Soluble Methane Monooxygenase.

Aerobic life is possible because the molecular structure of oxygen (O2) makes direct reaction with most organic materials at ambient temperatures an exceptionally slow process. Of course, these reactions are inherently very favorable, and they occur rapidly with the release of a great deal of energy at high temperature. Nature has been able to tap this sequestered reservoir of energy with great spatial and temporal selectivity at ambient temperatures through the evolution of oxidase and oxygenase enzymes. One mechanism used by these enzymes for O2 activation has been studied in detail for the soluble form of the enzyme methane monooxygenase. These studies have revealed the step-by-step process of O2 activation and insertion into the ultimately stable C-H bond of methane. Additionally, an elegant regulatory mechanism has been defined that enlists size selection and quantum tunneling to allow methane oxidation to occur specifically in the presence of more easily oxidized substrates.

Rapid shift in methane carbon isotopes suggests microbial emissions drove record high atmospheric methane growth in 2020-2022.

The growth rate of the atmospheric abundance of methane (CH4) reached a record high of 15.4 ppb yr-1 between 2020 and 2022, but the mechanisms driving the accelerated CH4 growth have so far been unclear. In this work, we use measurements of the 13C:12C ratio of CH4 (expressed as δ13CCH4) from NOAA's Global Greenhouse Gas Reference Network and a box model to investigate potential drivers for the rapid CH4 growth. These measurements show that the record-high CH4 growth in 2020-2022 was accompanied by a sharp decline in δ13CCH4, indicating that the increase in CH4 abundance was mainly driven by increased emissions from microbial sources such as wetlands, waste, and agriculture. We use our box model to reject increasing fossil fuel emissions or decreasing hydroxyl radical sink as the dominant driver for increasing global methane abundance.

Inverse modeling of 2010-2022 satellite observations shows that inundation of the wet tropics drove the 2020-2022 methane surge.

Atmospheric methane concentrations rose rapidly over the past decade and surged in 2020-2022 but the causes have been unclear. We find from inverse analysis of GOSAT satellite observations that emissions from the wet tropics drove the 2010-2019 increase and the subsequent 2020-2022 surge, while emissions from northern mid-latitudes decreased. The 2020-2022 surge is principally contributed by emissions in Equatorial Asia (43%) and Africa (30%). Wetlands are the major drivers of the 2020-2022 emission increases in Africa and Equatorial Asia because of tropical inundation associated with La Niña conditions, consistent with trends in the GRACE terrestrial water storage data. In contrast, emissions from major anthropogenic emitters such as the United States, Russia, and China are relatively flat over 2010-2022. Concentrations of tropospheric OH (the main methane sink) show no long-term trend over 2010-2022 but a decrease over 2020-2022 that contributed to the methane surge.

Increased methane emissions from oil and gas following the Soviet Union's collapse.

Global atmospheric methane concentrations rose by 10 to 15 ppb/y in the 1980s before abruptly slowing to 2 to 8 ppb/y in the early 1990s. This period in the 1990s is known as the "methane slowdown" and has been attributed in part to the collapse of the former Soviet Union (USSR) in December 1991, which may have decreased the methane emissions from oil and gas operations. Here, we develop a methane plume detection system based on probabilistic deep learning and human-labeled training data. We use this method to detect methane plumes from Landsat 5 satellite observations over Turkmenistan from 1986 to 2011. We focus on Turkmenistan because economic data suggest it could account for half of the decline in oil and gas emissions from the former USSR. We find an increase in both the frequency of methane plume detections and the magnitude of methane emissions following the collapse of the USSR. We estimate a national loss rate from oil and gas infrastructure in Turkmenistan of more than 10% at times, which suggests the socioeconomic turmoil led to a lack of oversight and widespread infrastructure failure in the oil and gas sector. Our finding of increased oil and gas methane emissions from Turkmenistan following the USSR's collapse casts doubt on the long-standing hypothesis regarding the methane slowdown, begging the question: "what drove the 1992 methane slowdown?"

Methane fueled lake pelagic food webs in a Cretaceous greenhouse world.

Methane (CH4) is a potent greenhouse gas but also an important carbon and energy substrate for some lake food webs. Understanding how CH4 incorporates into food webs is, therefore, crucial for unraveling CH4 cycling and its impacts on climate and ecosystems. However, CH4-fueled lake food webs from pre-Holocene intervals, particularly during greenhouse climates in Earth history, have received relatively little attention. Here, we present a long-term record of CH4-fueled pelagic food webs across the Cretaceous Oceanic Anoxic Event 1a (~120 Mya) that serves as a geological analog to future warming. We show an exceptionally strong expansion of both methanogens and CH4-oxidizing bacteria (up to 87% of hopanoid-producing bacteria) during this Event. Grazing on CH4-oxidizing bacteria by zooplankton (up to 47% of ciliate diets) within the chemocline transferred substantial CH4-derived carbon to the higher trophic levels, representing an important CH4 sink in the water column. Our findings suggest that as Earth warms, microbial CH4 cycling could restructure food webs and fundamentally alter carbon and energy flows and trophic pathways in lake ecosystems.

