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At least 379 records · Page 21

Martian Atmospheric Methane Plumes from Meteor Shower Infall: A Hypothesis

Methane plumes in the martian atmosphere have been detected using Earth-based spectroscopy, the Planetary Fourier Spectrometer on the ESA Mars Express mission, and the NASA Mars Science Laboratory. The methane's origin remains a mystery, with proposed sources including volcanism, exogenous sources like impacts and interplanetary dust, aqueous alteration of olivine in the presence of carbonaceous material, release from ancient deposits of methane clathrates, and/or biological activity. To date, none of these phenomena have been found to reliably correlate with the detection of methane plumes. An additional source exists, however: meteor showers could generate martian methane via UV pyrolysis of carbon-rich infall material. We find a correlation between the dates of Mars/cometary orbit encounters and detections of methane on Mars. We hypothesize that cometary debris falls onto Mars during these interactions, depositing freshly disaggregated meteor shower material in a regional concentration. The material generates methane via UV photolysis, resulting in a localized "plume" of short-lived methane.

Fries, M.↗

Methane Metabolism by Yeast for Solar System Exploration

Exploration of the solar system is constrained by the cost of moving mass off Earth. Producing materials in situ will reduce the mass that must be delivered from earth. CO2 is abundant on Mars and manned spacecraft. On the ISS, NASA reacts excess CO2 with H2 to generate CH4 and H2O using the Sabatier System. The resulting water is recovered into the ISS, but the methane is vented to space. Thus, there is a capability need for systems that convert methane into valuable materials. Methanotrophic bacteria consume methane but these are poor synthetic biology platforms. Thus, there is a knowledge gap in utilizing methane in a robust and flexible synthetic biology platform. The yeast Pichia pastoris is a refined microbial factory that is used widely by industry because it efficiently secretes products. Pichia could produce a variety of useful products in space. Pichia does not consume methane but robustly consumes methanol, which is one enzymatic step removed from methane. Our goal is to engineer Pichia to consume methane thereby creating a powerful methane-consuming microbial factory.

Galazka, Jonathan M.↗

XSP Methane Sensors Test and Evaluation Project “M-Step”

Methane sensor technology is employed in industry sectors from oil and gas to agriculture, landfills, and monitoring of natural emissions. The US oil and gas sector is extensive in scale, critical to fulfilling US energy needs, and deals with commodities presenting enormous challenges for personnel safety and the environment. Thus, it is imperative that they have accurate and responsive sensors to detect hazardous gases such as methane. US space launch systems will increasingly also use liquefied methane and liquefied natural gas (LNG), which is mostly methane, in quantities large and small, as main and auxiliary propulsion and power. Some of these systems will be reusable, which adds the unique challenge of processing a vehicle that has residual commodities and has returned to its launch site to be readied for its next launch. The methane sensors test and evaluation project (M-STEP) began within the context of a reusable launch system, the Defense Advanced Research Projects Agency (DARPA) Experimental Spaceplane (XSP) program, which would have employed a high-pressure gaseous methane and gaseous oxygen reaction control system. Although the XSP partnership between Boeing and DARPA was terminated by Boeing in early 2020, DARPA and KSC have continued to collaborate in the area of gas sensors with the hydrogen sensor test and evaluation project (H-STEP) and with M-STEP. The NASA Launch Services program (LSP) invested in M-STEP in FY 2021 “to evaluate and understand the state-of-the-art in methane gas sensors”. M-STEP and the LSP effort was complementary, pushing in the same direction to understand US launch system stakeholder needs and approaches, requirements internal (NASA) and external, and commercially available or forthcoming methane sensing technologies, practices, and approaches. In addition, M-STEP (as with H-STEP) enhances KSC capabilities and understanding of these technologies, informing agency investments and further research in these areas.

