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At least 91 records · Page 5

In Situ Measurements of N2O and CH4 During SOLVE on the ER-2 Using a New Tunable Diode Laser Instrument

This report is the final report for Cooperative Agreement NCC2-1105: 'In Situ Measurements of N2O and CH4 during SOLVE on the ER-2 using a new tunable diode laser instrument.' The tasks outlined in the proposal are listed below with a brief comment. The publications and the conference presentations are listed. Finally the important publications are attached. The Cooperative Agreement made possible a research effort to produce high precision and high accuracy in situ measurements of methane and nitrous oxide on the ER-2 during the SOLVE field campaign and to analyze these measurements. These measurements of CH4 and N2O were of utmost importance to studies of the ozone losses in the Arctic winter and spring. The concentrations measured over a large spatial and temporal range allowed the separation of the dynamical and chemical ozone loss. The most important results of the SOLVE program were contained in two scientific papers. This Cooperative Agreement allowed the participation of the Argus instrument in the program and the analysis of the data.

Jost, Hansjurg↗

Validation of the Measurement of Pollution in the Troposphere (MOPITT) Experiment by Ground-Based Infrared Solar Spectroscopic Measurements of Carbon Monoxide (CO) and Methane (CH4)

The goal of the MOPITT experiment is to enhance our knowledge of the lower atmosphere system and particularly how it interacts with the surface/ocean/biomass systems. The particular focus is the distribution, transport, sources and sinks of carbon monoxide and methane in the troposphere. The MOPITT instrument was launched on EOS TERRA satellite December 18, 1999. After the launch and until March 22, 2000 the MOPITT instrument was in engineering and calibration mode. Beginning March 23, 2000 through May 6, 2001 the instrument was in a science measurement mode with some calibration breaks. On May 7, 2001 a criocooler on a side B died and channels 1 - 4 became inoperational. The MOPITT resumed its scientific measurements on August 25, 2001 with channels 5 - 8. With some calibration breaks the instrument currently provides the data. The project has three elements to it: hardware, data analysis and modeling. The MOPITT instrument, on the NASA EOS Terra satellite, measures the upwelling infrared radiance. Using the technique of correlation spectroscopy, information regarding the distribution of atmospheric CO and CH4 can be extracted. By using appropriate data analysis techniques, concentration profiles of CO are currently obtained on a global basis at a reasonably high horizontal (approximately 22km) and vertical resolution (approximately 3km). Column amounts of methane will be derived over the sunlit side of the orbit. These profiles are assimilated into models to study the chemistry and dynamics of CO, CH4 and other constituents of the lower atmosphere.

Pougatchev, Nikita↗

Compact CH4 sensor based on difference frequency mixing of diode lasers in quasi-phasematched LiNbO3

A compact, portable and robust room temperature CH4 sensor is reported. By difference frequency mixing a 500 mW alpha-DFB diode laser at 1066 nm and an erbium-doped fiber amplified 1574 nm DFB diode laser in periodically poled lithium niobate up to 7 (mu)W of narrowband radiation at 3.3 microns is generated. Real-time monitoring of CH4 over a 7 day period using direct absorption in an open-path multipass cell (L = 36 m) demonstrates a detection precision of +/- 14 ppb.

NASA Discipline Environmental Health↗

Vibrational energy levels for CH4 from an ab initio potential

Many areas of astronomy and astrophysics require an accurate high temperature spectrum of methane (CH4). The goal of the present research is to determine an accurate ab initio potential energy surface (PES) for CH4. As a first step towards this goal, we have determined a PES including up to octic terms. We compare our results with experiment and to a PES based on a quartic expansion. Our octic PES gives good agreement with experiment for all levels, while the quartic PES only for the lower levels.

