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All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Methane emissions from MBT landfills

Highlights: • Compilation of methane generation potential of mechanical biological treated (MBT) municipal solid waste. • Impacts and kinetics of landfill gas production of MBT landfills, approach with differentiated half-lives. • Methane oxidation in the waste itself and in soil covers. • Estimation of methane emissions from MBT landfills in Germany. - Abstract: Within the scope of an investigation for the German Federal Environment Agency (“Umweltbundesamt”), the basics for the estimation of the methane emissions from the landfilling of mechanically and biologically treated waste (MBT) were developed. For this purpose, topical research including monitoring results regarding the gas balance at MBT landfills was evaluated. For waste treated to the required German standards, a methane formation potential of approximately 18–24 m{sup 3} CH{sub 4}/t of total dry solids may be expected. Monitoring results from MBT landfills show that a three-phase model with differentiated half-lives describes the degradation kinetics in the best way. This is due to the fact that during the first years of disposal, the anaerobic degradation processes still proceed relatively intensively. In addition in the long term (decades), a residual gas production at a low level is still to be expected. Most of the soils used in recultivation layer systems at German landfills show a relatively high methane oxidation capacity up to 5 l CH{sub 4}/(m{sup 2} h). However, measurements at MBT disposal sites indicate that the majority of the landfill gas (in particular at non-covered areas), leaves the landfill body via preferred gas emission zones (hot spots) without significant methane oxidation. Therefore, rather low methane oxidation factors are recommended for open and temporarily covered MBT landfills. Higher methane oxidation rates can be achieved when the soil/recultivation layer is adequately designed and operated. Based on the elaborated default values, the First Order Decay (FOD) model of the IPCC Guidelines for National Greenhouse Gas Inventories, 2006, was used to estimate the methane emissions from MBT landfills. Due to the calculation made by the authors emissions in the range of 60,000–135,000 t CO{sub 2-eq.}/a for all German MBT landfills can be expected. This wide range shows the uncertainties when the here used procedure and the limited available data are applied. It is therefore necessary to generate more data in the future in order to calculate more precise methane emission rates from MBT landfills. This is important for the overall calculation of the climate gas production in Germany which is required once a year by the German Government.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Three Decades of Wetland Methane Surface Flux Modeling by Earth System Models–Advances, Applications, and Challenges

Earth System Models (ESMs) simulate the exchange of mass and energy between the land surface and the atmosphere, with a key focus on modeling natural greenhouse gas feedbacks. Methane is the second most important greenhouse gas after carbon dioxide. There are growing concerns over the rapidly increasing methane concentration in the atmosphere, underscoring the need for accurate global modeling of its emissions using ESMs. Of the multitude of sources of methane globally, wetlands are the largest natural emitters for methane, leading to significant efforts targeting their representation in ESMs with a special focus on their methane emissions. In this review, we first provide a historical overview of including wetland–methane components in ESMs and how methane modeling approaches have evolved over time. Second, we discuss recent modeling advancements that show promise for improvements in methane emissions predictions, namely the coupling of surface and atmospheric modules of ESMs, the representation of microtopography and transport mechanisms, the resolution of microbial processes at different spatial–temporal scales, and the improved mapping of wetland area extent across the different wetland types. Third, we shed light on the different challenges hindering accurate estimations of wetland–methane emissions, as shown by the consistent discrepancy between bottom–up and top–down models' predictions. Finally, we emphasize that more detailed representation of biogeochemistry and dynamic hydrology while resolving the within–wetland vegetation heterogeneity should improve model predictions, especially when coupled with expanding ground–based measurement networks and high–resolution remote sensing mapping of methane–relevant variables, such as water elevation, water table depth, and methane concentration.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Low-temperature activation of methane on doped single atoms: descriptor and prediction

