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At least 19 records

The Cheshire-cat-like Behavior of 2nu(sub 3) Overtone of Co2 near 2.134 micron: NIR Lab Spectra of Solid CO2 in H2O and CH3OH

Infrared (IR) spectra have demonstrated that solid H2O is very common in the outer Solar System, and solid carbon dioxide (CO2) has been detected on icy satellites, comets, and planetismals throughout the outer Solar System. In such environments, CO2 and H2O must sometimes be mixed at a molecular level, changing their IR absorption features. In fact, the IR spectra of CO2-H2O mixtures are not equivalent to a linear combination of the spectra of the pure materials. Laboratory IR spectra of pure CO2 and H2O have been published but a lack of near-IR spectra of CO2-H2O mixtures has made the interpretation of outer Solar System spectra more difficult. We present near infrared (IR) spectra of CO2 in H2O and in CH3OH compared to that of pure solid CO2 and find significant differences. Peaks not present in either pure H2O or pure CO2 spectra become evident. First, the CO2 (2nu(sub 3)) overtone near 2.134 micron (4685/ cm) that is not seen in pure solid CO2 is prominent in the spectrum of a CO2/H2O = 25 mixture. Second, a 2.74 micron (3650/ cm) dangling OH feature of water (and a potentially related peak at 1.89 micron) appear in the spectra of CO2-H2O ice mixtures, but may not be specific to the presence of CO2. Other CO2 peaks display shifts in position and increased width because of intermolecular interactions with water. Changes in CO2 peak positions and profiles on warming of a CO2/H2O = 5 mixture are consistent with 'segregation' of the ice into nearly pure separate components. Absolute strengths for absorptions of CO2 in solid H2O are estimated. Similar results are observed for CO2 in solid CH3OH. Since the CO2 ( 2nu(sub 3)) overtone near 2.134 micron (4685/ cm) is not present in pure CO2 but prominent in mixtures it may be a good observational indicator of whether solid CO2 is a pure material or intimately mixed with other molecules. Significant changes in the near IR spectrum of solid CO2 in the presence of H2O and CH3OH means that the abundance of solid CO2 in the outer Solar System may have been under-estimated in those environments where solid CO2 and H2O or CH3OH are mixed.

Bernstein, Max↗

Effects of CO2 on stomatal conductance: do stomata open at very high CO2 concentrations?

Potato and wheat plants were grown for 50 d at 400, 1000 and 10000 micromoles mol-1 carbon dioxide (CO2). and sweetpotato and soybean were grown at 1000 micromoles mol-1 CO2 in controlled environment chambers to study stomatal conductance and plant water use. Lighting was provided with fluorescent lamps as a 12 h photoperiod with 300 micromoles m-2 s-1 PAR. Mid-day stomatal conductances for potato were greatest at 400 and 10000 micromoles mol-1 and least at 1000 micromoles mol-1 CO2. Mid-day conductances for wheat were greatest at 400 micromoles mol-1 and least at 1000 and 10000 micromoles mol-1 CO2. Mid-dark period conductances for potato were significantly greater at 10000 micromoles mol-1 than at 400 or 1000 micromoles mol-1, whereas dark conductance for wheat was similar in all CO2 treatments. Temporarily changing the CO2 concentration from the native 1000 micromoles mol-1 to 400 micromoles mol-1 increased mid-day conductance for all species, while temporarily changing from 1000 to 10000 micromoles mol-1 also increased conductance for potato and sweetpotato. Temporarily changing the dark period CO2 from 1000 to 10000 micromoles mol-1 increased conductance for potato, soybean and sweetpotato. In all cases, the stomatal responses were reversible, i.e. conductances returned to original rates following temporary changes in CO2 concentration. Canopy water use for potato was greatest at 10000, intermediate at 400, and least at 1000 micromoles mol-1 CO2, whereas canopy water use for wheat was greatest at 400 and similar at 1000 and 10000 micromoles mol-1 CO2. Elevated CO2 treatments (i.e. 1000 and 10000 micromoles mol-1) resulted in increased plant biomass for both wheat and potato relative to 400 micromoles mol-1, and no injurious effects were apparent from the 10000 micromoles mol-1 treatment. Results indicate that super-elevated CO2 (i.e. 10000 micromoles mol-1) can increase stomatal conductance in some species, particularly during the dark period, resulting in increased water use and decreased water use efficiency.

