Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Methane”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Seasonal and interannual variability in wetland methane emissions simulated by CLM4Me' and CAM-chem and comparisons to observations of concentrations

Understanding the temporal and spatial variation of wetland methane emissions is essential to the estimation of the global methane budget. Our goal for this study is three-fold: (i) to evaluate the wetland methane fluxes simulated in two versions of the Community Land Model, the Carbon-Nitrogen (CN; i.e., CLM4.0) and the Biogeochemistry (BGC; i.e., CLM4.5) versions using the methane emission model CLM4Me' so as to determine the sensitivity of the emissions to the underlying carbon model; (ii) to compare the simulated atmospheric methane concentrations to observations, including latitudinal gradients and interannual variability so as to determine the extent to which the atmospheric observations constrain the emissions; (iii) to understand the drivers of seasonal and interannual variability in atmospheric methane concentrations. Simulations of the transport and removal of methane use the Community Atmosphere Model with chemistry (CAM-chem) model in conjunction with CLM4Me' methane emissions from both CN and BGC simulations and other methane emission sources from literature. In each case we compare model-simulated atmospheric methane concentration with observations. In addition, we simulate the atmospheric concentrations based on the TransCom wetland and rice paddy emissions derived from a different terrestrial ecosystem model, Vegetation Integrative Simulator for Trace gases (VISIT). Our analysis indicates CN wetland methane emissions are higher in the tropics and lower at high latitudes than emissions from BGC. In CN, methane emissions decrease from 1993 to 2004 while this trend does not appear in the BGC version. In the CN version, methane emission variations follow satellite-derived inundation wetlands closely. However, they are dissimilar in BGC due to its different carbon cycle. CAM-chem simulations with CLM4Me' methane emissions suggest that both prescribed anthropogenic and predicted wetlands methane emissions contribute substantially to seasonal and interannual variability in atmospheric methane concentration. Simulated atmospheric CH 4 concentrations in CAM-chem are highly correlated with observations at most of the 14 measurement stations evaluated with an average correlation between 0.71 and 0.80 depending on the simulation (for the period of 1993–2004 for most stations based on data availability). Our results suggest that different spatial patterns of wetland emissions can have significant impacts on Northern and Southern hemisphere (N–S) atmospheric CH 4 concentration gradients and growth rates. In conclusion, this study suggests that both anthropogenic and wetland emissions have significant contributions to seasonal and interannual variations in atmospheric CH 4 concentrations. However, our analysis also indicates the existence of large uncertainties in terms of spatial patterns and magnitude of global wetland methane budgets, and that substantial uncertainty comes from the carbon model underlying the methane flux modules.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1996

Regulation of Methane Oxidation in a Freshwater Wetland by Water Table Changes and Anoxia

The effects of water table fluctuations and anoxia on methane emission and methane oxidation were studied in a freshwater marsh. Seasonal aerobic methane oxidation rates varied between 15% and 76% of the potential diffusive methane flux (diffusive flux in the absence of aerobic oxidation). On an annual basis, approximately 43% of the methane diffusing into the oxic zone was oxidized before reaching the atmosphere. The highest methane oxidation was observed when the water table was below the peat surface. This was confirmed in laboratory experiments where short-term decreases in water table levels increased methane oxidation but also net methane emission. Although methane emission was generally not observed during the winter, stems of soft rush (Juncus effusus) emitted methane when the marsh was ice covered. Indigenous methanotrophic bacteria from the wetiand studied were relatively anoxia tolerant. Surface peat incubated under anoxic conditions maintained 30% of the initial methane oxidation capacity after 32 days of anoxia. Methanotrophs from anoxic peat initiated aerobic methane oxidation relatively quickly after oxygen addition (1-7 hours). These results were supported by culture experiments with the methanotroph Methylosinus trichosporium OB3b. This organism maintained a greater capacity for aerobic methane oxidation when starved under anoxic compared to oxic conditions. Anoxic incubation of M. trichosporium OB3b in the presence of sulfide (2 mM) and a low redox potential (-110 mV) did not decrease the capacity for methane oxidation relative to anoxic cultures incubated without sulfide. The results suggest that aerobic methane oxidation was a major regulator of seasonal methane emission front the investigated wetland. The observed water table fluctuations affected net methane oxidation presumably due to associated changes in oxygen gradients. However, changes from oxic to anoxic conditions in situ had relatively little effect on survival of the methanotrophic bacteria and thus on methane oxidation potential per se.

