Search

We use optical–optical double-resonance spectroscopy with a continuous wave (CW) pump and a cavity-enhanced frequency comb probe to measure the energy levels of methane in the upper part of the triacontad polyad (P6) with higher rotational quantum numbers than previously assigned. A high-power CW optical parametric oscillator, tunable around 3000 cm−1, is consecutively locked to the P(7, A2), Q(7, A2), R(7, A2), and Q(6, F2) transitions in the ν3 band, and a comb covering the 5800–6100 cm−1 range probes sub-Doppler ladder-type transitions from the pumped levels with J′ = 6 to 8, respectively. We report 118 probe transitions in the 3ν3 ← ν3 spectral range with uncertainties down to 300 kHz (1 × 10−5 cm−1), reaching 84 unique final states in the 9070–9370 cm−1 range with rotational quantum numbers J between 5 and 9. We assign these states using combination differences and by comparison with theoretical predictions from a new ab initio-based effective Hamiltonian and dipole moment operator. This is the first line-by-line experimental verification of theoretical predictions for these hot-band transitions, and we find a better agreement of transition wavenumbers with the new calculations compared to the TheoReTS/HITEMP and ExoMol databases. We also compare the relative intensities and find an overall good agreement with all three sets of predictions. Finally, we report the wavenumbers of 27 transitions in the 2ν3 spectral range, observed as V-type transitions from the ground state, and compare them to the new Hamiltonian, HITRAN2020, ExoMol, and the WKMLC line lists. [ABSTRACT FROM AUTHOR]

We have performed classical molecular dynamics simulations using the fully polarizable Atomic Multipole Optimized Energetics for Biomolecular Applications (AMOEBA) forcefield implemented within the Tinker package to determine whether a more adequate treatment of electrostatics is sufficient to correctly describe the mixing of methane with water under high pressure conditions. We found a significant difference between the ability of AMOEBA and other classical, computationally cheaper forcefields, such as TIP3P, simple point charge–extended, TIP4P, and optimized potentials for liquid simulations–all atom. While the latter models fail to detect any effect of pressure on the miscibility of methane in water, AMOEBA qualitatively captures the experimental observation of the increased solubility of methane in water with pressure. At higher temperatures, the solubility of water in methane also increases; this seems to be associated with the breakdown of the fourfold hydrogen-bonded water network structure: bonding in water is weaker, so the energy cost of solution is lowered. [ABSTRACT FROM AUTHOR]

Hydrocarbon contamination is associated with light transmission losses in modern lithography machines, which contain extreme-ultraviolet-induced plasma. A volume-averaged global and deposition/etch surface model of a reference hydrogen/methane inductive discharge is developed to investigate the plasma–surface interactions. The simulation results are validated against a wide variety of experiments and verified with respect to multiple sets of computational data. The deposition rate is calculated for a variation in methane impurity (10–10 000 ppm), power, pressure, and net mass flow. The simulations conclude that the hydrocarbon plasma deposition can be minimized by reducing methane impurity and excluding solid organic structures. [ABSTRACT FROM AUTHOR]

Improving the catalytic performance of materials based on cerium oxide (CeO2) for the activation of methane (CH4) can be achieved through the following strategies: mixture of CeO2 with different oxides (e.g., CeO2–La2O3) and the use of particles with different sizes. In this study, we present a theoretical investigation of the initial CH4 dehydrogenation on (La2Ce2O7)n clusters, where n = 2, 4, and 6. Our framework relies on density functional theory calculations combined with the unity bond index–quadratic exponential potential approximation. Our results indicate that chemical species arising from the first dehydrogenation of CH4, that is, CH3 and H, bind through the formation of C–O and H–O bonds with the clusters, respectively. The coordination of the adsorption site and the chemical environment plays a crucial role in the magnitude of the adsorption energy; for example, species adsorb more strongly in the low-coordinated topO sites located close to the La atoms. Thus, it affects the activation energy barrier, which tends to be lower in configurations where the adsorption of the chemical species is stronger. During CH4 dehydrogenation, the CH3 radical can be present in a planar or tetrahedral configuration. Its conformation changes as a function of the charge transference between the molecule and the cluster, which depends on the CH3-cluster distance. Finally, we analyze the effects of the Hubbard effective parameter (Ueff) on adsorption properties, as the magnitude of localization of Ce f-states affects the hybridization of the interaction between the molecule and the clusters and hence the magnitude of the adsorption energies. We obtained a linear decrease in the adsorption energies by increasing the Ueff parameter; however, the activation energy is only slightly affected. [ABSTRACT FROM AUTHOR]

There is a longstanding difficulty that time-dependent density functional theory relying on adiabatic local density approximation is not applicable to the electron dynamics, for example, for an initially excited state, such as in photochemical reactions. To overcome this, we develop non-adiabatic excited-state time-dependent GW molecular dynamics (TDGW) on the basis of the extended quasiparticle theory. Replacing Kohn–Sham orbitals/energies with correlated, interacting quasiparticle orbitals/energies allows the full correspondence to the excited-state surfaces and corresponding total energies, with satisfying extended Koopmans' theorem. We demonstrate the power of TDGW using methane photolysis, CH 4 → CH 3 • + H , an important initiation reaction for combustion/pyrolysis and hydrogen production of methane. We successfully explore several possible pathways and show how this reaction dynamics is captured accurately through simultaneously time-tracing all quasiparticle levels. TDGW scales as O ( N B 3 - 4 ) , where NB is the number of basis functions, which is distinctly advantageous to performing dynamics using configuration interaction and coupled cluster methods. [ABSTRACT FROM AUTHOR]

A significant share of anthropogenic global warming comes from livestock production. There is debate about whether there can be any role for livestock in a climatically sustainable future; the debate is particularly heated for cows and sheep, largely due to the methane they burp out. However, short-lived gases like methane affect climate in a fundamentally different way than long-lived gases like carbon dioxide. Consequently, climate stabilization does not require zeroing-out cattle herds. But this doesn't mean we can eat our beef and have it (a tolerable climate) too—livestock still contribute to global warming. Preventing or limiting future growth in livestock-related emissions can represent a sensible part of the portfolio of responses to the climate crisis, particularly when carbon dioxide emissions are not on track to reach net zero sufficiently quickly. [ABSTRACT FROM AUTHOR]

Resource partitioning is central to the incredible productivity of microbial communities, including gigatons in annual methane emissions through syntrophic interactions. Previous work revealed how a sulfate reducer (Desulfovibrio vulgaris, Dv) and a methanogen (Methanococcus maripaludis, Mm) underwent evolutionary diversification in a planktonic context, improving stability, cooperativity, and productivity within 300-1000 generations. Here, we show that mutations in just 15 Dv and 7 Mm genes within a minimal assemblage of this evolved community gave rise to co-existing ecotypes that were spatially enriched within a few days of culturing in a fluidized bed reactor. The spatially segregated communities partitioned resources in the simulated subsurface environment, with greater lactate utilization by attached Dv but partial utilization of resulting H2 by low affinity hydrogenases of Mm in the same phase. The unutilized H2 was scavenged by high affinity hydrogenases of planktonic Mm, producing copious amounts of methane. Our findings show how a few mutations can drive resource partitioning amongst niche-differentiated ecotypes, whose interplay synergistically improves productivity of the entire mutualistic community.

