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All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Global tropospheric methane: An indication of atmosphere-biosphere-climate interactions?

Methane is an important atmospheric gas with potentially critical roles in both photochemical and radiation transfer processes. A major natural source of atmospheric methane involves anaerobic fermentation of organic materials in wetland soils and sediments. A data base of field measurements of atmospheric methane was used in the development of a global methane emissions inventory. Calculations support the following hypotheses: (1) Human activities currently produce methane at a rate approximately equal to natural resources (these rapidly increasing anthropogenic sources can explain most of the recent increase observed in tropospheric methane); and (2) Prior to 200 B.P. (before the present), the influence of climate on wetland extent and distribution was probably a dominant factor controlling global biogenic methane emissions to the atmosphere.

Harriss, Robert C.↗
DOE OSTI2025

Integrated Methane Monitoring Platform Extension, Volume I: Final Technical Report

The IMMPE project, DE-FE0032284, was to enhance methane monitoring technologies and their applications across various natural gas asset classes. The scope included deploying advanced methane detection and monitoring technologies to identify and mitigate fugitive methane emissions, measuring emission rates, and assessing impacts. The findings included the successful mitigation of identified emissions and quantification of emission rates. A key outcome was the development of a comprehensive template and summary of recommendations for methane emissions monitoring, which is replicable for both upstream and downstream applications. Furthermore, the project emphasized the importance of education by providing training opportunities for technicians and regulators, thereby fostering awareness and promoting the adoption of cost-effective methane emissions monitoring and management techniques.

02 PETROLEUM↗
DOE OSTI2025

Free-Energy Landscapes and Surface Dynamics in Methane Activation on Ni(511) via Machine Learning and Enhanced Sampling

Methane activation on stepped Ni(511) surfaces involves the rearrangement of surface atoms as the chemical reaction proceeds. This process is particularly sensitive to temperature. Using machine-learned interatomic potentials (MLIPs) coupled with enhanced sampling techniques, we investigate the activation of methane under realistic operando conditions. Our analysis reveals that methane dissociation occurs predominantly at step-edge nickel atoms. As CH x (where x = 3 or 4) species bind to additional surface nickel atoms, their reduced mobility leads to entropic penalties that suppress certain configurations and transition states. This is reflected in the underlying free energy surfaces, where configurations such as methyl binding to hollow sites and activation routes involving two nickel atoms become unfavorable as temperature increases. At elevated temperatures, methane activation extends from step-edge sites to terrace regions because of reduced free-energy barriers and enhanced surface dynamics. By decomposing the free-energy into enthalpic and entropic contributions, we uncover temperature-dependent shifts in the preferences of methane for the relevant active sites and arrive at a detailed molecular picture of methane activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The Kinetic Consequences of Water on Catalytic Methane Pyrolysis

Hydrogen production from biomass and natural gas has emerged as a prominent research area in response to the growing demand for energy from alternative sources that minimize CO 2 emissions. In this study, we investigate the impact of water, which is present in and generated from biomass-derived streams, on carbon nanotube (CNT) growth and hydrogen production during methane decomposition using Ni–Mo/MgO as a catalyst. We reveal here that the role of water on CNT growth is highly complex; its effect depends on the stage of growth at which the water is incorporated. When water is introduced at the beginning of methane decomposition ( t = 0 h), methane conversion rates are negatively impacted. We hypothesize that water inhibits the significant phase changes the Ni–Mo/MgO catalyst undergoes during catalyst carburization. In contrast, the incorporation of a small percentage of water after a stabilization period ( t = 3 h) results in methane conversion rate enhancements that scale with the introduced water partial pressure as water selectively reacts with amorphous carbon deposits that lead to catalyst deactivation, thus prolonging the lifetime of some of the most active sites. Moreover, water incorporation after stabilization significantly reduces the apparent activation energy. Density Functional Theory (DFT) calculations reveal that water preferentially interacts with carbon fragments on the catalyst surface to remove carbon deposits with a barrier lower than that required for methane activation, further supporting its role in cleaning active sites on the catalyst surface. Characterization of the resulting carbon nanotubes reveals the formation of more graphitic materials produced in the presence of water, highlighting the impact of water on nanotube properties. These results provide clarity toward the many ways in which water, or cofeeding of biomass-derived materials, may impact catalytic methane pyrolysis rates.

