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At least 685 records · Page 38

Mo 6 S 8 -based single-metal-atom catalysts for direct methane to methanol conversion

The single atom catalysts have been attracting much attention for catalysis. Here, the significant influence of single-metal-atom (M = K, Ti, Fe, Co, Ni, Cu, Rh) doping on a Mo 6 S 8 cluster was revealed for the direct methane to methanol conversion in water stream using density functional theory calculations. It was found that all single atom dopants help to facilitate the conversion via the steam reforming of methane (SRM). The single Fe atom on Mo 6 S 8 (Fe—Mo 6 S 8 ) exhibits the most significant promoting effect, which is followed by Ni, Co, Rh—Mo 6 S 8 > K, Ti, Cu—Mo 6 S 8 > Mo 6 S 8 in a decreasing sequence. The enhanced activity by single atom doping on Mo 6 S 8 is mainly associated with the interplay between the ensemble effect via the direct participation of an active M dopant and the site confinement imposed by doping of a single M atom, in tuning the methane conversion and methanol selectivity. It generates the new active center, M, which confines the SRM to occur at the M—Mo bridge sites and facilitates the selective production of methanol. An adequate single-atom promoter should not only bind *OH or *O moderately, being strongly enough to help water dissociation and weakly enough to allow the oxidation of methane, but also impose the confinement effect to facilitate the C—O bond association and production of methanol. Our results highlight the importance of the interplay among ligand, ensemble, and confinement effects in promoting the complex SRM over single atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Decomposition of methane diluted with inert gas in an RF discharge cell

Decomposition of methane using non-thermal plasmas is an attractive route for producing hydrogen-rich gases and valuable carbon nanomaterials. Understanding how plasma discharge modes influence methane decomposition in optimizing plasma-assisted chemical conversion remains unexplored. This study explores the coupling between the discharge structure and product selectivity in RF capacitively coupled discharges operating in methane/inert gas mixtures in the pressure range of 2–3 torr. Under our experimental conditions the discharge exhibits mode transitions from uniform to striated in Ar and Kr and from diffuse to contracted in Ar and Kr with <5% CH 4 . The discharges in He and Ne remained uniform under our operating conditions, and their mixtures with CH 4 remained diffuse. A 0-d model for Ar/CH 4 discharge established a threshold for contraction while also asserting the importance of Ar$^{*}_{\textrm{m}}$ in the dissociation and ionization processes. The highest degree of methane decomposition, >99.7% with the main products of acetylene and graphitized solid carbon was achieved in the contracted discharge mode for both Kr or Ar with ⩽5% CH 4 . We demonstrate that contraction can play a crucial role in the effective decomposition of methane with value-added products and that both the electronic and thermal properties of plasma gas are responsible for this effect.

RF plasma↗

A nitrogenase-like enzyme system catalyzes methionine, ethylene, and methane biogenesis

Bacterial production of hydrocarbon gases like ethylene and methane affects soil ecosystems and the climate. This study reveals that methane and ethylene from land and freshwater bacteria are directly produced by a previously unknown methionine biosynthesis pathway. This pathway employs a nitrogenase-like reductase that is distinct from known nitrogenases and nitrogenase-like reductases. The nitrogenase-like methylthio-alkane reductase specifically functions in carbon-sulfur bond breakage to reduce ubiquitous and significant volatile organic sulfur compounds such as dimethyl sulfide and (2-methylthio)ethanol. The liberated methanethiol serves as the immediate precursor to methionine. Whereas ethylene or methane is released into the environment. This pathway provides a biological route to the synthesis of ethylene in the absence of oxygen. Finally, anaerobic ethylene production by this pathway apparently explains the long-standing observation of ethylene accumulation in oxygen-depleted soils Methane production reveals an additional bacterial pathway that is distinct from archaeal methanogenesis.

