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Asymmetric Warming/Cooling Response to CO2 Increase/Decrease Mainly Due to Non-Logarithmic Forcing, not Feedbacks

We explore the CO2 dependence of effective climate sensitivity (SG) with symmetric abrupt and transient CO2 forcing, spanning the range 1/8×, 1/4×, 1/2×, 2×, 4×, and 8×CO2, using two state-of-the-art fully coupled atmosphere-ocean-sea-ice-land models. In both models, under abrupt CO2 forcing, we find an asymmetric response in surface temperature and SG. The surface global warming at 8×CO2 is more than one third larger than the corresponding cooling at 1/8×CO2, and SG is CO2 dependent, increasing non-monotonically from 1/8×CO2 to 8×CO2. We find similar CO2 dependence in the transient runs, forced with -1%yr−1CO2 and +1%yr−1CO2 up to 1/8×CO2 and 8×CO2, respectively. The non-logarithmic radiative forcing – not the changing feedbacks – primarily explains the dependence of SG on CO2, particularly at low CO2 levels. The changing feedbacks, however, explain SG’s non-monotonic behavior.

climate sensitivity↗

CO2 exchange in the Hudson Bay lowlands: Community characteristics and multispectral reflectance properties

Net ecosystem CO2 exchange was measured during the 1990 growing season (June to August) along a transect starting 10 km inland from James Bay and extending 100 km interior to Kinosheo Lake, Ontario. Sites were chosen in three distinct areas: a coastal fen, an interior fen, and a bog. For the most productive sites in the bog, net daily uptake rates reached a maximum of 2.5 g C-CO2 m(exp -2)/d with an area-weighted exchange of 0.3 g C-CO2 m(exp -2)/d near midsummer. This site was estimated to be a net carbon source of 9 g C-CO2 m(exp -2) to the atmosphere over a 153-day growing season. The interior fen was less productive on a daily basis with a net maximum uptake of 0.5 g C-CO2 m(exp -2)/d and with corresponding area-weighted uptake of 0.1 g C-CO2 m(exp -2)/d during midsummer. Early and late season release of carbon to the atmosphere resulted in a net loss of 21 g C-CO2 m(exp -2) over the growing season from this site. The coastal fen was the most productive site with uptake rates peaking near 1.7 g C-CO2 m(exp -2)/d which corresponded to an area-weighted uptake of 0.8 g C-CO2 m(exp -2)/d during midsummer and an estimated net uptake of 6 g C-CO2 m(exp -2) for the growing season. Associated with net CO2 exchange measurements, multispectral reflectance properties of the sites were measured over the growing season using portable radiometers. These properties were related to exchange rates with the goal of examining the potential for satellite remote sensing to monitor biosphere/atmosphere CO2 exchange in this biome. The normalized difference vegetation index (NDVI) computed from surface reflectance was correlated with net CO2 exchange for all sites with the exception of areas with large proportions of Sphagnum moss cover. These mosses have greater near-infrared reflectance than typical surrounding vegetation and may require special adjustment for regional exchange/remote sensing applications.

Whiting, Gary J.↗

Monitoring of Volcanogenic CO2-Induced Tree Kills with AVIRIS Image Data at Mammoth Mountain, California

