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Northern and Southern Hemisphere Ground-Based Infrared Spectroscopic Measurements of Tropospheric Carbon Monoxide and Ethane

Time series of CO and C2H, measurements have been derived from high-resolution infrared solar spectra recorded in Lauder, New Zealand (45.0 degrees S, 169.7 degrees E, altitude 0.37 km), and at the U.S. National Solar Observatory (31.9 degrees N, 11, 1.6 degrees W, altitude 2.09 km) on Kitt Peak. Lauder observations were obtained between July 1993 and November 1997, while the Kitt Peak measurements were recorded between May 1977 and December 1997. Both databases were analyzed with spectroscopic parameters that included significant improvements for C2H6 relative to previous studies. Target CO and C2H6 lines were selected to achieve similar vertical samplings based on averaging kernels. These calculations show that partial columns from layers extending from the surface to the mean tropopause and from the mean tropopause to 100 km are nearly independent. Retrievals based on a semiempirical application of the Rodgers optimal estimation technique are reported for the lower layer, which has a broad maximum in sensitivity in the upper troposphere. The Lauder CO and C2H, partial columns exhibit highly asymmetrical seasonal cycles with minima in austral autumn and sharp peaks in austral spring. The spring maxima are the result of tropical biomass burning emissions followed by deep convective vertical transport to the upper troposphere and long-range horizontal transport. Significant year-to-year variations are observed for both CO and C2H6, but the measured trends, (+0.37 +/- 0.57)% yr(exp -1) and (-0.64 +/- 0.79)% yr(exp -1), I sigma, respectively, indicate no significant long-term changes. The Kitt Peak data also exhibit CO and C2H6, seasonal variations in the lower layer with trends equal to (-0.27 +/- 0.17)% yr(exp -1) and (-1.20 +/- 0.35)% yr(exp -1), 1 sigma, respectively. Hence a decrease in the Kitt Peak tropospheric C2H6 column has been detected, though the CO trend is not significant. Both measurement sets are compared with previous observations, reported trends, and three-dimensional model calculations.

Rinsland, Curtis P.↗

Carbon Monoxide Distributions and Atmosphere Transports over Southern Africa

Sources and transports of CO as measured by the Measurement of Air Pollution from Space (MAPS) over a substantial sector of the southern hemisphere between South America and southern Africa are described by air parcel trajectories based upon European Center for Medium Range Weather Forecasts (ECMWF) model data fields. Observations, made by NASA Shuttle astronauts during the October 1994 mission, of vegetation fires suggest a direct relationship between in situ biomass burning, at least over South America and southern Africa, and coincident tropospheric measurements of CO. Results of this paper indicate that the transport of CO from the surface to the levels of maximum MAPS sensitivity (about 450 hPa) over these regions is not of a direct nature due largely to the well stratified atmospheric environment. The atmospheric transport of CO from biomass burning within this region is found to occur over intercontinental scales over numbers of days to more than a week. Three distinct synoptic circulation and transport classes are found to have occurred over southern Africa during the October 1994 MAPS experiment: (1) transport from South America and Africa to southern Africa associated with elevated MAPS measured CO (> 150 ppbv); (2) weakening anticyclonic transport from South America associated with moderate CO (< 150 ppbv and > 105 ppbv); and (3) transport from the high southern latitudes associated with low CO (<105 ppbv).

Garstang, Michael↗

Northern and Southern Hemisphere Ground-Based Infrared Spectroscopic Measurements of Tropospheric Carbon Monoxide and Ethane