Catalytic transformation of methane under mild conditions remains a grand challenge. Fundamental understanding of C–H activation of methane is crucial for designing a catalyst for the utilization of methane at low temperature. Recent experiments show that strong methane chemisorption on oxides of precious metals leads to facile C–H activation. However, only a very few such oxides are capable (for example, IrO 2 and PdO). Here we show for the first time that strong methane chemisorption and facile C–H activation can be accomplished by single transition-metal atoms on TiO 2 , some of which are even better than IrO 2 . Using methane adsorption energy as a descriptor, we screened over 30 transition-metal single atoms doped on TiO 2 for the chemisorption of methane by replacing a surface Ti atom with a single atom of another transition metal. It is found that the adsorption energies of methane on a single atom of Pd, Rh, Os, Ir, and Pt doped on rutile TiO 2 (110) are greater than or similar to those on rutile IrO 2 (110), a benchmark for the chemisorption of methane on transition oxides. Electronic structure analysis uncovered orbital overlap and mixing between methane and the single atom, as well as significant localization of the charge between the molecule and the surface, demonstrating chemical bonding of CH 4 to doped single atoms. Facile C–H dissociation has been found on the single-atom sites with the transition state energies lower than desorption energies. We report our computational studies predict that Pd, Rh, Os, Ir, and Pt single atoms on rutile TiO 2 (110) can activate C–H of methane at a temperature lower than 25 °C.

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

Members of the Genus Methylobacter Are Inferred To Account for the Majority of Aerobic Methane Oxidation in Oxic Soils from a Freshwater Wetland

ABSTRACT Microbial carbon degradation and methanogenesis in wetland soils generate a large proportion of atmospheric methane, a highly potent greenhouse gas. Despite their potential to mitigate greenhouse gas emissions, knowledge about methane-consuming methanotrophs is often limited to lower-resolution single-gene surveys that fail to capture the taxonomic and metabolic diversity of these microorganisms in soils. Here our objective was to use genome-enabled approaches to investigate methanotroph membership, distribution, and in situ activity across spatial and seasonal gradients in a freshwater wetland near Lake Erie. 16S rRNA gene analyses demonstrated that members of the methanotrophic Methylococcales were dominant, with the dominance largely driven by the relative abundance of four taxa, and enriched in oxic surface soils. Three methanotroph genomes from assembled soil metagenomes were assigned to the genus Methylobacter and represented the most abundant methanotrophs across the wetland. Paired metatranscriptomes confirmed that these Old Woman Creek (OWC) Methylobacter members accounted for nearly all the aerobic methanotrophic activity across two seasons. In addition to having the capacity to couple methane oxidation to aerobic respiration, these new genomes encoded denitrification potential that may sustain energy generation in soils with lower dissolved oxygen concentrations. We further show that Methylobacter members that were closely related to the OWC members were present in many other high-methane-emitting freshwater and soil sites, suggesting that this lineage could participate in methane consumption in analogous ecosystems. This work contributes to the growing body of research suggesting that Methylobacter may represent critical mediators of methane fluxes in freshwater saturated sediments and soils worldwide. IMPORTANCE Here we used soil metagenomics and metatranscriptomics to uncover novel members within the genus Methylobacter . We denote these closely related genomes as members of the lineage OWC Methylobacter . Despite the incredibly high microbial diversity in soils, here we present findings that unexpectedly showed that methane cycling was primarily mediated by a single genus for both methane production (“ Candidatus Methanothrix paradoxum”) and methane consumption (OWC Methylobacter ). Metatranscriptomic analyses revealed that decreased methanotrophic activity rather than increased methanogenic activity possibly contributed to the greater methane emissions that we had previously observed in summer months, findings important for biogeochemical methane models. Although members of this Methylococcales order have been cultivated for decades, multi-omic approaches continue to illuminate the methanotroph phylogenetic and metabolic diversity harbored in terrestrial and marine ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Gene and transcript abundances of bacterial type III secretion systems from the rumen microbiome are correlated with methane yield in sheep