10 SYNTHETIC FUELS↗

Subgroup Characteristics of Marine Methane-Oxidizing ANME-2 Archaea and Their Syntrophic Partners as Revealed by Integrated Multimodal Analytical Microscopy

Phylogenetically diverse environmental ANME archaea and sulfate-reducing bacteria cooperatively catalyze the anaerobic oxidation of methane oxidation (AOM) in multicelled consortia within methane seep environments. To better understand these cells and their symbiotic associations, we applied a suite of electron microscopy approaches, including correlative fluorescence in situ hybridization-electron microscopy (FISH-EM), transmission electron microscopy (TEM), and serial block face scanning electron microscopy (SBEM) three-dimensional (3D) reconstructions. FISH-EM of methane seep-derived consortia revealed phylogenetic variability in terms of cell morphology, ultrastructure, and storage granules. Representatives of the ANME-2b clade, but not other ANME-2 groups, contained polyphosphate-like granules, while some bacteria associated with ANME-2a/2c contained two distinct phases of iron mineral chains resembling magnetosomes. 3D segmentation of two ANME-2 consortium types revealed cellular volumes of ANME and their symbiotic partners that were larger than previous estimates based on light microscopy. Polyphosphate-like granule-containing ANME (tentatively termed ANME-2b) were larger than both ANME with no granules and partner bacteria. This cell type was observed with up to 4 granules per cell, and the volume of the cell was larger in proportion to the number of granules inside it, but the percentage of the cell occupied by these granules did not vary with granule number. Here, these results illuminate distinctions between ANME-2 archaeal lineages and partnering bacterial populations that are apparently unified in their ability to perform anaerobic methane oxidation.

59 BASIC BIOLOGICAL SCIENCES↗

Synthetic Methane-Consuming Communities from a Natural Lake Sediment

The factors and processes that influence the behavior and functionality of ecosystems inhabited by complex microbiomes are still far from being clearly understood. Synthetic microbial communities provide reduced-complexity models that allow an examination of ecological theories under defined and controlled conditions. In this study, we applied a multiphasic approach to study synthetic methane-oxidizing communities and species interactions as proxies to the natural communities. Our results confirm that, under selective pressures, natural-sediment communities of high complexity simplify rapidly, selecting for several major functional guilds, the major partners in methane oxidation being the Methylococcaceae methanotrophs and the Methylophilaceae methylotrophs, along with minor but persistent partners, members of Burkholderiales and Flavobacteriales. As a proof of concept, we established minimalist synthetic communities that were representative of the four functional guilds to demonstrate the dependency of the non-methane-utilizing species on the methanotrophs as the primary carbon-providing species. We observed that in communities consisting of multiple representatives of the key guilds, members of the same guild appeared to compete for resources. For example, when two methanotrophs of the same family were present, the two expressed similar key methanotrophy pathways and responded similarly to changing environmental conditions, suggesting that they perform a similar keystone function in situ. Similar observations were made for the Methylophilaceae. However, differences were noted in the expression of auxiliary and unique genes among strains of the same functional guild, reflecting differential adaptation and suggesting mechanisms for competition. At the same time, differences were also noted in the performances of partners with specific metabolic schemes. For example, a mutant of Methylotenera mobilis impaired in nitrate utilization behaved as a more efficient cooperator in methane consumption, suggesting that the loss of function may lead to changes in communal behavior. Overall, we demonstrate the robust nature of synthetic communities built of native lake sediment strains and their utility in addressing important ecological questions while using a simplified model.

54 ENVIRONMENTAL SCIENCES↗

Gathering pipeline methane emissions in Fayetteville shale pipelines and scoping guidelines for future pipeline measurement campaigns

Gathering pipelines, which transport gas from well pads to downstream processing, are a sector of the natural gas supply chain for which little measured methane emissions data are available. This study performed leak detection and measurement on 96 km of gathering pipeline and the associated 56 pigging facilities and 39 block valves. The study found one underground leak accounting for 83% (4.0 kg CH 4 /hr) of total measured emissions. Methane emissions for the 4684 km of gathering pipeline in the study area were estimated at 402 kg CH 4 /hr [95 to 1065 kg CH 4 /hr, 95% CI], or 1% [0.2% to 2.6%] of all methane emissions measured during a prior aircraft study of the same area. Emissions estimated by this study fall within the uncertainty range of emissions estimated using emission factors from EPA's 2015 Greenhouse Inventory and study activity estimates. While EPA's current inventory is based upon emission factors from distribution mains measured in the 1990s, this study indicates that using emission factors from more recent distribution studies could significantly underestimate emissions from gathering pipelines. To guide broader studies of pipeline emissions, we also estimate the fraction of the pipeline length within a basin that must be measured to constrain uncertainty of pipeline emissions estimates to within 1% of total basin emissions. The study provides both substantial insight into the mix of emission sources and guidance for future gathering pipeline studies, but since measurements were made in a single basin, the results are not sufficiently representative to provide methane emission factors at the regional or national level.

