Photolysis of CO2 at 1849 A
Carbon dioxide photolysis at 1849 A and various pressures, suggesting gas dissociation at wavelengths with appreciable absorption
Demore, W. B.↗
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Manned Mission Planning Considerations when Using a Non-Regenerable CO2 Removal System
As the commercial spacecraft industry increases in size, there will be a corresponding increase in the number of manned spacecraft built and operationally flown each year. Industry teams for these new spacecraft will have multiple design and operational choices to make for each of these spacecraft s subsystems. The carbon dioxide (CO2) removal subsystem of the environmental control and life support system is one that presents such challenges. This paper seeks to aid industry in making design and operations choices by providing a document containing lessons learned by the Space Shuttle Program s Operations team, with specific focus given to the non-regenerable CO2 removal system currently used by the Space Shuttle. Carbon dioxide, one of the key byproducts of respiration, can lead to injury and death if allowed to build up in a spacecraft s habitable environment. Therefore, any spacecraft s environmental control and life support system must contain a method for removing this hazard. These removal systems can either be non-regenerable or regenerable. While this paper defines the difference between these types and presents a generic comparison of their capabilities, the focus is specifically on the Space Shuttle s CO2 removal systems. This will include a short discussion of the Space Shuttle s regenerable amine solid absorption system that was part of the Extended Duration Orbiter (EDO) modification, however, emphasis is given to the non-regenerable Lithium Hydroxide canister system used as the prime removal method employed by the Space Shuttle, including a discussion on why this method was chosen over a regenerable system. A full exposition is given on all of the considerations required for mission planning when using a non-regenerable CO2 removal system. Key discussion items include: airflow lessons learned, recent physiological issues related to short term and long term exposure and how lower levels may be more harmful than previously thought, lithium hydroxide dust issues, mass vs. stowage comparisons, cost, complexity considerations, operational margin considerations, timing considerations with respect to the crew s schedule, and logistical management. The conclusion of the paper finalizes the discussion and contains a listing of considerations in regards to CO2 management using a non-regenerable removal system in the near future.
DeSimpelaere, Edward↗
Airborne Measurements of Atmospheric Pressure made Using an IPDA Lidar Operating in the Oxygen A-Band
We report airborne measurements of atmospheric pressure made using an integrated path differential absorption (IPDA) lidar that operates in the oxygen A-band near 765 nm. Remote measurements of atmospheric temperature and pressure are needed for NASA s Active Sensing of CO2 Emissions Over Nights, Days, and Seasons (ASCENDS) mission to measure atmospheric CO2. Accurate measurements of tropospheric CO2 on a global scale are very important in order to better understand its sources and sinks and to improve our predictions of climate change. The goal of ASCENDS is to determine the CO2 dry mixing ratio with lidar measurements from space at a level of ~1 ppm. Analysis to date shows that with current weather models, measurements of both the CO2 column density and the column density of dry air are needed. Since O2 is a stable molecule that uniformly mixed in the atmosphere, measuring O2 absorption in the atmosphere can be used to infer the dry air density. We have developed an airborne (IPDA) lidar for Oxygen, with support from the NASA ESTO IIP program. Our lidar uses DFB-based seed laser diodes, a pulsed modulator, a fiber laser amplifier, and a non-linear crystal to generate wavelength tunable 765 nm laser pulses with a few uJ/pulse energy. The laser pulse rate is 10 KHz, and average transmitted laser power is ~20 mW. Our lidar steps laser pulses across a selected line O2 doublet near 764.7 nm in the Oxygen A-band. The direct detection lidar receiver uses a 20 cm diameter telescope, a Si APD detector in Geiger mode, and a multi-channel scalar to detect and record the time resolved laser backscatter in 40 separate wavelength channels. Subsequent analysis is used to estimate the transmission line shape of the doublet for the laser pulses reflected from the ground. Ground based data analysis allows averaging from 1 to 60 seconds to increase SNR in the transmission line shape of the doublet. Our retrieval algorithm fits the expected O2 lineshapes against the measurements and determines the atmospheric pressure by minimizing the error between the observations and model. We first demonstrated our airborne lidar during flights during summer 2010. We made several improvements and made measurements during the Ascends flights during July 2011. More information about the technique, lidar instrument, airborne measurements, and pressure estimates will be described in the presentation.