The direct conversion of methane to methanol has attracted increasing interest due to abundant and low-cost natural gas resources. Herein, by anchoring Cr-oxo/-oxyhydroxides on UiO-66 metal–organic frameworks, we demonstrate that reactive anionic oxyl radicals can be formed by controlling the coordination environment based on the results of density functional theory calculations. The anionic oxyl radicals produced at the completely oxidized CrVI site acted as the active species for facile methane activation. The thermodynamically stable CrVI-oxo/-oxyhydroxides with the anionic oxyl radicals catalyze the activation of the methane C–H bond through a homolytic mechanism. An analysis of the results showed that the catalytic performance of the active oxyl species correlates with the reaction energy of methane activation and H adsorption energies. Following methanol formation, N2O can regenerate the active sites on the most stable CrVI oxyhydroxides, i.e., the Cr(O)4Hf species. The present study demonstrated that the anionic oxyl radicals formed on the anchored CrVI oxyhydroxides by tuning the coordination environment enabled facile methane activation and facilitated methanol production. [ABSTRACT FROM AUTHOR]

The interaction between electrons and methane is studied with a particular focus on describing the dynamics of elastic and electronic excitation processes under the influence of the multichannel coupling effects. Elastic and electronically inelastic integral and differential cross sections are reported. These cross sections were calculated with the Schwinger multichannel method implemented with norm-conserving pseudopotentials within the minimal orbital basis for single-configuration interaction approach with up to 181 open channels. While an excellent agreement with previously published data is found in the elastic channel, the comparisons involving electronic excitation cross sections reveal significant discrepancies. Furthermore, the lack of reliable experimental data regarding the electronically inelastic channels hampers a more detailed analysis of the theoretical results. Additionally, total ionization and total cross sections for electron collisions with methane are also presented. By highlighting the current theoretical challenges in dealing with electron-induced electronic excitation of molecules, we seek to contribute to a deeper understanding of this scattering process and, thus, pave the way for future research. [ABSTRACT FROM AUTHOR]

Before hydrates can be widely used in industry, we should better understand the problematic issues of hydrate nucleation, particularly its stochastic nature. Here, we report on measurements of the nucleation probability of mixed-gas hydrates in which the guest molecules are a mixture of methane and propane. For the pure cases, at a supersaturation near 1.0, we had previously measured an induction time for the methane hydrate of about 1 h, whereas for the propane hydrate, it was over one day. Using the same experimental setup, we examine here the nucleation probability for a mixture of 90% methane and 10% propane as the guest gas for a range of supersaturations. For the experiments, the temperature was 274 ± 0.5 K and the stirring rate was about 300 rpm. The experiments were repeated at least ten times under the same condition, exchanging the sample water every time. We define the nucleation probability at a given time as the fraction of trials that nucleated by that time and then determine the nucleation probability distribution. The resulting nucleation frequency is found to have a power-law relation to supersaturation. Then, we examine how the nucleation frequency is affected by the existence of ultrafine bubbles in the initial water. We find that the ultrafine bubbles increase the nucleation frequency but much less than that of typical changes in supersaturation. [ABSTRACT FROM AUTHOR]

The roles of Asgard archaea in eukaryogenesis and marine biogeochemical cycles are well studied, yet their contributions in soil ecosystems remain unknown. Of particular interest are Asgard archaeal contributions to methane cycling in wetland soils. To investigate this, we reconstructed two complete genomes for soil-associated Atabeyarchaeia, a new Asgard lineage, and a complete genome of Freyarchaeia, and predicted their metabolism in situ. Metatranscriptomics reveals expression of genes for [NiFe]-hydrogenases, pyruvate oxidation and carbon fixation via the Wood-Ljungdahl pathway. Also expressed are genes encoding enzymes for amino acid metabolism, anaerobic aldehyde oxidation, hydrogen peroxide detoxification and carbohydrate breakdown to acetate and formate. Overall, soil-associated Asgard archaea are predicted to include non-methanogenic acetogens, highlighting their potential role in carbon cycling in terrestrial environments.

UNLABELLED: Methyl-coenzyme M reductase (MCR) catalyzes the final step of methanogenesis, the microbial metabolism responsible for nearly all biological methane emissions to the atmosphere. Decades of biochemical and structural research studies have generated detailed insights into MCR function in vitro, yet very little is known about the interplay between MCR and methanogen physiology. For instance, while it is routinely stated that MCR catalyzes the rate-limiting step of methanogenesis, this has not been categorically tested. In this study, to gain a more direct understanding of MCRs control on the growth of Methanosarcina acetivorans, we generate a strain with an inducible mcr operon on the chromosome, allowing for careful control of MCR expression. We show that MCR is not growth rate-limiting in substrate-replete batch cultures. However, through careful titration of MCR expression, growth-limiting state(s) can be obtained. Transcriptomic analysis of M. acetivorans experiencing MCR limitation reveals a global response with hundreds of differentially expressed genes across diverse functional categories. Notably, MCR limitation leads to strong induction of methylsulfide methyltransferases, likely due to insufficient recycling of metabolic intermediates. In addition, the mcr operon is not transcriptionally regulated, i.e., it is constitutively expressed, suggesting that the overabundance of MCR might be beneficial when cells experience nutrient limitation or stressful conditions. Altogether, we show that there is a wide range of cellular MCR concentrations that can sustain optimal growth, suggesting that other factors such as anabolic reactions might be rate-limiting for methanogenic growth. IMPORTANCE: Methane is a potent greenhouse gas that has contributed to ca. 25% of global warming in the post-industrial era. Atmospheric methane is primarily of biogenic origin, mostly produced by microorganisms called methanogens. Methyl-coenzyme M reductase (MCR) catalyzes methane formatio in methanogens. Even though MCR comprises ca. 10% of the cellular proteome, it is hypothesized to be growth-limiting during methanogenesis. In this study, we show that Methanosarcina acetivorans cells grown in substrate-replicate batch cultures produce more MCR than its cellular demand for optimal growth. The tools outlined in this study can be used to refine metabolic models of methanogenesis and assay lesions in MCR in a higher-throughput manner than isolation and biochemical characterization of pure protein.

Climate changes significantly impact greenhouse gas emissions from wetland soil. Specifically, wetland soil may be exposed to oxygen (O2) during droughts, or to sulfate (SO42-) as a result of sea level rise. How these stressors - separately and together - impact microbial food webs driving carbon cycling in the wetlands is still not understood. To investigate this, we integrated geochemical analysis, proteogenomics, and stoichiometric modeling to characterize the impact of elevated SO42- and O2 levels on microbial methane (CH4) and carbon dioxide (CO2) emissions. The results uncovered the adaptive responses of this community to changes in SO42- and O2 availability and identified altered microbial guilds and metabolic processes driving CH4 and CO2 emissions. Elevated SO42- reduced CH4 emissions, with hydrogenotrophic methanogenesis more suppressed than acetoclastic. Elevated O2 shifted the greenhouse gas emissions from CH4 to CO2. The metabolic effects of combined SO42- and O2 exposures on CH4 and CO2 emissions were similar to those of O2 exposure alone. The reduction in CH4 emission by increased SO42- and O2 was much greater than the concomitant increase in CO2 emission. Thus, greater SO42- and O2 exposure in wetlands is expected to reduce the aggregate warming effect of CH4 and CO2. Metaproteomics and stoichiometric modeling revealed a unique subnetwork involving carbon metabolism that converts lactate and SO42- to produce acetate, H2S, and CO2 when SO42- is elevated under oxic conditions. This study provides greater quantitative resolution of key metabolic processes necessary for the prediction of CH4 and CO2 emissions from wetlands under future climate scenarios.