Background: Ruminants are important contributors to global methane emissions via microbial fermentation in their reticulo-rumens. This study is part of a larger program, characterising the rumen microbiomes of sheep which vary naturally in methane yield (g CH4/kg DM/day) and aims to defne diferences in microbial communities, and in gene and transcript abundances that can explain the animal methane phenotype. Methods: Rumen microbiome metagenomic and metatranscriptomic data were analysed by Gene Set Enrichment, sparse partial least squares regression and the Wilcoxon Rank Sum test to estimate correlations between specifc KEGG bacterial pathways/genes and high methane yield in sheep. KEGG genes enriched in high methane yield sheep were reassembled from raw reads and existing contigs and analysed by MEGAN to predict their phylogenetic origin. Protein coding sequences from Succinivibrio dextrinosolvens strains were analysed using Efective DB to predict bacterial type III secreted proteins. The efect of S. dextrinosolvens strain H5 growth on methane formation by rumen methanogens was explored using co-cultures. Results: Detailed analysis of the rumen microbiomes of high methane yield sheep shows that gene and transcript abundances of bacterial type III secretion system genes are positively correlated with methane yield in sheep. Most of the bacterial type III secretion system genes could not be assigned to a particular bacterial group, but several genes were afliated with the genus Succinivibrio, and searches of bacterial genome sequences found that strains of S. dextrinosolvens were part of a small group of rumen bacteria that encode this type of secretion system. In co-culture experiments, S. dextrinosolvens strain H5 showed a growth-enhancing efect on a methanogen belonging to the order Methanomassiliicoccales, and inhibition of a representative of the Methanobrevibacter gottschalkii clade. Conclusions: This is the frst report of bacterial type III secretion system genes being associated with high methane emissions in ruminants, and identifes these secretions systems as potential new targets for methane mitigation research. The effects of S. dextrinosolvens on the growth of rumen methanogens in co-cultures indicate that bacteriamethanogen interactions are important modulators of methane production in ruminant animals.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Co-synthesis of Hydrogen and High-Value Carbon Products from Methane Pyrolysis

The ARPA-E Methane Pyrolysis Project successfully developed a scalable technology for hydrogen production with low-CO x emission through methane pyrolysis, co-producing high-value carbon nanotubes (CNTs). The project focused on optimizing reactor design, enhancing catalyst performance, and assessing techno-economic feasibility to create a commercially viable and environmentally sustainable process. The fluidized bed reactor achieved over 90% methane (CH 4 ) conversion by using a 5% CO 2 co-feed, which stabilizes carbon yields and minimizes catalyst deactivation. This setup allowed for continuous operation across ten cycles, each consisting of a 14-minute pyrolysis phase followed by a 10-minute dislodging phase to remove a fraction of the accumulated carbon, resulting in stable performance and high-quality CNT production. In parallel, monolith reactors coated with Fe demonstrated a sustained methane conversion of 73% while producing CNTs with high crystallinity. Although promising for continuous operation, monolith reactors face challenges in coating durability and scalability, highlighting areas for further optimization in commercial applications. Catalyst formulation played a key role in enhancing process efficiency. The core catalyst used was 5%Fe/Al 2 O 3 (wt%), optimized through wet impregnation, which improved CNT morphology, yielding longer and more uniform CNTs. The catalyst's performance was further enhanced by adding promoters: 2.5 wt% Ni increased methane conversion close to the thermodynamic limit, while 2.5 wt% Mn improved CNT alignment and crystallinity, and 1.5 wt% NaCl boosted CNT morphology but slightly lowered methane conversion. These adjustments allowed the reactor to maintain high methane conversion while producing high-quality CNTs, enabling stable performance over multiple cycles. To address carbon buildup and ensure uninterrupted operation, a pneumatic conveying tube was implemented for effective carbon dislodging in the fluidized bed configuration. CO 2 and H 2 O co-feeds were also introduced to enhance carbon removal, with CO 2 boosting CNT yield by approximately 15%. This setup enabled stable reactor operation across multiple cycles, preventing clogging and minimizing catalyst wear, making the process suitable for industrial scaling. Techno-economic analysis (TEA) projected hydrogen production costs between $\$$1.00 and $\$$1.64 per kilogram, with CNT values assumed at $\$$375/ton and $\$$100/ton. The life cycle assessment showed that CO 2 emissions could be as low as 0.64 kg CO 2 e/kg H 2 at 95% methane conversion assuming an electricity input of 50 kg CO 2 e/MWh. Even at 50% methane conversion, emissions remained below 1 kg CO 2 e/kg H 2 , demonstrating the process's low-emission potential and making it a viable alternative to traditional steam methane reforming. Overall, the results from this project demonstrate the feasibility of a pyrolysis process where carbon is continuously removed from the catalyst surface and hydrogen is continuously produced until a catalyst regeneration step is required to fully clean the catalyst surface and renew catalyst performance. Major open challenges are related to avoiding the loss of catalyst material in the dislodged carbon during fluidized bed conditions, since our best result demonstrated a carbon purity of ~70 wt. % (rest being iron and alumina). A monolith reactor was used to favor dislodgement of carbon compared to fluidized bed conditions but our results do not demonstrate an advantage of the monolith configuration. Catalyst performance was similar to fluidized bed conditions with slower deactivation rates overall, but we could not observe carbon dislodging in any of the tens of experiments that were run at Stanford. Our results show that the most relevant areas of improvement are related to the fundamental understanding of the iron-carbon interface for dislodging, and the development of catalyst that can produce CNTs via a base-growth mechanism such that catalyst is not lost in the dislodgement steps. The final report documents all findings and methodologies in detail, providing a valuable resource for the scientific community. By building on these results, researchers can further advance methane pyrolysis technology, moving toward a more sustainable, scalable pathway for hydrogen production. This work lays the foundation for future research and commercial efforts to reduce emissions in hydrogen production while generating valuable carbon products.