Riris, Haris↗
Space-Based Near-Infrared CO2 Measurements: Testing the Orbiting Carbon Observatory Retrieval Algorithm and Validation Concept Using SCIAMACHY Observations over Park Falls, Wisconsin
Space-based measurements of reflected sunlight in the near-infrared (NIR) region promise to yield accurate and precise observations of the global distribution of atmospheric CO2. The Orbiting Carbon Observatory (OCO) is a future NASA mission, which will use this technique to measure the column-averaged dry air mole fraction of CO2 (XCO2) with the precision and accuracy needed to quantify CO2 sources and sinks on regional scales (approx.1000 x 1000 sq km and to characterize their variability on seasonal timescales. Here, we have used the OCO retrieval algorithm to retrieve XCO2 and surface pressure from space-based Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) measurements and from coincident ground-based Fourier transform spectrometer (FTS) measurements of the O2 A band at 0.76 mm and the 1.58 mm CO2 band for Park Falls,Wisconsin. Even after accounting for a systematic error in our representation of the O2 absorption cross sections, we still obtained a positive bias between SCIAMACHY and FTS XCO2 retrievals of approx.3.5%. Additionally, the retrieved surface pressures from SCIAMACHY systematically underestimate measurements of a calibrated pressure sensor at the FTS site. These findings lead us to speculate about inadequacies in the forward model of our retrieval algorithm. By assuming a 1% intensity offset in the O2 A band region for the SCIAMACHY XCO2 retrieval, we significantly improved the spectral fit and achieved better consistency between SCIAMACHY and FTS XCO2 retrievals. We compared the seasonal cycle of XCO2 at Park Falls from SCIAMACHY and FTS retrievals with calculations of the Model of Atmospheric Transport and Chemistry/Carnegie-Ames-Stanford Approach (MATCH/CASA) and found a good qualitative agreement but with MATCH/CASA underestimating the measured seasonal amplitude. Furthermore, since SCIAMACHY observations are similar in viewing geometry and spectral range to those of OCO, this study represents an important test of the OCO retrieval algorithm and validation concept using NIR spectra measured from space. Finally, we argue that significant improvements in precision and accuracy could be obtained from a dedicated CO2 instrument such as OCO, which has much higher spectral and spatial resolutions than SCIAMACHY. These measurements would then provide critical data for improving our understanding of the carbon cycle and carbon sources and sinks.
carbon dioxide↗
Mars - Near-infrared spectral reflectance and compositional implication
Several distinct absorption features, some recognized for the first time, are evident in a newly obtained reflectance spectrum (wavelengths = 0.62-2.6 microns, reciprocal dispersion = 83) of the integral disk of Mars. The effects of Martian atmospheric CO2 have been removed from the spectrum to arrive at a reflectance spectrum that is believed to be due mostly to surface material. Absorptions, at 1.22, 1.55, and 2.05 microns are interpreted to indicate the presence of H2O ice plus high desiccated mineral hydrate, although an H2O ice phase with strongly shifted fundamental frequencies cannot be ruled out. Ferrosilicate and ferric oxide bands near and shortward of 1.0 micron are confirmed. The new observations were made on April 21-23, 1976, universal time, at the 2.24-m telescope on Mauna Kea, Hawaii, using a newly developed infrared spectrometer.
Mccord, T. B.↗
A discussion of CO and O on Venus and Mars
The absorption of solar ultraviolet radiation in the wavelength range 2000 to 2200 A by CO2 strongly reduces the dissociation rate of HCl on Venus. The Cl catalytic reaction for the rapid recombination of O and CO and the yellow coloration of the Venus haze by OCl(-) and Cl3(-) appears to be unlikely. At the time of the Martian dust storm, the dissociation of H2O in the vicinity of the surface may vanish. The increase of dissociation at high altitudes, however, can be the source of H atoms in the upper atmosphere. The H atoms from the dissociation of hydrides may catalyze the recombination of CO and O in the lower atmospheres of these planets according to the following scheme: H + CO + M yields HCO + M, and HCO + O yields H + CO2. In the case of Venus, there may be other kinds of sinks for the photodissociation products, and its chemical environment might be more complex than that of Mars.