Time series of CO and C2H6 measurements have been derived from high resolution infrared solar spectra recorded in Lauder, New Zealand (45.0 deg S, 169.7 deg E, altitude 0.37 km) and at the U. S. National Solar Observatory (31.90 deg N, 111.6 deg W, altitude 2.09 km) on Kitt Peak. Lauder observations were obtained between July 1993 and November 1997 while the Kitt Peak measurements were recorded between May 1977 and December 1997. Both databases were analyzed with spectroscopic parameters that included significant improvements for C2H6 relative to previous studies. Target CO and C2H6 lines were selected to achieve similar vertical samplings based on averaging kernels. These calculations show that partial columns from layers extending from the surface to the mean tropopause and from the mean tropopause to 100 km are nearly independent. Retrievals based on a semiempirical application of the Rodgers optimal estimation technique are reported for the lower layer, which has a broad maximum in sensitivity in the upper troposphere. The Lauder CO and C2H6 partial columns exhibit highly asymmetrical seasonal cycles with minima in austral autumn and sharp peaks in austral spring. The spring maxima are the result of tropical biomass burning emissions followed by deep convective vertical transport to the upper troposphere and long-range horizontal transport. Significant year-to-year variations are observed for both CO and C2H6, but the measured trends, (+0.37 +/- 0.57)%/ yr and (-0.64 +/- 0.79)%/ yr, 1 sigma, respectively, indicate no significant long-term changes. The Kitt Peak data also exhibit CO and C2H6 seasonal variations in the lower layer with trends equal to (-0.27 +/- 0.17)%/ yr and (-1.20 +/- 0.35)%/ yr, 1 sigma, respectively. Hence, a decrease in the Kitt Peak tropospheric C2H6 column has been detected, though the CO trend is not significant. Both measurement sets are compared with previous observations, reported trends, and three-dimensional model calculations.

Rinsland, Curtis P.↗

Cosmic: Carbon Monoxide And Soot In Microgravity Inverse Combustion

Almost seventy percent of fire related deaths are caused by the inhalation of toxins such as CO and soot that are produced when fires become underventilated.(1) Although studies have established the importance of CO formation during underventilated burning,(2) the formation processes of CO (and soot) in underventilated fires are not well understood. The goal of the COSMIC project is to study the formation processes of CO and soot in underventilated flames. A potential way to study CO and soot production in underventilated flames is the use of inverse diffusion flames (IDFs). An IDF forms between a central air jet and a surrounding fuel jet. IDFs are related to underventilated flames because they may allow CO and soot to escape unoxidized. Experiments and numerical simulations of laminar IDFs of CH4 and C2H4 were conducted in 1-g and micro-g to study CO and soot formation. Laminar flames were studied because turbulent models of underventilated fires are uncertain. Microgravity was used to alter CO and soot pathways. A IDF literature survey, providing background and establishing motivation for this research, was presented at the 5th IWMC.(3) Experimental results from 1-g C2H4 IDFs and comparisons with simulations, demonstrating similarities between IDFs and underventilated fires, were presented at the 6th IWMC.(4) This paper will present experimental results from micro-g and 1-g IDFs of CH4 and C2H4 as well as comparisons with simulations, further supporting the relation between IDFs and underventilated flames.

Mikofski, M. A.↗

Oscillator Strengths and Predissociation Widths for Rydberg Transitions in Carbon Monoxide

CO is used as a probe of astronomical environments ranging from planetary atmospheres and comets to interstellar clouds and the envelopes surrounding stars near the end of their lives. One of the processes controlling the CO abundance and the ratio of its isotopomers is photodissociation. Accurate oscillator strengths for Rydberg transitions are needed for modeling this process. Absorption bands were analyzed by synthesizing the profiles with codes developed independently in Meudon and Toledo. Each synthetic spectrum was adjusted to match the experimental one in a non-linear least-squares fitting procedure with the band oscillator strength, the line width (instrumental and predissociation.

Federman, Steven R.↗

Effects of the 2006 El Nino on Tropospheric Ozone and Carbon Monoxide: Implications for Dynamics and Biomass Burning

We have studied the effects of the 2006 El Nino on tropospheric O3 and CO at tropical and sub-tropical latitudes measured from the OMI and MLS instruments on the Aura satellite. The 2006 El Nino-induced drought allowed forest fires set to clear land to burn out of control during October and November in the Indonesian region. The effects of these fires are clearly seen in the enhancement of GO concentration measured from the MLS instrument. We have used a global model of atmospheric chemistry and transport (GMI CTM) to quantify the relative irrrportance of biomass burning and large scale transport: in producing observed changes in tropospheric O3 and CO . The model results show that during October and November both biomass burning and meteorological changes contributed almost equally to the observed increase in tropospheric O3 in the Indonesian region. The biomass component was 4-6 DU but it was limited to the Indonesian region where the fires were most intense, The dynamical component was 4-8 DU but it covered a much larger area in the Indian Ocean extending from South East Asia in the north to western Australia in the south. By December 2006, the effect of biomass taming was reduced to zero and the obsemed changes in tropospheric O3 were mostly due to dynamical effects. The model results show an increase of 2-3% in the global burden of tropospheric ozone. In comparison, the global burdean of CO increased by 8-12%.