Roslev, Peter↗
NASA NTRS2020

Exploring a Potentially Significant New(?) Mechanism for Methane Generation on Mars

An unexplored mechanism for methane production on Mars is presented here. Meteor showers have been hypothesized [1] as an explanation for episodic martian methane events [2-7], as the timing of meteor showers consistently correlates with the episodic methane events. The hypothesis [1] relied on production of methane via UV photolysis of extraterrestrial carbonaceous material [8,9] following dissemination of material into the martian atmosphere and onto the surface. Recently, new insights have emerged about an overlooked mechanism for methane production – plasma methanation [10,11] of martian atmospheric CO2 in meteor plasma. This mechanism can generate methane in addition to that produced by the previously explored methods of direct thermal evolution and UV photolysis, adding to the total methane budget produced through meteor infall. It also delivers methane in a rapid manner consistent with past observations of episodic methane “plumes” on Mars, and at altitudes where methane is rapidly removed afterwards. Methane produced by plasma methanation occurs at high altitude, which matches observations made on Mars where measurements collected through the full thickness of the martian atmosphere are of consistently higher methane concentrations (>10 ppbv [2-6]) than those recorded on the surface by the Mars Science Laboratory (MSL) rover (<10 ppbv [7]). High-altitude methane should be detected by the ESA Trace Gas Orbiter (TGO) which has not noted any methane to date. This result is puzzling regardless of the source of methane, but may be explained by the random nature of meteor shower outbursts – a significant infall may simply not have occurred (yet) during the ~3-Earth-year period of TGO observations.

Fries, M.↗
DOE OSTI2024

In situ aerobic methane oxidation rates in a stratified lake

Abstract Microbial aerobic methane oxidation is an important sink for aquatic methane worldwide. Despite its importance to global methane fluxes, few aerobic methane oxidation rates have been obtained in freshwater or marine environments without imposing changes to the microbial community through use of ex situ methods. A novel in situ incubation method for continuous time‐series measurements was used in Jordan Lake, North Carolina, during 2020–2021, to determine reaction kinetics for aerobic methane oxidation rates across a wide range of naturally varying methane (55–1833 nM) and dissolved oxygen (DO; 28–366 μM) concentrations and temperatures (17–30°C). Methane oxidation began immediately at the start of each of 21 incubations and methane oxidation rates were 1 st order with respect to methane. The data density allowed for accurate calculation of 1 st ‐order rate constants,k, that ranged from 0.018 to 0.462 h −1 (R 2 > 0.967). Addition of ammonium (20–45 μM) to natural concentrations ranging from 0.057 to 2.4 μM did not change aerobic methane oxidation rate kinetics, suggesting that the natural population of aerobic methane oxidizers in this eutrophic lake was not nitrogen limited. Values ofkinversely correlated most strongly with initial DO concentrations (R 2 = 0.82) rather than temperature. Values forkincreased with Julian day throughout our sampling period, suggesting seasonal influences on methane oxidation via responses to geochemical changes or shifts in microbial community abundance and composition. These experiments demonstrate a high variability in the enzymatic capacity for 1 st ‐order methane oxidation rates in this eutrophic lake that is tightly and inversely coupled to oxygen concentrations. Measurements of in situ aerobic methane oxidation rate constants allow for the direct quantification and modeling of the microbial community's capacity for methane oxidation over a wide range of natural methane concentrations.

Marine & Freshwater Biology↗
NASA NTRS1998

[Sources of Methane in the Boreal Region]