08 HYDROGEN↗
DOE OSTI2025

Hydrological Controls on Riverbed Methane Emissions: A Numerical Investigation of Hydrodynamic and Ebullitive Mechanisms from Site to Basin Scales

Methane production and emission from riverbed sediments constitute a significant yet underexplored component of the river methane budget. Despite their importance, a mechanistic and quantitative understanding of these processes under dynamic flow conditions remains elusive, particularly at the basin scale. In this study, we investigate the multiscale (site-to-basin) mechanisms governing methane emissions from riverbeds, focusing on the interplay between biogeochemical processes and hydrological dynamics. We developed a reactive transport model that integrates methane production with hydrodynamic and ebullitive pathways and coupled it with a basin-scale groundwater flow model to simulate methane emissions across scales. By incorporating key factors such as vertical hydrological exchange flow (VHEF), particulate organic carbon availability, sediment properties, and temperature sensitivity, our model captures the spatiotemporal variability of methane ebullition at both the site and basin scales. Our results reveal that methane ebullition is strongly modulated by VHEF, with lower flow rates promoting methane accumulation and subsequent ebullition. Sensitivity analyses underscore nonlinear responses of methane fluxes to environmental drivers. Furthermore, these findings emphasize the critical roles of sediment composition, hydrological exchange, and environmental conditions in shaping methane dynamics. Overall, this work advances our understanding of riverine methane emissions and offers insights for guiding climate models and mitigation strategies.

Fluxes↗
DOE OSTI2015

Expression of barley SUSIBA2 transcription factor yields high-starch low-methane rice

Atmospheric methane is the second most important greenhouse gas after carbon dioxide, and is responsible for about 20% of the global warming effect since pre-industrial times. Rice paddies are the largest anthropogenic methane source and produce 7–17% of atmospheric methane. Warm waterlogged soil and exuded nutrients from rice roots provide ideal conditions for methanogenesis in paddies with annual methane emissions of 25–100-million tonnes. This scenario will be exacerbated by an expansion in rice cultivation needed to meet the escalating demand for food in the coming decades4. There is an urgent need to establish sustainable technologies for increasing rice production while reducing methane fluxes from rice paddies. However, ongoing efforts for methane mitigation in rice paddies are mainly based on farming practices and measures that are difficult to implement5. Despite proposed strategies to increase rice productivity and reduce methane emissions4,6, no high-starch low-methane-emission rice has been developed. Here we show that the addition of a single transcription factor gene, barley SUSIBA2, conferred a shift of carbon flux to SUSIBA2 rice, favouring the allocation of photosynthates to aboveground biomass over allocation to roots. The altered allocation resulted in an increased biomass and starch content in the seeds and stems, and suppressed methanogenesis, possibly through a reduction in root exudates. Three-year field trials in China demonstrated that the cultivation of SUSIBA2 rice was associated with a significant reduction in methane emissions and a decrease in rhizospheric methanogen levels. SUSIBA2 rice offers a sustainable means of providing increased starch content for food production while reducing greenhouse gas emissions from rice cultivation. Approaches to increase rice productivity and reduce methane emissions as seen in SUSIBA2 rice may be particularly beneficial in a future climate with rising temperatures resulting in increased methane emissions from paddies.