Methane/chemistry↗

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

Until recently, the stable isotopic composition of chemically and datively important stratospheric species, such as ozone (O3), carbon dioxide (CO2), nitrous oxide (N2O), and methane (CH4), was largely unexplored, despite indications from the few measurements available and theoretical studies that global-scale isotopic variations will provide a unique tool for quantifying rates of global-scale mass transport into, within, and out of the stratosphere and for understanding the mechanisms of chemical reactions involved in ozone production. The number and geographical extent of observations are beginning to increase rapidly, however, as access to the stratosphere, both directly and by remote-sensing, has increased over the last 10 years and as new analytical techniques have been developed that make global-scale isotope measurements by whole-air sampling more feasible. The objective of this study, begun in April 1999, is to incorporate into the Livermore 2D model the likely photochemical fractionation processes that determine the isotopic compositions of stratospheric CO2, N2O, CH4, and O3, and to use the model results and new observations from NASA field campaigns in 1996 and 1997 to investigate stratospheric chemistry and mass transport. Additionally, since isotopic signatures from the stratosphere are transferred to the troposphere by downward transport at middle and high latitudes, the isotopic compositions may also serve as sensitive tracers of stratosphere-totroposphere transport. Comparisons of model results with stratospheric and upper tropospheric observations from these campaigns, as well as with ground-based observations from new NOAA and NSF-sponsored studies, will help determine whether the magnitudes of the stratospheric fractionation processes are large enough to use as global-scale tracers of transport into the troposphere and, if so, will be used to help constrain the degree of coupling between the troposphere and the stratosphere.

Boering, Kristie A.↗

Kinetics of the CI(2PJ) + CH4 Reaction: Effects of Secondary Chemistry Below 300k

Because of the relatively large disagreement among earlier measurements at low temperatures, the results were examined for possible effects of non-Boltzmann spin distribution and vibrational excitation of CH4, secondary chemistry of CH3 radicals,and impuities in the CH4 source.

atmospheric chemistry kinetics low temperature↗

Satellite Boreal Measurements over Alaska and Canada During June-July 2004: Simultaneous Measurements of Upper Tropospheric CO, C2H6, HCN, CH3Cl, CH4, C2H2, CH2OH, HCOOH, OCS, and SF6 Mixing Ratios

Simultaneous ACE (Atmospheric Chemistry Experiment) upper tropospheric CO, C2H6, HCN, CH3Cl, CH4 , C2H2 , CH30H, HCOOH, and OCS measurements show plumes up to 185 ppbv (10 (exp -9) per unit volume) for CO, 1.36 ppbv for C2H6, 755 pptv (10(exp -12) per unit volume) for HCN, 1.12 ppbv for CH3C1, 1.82 ppmv, (10(exp -6) per unit volume) for CH4, 0.178 ppbv for C2H2, 3.89 ppbv for CH30H, 0.843 ppbv for HCOOH, and 0.48 ppbv for OCS in western Canada and Alaska at 50 deg N-68 deg N latitude between 29 June and 23 July 2004. Enhancement ratios and emission factors for HCOOH, CH30H, HCN, C2H6, and OCS relative to CO at 250-350 hPa are inferred from measurements of young plumes compared with lower mixing ratios assumed to represent background conditions based on a CO emission factor derived from boreal measurements. Results are generally consistent with the limited data reported for various vegetative types and emission phases measured in extratropical forests including boreal forests. The low correlation between fire product emission mixing ratios and the S176 mixing ratio is consistent with no significant SF6 emissions from the biomass fires.

Rinsland, Curtis P.↗

Low-Cost Miniaturized Laser Heterodyne Radiometer for Highly Sensitive Detection of CO2 and CH4 in the Atmospheric Column

We present a new passive ground-network instrument capable of measuring carbon dioxide (CO2) at 1.57 microns and methane (CH4) at 1.62 microns -- key for validation of OCO-2, ASCENDS, OCO-3, and GOSAT. Designed to piggy-back on an AERONET sun tracker (AERONET is a global network of more than 450 aerosol sensing instruments), this instrument could be rapidly deployed into the established AERONET network of ground sensors. Because aerosols induce a radiative effect that influences terrestrial carbon exchange, this simultaneous measure of aerosols and carbon cycle gases offers a uniquely comprehensive approach. This instrument is a variation of a laser heterodyne radiometer (LHR) that leverages recent advances in telecommunications lasers to miniaturize the instrument (the current version fits in a carry-on suitcase). In this technique, sunlight that has undergone absorption by the trace gas is mixed with laser light at a frequency matched to a trace gas absorption feature in the infrared (IR). Mixing results in a beat signal in the RF (radio frequency) region that can be related to the atmospheric concentration. By dividing this RF signal into a filter bank, concentrations at different altitudes can be resolved. For a one second integration, we estimate column sensitivities of 0.1 ppmv for CO2, and <1 ppbv for CH4.