03 NATURAL GAS↗

Global compilation of soil methane uptake measurements from 1984 to 2018

This data package contains a global compilation of soil methane uptake measurements collected from published field studies between 1989 and 2022. The dataset was developed to support machine learning (ML) estimation of the global terrestrial methane soil sink and includes monthly methane uptake rates, measurement dates, site coordinates, and associated ecosystem information from different ecosystems. Data were compiled from 164 peer-reviewed publications across approximately 260 study sites, resulting in ~12,000 monthly observations after quality control screening and removal of manipulated experimental treatments. The database was further processed to generate site-averaged methane uptake estimates for comparison between process-based (PB) and ML models.

earth science↗

Systems Level Dissection of Anaerobic Methane Cycling: Quantitative Measurements of Single Cell Ecophysiology, Genetic Mechanisms, and Microbial Interactions

The global biological CH4 cycle is largely controlled through coordinated and often intimate microbial interactions between archaea and bacteria, the majority of which are still unknown or have been only cursorily identified. Members of the methanotrophic archaea, aka ‘ANME’, are believed to play a major role in the cycling of methane in anoxic environments coupled to sulfate, nitrate, and possibly iron and manganese oxides, frequently forming diverse physical and metabolic partnerships with a range of bacteria. The thermodynamic challenges overcome by the ANME and their bacterial partners and corresponding slow rates of growth are common characteristics in anaerobic ecosystems, and, in stark contrast to most cultured microorganisms, this type of energy and resource limited microbial lifestyle is likely the norm in the environment. While we have gained an in-depth systems level understanding of fast-growing, energy-replete microorganisms, comparatively little is known about the dynamics of cell respiration, growth, protein turnover, gene expression, and energy storage in the slow-growing microbial majority. These fundamental properties, combined with the observed metabolic and symbiotic versatility of methanotrophic ANME, make these cooperative microbial systems a relevant (albeit challenging) system to study and for which to develop and optimize culture-independent methodologies, which enable a systems-level understanding of microbial interactions and metabolic networks. We used an integrative systems biology approach to study anaerobic sediment microcosms and methane-oxidizing bioreactors and expanded our understanding of the methanotrophic ANME archaea, their interactions with physically-associated bacteria, ecophysiological characteristics, and underlying genetic basis for cooperative microbial methane-oxidation linked with different terminal electron acceptors. Our approach is inherently multi-disciplinary and multi-scaled, combining transcriptional and proteomic analyses with high resolution microscopy techniques, and stable isotopic and chemical analyses that span community level ‘omics investigations (cm scale) to interspecies consortia (µm scale), to the individual cell and its subcellular components (nm scale). We have organized our methodological approach into three broad categories, RNA-based, Protein-targeted and Geochemical, each encompassing a range of scales, with many techniques and resulting datasets that are highly complementary with one another, and together, offer a unique systems-level perspective of methane-based microbial interactions.

03 NATURAL GAS↗

Long-Term Methane Emissions Rate Quantification and Alert System for Natural Gas Storage Wells and Fields

The Department of Energy (DOE) National Energy Technology Laboratory (NETL) and other critical stakeholders (e.g., U.S. Environmental Protection Agency (USEPA), state regulators, and industry) seek to more accurately characterize and quantify methane emissions from natural gas storage wells. These efforts will reduce uncertainties in estimates of these emissions in USEPA’s current Green House Gas Inventory (GHGI) under their Greenhouse Gas Reporting Program (GHGRP; EPA, 2016). Emission factors currently used to estimate methane emissions from gas storage wells are the same factors used for onshore natural gas production wells (USEPA, 2016). This study has developed a robust and representative dataset of emissions from disaggregated gas station wellhead components and related emission factors that will inform future enhancements to the GHGI and GHGRP. Extensive methane emissions measurements and meteorological data were collected from three active storage facilities representing two of the three types of storage facilities (i.e., depleted gas reservoir and salt cavern) to support development of emissions factors specifically for gas storage wells and associated components. Methane emissions were quantified from both above-ground components (e.g., pipe fittings and valves) and seepage from the ground surface in proximity to gas storage wellheads.