The oxygenation of Earths atmosphere represents the quintessential transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution; molecular clock models indicate the diversification and ecological expansion of respiratory metabolisms in the several hundred million years following atmospheric oxygenation. Across this same interval, the geological record preserves 13C enrichment in some carbonate rocks, called the Lomagundi-Jatuli excursion (LJE). By combining data from geologic and genomic records, a self-consistent metabolic evolution model emerges for the LJE. First, fermentation and methanogenesis were major processes remineralizing organic carbon before atmospheric oxygenation. Once an ozone layer formed, shallow water and exposed environments were shielded from UVB/C radiation, allowing the expansion of cyanobacterial primary productivity. High primary productivity and methanogenesis led to preferential removal of 12C into organic carbon and CH4. Extreme and variable 13C enrichments in carbonates were caused by 13C-depleted CH4 loss to the atmosphere. Through time, aerobic respiration diversified and became ecologically widespread, as did other new metabolisms. Respiration displaced fermentation and methanogenesis as the dominant organic matter remineralization processes. As CH4 loss slowed, dissolved inorganic carbon in shallow environments was no longer highly 13C enriched. Thus, the loss of extreme 13C enrichments in carbonates marks the establishment of a new microbial mat ecosystem structure, one dominated by respiratory processes distributed along steep redox gradients. These gradients allowed the exchange of metabolic by-products among metabolically diverse organisms, providing novel metabolic opportunities. Thus, the microbially induced oxygenation of Earths atmosphere led to the transformation of microbial ecosystems, an archetypal example of planetary microbiology.IMPORTANCEThe oxygenation of Earths atmosphere represents the most extensive known chemical transformation of a planetary surface by microbial processes. In turn, atmospheric oxygenation transformed metabolic evolution by providing oxidants independent of the sites of photosynthesis. Thus, the evolutionary changes during this interval and their effects on planetary-scale biogeochemical cycles are fundamental to our understanding of the interdependencies among genomes, organisms, ecosystems, elemental cycles, and Earths surface chemistry through time.

Methane is a major contributor to anthropogenic greenhouse gas emissions. Identifying large sources of methane, particularly from the oil and gas sectors, will be essential for mitigating climate change. Aircraft-based methane sensing platforms can rapidly detect and quantify methane point-source emissions across large geographic regions, and play an increasingly important role in industrial methane management and greenhouse gas inventory. We independently evaluate the performance of five major methane-sensing aircraft platforms: Carbon Mapper, GHGSat-AV, Insight M, MethaneAIR, and Scientific Aviation. Over a 6 week period, we released metered gas for over 700 single-blind measurements across all five platforms to evaluate their ability to detect and quantify emissions that range from 1 to over 1,500 kg(CH4)/h. Aircraft consistently quantified releases above 10 kg(CH4)/h, and GHGSat-AV and Insight M detected emissions below 5 kg(CH4)/h. Fully blinded quantification estimates for platforms using downward-facing imaging spectrometers have parity slopes ranging from 0.76 to 1.13, with R2 values of 0.61 to 0.93; the platform using continuous air sampling has a parity slope of 0.5 (R2 = 0.93). Results demonstrate that aircraft-based methane sensing has matured since previous studies and is ready for an increasingly important role in environmental policy and regulation.

Methane is a powerful greenhouse gas, more potent than carbon dioxide, and emitted from a variety of natural sources including wetlands, permafrost, mammalian guts and termites. As increases in global temperatures continue to break records, quantifying the magnitudes of key methane sources has never been more pertinent. Over the last 40 years, the contribution of termites to the global methane budget has been subject to much debate. The most recent estimates of termite emissions range between 9 and 15 Tg CH4 year-1, approximately 4% of emissions from natural sources (excluding wetlands). However, we argue that the current approach for estimating termite contributions to the global methane budget is flawed. Key parameters, namely termite methane emissions from soil, deadwood, living tree stems, epigeal mounds and arboreal nests, are largely ignored in global estimates. This omission occurs because data are lacking and research objectives, crucially, neglect variation in termite ecology. Furthermore, inconsistencies in data collection methods prohibit the pooling of data required to compute global estimates. Here, we summarise the advances made over the last 40 years and illustrate how different aspects of termite ecology can influence the termite contribution to global methane emissions. Additionally, we highlight technological advances that may help researchers investigate termite methane emissions on a larger scale. Finally, we consider dynamic feedback mechanisms of climate warming and land-use change on termite methane emissions. We conclude that ultimately the global contribution of termites to atmospheric methane remains unknown and thus present an alternative framework for estimating their emissions. To significantly improve estimates, we outline outstanding questions to guide future research efforts.

Methane (CH4) is a potent greenhouse gas emitted by archaea in anaerobic environments such as wetland soils. Tidal freshwater wetlands are predicted to become increasingly saline as sea levels rise due to climate change. Previous work has shown that increases in salinity generally decrease CH4 emissions, but with considerable variation, including instances where salinization increased CH4 flux. We measured microbial community composition, biogeochemistry, and CH4 flux from field samples and lab experiments from four different sites across a wide geographic range. We sought to assess how site differences and microbial ecology affect how CH4 emissions are influenced by salinization. CH4 flux was generally, but not always, positively correlated with CO2 flux, soil carbon, ammonium, phosphate, and pH. Methanogen guilds were positively correlated with CH4 flux across all sites, while methanotroph guilds were both positively and negatively correlated with CH4 depending on site. There was mixed support for negative relationships between CH4 fluxes and concentrations of alternative electron acceptors and abundances of taxa that reduce them. CH4/salinity relationships ranged from negative, to neutral, to positive and appeared to be influenced by site characteristics such as pH and plant composition, which also likely contributed to site differences in microbial communities. The activity of site-specific microbes that may respond differently to low-level salinity increases is likely an important driver of CH4/salinity relationships. Our results suggest several factors that make it difficult to generalize CH4/salinity relationships and highlight the need for paired microbial and flux measurements across a broader range of sites.

Although CO2 impacts the environment negatively, it can be a valuable resource due to its carbon content. The U.S. industry emits over 825 Mt of CO2 annually, with an expected increase in the future. This article analyzes 27 different technology combinations for capturing and using CO2 for industrial feedstocks, including the production of synthetic methane, methanol, and Fischer-Tropsch fuels. The study also estimates and compares the energy requirements for capturing and converting CO2 from 16 different industrial sources, as well as the energy requirements for hydrogen production through state-of-the-art and emerging electrolyzer technologies. Additionally, the study develops a combined scenario that outlines a design for applying an inclusive approach to achieve net-zero CO2 emissions in the industrial sector, incorporating multiple decarbonization measures. The results suggest that the use of CO2 for methane production has the potential to replace all natural gas demands considered in the base case and combined scenarios. However, using CO2 utilization-based Fischer-Tropsch products alone to replace naphtha feedstock and transportation fuels is not sufficient to achieve complete decarbonization in the studied end uses. CO2 utilization-based methanol could potentially substitute for several times the current U.S. methanol production and meet the current global demand for methanol. Moreover, the study conducts an economic analysis to estimate the costs of CO2 utilization, which vary for different industrial sectors and depend on the technologies employed. Overall, this study provides valuable information for policymakers and industry stakeholders who are striving to develop effective strategies to decarbonize the industrial sector.