Tracy L. Gibson↗

Wetland Emission and Atmospheric Sink Changes Explain Methane Growth in 2020

Atmospheric methane growth reached an exceptionally high rate of 15.1 ± 0.4 parts per billion per year in 2020 despite a probable decrease in anthropogenic methane emissions during COVID-19 lockdowns(1). Here we quantify changes in methane sources and in its atmospheric sink in 2020 compared with 2019. We find that, globally, total anthropogenic emissions decreased by 1.2 ± 0.1 teragrams of methane per year (Tg CH4 yr−1), fire emissions decreased by 6.5 ± 0.1 Tg CH4 yr−1 and wetland emissions increased by 6.0 ± 2.3 Tg CH4 yr−1. Tropospheric OH concentration decreased by 1.6 ± 0.2 per cent relative to 2019, mainly as a result of lower anthropogenic nitrogen oxide (NOx) emissions and associated lower free tropospheric ozone during pandemic lockdowns(2). From atmospheric inversions, we also infer that global net emissions increased by 6.9 ± 2.1 Tg CH4 yr−1 in 2020 relative to 2019, and global methane removal from reaction with OH decreased by 7.5 ± 0.8 Tg CH4 yr−1. Therefore, we attribute the methane growth rate anomaly in 2020 relative to 2019 to lower OH sink (53 ± 10 per cent) and higher natural emissions (47 ± 16 per cent), mostly from wetlands. In line with previous findings(3,4,) our results imply that wetland methane emissions are sensitive to a warmer and wetter climate and could act as a positive feedback mechanism in the future. Our study also suggests that nitrogen oxide emission trends need to be taken into account when implementing the global anthropogenic methane emissions reduction pledge(5).

Shushi Peng↗

Modeling the Formation of Hydrate-Filled Veins in Fine-Grained Sediments from in Situ Microbial Methane

Continental margin sediments are dominantly fine-grained silt and clay, and methane hydrates in these sediments are often found in semi-vertical veins and fractures. In several instances, these hydrate veins occupy discrete depth intervals that are a few tens of meters thick and are surrounded by hydrate-free sediments. As they are not connected with gas sources beneath the base of the gas hydrate stability zone (GHSZ), these isolated hydrate-bearing intervals have been interpreted as formed by in situ microbial methane. To investigate the formation of these hydrate deposits, we applied a time-dependent advection-diffusion-reaction model that includes the effects of sedimentation, compaction, solute diffusion, and microbial methane generation. Microbial methane generation depends on the amount of metabolizable organic carbon deposited at the seafloor, whose progressive degradation produces methane beneath the sulfate reduction zone. If the amount of organic carbon entering the methanogenic zone is kept constant in time, we found that the computed amounts of hydrate formed in discrete intervals within the GHSZ are well below those estimated from observations. On the other hand, if the deposition of organic carbon is higher in a given time interval, methane generation during burial is more intense in the corresponding sediment interval, resulting in enhanced hydrate formation. With variations in organic carbon deposition comparable to those generally observed in continental margins, our model was able to reproduce the methane hydrate contents that were estimated from drilling. These results support the suggestion that in situ microbial generation associated with transient organic carbon deposition is the source of methane that forms isolated intervals of hydrate-filled veins in fine-grained sediments.

58 GEOSCIENCES↗

Engineering PdAu/CeO 2 Alloy/Oxide Interfaces for Selective Methane‐to‐Methanol Conversion with Water