In determining the global methane budget the sources of methane must be balanced with the sinks and atmospheric inventory. The approximate contribution of the different methane sources to the budget has been establish showing the major terrestrial inputs as rice, wetlands, bogs, fens, and tundra. Measurements and modeling of production in these sources suggest that temperature, water table height and saturation along with substratum composition are important in controlling methane production and emission. The isotopic budget of 13 C and D/H in methane can be used as a tool to clarify the global budget. This approach has achieved success at constraining the inputs. Studies using the isotopic approach place constraints on global methane production from different sources. Also, the relation between the two biogenic production pathways, acetate fermentation and CO2 reduction, and the effect of substratum composition can be made using isotope measurements shows the relation between the different biogenic, thermogenic and anthropogenic sources of methane as a function of the carbon and hydrogen isotope values for each source and the atmosphere, tropospheric composition. Methane emissions from ponds and fens are a significant source in the methane budget of the boreal region. An initial study in 1993 and 1994 on the isotopic composition of this methane source and the isotopic composition in relation to oxidation of methane at the sediment surface of the ponds or fen was conducted as part of our BOREAS project. The isotopic composition of methane emitted by saturated anoxic sediment is dependent on the sediment composition and geochemistry, but will be influenced by in situ oxidation, in part, a function of rooted plant activity. The influence of oxidation mediated by rooted plant activities on the isotopic composition of methane is not well known and will depend on the plant type, sediment temperature, and numerous other variables. Information on this isotopic composition is important in both understanding the bio-geochemistry of the system and also in determining the regional and global inputs for the methane isotope budget. In determining the destruction of methane for balancing the atmospheric methane budget soil oxidation must be considered.

Source record↗
DOE OSTI2016

Cryptic Methane Emissions from Upland Forest Ecosystems

This exploratory research on Cryptic Methane Emissions from Upland Forest Ecosystems was motivated by evidence that upland ecosystems emit 36% as much methane to the atmosphere as global wetlands, yet we knew almost nothing about this source. The long-term objective was to refine Earth system models by quantifying methane emissions from upland forests, and elucidate the biogeochemical processes that govern upland methane emissions. The immediate objectives of the grant were to: (i) test the emerging paradigm that upland trees unexpectedly transpire methane, (ii) test the basic biogeochemical assumptions of an existing global model of upland methane emissions, and (iii) develop the suite of biogeochemical approaches that will be needed to advance research on upland methane emissions. We instrumented a temperate forest system in order to explore the processes that govern upland methane emissions. We demonstrated that methane is emitted from the stems of dominant tree species in temperate upland forests. Tree emissions occurred throughout the growing season, while soils adjacent to the trees consumed methane simultaneously, challenging the concept that forests are uniform sinks of methane. High frequency measurements revealed diurnal cycling in the rate of methane emissions, pointing to soils as the methane source and transpiration as the most likely pathway for methane transport. We propose the forests are smaller methane sinks than previously estimated due to stem emissions. Stem emissions may be particularly important in upland tropical forests characterized by high rainfall and transpiration, resolving differences between models and measurements. The methods we used can be effectively implemented in order to determine if the phenomenon is widespread.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2018

GES DISC Long-Term Data Analysis Services Using AIRS and CMS Methane Data as an Example

NASA Goddard Earth Sciences Data and Information Services Center (GES DISC) archives and distributes rich collections of data on atmospheric greenhouse gases from multiple satellite missions and model results. Among those greenhouse gases, atmospheric methane is a powerful greenhouse gas contributing ~0.5 (W/m^2) to total radiative forcing, and its concentration has increased by about 150% since 1750. Observations or estimates of methane emissions typically have sparse spatial and temporal coverage. The lack of comprehensive spatial and temporal coverage of methane source and sink observations has made analyzing atmospheric methane trends challenging. In this study the GES DISC aims to provide the community with the resources to better understand changes in atmospheric methane concentrations and the underlying causes. We will utilize methane datasets from Atmospheric Infrared Sounder (AIRS) retrieved methane concentration and three Carbon Monitoring System (CMS) methane emission datasets (in regions of North America, Canada, and Mexico) to compare AIRS methane growth with corresponding CMS regional methane emissions. Comparisons of AIRS methane growth rates and CMS methane emissions suggests wetland emissions may impact methane growth rate trends over North America. As the record for CMS methane data is extended, both datasets can be used in conjunction to better understand impacts on atmospheric methane trends. GES DISCs new anomaly tool can also be used on select datasets to further quantify trends in atmospheric greenhouse gases.