NASA Discipline Life Support Systems↗

Comparison of Surface and Column Variations of CO2 Over Urban Areas for Future Active Remote CO2 Sensors

High resolution in-situ CO2 measurements were recorded onboard the NASA P-3B during the DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) Field Campaign, to investigate the ability of space-based observations to accurately assess near surface conditions related to air quality. This campaign includes, Washington DC/Baltimore, MD (July 2011), San Joaquin Valley, CA (January - February 2013), Houston, TX (September 2013), and Denver, CO (July-August 2014). Each of these campaigns consisted of missed approaches and approximately two hundred vertical soundings of CO2 within the lower troposphere (surface to about 5 km). In this study, surface (0 - 1 km) and column-averaged (0 - 3.5 km) CO2 mixing ratio values from the vertical soundings in the four geographically different urban areas are used to investigate the temporal and spatial variability of CO2 within the different urban atmospheric emission environments. Tracers such as CO, CH2O, NOx, and NMHCs are used to identify the source of CO2 variations in the urban sites. Additionally, we apply nominal CO2 column weighting functions for potential future active remote CO2 sensors operating in the 1.57-microns and 2.05-microns measurement regions to convert the in situ CO2 vertical mixing ratio profiles to variations in CO2 column optical depths, which is what the active remote sensors actually measure. Using statistics calculated from the optical depths at each urban site measured during the DISCOVER-AQ field campaign and for each nominal weighting function, we investigate the natural variability of CO2 columns in the lower troposphere; relate the CO2 column variability to the urban surface emissions; and show the measurement requirements for the future ASCENDS (Active Sensing of CO2 Emissions over Nights, Days, and Seasons) in the continental U.S. urban areas.

Choi, Yonghoon↗

The Relationship Between CO2 Levels and CO2 Related Symptoms Reported on the ISS

Medical Operations, Toxicology, and the Lifetime Surveillance of Astronaut Health collaborated to assess the association of CO2 levels on board the International Space Station and USOS crew reported symptoms inflight, i.e. headache and vision changes. Private Medical Conference (PMC) documents and the weekly Space Medicine Operations Team (SMOT) Notes were used to provide a robust data set of inflight medical events. All events and non‐events were documented independent of CO2 levels and other potential contributors. Average (arithmetic mean) and single point maximum ppCO2 was calculated for the 24 hours and 7 days prior to the PMC or SMOT date and time provided by LSAH. Observations falling within the first 7 days of flight (147) were removed from the datasets analyzed to avoid confounding with Space Adaptation Syndrome. The final analysis was based on 1716 observations. For headache, 46 headaches were observed. CO2 level, age at launch, time inflight, and data source were all significantly associated with headache. In particular, for each 1 mmHg increase in CO2, the odds of a crewmember reporting a headache doubled. For vision changes, 29 reports of vision changes were observed. These observations were not found to be statistically associated with CO2 levels as analyzed. While the incidence of headache has was not high (~3%), headaches may be an indicator of underlying increases in intracranial pressure, which may result likely from the synergy between CO2‐induced cerebral vasodilatation and decreased venous drainage in microgravity. Vision changes were inconsistently reported and as a result did not align appropriately with the CO2 levels. Further analysis is needed. Our results support ongoing efforts to lower the CO2 exposure limits in spacecraft.