03 NATURAL GAS↗

Comparative Performance of Gaussian Plume and Backward Lagrangian Stochastic Models for Near-Field Methane Emission Estimation Using a Single Controlled Release Experiment

Methane (CH 4 ) is a major component of natural gas and a potent greenhouse gas. Increasing atmospheric methane concentrations are attributed to emissive anthropogenic activities by an average of 13 ppb per yr since 2020 and are linked to a changing global climate. Mitigating CH 4 emissions from oil and gas production sites has recently become a target to reduce overall greenhouse gas emissions; however, monitoring the efficacy of mitigation strategies depends on accurate quantification of CH 4 emissions at the facility-level. Near-field quantification of methane (CH 4 ) emissions from oil and gas (O&G) facilities remains challenging due to the effects of atmospheric variability and sensor configuration on atmospheric dispersion models. This study evaluates the performance of two atmospheric dispersion models, the Gaussian plume (GP) and backward Lagrangian stochastic (bLS), by comparing calculated CH 4 emissions to controlled single-point emissions between 0.4 and 5.2 kg CH 4 h −1 . Emissions were calculated by both models using 121 individual sets of measurements comprising five-minute averaged downwind methane mixing ratios and matching meteorological data. The comparison shows that the bLS approach achieved a higher proportion of emission estimates within a factor of two (FAC2) of the known emission rates compared to the GP approach. The emissions calculated by the bLS model also had a lower multiplicative error and reduced bias relative to GP. Other error-based metrics further confirmed the bLS model performed better, as it yielded lower RMSE and MAE than GP. Statistical analysis of the emission data shows that the lateral and vertical alignment of the source and the sensor plays a critical role in emission estimations, as measurements made closer to the plume centerline and at a distance between 40 and 80 m downwind yielded the best FAC2 agreement. High wind meander degraded the ability of both approaches to generate representative emissions, particularly with the GP approach, as it violates the modeling approach’s assumption of steady-state emissions. Data suggest emissions calculated by the bLS model are comprehensively in better agreement, but the computational demands of the modeling approach and integration into fenceline systems limit real-time applicability. While these results provide insight into model performance under controlled near-field conditions, their applicability to more complex or heterogeneous oil and gas production environments (e.g., the regions Marcellus or Unita Basins) remains limited and uncertain.

gaussian plume↗

Microwave-Driven Plasma-Mediated Methane Cracking: Product Carbon Characterization

Methane is the primary industrial H 2 source, with the vast majority produced by steam reforming of methane—a highly CO 2- and water-intensive process. Alternatives to steam reforming, such as microwave-driven plasma-mediated methane decomposition, offer benefits of no water consumption and zero CO 2 process emissions while also producing solid carbon formed by pyrolytic reactions and aided by a plasma reactive environment. The economic viability of pyrolytic methane decomposition as a hydrogen source will depend upon the commercial applications of the solid carbon product—which, in turn, will depend upon its physical and chemical characteristics. This study focuses on material characterization of the solid carbon (secondary) product. Characterization by high-resolution transmission electron microscopy reveals forms ranging from graphitic to amorphous. Thermogravimetric analyses reveal three forms by their differing oxidative reactivity, while X-ray diffraction analyses support the different crystalline forms as suggested by Thermogravimetric analysis. Plasma perturbation of the radical pool, elevating radical temperatures and boosting concentrations, is proposed as altering the reaction paths towards solid carbon formation, resulting in the different sp 2 forms.