Natural gas hydrates, mainly existing in permafrost and on the seabed, are expected to be a new energy source with great potential. The exploitation technology of natural gas hydrates is one of the main focuses of hydrate-related studies. In this study, a large-size liquid aqueous solution wrapping a methane hydrate system was established and molecular dynamics simulations were used to investigate the phase equilibrium conditions of methane hydrate at different methane concentrations and interfacial geometries. It is found that the methane concentration of a solution significantly affects the phase equilibrium of methane hydrates. Different methane concentrations at the same temperature and pressure can lead to hydrate formation or decomposition. At the same temperature and pressure, in a system reaching equilibrium, the size of spherical hydrate clusters is coupled to the solution concentration, which is proportional to the Laplace pressure at the solid–liquid interface. Lower solution concentrations reduce the phase equilibrium temperature of methane hydrates at the same pressure; as the concentration increases, the phase equilibrium temperature gradually approaches the actual phase equilibrium temperature. In addition, the interfacial geometry of hydrates affects the thermodynamic stability of hydrates. The spherical hydrate particles have the highest stability for the same volume. Through this study, we provide a stronger foundation to understand the principles driving hydrate formation/dissociation relevant to the exploitation of methane hydrates. [ABSTRACT FROM AUTHOR]

Photofragment spectroscopy is used to measure the vibrational spectra of V 2 + (CH 4) n (n = 1–4), V 3 + (CH 4) n (n = 1–3), and V x + (CH 4) (x = 4–8) in the C–H stretching region (2550–3100 cm−1). Spectra are measured by monitoring loss of CH4. The experimental spectra are compared to simulations at the B3LYP+D3/6-311++G(3df,3pd) level of theory to identify the geometry of the ions. Multi-reference configuration interaction with Davidson correction (MRCI+Q) calculations are also carried out on V 2 + and V 3 + . The methane binding orientation in V 2 + (CH 4) n (n = 1–4) evolves from η3 to η2 as more methane molecules are added. The IR spectra of metal-methane clusters can give information on the structure of metal clusters that may otherwise be hard to obtain from isolated clusters. For example, the V 3 + (CH 4) n (n = 1–3) experimental spectra show an additional peak as the second and third methane molecules are added to V 3 + , which indicates that the metal atoms are not equivalent. The V x + (CH 4) show a larger red shift in the symmetric C–H stretch for larger clusters with x = 5–8 than for the small clusters with x = 2, 3, indicating increased covalency in the interaction of larger vanadium clusters with methane. [ABSTRACT FROM AUTHOR]

Methanogens are a diverse group of Archaea that obligately couple energy conservation to the production of methane. Some methanogens encode alternate pathways for energy conservation, like anaerobic respiration, but the biochemical details of this process are unknown. We show that a multiheme c-type cytochrome called MmcA from Methanosarcina acetivorans is important for intracellular electron transport during methanogenesis and can also reduce extracellular electron acceptors like soluble Fe3+ and anthraquinone-2,6-disulfonate. Consistent with these observations, MmcA displays reversible redox features ranging from -100 to -450 mV versus SHE. Additionally, mutants lacking mmcA have significantly slower Fe3+ reduction rates. The mmcA locus is prevalent in members of the Order Methanosarcinales and is a part of a distinct clade of multiheme cytochromes that are closely related to octaheme tetrathionate reductases. Taken together, MmcA might act as an electron conduit that can potentially support a variety of energy conservation strategies that extend beyond methanogenesis.

Redox processes, aqueous and solid-phase chemistry, and pH dynamics are key drivers of subsurface biogeochemical cycling and methanogenesis in terrestrial and wetland ecosystems but are typically not included in terrestrial carbon cycle models. These omissions may introduce errors when simulating systems where redox interactions and pH fluctuations are important, such as wetlands where saturation of soils can produce anoxic conditions and coastal systems where sulfate inputs from seawater can influence biogeochemistry. Integrating cycling of redox-sensitive elements could therefore allow models to better represent key elements of carbon cycling and greenhouse gas production. We describe a model framework that couples the Energy Exascale Earth System Model (E3SM) Land Model (ELM) with PFLOTRAN biogeochemistry, allowing geochemical processes and redox interactions to be integrated with land surface model simulations. We implemented a reaction network including aerobic decomposition, fermentation, sulfate reduction, sulfide oxidation, methanogenesis, and methanotrophy as well as pH dynamics along with iron oxide and iron sulfide mineral precipitation and dissolution. We simulated biogeochemical cycling in tidal wetlands subject to either saltwater or freshwater inputs driven by tidal hydrological dynamics. In simulations with saltwater tidal inputs, sulfate reduction led to accumulation of sulfide, higher dissolved inorganic carbon concentrations, lower dissolved organic carbon concentrations, and lower methane emissions than simulations with freshwater tidal inputs. Model simulations compared well with measured porewater concentrations and surface gas emissions from coastal wetlands in the Northeastern United States. These results demonstrate how simulating geochemical reaction networks can improve land surface model simulations of subsurface biogeochemistry and carbon cycling.

Estuarine wetlands harbor considerable carbon stocks, but rising sea levels could affect their ability to sequester soil carbon as well as their potential to emit methane (CH4). While sulfate loading from seawater intrusion may reduce CH4 production due to the higher energy yield of microbial sulfate reduction, existing studies suggest other factors are likely at play. Our study of 11 wetland complexes spanning a natural salinity and productivity gradient across the San Francisco Bay and Delta found that while CH4 fluxes generally declined with salinity, they were highest in oligohaline wetlands (ca. 3-ppt salinity). Methanogens and methanogenesis genes were weakly correlated with CH4 fluxes but alone did not explain the highest rates observed. Taxonomic and functional gene data suggested that other microbial guilds that influence carbon and nitrogen cycling need to be accounted for to better predict CH4 fluxes at landscape scales. Higher methane production occurring near the freshwater boundary with slight salinization (and sulfate incursion) might result from increased sulfate-reducing fermenter and syntrophic populations, which can produce substrates used by methanogens. Moreover, higher salinities can solubilize ionically bound ammonium abundant in the lower salinity wetland soils examined here, which could inhibit methanotrophs and potentially contribute to greater CH4 fluxes observed in oligohaline sediments.IMPORTANCELow-level salinity intrusion could increase CH4 flux in tidal freshwater wetlands, while higher levels of salinization might instead decrease CH4 fluxes. High CH4 emissions in oligohaline sites are concerning because seawater intrusion will cause tidal freshwater wetlands to become oligohaline. Methanogenesis genes alone did not account for landscape patterns of CH4 fluxes, suggesting mechanisms altering methanogenesis, methanotrophy, nitrogen cycling, and ammonium release, and increasing decomposition and syntrophic bacterial populations could contribute to increases in net CH4 flux at oligohaline salinities. Improved understanding of these influences on net CH4 emissions could improve restoration efforts and accounting of carbon sequestration in estuarine wetlands. More pristine reference sites may have older and more abundant organic matter with higher carbon:nitrogen compared to wetlands impacted by agricultural activity and may present different interactions between salinity and CH4. This distinction might be critical for modeling efforts to scale up biogeochemical process interactions in estuarine wetlands.