carbon nanotubes↗
DOE OSTI2024

Hydrogen, Methane, Brine Flow Behavior, and Saturation in Sandstone Cores During H 2 and CH 4 Injection and Displacement

Large-scale underground hydrogen storage (UHS) is a critical component in the emerging hydrogen economy. Knowledge of multiphase flow behavior involving hydrogen in storage reservoir formations is crucial to characterizing hydrogen transport properties and essential for the deliverability and storage operations of UHS. There are still many gaps in fully understanding hydrogen–methane–brine multiphase phase flow that require further investigation. In this work, H 2 and CH 4 were injected through brine-saturated sandstone cores using a tri-axial core holder system fitted with flow rate meters and pressure transducers, while the effluent gas concentrations were analyzed using an online micro gas chromatograph. Brine displacement, permeability, and gas breakthrough curves were measured. We studied the flow behavior of hydrogen and methane in sandstone cores through testing brine displacement by gas injection and comparing the hydrogen displacement of methane with the methane displacement of hydrogen. We also tested the differences between horizontal and vertical flow in brine displacement. The results showed that brine displacement was more efficient in a core with higher permeability and porosity, resulting in a higher initial gas saturation. A higher gas injection rate brought about faster gas breakthrough measured by pore volume and sharper concentration curves. Hydrogen did not exhibit abnormal flow in the sandstone when the flow was horizontal and downward vertical. Gas overriding was observed in brine displacements when the flow was horizontal, with hydrogen showing this behavior more profoundly compared to methane. Downward vertical gas injection induced higher efficiency brine displacement compared to horizontal displacement and resulted in a higher initial gas saturation in the sandstone cores. These findings address critical knowledge gaps regarding gas flow patterns and displacement behaviors during hydrogen injection and recovery phases in UHS facilities using methane as the cushion gas. The insights from this research offer valuable guidance for optimizing UHS systems, ensuring operational efficiency, and advancing sustainable energy solutions in alignment with decarbonization goals.

08 HYDROGEN↗
DOE OSTI2025

Creating Accurate Methane Emission Inventories through Data-Driven Airborne Survey Strategies

Because natural gas emits less carbon than other fossil fuels, it holds promise as a green energy transition fuel. However, the overall carbon footprint of natural gas is significantly elevated by methane emissions that occur during its production and transmission (Cusworth et al. 2022). Methane “super-emitters,” while comprising only about 1% of sites, are responsible for the majority of oil- and gas-sourced methane emissions, making their detection and mitigation critical in reducing the climate impact of natural gas and in meeting national and global sustainability goals (Sherwin et al. 2024). Yet, despite advancements in detection, significant uncertainties remain regarding the size, frequency, and duration distributions of methane emissions (e.g., Frankenberg et al. 2016, Cusworth et al. 2022, Chen, Sherwin et al. 2022, Conrad et al. 2023, Johnson et al. 2023, Sherwin et al. 2024) underscoring the need for comprehensive emissions inventories segmented by basin across the US. Airborne surveys are well-suited for collecting data to build these comprehensive, basin-level inventories because they allow for extensive spatial coverage, and have the spatial resolution, and the sensitivity to pinpoint individual methane sources. As remote sensing technologies enable rapid basin-scale surveys, it is imperative to establish scientifically and statistically robust standards to generate reliable and actionable emissions inventories. Recent work has shown that differences in airborne sampling strategies, detection technologies, and analysis can lead to large differences between survey conclusions if not correctly accounted for (Chen et al. 2024). This elevates the importance of incorporating proper sampling and analysis techniques when designing a methane emissions monitoring campaign to produce accurate results and facilitate cross-study comparisons. In this paper, we describe a survey strategy designed using the latest conclusions from the literature to align results from different aerial surveys. We identify several sampling and analysis principles, including large sample sizes, balanced sampling across oil and gas production, careful survey area definition, and a unified protocol for analysis, to be vital to producing an unbiased estimate of basin-scale emissions. We present results from a Department of Energy-funded project that deployed this survey strategy in two understudied oil and gas- producing regions in the United States: the Haynesville Basin in Texas and Louisiana, and the Woodford Shale in the Anadarko Basin in Oklahoma.