The direct conversion of methane-to-methanol remains a critical challenge in methane valorization. In this study, we unveil the crucial role of PdAu/CeO 2 catalysts in enabling selective methane transformation under mild conditions, using only water as the sole oxidant. Through a combination of experimental techniques, including XPS and catalytic testing, alongside density functional theory (DFT) calculations, we demonstrate that a Pd 0.3 Au 0.7 /CeO 2 catalyst, which predominantly exposes isolated Pd atoms, achieves remarkable methanol selectivity (∼80%) at 500 K with a 1:1 methane-to-water ratio. While Pd/CeO 2 efficiently activates methane, its tendency for overreaction leads to complete methanol decomposition, thereby limiting selectivity. Alloying Pd with Au on ceria mitigates this over-reactivity, preventing methanol degradation while maintaining sufficient catalytic activity. The PdAu/CeO 2 composite exhibits a synergistic effect: Pd in contact with the ceria support facilitates methane activation and water dissociation, while Au fine-tunes reactivity to promote methanol formation. DFT calculations confirm that isolated Pd sites at the PdAu/CeO 2 interface play a key role in balancing activity and selectivity. This work underscores the importance of alloy/oxide interfaces in controlling selective methane conversion with water and offers valuable insights for designing highly efficient catalysts for methanol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methane and nitrous oxide porewater concentrations and surface fluxes of a regulated river

Greenhouse gas (GHG) emissions from rivers are a critical missing component of current global GHG models. Their exclusion is mainly due to a lack of in-situ measurements and a poor understanding of the spatiotemporal dynamics of GHG production and emissions, which prevents optimal model parametrization. We combined simultaneous observations of porewater concentrations along different beach positions and depths, and surface fluxes of methane and nitrous oxide at a plot scale in a large regulated river during three water stages: rising, falling, and low. Our goal was to gain insights into the interactions between hydrological exchanges and GHG emissions and elucidate possible hypotheses that could guide future research on the mechanisms of GHG production, consumption, and transport in the hyporheic zone (HZ). Results indicate that the site functioned as a net source of methane. Surface fluxes of methane during river water stages at three beach positions (shallow intermediate and deep) correlated with porewater concentrations of methane. However, fluxes were significantly higher in the intermediate position during low water stage, suggesting that low residence time increased methane emissions. Vertical profiles of methane peaked at different depths, indicating an influence of the magnitude and direction of the hyporheic mixing during the different river water stages on methane production and consumption. The site acted as either a sink or a source of nitrous oxide depending on the elevation of the water column. Nitrous oxide porewater concentrations peaked at the upper layers of the sediment throughout the different water stages. River hydrological stages significantly influenced porewater concentrations and fluxes of GHG, probably by influencing heterotrophic respiration (production and consumption processes) and transport to and from the HZ. Our results highlight the importance of including dynamic hydrological exchanges when studying and modeling GHG production and consumption in the HZ of large rivers.

54 ENVIRONMENTAL SCIENCES↗

Insights into Designing an Efficient and Reliable Microwave-Assisted Methane Dehydroaromatization Process: Effect of Microwave Absorber on Catalyst Performance

Microwave-assisted methane dehydroaromatization has the potential to address challenges of traditional dehydroaromatization reactions. However, catalysts for microwave-enhanced reaction systems require effective coupling of fields with the catalyst to produce heat and reach reaction temperatures. Here, this work presents an in-depth understanding of the effect of the addition of silicon carbide as a microwave absorber on catalyst performance among other variables, the viability of the microwave reactor configuration, and insights into designing an effective and reliable microwave-based methane dehydroaromatization process. The effect of other parameters including temperature, weight hourly space velocity, role of microwave absorber, and methane concentration during microwave-assisted methane dehydroaromatization reaction are studied. Mo/ZSM-5 was found to suffer from low permittivity and nonuniform heating under microwave conditions. Mixing silicon carbide powder as a microwave absorber with the catalyst was found to provide more uniform heating. When assessing the catalytic performance of the mixture, it was found that higher methane partial pressures at 2000 cc/g cat .h and a temperature range of 500-600°C produced the highest amount of benzene. The formation of graphitic carbon on the spent catalyst increased with temperature, gas-solid contact period, and methane concentration, which resulted in higher methane conversion and benzene selectivity. The study indicates that under microwave heating the presence of localized carbon enhanced catalyst life by coupling with microwave energy, leading to localized heating, and improving benzene selectivity.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Methane Removal from Air: Challenges and Opportunities