Methane (CH4) and nitrous oxide (N2O) are major greenhouse gases that are predominantly generated by microbial activities in anoxic environments. N2O inhibition of methanogenesis has been reported, but comprehensive efforts to obtain kinetic information are lacking. Using the model methanogen Methanosarcina barkeri strain Fusaro and digester sludge-derived methanogenic enrichment cultures, we conducted growth yield and kinetic measurements and showed that micromolar concentrations of N2O suppress the growth of methanogens and CH4 production from major methanogenic substrate classes. Acetoclastic methanogenesis, estimated to account for two-thirds of the annual 1 billion metric tons of biogenic CH4, was most sensitive to N2O, with inhibitory constants (KI) in the range of 18-25 μM, followed by hydrogenotrophic (KI, 60-90 μM) and methylotrophic (KI, 110-130 μM) methanogenesis. Dissolved N2O concentrations exceeding these KI values are not uncommon in managed (i.e. fertilized soils and wastewater treatment plants) and unmanaged ecosystems. Future greenhouse gas emissions remain uncertain, particularly from critical zone environments (e.g. thawing permafrost) with large amounts of stored nitrogenous and carbonaceous materials that are experiencing unprecedented warming. Incorporating relevant feedback effects, such as the significant N2O inhibition on methanogenesis, can refine climate models and improve predictive capabilities.

Seawater intrusion into freshwater wetlands causes changes in microbial communities and biogeochemistry, but the exact mechanisms driving these changes remain unclear. Here we use a manipulative laboratory microcosm experiment, combined with DNA sequencing and biogeochemical measurements, to tease apart the effects of sulfate from other seawater ions. We examined changes in microbial taxonomy and function as well as emissions of carbon dioxide, methane, and nitrous oxide in response to changes in ion concentrations. Greenhouse gas emissions and microbial richness and composition were altered by artificial seawater regardless of whether sulfate was present, whereas sulfate alone did not alter emissions or communities. Surprisingly, addition of sulfate alone did not lead to increases in the abundance of sulfate reducing bacteria or sulfur cycling genes. Similarly, genes involved in carbon, nitrogen, and phosphorus cycling responded more strongly to artificial seawater than to sulfate. These results suggest that other ions present in seawater, not sulfate, drive ecological and biogeochemical responses to seawater intrusion and may be drivers of increased methane emissions in soils that received artificial seawater addition. A better understanding of how the different components of salt water alter microbial community composition and function is necessary to forecast the consequences of coastal wetland salinization.

Forages and concentrates have consistently distinct patterns of fermentation in the rumen, with forages producing more methane (CH4) per unit of digested organic matter (OM) and higher acetate to propionate ratio than concentrates. A mechanism based on the Monod function of microbial growth has been proposed to explain the distinct fermentation pattern of forages and concentrates, where greater dilution rates and lower pH associated with concentrate feeding increase dihydrogen (H2) concentration through increasing methanogens growth rate and decreasing methanogens theoretically maximal growth rate, respectively. Increased H2 concentration would in turn inhibit H2 production, decreasing methanogenesis, inhibit H2-producing pathways such as acetate production via pyruvate oxidative decarboxylation, and stimulate H2-incorporating pathways such as propionate production. We examined the hypothesis that equalizing dilution rates in serial rumen cultures would result in a similar fermentation profile of a high forage and a high concentrate substrate. Under a 2 × 3 factorial arrangement, a high forage and a high concentrate substrate were incubated at dilution rates of 0.14, 0.28, or 0.56 h-1 in eight transfers of serial rumen cultures. Each treatment was replicated thrice, and the experiment repeated in two different months. The high concentrate substrate accumulated considerably more H2 and formate and produced less CH4 than the high forage substrate. Methanogens were nearly washed-out with high concentrate and increased their initial numbers with high forage. The effect of dilution rate was minor in comparison to the effect of the type of substrate. Accumulation of H2 and formate with high concentrate inhibited acetate and probably H2 and formate production, and stimulated butyrate, rather than propionate, as an electron sink alternative to CH4. All three dilution rates are considered high and selected for rapidly growing bacteria. The archaeal community composition varied widely and inconsistently. Lactate accumulated with both substrates, likely favored by microbial growth kinetics rather than by H2 accumulation thermodynamically stimulating electron disposal from NADH into pyruvate reduction. In this study, the type of substrate had a major effect on rumen fermentation largely independent of dilution rate and pH.

The flame resistance characteristics of corrugated flame-retardant system for hydrogen/methane explosion were researched by visualization experiment. The influence laws of structure parameter and hydrogen doping ratio on the explosion resistance parameters were summarized. Result indicates that the flame could be effectively quenched and there was a clear correspondence between flame propagation and explosion parameters at the front and rear ends. Flame propagation at the front-end could be greatly affected by flame-retardant system, thereby affecting its propagation velocity inside the narrow channel. As the flame resistance failed, the flame at the rear-end would appear an obvious acceleration. As the porosity and hydrogen ratio increased, the failure probability continued to increase. An increase in flame-retardant element thickness was conducive to flame resistance success. Above factors could affect the flame resistance effect by influencing the intensities of flame and pressure wave entering front-end of flame-retardant system, as well as the degree of weakening inside the narrow channel. • Flame resistance characteristic of corrugated flame-retardant system was researched. • Pressure change, flame temperature and its propagation characteristic were obtained. • Influence law and mechanism of working condition on flame resistance were analyzed. • Correlation between flame resistance process and explosion parameters was explored. • Effective suggestion for practical application and protection methods were proposed. [ABSTRACT FROM AUTHOR]

Recovering energy from biomass and treating organic waste can be done effectively through a biogas digester system. However, monitoring the performance and control of the system to produce biogas is possible through the online process. Therefore, this study developed a novel low-cost gas and temperature profiling system (GTPS) and data acquisition system (DAS) used in biogas digester. The GTPS is designed to monitor and record the amount of methane (CH4) and carbon dioxide (CO2), the main constituent of biogas, from 0 to 100% and to measure the slurry temperature in the digester using a K-type thermocouple. To test the developed monitoring system, the biogas yield (%) and temperature were monitored, and the result obtained agreed with that reported and obtained in the literature (50–70% and 30−40%) for CH4 and CO2, respectively, followed by the desired mesophilic temperature condition for biogas production (20–35 °C). The study employed an RS-232/RS-485 converter for data communication and a low-cost thermocouple module (isolated analog input) that was installed in the data acquisition system. Interestingly, the application of the converter equipment has never been used in any study on monitoring a biogas digester. [ABSTRACT FROM AUTHOR]

The dissociation of methane is not only an important reaction step in catalytic processes, but also of fundamental interest. Dynamical effects during the dissociative chemisorption of methane on metal surfaces cause significant differences in computed reaction rates, compared to what is predicted by typical transition state theory (TST) models. It is clear that for a good understanding of the catalytic activation of methane dynamical simulations are required. In this paper, a general blueprint is provided for performing dynamical simulations of the dissociative chemisorption of methane on metal surfaces, by employing either the quasi-classical trajectory or ring polymer molecular dynamics approach. If the computational setup is constructed with great care-since results can be affected considerably by the setup - chemically accurate predictions are achievable. Although this paper concerns methane dissociation, the provided blueprint is, so far, applicable to the dissociative chemisorption of most molecules. [ABSTRACT FROM AUTHOR]