03 NATURAL GAS↗
DOE OSTI2025

Methane pyrolysis by Joule heating for graphitic carbon and hydrogen production

The global energy transition toward sustainability requires technologies that can decarbonize energy carriers and fuels while producing valuable materials. Methane, a primary component of natural gas, is both a high-energy-density fuel and a significant greenhouse gas. This study reports an approach for methane pyrolysis utilizing Joule heating within the deposition substrate to drive the endothermic reaction. With electric current passing through a resistive porous carbon cloth, heat is generated to break C-H bonds of methane molecules. Here, the decomposition of methane as it flows through the cloth results in hydrogen production and the formation of conformally layered graphite around the carbon fibers. The effects of input power, chamber pressure, feedstock flow rate, and process duration on hydrogen and graphite production are characterized via in situ mass spectrometry and laser absorption spectroscopy, resulting in methane conversion rates up to 88%, with hydrogen and carbon yields of 82% and 72%, respectively. Material characterization verifies uniform high-quality graphite deposition, with a Raman I D /I G ratio of 0.1 and 3.38 Å d-spacing. This Joule heating method for catalyst-free methane pyrolysis offers the potential for advancing hydrogen production technology by simultaneously producing valuable materials such as solid graphite, thus enhancing the economic viability of the fuel decarbonization process.

Energy Resources↗
NASA NTRS1974

Pressurant requirements for discharge of liquid methane from a 1.52-meter-(5-ft-) diameter spherical tank under both static and slosh conditions

Pressurized expulsion tests were conducted to determine the effect of various physical parameters on the pressurant gas (methane, helium, hydrogen, and nitrogen) requirements during the expulsion of liquid methane from a 1.52-meter-(5-ft-) diameter spherical tank and to compare results with those predicted by an analytical program. Also studied were the effects on methane, helium, and hydrogen pressurant requirements of various slosh excitation frequencies and amplitudes, both with and without slosh suppressing baffles in the tank. The experimental results when using gaseous methane, helium, and hydrogen show that the predictions of the analytical program agreed well with the actual pressurant requirements for static tank expulsions. The analytical program could not be used for gaseous nitrogen expulsions because of the large quantities of nitrogen which can dissolve in liquid methane. Under slosh conditions, a pronounced increase in gaseous methane requirements was observed relative to results obtained for the static tank expulsions. Slight decreases in the helium and hydrogen requirements were noted under similar test conditions.

Dewitt, R. L.↗
NASA NTRS1974

Bio-conversion of water hyacinths into methane gas, part 1

Bio-gas and methane production from the microbial anaerobic decomposition of water hyacinths (Eichhornia crassipes) (Mart) Solms was investigated. These experiments demonstrated the ability of water hyacinths to produce an average of 13.9 ml of methane gas per gram of wet plant weight. This study revealed that sample preparation had no significant effect on bio-gas and/or methane production. Pollution of water hyacinths by two toxic heavy materials, nickel and cadmium, increased the rate of methane production from 51.8 ml/day for non-contaminated plants incubated at 36 C to 81.0 ml/day for Ni-Cd contaminated plants incubated at the same temperature. The methane content of bio-gas evolved from the anaerobic decomposition of Ni-Cd contaminated plants was 91.1 percent as compared to 69.2 percent methane content of bio-gas collected from the fermentation of non-contaminated plants.