Cold seep formation from salt diapir-controlled deep biosphere oases.

Deep sea cold seeps are sites where hydrogen sulfide, methane, and other hydrocarbon-rich fluids vent from the ocean floor. They are an important component of Earth's carbon cycle in which subsurface hydrocarbons form the energy source for highly diverse benthic micro- and macro-fauna in what is otherwise vast and spartan sea scape. Passive continental margin cold seeps are typically attributed to the migration of hydrocarbons generated from deeply buried source rocks. Many of these seeps occur over salt tectonic provinces, where the movement of salt generates complex fault systems that can enable fluid migration or create seals and traps associated with reservoir formation. The elevated advective heat transport of the salt also produces a chimney effect directly over these structures. Here, we provide geophysical and geochemical evidence that the salt chimney effect in conjunction with diapiric faulting drives a subsurface groundwater circulation system that brings dissolved inorganic carbon, nutrient-rich deep basinal fluids, and potentially overlying seawater onto the crests of deeply buried salt diapirs. The mobilized fluids fuel methanogenic archaea locally enhancing the deep biosphere. The resulting elevated biogenic methane production, alongside the upward heat-driven fluid transport, represents a previously unrecognized mechanism of cold seep formation and regulation.

A hybrid photocatalytic system enables direct glucose utilization for methanogenesis.

Integration of methanogenic archaea with photocatalysts presents a sustainable solution for solar-driven methanogenesis. However, maximizing CH4 conversion efficiency remains challenging due to the intrinsic energy conservation and strictly restricted substrates of methanogenic archaea. Here, we report a solar-driven biotic-abiotic hybrid (biohybrid) system by incorporating cadmium sulfide (CdS) nanoparticles with a rationally designed methanogenic archaeon Methanosarcina acetivorans C2A, in which the glucose synergist protein and glucose kinase, an energy-efficient route for glucose transport and phosphorylation from Zymomonas mobilis, were implemented to facilitate nonnative substrate glucose for methanogenesis. We demonstrate that the photo-excited electrons facilitate membrane-bound electron transport chain, thereby augmenting the Na+ and H+ ion gradients across membrane to enhance adenosine triphosphate (ATP) synthesis. Additionally, this biohybrid system promotes the metabolism of pyruvate to acetyl coenzyme A (AcCoA) and inhibits the flow of AcCoA to the tricarboxylic acid (TCA) cycle, resulting in a 1.26-fold augmentation in CH4 production from glucose-derived carbon. Our results provide a unique strategy for enhancing methanogenesis through rational biohybrid design and reprogramming, which gives a promising avenue for sustainably manufacturing value-added chemicals.

Tracing sources of atmospheric methane using clumped isotopes.

We apply a recently developed measurement technique for methane (CH4) isotopologues* (isotopic variants of CH4-13CH4, 12CH3D, 13CH3D, and 12CH2D2) to identify contributions to the atmospheric burden from fossil fuel and microbial sources. The aim of this study is to constrain factors that ultimately control the concentration of this potent greenhouse gas on global, regional, and local levels. While predictions of atmospheric methane isotopologues have been modeled, we present direct measurements that point to a different atmospheric methane composition and to a microbial flux with less clumping (greater deficits relative to stochastic) in both 13CH3D and 12CH2D2 than had been previously assigned. These differences make atmospheric isotopologue data sufficiently sensitive to variations in microbial to fossil fuel fluxes to distinguish between emissions scenarios such as those generated by different versions of EDGAR (the Emissions Database for Global Atmospheric Research), even when existing constraints on the atmospheric CH4 concentration profile as well as traditional isotopes are kept constant.

Excess methane emissions from shallow water platforms elevate the carbon intensity of US Gulf of Mexico oil and gas production.

The Gulf of Mexico is the largest offshore fossil fuel production basin in the United States. Decisions on expanding production in the region legally depend on assessments of the climate impact of new growth. Here, we collect airborne observations and combine them with previous surveys and inventories to estimate the climate impact of current field operations. We evaluate all major on-site greenhouse gas emissions, carbon dioxide (CO2) from combustion, and methane from losses and venting. Using these findings, we estimate the climate impact per unit of energy of produced oil and gas (the carbon intensity). We find high methane emissions (0.60 Tg/y [0.41 to 0.81, 95% confidence interval]) exceeding inventories. This elevates the average CI of the basin to 5.3 g CO2e/MJ [4.1 to 6.7] (100-y horizon) over twice the inventories. The CI across the Gulf varies, with deep water production exhibiting a low CI dominated by combustion emissions (1.1 g CO2e/MJ), while shallow federal and state waters exhibit an extraordinarily high CI (16 and 43 g CO2e/MJ) primarily driven by methane emissions from central hub facilities (intermediaries for gathering and processing). This shows that production in shallow waters, as currently operated, has outsized climate impact. To mitigate these climate impacts, methane emissions in shallow waters must be addressed through efficient flaring instead of venting and repair, refurbishment, or abandonment of poorly maintained infrastructure. We demonstrate an approach to evaluate the CI of fossil fuel production using observations, considering all direct production emissions while allocating to all fossil products.