Elevated cold CO2 emissions from the flank of Mammoth Mountain volcano on the southwest rim of the Long Valley Caldera, eastern California, have been the cause of over 100 acres of dead trees in that area since 1990. The source of the CO2 gas is thought to be from one or more magmatic intrusion(s) beneath Mammoth Mountain and is probably related to a period of seismic unrest that began in 1989. The gas rises to the surface probably from depths of a few kilometers, along faults and fracture zones. The gas is at ambient temperature and diffuses from the soil rather than discharging from distinct vents. Typically, soil gas concentrations in tree-kill areas range from 10% to over 90% CO2 by volume, as compared to normal background of < 1% in healthy forest. The gas composition is predominantly CO2 mixed with air (sulfur gases are not elevated), and C and He isotopic ratios are consistent with a magmatic origin for the gas. The total CO2 emission has been estimated at 1200 tons/day, comparable to the emissions at Kilauea. Some of the dead trees are as old as 250 years, suggesting that similar anomalous gas discharge has not occurred over the previous few hundred years. The delta C-13/12 ratio in the Mammoth Mountain CO2 emission averages about -4.5 (PDB standard). This is consistent with a mantle source for the carbon. However, the large volume of the emission suggests that not all of the CO2 is necessarily being generated from the 1989 intrusion. The voluminous gas could be leaking from a vapor-rich zone, capped by an impermeable layer, that was supplied CO2 from degassing of many small magma bodies that intruded beneath the mountain over a period of decades or centuries. Earthquakes in 1989 could have fractured the capping layer and provided pathways for the escape Of CO2 to the surface. Alternatively, some of the CO2 could be derived from contact metamorphism of carbonate rocks intruded by magma. Carbonate-bearing Paleozoic roof pendents crop out in close proximity to Mammoth Mountain. It is possible that similar rocks could occur at depth beneath Mammoth Mountain, and could have contributed CO2 from thermal decomposition caused from recent intrusions. We hope to determine the C-13/12 ratio of a suite of samples to demonstrate if the carbonate rocks could be the source of at least part of the 1990-97 CO2 emission. To better understand the behavior of the CO2 gas, we have used hyperspectral imagery data of Mammoth Mountain acquired from the Airborne Visual/Infrared Imaging Spectrometer (AVIRIS) to map out areas of dead trees. The areas of tree kill have increased in size from about 50 acres in 1994 to about 100 acres in 1997. Tree kill is the major surface manifestation of the carbon dioxide flux at Mammoth Mountain, is widely dispersed, and has been cursorily mapped by regular field mapping techniques in the area. Initial investigations using airborne digital imagery from the Thematic Mapper Simulator (NS001) and AVIRIS instruments have shown extremely encouraging results for complete delineation of the vegetation anomalies. The most successful maps (when compared with ground truth) were developed using AVIRIS data with spectral angle mapper and matched filter algorithms with a data set that was reduced to maximum variance via the minimum noise fraction transformation. The result of this work is a series of maps that show the tree kill areas occurring in an halo-pattern surrounding the base of Mammoth Mountain. We are applying these same techniques to earlier AVIRIS images of Mammoth Mountain to examine the progression of the tree kill areas over time. Temporal maps of the tree kill areas may assist in constructing a picture of the structure beneath Mammoth Mountain.

Hausback, Brian P.↗

Using CO2:CO Correlations to Improve Inverse Analyses of Carbon Fluxes

Observed correlations between atmospheric concentrations of CO2 and CO represent potentially powerful information for improving CO2 surface flux estimates through coupled CO2-CO inverse analyses. We explore the value of these correlations in improving estimates of regional CO2 fluxes in east Asia by using aircraft observations of CO2 and CO from the TRACE-P campaign over the NW Pacific in March 2001. Our inverse model uses regional CO2 and CO surface fluxes as the state vector, separating biospheric and combustion contributions to CO2. CO2-CO error correlation coefficients are included in the inversion as off-diagonal entries in the a priori and observation error covariance matrices. We derive error correlations in a priori combustion source estimates of CO2 and CO by propagating error estimates of fuel consumption rates and emission factors. However, we find that these correlations are weak because CO source uncertainties are mostly determined by emission factors. Observed correlations between atmospheric CO2 and CO concentrations imply corresponding error correlations in the chemical transport model used as the forward model for the inversion. These error correlations in excess of 0.7, as derived from the TRACE-P data, enable a coupled CO2-CO inversion to achieve significant improvement over a CO2-only inversion for quantifying regional fluxes of CO2.