Shimizu, M.↗
Mariner-9 based simulation of radiative convective temperature changes in the Martian dust-laden atmosphere-soil system
A numerical simulation of radiative, conductive, and convective heat transfer of the Martian dust-laden atmosphere-soil system is presented with particular emphasis given to heating/cooling in regions of sharp variation in temperature or absorption and its resultant impact on outgoing planetary spectral radiance, as measured by the Mariner 9 IRIS. Thermal coupling between the ground and atmospheric subsystems is modeled by the total heat flux balance at the interface. In the simulation procedure, local thermodynamic equilibrium (LTE) is assumed, and a combined strong-weak line transmission function permits short- and long-range exchanges of energy from the surface toward space. Direct absorption of insolation in the near-IR bands by both silicate dust and CO2 is incorporated.
Dannevik, W. P.↗
Development of tunable high pressure CO2 laser for lidar measurements of pollutants and wind velocities
The problem of laser energy extraction at a tunable monochromatic frequency from an energetic high pressure CO2 pulsed laser plasma, for application to remote sensing of atmospheric pollutants by Differential Absorption Lidar (DIAL) and of wind velocities by Doppler Lidar, was investigated. The energy extraction principle analyzed is based on transient injection locking (TIL) at a tunable frequency. Several critical experiments for high gain power amplification by TIL are presented.
Levine, J. S.↗
CO2 DIAL sensitivity studies for measurements of atmospheric trace gases
An analysis is presented of the accuracy of infrared differential absorption lidar (DIAL) measurements of trace constituents in the atmosphere. Expressions are derived for the signal-to-noise ratios applicable in the detection of a signal from a scattering cell for the cases of single-detection heterodyne detection and direct detection. Results of computer simulations of the expectation value of the measured return for various measurement conditions are presented which illustrate the sensitivities of plume measurements for horizontal range-resolved and vertical content measurements of NH3 in heterodyne and direct detection. Advantages for long-range measurements of the use of rare isotope laser frequencies, tuning by collision broadening, and closely spaced on and off frequencies are pointed out.
Brockman, P.↗
Warming Early Mars by Impact Degassing of Reduced Greenhouse Gases
Reducing greenhouse gases are once again the latest trend in finding solutions to the early Mars climate dilemma. In its current form collision induced absorptions (CIA) involving H2 and/or CH4 provide enough extra greenhouse power in a predominately CO2 atmosphere to raise global mean surface temperatures to the melting point of water provided the atmosphere is thick enough and the reduced gases are abundant enough. Surface pressures must be at least 500 mb and H2 and/or CH4 concentrations must be at or above the several percent level for CIA to be effective. Atmospheres with 1-2 bars of CO2 and 2- 10% H2 can sustain surface environments favorable for liquid water. Smaller concentrations of H2 are sufficient if CH4 is also present. If thick CO2 atmospheres with percent level concentrations of reduced gases are the solution to the faint young Sun paradox for Mars, then plausible mechanisms must be found to generate and sustain the gases. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolyis, oxidation, and escape to space. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks. In this paper we focus on impact delivered reduced gases.
