric scenarios (e.g., atmospheres dominated by H2, H2O, CO2, or O2). We find that H2O and CH4 present in a low mean molecular weight atmosphere could be detected with HST in one transit for the two outermost planets, while H2O in a clear steam atmosphere could be detected in six transits or fewer with HST for all three planets. We predict that observations using JWST/NIRISS would be capable of detecting a clear steam atmosphere in one transit for each planet and H2O absorption in a hazy steam atmosphere in two transits or less. In a clear, desiccated atmosphere, O2 absorption may be detectable for all three planets with NIRISS. If the L 98-59 planets possess a clear, Venus-like atmosphere, NIRSpec could detect CO2 within 26 transits for each planet, but the presence of H2SO4 clouds would significantly suppress CO2 absorption. The L 98-59 system is an excellent laboratory for comparative planetary studies of transiting multiplanet systems, and observations of the system via HST and JWST would present a unique opportunity to test the accuracy of the models presented in this study.

Daria Pidhorodetska↗

Deep Learning Potential For Investigation of Chemical Conversion of CO2 at Air-Reactive Deep Eutectic Solvent Interface

Capturing CO2 from air is urgent to battle against the climate change. Traditional CO2 capture by alkaline solution or aqueous amine has high regeneration cost, equipment corrosion, and amine leakage. Deep eutectic solvents (DESs) are promising alternatives with low corrosion, non-toxicity, and biodegradable nature. Functionalized DESs can capture and convert CO2 at low partial pressures. Developing reactive DESs for efficient CO2 capture needs a foundational understanding of the reaction-transport coupling of CO2 at the air-DES interface. In this study, we develop a deep learning potential (DLP) to investigate the absorption and reaction of CO2 at the air-DES interface (DES: 1-ethyl-3-methylimidazolium 2-cyanopyrrolide ([Emim][2-CNpyr]) and ethylene glycol (EG)). The DLP model allows us to simulate chemical reactions at a lower computational cost with ab initio accuracy. By analyzing reaction free energy surfaces, molecular interactions among CO2, DES components and reaction products, and transport of CO2 through the interface, we identify three main reaction pathways of CO2 at the interface: forming carboxylate with [Emim], carbamate with [2-CNpyr], and carbonate with EG. The mechanistic understanding of CO2 chemisorption at the interface will facilitate the development of novel direct air capture technology using DESs.

Nguyen, Manh Tien↗

Evaluation of Ionic Liquids for Closed Air Revitalization

This document is the final report resulting from the work conducted by undergraduate students at the University of South Alabama during the 2018/2019 academic year and was prepared by the undergraduate students. As NASA pushes the boundaries further into space, the current technologies within the various life support systems must be improved upon. One such improvement is needed to the current air revitalization systems, specifically sorbents that can capture CO2 more effectively from enclosed habitats. Ionic liquids (ILs) have been considered as absorbents for flue gas, but little research has been done to test the ability of ILs at ambient pressures and relatively low concentration of CO2. The experiment outlined below utilizes the task-specific ionic liquid, tetramethylammonium taurinate (TMN), in a commercial off the shelf absorption system to capture CO2. The CO2 stream is combined with nitrogen to produce an inlet gas concentration relevant to close air revitalization applications. At an inlet gas flow with a CO2 partial pressure of 3.8 torr the system was capable of removing just under 97% of the inlet CO2. The concentration of CO2 in the outlet stream, partial pressure 0.16 torr, was less than that of atmospheric air. The duty required to separate the absorbed gas from the ionic liquid as well to cool the ionic liquid to be reintroduced to the column were acquired utilizing laboratory cooling/heating baths. These results show that TMN may be an efficient candidate for consideration in closed air revitalization.

Duck, Gerald↗

Spatial variability in the seasonal south polar cap of Mars

The first comprehensive discussion of the south seasonal polar cap spectra obtained by the Mariner 7 infrared spectrometer in the short-wavelength region (2-4 microns) is presented. The infrared spectra is correlated with images acquired by the wide-angle camera. Significant spectral variation is noted in the cap interior and regions of varying water frost abundance, CO2 ice/frost cover, and CO2-ice path length can be distinguished. Many of these spectral variations correlate with heterogeneity noted in the camera images, but certain significant infrared spectral variations are not discernible in the visible. Simple reflectance models are used to classify the observed spectral variations into four regions. Region I is at the cap edge, where there is enhanced absorption beyond 3 microns inferred to be caused by an increased abundance of water frost. The increase in water abundance over that in the interior is on the level of a few parts per thousand or less. Region II is the typical cap interior characterized by spectral features of CO2 ice at grain sizes of several millimeters to centimeters. These spectra also indicate the presence of water frost at the parts per thousand level. A third, unusual region (III), is defined by three spectra in which weak CO2 absorption features are as much as twice as strong as in the average cap spectra and are assumed to be caused by an increased path length in the CO2. Such large paths are inconsistent with the high reflectance in the visible and at 2.2 microns and suggest layered structures or deposition conditions that are not accounted for in current reflectance models. The final region (IV) is an area of thinning frost coverage or transparent ice well in the interior of the seasonal cap. These spectra are a combination of CO2 and ground signatures.