Palmer, Paul I.↗

Calibrating Laser Gas Measurements by Use of Natural CO2

An improved method of calibration has been devised for instruments that utilize tunable lasers to measure the absorption spectra of atmospheric gases in order to determine the relative abundances of the gases. In this method, CO2 in the atmosphere is used as a natural calibration standard. Unlike in one prior calibration method, it is not necessary to perform calibration measurements in advance of use of the instrument and to risk deterioration of accuracy with time during use. Unlike in another prior calibration method, it is not necessary to include a calibration gas standard (and the attendant additional hardware) in the instrument and to interrupt the acquisition of atmospheric data to perform calibration measurements. In the operation of an instrument of this type, the beam from a tunable diode laser or a tunable quantum-cascade laser is directed along a path through the atmosphere, the laser is made to scan in wavelength over an infrared spectral region that contains one or two absorption spectral lines of a gas of interest, and the transmission (and, thereby, the absorption) of the beam is measured. The concentration of the gas of interest can then be calculated from the observed depth of the absorption line(s), given the temperature, pressure, and path length. CO2 is nearly ideal as a natural calibration gas for the following reasons: CO2 has numerous rotation/vibration infrared spectral lines, many of which are near absorption lines of other gases. The concentration of CO2 relative to the concentrations of the major constituents of the atmosphere is well known and varies slowly and by a small enough amount to be considered constant for calibration in the present context. Hence, absorption-spectral measurements of the concentrations of gases of interest can be normalized to the concentrations of CO2. Because at least one CO2 calibration line is present in every spectral scan of the laser during absorption measurements, the atmospheric CO2 serves continuously as a calibration standard for every measurement point. Figure 1 depicts simulated spectral transmission measurements in a wavenumber range that contains two absorption lines of N2O and one of CO2. The simulations were performed for two different upper-atmospheric pressures for an airborne instrument that has a path length of 80 m. The relative abundance of CO2 in air was assumed to be 360 parts per million by volume (approximately its natural level in terrestrial air). In applying the present method to measurements like these, one could average the signals from the two N2O absorption lines and normalize their magnitudes to that of the CO2 absorption line. Other gases with which this calibration method can be used include H2O, CH4, CO, NO, NO2, HOCl, C2H2, NH3, O3, and HCN. One can also take advantage of this method to eliminate an atmospheric-pressure gauge and thereby reduce the mass of the instrument: The atmospheric pressure can be calculated from the temperature, the known relative abundance of CO2, and the concentration of CO2 as measured by spectral absorption. Natural CO2 levels on Mars provide an ideal calibration standard. Figure 2 shows a second example of the application of this method to Mars atmospheric gas measurements. For sticky gases like H2O, the method is particularly powerful, since water is notoriously difficult to handle at low concentrations in pre-flight calibration procedures.

Webster, Chris↗

Lidar Observations of Atmospheric CO2 Column During 2014 Summer Flight Campaigns

Advanced knowledge in atmospheric CO2 is critical in reducing large uncertainties in predictions of the Earth' future climate. Thus, Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS) from space was recommended by the U.S. National Research Council to NASA. As part of the preparation for the ASCENDS mission, NASA Langley Research Center (LaRC) and Exelis, Inc. have been collaborating in development and demonstration of the Intensity-Modulated Continuous-Wave (IM-CW) lidar approach for measuring atmospheric CO2 column from space. Airborne laser absorption lidars such as the Multi-Functional Fiber Laser Lidar (MFLL) and ASCENDS CarbonHawk Experiment Simulator (ACES) operating in the 1.57 micron CO2 absorption band have been developed and tested to obtain precise atmospheric CO2 column measurements using integrated path differential absorption technique and to evaluate the potential of the space ASCENDS mission. This presentation reports the results of our lidar atmospheric CO2 column measurements from 2014 summer flight campaign. Analysis shows that for the 27 Aug OCO-2 under flight over northern California forest regions, significant variations of CO2 column approximately 2 ppm) in the lower troposphere have been observed, which may be a challenge for space measurements owing to complicated topographic condition, heterogeneity of surface reflection and difference in vegetation evapotranspiration. Compared to the observed 2011 summer CO2 drawdown (about 8 ppm) over mid-west, 2014 summer drawdown in the same region measured was much weak (approximately 3 ppm). The observed drawdown difference could be the results of the changes in both meteorological states and the phases of growing seasons. Individual lidar CO2 column measurements of 0.1-s integration were within 1-2 ppm of the CO2 estimates obtained from on-board in-situ sensors. For weak surface reflection conditions such as ocean surfaces, the 1- s integrated signal-to-noise ratio (SNR) of lidar measurements at 11 km altitude reached 376, which was equivalent to a 10-s CO2 error 0.33 ppm. For the entire processed 2014 summer flight campaign data, the mean differences between lidar remote sensed and in-situ estimated CO2 values were about -0.013 ppm. These results indicate that current laser absorption lidar approach could meet space measurement requirements for CO2 science goals.