Haberle, R. M.↗
The 2140 cm-1 (4.673 microns) solid CO band: the case for interstellar O2 and N2 and the photochemistry of nonpolar interstellar ice analogs
The infrared spectra of CO frozen in nonpolar ices containing N2, CO2, O2, and H2O and the UV photochemistry of these interstellar/precometary ice analogs are reported. The spectra are used to test the hypothesis that the narrow 2140 cm-1 (4.673 microns) interstellar absorption feature attributed to solid CO might be produced by CO frozen in ices containing nonpolar species such as N2 and O2. It is shown that mixed molecular ices containing CO, N2, O2, and CO2 provide a good match to the interstellar band at all temperatures between 12 and 30 K both before and after photolysis. The optical constants (real and imaginary parts of the index of refraction) in the region of the solid CO feature are reported for several of these ices. The N2 and O2 absorptions at 2328 cm-1 (4.296 microns) and 1549 cm-1 (6.456 microns), respectively, are also shown. The best matches between the narrow interstellar band and the feature in the laboratory spectra of nonpolar ices are for samples which contain comparable amounts of N2, O2, CO2, and CO. Co-adding the CO band from an N2:O2:CO2:CO = 1:5:1/2:1 ice with that of an H2O:CO = 20:1 ice provides an excellent fit across the entire interstellar CO feature. The four-component, nonpolar ice accounts for the narrow 2140 cm-1 portion of the feature which is associated with quiescent regions of dense molecular clouds. Using this mixture, and applying the most recent cosmic abundance values, we derive that between 15% and 70% of the available interstellar N is in the form of frozen N2 along several lines of sight toward background stars. This is reduced to a range of 1%-30% for embedded objects with lines of sight more dominated by warmer grains. The cosmic abundance of O tied up in frozen O2 lies in the 10%-45% range toward background sources, and it is between 1% and 20% toward embedded objects. The amount of oxygen tied up in CO and CO2 frozen in nonpolar ices can be as much as 2%-10% toward background sources and on the order of 0.2%-5% for embedded objects. Similarly 3%-13% of the carbon is tied up in CO and CO2 frozen in nonpolar ices toward field stars, and 0.2%-6% toward embedded objects. These numbers imply that most of the N is in N2, and a significant fraction of the available O is in O2 in the most quiescent regions of dense clouds. Ultraviolet photolysis of these ices produces a variety of photoproducts including CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. XCN is not produced in these experiments, placing important constraints on the origin of the enigmatic interstellar XCN feature. N2O and CO3 have not been previously considered as interstellar ice components.
NASA Discipline Exobiology↗
Optical properties of solid CO2 - Application to Mars
Using a special low-temperature cell, thick layers of solid CO2 are grown on an infrared-transparent window. The transmission spectra of solid CO2 is measured from 4000 to 360 kaysers (2.5-27.8 microns). The complex index of refraction is derived for samples of different thicknesses. Scattering in the samples is the major source of error. Away from the major absorption bands the imaginary index is very low. The absorption coefficient is of the order of 1 kayser. The emissivity in the Viking IRTM 20-micron band of a solid surface of CO2 is estimated at 0.72 + 0.17 or -0.10. Snowlike deposits have similar or lower emissivity. The results of this paper relieve the need for exceptional meteorology to explain Martian brightness temperatures below the CO2 frost point.
Ditteon, R.↗
An Efficient Single Frequency Ho:YLF Laser for IPDA Lidar Applications
A highly efficient, versatile, single frequency 2-micron pulsed laser can be used in a pulsed Differential Absorption Lidar (DIAL) / Integrated Path Differential Absorption (IPDA) instrument to make precise, high-resolution measurements to investigate sources and sinks of CO2. For a direct detection IPDA lidar, the desired 2 m Ho:YLF laser should generate 30-40 mJ pulses at the repetition rate of 100 to 200 Hz, with short pulse length (<100 ns) and better than 2% wall plug efficiency. A Tm fiber laser in-band pumped Ho:YLF laser has been developed to meet this technical challenge. This Ho:YLF laser is designed in a four mirror ring resonator with bow tie configuration, which helps to obtain high beam quality. It is end-pumped by a 40 W linearly polarized Tm fiber laser at 1.94μm. The resonator length is 1.10 meters with output coupler reflectivity at 45%. The laser crystal size is 3 x 3 x 60 mm (w, h, l) with a doping concentration of 0.5% Holmium. The laser beam and pump beam are mode-matched in the active medium. Thus, the pump and laser beams have the same confocal parameters. Mode-matching is also helpful for operating the laser in a single transverse mode. The laser beam waist is slightly less than 0.5 mm at the center of the laser crystal. Based on quasi-four level modeling, pump absorption and saturation depend on laser intensity. Laser amplification and saturation also depend on the pump intensity in the crystal. The laser is injection seeded to obtain the single frequency required by an IPDA lidar