VanBaalen, M.↗

Progress of 2.05 μm Fiber Laser Development for CO2 DIAL Measurements of Martian CO2 and Pressure

The Decadal Survey by the US National Academy of Sciences in the United States and NASA’s Science Mission Directorate (SMD) Science Plan both require global CO2 observations for the Martian atmospheric pressure, dynamics and CO2 variations. However, there are significant observational gaps in polar regions and during nighttime for global air pressure and CO2 on Mars. Therefore, recently we proposed a new concept of Martian differential absorption lidar (DIAL) operating in the 2.05 μm CO2 absorption band for global, including poles, atmospheric CO2 and pressure observations day and night. Based on the concept, we are awarded to develop 2.05 μm fiber lasers by the NASA Planetary Instrument Concepts for the Advancement of Solar System Observations (PICASSO) Program. The laser is designed to be an all-fiber master oscillator and power amplifier (MOPA) system with laser out put of ~3 mJ at a repetition frequency of 2 kHz. The primary master oscillator (PMO) is locked to the center (2.0504280 μm) of the selected CO2 absorption line. The frequency of a second MO (SMO) is locked to that of PMO. This SMO frequency is adjustable and switched between the online (2.05044156 μm) and offline (2.05050812 μm) wavelengths. The online wavelength is optimally selected so that the CO2 absorption optical depth (AOD) is ~1.1 at 3 km and the measurement in the low Martian atmosphere has largest signal-to-noise ratio. The online wavelength can also be adjusted to a line slope location where AOD is larger to observe atmospheric pressure at higher altitudes. We will present more details about this project and instrument development.

CO2↗

Wheat response to CO2 enrichment: CO2 exchanges transpiration and mineral uptakes

When simulating canopies planted in varied densities, researchers were able to demonstrate that increase of dry matter production by enhancing CO2 quickly becomes independant of increase of leaf area, especially above leaf area index of 2; dry matter gain results mainly from photosynthesis stimulation per unit of surface (primary CO2 effect). When crop density is low (the plants remaining alone a longer time), the effects of increasing leaf surface (tillering, leaf elongation here, branching for other plants etc.) was noticeable and dry matter simulation factor reached 1.65. This area effect decreased when canopy was closed in, as the effect of different surfaces no longer worked. The stimulation of photosynthesis reached to the primary CO2 effect. The accumulation in dry matter which was fast during that phase made the original weight advantage more and more neglectible. Comparison with short term measurements showed that first order long term effect of CO2 in wheat is predictible with short term experiment, from the effect of CO2 on photosynthesis measured on reference sample.

Andre, M.↗

Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

Abel, Robert W.↗

Optical properties of CO2 ice and CO2 snow from ultraviolet to infrared: Application to frost deposits and clouds on Mars

Researchers found that it is possible to grow large clear samples of CO2 ice at Mars-like temperatures of 150-170K if a temperature controlled refrigerator is connected to an isolated two-phase pure CO2 system. They designed a chamber for transmission measurements whose optical path between the 13mm diameter window is adjustable from 1.6mm to 107mm. This will allow measurements of linear absorption down to less than 0.01 cm (exp -1). A preliminary transmission spectrum of a thick sample of CO2 ice in the near infrared was obtained. Once revised optical constants have been determined as a function of wavelength and temperature, they can be applied to spectral reflectance/emissivity models for CO2 snow surfaces, both pure and contaminated with dust and water ice, using previously established approaches. It will be useful, also, to develop an infrared scattering-emission cloud radiance model (especially as viewed from near the limb) in order to develop a strategy for the identification of CO2 cloud layers by the atmospheric infrared radiometer instrument on the Mars Observer.