Calvin, Wendy M.↗

Hybrid Absorption–Crystallization Strategies for the Direct Air Capture of CO2 Using Phase-Changing Guanidium Bases: Insights from in Operando X-ray Scattering and Infrared Spectroscopy Measurements

Efforts to limit rising concentrations of CO 2 have motivated the development of negative emission technologies. Direct air capture (DAC) of CO 2 is one of the negative emissions technologies that has been proposed for the direct removal of CO 2 from the atmosphere. Phase-changing bis(iminonoguanidine) (BIG) sorbents have been developed for the direct air capture of CO 2 . These phase changing sorbents, specifically glyoxal-bis(iminoguanidine) (GBIG), involve (1) CO 2 absorption with aqueous amino acid salts, such as K- or Na-glycinate to yield bicarbonate-rich solutions, (2) crystallization of the bicarbonate anions with a BIG solid, which regenerates the amino acid, and (3) solid-state CO 2 release from the carbonate crystals and BIG regeneration. Despite the promising potential of these materials, their structural evolution during the thermal regeneration of the BIG solids, chemical regeneration of the sodium or potassium glycinate solvents, and the crystallization behavior of CO 2 -loaded BIG bicarbonate remain to be evaluated and understood in detail. The aim of this study is to probe these knowledge gaps. In situ wide-angle X-ray Scattering (WAXS) results show that CO 2 and water molecules in GBIG bicarbonate are simultaneously released in a single step during the thermal regeneration of the sorbent at 97 – 134 °C. In situ ATR-FTIR measurements showed that sodium glycinate and GBIG bicarbonate are simultaneously generated when GBIG, glycine, and sodium bicarbonate are reacted. The crystallization of GBIG bicarbonate from GBIG and CO 2 -loaded monoethanolamine (MEA) occurs rapidly in the first 10 min of the reaction, as determined using in situ GI-SAXS measurements. Overall, the insights from these studies are essential for the scalable implementation of CO 2 capture technologies using these phase-changing sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An efficient and accurate technique to compute the absorption, emission, and transmission of radiation by the Martian atmosphere

CO2 comprises 95 pct. of the composition of the Martian atmosphere. However, the Martian atmosphere also has a high aerosol content. Dust particles vary from less than 0.2 to greater than 3.0. CO2 is an active absorber and emitter in near IR and IR wavelengths; the near IR absorption bands of CO2 provide significant heating of the atmosphere, and the 15 micron band provides rapid cooling. Including both CO2 and aerosol radiative transfer simultaneously in a model is difficult. Aerosol radiative transfer requires a multiple scattering code, while CO2 radiative transfer must deal with complex wavelength structure. As an alternative to the pure atmosphere treatment in most models which causes inaccuracies, a treatment was developed called the exponential sum or k distribution approximation. The chief advantage of the exponential sum approach is that the integration over k space of f(k) can be computed more quickly than the integration of k sub upsilon over frequency. The exponential sum approach is superior to the photon path distribution and emissivity techniques for dusty conditions. This study was the first application of the exponential sum approach to Martian conditions.

