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At least 505 records · Page 28

Optical constants of solid methane

Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH4 for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. Preliminary results are presented on the optical constants of solid methane for the 0.4 to 2.6 micrometer region. Deposition onto a substrate at 10 K produces glassy (semi-amorphous) material. Annealing this material at approximately 33 K for approximately 1 hour results in a crystalline material as seen by sharper, more structured bands and negligible background extinction due to scattering. The constant k is reported for both the amorphous and the crystalline (annealed) states. Typical values (at absorption maxima) are in the .001 to .0001 range. Below lambda = 1.1 micrometers the bands are too weak to be detected by transmission through the films less than or equal to 215 micrometers in thickness, employed in the studies to date. Using previously measured values of the real part of the refractive index, n, of liquid methane at 110 K, n is computed for solid methane using the Lorentz-Lorenz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for condensed CH4.

Khare, Bishun N.↗

Consumption of atmospheric methane by tundra soils

The results of field and laboratory experiments on methane consumption by tundra soils are reported. For methane concentrations ranging from below to well above ambient, moist soils are found to consume methane rapidly; in nonwaterlogged soils, equilibration with atmospheric methane is fast relative to microbial oxidation. It is concluded that lowering of the water table in tundra as a resulting from a warmer, drier climate will decrease methane fluxes and could cause these areas to provide negative feedback for atmospheric methane.

Whalen, S. C.↗

Optical constants of solid methane

Methane is the most abundant simple organic molecule in the outer solar system bodies. In addition to being a gaseous constituent of the atmospheres of the Jovian planets and Titan, it is present in the solid form as a constituent of icy surfaces such as those of Triton and Pluto, and as cloud condensate in the atmospheres of Titan, Uranus, and Neptune. It is expected in the liquid form as a constituent of the ocean of Titan. Cometary ices also contain solid methane. The optical constants for both solid and liquid phases of CH4 for a wide temperature range are needed for radiative transfer calculations, for studies of reflection from surfaces, and for modeling of emission in the far infrared and microwave regions. The astronomically important visual to near infrared measurements of solid methane optical constants are conspicuously absent from the literature. Preliminary results are presented of the optical constants of solid methane for the 0.4 to 2.6 micron region. K is reported for both the amorphous and the crystalline (annealed) states. Using the previously measured values of the real part of the refractive index, n, of liquid methane at 110 K n is computed for solid methane using the Lorentz-Lorentz relationship. Work is in progress to extend the measurements of optical constants n and k for liquid and solid to both shorter and longer wavelengths, eventually providing a complete optical constants database for condensed CH4.

Khare, Bishun N.↗

Profiles of alpha 13 C and alpha D in methane from the lower stratosphere

Methane is an important greenhouse gas of biogenic and anthropogenic origin for which global budgets are being constructed from a variety of data. One approach to the global methane budget is the use of the stable isotopes C-13 and D, and the radionuclide C-14 as tracers. The authors measured the isotopic composition of methane from various sources and in tropospheric air for a number of locations. Here, the authors report on the isotopic composition of methane from the lower stratosphere. Measurements of this concentration in the stratosphere can yield estimates for the kinetic isotope effects in the methane destruction reactions. These effects have to be known for quantitative isotopic methane budgets.

Wahlen, Martin↗

Three-Dimensional Model Synthesis of the Global Methane Cycle

A synthesis of the global methane cycle is presented to attempt to generate an accurate global methane budget. Methane-flux measurements, energy data, and agricultural statistics are merged with databases of land-surface characteristics and anthropogenic activities. The sources and sinks of methane are estimated based on atmospheric methane composition and variations, and a global 3D transport model simulates the corresponding atmospheric responses. The geographic and seasonal variations of candidate budgets are compared with observational data, and the available observations are used to constrain the plausible methane budgets. The preferred budget includes annual destruction rates and annual emissions for various sources. The lack of direct flux measurements in the regions of many of these fluxes makes the unique determination of each term impossible. OH oxidation is found to be the largest single term, although more measurements of this and other terms are recommended.