measurement. The seed beam is entered into the resonator through an output coupler. The laser is mounted on a water cooled optical bench for stable and reliable operation. The size of the optical bench is 22.16 x 9.20 x 1.25 inches. It is stiffened so that the laser can be operated in any orientation of the optical bench. This packaged Ho:YLF laser is designed for either mobile trailer or airborne platform operation. The engineering prototype Ho:YLF laser has been fully characterized to demonstrate laser performance. Figure 1 shows the laser output power as a function of pump power at different pulse repetition rates from 100 Hz to 333 Hz. The threshold of the laser is less than 14 W. The slope efficiencies are 28%, 40%, 41% and 43% for pulse repetition rates of 100, 200, 250 and 333 Hz, respectively. Maximum power increases with the pulse repetition rate. Output power of 4.2 W, 6 W, 6.7 W, and 7.7 W is achieved for pulse repetition rates of 100, 200, 250 and 333Hz, respectively. This represents the optical conversion efficiency of 16.7%, 22.4%, 23.7%, and 26.5% at these various pulse repletion rates. It is the most efficient and compact Ho:YLF laser demonstrated in the high pulse energy (>20mJ) and moderate pulse repetition rate (100's Hz) operation range. As shown in Figure 1, the maximum pulse energy at 100 Hz is 42 mJ. This is limited due to optical damage. The laser stability is characterized and found to be very stable. A relative pulse energy standard deviation of 2% was measured. The beam quality of the Ho:YLF was measured by a Spiricon infrared laser beam camera. Figure 2 shows the beam profile image of the laser. Both the X-profile of the beam (horizontal direction) and the Y-profile of the beam (vertical direction) are well fitted by a Gaussian profile. The qualitative beam quality measurement shows excellent beam quality in both axis. The M-square value for the laser beam is measured at 1.06 and 1.09 for the x and y axis respectively.-
Yu, J.↗
Studies of the airglow, the aurora, the ion and neutral composition, and the chemistry of the terrestrial atmosphere
Results obtained by rocket-borne optical spectrometry are presented. Composition measurements and auroral studies are reported. The production of N (D-2) atoms by photo-absorption processes, and by electron impact excitation of N2 are discussed along with vibrationally excited CO2(+) ions in planetary atmospheres.
Zipf, E. C., Jr.↗
Infrared heterodyne spectrometer measurements of vertical profile of tropospheric ammonia and ozone
Remote sensing of the concentration and vertical distribution of atmospheric gases has been carried out using a dual CO2 laser multichannel infrared heterodyne spectrometer (IHS). The high specificity and nearly quantum-noise-limited sensitivity of the IHS provide the capability of scanning individual signature lines of selected atmospheric constituents in the 9 to 11 micron region. A comprehensive investigation of the spectral overlap between CO2 laser local oscillator transitions and selected atmospheric constituents was performed; measurements of the atmospheric absorption of solar radiation from the ground were carried out at selected laser transitions for ammonia and ozone.
Peyton, B. J.↗
High Resolution 4.7 Micron Keck/NIRSPEC Spectra of Protostars: Ices and Infalling Gas in the Disk of L1489 IRS - 1
We explore the infrared M band (4.7 micron) spectrum of the class I protostar L1489 IRS in the Taurus Molecular Cloud. This is the highest resolution wide coverage spectrum at this wavelength of a low mass protostar observed to date (R =25,000; (Delta)v =12 km s(exp -1). A large number of narrow absorption lines of gas phase (12)CO, (13)CO, and C(sup 18)O are detected, as well as a prominent band of solid (12)CO. The gas phase (12)CO lines have red shifted absorption wings (up to 100 km s(exp -1)), which likely originate from warm disk material falling toward the central object. Both the isotopes and the extent of the (12)CO line wings are successfully fitted with a contracting disk model of this evolutionary transitional object. This shows that the inward motions seen in millimeter wave emission lines continue to within approx. 0.1 AU from the star. The amount of high velocity infalling gas is however overestimated by this model, suggesting that only part of the disk is infalling, e.g. a hot surface layer or hot gas in magnetic field tubes. The colder parts of the disk are traced by the prominent CO ice band. The band profile results from CO in 'polar' ices (CO mixed with H2O), and CO in 'apolar' ices. At the high spectral resolution, the 'apolar' component is, for the first time, resolved into two distinct components, likely due to pure CO and CO mixed with CO2, O2 and/or N2. The ices have probably experienced thermal processing in the upper disk layer traced by our pencil absorption beam: much of the volatile 'apolar' ices has evaporated, the depletion factor of CO onto grains is remarkably low (approx. 7%), and the CO2 traced in the CO band profile was possibly formed energetically. This study shows that high spectral resolution 4.7 micron observations provide important and unique information on the dynamics and structure of protostellar disks and the origin and evolution of ices in these disks.