Lin, Bing↗

The Effect of Europa and Enceladus Analog Seawater Composition on Isotopic Measurements of Volatile CO2

Science goals for icy ocean worlds missions include characterizing the chemical compositionof the surface and interior using remote sensing and in situ techniques. The next class of flightmass spectrometers for these missions will obtain compositional identifications and isotope ratiomeasurements of volatiles evolved from the ice surface (exosphere) and plumes. These massspectra will be combined with data from other flight instruments to infer the composition of theinterior from volatiles. To ensure accurate interpretation of these measurements, it is critical toverify whether the fundamental assumption that volatiles observed in icy ocean world exospheresor plumes will be a direct reflection of the sub-ice ocean. The present study evaluates whether isotopologues from an initial CO2 gas fractionate by interacting with seawater (brine) of varyingsalt composition and concentration. δ13CCO2 are affected by the pH of the brine and subsequentspeciation of {CO2}, where {CO2} represents the combination of CO2, H2CO3, HCO3-, and CO32-.{CO2} for low pH brines hypothesized for Europa will preferentially speciate as CO2. Analyzedδ13CCO2 for low pH brines are within error of the original δ13CCO2, demonstrating that volatile CO2in a low pH system will be a direct reflection of the original CO2. However, Europa’s radiativeenvironment and rapid depressurization due to plume ejection may impose fractionation effects.In contrast, high pH systems relevant to Enceladus or a more alkaline Europa are expected toform all carbonate species, while favoring speciation as HCO3-. High pH brines in theseexperiments include both an original CO2 gas and an isotopically distinct HCO3- (from NaHCO3salt). These alkaline experiments demonstrate that δ13CCO2 values are highly variable, and dependon the concentration of the dominant carbonate species, (Na)HCO3-. Mass balance estimatesindicate that measured δ13CCO2 is a thermodynamically predictable mixture of both carbonsources, suggesting that measurements of δ13C at Enceladus would directly reflect of the sourcesof CO2 and carbonate buffering in the ocean. δ18O measurements for CO2 interacting with KCland MgCl2 follow established models for δ18O-ionic strength. CO2 interacting with MgSO4,Na2SO4, and NaCl demonstrate an offset from established δ18O-ionic strength models dependingon the concentration of initial CO2. These results suggest that current predictive models for δ18Oin brines need to be resolved for changing concentrations of CO2

Ocean Worlds↗

Effects of surface temperature and clouds on the CO2 forcing

The effects of surface temperature and clouds on the CO2 forcing are studied, based on use of the Colorado State University GCM. Results are reported from a pair of perpetual July simulations in which the sea surface temperatures differ by 4 K. The precipitable water is about 1.5 times larger in the warm run. The increased water vapor concentration amplifies the radiative effects of CO2, leading to greater CO2 forcing in the warm run. In the colder run the globally averaged reduction in upward longwave radiation due to a doubling of CO2 is 4.3 W/sq m at the level of maximum forcing, or the 'CO2 tropopause'. Above and below this level the CO2 forcing decreases, resulting in a net tropospheric warming of 0.033 K/day and a net stratospheric cooling. In the warm run the CO2 forcing at the CO2 tropopause is 4.6 W/sq m, and is associated with a tropospheric warming of 0.04 K/day. The clear-sky CO2 forcing at the CO2 tropopause is 5.0 W/sq m in the cold run, and 5.2 W/sq m in the warm run. By blocking infrared radiation that would otherwise be blocked by CO2, the clouds reduce the CO2 forcing of the surface-troposphere system by 0.66 W/sq m in the cold run, and by 0.59 W/sq m in the warm run.