Su, J.↗
DOE OSTI2023

Mitigation of ventilation air methane (VAM) using novel methanotrophic coating materials: a technical analysis

Abstract Ventilation air methane (VAM) is a potent greenhouse gas source originating from geological wells, current and extinct mineshafts and other terrestrial conduits venting methane to the atmosphere, contributing to global methane emissions and disproportionate warming potential. Herein, we introduce the concept of the methanotrophic material as an engineering solution. Such materials should be capable of converting methane at ambient temperatures and pressures to a binder product, capturing and permanently sequestering the methane while simultaneously restricting its further emission. While such materials are currently under research development, this goal is supported and facilities by the mathematical framework, introduced and used herein, to evaluate the ability to convert methane, using currently published activity data. We include a case study of the conversion of a characteristic stream of VAM (0.6% methane in air, 1.7 × 10 8 l hr −1 equivalent to 100 000 standard cubic feet per minute). We show that when appropriately designed, such systems require a surface coverage of less than 1000 m of mine tunnel length (equivalent to 20 000 m 2 areal coverage) in order to reduce the methane emission from this stream by over 99%. Finally, we highlight formaldehyde as a reactive intermediate of methane oxidation which may itself be incorporated into these coating materials. As a component of binders and polymers already used ubiquitously in commercial products, this intermediate ultimately allows these systems to sequester the carbon from methane in a stable and solid form. The results presented here are easily extended to the treatment of other methane streams—either more concentrated or dilute—and the results herein will guide the design and development of a new class of carbon-negative materials.

Environmental Sciences & Ecology↗
DOE OSTI2017

Communal Metabolism of Methane and the Rare Earth Element Switch

The metabolism of methane is a vital part of the biogeochemical cycling of carbon. Methane is also a major contributor to climate change. A specialized group of microbes that consume methane, the methanotrophs, represent a natural filter preventing even faster accumulation of methane in the atmosphere. Methanotrophy can proceed via both anaerobic and aerobic modes. The anaerobic methanotrophs, represented by both archaea and bacteria, all appear to be engaged in syntrophic interdependencies with other species, to overcome the energetic barriers of methane metabolism in the absence of oxygen. In contrast, aerobic methanotrophy can be carried out by pure cultures of bacteria. However, a concept of communal function in aerobic methane oxidation has been gaining momentum, based on data regarding the natural cooccurrence of specific functional guilds and results from laboratory manipulations. The mechanistic details of how and why the methanotrophs share their carbon with other species, and whether and what they gain in return, are still sparse. In this minireview, we highlight recent studies that led to this new concept of community function in aerobic methane oxidation. We first discuss stable isotope probing experiments employing heavy-carbon-labeled methane and tracing methane carbon consumption. We then present an analysis of data on microcosm community dynamics. We also report on the role of a synthetic community approach in elucidating the principles of carbon flow and species cooperation in methane consumption. Finally, we touch on the role of lanthanides, which are rare Earth elements previously thought to be biologically inert, in bacterial metabolism of methane.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2015

Patterns in wetland microbial community composition and functional gene repertoire associated with methane emissions