Wilson, Emily L.↗

A 4 U Laser Heterodyne Radiometer for Methane (CH4) and Carbon Dioxide (CO2) Measurements from an Occultation-Viewing CubeSat

We present a design for a 4 U (20 cm 20 cm 10 cm) occultation-viewing laser heterodyne radiometer (LHR) that measures methane (CH4), carbon dioxide (CO2) and water vapor(H2O) in the limb that is designed for deployment on a 6 U CubeSat. The LHR design collects sunlight that has undergone absorption by the trace gas and mixes it with a distributive feedback (DFB) laser centered at 1640 nm that scans across CO2, CH4, and H2O absorption features. Upper troposphere lower stratosphere measurements of these gases provide key inputs to stratospheric circulation models: measuring stratospheric circulation and its variability is essential for projecting how climate change will affect stratospheric ozone.

occultation↗

New Approach to Characterize CO2 and CH4 Emissions over Sacramento, California Using an Airborne Aircraft Measurement

Emission fluxes of carbon dioxide (CO2) and methane (CH4) over Sacramento, California, USA, are estimated using an aircraft equipped with a cavity ring-down greenhouse gas sensor through the Alpha Jet Atmospheric eXperiment (AJAX). To better quantify the emission fluxes over the entire city and two small point sources within the area, we designed flights in a cylindrical pattern and computed the emission fluxes from 9 flights over all seasons using the Kriging method based on Gausss divergence theorem. The concentrations at the downwind side of Sacramento show somewhat persistent patterns among the 9 flights, but the magnitudes and locations of the fluxes vary depending on the individual weather conditions and seasonality on a given flight day. The net emission fluxes tend to be smaller in summer (July) than winter (November). Both trace gas mixing ratios as well as the wind speed and direction show high spatial variability both horizontally and vertically. The local maximum emission fluxes over a landfill and a rice field measured on July 29, 2015, were 2-3 times lower than the maximum measured over the entire city. These low emission fluxes suggest that not only the local source but also the transport of greenhouse gases due to diurnal and seasonal variation in winds have a strong effect on the CO2 and CH4 flux estimation of the both local emissions and city-size emissions. Our results highlight that the aircraft-based approach is effective and useful for capturing city-size emission fluxes and estimating the greenhouse gas emissions and its sources.

airborne↗

Methane on Mars: New Insights into the Sensitivity of CH4 with the NOMAD/ExoMars Spectrometer Through Its First In-Flight Calibration

The Nadir and Occultation for MArs Discovery instrument (NOMAD), onboard the ExoMars Trace Gas Orbiter (TGO) spacecraft was conceived to observe Mars in solar occultation, nadir, and limb geometries, and will be able to produce an outstanding amount of diverse data, mostly focused on properties of the atmosphere. The infrared channels of the instrument operate by combining an echelle grating spectrometer with an Acousto- Optical Tunable Filter (AOTF). Using in-flight data, we characterized the instrument performance and parameterized its calibration. In particular: an accurate frequency calibration was achieved, together with its variability due to thermal effects on the grating. The AOTF properties and transfer function were also quantified, and we developed and tested a realistic method to compute the spectral continuum transmitted through the coupled grating and AOTF system. The calibration results enabled unprecedented insights into the important problem of the sensitivity of NOMAD to methane abundances in the atmosphere. We also deeply characterized its performance under realistic conditions of varying aerosol abundances, diverse albedos and changing illumination conditions as foreseen over the nominal mission. The results show that, in low aerosol conditions, NOMAD single spectrum, 1σ sensitivity to CH4 is around 0.33 ppbv at 20 km of altitude when performing solar occultation's, and better than 1 ppbv below 30 km. In dusty conditions, we show that the sensitivity drops to 0 below 10 km. In Nadir geometry, results demonstrate that NOMAD will be able to produce seasonal maps of CH4 with a sensitivity around 5 ppbv over most of planet's surface with spatial integration over 5×5° bins. Results show also that such numbers can be improved by a factor of ~10 to ~30 by data binning. Overall, our results quantify NOMAD's capability to address the variable aspects of Martian climate.