Schmitt, Christina↗

Spectral identification of chemisorbed CO2 and application to Mars analog materials

The goal of this work is to identify the spectral signature of chemisorbed CO2, to test the efficacy of carbonate formation on Mars-analog materials via CO2 chemisorption, and to identify the surface-chemical characteristics of good chemisorbents, with the intent of assessing the possible geochemical importance of CO2 chemisorption as a quasipermanent CO2 sink in the Martian environment. Our approach is to search for infrared spectral bands that result from chemisorption of CO2 molecules onto chemical reagents and Mars-analog materials, and to identify the salient differences in adsorbents that favor strong, permanent CO2 chemisorption. The total amount of CO2 in the early Martian atmosphere, and consequent surface temperatures, are unknown. A CO2 greenhouse may not have been an adequate mechanism under any circumstances; however, it if were, then most of that CO2 must still be in the near-surface environment; no escape mechanism that could remove it after the decline of channeling has been identified. The only plausible reservoir is carbonate, and there are various remote sensing techniques that can be used to search for it. We are investigating CO2 chemisorption as a permanent CO2 sink, and to aid in interpretation of remotely sensed IR spectra of Mars. A common effect reported in CO2 adsorption studies is the formation of a layer of carbonate or bicarbonate anions on adsorbents that have OH- groups available on their surfaces. Inorganic hydroxyls occur on phyllosilicates, amorphous silicates, metal oxides and hydroxides; it is the most abundant and reactive surface functional group on the surfaces of terrestrial silicates. The process responsible for the reaction is chemisorption. Chemisorption is distinguished from physical adsorption in that there is a transfer of electrons between species, and the formation of a chemical bond. The heat of chemisorption is typically of the same order as heats of chemical reaction (i.e., a few hundred to a few thousand kJ/mole), as opposed to heats of physical adsorption (a few kJ per mole). Chemisorption is an activated process that is promoted by an increase in temperature - quite the opposite of physical adsorption. Chemisorption is not reversible in the sense that physical adsorption is.

Zent, A. P.↗

An observational search for CO2 ice clouds on Mars

CO2 ice clouds were first directly identified on Mars by the Mariner 6 and 7 infrared spectrometer limb scans. These observations provided support for early theoretical modeling efforts of CO2 condensation. Mariner 9 IRIS temperature profiles of north polar hood clouds were interpreted as indicating that these clouds were composed of H2O ice at lower latitudes and CO2 ice at higher latitudes. The role of CO2 condensation on Mars has recently received increased attention because (1) Kasting's model results indicated that CO2 cloud condensation limits the magnitude of the proposed early Mars CO2/H2O greenhouse, and (2) Pollack el al.'s GCM results indicated that the formation of CO2 ice clouds is favorable at all polar latitudes during the fall and winter seasons. These latter authors have shown that CO2 clouds play an important role in the polar energy balance, as the amount of CO2 contained in the polar caps is constrained by a balance between latent heat release, heat advected from lower latitudes, and thermal emission to space. The polar hood clouds reduce the amount of CO2 condensation on the polar caps because they reduce the net emission to space. There have been many extensive laboratory spectroscopic studies of H2O and CO2 ices and frosts. In this study, we use results from these and other sources to search for the occurrence of diagnostic CO2 (and H2O) ice and/or frost absorption features in ground based near-infrared imaging spectroscopic data of Mars. Our primary goals are (1) to try to confirm the previous direct observations of CO2 clouds on Mars; (2) to determine the spatial extent, temporal variability, and composition (H2O/CO2 ratio) of any clouds detected; and (3) through radiative transfer modeling, to try to determine the mean particle size and optical depth of polar hood clouds, thus, assessing their role in the polar heat budget.

Bell, James F., III↗

Growth, pod, and seed yield, and gas exchange of hydroponically grown peanut in response to CO2 enrichment

The effects of elevated CO2 on growth, pod, and seed yield, and gas exchange of 'Georgia Red' peanut (Arachis hypogaea L.) were evaluated under controlled environmental conditions. Plants were exposed to concentrations of 400 (ambient), 800, and 1200 micromoles mol-1 CO2 in reach-in growth chambers. Foliage fresh and dry weights increased with increased CO2 up to 800 micromoles mol-1, but declined at 1200 micromoles mol-1. The number and the fresh and dry weights of pods also increased with increasing CO2 concentration. However, the yield of immature pods was not significantly influenced by increased CO2. Total seed yield increased 33% from ambient to 800 micromoles mol-1 CO2, and 4% from 800 to 1200 micromoles mol-1 CO2. Harvest index increased with increasing CO2. Branch length increased while specific leaf area decreased linearly as CO2 increased from ambient to 1200 micromoles mol-1. Net photosynthetic rate was highest among plants grown at 800 micromoles mol-1. Stomatal conductance decreased with increased CO2. Carboxylation efficiency was similar among plants grown at 400 and 800 micromoles mol-1 and decreased at 1200 micromoles mol-1 CO2. These results suggest that CO2 enrichment from 400 to 800 micromoles mol-1 had positive effects on peanut growth and yield, but above 800 micromoles mol-1 enrichment seed yield increased only marginally.