42 ENGINEERING↗

Catalytic Hydrogen Production from Methane: A Review on Recent Progress and Prospect

Natural gas (Methane) is currently the primary source of catalytic hydrogen production, accounting for three quarters of the annual global dedicated hydrogen production (about 70 M tons). Steam&ndash;methane reforming (SMR) is the currently used industrial process for hydrogen production. However, the SMR process suffers with insufficient catalytic activity, low long-term stability, and excessive energy input, mostly due to the handling of large amount of CO 2 coproduced. With the demand for anticipated hydrogen production to reach 122.5 M tons in 2024, novel and upgraded catalytic processes are desired for more effective utilization of precious natural resources. In this review, we summarized the major descriptors of catalyst and reaction engineering of the SMR process and compared the SMR process with its derivative technologies, such as dry reforming with CO 2 (DRM), partial oxidation with O 2 , autothermal reforming with H 2 O and O 2 . Finally, we discussed the new progresses of methane conversion: direct decomposition to hydrogen and solid carbon and selective oxidation in mild conditions to hydrogen containing liquid organics (i.e., methanol, formic acid, and acetic acid), which serve as alternative hydrogen carriers. We hope this review will help to achieve a whole picture of catalytic hydrogen production from methane.

08 HYDROGEN↗

Accessibility of Pores to Methane in New Albany Shale Samples of Varying Maturity Determined Using SANS and USANS

The accessibility of pores to methane has been investigated in Devonian New Albany Shale Formation early-mature (Ro = 0.50%) to post-mature (Ro = 1.40%) samples. A Marcellus Shale Formation sample was included to expand the maturation range to Ro 2.50%. These are organic matter-rich rocks with total organic carbon (TOC) values of 3.4 to 14.4% and porosity values of 2.19 to 6.88%. Contrast matching small-angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) techniques were used to generate porosity-related data before and after pressure cycling under hydrostatic (in a vacuum and at 500 bar of deuterated methane) and uniaxial stress (0 to ca. 350 bar) conditions. Our results showed that the accessible porosity was small for the samples studied, ranging from zero to 2.9%. No correlation between the accessible porosity and TOC or mineralogical composition was revealed, and the most likely explanation for porosity variation was related to the thermal transformation of organic matter and hydrocarbon generation. Pressure caused improvements in accessible porosity for most samples, except the oil window sample (Ro = 0.84%). Our data show that densification of methane occurs in nanopores, generally starting at diameters smaller than 20 nm, and that the distribution of methane density is affected by pressure cycling.

03 NATURAL GAS↗

The Role of Retardation, Attachment and Detachment Processes during Microbial Coal-Bed Methane Production after Organic Amendment

Microbially enhanced coal-bed methane could allow for a more sustainable method of harvesting methane from un-mineable coaldbeds. The model presented here is based on a previously validated batch model; however, this model system is based on upflow reactor columns compared to previous experiments and now includes flow, transport and reactions of amendment as well as intermediate products. The model implements filtration and retardation effects, biofilm decay, and attachment and detachment processes of microbial cells due to shear stress. The model provides additional insights into processes that cannot be easily observed in experiments. This study improves the understanding of complex and strongly interacting processes involved in microbially enhanced coal-bed methane production and provides a powerful tool able to model the entire process of enhancing methane production and transport during microbial stimulation.

54 ENVIRONMENTAL SCIENCES↗

Common practices for quantifying methane emissions from plumes detected by remote sensing

This document provides a set of community-accepted practices for quantifying methane emissions based on plumes detected via spectroscopic remote sensing. Its primary goal is to promote consistency in the generation, validation, reporting, and quality assessment of methane emission estimates derived from remote sensing radiances. Developed by subject matter experts with deep experience across all stages of the measurement process, this guidance reflects a critical evaluation of current methodologies and highlights key practices needed to produce reliable, interoperable, and traceable products. The focus is specifically on methane emissions quantified from distinct plumes originating from localized sources, rather than diffuse emissions spread over large regions, which are beyond the scope of this work. This document is intended to serve both data producers and users. For producers, it offers a framework for aligning with field-recognized standards to ensure their outputs meet rigorous quality and transparency criteria. For users, it provides a reference to assess dataset fitness-for-purpose by highlighting essential metadata, assumptions, and methodological choices that underpin emission estimates. By fostering a shared understanding of best practices, this work aims to enhance comparability, confidence, and utility of remotely sensed methane emission products.