Driven by increasing greenhouse gas (GHG) concentrations in the atmosphere, extreme weather events have become more frequent and their impacts on human lives have become more severe. Therefore, the need for short-term GHG mitigations is urgent. Recently, methane has been recognized as an important mitigation target due to its high global warming potential (GWP). However, methane’s low concentration in the atmosphere and stable molecular structure make its removal from the air highly challenging. This review first discusses the fundamental aspects of the challenges in atmospheric methane removal and then briefly reviews the existing research strategies following the mechanisms of natural methane sinks. Although still in its infancy, recent research on methane removal from the air holds great potential for slowing down global warming. At the same time, it is important to carefully examine the energy consumption of these methane removal strategies and whether they will be able to achieve net GHG reduction. In addition, due to the scale of methane removal from the air, any potential solution’s environmental impacts must be carefully evaluated before it can be implemented in practice.

54 ENVIRONMENTAL SCIENCES↗

Methane Upgrading of Acetic Acid as a Model Compound for a Biomass-Derived Liquid over a Modified Zeolite Catalyst

The technical feasibility of coaromatization of acetic acid derived from biomass and methane was investigated under mild reaction conditions (400 °C and 30 bar) over silver-, zinc-, and/or gallium-modified zeolite catalysts. On the basis of GC-MS, Micro-GC, and TGA analysis, more light aromatic hydrocarbons, less phenol formation, lower coke production, and higher methane conversion are observed over 5%Zn-1%Ga/ZSM-5 catalyst in comparison with catalytic performance over the other catalysts. Direct evidence of methane incorporation into aromatics over 5%Zn-1%Ga/ZSM-5 catalyst is witnessed in 1 H, 2 H, and 13 C NMR spectra, revealing that the carbon from methane prefers to occupy the phenyl carbon sites and the benzylic carbon sites, and the hydrogen of methane favors the aromatic and benzylic substitutions of product molecules. In combination with the 13 C NMR results for isotopically labeled acetic acid ( 13 CH 3 COOH and CH 3 13 COOH), it can be seen that the methyl and carbonyl carbons of acetic acid are equally involved in the formation of ortho, meta and para carbons of the aromatics, whereas the phenyl carbons directly bonded with alkyl substituent groups and benzylic carbons are derived mainly from the carboxyl carbon of acetic acid. After various catalyst characterizations by using TEM, XRD, DRIFT, NH 3 -TPD, and XPS, the excellent catalytic performance might be closely related to the highly dispersed zinc and gallium species on the zeolite support, moderate surface acidity, and an appropriate ratio of weak acidic sites to strong acidic sites as well as the fairly stable oxidation state during acetic acid conversion under a methane environment. Two mechanisms of the coaromatization of acetic acid and methane have also been proposed after consulting all the collected data in this study. In conclusion, the results reported in this paper could potentially lead to more cost-effective utilization of abundant natural gas and biomass.

09 BIOMASS FUELS↗

Experimental and Modeling Study of Methane Adsorption onto Partially Saturated Shales

Shale gas equilibrates through gas-liquid-solid interactions in reservoirs, but the role of moisture is rarely investigated. To determine how adsorbed water influences methane behavior, three carboniferous shale samples from the Qaidam Basin, China, were humidified at five levels up to a relative humidity of 89%, and their methane capacities at pressures up to 12 MPa were studied. The experimental results indicate that two water-related mechanisms, “water blocking for methane transport” and “surface competition for gas-solid interaction,” are primarily responsible for the methane capacity variations. A compositional comparison suggests that a high abundance of clay minerals plays a favorable role in methane migration by retaining water in interlayer pores. Based on the experimental data, an optimized method for calculating the adsorption amount based on an approximation of density distribution is proposed. The model predicts the average thickness of the adsorption layer and the adsorbed methane density distribution on the surface at a given pressure. Here, the methane adsorption layer “thins” in a stepped pattern by up to 45% in the presence of water, with little further change observed at relative humidities greater than 75% in the studied samples.