Boogert, A. C. A.↗
Contribution of the AIRS Shortwave Sounding Channels to Retrieval Accuracy
AIRS contains 2376 high spectral resolution channels between 650/cm and 2665/cm, including channels in both the 15 micron (near 667/cm) and 4.2 micron (near 2400/cm) COP sounding bands. Use of temperature sounding channels in the 15 micron CO2 band has considerable heritage in infra-red remote sensing. Channels in the 4.2 micron CO2 band have potential advantages for temperature sounding purposes because they are essentially insensitive to absorption by water vapor and ozone, and also have considerably sharper lower tropospheric temperature sounding weighting functions than do the 15 micron temperature sounding channels. Potential drawbacks with regard to use of 4.2 micron channels arise from effects on the observed radiances of solar radiation reflected by the surface and clouds, as well as effects of non-local thermodynamic equilibrium on shortwave observations during the day. These are of no practical consequences, however, when properly accounted for. We show results of experiments performed utilizing different spectral regions of AIRS, conducted with the AIRS Science Team candidate Version 5 algorithm. Experiments were performed using temperature sounding channels within the entire AIRS spectral coverage, within only the spectral region 650/cm to 1614 /cm; and within only the spectral region 1000/cm-2665/cm. These show the relative importance of utilizing only 15 micron temperature sounding channels, only the 4.2 micron temperature sounding channels, and both, with regards to sounding accuracy. The spectral region 2380/cm to 2400/cm is shown to contribute significantly to improve sounding accuracy in the lower troposphere, both day and night.
Susskind, Joel↗
Quantifying the Hypervolatile Abundances in Jupiter-family Comet 46P/Wirtanen
We present analysis of IR and optical spectroscopy of Jupiter-family comet (JFC) 46P/Wirtanen obtained in 2019 January, when the comet had sufficient geocentric velocity to enable studies of the hypervolatiles CO and CH4, as well as [OI] emission. These species could not be studied near closest approach in mid-December because there was insufficient Doppler shift to separate the cometary emission from their corresponding telluric absorption lines. We employed the [OI] observations as a proxy for the CO2/H2O ratio, as CO2 cannot be observed directly from the ground, and space-based assets sensitive to CO2 were not able to observe 46P during this apparition. We focused our analysis on H2O, CO, CH4, C2H6, CH3OH, and CO2 (via [OI] emission). We detected strong emissions from H2O, C2H6, and CH3OH. Over the 3 nights, we found evidence for changing mixing ratios, mostly due to a variable H2O production rate. In 46P, C2H6 and CH3OH are enriched compared to cometary averages, with mixing ratios relative to H2O of ∼1% and ∼3%, respectively. Measurements of CH4 and CO have been especially rare in JFCs. We report significant 3σ upper limits on CH4/H2O<0.97% and CO/H2O<0.54%. They place CH4 being near-average or depleted, and CO being strongly depleted in 46P compared with Oort cloud comets. 46P has comparable CO/H2O to the few other measurements in JFCs, but enriched in C2H6 and CH3OH. Our inferred CO2/H2O mixing ratio is∼15%, though accounting for systematic uncertainties from the lack of knowledge of [OI] photochemistry means a value between 10% and 20% is likely. The compositional profile of46P is similar to another small, hyperactive comet: 103P/Hartley 2. The mechanism of CO2-driven water-rich ice grain production proposed for 103P/Hartley 2 may be operating on 46P as well.
Comets↗