Fung, I.↗

Methane transport mechanisms and isotopic fractionation in emergent macrophytes of an Alaskan tundra lake

The stable carbon isotopic composition of methane associated with and emitted by the two dominant emergent macrophytes abundant in the many Alaskan tundra lakes, Carex rostrata and Arctophila fulva, is determined. The carbon isotopic composition of the methane was -58.6 +/- 0.5 (n=2) for Arctophila and -66.6 +/- 2.5 (n=6) for Carex. The methane emitted by these species is depleted in C-13 by 12 per mil for Arctophila and 18 per mil for Carex relative to methane withdrawn from plant stems 1-2 cm below the waterline. The results suggest more rapid transport of (C-12)H4 relative to (C-13)H4 through plants to the atmosphere. Plant stem methane concentrations ranged from 0.2 to 4.0 percent in Arctophila, with an isotopic composition of -46.1 +/- 4.3 percent (n=8). Carex stem methane concentrations ranged from 150 to 1200 ppm, with an isotopic composition of -48.3 +/- 1.4 per mil (n=3).

Chanton, Jeffrey P.↗

Long term monitoring of methane in the atmosphere by multiplex gas chromatography

Methane is of interest in the study of the Earth's atmosphere because of its implication in the future global warming of the surface. This warming is produced by the absorption of infrared energy by trace gases. It has been estimated that in the next 40 to 50 years, methane could contribute 20 to 25 pct. as much atmospheric warming as that expected from carbon dioxide increases. Studies to examine sources, sinks, and cycles of methane will require analytical methods capable of continuous unattended measurement with temporal resolution of an hour or less for weeks at a time. Gas chromatography (GC) is one of the most practical methods available to conduct the analysis of air, but limitations in this technique still exist which can be alleviated with multiplex GC (MGC). MGC is a technique where many samples are pseudo-randomly introduced to the chromatograph without regard to the length of time required for an analysis. The resulting data must then be reduced using computational methods such as cross correlation. In the technique reported, a tube packed with silver oxide was used at the inlet of the GC column to create concentration pulses of methane in a sample stream of air. By using only one carrier, i.e., ambient air, an effective and accurate method to monitor the variations in concentration of methane in the atmosphere over long periods of time was developed. Methane in ambient air was monitored for an eight day period and an interesting temporal variability was found. This work has shown the utility of a relatively simple MGC for the analysis of a real environmental sample.

Valentin, Jose R.↗

Mars methane engine

The feasibility of an internal combustion engine operating on a mixture of methane, carbon dioxide, and oxygen has been verified by previous design groups for the Mars Methane Engine Project. Preliminary stoichiometric calculations examined the theoretical fuel-air ratios needed for the combustion of methane. Installation of a computer data acquisition system along with various ancillary components will enable the performance of the engine, running on the described methane mixture, to be optimized with respect to minimizing excess fuel. Theoretical calculations for stoichiometric combustion of methane-oxygen-carbon dioxide mixtures yielded a ratio of 1:2:4.79 for a methane-oxygen-carbon dioxide mixture. Empirical data shows the values to be closer to 1:2.33:3.69 for optimum operation.

Bui, Hung↗

Eddy correlation measurements of methane fluxes using a tunable diode laser at the Kinosheo Lake tower site during the Northern Wetlands Study (NOWES)

As part of the Canadian Northern Wetlands Study (NOWES) measurements of methane flux were made at the Kinosheo Lake tower site for a 1-month period during the 1990 summer intensive. The measurements were made with a diode-laser-based methane sensor using the eddy correlation technique. Measurements of the methane fluxes were made at two levels, 5 or 18 m. Approximately 900 half-hour average methane flux measurements were obtained. Weak temporal and diurnal trends were observed in the data. Fluxes averaged over the study period showed an overall methane emission of 16 mg CH4 m(exp -2)/d with a daytime average of 20 mg CH4 m(exp -2)/d and a nighttime average of 9 mg CH4 m(exp -2)/d. The effect of emission footprint was evident in the data. A strong relationship between the daily average methane flux and wet bog temperature at 20-cm depth was observed.

Edwards, G. C.↗

Photochemistry of Methane in Model Atmospheres of Jupiter and Titan

The two central findings were 1) hydrogen atoms and hydrogen molecules photodissociated from methane are relatively richer in H than in D in other words deuterium atoms have a greater probability of remaining attached to the carbon atom. Titan, a moon of Saturn has an atmosphere which is largely nitrogen but also contains about 3% methane as well as smaller amounts of C2 and C3 hydrocarbons. If all these hydrocarbons are of biological origin, the isotopic scrambling occurring in living organisms would result in equal D atom abundances. On the other hand, if the higher hydrocarbons are derived from methane by photodissociation of methane, they should be richer in D than methane. Precise values for the enrichment were derived from our photochemical data. 2) When methane is dissociated by vuv light, methylene is produced in a singlet state. This explains why the higher hydrocarbons are sparse on Jupiter but relatively rich on Titan.