Chandra, S.↗

TES Carbon Monoxide Validation during the Two AVE Campaigns using the Argus and ALIAS Instruments on NASA's WB-57F

The Aura Validation Experiment (AVE) focuses on validating Aura satellite measurements of important atmospheric trace gases using ground-based, aircraft, and balloon-borne instruments. Global satellite observations of CO from the Tropospheric Emission Spectrometer (TES) on the EOS Aura satellite have been ongoing since September 2004. This paper discusses CO validation experiments during the Oct-AVE (2004 Houston, Texas) and CR-AVE (2006 San Jose, Costa Rica) campaigns. The coincidences in location and time between the satellite observations and the available in situ profiles for some cases are not ideal. However, the CO distribution patterns in the two validation flight areas are shown to have very little variability in the aircraft and satellite . observations, thereby making them suitable for validation comparisons. TES CO profiles, which typically have a retrieval uncertainty of 10-20%, are compared with in situ CO measurements from NASA Ames Research Center's Argus instrument taken on board the WB-57F aircraft during Oct-AVE. TES CO retrievals during CR-AVE are compared with in situ measurements from Jet Propulsion Laboratory's Aircraft Laser Infrared Absorption Spectrometer (ALIAS) instrument as well as with the Argus instrument, both taken on board the WB-57F aircraft. During CR-AVE, the average overall difference between ALIAS and Argus CO was 4%, with the ALIAS measurement higher. During individual flights, 2-min time-averaged differences between the two in situ instruments had standard deviation of 14%. The TES averaging kernels and a priori constraint profiles for CO are applied to the in situ data for proper comparisons to account for the reduced vertical resolution and the influence of the a priori in the satellite-derived profile. In the TES sensitive pressure range, approx.700-200 hPa, the in situ profiles and TES profiles agree within 5-10%, less than the variability in CO distributions obtained by both TES and the aircraft instruments in the two regions. TES CO is slightly lower than in situ measurements in the Houston area (midlatitudes) and slightly higher than in situ CO measurements in the Costa Rica region (tropical).

Lopez, Jinena P.↗

Evidence of Convective Redistribution of Carbon Monoxide in Aura Tropospheric Emission Sounder (TES) and Microwave Limb Sounder (MLS) Observations

Vertical convective transport is a key element of the tropospheric circulation. Convection lofts air from the boundary layer into the free troposphere, allowing surface emissions to travel much further, and altering the rate of chemical processes such as ozone production. This study uses satellite observations to focus on the convective transport of CO from the boundary layer to the mid and upper troposphere. Our hypothesis is that strong convection associated with high rain rate regions leads to a correlation between mid level and upper level CO amounts. We first test this hypothesis using the Global Modeling Initiative (GMI) chemistry and transport model. We find the correlation is robust and increases as the precipitation rate (the strength of convection) increases. We next examine three years of CO profiles from the Tropospheric Emission Sounder (TES) and Microwave Limb Sounder (MLS) instruments aboard EOS Aura. Rain rates are taken from the Tropical Rainfall Measuring Mission (TRMM) 3B-42 multi-satellite product. Again we find a correlation between mid-level and upper tropospheric CO, which increases with rain rate. Our result shows the critical importance of tropical convection in coupling vertical levels of the troposphere in the transport of trace gases. The effect is seen most clearly in strong convective regions such as the Inter-tropical Convergence Zone.