58 GEOSCIENCES↗

Barometric Pumping Through Fractured Rock: A Mechanism for Venting Deep Methane to Mars' Atmosphere

Abstract Both the source of methane on Mars and the mechanism for transmission from the subsurface to the atmosphere are not fully understood. Previous seepage simulations have invoked relatively shallow subsurface sources to explain observed methane signatures on Mars. We propose that barometric‐pressure pumping through fracture networks could be an effective mechanism for methane transport from the deep subsurface on Mars. Using atmospheric pressure data gathered by Curiosity as input, we simulate methane gas transport from depths of 200 m to the surface. Even with such a deep source, our model reproduces the observed seasonality of methane, and the simulated surface methane fluxes fall within the range of previous estimates derived from atmospheric observations. Because 200 m is the likely minimum hospitable depth for living methanogenic microbes, our fracture network model indirectly reinvigorates the possibility of a microbial source of methane on Mars.

58 GEOSCIENCES↗

Machine Learning Driven Sensitivity Analysis of E3SM Land Model Parameters for Wetland Methane Emissions

Methane (CH 4 ) is globally the second most critical greenhouse gas after carbon dioxide, contributing to 16%–25% of the observed atmospheric warming. Wetlands are the primary natural source of methane emissions globally. However, wetland methane emission estimates from biogeochemistry models contain considerable uncertainty. One of the main sources of this uncertainty arises from the numerous uncertain model parameters within various physical, biological, and chemical processes that influence methane production, oxidation, and transport. Sensitivity Analysis (SA) can help identify critical parameters for methane emission and achieve reduced biases and uncertainties in future projections. This study performs SA for 19 selected parameters responsible for critical biogeochemical processes in the methane module of the Energy Exascale Earth System Model (E3SM) land model (ELM). The impact of these parameters on various CH 4 fluxes is examined at 14 FLUXNET- CH 4 sites with diverse vegetation types. Given the extensive number of model simulations needed for global variance-based SA, we employ a machine learning (ML) algorithm to emulate the complex behavior of ELM methane biogeochemistry. We found that parameters linked to CH 4 production and diffusion generally present the highest sensitivities despite apparent seasonal variation. Comparing simulated emissions from perturbed parameter sets against FLUXNET-CH 4 observations revealed that better performances can be achieved at each site compared to the default parameter values. This presents a scope for further improving simulated emissions using parameter calibration with advanced optimization techniques.

54 ENVIRONMENTAL SCIENCES↗

Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts

An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in catalysis, as typically it involves expensive or corrosive oxidants or reaction media(5-8) that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. Here, we find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolitesupported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. Finally, we anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.

09 BIOMASS FUELS↗

Protection and enrichment: how two different carbonaceous biofilm supports improve methane yield from encapsulated anaerobic microorganisms

Encapsulating anaerobic microorganisms allows for the separation of the solids retention time from the hydraulic retention time during anaerobic wastewater treatment. The harsh chemistries involved in the process of encapsulation can have adverse effects on microorganisms for anaerobic digestion, especially methanogens, and can lead to lower methane yields after encapsulation. Improving the survival and maintaining activity of anaerobic communities during encapsulation will likely be the key to improving methane yield. In this study, we investigated the encapsulation of biomass grown as biofilms on two carbonaceous materials, biochar and powdered activated carbon (PAC), to improve methane yield. Microorganisms grown as biofilms on biochar and PAC were encapsulated in polyethylene glycol (PEG) and incubated for 10 days. After 10 days, the unamended control capsules produced 81.6 ± 5.4 μmol of methane, while PAC-amended capsules produced 129.8 ± 1.9 μmol and biochar-amended capsules produced 432.96 ± 20.8 μmol methane, with the differences being statistically significant (p < 0.05). In biochar, a higher relative abundance of methanogens led to increased methane production capacity. The ratio of the methyl coenzyme M reductase (mcrA) genes to total 16S rRNA genes in the encapsulated biochar-supported biofilms was significantly higher than that in the encapsulated unsupported (p = 4.9 × 10 −5 ) and the PAC-supported biofilms (p = 0.012). Biochar-supported biofilms also had higher methane output per mcrA or 16S rRNA gene copy number. For the PAC, biofilms were protected from ammonium persulfate (APS), a powerful oxidant used in the encapsulation process. PAC removed 92% of dissolved APS, reducing exposure of the methanogens to this chemical. Unfortunately, this removal of APS compromised capsule stability, limiting the amount of PAC that could be added to the capsules. Furthermore, amendments that improve survival and activity of methanogens should be used in the capsules instead of those that protect methanogens by interfering with encapsulant polymerization chemistry.