Bersohn, Richard↗

Methane-Powered Vehicles

Liquid methane is beginning to become an energy alternative to expensive oil as a power source for automotive vehicles. Methane is the principal component of natural gas, costs less than half as much as gasoline, and its emissions are a lot cleaner than from gasoline or diesel engines. Beech Aircraft Corporation's Boulder Division has designed and is producing a system for converting cars and trucks to liquid methane operation. Liquid methane (LM) is a cryogenic fuel which must be stored at a temperature of 260 degrees below zero Fahrenheit. The LM system includes an 18 gallon fuel tank in the trunk and simple "under the hood" carburetor conversion equipment. Optional twin-fuel system allows operator to use either LM or gasoline fuel. Boulder Division has started deliveries for 25 vehicle conversions and is furnishing a liquid methane refueling station. Beech is providing instruction for Northwest Natural Gas, for conversion of methane to liquid state.

Source record↗

Methane Production by Microbial Mats Under Low Sulfate Concentrations

Cyanobacterial mats collected in hypersaline salterns were incubated in a greenhouse under low sulfate concentrations ([SO4]) and examined for their primary productivity and emissions of methane and other major carbon species. Atmospheric greenhouse warming by gases such as carbon dioxide and methane must have been greater during the Archean than today in order to account for a record of moderate to warm paleoclemates, despite a less luminous early sun. It has been suggested that decreased levels of oxygen and sulfate in Archean oceans could have significantly stimulated microbial methanogenesis relative to present marine rates, with a resultant increase in the relative importance of methane in maintaining the early greenhouse. We maintained modern microbial mats, models of ancient coastal marine communities, in artificial brine mixtures containing both modern [SO4=] (ca. 70 mM) and "Archean" [SO4] (less than 0.2 mM). At low [SO4], primary production in the mats was essentially unaffected, while rates of sulfate reduction decreased by a factor of three, and methane fluxes increased by up to ten-fold. However, remineralization by methanogenesis still amounted to less than 0.4 % of the total carbon released by the mats. The relatively low efficiency of conversion of photosynthate to methane is suggested to reflect the particular geometry and chemical microenvironment of hypersaline cyanobacterial mats. Therefore, such mats w-ere probably relatively weak net sources of methane throughout their 3.5 Ga history, even during periods of low- environmental levels oxygen and sulfate.

Bebout, Brad M.↗

Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

Levine, J. S.↗

Measurement of the Isotopic Signatures of Water on Mars: Implications for Studying Methane

The recent discovery of methane on Mars has led to much discussion concerning its origin. On Earth, the isotopic signatures of methane vary with the nature of its production. Specifically, the ratios among 12CH4, 13CH4, and 12CH3D differ for biotic and abiotic origins. On Mars, measuring these ratios would provide insights into the origins of methane and measurements of water isotopologues co-released with methane would assist in testing their chemical relationship. Since 1997, we have been measuring HDO and H2O in Mars atmosphere and comparing their ratio to that in Earth s oceans. We recently incorporated a line-by-line radiative transfer model (LBLRTM) into our analysis. Here, we present a map for [HDO]/[H2O] along the central meridian (1541W) for Ls 501. From these results, we constructed models to determine the observational conditions needed to quantify the isotopic ratios of methane in Mars atmosphere. Current ground-based instruments lack the spectral resolution and sensitivity needed to make these measurements. Measurements of the isotopologues of methane will likely require in situ sampling.

Novak, R. E.↗

Martian Methane From a Cometary Source: A Hypothesis

In recent years, methane in the martian atmosphere has been detected by Earth-based spectroscopy, the Planetary Fourier Spectrometer on the ESA Mars Express mission, and the NASA Mars Science Laboratory. The methane's origin remains a mystery, with proposed sources including volcanism, exogenous sources like impacts and interplanetary dust, aqueous alteration of olivine in the presence of carbonaceous material, release from ancient deposits of methane clathrates, and/or biological activity. An additional potential source exists: meteor showers from the emission of large comet dust particles could generate martian methane via UV pyrolysis of carbon-rich infall material. We find a correlation between the dates of Mars/cometary orbit encounters and detections of methane on Mars. We hypothesize that cometary debris falls onto Mars during these interactions, generating methane via UV photolysis.