long-term data analysis↗
NASA NTRS2015

Investigations of Methane Production in Hypersaline Environments

The recent reports of methane in the atmosphere of Mars, as well as the findings of hypersaline paleo-environments on that planet, have underscored the need to evaluate the importance of biological (as opposed to geological) trace gas production and consumption. Methane in the atmosphere of Mars may be an indication of life but might also be a consequence of geologic activity and/or the thermal alteration of ancient organic matter. Hypersaline environments have now been reported to be extremely likely in several locations in our solar system, including: Mars, Europa, and Enceladus. Modern hypersaline microbial mat communities, (thought to be analogous to those present on the early Earth at a period of time when Mars was experiencing very similar environmental conditions), have been shown to produce methane. However, very little is known about the physical and/or biological controls imposed upon the rates at which methane, and other important trace gases, are produced and consumed in these environments. We describe here the results of our investigations of methane production in hypersaline environments, including field sites in Chile, Baja California Mexico, California, USA and the United Arab Emirates. We have measured high concentrations of methane in bubbles of gas produced both in the sediments underlying microbial mats, as well as in areas not colonized by microbial mats in the Guerrero Negro hypersaline ecosystem, Baja California Mexico, in Chile, and in salt ponds on the San Francisco Bay. The carbon isotopic (δ13C) composition of the methane in the bubbles exhibited an extremely wide range of values, (ca. -75 per mille ca. -25 per mille). The hydrogen isotopic composition of the methane (δ2H) ranged from -60 to -30per mille and -450 to -350per mille. These isotopic values are outside of the range of values normally considered to be biogenic, however incubations of the sediments in contact with these gas bubbles reveals that the methane is indeed being produced by these sediments. Substrate limitation of methanogenesis in these environments, and not methane oxidation, would explain the isotopic values of the methane in these environments. Incubations with both isotopically labeled and unlabeled putative substrates for methanogenesis have shown that the substrates most important for methanogenesis in these environments are the so-called non-competitive substrates, e.g., methylamines, dimethylsulfide, and methanol. Acetate and bicarbonate appear not to be important substrates for methanogens in these environments. Extraction of DNA and analysis of a gene used for methane production (mcrA) has revealed that the community composition of methanogens is consistent with organisms known to use non-competitive substrates. Our work has shown that hypersaline environments have the potential to both produce and preserve methane for analysis, e.g., by capable rovers. Our work expends the range of methane isotopic values now known to be produced by active methanogenesis

hypersaline paleo-environments↗
DOE OSTI2022

Cryptic Methane-Cycling by Methanogens During Multi-Year Incubation of Estuarine Sediment

As marine sediments are buried, microbial communities transition from sulfate-reduction to methane-production after sulfate is depleted. When this biogenic methane diffuses into the overlying sulfate-rich sediments, it forms a sulfate-methane transition zone (SMTZ) because sulfate reducers deplete hydrogen concentrations and make hydrogenotrophic methanogenesis exergonic in the reverse direction, a process called the anaerobic oxidation of methane (AOM). Microbial participation in these processes is often inferred from geochemistry, genes, and gene expression changes with sediment depth, using sedimentation rates to convert depth to time. Less is known about how natural sediments transition through these geochemical states transition in real-time. We examined 16S rRNA gene amplicon libraries and metatranscriptomes in microcosms of anoxic sediment from the White Oak River estuary, NC, with three destructively sampled replicates with methane added (586-day incubations) and three re-sampled un-amended replicates (895-day incubations). Sulfate dropped to a low value (∼0.3 mM) on similar days for both experiments (312 and 320 days, respectively), followed by a peak in hydrogen, intermittent increases in methane-cycling archaea starting on days 375 and 362 (mostly Methanolinea spp. and Methanosaeta spp., and Methanococcoides sp. ANME-3), and a methane peak 1 month later. However, methane δ 13 C values only show net methanogenesis 6 months after methane-cycling archaea increase and 4 months after the methane peak, when sulfate is consistently below 0.1 mM and hydrogen increases to a stable 0.61 ± 0.13 nM (days 553–586, n = 9). Sulfate-reducing bacteria (mostly Desulfatiglans spp. and Desulfosarcina sp. SEEP-SRB1) increase in relative abundance only during this period of net methane production, suggesting syntrophy with methanogens in the absence of sulfate. The transition from sulfate reduction to methane production in marine sediments occurs through a prolonged period of methane-cycling by methanogens at low sulfate concentrations, and steady growth of sulfate reducers along with methanogens after sulfate is depleted.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Co-aromatization of olefin and methane over Ag-Ga/ZSM-5 catalyst at low temperature