Lindner, Bernhard Lee↗

Non-invasive optical detection of glucose in cell culture nutrient medium

The objective of the proposed research was to begin the development of a non-invasive optical sensor for measuring glucose concentration in the output medium of cell cultures grown in a unique NASA bioreactor referred to as an integrated rotating-wall vessel (IRWV). The input, a bovine serum based nutrient media, has a known glucose concentration. The cells within the bioreactor digest a portion of the glucose. Thus, the non-invasive optical sensor is needed to monitor the decrease in glucose due to cellular consumption since the critical parameters for sustained cellular productivity are glucose and pH. Previous glucose sensing techniques have used chemical reactions to quantify the glucose concentration. Chemical reactions, however, cannot provide for continuous, real time, non-invasive measurement as is required in this application. Our effort while in the fellowship program was focused on the design, optical setup, and testing of one bench top prototype non-invasive optical sensor using a mid-infrared absorption spectroscopy technique. Glucose has a fundamental vibrational absorption peak in the mid-infrared wavelength range at 9.6 micron. Preliminary absorption data using a CO2 laser were collected at this wavelength for water based glucose solutions at different concentrations and one bovine serum based nutrient medium (GTSF) with added glucose. The results showed near linear absorption responses for the glucose-in-water data with resolutions as high at 108 mg/dl and as low as 10 mg/dl. The nutrient medium had a resolution of 291 mg/dl. The variability of the results was due mainly to thermal and polarization drifts of the laser while the decrease in sensitivity to glucose in the nutrient medium was expected due to the increase in the number of confounders present in the nutrient medium. A multispectral approach needs to be used to compensate for these confounders. The CO2 laser used for these studies was wavelength tunable (9.2 to 10.8 micrometers), however, it was to unstable across wavelengths to test the multispectral approach. From this research, further NASA support was obtained to continue the work throughout the year in which a more stable light source will be used at smaller, near-infrared, wavelengths. It is anticipated that a more compact, non-invasive, optical glucose sensor will be realized which can be used with a bioreactor on future space shuttle missions. It is also anticipated that a multispectral optical sensor may be used to determine the concentration of other molecules needed within the NASA bioreactor, such as fructose and galactose.

Cote, Gerald L.↗

Continuous-Wave, Diode-Pumped, Tunable Tm,Ho:YLF Laser

Unique features include high efficiency and tunability at wavelengths near 2.067 micrometers. Continuous-wave, diode-pumped Tm,Ho:YLF laser tuned by tilting Fabry-Perot etalon and/or adjusting temperature of Tm,Ho:YLF crystal. Proposed for use in remote sensing of winds and in remote sensing of CO2 and H2O, of which many strong absorption lines over-lap laser tuning range. Range extended by tuning to wave-length between CO2 and H2O absorption peaks.

Mcguckin, Brendan T.↗

The CO2-Broadened H2O Continuum in the 100-1500 cm(sup -1) Region: Measurements, Predictions and Empirical Model

Transmission spectra of H2O+CO2 mixtures have been recorded, at 296, 325 and 366 K, for various pressures and mixture compositions using two experimental setups. Their analysis enables to retrieve values of the “continuum” absorption by the CO2-broadened H2O line wings between 100 and 1500 cm(exp -1). The results are in good agreement with those, around 1300 cm(exp -1), of the single previous experimental study available. Comparisons are also made with direct predictions based on line-shape correction factors X calculated, almost thirty years ago, using a quasistatic approach and an input H2O-CO2 intermolecular potential. They show that this model quite nicely predicts, with slightly overestimated values, the continuum over a spectral range where it varies by more than three orders of magnitude. An empirical correction is proposed, based on the experimental data, which should be useful for radiative transfer and climate studies in CO2 rich planetary atmospheres.

CO2↗

Pulsed Airborne Lidar Measurements of C02 Column Absorption

We report on airborne lidar measurements of atmospheric CO2 column density for an approach being developed as a candidate for NASA's ASCENDS mission. It uses a pulsed dual-wavelength lidar measurement based on the integrated path differential absorption (IPDA) technique. We demonstrated the approach using the CO2 measurement from aircraft in July and August 2009 over four locations. The results show clear CO2 line shape and absorption signals, which follow the expected changes with aircraft altitude from 3 to 13 km. The 2009 measurements have been analyzed in detail and the results show approx.1 ppm random errors for 8-10 km altitudes and approx.30 sec averaging times. Airborne measurements were also made in 2010 with stronger signals and initial analysis shows approx. 0.3 ppm random errors for 80 sec averaging times for measurements at altitudes> 6 km.

Abshire, James B.↗

Laboratory Spectra of CO2 Vibrational Modes in Planetary Ice Analogs

Laboratory spectra have shown that CO2 is a powerful diagnostic tool for analyzing infrared data from remote observations, as it has been detected on icy moons in the outer Solar System as well as dust grain surfaces in the interstellar medium (ISM). IR absorption band profiles of CO2 within ice mixtures containing H2O and CH3OH change with respect to temperature and mixture ratios. In this particular study, the CO2 asymmetric stretching mode near 4.3 m (2350 cm (exp-1)), overtone mode near 1.97 m (5080 cm (exp-1)), and the combination bands near 2.7 m (3700 cm (exp-1)), 2.8 m (3600 cm (exp-1)), and 2.02 m (4960 cm (exp -1)), are systematically observed in different mixtures with H2O and CH3OH in temperature ranges from 15K to 150 K. Additionally, some high-temperature deposits (T greater than 50 K) of H2O, CH3OH, and CO2 ice mixtures were performed. These data may then be used to interpret infrared observational data obtained from icy surfaces in the outer Solar System and beyond.