The C−C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom‐efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. However, the inherent thermodynamic stability and kinetic inertness of CH4 and CO2 present obstacles to achieving efficient and selective conversion at room temperature. Our study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq−) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions(⋅CO2−) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation‐synthesized CuO‐anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L−1 of CH3COOH with near‐unity selectivity (>95 %). These findings offer valuable insights for catalyst design and implementation in radiation‐induced chemical conversion. [ABSTRACT FROM AUTHOR]

The C−C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom‐efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. However, the inherent thermodynamic stability and kinetic inertness of CH4 and CO2 present obstacles to achieving efficient and selective conversion at room temperature. Our study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq−) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions(⋅CO2−) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation‐synthesized CuO‐anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L−1 of CH3COOH with near‐unity selectivity (>95 %). These findings offer valuable insights for catalyst design and implementation in radiation‐induced chemical conversion. [ABSTRACT FROM AUTHOR]

Unmanned aerial vehicles (UAVs) equipped with a miniaturized sensor package were developed for aerial observations, which realizes aerial observations affordable to scientists in atmospheric science and achieves aerial measurements in high spatial resolution. UAVs are deployed to a variety of aerial detecting tasks in different scientific scenarios including chemical industry parks (CIPs) with hazardous gases emissions, and some places difficult for humans to reach. In this study, UAV sensing technology was deployed to detect air pollutants in a suburb, a CIP and a natural gas plant, respectively. The effects of atmospheric conditions such as the atmospheric boundary layer height, long-distance transport and atmospheric stability on the spatiotemporal variations of the air pollutants vertical profiles were investigated by the UAV. The UAV with the sensor package was deployed to capture the methane (CH4) leakages in a natural gas plant. The spatiotemporal variations of CH4 in both vertical and horizontal directions studied by UAV were employed to calculate accurate CH4 emissions, which is crucial to reducing the emissions of greenhouse gases. The low-cost UAV sensing technology for air pollutants was developed by Dr. Xiaobing Pang, who was funded by the Newton Fellowship in 2009 and worked in the University of York. This article is part of the theme issue 'Celebrating the 15th anniversary of the Royal Society Newton International Fellowship'. [ABSTRACT FROM AUTHOR]

The C−C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom‐efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. However, the inherent thermodynamic stability and kinetic inertness of CH4 and CO2 present obstacles to achieving efficient and selective conversion at room temperature. Our study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq−) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions(⋅CO2−) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation‐synthesized CuO‐anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L−1 of CH3COOH with near‐unity selectivity (>95 %). These findings offer valuable insights for catalyst design and implementation in radiation‐induced chemical conversion. [ABSTRACT FROM AUTHOR]

The C−C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom‐efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. However, the inherent thermodynamic stability and kinetic inertness of CH4 and CO2 present obstacles to achieving efficient and selective conversion at room temperature. Our study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq−) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions(⋅CO2−) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation‐synthesized CuO‐anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L−1 of CH3COOH with near‐unity selectivity (>95 %). These findings offer valuable insights for catalyst design and implementation in radiation‐induced chemical conversion. [ABSTRACT FROM AUTHOR]

Direct photocatalytic conversion of methane to value-added C1 oxygenate with O2 is of great interest but presents a significant challenge in achieving highly selective product formation. Herein, a general strategy for the construction of copper single-atom catalysts with a well-defined coordination microenvironment is developed on the basis of metal-organic framework for selective photo-oxidation of CH4 to HCHO. We propose the directional activation of O2 on the mono-copper site breaks the original equilibrium and tilts the balance of radical formation almost completely toward •OOH. The synchronously generated •OOH and •CH3 radicals rapidly combine to form HCHO while inhibiting competing reactions, thus resulting in ultra-highly selective HCHO production (nearly 100%) with a time yield of 2.75 mmol gcat−1 h−1. This work highlights the potential of rationally designing reaction sites to manipulate reaction pathways and achieve selective CH4 photo-oxidation, and could guide the further design of high-performance single-atom catalysts to meet future demand. Selective photo-oxidation of CH4 to value-added C1 oxygenates remains challenging. Here, the authors propose construct mono-copper sites within a framework platform to optimize O2 activation, enabling highly selective conversion of CH4 to HCHO. [ABSTRACT FROM AUTHOR]

The USA has committed to cutting its emissions of methane, an extremely potent greenhouse gas, by at least 30% by 2030 (‘30 × 30’). This is part of the Global Methane Pledge, signed by 155 countries, to keep global warming within 1.5 °C and thereby to forestall the disastrous effects of ‘runaway climate change’. It will be a major challenge for the USA to reach 30 × 30 and there is no consensus on how to do so. This paper provides a concrete, data‐driven roadmap to indicate how to reach 30 × 30 feasibly, focusing on two enormous sources of methane emissions: organic waste and oil and gas production. It calculates that building approximately 4700 anaerobic digesters (ADs) to process food waste and animal manure would cost about $74.2 billion in capital expenditure (capex) and cut 13.6% of total US methane emissions per year. On average, each project would take roughly 2–6 years to build. Of the various methane mitigation measures analyzed in the oil and gas sectors, the most impactful would be full compliance with the US Environmental Protection Agency's (EPA's) revised New Source Performance Standards (NSPS) for oil and gas production by 2029. This would cut 17.5% of total US methane emissions annually, at a cumulative capex of $20.7 billion from 2024 to 2029. Together, the 13.6% cut from food waste and manure ADs and the 17.5% cut from full NSPS compliance would amount to a 31.5% reduction, exceeding the 30 × 30 goal. Greater clarity from the federal government on funding eligibility and additional incentives would accelerate the buildout of ADs. [ABSTRACT FROM AUTHOR]

This paper focuses on a dual-fuel injector to characterize the ignition delay time (IDT), flame propagation, and flame spectral distribution of diesel and methane combustion. To gain an insight into the combustion characteristics of diesel pilot-ignited methane dual-fuel combustion with a high-pressure direct injection (HPDI) strategy under various conditions, the ignition and combustion processes are obtained by a high-speed color camera. The variables such as diesel injection pressure (DIP), diesel injection duration (DID), fuel relative injection interval time (RIT), ambient temperature (AT), and ambient pressure (AP) are varied according to engine-like conditions for a better understanding of the relation between the operating conditions and combustion characteristics. The results show that methane jets inhibited the IDT of diesel, while the conditions and ignition of diesel also determined the ignition of methane. Premixed flame always exists at the initial combustion, the development of the flame propagation indicates that the entrainment between diesel and methane plays a crucial role in the flame velocity and combustion intensity. According to sensitivity analysis, the IDT, Flame tip penetration (P), Flame tip velocity (V), and Flame area (FA) are most sensitive to the AT, and at least 4, 3, 2, and 7 times to the other variables each. However, the area ratio of chemiluminescence to soot incandescence (B/R) is most sensitive to AP, which is at least 14 times the other variables. • The effects of 5 variables on diesel ignition high-pressure methane combustion characteristics are studied. • A segmentation method for chemiluminescence and soot incandescence has been proposed. • The sensitivity of combustion characteristic parameters to variables is quantitatively analyzed. [ABSTRACT FROM AUTHOR]