McrD binds asymmetrically to methyl-coenzyme M reductase improving active-site accessibility during assembly.

Methyl-coenzyme M reductase (MCR) catalyzes the formation of methane, and its activity accounts for nearly all biologically produced methane released into the atmosphere. The assembly of MCR is an intricate process involving the installation of a complex set of posttranslational modifications and the unique Ni-containing tetrapyrrole called coenzyme F430. Despite decades of research, details of MCR assembly remain largely unresolved. Here, we report the structural characterization of MCR in two intermediate states of assembly. These intermediate states lack one or both F430 cofactors and form complexes with the previously uncharacterized McrD protein. McrD is found to bind asymmetrically to MCR, displacing large regions of the alpha subunit and increasing active-site accessibility for the installation of F430-shedding light on the assembly of MCR and the role of McrD therein. This work offers crucial information for the expression of MCR in a heterologous host and provides targets for the design of MCR inhibitors.

Geostationary satellite observations of extreme and transient methane emissions from oil and gas infrastructure.

We demonstrate geostationary satellite monitoring of large transient methane point sources with the US Geostationary Operational Environmental Satellites (GOES). GOES provides continuous 5- to 10-min coverage of the Americas at 1 to 2 km nadir pixel resolution in two shortwave infrared spectral bands from which large methane plumes can be retrieved. We track the full evolution of an extreme methane release from the El Encino-La Laguna natural gas pipeline in Durango, Mexico on 12 May 2019. The release lasted 3 h at a variable rate of 260 to 550 metric tons of methane per hour and totaled 1,130 to 1,380 metric tons. We report several other detections of transient point sources from oil/gas infrastructure, from which we infer a detection limit of 10 to 100 t h-1. Our results show that extreme releases of methane can last less than an hour, as from deliberate venting, and would thus be difficult to identify and quantify with low-Earth orbit satellites.

Respiration-driven methanotrophic growth of diverse marine methanogens.

Anaerobic marine environments are the third largest producer of the greenhouse gas methane. The release to the atmosphere is prevented by anaerobic 'methanotrophic archaea (ANME) dependent on a symbiotic association with sulfate-reducing bacteria or direct reduction of metal oxides. Metagenomic analyses of ANME are consistent with a reverse methanogenesis pathway, although no wild-type isolates have been available for validation and biochemical investigation. Herein is reported the characterization of methanotrophic growth for the diverse marine methanogens Methanosarcina acetivorans C2A and Methanococcoides orientis sp. nov. Growth was dependent on reduction of either ferrihydrite or humic acids revealing a respiratory mode of energy conservation. Acetate and/or formate were end products. Reversal of the well-characterized methanogenic pathways is remarkably like the consensus pathways for uncultured ANME based on extensive metagenomic analyses.

Observation-derived 2010-2019 trends in methane emissions and intensities from US oil and gas fields tied to activity metrics.

The United States is the world's largest oil/gas methane emitter according to current national reports. Reducing these emissions is a top priority in the US government's climate action plan. Here, we use a 2010 to 2019 high-resolution inversion of surface and satellite observations of atmospheric methane to quantify emission trends for individual oil/gas production regions in North America and relate them to production and infrastructure. We estimate a mean US oil/gas methane emission of 14.8 (12.4 to 16.5) Tg a-1 for 2010 to 2019, 70% higher than reported by the US Environmental Protection Agency. While emissions in Canada and Mexico decreased over the period, US emissions increased from 2010 to 2014, decreased until 2017, and rose again afterward. Increases were driven by the largest production regions (Permian, Anadarko, Marcellus), while emissions in the smaller production regions generally decreased. Much of the year-to-year emission variability can be explained by oil/gas production rates, active well counts, and new wells drilled, with the 2014 to 2017 decrease driven by reduction in new wells and the 2017 to 2019 surge driven by upswing of production. We find a steady decrease in the oil/gas methane intensity (emission per unit methane gas production) for almost all major US production regions. The mean US methane intensity decreased from 3.7% in 2010 to 2.5% in 2019. If the methane intensity for the oil/gas supply chain continues to decrease at this pace, we may expect a 32% decrease in US oil/gas emissions by 2030 despite projected increases in production.