54 ENVIRONMENTAL SCIENCES↗

The Presence of Methane in the Atmosphere of an Extrasolar Planet

Molecules present in the atmospheres of extrasolar planets are expected to influence strongly the balance of atmospheric radiation, to trace dynamical and chemical processes, and to indicate the presence of disequilibrium effects. As molecules have the potential to reveal atmospheric conditions and chemistry, searching for them is a high priority. The rotational-vibrational transition bands of water, carbon monoxide and methane are anticipated to be the primary sources of non-continuum opacity in hot-Jupiter planets. As these bands can overlap in wavelength, and the corresponding signatures from them are weak, decisive identification requires precision infrared spectroscopy. Here we report a near-infrared transmission spectrum of the planet HD 189733b that shows the presence of methane. Additionally, a resolved water vapour band at 1.9 (micro)m confirms the recent claim4 of water in this object. On thermochemical grounds, carbon monoxide is expected to be abundant in the upper atmosphere of hot-Jupiter planets, but is not identifiable here; therefore the detection of methane rather than carbon monoxide in such a hot planet could signal the presence of a horizontal chemical gradient away from the permanent dayside, or it may imply an ill-understood photochemical mechanism that leads to an enhancement of methane.

atmospheric radiation↗

Interactive Ozone and Methane Chemistry in GISS-E2 Historical and Future Climate Simulations

The new generation GISS climate model includes fully interactive chemistry related to ozone in historical and future simulations, and interactive methane in future simulations. Evaluation of ozone, its tropospheric precursors, and methane shows that the model captures much of the largescale spatial structure seen in recent observations. While the model is much improved compared with the previous chemistry-climate model, especially for ozone seasonality in the stratosphere, there is still slightly too rapid stratospheric circulation, too little stratosphere-to-troposphere ozone flux in the Southern Hemisphere and an Antarctic ozone hole that is too large and persists too long. Quantitative metrics of spatial and temporal correlations with satellite datasets as well as spatial autocorrelation to examine transport and mixing are presented to document improvements in model skill and provide a benchmark for future evaluations. The difference in radiative forcing (RF) calculated using modeled tropospheric ozone versus tropospheric ozone observed by TES is only 0.016W/sq. m. Historical 20th Century simulations show a steady increase in whole atmosphere ozone RF through 1970 after which there is a decrease through 2000 due to stratospheric ozone depletion. Ozone forcing increases throughout the 21st century under RCP8.5 owing to a projected recovery of stratospheric ozone depletion and increases in methane, but decreases under RCP4.5 and 2.6 due to reductions in emissions of other ozone precursors. RF from methane is 0.05 to 0.18W/ sq. m higher in our model calculations than in the RCP RF estimates. The surface temperature response to ozone through 1970 follows the increase in forcing due to tropospheric ozone. After that time, surface temperatures decrease as ozone RF declines due to stratospheric depletion. The stratospheric ozone depletion also induces substantial changes in surface winds and the Southern Ocean circulation, which may play a role in a slightly stronger response per unit forcing during later decades. Tropical precipitation shifts south during boreal summer from 1850 to 1970, but then shifts northward from 1970 to 2000, following upper tropospheric temperature gradients more strongly than those at the surface.

Ozone↗

Gridded National Inventory of U.S. Methane Emissions

We present a gridded inventory of US anthropogenic methane emissions with 0.1 deg x 0.1 deg spatial resolution, monthly temporal resolution, and detailed scale dependent error characterization. The inventory is designed to be onsistent with the 2016 US Environmental Protection Agency (EPA) Inventory of US Greenhouse Gas Emissionsand Sinks (GHGI) for 2012. The EPA inventory is available only as national totals for different source types. We use a widerange of databases at the state, county, local, and point source level to disaggregate the inventory and allocate the spatial and temporal distribution of emissions for individual source types. Results show large differences with the EDGAR v4.2 global gridded inventory commonly used as a priori estimate in inversions of atmospheric methane observations. We derive grid-dependent error statistics for individual source types from comparison with the Environmental Defense Fund (EDF) regional inventory for Northeast Texas. These error statistics are independently verified by comparison with the California Greenhouse Gas Emissions Measurement (CALGEM) grid-resolved emission inventory. Our gridded, time-resolved inventory provides an improved basis for inversion of atmospheric methane observations to estimate US methane emissions and interpret the results in terms of the underlying processes.

Methane↗