Liuzzi, Giuliano↗

Effect of Assimilating SMAP Soil Moisture on CO2 and CH4 Fluxes through Direct Insertion in a Land Surface Model

Soil moisture impacts the biosphere–atmosphere exchange of CO2 and CH4 and plays an important role in the terrestrial carbon cycle. A better representation of soil moisture would improve coupled carbon–water dynamics in terrestrial ecosystem models and could potentially improve model estimates of large-scale carbon fluxes and climate feedbacks. Here, we investigate using soil moisture observations from the Soil Moisture Active Passive (SMAP) satellite mission to inform simulated carbon fluxes in the global terrestrial ecosystem model LPJ-wsl. Results suggest that the direct insertion of SMAP reduces the bias in simulated soil moisture at in situ measurement sites by 40%, with a greater improvement at temperate sites. A wavelet analysis between the model and measurements from 26 FLUXNET sites suggests that the assimilated run modestly reduces the bias of simulated carbon fluxes for boreal and subtropical sites at 1–2-month time scales. At regional scales, SMAP soil moisture can improve the estimated responses of CO2 and CH4 fluxes to extreme events such as the 2018 European drought and the 2019 rainfall event in the Sudd (Southern Sudan) wetlands. The simulated improvements to land–surface carbon fluxes using the direct insertion of SMAP are shown across a variety of timescales, which suggests the potential of SMAP soil moisture in improving the model representation of carbon–water coupling.

SMAP↗

Time-Resolved OH-PLIF Assessment of Deflagrations Levels in a CH4-O2 Rotating Detonation Rocket Combustor

The parasitic loss incurred by deflagrative pre-burning is considered to be one of the key challenges to the effective implementation of rotating detonation engine (RDE) systems. Thus far, there have been relatively limited high fidelity, spatio-temporally resolved measurements of the pre-burning process as a function of the reactant conditions and composition within an RDE. In this work, simultaneous high-repetition-rate broadband OH* chemiluminescence and OH planar laser-induced fluorescence (PLIF) imaging are employed to investigate deflagrative burning dynamics in a fully optically accessible CH4-O2 RDE as compared to a H2-air systems under the same conditions. A custom-built optical parametric oscillator (OPO) is coupled with a high-repetition-rate burst-mode laser to generate the 284 nm source for the excitation of the Q1(9) transition of the OH radical. Significant deflagrative burning is observed throughout the chamber as a consequence of the oxygen-rich environment. Trailing wave systems that consume unburned reactants in the region immediately following the primary detonation wave are observed. The formation of a product gas recirculation zone that entrains and combusts incoming reactants is observed, and quantitative analysis is performed to gain valuable insight into deflagration characteristics. At an oxidizer mass flux of Gox ≈ 350kg/m2/s, it is found that the levels of pre-wave burning in CH4-O2 are a factor of ∼2-3 times higher than in H2-air in the region directly ahead of the detonation wave at a global equivalence ratio Φ ≈ 1.0. This study highlights the key roles of ignition delay and turbulent mixing of the combustion product and reactant fields on the levels of pre-burning and establishes a methodology for further investigation, such as for the effects of various RDE inlet configurations.