Wolverton, B. C.↗
NASA NTRS1983

Photochemistry of methane in the earth's early atmosphere

The photochemical behavior of methane in the early terrestrial atmosphere is investigated with a detailed model in order to determine how much CH4 might have been present and what types of higher hydroocarbons could have been formed. It is found that any primordial methane accumulated during the course of earth accretion would have been dissipated by photochemical reactions in the atmosphere in a geologically short period of time after the segregation of the core. Abiotic sources of methane are not likely to have been large enough to sustain CH4 mixing ratios as high as 10 to the -6th, the threshold for a possible methane greenhouse, with a CO-rich atmosphere being a possible exception. After the origin of life an increasing biogenic source of methane may have driven CH4 mixing ratios well above 10 to the 6th. The rise of atmospheric oxygen in the early Proterozoic may have led to a more rapid photochemical destruction of methane, lowering the mixing ratio to its present value.

Kasting, J. F.↗
NASA NTRS1983

Interpretation of the 6818.9-A methane feature observed on Jupiter, Saturn, and Uranus

High-resolution (0.1-A) spectra of the 6818.9-A methane feature obtained for Jupiter, Saturn, and Uranus by Baines, Schempp, and Smith (1969) are modeled using a doubling and adding code after Hansen (1983). The feature's rotational quantum number is estimated using the relatively homogeneous atmosphere of Saturn, with only J = 0 and J = 1 fitting the observational constraints. The aerosol content within Saturn's northern temperate region is shown to be substantially less than at the equator, indicating a haze only half as optically thick. Models of Jupiter's atmosphere are consistent with the rotational quantum-number assignment. Synthetic line profiles of the 6818.9-A feature observed on Uranus reveal that a substantial haze exists at or above the methane condensation region with an optical depth eight times greater than previously reported. Seasonal effects are indicated. The methane column abundance is 5 + or - 1 km-am. The mixing ratio of methane to hydrogen within the deep unsaturated region of the planet is 0.045 + or - 0.025, based on an H2 column abundance of 240 + or - 60 km-am (Smith, Macy, and Pilcher /1980/), thus indicating that methane comprises between one-sixth and one-half of the planet's mass. However, proper reevaluation of H2 quadrupole features accounting for the haze reported here may significantly reduce the relative methane abundance.

Baines, K. H.↗
NASA NTRS1984

Atmospheric methane in the recent and ancient atmospheres Concentrations, trends, and interhemispheric gradient

Rasmussen and Khalil (1981) have shown that the concentration of methane is increasing in the earth's atmosphere. A continuing increase of methane may perturb the global environment in the future by warming the earth and leading to more ozone and carbon monoxide in the atmosphere. It appears that the present concentration of methane may be more than twice as high as the natural levels of 150 years ago. An analysis of air bubbles buried long ago in polar ice makes it possible to deduce the concentrations of methane in the old and ancient atmospheres. The present investigation is concerned with the results of an analysis of more than 80 ice core samples, taking into account both polar regions of the earth. The samples range in age from about 100 to nearly 3000 years old. It is found that the concentration of methane started changing significantly about 150 years ago. These findings suggest that the increase of methane is probably indirectly caused by the rapid increase of human population.

Rasmussen, R. A.↗
NASA NTRS1988

Tropospheric methane from an Amazonian floodplain lake

The sources of methane and its flux to the troposphere from the Amazonian floodplain were investigated during the dry season of July and August 1985, using measurements of methane concentration gradients obtained aboard a houseboat laboratory anchored in Lago Calado, a stratified dendritic lake of about 6-sq km area located near the center of the Amazon Basin. Methane concentrations in the mixed layer of the lake were found to vary from 0.0001 to 0.0055 mM, with no consistent temporal trend. The measured methane flux from the surface of the open lake to the atmosphere averaged 27 mg CH4/sq m per day, consistent with the buildup in ambient methane in the nocturnal surface mixed layer of the troposphere. Ebullition contributed 70 percent to the average total flux. The source of methane to the lake and, ultimately, to the troposphere is the benthic sediments.

Crill, Patrick M.↗
NASA NTRS1990

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.↗
NASA NTRS1990

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.↗
NASA NTRS1989

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.↗
NASA NTRS1985

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.↗
NASA NTRS1982

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↗