The massive exploitation of shale gas in the past decade has boosted the production of natural gas and reduced its price dramatically. The methane activation and following conversion into more valuable fuels and chemicals have thus become more and more attractive, while the introduction of hydrocarbons to enhance the methane activation at mild conditions represents a promising approach. In the present work, the co-aromatization of methane with propylene has been studied at 400 °C. The presence of methane would increase the toluene to benzene ratio as well as the average carbon number of the formed liquid aromatic products compared to its propylene alone counterpart. Among the gas products, the formations of C 3 H 8 , C 4 H 8 and C 4 H 10 also get promoted when methane is present. The incorporation of methane into the product molecules is also directly evidenced by the 1 H, 2 D and 13 C NMR spectroscopy of the liquid products obtained from the reaction between propylene (or styrene) and isotope labelled methane. Hydrogen from methane would contribute a large portion of the hydrogen in the product molecules, while the benzylic and aromatic hydrogen sites are favored compared with those on the alkyl side chains. The activation of methane is also observed in the DRIFT spectra when deuterium enriched methane is engaged as the methane source and evidenced by the escalated exothermic feature when olefin aromatization takes place under methane environment. The excellent catalytic performance of Ag-Ga/ZSM-5 might be because of the better dispersion of Ag and Ga on the ZSM-5 surface and moderate amount of strong Brosted and Lewis surface acid sites. All the observations suggest that methane might be activated nonoxidatively and converted into aromatics if suitable catalyst is charged under the assistance of co-existing olefin. In conclusion, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and petrochemical intermediates.

09 BIOMASS FUELS↗
DOE OSTI2016

Diverse origins of Arctic and Subarctic methane point source emissions identified with multiply-substituted isotopologues

Methane is a potent greenhouse gas, and there are concerns that its natural emissions from the Arctic could act as a substantial positive feedback to anthropogenic global warming. Determining the sources of methane emissions and the biogeochemical processes controlling them is important for understanding present and future Arctic contributions to atmospheric methane budgets. We apply measurements of multiply-substituted isotopologues, or clumped isotopes, of methane as a new tool to identify the origins of ebullitive fluxes in Alaska, Sweden and the Arctic Ocean. When methane forms in isotopic equilibrium, clumped isotope measurements indicate the formation temperature. In some microbial methane, however, non-equilibrium isotope effects, probably related to the kinetics of methanogenesis, lead to low clumped isotope values. We identify four categories of emissions in the studied samples: thermogenic methane, deep subsurface or marine microbial methane formed in isotopic equilibrium, freshwater microbial methane with non-equilibrium clumped isotope values, and mixtures of deep and shallow methane (i.e., combinations of the first three end members). Mixing between deep and shallow methane sources produces a non-linear variation in clumped isotope values with mixing proportion that provides new constraints for the formation environment of the mixing end-members. Analyses of microbial methane emitted from lakes, as well as a methanol-consuming methanogen pure culture, support the hypothesis that non-equilibrium clumped isotope values are controlled, in part, by kinetic isotope effects induced during enzymatic reactions involved in methanogenesis. Our results indicate that these kinetic isotope effects vary widely in microbial methane produced in Arctic lake sediments, with non-equilibrium Δ 18 values spanning a range of more than 5‰.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Assessing the response of methane hydrates to environmental change at the Svalbard continental margin

This project reflects the results of cooperative research efforts between the US Department of Energy and scientists from Norway and Germany, who collaboratively designed the study, collected and analyzed samples from the water column and sediment and arrive at conclusions presented in joint publications. The main goal of the project was to assess the role of gas hydrate deposits in modulating methane discharge revealed through water column data, and assess the changes in environmental parameters, geochemical and microbiological conditions that drive the methane release in this high latitude region. Samples and data were collected from seven expeditions that encompassed extensive water column surveys, gravity coring, remotely-operated towed instrumentation and seafloor drilling campaigns. Geochemical and microbiological results were interpreted in the context of correlative geophysical data and numerical models, to generate a comprehensive and interdisciplinary view of the processes operating along the Svalbard margin. Incubation experiments complement the filed observations and provide additional data on the microbiological response to methane change. Collectively our results show that methane seepage in this margin is a component of a large methane plume, the Svalbard plume, which is not associated with gas hydrate processes. Consistently, numerical models of data from shallow (gravity cores offshore Storfjordrenna, bearing gas hydrate) and deep (MeBo drilling offshore Prins Karls Foreland) sediment samples show that methane and gas hydrate dynamics at sites that lie within the upper edge of gas hydrate stability are not responding to modern changes in bottom water temperature. Rather the data point to a long history of methane release, dominantly controlled by large scale Earth system changes (e.g., geology, oceanography, and glaciology) with gas hydrate as a temporary methane reservoir. Further results document the episodicity of the methane release, the role of microbes in sequestering methane carbon into authigenic carbonate, reaction networks involved in carbon recycling pathways at the sulfate-methane transition, and response of microbial communities to changes in methane flux allowing for a richer understanding of microbial ecology in response to change at methane seep sites.