Wetland restoration on peat islands previously drained for agriculture has potential to reverse land subsidence and sequester atmospheric carbon dioxide as peat accretes. However, the emission of methane could potentially offset the greenhouse gas benefits of captured carbon. As microbial communities play a key role in governing wetland greenhouse gas fluxes, we are interested in how microbial community composition and functions are associated with wetland hydrology, biogeochemistry, and methane emission, which is critical to modeling the microbial component in wetland methane fluxes and to managing restoration projects for maximal carbon sequestration. Here, we couple sequence-based methods with biogeochemical and greenhouse gas measurements to interrogate microbial communities from a pilot-scale restored wetland in the Sacramento-San Joaquin Delta of California, revealing considerable spatial heterogeneity even within this relatively small site. A number of microbial populations and functions showed strong correlations with electron acceptor availability and methane production; some also showed a preference for association with plant roots. Marker gene phylogenies revealed a diversity of major methane-producing and -consuming populations and suggested novel diversity within methanotrophs. Methanogenic archaea were observed in all samples, as were nitrate-, sulfate-, and metal-reducing bacteria, indicating that no single terminal electron acceptor was preferred despite differences in energetic favorability and suggesting spatial microheterogeneity and microniches. Notably, methanogens were negatively correlated with nitrate-, sulfate-, and metal-reducing bacteria and were most abundant at sampling sites with high peat accretion and low electron acceptor availability, where methane production was highest. Wetlands are the largest nonanthropogenic source of atmospheric methane but also a key global carbon reservoir. Characterizing belowground microbial communities that mediate carbon cycling in wetlands is critical to accurately predicting their responses to changes in land management and climate. Here, we studied a restored wetland and revealed substantial spatial heterogeneity in biogeochemistry, methane production, and microbial communities, largely associated with the wetland hydraulic design. We observed patterns in microbial community composition and functions correlated with biogeochemistry and methane production, including diverse microorganisms involved in methane production and consumption. We found that methanogenesis gene abundance is inversely correlated with genes from pathways exploiting other electron acceptors, yet the ubiquitous presence of genes from all these pathways suggests that diverse electron acceptors contribute to the energetic balance of the ecosystem. These investigations represent an important step toward effective management of wetlands to reduce methane flux to the atmosphere and enhance belowground carbon storage.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Exploring Electrocatalysis of Methane on Transition Metal Surfaces

Methane is a potent greenhouse gas because it has a heat-absorbing ability that is 20 times stronger than the better-known carbon dioxide. It is also the dominant component of nature gas (>70%). Its current greenhouse effect is only second to carbon dioxide largely because of its relatively low atmospheric concentration. Alarmingly, however, the latter has seen a 1.5-time increase since 1750, mainly due to anthropogenic livestock farming, coal and natural gas mining, and organic matter decomposing in waste landfills. Mitigating such a trend effectively and efficiently is therefore highly desirable and intensely sought for. This final technical report describes some exciting research progresses made over the last three years supported financially by the aforementioned award. The research conducted focused on exploring electrochemical direct methane to methanol (DMTM) conversion under mild conditions. The goal of research was to explore the possibility of developing potentially game-changing electrocatalysts and electrocatalysis that can convert methane directly to methanol in a most sustainable way for curbing its effect on global warming. Progress has been made in the following three directions. First, by adapting a hydrogen fuel-cell configuration that enables gaseous methane to be transported directly to the electrocatalyst surface, we have overcome the perennial difficulty in measuring activity of methane electro-oxidation at low temperature and ambient pressure that has prevented any meaningful studies of electrocatalysis of methane conversion thus far. Second, we have developed a novel and operational in situ electrochemical infrared (IR) spectral cell for studying electrocatalysis of direct methane to methanol conversion. This novel cell is also expected to alleviate the measuring difficulty caused by low solubility of methane in aqueous electrolyte and low sticking coefficient for methane adsorption onto transition metal surface. It will improve significantly the IR’s signal to noise ratio. Third, we have successfully synthesized nano-sizing copper (Cu) exchanged zeolite mordenite (Cu-ZMOR) and coated it with carbon that enabled electrochemical access to the encaged Cu ions. This opens a door to unravel the chemistry of Cu ions in catalyzing direct methane to methanol conversion under mild experimental conditions. Altogether, these progresses achieved have laid a solid foundation for further exploring electrocatalysis of direct methane to methanol conversion in general where there exists “a plenty of room” for new discoveries and developments.