Resource recovery↗

Thermodynamic properties and diffusion of water + methane binary mixtures

Thermodynamic and diffusion properties of water + methane mixtures in a single liquid phase are studied using NVT molecular dynamics. An extensive comparison is reported for the thermal pressure coefficient, compressibilities, expansion coefficients, heat capacities, Joule-Thomson coefficient, zero frequency speed of sound, and diffusion coefficient at methane concentrations up to 15% in the temperature range of 298–650 K. The simulations reveal a complex concentration dependence of the thermodynamic properties of water + methane mixtures. The compressibilities, heat capacities, and diffusion coefficients decrease with increasing methane concentration, whereas values of the thermal expansion coefficients and speed of sound increase. Increasing methane concentration considerably retards the self-diffusion of both water and methane in the mixture. These effects are caused by changes in hydrogen bond network, solvation shell structure, and dynamics of water molecules induced by the solvation of methane at constant volume conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methods and Models for Analyzing Methane Sorption Capacity of Coal Based on Its Physicochemical Characteristics

The authors study the influence of physicochemical parameters on methane adsorption capacity of coal and offer the analytical method for the methane adsorption capacity for three-phased condition of methane. It is found that in the depth interval to 300 m below surface, methane adsorption capacity measured in lab can exceed natural gas content of coal obtained from geological exploration data by 30%, and the change in the thermodynamic condition of coal–methane system brings irreversible physicochemical consequences in terms of the altered ratios of physical states of the main components. There is no linear connection between natural gas content of a coal bed and its methane adsorption capacity with respect to occurrence depth. The application of Big Data in treatment and interpretation of large data flows is described. The theoretical data predicted using the proposed method and the experimental data on methane content of Kuzbass coal agree.

01 COAL, LIGNITE, AND PEAT↗

Machine Learning Application to Assess Occurrence and Saturations of Methane Hydrate in Marine Deposits Offshore India

Artificial Neural Networks (ANN) were used to assess methane hydrate occurrence and saturation in marine sediments offshore India. The ANN analysis classifies the gas hydrate occurrence into three types: methane hydrate in pore space, methane hydrate in fractures, or no methane hydrate. Further, predicted saturation characterizes the volume of gas hydrate with respect to the available void volume. Log data collected at six wells, which were drilled during the India National Gas Hydrate Program Expedition 02 (NGHP-02), provided a combination of well log measurements that were used as input for machine learning (ML) models. Well log measurements included density, porosity, electrical resistivity, natural gamma radiation, and acoustic wave velocity. Combinations of well logs used in the ML models provide good overall balanced accuracy (0.79 to 0.86) for the prediction of the gas hydrate occurrence and good accuracy (0.68 to 0.92) for methane hydrate saturation prediction in the marine accumulations against reference data. The accuracy scores indicate that the ML models can successfully predict reservoir characteristics for marine methane hydrate deposits. In conclusion, the results indicate that the ML models can either augment physics-driven methods for assessing the occurrence and saturation of methane hydrate deposits or serve as an independent predictive tool for those characteristics.

58 GEOSCIENCES↗