Direct oxidation of methane into value‐added chemicals is considered as one of the holy grails in chemistry and catalysis. Considerable efforts have been devoted to developing advanced catalyst systems operated under mild conditions, and mononuclear metal species, which are currently in the spotlight of methane oxidation, have shown great advantages and addressed significant attention. In this concept, we highlight the recent breakthroughs and developments in monomeric metal species for low‐temperature (<100 °C) methane oxidation. Emphasis is put on the identification and validation of monomeric metal species as the intrinsic active sites. Promising characterization approaches for identifying catalytically relevant features of physicochemical properties of monomeric metal species are discussed, as well as the emerging insights on the development of in situ characterization technologies. Finally, the open challenges and outlooks for rational development of monomeric metal catalysts for methane valorization are examined for guiding further developments and inspiring the future work. [ABSTRACT FROM AUTHOR]

Inland waters are important sources of the greenhouse gases carbon dioxide (CO2) and methane (CH4). Ponds have amongst the highest CO2 and CH4 fluxes of all aquatic ecosystems, yet seasonal variation in fluxes remain poorly characterized, creating challenges for accurately estimating annual emissions. Further, ponds can exhibit a range of mixing regimes, yet the impact of mixing regimes on gas emissions remains unclear. Here, we assessed annual dynamics of CO2 and CH4 in four temperate ponds (Minnesota, USA) that varied in mixing regimes. The ponds ranged from annual sinks to sources of CO2 (−1 to 15 mol m−2 yr−1) and were all significant sources of CH4 (4.3–8.2 mol m−2 yr−1), with annual fluxes in CO2 equivalents of 1.8–4.1 kg CO2-eq. m−2 yr−1. Mixing regimes impacted CO2 and CH4 dynamics, as stratified periods were associated with more anoxia, greater accumulation of gases in the bottom waters, higher emissions of CH4, and lower fluxes of CO2. Ponds with stronger summer stratification also had increased CO2 and CH4 fluxes associated with fall turnover. Overall, the two ponds with the strongest stratification had higher annual fluxes (2.6, 4.1 kg CO2-eq. m−2 yr−1) compared to the two ponds that more frequently mixed (1.8, 2.2 kg CO2-eq. m−2 yr−1). [ABSTRACT FROM AUTHOR]

In the methane oxidation reaction using H 2 O 2 as an oxidant, the oxygen vacancies in the ceria, which could be formed in the reaction between it and H 2 O 2 , could decompose H 2 O 2 into reactive oxygen species instead of the useless H 2 O and O 2. By adjusting the contents of oxygen vacancies, the ceria's function could be shifted from inhibiting to promoting. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] Improving ligand-to-active metal charge transfer (LAMCT) by finely tuning the organic ligand is a decisive strategy to enhance charge transfer in metal organic frameworks (MOFs)-based catalysts. However, in most MOFs loaded with active metal catalysts, electron transmission encounters massive obstacle at the interface between the two constituents owing to poor LAMCT. Herein, amines (–NH 2) functionalized MOFs (NH 2 -MIL-101(Cr)) encapsulated active metal Pt nanoclusters (NCs) catalysts are synthesized by the polyol reduction method and utilized for the photoreduction of CO 2. Surprisingly, the introduction of –NH 2 (electron donating) groups within the matrix of MIL-101(Cr) improved the electron migration through the LAMCT process, fostering a synergistic interaction with Pt. The combined experimental analysis exposed the high number of metallic Pt (Pt0) in Pt@NH 2 -MIL-101(Cr) catalyst through seamless electron shuttling from N of –NH 2 group to excited Pt generating versatile hybrid Pt-N catalytic centres. Consequently, these versatile hybrid catalytic centres act as electro-nucleophilic centres, which enable the efficient and selective conversion of C O bond in CO 2 to harvest CH 4 (131.0 µmol.g−1) and maintain excellent stability and selectivity for consecutive five rounds, superior to Pt@MIL-101(Cr) and most reported catalysts. Our study verified that the precise tuning of organic ligands in MOFs immensely improves the surface-active centres, electron migration, and catalytic selectivity of the excited Pt NCs catalysts encaged inside MOFs through an improved LAMCT pathway. [ABSTRACT FROM AUTHOR]

The oxalate-carbonate pathway (OCP) involves degradation of soil oxalate to carbonate. To exploit and manage this natural mineralization of assimilated atmospheric CO2 into stable carbonates, improved understanding of this complex biotransformation process is needed. A strain of oxalate-degrading bacteria, Azospirillum sp. OX-1, was isolated from soil, and its secondary products of calcium oxalate degradation were analyzed and characterized using SEM, XRD, TG/DTG-DTA and FTIR-spectroscopy. The molecular mechanism of calcium oxalate degradation was also analyzed using proteomics. The results showed, for the first time, that OX-1 could not only degrade calcium oxalate to calcium carbonate, but also that the process was accompanied by synthesis of methane. Proteomic analysis demonstrated that OX-1 has a dual enzyme system for calcium oxalate degradation, using formyl-CoA transferase (FRC) and thiamine pyrophosphate (ThDP)-dependent oxalyl-CoA decarboxylase (OXC) to form calcium carbonate. Up-regulated expression of enzymes related to methane synthesis was also detected during calcium oxalate degradation. Since methane is also a potent greenhouse gas, these new results suggest that the utility of exploiting the OCP to reduce atmospheric CO2 must be re-evaluated and that further studies should be conducted to reveal how widespread the methane producing capacity of strain OX-1 is in other bacteria and soil environments. [ABSTRACT FROM AUTHOR]

To accurately assess the current atmospheric methane budget and its future trends, it is essential to apportion and quantify the anthropogenic methane emissions to specific sources. This poses a significant challenge in the under‐sampled Middle East, where estimates predominantly depend on remote sensing observations and bottom‐up reporting of national emissions. Here, we present in situ shipborne observations of greenhouse gases (GHGs) and non‐methane hydrocarbons (NMHCs) collected along a >10,000‐km route from Vigo, Spain, to Abu Dhabi, UAE. By comparing our observations with Lagrangian dispersion model simulations, coupled with two methane emission inventories, we identify periods of considerable mismatch and apportion the responsible sources. Employing interspecies relationships with NMHCs has enabled the characterization of methane emissions from oil and gas (O&G) operations, urban centers, Red Sea deep water, enteric fermentation, and agriculture across diverse atmospheric environments. Our analysis reveals that the Suez area is a regional emission hotspot, where simulations consistently underestimate the methane emission sources. Importantly, the Middle Eastern O&G sector has been identified as an additional source of considerable uncertainty. Here, methane emissions were alternately underestimated and overestimated by the two inventories, exposing significant gaps in our understanding of fuel exploitation‐related emissions in the Middle East. This underscores the need for further targeted field campaigns and long‐term observations to improve the accuracy of emission data in the inventories. Plain Language Summary: For the mitigation of human‐induced methane emissions, a detailed characterization of its numerous sources is vital. This is particularly challenging in understudied regions where the source attribution and emission strength thus far relies on satellite observations and country reports. Although such data, representing the entire atmospheric column, are invaluable, source specific emission estimates remain highly uncertain. In this study, we used shipborne measurements of methane to evaluate the performance of two emission inventories commonly used in computer‐based models to simulate methane atmospheric concentrations. The relationships between methane and various co‐emitted reactive trace gases revealed the causes of discrepancies between observations and model simulations. Our results show that, while models are generally reliable at capturing high methane concentrations, they are deficient in the Suez and Middle East areas due to inadequate characterization of emissions from Oil and Gas operations. The research outcomes of this study underscore the crucial role of ground‐based observations in improving the accuracy of methane emission inventories and their reporting, and in supporting evidence‐based policies to mitigate climate change and improve air quality. Key Points: The Suez Canal and the Gulf of Suez are regional pollution hotspots with underestimated methane emission sourcesDiscrepancies between observed and modeled methane mixing ratios were resolved using non‐methane hydrocarbon observationsMethane sources from the oil and gas exploitation sector in the Middle East are particularly uncertain in emission inventories [ABSTRACT FROM AUTHOR]