03 NATURAL GAS↗
DOE OSTI2020

Automated, Unmanned Detection and Quantification of Fugitive Methane Emissions

Compressor stations used to move natural gas are one of the largest sources of fugitive methane emissions in the midstream sector, accounting for approximately 50% of all fugitive emissions (Zimmerle et al., 2015). This problem is most widespread at reciprocating compressors (Subramanian et al., 2015) where faulty seals are a key contributor to methane emissions (Johnson et al., 2015). As such, there is a significant need for a robust technology that could provide an early indication of an unexpected emission. Equally important, the technology needs to be able to account for biogenic versus anthropogenic sources of methane. One means of indirectly making this determination, is to leverage optical technologies that can autonomously pinpoint the source of such leaks. This presentation discusses recent work funded by the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL), focused on the development of an innovative remote sensing technology that can reliably and autonomously detect fugitive methane emissions in near real-time, using computer vision and deep learning. The technology called the Smart Methane Leak Detection (SLED/M) system was initially developed to monitor facilities such as compressor stations in a stationary, pan-tilt-zoom configuration. The system has recently been adapted to monitor facilities from an unmanned aerial system (UAS). The speed and maneuverability of UAS platforms are attractive to leak detection and repair program operators, but introduce several challenges. Many existing methane detection algorithms rely on mostly static backgrounds becoming unusable with motion. In addition, top-down views of fugitive methane emissions present differently in Optical Gas Imagers (OGI) compared to looking across the plume. Our work has focused on overcoming these challenges, enhancing the operators ability to detect methane emissions, and pinpoint their sources. Another recent adaptation to SLED/M is the ability to quantify methane emissions using passive sensors (OGI, thermal camera), environmental conditions, plume modeling, and deep learning. SLED/M advances the state-of-the-art for methane emission detection and quantification by focusing on three key critical criteria for effective methane emission mitigation: (1) autonomy (no need for a human to be in the loop), (2) high reliability (low false alarm rates), and (3) real-time performance. Results from this work will be presented.

03 NATURAL GAS↗
DOE OSTI2020

Pathways for methane emissions and oxidation that influence the net carbon balance of a subtropical cypress swamp

We evaluated the major pathways for methane emissions from wetlands to the atmosphere at four wetland sites in the Big Cypress National Preserve in southwest Florida. Methane oxidation was estimated based on the d13C-CH4 of surface water, porewater, and bubbles to evaluate mechanisms that limit surface water emissions. Spatially-scaled methane fluxes were then compared to organic carbon burial rates. The pathway with the lowest methane flux rate was diffusion from surface waters (3.50 ± 0.22 mmol m-2 d-1). Microbial activity in the surface water environment and/or shallow oxic sediment layer oxidized 26 ± 3% of the methane delivered from anerobic sediments to the surface waters. The highest rates of diffusion were observed at the site with the lowest extent of oxidation. Ebullition flux rates were 2.2 times greater than diffusion and more variable (7.79 ± 1.37 mmol m-2 d-1). Methane fluxes from non-inundated soils were 1.6 times greater (18.4 ± 5.14 mmol m-2 d-1) than combined surface water fluxes. Methane flux rates from cypress knees (emergent cypress tree root structures) were 3.7 and 2.3 times higher (42.0 ± 6.33 mmol m-2 d-1) than from surface water and soils, respectively. Cypress knee flux rates were highest at the wetland site with the highest porewater methane partial pressure, suggesting that the emergent root structures allow methane produced in anaerobic sediment layers to bypass oxidation in aerobic surface waters or shallow sediments. Scaled across the four wetlands, emissions from surface water diffusion, ebullition, non-inundated soils, and knees contributed to 14 ± 2%, 25 ± 6%, 34 ± 10%, and 26 ± 5% of total methane emissions, respectively. When considering only the three wetlands with cypress knees present, knee emissions contributed to 39 ± 5% of the total scaled methane emissions. Finally, the molar ratio of CH4 emissions to OC burial ranged from 0.03 to 0.14 in the wetland centers indicating that all four wetland sites are net sources of atmospheric warming potential on 20-100 yr timescales, but net sinks over longer time scales (500 yr) with the exception of one wetland site that was a net source even over 500 yr time scales.