NASA Discipline Life Support Systems↗

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.↗

Laser Sounder for Measuring Atmospheric CO2 Concentrations: Progress Toward Ascends

The next generation of space-based, active remote sensing instruments for measurement of tropospheric CO2 promises a capability to quantify global carbon sources and sinks at regional scales. Active (laser) methods will extend CO2 measurement coverage in time, space, and perhaps precision such that the underlying mechanisms for carbon exchange at the surface can be understood with .sufficient detail to confidently project the future of carbon-climate interaction and the influence of remediative policy actions. The recent Decadal Survey for Earth Science by the US National Research Council has recommended such a mission called the Active Sensing of CO2 Emissions over Nights, Days, and Seasons (ASCENDS) for launch in 2013-2016. We have been developing a laser technique for measurement of tropospheric CO2 for a number of years. Our immediate goal is to develop and demonstrate the method and instrument technology that will permit measurements of the CO2 column abundance over a horizontal path and from aircraft at the few-ppmv level. Our longer-term goal is to demonstrate the required capabilities of the technique, develop a space mission approach, and design the instrument for an ASCENDS-type mission. Our approach is to use a dual channel laser absorption spectrometer (i.e., differential absorption in altimeter mode), which continuously measures from a near-polar circular orbit. We use several co-aligned tunable fiber laser transmitters allowing simultaneous measurement of the absorption from a CO2 line in the 1570 nm band, O2 extinction in the oxygen A-band (near 765 nm), and aerosol backscatter in the same measurement path. We measure the energy of the laser echoes at nadir reflected from land and water surfaces, day and night. The lasers have spectral widths much narrower than the gas absorption lines and are turned on and off the selected CO2 and O2 lines at kHz rates. The gas extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on and off-line singnals via the DIAL technique. We used pulsed laser signals, photon counting detectors, and time gating to isolate the laser returns from the surface, and to reject photons scattered from thin clouds and aerosols. High signal-to-noise ratios are required and the CO2 estimates can be sensitive to small drifts or other errors in the instrument, so the absorption estimates need to be quite stable for hours. We have constructed a breadboard version of the CO2 sensor that uses a low power fiber laser and a 20 cm diameter telescope. We have used it to make measurements of CO2 absorption in the laboratory and over 200-m to 2-km long open horizontal paths. These have been done in several sessions extending over multiple days, which allows us to assess the measurement stability and to compare absorption variations to readings from an external in situ CO2 sensor. We have also calculated characteristics of the technique for space including its expected measurement performance for different modulation types, and have performed an initial space mission accommodation study. We sill describe these results in the presentation.

Abshire, J. B.↗

Acute and Chronic Exposure to CO2 in Space Flight

Spacecraft and space stations, similar to other habitable confined spaces such as submarines, need to provide a breathable atmosphere for their inhabitants. The inevitable production of CO2 during respiration necessitates life support systems that "scrub" the atmosphere and lower CO2 levels. Due to operational limitations associated with space flight (limited mass, volume, power, and consumables) CO2 is not scrubbed down to its terrestrial equivalent of 0.03% CO2 (ppCO2 of 0.23 mmHg), but is kept below 0.7% (ppCO2 of 5.3 mmHg), a level established in NASA s 180-day mission Spacecraft Maximum Allowable Concentration (SMAC) to be safe and unlikely to cause symptoms. Reports of space flight crewmembers becoming symptomatic with headaches, fatigue, and malaise at levels below those known to cause such symptoms terrestrially has prompted studies measuring the levels of CO2 on both the space shuttle and the space station. Data from cabin atmosphere sampling were collected on space shuttle missions STS-113, STS-122, STS-123, and International Space Station Expeditions 12-15 and 17, and the measured CO2 levels were then correlated to symptoms reported by the crew. The results indicate that a correlation exists between CO2 levels and symptomatology, however causality cannot be established at this time. While the short-term effects of elevated CO2 exposure are well known terrestrially, less is known regarding potential long-term effects of prolonged exposure to a CO2-rich environment or how the physiological changes caused by microgravity may interact with such exposures. Other challenges include limitations in the CO2 monitors used, lack of convection in the microgravity environment, and formation of localized CO2 pockets. As it is unclear if the unique environment of space increases sensitivity to CO2 or if other confounding factors are present, further research is planned to elucidate these points. At the same time, efforts are underway to update the SMAC to a lower level