Manyin, Michael↗

Catalyst for Carbon Monoxide Oxidation

In many applications, it is highly desirable to operate a CO2 laser in a sealed condition, for in an open system the laser requires a continuous flow of laser gas to remove the dissociation products that occur in the discharge zone of the laser, in order to maintain a stable power output. This adds to the operating cost of the laser, and in airborne or space applications, it also adds to the weight penalty of the laser. In a sealed CO2 laser, a small amount of CO2 gas is decomposed in the electrical discharge zone into corresponding quantities of CO and O2. As the laser continues to operate, the concentration of CO2 decreases, while the concentrations of CO and O2 correspondingly increase. The increasing concentration of O2 reduces laser power, because O2 scavenges electrons in the electrical discharge, thereby causing arcing in the electric discharge and a loss of the energetic electrons required to boost CO2 molecules to lasing energy levels. As a result, laser power decreases rapidly. The primary object of this invention is to provide a catalyst that, by composition of matter alone, contains chemisorbed water within and upon its structure. Such bound moisture renders the catalyst highly active and very long-lived, such that only a small quantity of it needs to be used with a CO2 laser under ambient operating conditions. This object is achieved by a catalyst that consists essentially of about 1 to 40 percent by weight of one or more platinum group metals (Pt, Pd, Rh, Ir, Ru, Os, Pt being preferred); about 1 to 90 percent by weight of one or more oxides of reducible metals having multiple valence states (such as Sn, Ti, Mn, Cu, and Ce, with SnO2 being preferred); and about 1 to 90 percent by weight of a compound that can bind water to its structure (such as silica gel, calcium chloride, magnesium sulfate, hydrated alumina, and magnesium perchlorate, with silica gel being preferred). Especially beneficial results are obtained when platinum is present in the catalyst composition in an amount of about 5 to 25 (especially 7) percent by weight, SnO2 is present in an amount of about 30 to 40 (especially 40) percent by weight, and silica gel is present in an amount of 45 to 55 (especially 50) percent by weight. The composition of this catalyst was suggested by preliminary experiments in which a Pt/SnO2 catalyst was needed for bound water to enhance its activity. These experimental results suggested that if the water were bound to the surface, this water would enhance and prolong catalyst activity for long time periods. Because the catalyst is to be exposed to a laser gas mixture, and because a CO2 laser can tolerate only a very small amount of moisture, a hygroscopic support for the catalyst would provide the needed H2O into the gas. Silica gel is considered to be superior because of its property to chemisorb water on its surface over a wide range of moisture content.

Davis, Patricia↗

Methane, Carbon Monoxide, and Ammonia in Brown Dwarfs and Self-Luminous Giant Planets

We address disequilibrum abundances of some simple molecules in the atmospheres of solar composition brown dwarfs and self-luminous extrasolar giant planets using a kinetics-based 1D atmospheric chemistry model. Our approach is to use the full kinetics model to survey the parameter space with effective temperatures between 500 K and 1100 K. In all of these worlds equilibrium chemistry favors CH4 over CO in the parts of the atmosphere that can be seen from Earth, but in most disequilibrium favors CO. The small surface gravity of a planet strongly discriminates against CH4 when compared to an otherwise comparable brown dwarf. If vertical mixing is like Jupiter's, the transition from methane to CO occurs at 500 K in a planet. Sluggish vertical mixing can raise this to 600 K; clouds or more vigorous vertical mixing could lower this to 400 K. The comparable thresholds in brown dwarfs are 1100±100 K. Ammonia is also sensitive to gravity, but unlike CH4/CO, the NH3/N2 ratio is insensitive to mixing, which makes NH3 a potential proxy for gravity. HCN may become interesting in high gravity brown dwarfs with very strong vertical mixing. Detailed analysis of the CO-CH4 reaction network reveals that the bottleneck to CO hydrogenation goes through methanol, in partial agreement with previous work. Simple, easy to use quenching relations are derived by fitting to the complete chemistry of the full ensemble of models. These relations are valid for determining CO, CH4, NH3, HCN, and CO2 abundances in the range of self-luminous worlds we have studied but may not apply if atmospheres are strongly heated at high altitudes by processes not considered here (e.g., wave breaking).

Planets and satellites↗