Utilizing imaging spectroscopy technology to identify methane super‐emitters plays a vital role in mitigating methane emissions in the Oil & Gas (O&G) sector. While earlier research has uncovered significant point‐source methane emissions from O&G production in the US and Canada, which are key regions with large methane emissions, a comprehensive post‐COVID‐19 survey has been notably absent. Here, we perform a detailed survey of methane super‐emitters across multiple basins of North America (Marcellus Shale, Haynesville/Bossier Shale, Permian Basin and Montney Shale) using the new Chinese Gaofen5‐01A/02 (GF5‐01A/02) satellite measurements during 2022–2023. We detect 139 individual methane plumes emanating from 122 point sources, with flux rates ranging from 519 to 16,071 kg hr−1. These emissions exhibit a highly skewed and heavy‐tailed distribution, constituting approximately 23% of the flux inversion with TROPOMI in the sample region, with a range of 13%–40%. Moreover, we observe a 66.7% reduction in methane emissions in Permian Basin during COVID‐19, followed by fluctuations until spring 2023. By summer 2023, methane emissions rebound to twice their previous magnitude (1.68 ± 0.58 Tg a−1). Using these point‐source surveys, we further quantify a regional methane emission of 2.69 ± 0.86 Tg a−1 in Permian Basin. This estimation closely aligns with top‐down inversions (2.22 ± 0.40 Tg a−1) from TROPOMI. The upscale estimation underscores the effectiveness of high‐resolution remote sensing measurements in improving bottom‐up emissions inventories and refining regional methane emission assessments. Our results highlight the potential climate benefits derived from regular monitoring and specific remediation efforts focused on relatively few strong point‐source emissions. Plain Language Summary: Reducing methane (CH4) leaks from Oil & Gas (O&G) production is crucial for abating climate change. However, detecting these abnormal CH4 emissions globally is challenging as they often occur unexpectedly. Satellite remote sensing with hyperspectral imaging spectrometer provides an effective approach for top‐down monitoring. These instruments produce CH4 plume maps, enabling the quantification of emissions. In this research, we conduct a comprehensive survey in major O&G basins of North America during 2022–2023 using the new Chinese Gaofen5‐01A/02 satellite. Through repeated observations by high‐resolution satellites, we capture CH4 emission dynamics in sample basins and quantify their contribution to regional methane budget. Our results demonstrate the value of high‐resolution satellite observations in reducing uncertainties in quantifying anthropogenic CH4 emission and supporting strategies for emission mitigation. Key Points: The new Chinese Gaofen5‐01A/02 hyperspectral satellite missions have great capability in methane mappingWe find substantial methane point‐source emissions in Permian Basin after COVID‐19 during 2022–2023Satellite‐based survey can effectively improve bottom‐up regional methane emissions inventories [ABSTRACT FROM AUTHOR]

The present work proposes the application of CH 4 and H 2 synergy to improve the performance of the Wankel rotary engine (WRE). The whole work was experimentally conducted at 1500 r/min. The results indicate that CH 4 WRE can achieve similar power and significantly higher thermal efficiency than gasoline WRE based on quantitative control, with a maximum absolute efficiency improvement of 11.4%. At the same time, it also can achieve 64% and 77% maximum reduction of CO and NO emissions, respectively. CH 4 –H 2 synergy can further improve the performance of CH 4 -fueled WRE, which can broaden the lean flammability limits and make qualitative control application possible. Compared with CH 4 WRE with quantitative control, qualitative control hybrid fuel WRE can achieve a maximum relative improvement of 6.54% in brake thermal efficiency and significantly reduced NO and CO emissions. However, the extent of qualitative control is limited by cyclic variation. Overall, CH 4 –H 2 synergy can be a potential alternative to elevate the performance of WRE, the key to which is the reasonable match of synergy level and qualitative control extent. • Comparison of performances between CH4 and gasoline Wankel rotary engines. • CH4 has significant advantages in efficiency, CO and NO emission than gasoline. • CH4–H2 synergy can further improve the performance of the CH4 Wankel rotary engine. • Blending H2 coupling qualitative control is a good load control model in CH4 WRE. [ABSTRACT FROM AUTHOR]

Nonsymmetrical oxygen-bridged binuclear copper centers have been proposed and modeled as intermediates and transition states in several C-H oxidation pathways, leading to the postulation that structural dissymmetry enhances the reactivity of the bridging oxygen. However, experimentally characterizing the structure and reactivity of these transient species is remarkably challenging. Here, we report the high-pressure synthesis of a metastable nonsymmetrical dicopper-µ-oxo compound with exceptional reactivity toward the mono-oxygenation of aliphatic C-H bonds. The nonequivalent coordination environment of copper stabilizes localized mixed valency and greatly enhances the hydrogen atom abstraction activity of the bridging oxygen, enabling room-temperature hydroxylation of methane under pressure. These findings highlight the role of dissymmetry in the reactivity of binuclear copper centers and demonstrate precise control of molecular structures by mechanical means. [ABSTRACT FROM AUTHOR]

Terrestrial mud volcanoes represent surface features of channels for subsurface methane transport and, therefore, constitute an important source of methane emission from natural environments. How microbial processes regulate methane emissions in terrestrial mud volcanoes has yet to be fully addressed. This study demonstrated the geochemical characteristics and microbial communities of four mud volcano and seep sites in two geological settings of Sicily, Italy. At sites within the accretionary wedge that exhibited higher methane and sulfate concentrations, the communities were dominated by members capable of catalyzing methane and sulfate metabolisms and organic degradation. In particular, both anaerobic and aerobic methanotrophs were abundant and their abundance distribution coincided with the geochemical transition. In contrast, the sites near Mount Etna were characterized by high fluid salinity, CO2, and low methane and sulfate concentrations, with communities consisting of halophilic organic degraders and sulfur metabolizers, along with a minor presence of aerobic methanotrophs. Substantial variations in community composition and geochemistry across spatial and vertical redox gradients suggest that physicochemical contexts imposed by the geology, fluid path, and source characteristics play a vital role in shaping community composition and cycling of methane, sulfur and organic carbon in Sicily mud volcanoes. [ABSTRACT FROM AUTHOR]

Extensive data on the characteristics and performance of the catalysts synthesized and tested for methane oxidative coupling (OCM) is available in thousands of reports published during the last four decades. Revisiting and analyzing the general trends recognizable in those data could improve the current understanding of the catalyst functionality under different reaction conditions. This is instrumental in determining the direction of future research aiming for more efficient OCM catalysts and reactors. These are the subjects of the comprehensive analysis reported in this paper, which covers the main aspects associated with the analysis of the OCM catalytic performance, including the catalyst characteristics, reaction mechanism, and reactor operation. Special attention was devoted to analyzing these aspects in the framework of thermal-reaction engineering and, accordingly, critically reviewing the reported catalytic performances in the literature. [ABSTRACT FROM AUTHOR]