Alexander, D.↗

Pulsed Lidar Measurements of Atmospheric CO2 Column Absorption in the ASCENDS 2011 Airborne Campaign

We have previously demonstrated an efficient pulsed, wavelength-resolved IPDA lidar technique for measuring the tropospheric CO2 concentrations as a candidate for NASA's ASCENDS mission. Our team participated in the 2010 ASCENDS airborne campaigns we flew airborne version of the CO2 and O2 lidar on the NASA DC-8. The CO2 lidar measures the atmospheric backscatter profiles and shape of the 1572.33 nm absorption line using 250 mW average laser power, 30 wavelength samples per scan and 300 scans per second. Most flights had 5-6 altitude steps to greater than 12 km, and clear CO2 line shapes were observed at all altitudes. Our post-flight analysis estimated the Iidar range and pulse energies at each wavelength every second. We then solved for the best-fit CO2 absorption line shape, and calculated the Differential Optical Depth (DOD) at the line peak. We compared these to CO2 DODs calculated from spectroscopy based on HITRAN 2008 and the conditions from airborne in-situ readings. Analysis of the 2010 measurements over the Pacific Ocean and Lamont OK shows the expected -linear change of the peak DOD with altitude. For measurements at altitudes greater than 6 km the random errors were approximately 0.3 ppm for 80 sec averaging times. After the 2010 flights we improved the airborne lidar's scan uniformity, calibration and receiver sensitivity. Our team participated in the seven ASCENDS science flights during late July and August 2011. These flights were made over a wide variety of surface and cloud conditions near the US, including over the central valley of California, over several mountain ranges, over both broken and solid stratus cloud deck over the Pacific Ocean, snow patches on mountain tops, over thin and broken clouds above the US Southwest and Iowa, and over forests near the WLEF tower in Wisconsin. Analyses show the retrievals of lidar range and CO2 column absorption, as wen as estimates of CO2 mixing ratio worked well when measuring over topography with rapidly changing height and reflectivity, through thin clouds and to stratus cloud tops. For regions where the CO2 concentration was relatively constant, the measured CO2 absorption profile (averaged for 50 sec) matched the predicted profile to better than 1% RMS error for all flight altitudes. For 1 & 10 second averaging, the scatter in the retrievals was limited by signal shot noise (i.e. the sigual photon count). Analysis to date shows the decrease in CO2 due to vegetation when flying easterward over the Great Plains as well as the increase in CO2 concentration in the vicinity ofthe coal-fired power plant in New Mexico. Examples of these and other results will be presented.

Abshire, James B.↗

Iron-Rich Carbonates as the Potential Source of Evolved CO2 Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater

The Sample Analysis at Mars (SAM) instrument detected at least 4 distinct CO2 release during the pyrolysis of a sample scooped from the Rocknest (RN) eolian deposit. The highest peak CO2 release temperature (478-502 C) has been attributed to either a Fe-rich carbonate or nano-phase Mg-carbonate. The objective of this experimental study was to evaluate the thermal evolved gas analysis (T/EGA) characteristics of a series of terrestrial Fe-rich carbonates under analog SAM operating conditions to compare with the RN CO2 releases. Natural Fe-rich carbonates (<53 microns) with varying Fe amounts (Fe(0.66)X(0.34)- to Fe(0.99)X(0.01)-CO3, where X refers to Mg and/or Mn) were selected for T/EGA. The carbonates were heated from 25 to 715 C (35 C/min) and evolved CO2 was measured as a function of temperature. The highest Fe containing carbonates (e.g., Fe(0.99)X(0.01)-CO3) yielded CO2 peak temperatures between 466-487 C, which is consistent with the high temperature RN CO2 release. The lower Fe-bearing carbonates (e.g., Fe(0.66)X(0.34)CO3) did not have peak CO2 release temperatures that matched the RN peak CO2 temperatures; however, their entire CO2 releases did occur within RN temperature range of the high temperature CO2 release. Results from this laboratory analog analysis demonstrate that the high temperature RN CO2 release is consistent with Fe-rich carbonate (approx.0.7 to 1 wt.% FeCO3). The similar RN geochemistry with other materials in Gale Crater and elsewhere on Mars (e.g., Gusev Crater, Meridiani) suggests that up to 1 wt. % Fe-rich carbonate may occur throughout the Gale Crater region and could be widespread on Mars. The Rocknest Fe-carbonate may have formed from the interaction of reduced Fe phases (e.g., Fe2+ bearing olivine) with atmospheric CO2 and transient water. Alternatively, the Rocknest Fe-carbonate could be derived by eolian processes that have eroded distally exposed deep crustal material that possesses Fe-carbonate that may have formed through metamorphic and/or metasomatic processes.