Propulsion↗

Spatial Heterogeneity in CO2, CH4, and Energy Fluxes: Insights from Airborne Eddy Covariance Measurements Over the Mid-Atlantic Region

The exchange of carbon between the Earth’s atmosphere and biosphere influences the atmospheric abundances of carbon dioxide (CO2) and methane (CH4). Airborne eddy covariance can quantify surface-atmosphere exchange from landscape-to-regional scales, offering a unique perspective on carbon cycle dynamics. We use extensive airborne measurements to quantify fluxes of sensible heat, latent heat, CO2, and CH4across multiple ecosystems in the Mid-Atlantic region during September 2016 and May 2017. In conjunction with footprint analysis and land cover information, we use the airborne dataset to explore the effects of landscape heterogeneity on measured fluxes. Our results demonstrate large variability in CO2 uptake over mixed agricultural and forested sites, with fluxes ranging from -3.4 ± 0.7 to -11.5 ± 1.6μmol m-2s-1 for croplands and -9.1 ± 1.5 to -22.7 ± 3.2μmol m-2s-1for forests. We also report substantial CH4emissions of 32.3 ± 17.0to 76.1 ± 29.4nmol m-2s-1 from a brackish herbaceous wetland and 58.4± 12.0 to 181.2 ± 36.8nmol m-2s-1 from a freshwater forested wetland. Comparison of ecosystem-specific aircraft observations with measurements from eddy covariance flux towers along the flight path demonstrate that towers capture ~30–75% of the regional variability in ecosystem fluxes. Diel patterns measured at the tower sites suggest that peak, midday flux measurements from aircraft accurately predicts net daily CO2exchange. We discuss next steps in applying airborne observations to evaluate bottom-up flux models and improve understanding of the biophysical processes that drive carbon exchange from landscape-to-regional scales.

airborne measurements to quantify fluxes of sensib↗

Physisorption of Ar, Kr, CH4, and N2 on 304 stainless steel at very low pressures.

Determination of physisorption isotherms of these gases on stainless steel by pressure change measurements in very low pressure cryogenic baths where a steel nipple was brought in contact with the test gas at 77 to 90 K in a sealed constant-volume system. The position of the nipple in the gas was changed in such a manner that gas adsorption on a 47.5 sq cm area of the steel surface could be measured. The Dubinin-Radushkevich (DR) equation (1947) was used for an empirical description of isotherms at different temperatures. The mean adsorption energies calculated from the DR plots were 1290, 1545, 1490 and 1903 cal/mol for Ar, Kr, CH4 and N2, respectively, being about 10% higher than the corresponding values on Pyrex.

Troy, M.↗

Dissociation of CH4 by electron impact: Production of metastable hydrogen and carbon fragments

Metastable fragments produced by electron impact excitation of CH4 have been investigated for incident electron energies from threshold to 300 eV. Only metastable hydrogen and carbon atoms were observed. Onset energies for the production of metastable hydrogen atoms were observed at electron impact energies of 22.0 + or - .5 eV, 25.5 + or - .6 eV, 36.7 + or - .6 eV and 66 + or - 3 eV, and at 26.6 + or - .6 eV for the production of metastable carbon atoms. Most of the fragments appear to have been formed in high-lying Rydberg states. The total metastable hydrogen cross section reaches a maximum value of approximately 1 X 10 to the minus 18th power sq cm at 100 eV. At the same energy, the metastable carbon cross section is 2 x 10 to the minus 19th power sq cm.

Finn, T. G.↗

VUV dissociative excitation cross sections of H2O, NH3, and CH4 by electron impact

Absolute excitation functions for excited fragments resulting from electron bombardment of H2O, NH3, and CH4 by low-energy electrons (0 to 300 eV) have been measured in the vacuum ultraviolet (1100 to 1950 A). The predominant emission for each molecule was the H Lyman-alpha line, while the O I, N I, C I, and C II emissions were at least an order of magnitude weaker. Absolute cross sections at 100 eV are given along with the appearance potential of the various processes and the possible dissociative-excitation channels through which such processes proceed.

Morgan, H. D.↗

Further development of a global pollution model for CO, CH4, and CH2 O

Global tropospheric pollution models are developed that describe the transport and the physical and chemical processes occurring between the principal sources and sinks of CH4 and CO. Results are given of long term static chemical kinetic computer simulations and preliminary short term dynamic simulations.

Peters, L. K.↗