Hansen, Gary B.↗

Integration of the electrochemical depolorized CO2 concentrator with the Bosch CO2 reduction subsystem

Regenerative processes for the revitalization of spacecraft atmospheres require an Oxygen Reclamation System (ORS) for the collection of carbon dioxide and water vapor and the recovery of oxygen from these metabolic products. Three life support subsystems uniquely qualified to form such an ORS are an Electrochemical CO2 Depolarized Concentrator (EDC), a CO2 Reduction Subsystem (BRS) and a Water Electrolysis Subsystem (WES). A program to develop and test the interface hardware and control concepts necessary for integrated operation of a four man capacity EDC with a four man capacity BRS was successfully completed. The control concept implemented proved successful in operating the EDC with the BRS for both constant CO2 loading as well as variable CO2 loading, based on a repetitive mission profile of the Space Station Prototype (SSP).

Schubert, F. H.↗

Optical properties of CO2 ice and CO2 snow in the ultraviolet, visible, and infrared

The project was to measure the optical constants of CO2 ice in the spectral regions of weak absorption. Many previous measurements had been made by others in the strong absorption bands, but the weak regions had been poorly measured or not measured at all. In these regions the emissivity of CO2 frost and CO2 clouds is quite sensitive to particle sizes and to the value of the absorption coefficient, so the new measurements will have applications to energy budget and remote sensing of the Martian surface and atmosphere. During the time period covered by this grant, a method was developed for growing clear crystals of CO2, 4 cm in length. An apparatus was constructed for accurate measurement of spectral transmission through these crystals, for wavelengths 0.18-3.8 micrometers, covering the near-ultraviolet, visible, and near-infrared regions, bounded by the strong ultraviolet absorption and the 4.3-micrometer band. Our new best estimate of the spectral absorption coefficient (expressed as imaginary refractive index) is shown. It is a composite result of many measurements on dozens of crystals. Now that we have a good dataset for the shortwave absorption spectrum, the focus of the research has moved to the thermal infrared, for which a Fourier Transform interferometer has been adapted for use with C02-ice crystals.

Warren, Stephen↗

A theoretical study of Mg(CO2)n(+) and Sr(CO2)n(+) for n = 1 and 2 and Mg2CO2(+)

The structure and binding energies are determined for Mg(CO2)n(+) and Sr(CO2)n(+) for n = 1 and 2. We also consider Mg2(+) and Mg2CO2(+) to compare the binding of CO2 to a single metal ion with the binding to a diatomic ion. The vertical excitation energies are computed for all species. The potential energy curves for the low-lying states of Mg2(+) are reported. The MgCO2(+) results are in good agreement with the experimental results of Duncan and co-workers.

Sodupe, Mariona↗

Modeling of collision induced absorption spectra of CO2-CO2 pairs for planetary atmosphere of Venus

The objective of the proposal was to model the rototranslational and rotovibrational collision induced absorption spectral bands of importance for the radiative transfer analysis of the atmosphere of Venus. Our main task has involved CO2 pairs. The approach is not straightforward: whereas computational techniques to compute CIA spectra of small linear molecules exist, and were successfully applied to molecules like H2 or N2, they fail when applied to large molecules like CO2. For small molecules one can safely assume that the interaction potential is isotropic. The same approximation does not work for CO2, and when employed, it gives an incorrect band shape and only 50 percent of the CIA intensity.

Borysow, Aleksandra↗

Excitation of CO2/+/ by electron impact on CO2

Consideration of a discrepancy concerning the correct value of the cross section for excitation of the CO2(+) B state by electron impact on CO2. It is suggested that the reason for the disparate results obtained by various authors for the B state can be traced to a calibration error due to scattered light. In particular, the tungsten filament lamps used in the experiments cited have very low intensity at wavelengths below 3000 A where the B state emissions occur, so that even a small amount of scattered light in the spectrometer will produce a large error in the measured cross section. In a remeasurement of the cross section for excitation of the B state at an energy of 150 eV it was found that at 2900 A the scattered light signal, if uncorrected for, would introduce an error of about 50%.