Ward, Nicholas D.↗
NASA NTRS1996

In Situ Analyses of Methane Oxidation Associated with the Roots and Rhizomes of a Bur Reed, Sparganium Eurycarpum, in a Maine Wetland

Methane oxidation associated with the belowground tissues of a common aquatic macrophyte, the burweed Sparganium euryearpum, was assayed in situ by a chamber technique with acetylene or methyl fluoride as a methanotrophic inhibitor at a headspace concentration of 3 to 4%. Acetylene and methyl fluoride inhibited both methane oxidation and peat methanogenesis. However, inhibition of methanogenesis resulted in no obvious short-term effect on methane fluxes. Since neither inhibitor adversely affected plant metabolism and both inhibited methanotrophy equally well, acetylene was employed for routine assays because of its low cost and ease of use. Root-associated methanotrophy consumed a variable but significant fraction of the total potential methane flux; values varied between 1 and 58% (mean +/- standard deviation, 27.0% +/- 6.0%), with no consistent temporal or spatial pattern during late summer. The absolute amount of methane oxidized was not correlated with the total potential methane flux; this suggested that parameters other than methane availability (e.g., oxygen availability) controlled the rates of methane oxidation. Estimates of diffusive methane flux and oxidation at the peat surface indicated that methane emission occurred primarily through aboveground plant tissues; the absolute magnitude of methane oxidation was also greater in association with roots than at the peat surface. However, the relative extent of oxidation was greater at the latter locus.

King, Gary M.↗
NASA NTRS1999

Methane Pyrolysis and Disposing Off Resulting Carbon

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is a waste of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduce the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (i) recover hydrogen from the excess methane produced by the S/E process, (ii) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (iii) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. The goals of a research program on recovery of hydrogen from methane are (in descending priority order): 1) Study the kinetics of pyrolysis to arrive at a pyrolysis reactor design that produces high yields in a confined volume at the lowest possible operating temperature; 2) Study the kinetics of carbon burnoff to determine whether high yields can be obtained in a confined volume at acceptable operating temperatures; and 3) Investigate catalytic techniques for depositing carbon as a fine soot which can be physically separated from the reactor. In the JPL program, we have made significant measurements in regard to goal 1, cursory measurements in regard to goal 2, and would plan to pursue goal 3 if additional resources are secured.

Sharma, P. K.↗
NASA NTRS1999

Methane Pyrolysis and Disposing Off Resulting Carbon

Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is wasteful of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduced the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (1) recover hydrogen from the excess methane produced by the S/E process, (2) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (3) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. Hydrogen may be obtained from methane by pyrolysis in the temperature range 10000-12000C. The main reaction products are hydrogen and carbon, though very small amounts of higher hydrocarbons, including aromatic hydrocarbons are formed. The conversion efficiency is about 95% at 12000C. One needs to distinguish between thermodynamic equilibrium conversion and conversion limited by kinetics in a finite reactor.

Sharma, P. K.↗
NASA NTRS2001

Modeling Modern Methane Emissions from Natural Wetlands: Interannual Variations 1982-1993 - 2

A global run of a process-based methane model [Walter et al., this issue] is performed using high-frequency atmospheric forcing fields from ECMWF reanalyses of the period from 1982 to 1993. We calculate global annual methane emissions to be 260 Tg/ yr. 25% of methane emissions originate from wetlands north of 30 deg. N. Only 60% of the produced methane is emitted, while the rest is re-oxidized. A comparison of zonal integrals of simulated global wetland emissions and results obtained by an inverse modeling approach shows good agreement. In a test with data from two wetlands, the seasonality of simulated and observed methane emissions agrees well. The effects of sub-grid scale variations in model parameters and input data are examined. Modeled methane emissions show high regional, seasonal and interannual variability. Seasonal cycles of methane emissions are dominated by temperature in high latitude wetlands, and by changes in the water table in tropical wetlands. Sensitivity tests show that +/- 1 C changes in temperature lead to +/- 20 % changes in methane emissions from wetlands. Uniform changes of +/- 20% in precipitation alter methane emissions by about +/- 18%. Limitations in the model are analyzed. Simulated interannual variations in methane emissions from wetlands are compared to observed atmospheric growth rate anomalies. Our model simulation results suggest that contributions from other sources than wetlands and/or the sinks are more important in the tropics than north-of 30 deg. N. In higher northern latitudes, it seems that a large part, of the observed interannual variations can be explained by variations in wetland emissions. Our results also suggest that reduced wetland emissions played an important role in the observed negative methane growth rate anomaly in 1992.

Walter, Bernadette P.↗