Fries, M.↗

Assessment of Lidar XCH4 Measurements During ACT-America 2019 for Boundary Layer Methane and Emission Model Constraint

Atmospheric methane is a potent and abundant greenhouse gas (GHG) with increasing importance due to rising emissions and their subsequent impact on radiative forcing, indicating an important driving role in climate change. The recent Earth Science Decadal Survey called for further understanding of the sources and sinks of atmospheric methane, the processes that will affect their future concentrations, and identified the need for advanced observing capabilities to elucidate these issues. HALO, a combined methane Differential Absorption Lidar and Aerosol/Cloud High Spectral Resolution Lidar participated in the ACT-America summer 2019 campaign to help constrain the emissions and transport of GHGs in the atmosphere to address some of the aforementioned science goals. In this presentation we will discuss the utility of using an in-situ point measurement versus lidar column measurement for inventory and source identification applications. Comparisons between column measurements of methane from in-situ and lidar will be made to assess whether point measurements are useful when the assumption of a well-mixed boundary layer, a practice commonly used in the community, is valid. We will also show that a lidar column measurement can apportion boundary layer methane from the column and has the ability to identify boundary layer methane enhancements in fair weather conditions using atmospheric backscatter signals, a measurement capability that has the potential to transform the observational strategies of future airborne carbon cycle science investigations. We will also present on the differences and utility of constraining emission models using an in-situ versus lidar column and asses the resulting uncertainties of each.

Rory A Barton-Grimley↗

Gulf of Mexico Health and Air Quality: Using NASA Earth Observations to Identify Potential Methane Sources for Improved Monitoring of Offshore Oil & Gas Activity in the Gulf of Mexico

The extraction, production, and transportation of oil and gas is a leading contributor to anthropogenic methane emissions via activities such as flaring and venting. The Bureau of Ocean and Energy Management (BOEM) has air quality jurisdiction offshore in the Gulf of Mexico and drafts regulations for criteria pollutants, while the Bureau of Safety and Environmental Enforcement (BSEE) enforces these regulations. Additionally, the non-profit organization SkyTruth monitors natural resources, including methane. BOEM, BSEE, and SkyTruth have partnered with NASA DEVELOP to use Earth observations to identify potential offshore methane sources in the Gulf of Mexico and to validate reported flaring activity. This information will allow BOEM and BSEE to make informed regulations regarding air pollution. Here, we cross-referenced BOEM infrastructure data with Suomi National Polar-orbiting Partnership (NPP) Visible Infrared Radiometer Suite (VIIRS) Nightfire data to validate operator-reported flaring. Sentinel-5p TROPOspheric Monitoring Instrument (TROPOMI) pollutant concentrations were used to validate VIIRS-detected flaring outside of the Gulf of Mexico where operator-reported data is unavailable. Using these methods, we identified the locations of offshore oil and gas infrastructure with known episodic flaring and venting in 2017 in the Gulf of Mexico, as well as offshore of South America and West Africa in 2021. Drawing upon retrieval methods used to detect onshore methane emissions, we proposed an analogous method utilizing sunglint to illuminate methane plumes over the ocean using Sentinel-2 Multispectral Imager (MSI) imagery. We detected two potential methane plumes – one at the Constitution complex in the Gulf of Mexico in July 2017 and one off the Coast of Lagos, West Africa, in July 2021.

Kate Howell↗

Plasma catalytic non-oxidative methane conversion to hydrogen and value-added hydrocarbons on zeolite 13X

Non-thermal plasma has unfolded highly efficient, safe to operate novel routes for methane conversion to hydrogen. In this work, methane conversion is performed under atmospheric dielectric barrier discharge (DBD) plasma with and without 13X zeolite-based catalysts i.e., 13X, Ga/13X, Pd/13X, and Pd-Ga/13X. Experimental results indicate that the plasma catalytic process delivered almost twofold higher product yield than the plasma only route. The binary Pd-Ga catalyst possesses highest catalytic performance with about 40 % CH 4 conversion at an input flowrate of 5 cm 3 min -1 and 2W due to the formation of the Pd-Ga alloy, which acts as catalytic active centre for activating C–H bonds. Product yield can be tailored by the catalyst design where the bimetallic Pd-Ga/13X preferably favours the hydrocarbon formation while H 2 is the dominant product obtained over the Pd/13X. The cleavage of C–H bonds of methane molecule over the plasma only route is mainly governed by energetic electrons in the gaseous phase the catalyst activity, and plasma-catalyst synergism play a significant role in the plasma catalysis process. Further, the findings from this work provide significant insights into the methane activation for subsequent optimization of the methane conversion processes operated on floating production, storage, and offloading vessels (FPSOVs). Exploiting untapped offshore natural gas reserves, where conventional pipeline systems are less economical.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