58 GEOSCIENCES↗
DOE OSTI2024

Addressing Low-Cost Methane Sensor Calibration Shortcomings with Machine Learning

Quantifying methane emissions is essential for meeting near-term climate goals and is typically carried out using methane concentrations measured downwind of the source. One major source of methane that is important to observe and promptly remediate is fugitive emissions from oil and gas production sites but installing methane sensors at the thousands of sites within a production basin is expensive. In recent years, relatively inexpensive metal oxide sensors have been used to measure methane concentrations at production sites. Current methods used to calibrate metal oxide sensors have been shown to have significant shortcomings, resulting in limited confidence in methane concentrations generated by these sensors. To address this, we investigate using machine learning (ML) to generate a model that converts metal oxide sensor output to methane mixing ratios. To generate test data, two metal oxide sensors, TGS2600 and TGS2611, were collocated with a trace methane analyzer downwind of controlled methane releases. Over the duration of the measurements, the trace gas analyzer’s average methane mixing ratio was 2.40 ppm with a maximum of 147.6 ppm. The average calculated methane mixing ratios for the TGS2600 and TGS2611 using the ML algorithm were 2.42 ppm and 2.40 ppm, with maximum values of 117.5 ppm and 106.3 ppm, respectively. A comparison of histograms generated using the analyzer and metal oxide sensors mixing ratios shows overlap coefficients of 0.95 and 0.94 for the TGS2600 and TGS2611, respectively. Overall, our results showed there was a good agreement between the ML-derived metal oxide sensors’ mixing ratios and those generated using the more accurate trace gas analyzer. This suggests that the response of lower-cost sensors calibrated using ML could be used to generate mixing ratios with precision and accuracy comparable to higher priced trace methane analyzers. This would improve confidence in low-cost sensors’ response, reduce the cost of sensor deployment, and allow for timely and accurate tracking of methane emissions.

03 NATURAL GAS↗
DOE OSTI2025

Temperature and Water Levels Collectively Regulate Methane Emissions From Subtropical Freshwater Wetlands

Abstract Wetlands are the largest and most climate‐sensitive natural sources of methane. Accurately estimating wetland methane emissions involves reconciling inversion (“top‐down”) and process‐based (“bottom‐up”) models within the global methane budget. However, estimates from these two model types are inherently interdependent and often reveal substantial discrepancies. To enhance the reliability of both approaches, we need a comprehensive understanding of wetland methane emissions and an independent high‐resolution long‐term flux data set. Here, we employed a data‐driven random forest approach to identify key variables influencing methane emissions from subtropical freshwater wetlands in the Southeastern United States. The model‐estimated monthly mean methane fluxes fit well with measured methane fluxes ( R 2 = 0.67) at four representative FLUXNET‐CH4 wetland sites across the region. Variable importance analysis highlighted the sensitivity of subtropical freshwater wetland methane emissions to variations in both temperature and water levels. High temperatures facilitate methanogenesis by enhancing microbial activities, while elevated water levels maintain anaerobic conditions necessary for methane production. Notably, the response of methane emissions to water level fluctuations is contingent on temperature conditions, and vice versa. Moreover, we constructed the first high‐spatial‐resolution (∼1 km × 1 km) and long‐term (1982–2010) gridded regional wetland methane flux product for the Southeastern United States, estimating annual methane emissions from subtropical freshwater wetlands in the region at 4.93 ± 0.11 Tg CH 4 yr −1 for 1982–2010. This new benchmark product holds promise for validating and parameterizing uncertain wetland methane emission processes in bottom‐up models and provides improved prior information for top‐down models.