Mentall, J. E.↗

Temperature dependence of vibrational relaxation in the HF, DF, HF-CO2, and DF-CO2 systems

The laser excited fluorescence method has been employed to determine rate constants for V to V, R and V to R, T relaxation HF (nu = 1) and DF(nu = 1) by CO2 over the temperature range from 295 to 670 K. The self-deactivation rates for HF(nu = 1) and DF(nu = 1) by ground state molecules and the rate of V to V, R transfer from HF(nu = 1) and DF(nu = 1) to the CO2 (00/0/1) state exhibit a marked decrease with increasing temperature. The results provide additional evidence for the conversion of the large vibrational energy defects of the present systems into rotational motion of the hydrogen halide under the influence of a sizable attractive intermolecular potential well.

Lucht, R. A.↗

Temperature dependence of vibrational relaxation in the HF-DF, HF-CO2, and DF-CO2 systems. II

Measurements of vibrational energy transfer probabilities are presented for the temperature range 205-360 K for HF-DF, HF-CO2, and DF-CO2 gas mixtures. The present results provide an accurate determination of the inverse temperature dependence of the energy transfer probabilities exhibited by these systems. Large deactivation effects caused by HF (DF) polymers were observed for temperatures below 220 K.

Lucht, R. A.↗

Comparative Analysis of Alternative Spectral Bands of CO2 and O2 for the Sensing of CO2 Mixing Ratios

We performed comparative studies to establish favorable spectral regions and measurement wavelength combinations in alternative bands of CO2 and O2, for the sensing of CO2 mixing ratios (XCO2) in missions such as ASCENDS. The analysis employed several simulation approaches including separate layers calculations based on pre-analyzed atmospheric data from the modern-era retrospective analysis for research and applications (MERRA), and the line-byline radiative transfer model (LBLRTM) to obtain achievable accuracy estimates as a function of altitude and for the total path over an annual span of variations in atmospheric parameters. Separate layer error estimates also allowed investigation of the uncertainties in the weighting functions at varying altitudes and atmospheric conditions. The parameters influencing the measurement accuracy were analyzed independently and included temperature sensitivity, water vapor interferences, selection of favorable weighting functions, excitations wavelength stabilities and other factors. The results were used to identify favorable spectral regions and combinations of on / off line wavelengths leading to reductions in interferences and the improved total accuracy.

Pliutau, Denis↗

Constraining Fossil Fuel CO2 Emissions from Urban Area Using OCO-2 Observations of Total Column CO2

Satellite observations of the total column dry-air CO2(XCO2) are expected to support the quantification and monitoring of fossil fuel CO2 (ffCO2) emissions from urban areas. We evaluate the utility of the Orbiting Carbon Observatory 2 (OCO-2) XCO2 retrievals to optimize whole-city emissions, using a Bayesian inversion system and high-resolution transport modeling. The uncertainties of constrained emissions related to transport model, satellite measurements, and local biospheric fluxes are quantified. For the first two uncertainty sources, we examine cities of different landscapes: “plume city” located in relatively flat terrain, represented by Riyadh and Cairo; “basin city” located in basin terrain, represented by Los Angeles (LA). The retrieved scaling factors of emissions and their uncertainties show prominent variabilities from track to track, due to the varying meteorological conditions and relative locations of the tracks transecting plumes. To explore the performance of multiple tracks in retrieving emissions, pseudo data experiments are carried out. The estimated least number of tracks required to constrain the total emissions for Riyadh (<10% uncertainty), Cairo (<10%), and LA (<5%) are 5, 8, and 7, respectively. Additionally, to evaluate the impact of biospheric fluxes on derivation of the ffXCO2 enhancements, we conduct simulations for Pearl River Delta metropolitan area. Significant fractions of local XCO2 enhancements associated with local biospheric XCO2 variations are shown, which potentially lead to biased estimates of ffCO2 emissions. We demonstrate that satellite measurements can be used to improve urban ffCO2 emissions with a sufficient amount of measurements and appropriate representations of the uncertainty components.

Xinxin Ye↗