White, Douglas↗

Transmission of CO2 in the atmosphere of Venus for the spectral region near 7 microns

The transmission in the 7-micron 'window' of Venus was calculated for a 7-layer model atmosphere. The synthetic spectra show that radiation from the layer 20-30 km above the surface would reach the top of the atmosphere between 6.2 and 7.0 microns if there were no absorption besides the isotopic CO2 bands; for the 7.0- to 8.2-micron region, the radiating level would be located 40-50 km above the surface of Venus. The brightness temperature for the entire region is 430 K; for the above two regions it is 494 and 341 K, respectively.

Young, L. G.↗

Ground Based Observation of Isotopic Oxygen in the Martian Atmosphere Using Infrared Heterodyne Spectroscopy

Infrared heterodyne spectra of isotopic CO2 in the Martian atmosphere were obtained using the Goddard Heterodyne Instrument for Planetary Wind and Composition, HIPWAC, which was interfaced with the 3-meter telescope at the NASA Infrared Telescope Facility- Spectra were colle cted at a resolution of lambda/delta lambda=10(exp 7). Absorption fea tures of the CO2 isotopologues have been identified from which isotop ic ratios of oxygen have been determined. The isotopic ratios O-17/O -16 and O-18/O-16 in the Martian atmosphere can be related to Martian atmospheric evolution and can be compared to isotopic ratios of oxyg en in the Earth's atmosphere. Isotopic carbon and oxygen are importa nt constraints on any theory for the erosion of the Martian primordia l atmosphere and the interaction between the atmosphere and surface o r subsurface chemical reservoirs. This investigation explored the pr esent abundance of the stable isotopes of oxygen in Mars' atmospheric carbon dioxide by measuring rovibrational line absorption in isotop ic species of CO2 using groundbased infrared heterodyne spectroscopy in the vicinity of the 9.6 micron and 10.6 micron CO2 lasing bands. T he target transitions during this observation were O-18 C-12 O-16 as well as O-178 C-12 O-16 and O-16 C-113 O-16 at higher resolving power of lambda/delta lambda=10(exp 7) and with high signal-to-noise ratio (longer integration time) in order to fully characterize the absorpt ion line profiles. The fully-resolved lineshape of both the strong n ormal-isotope and the weak isotopic CO2 lines were measured simultane ously in a single spectrum.

Smith, R. L.↗

The effect of polar clouds and dust on the radiative budget of the Martian polar cap

How ozone, clouds, and airborne dust affect CO2 ice formation and sublimation is examined to determine if they help explain the asymmetry in the residual polar caps. The radiative flux striking the surface is calculated for 57 solar and 10 IR wavelength intervals from 0 to 100 microns including the scatering, absorption, and emission by O3, CO2, clouds, and dust. UV absorption by H2O, O2, HO2, and H2O2 is also included, as is Rayleigh scattering. The discrete ordinate method of Stamnes et al. (1988) treats the emission, scattering, and absorption of monochromatic radiation.

Lindner, Bernhard L.↗

Nitrogen balance for wheat canopies (Triticum aestivum cv. Veery 10) grown under elevated and ambient CO2 concentrations

We examined the hypothesis that elevated CO2 concentration would increase NO3- absorption and assimilation using intact wheat canopies (Triticum aestivum cv. Veery 10). Nitrate consumption, the sum of plant absorption and nitrogen loss, was continuously monitored for 23 d following germination under two CO2 concentrations (360 and 1000 micromol mol-1 CO2) and two root zone NO3- concentrations (100 and 1000 mmol m3 NO3-). The plants were grown at high density (1780 m-2) in a 28 m3 controlled environment chamber using solution culture techniques. Wheat responded to 1000 micromol mol-1 CO2 by increasing carbon allocation to root biomass production. Elevated CO2 also increased root zone NO3- consumption, but most of this increase did not result in higher biomass nitrogen. Rather, nitrogen loss accounted for the greatest part of the difference in NO3- consumption between the elevated and ambient [CO2] treatments. The total amount of NO3(-)-N absorbed by roots or the amount of NO3(-)-N assimilated per unit area did not significantly differ between elevated and ambient [CO2] treatments. Instead, specific leaf organic nitrogen content declined, and NO3- accumulated in canopies growing under 1000 micromol mol-1 CO2. Our results indicated that 1000 micromol mol-1 CO2 diminished NO3- assimilation. If NO3- assimilation were impaired by high [CO2], then this offers an explanation for why organic nitrogen contents are often observed to decline in elevated [CO2] environments.

Non-NASA Center↗