He, Keqi [Earth and Climate Sciences Nicholas Scho↗
DOE OSTI2020

Assessment of Methane Generation from the Thermolysis of Organics in Caustic Waste

Methane generation has been detected during thermolytic Hydrogen Generation Rate (HGR) testing of SRS tank waste and in simulant samples. Simulant testing has shown methane generation in the presence of trimethylsilanol (TMS) and radioactive sample testing has shown methane generation in presence of methylmercury, both of which are found within SRS waste tanks. The 2019 report Evaluation of the Current State of Knowledge for Thermolysis of Organics within SRS Waste Forming Volatile Organic Compounds (VOCs) reviewed historical data and assessed literature pertaining to thermolytic methane generation. That review recommended undertaking thermolysis studies on simulated waste to detect and quantify VOCs. The purpose of this assessment is to review chemistry and current knowledge of organics in SRS waste to recommend which organics in SRS waste tanks, if any, should be tested for thermolytic methane generation. An evaluation of observed methane generation rates has been performed to assess the implication for current CSTF controls. Based on the inputs used in this report, it was concluded that no methane generation data observed to date has challenged the existing 5% organic contribution to the Composite Lower Flammability Limit (CLFL) assumption in the CSTF tank farm at temperatures below 100 °C. Evidence shows that thermolytic pathways to methane generation become significant at temperatures >100 °C in caustic waste. Currently, the influences of thermolytic methane production on the flammability of vessels at >100 °C (e.g., evaporators) is unclear. It is recommended that testing should be undertaken using the HGR experimental approach for methane generation. The initial simulant testing should obtain quantitative methane generation rates at elevated temperatures for methylated siloxanes/silanes and methylmercury with the goal of determining the current mechanism for thermolytic methane generation seen in SRS tank waste. The results of this testing should then be compiled and analyzed to ascertain the risk of challenging the current projected organic contribution of 5% to the CLFL at elevated temperatures. Following this testing, an evaluation of possible flammable gas generation in the 2H and 3H Evaporators should be performed to assess the risk of methane generation at the high temperatures employed by the evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Detectability of Arctic methane sources at six sites performing continuous atmospheric measurements

Understanding the recent evolution of methane emissions in the Arctic is necessary to interpret the global methane cycle. Emissions are affected by significant uncertainties and are sensitive to climate change, leading to potential feedbacks. A polar version of the CHIMERE chemistry-transport model is used to simulate the evolution of tropospheric methane in the Arctic during 2012, including all known regional anthropogenic and natural sources, in particular freshwater emissions which are often overlooked in methane modelling. CHIMERE simulations are compared to atmospheric continuous observations at six measurement sites in the Arctic region. In winter, the Arctic is dominated by anthropogenic emissions; emissions from continental seepages and oceans, including from the East Siberian Arctic Shelf, can contribute significantly in more limited areas. In summer, emissions from wetland and freshwater sources dominate across the whole region. The model is able to reproduce the seasonality and synoptic variations of methane measured at the different sites. We find that all methane sources significantly affect the measurements at all stations at least at the synoptic scale, except for biomass burning. In particular, freshwater systems play a decisive part in summer, representing on average between 11 and 26 % of the simulated Arctic methane signal at the sites. This indicates the relevance of continuous observations to gain a mechanistic understanding of Arctic methane sources. Sensitivity tests reveal that the choice of the land-surface model used to prescribe wetland emissions can be critical in correctly representing methane mixing ratios. The closest agreement with the observations is reached when using the two wetland models which have emissions peaking in August–September, while all others reach their maximum in June–July. Such phasing provides an interesting constraint on wetland models which still have large uncertainties at present. Also testing different freshwater emission inventories leads to large differences in modelled methane. Attempts to include methane sinks (OH oxidation and soil uptake) reduced the model bias relative to observed atmospheric methane. Here, the study illustrates how multiple sources, having different spatiotemporal dynamics and magnitudes, jointly influence the overall Arctic methane budget, and highlights ways towards further improved assessments.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2011

Robust IR Remote Sensing Technique of the Total Column of Trace Gases Including Carbon Dioxide and Methane