Sutter, B.↗

Lidar Measurements of Atmospheric CO2 From Regional to Global Scales

Atmospheric CO2 is a critical forcing for the Earth's climate and the knowledge on its distributions and variations influences predictions of the Earth's future climate. Large uncertainties in the predictions persist due to limited observations. This study uses the airborne Intensity-Modulated Continuous-Wave (IMCW) lidar developed at NASA Langley Research Center to measure regional atmospheric CO2 spatio-temporal variations. Further lidar development and demonstration will provide the capability of global atmospheric CO2 estimations from space, which will significantly advances our knowledge on atmospheric CO2 and reduce the uncertainties in the predictions of future climate. In this presentation, atmospheric CO2 column measurements from airborne flight campaigns and lidar system simulations for space missions will be discussed. A measurement precision of approx.0.3 ppmv for a 10-s average over desert and vegetated surfaces has been achieved. Data analysis also shows that airborne lidar CO2 column measurements over these surfaces agree well with in-situ measurements. Even when thin cirrus clouds present, consistent CO2 column measurements between clear and thin cirrus cloudy skies are obtained. Airborne flight campaigns have demonstrated that precise atmospheric column CO2 values can be measured from current IM-CW lidar systems, which will lead to use this airborne technique in monitoring CO2 sinks and sources in regional and continental scales as proposed by the NASA Atmospheric Carbon and Transport â€" America project. Furthermore, analyses of space CO2 measurements shows that applying the current IM-CW lidar technology and approach to space, the CO2 science goals of space missions will be achieved, and uncertainties in CO2 distributions and variations will be reduced.

Lin, Bing↗

The Impact of Prior Biosphere Models in the Inversion of Global Terrestrial CO2 Fluxes by Assimilating OCO-2 Retrievals

Atmospheric mixing ratios of carbon dioxide (CO2) are largely controlled by anthropogenic emissions and biospheric fluxes. The processes controlling terrestrial biosphere-atmosphere carbon exchange are currently not fully understood, resulting in terrestrial biospheric models having significant differences in the quantification of biospheric CO2 fluxes. Atmospheric transport models assimilating measured (in situ or space-borne) CO2 concentrations to estimate "top-down" fluxes, generally use these biospheric CO2 fluxes as a priori information. Most of the flux inversion estimates result in substantially different spatio-temporal posteriori estimates of regional and global biospheric CO2 fluxes. The Orbiting Carbon Observatory 2 (OCO-2) satellite mission dedicated to accurately measure column CO2 (XCO2) allows for an improved understanding of global biospheric CO2 fluxes. OCO-2 provides much-needed CO2 observations in data-limited regions facilitating better global and regional estimates of "top-down" CO2 fluxes through inversion model simulations. The specific objectives of our research are to: 1) conduct GEOS-Chem 4D-Var assimilation of OCO-2 observations, using several state-of-the-science biospheric CO2 flux models as a priori information, to better constrain terrestrial CO2 fluxes, and 2) quantify the impact of different biospheric model prior fluxes on OCO-2-assimilated a posteriori CO2 flux estimates. Here we present our assessment of the importance of these a priori fluxes by conducting Observing System Simulation Experiments (OSSE) using simulated OCO-2 observations with known "true" fluxes.

Biosphere↗