Progress on the development of a differential radiometer based upon the Fabry-Perot interferometer (FPI) for methane (CH4) and carbon dioxide (C02) detection in the atmosphere is presented. Methane measurements are becoming increasingly important as a component of NASA's programs to understand the global carbon cycle and quantifY the threat of global warming. Methane is the third most important greenhouse gas in the Earth's radiation budget (after water vapor and carbon dioxide) and the second most important anthropogenic contributor to global warming. The importance of global warming and air quality to society caused the National Research Council to recommend that NASA develop the following missions [1]: ASCENDS (Active Sensing of C02 Emissions over Nights, Days, and Seasons), GEOCAPE (Geostationary Coastal and Air Pollution Events), and GACM (Global Atmosphere Composition Mission). Though methane measurements are not specifically called out in these missions, ongoing environmental changes have raised the importance of understanding the methane budget. In the decadal survey is stated that "to close the carbon budget, we would also address methane, but the required technology is not obvious at this time. If appropriate and cost-effective methane technology becomes available, we strongly recommend adding a methane capability". In its 2007 report the International Panel on Climate Change identified methane as a key uncertainty in our understanding saying that the causes of recent changes in the growth rate of atmospheric CH4 are not well understood. What we do know is that methane arises from a number of natural sources including wet lands and the oceans plus man made sources from agriculture, as well as coal and petroleum production and distribution. It has recently been pointed out that large amount of methane are frozen in the permafrost of Canada and Siberia. There is a fear that melting of this permafrost driven by global warming may release large amounts of methane very suddenly further exacerbating climate change [2]. Last year our group began a joint effort with Johns Hopkins Applied Physics Laboratory to investigate the possibility of developing a small unmanned aerial vehicle (UAV) equipped to measure greenhouse gases-particularly methane. Although we are targeting our system for smaller UAV's the instrument will be directly applicable to missions involving larger NASA UAV's such as Global Hawk or even on missions utilizing manned aircraft. Because of its small size, inherent ruggedness and simplicity some version of our proposed instrument may find a role as a satellite instrument for NASA or NOAA.

Georgieva, E. M.↗
DOE OSTI2018

Catalytic generation of methane at 60–100 °C and 0.1–300 MPa from source rocks containing kerogen Types I, II, and III

Low temperature (60 and 100 °C) and long-term (6 months to 5 years) heating of pre-evacuated and sterilized shales and coals containing kerogen Types I (Mahogany Shale), II (Mowry Shale and New Albany Shale), and III (Springfield Coal and Wilcox Lignite) with low initial maturities (vitrinite reflectance Ro 0.39–0.62%) demonstrates that catalytically generated hydrocarbons may explain the occurrence of some non-biogenic natural gas accumulations where insufficient thermal maturity contradicts the conventional thermal cracking paradigm. Extrapolation of the observed rate of catalytic methanogenesis in the laboratory suggests that significant amounts of sedimentary organic carbon can be converted to relatively dry natural gas over tens of thousands of years in sedimentary basins at temperatures as low as 60 °C. Here, our laboratory experiments utilized source rock (shale and coal) chips sealed in gold and Pyrex® glass tubes in the presence of hydrogen-isotopically contrasting waters. Parallel heating experiments applied hydrostatic pressures from 0.1 to 300 MPa. Control experiments constrained the influence of pre-existing and residual methane in closed pores of rock chips that was unrelated to newly generated methane. This study’s experimental methane yields at 60 and 100 °C are 5–11 orders of magnitude higher than the theoretically predicted yields from kinetic models of thermogenic methane generation, which strongly suggests a contribution of catalytic methanogenesis. Higher temperature, longer heating time, and lower hydrostatic pressure enhanced catalytic methanogenesis. No clear relationships were observed between kerogen type or total organic carbon content and methane yields via catalysis. Catalytic methanogenesis was strongest in Mowry Shale where methane yields at 60 °C amounted to ~2.5 μmol per gram of organic carbon after one year of hydrous heating at ambient pressure. In stark contrast to the earlier findings of hydrogen isotopic exchange between water and thermogenic methane in hydrous pyrolysis experiments above 300 °C, the hydrogen isotopic composition of added water exerted limited influence on the δ2H value of methane generated catalytically at low temperatures. We hypothesize that the catalytic sites responsible for methanogenesis are located in hydrophobic microenvironments with limited access to water. The δ13CCH4 values of methane generated catalytically at 60–100 °C range from ~–57.6 to –41.4‰ and are thus similar to typical thermogenic methane (δ13CCH4 >–50‰) and microbially generated methane (<–55‰). Future studies need to evaluate the possibility that clumped isotope characteristics of catalytically generated methane can diagnose the low-temperature regime of catalytic methanogenesis. Furthermore, testing of freshly cored anoxic rocks is needed to determine whether the use of archived, oxygen-exposed rocks in geochemical maturation/catalysis studies introduces artifacts in experimental hydrocarbon yields.

58 GEOSCIENCES↗