Microbially induced precipitation of silica by anaerobic methane-oxidizing consortia and implications for microbial fossil preservation.

Authigenic carbonate minerals can preserve biosignatures of microbial anaerobic oxidation of methane (AOM) in the rock record. It is not currently known whether the microorganisms that mediate sulfate-coupled AOM-often occurring as multicelled consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB)-are preserved as microfossils. Electron microscopy of ANME-SRB consortia in methane seep sediments has shown that these microorganisms can be associated with silicate minerals such as clays [Chen et al., Sci. Rep. 4, 1-9 (2014)], but the biogenicity of these phases, their geochemical composition, and their potential preservation in the rock record is poorly constrained. Long-term laboratory AOM enrichment cultures in sediment-free artificial seawater [Yu et al., Appl. Environ. Microbiol. 88, e02109-21 (2022)] resulted in precipitation of amorphous silicate particles (~200 nm) within clusters of exopolymer-rich AOM consortia from media undersaturated with respect to silica, suggestive of a microbially mediated process. The use of techniques like correlative fluorescence in situ hybridization (FISH), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), and nanoscale secondary ion mass spectrometry (nanoSIMS) on AOM consortia from methane seep authigenic carbonates and sediments further revealed that they are enveloped in a silica-rich phase similar to the mineral phase on ANME-SRB consortia in enrichment cultures. Like in cyanobacteria [Moore et al., Geology 48, 862-866 (2020)], the Si-rich phases on ANME-SRB consortia identified here may enhance their preservation as microfossils. The morphology of these silica-rich precipitates, consistent with amorphous-type clay-like spheroids formed within organic assemblages, provides an additional mineralogical signature that may assist in the search for structural remnants of microbial consortia in rocks which formed in methane-rich environments from Earth and other planetary bodies.

Radiation and temperature drive diurnal variation of aerobic methane emissions from Scots pine canopy.

Methane emissions from plant foliage may play an important role in the global methane cycle, but their size and the underlying source processes remain poorly understood. Here, we quantify methane fluxes from the shoots of Scots pine trees, a dominant tree species in boreal forests, to identify source processes and environmental drivers, and we evaluate whether these fluxes can be constrained at the ecosystem-level by eddy covariance flux measurements. We show that shoot-level measurements conducted in forest, garden, or greenhouse settings; on mature trees and saplings; manually and with an automated CO2-, temperature-, and water-controlled chamber system; and with multiple methane analyzers all resulted in comparable daytime fluxes (0.144 ± 0.019 to 0.375 ± 0.074 nmol CH4 g-1 foliar d.w. h-1). We further find that these emissions exhibit a pronounced diurnal cycle that closely follows photosynthetically active radiation and is further modulated by temperature. These diurnal patterns indicate that methane production is associated with diurnal cycle of sunlight, indicating that this production is either a byproduct of photosynthesis-associated biochemical reactions (e.g., the methionine cycle) or produced through nonenzymatic photochemical reactions in plant biomass. Moreover, we identified a light-dependent component in stand-level methane fluxes, which showed order-of-magnitude agreement with shoot-level measurements (0.968 ± 0.031 nmol CH4 g-1 h-1) and which provides an upper limit for shoot methane emissions.

Efficient catalysts of surface hydrophobic Cu-BTC with coordinatively unsaturated Cu(I) sites for the direct oxidation of methane.

Selective oxidation of methane to organic oxygenates over metal-organic frameworks (MOFs) catalysts at low temperature is a challenging topic in the field of C1 chemistry because of the inferior stability of MOFs. Modifying the surface of Cu-BTC via hydrophobic polydimethylsiloxane (PDMS) at 235 °C under vacuum not only can dramatically improve its catalytic cycle stability in a liquid phase but also generate coordinatively unsaturated Cu(I) sites, which significantly enhances the catalytic activity of Cu-BTC catalyst. The results of spectroscopy characterizations and theoretical calculation proved that the coordinatively unsaturated Cu(I) sites made H2O2 dissociative into •OH, which formed Cu(II)-O active species by combining with coordinatively unsaturated Cu(I) sites for activating the C-H bond of methane. The high productivity of C1 oxygenates (CH3OH and CH3OOH) of 10.67 mmol gcat.-1h-1 with super high selectivity of 99.6% to C1 oxygenates was achieved over Cu-BTC-P-235 catalyst, and the catalyst possessed excellent reusability.

Photocatalytic chlorine atom production on mineral dust-sea spray aerosols over the North Atlantic.

Active chlorine in the atmosphere is poorly constrained and so is its role in the oxidation of the potent greenhouse gas methane, causing uncertainty in global methane budgets. We propose a photocatalytic mechanism for chlorine atom production that occurs when Sahara dust mixes with sea spray aerosol. The mechanism is validated by implementation in a global atmospheric model and thereby explaining the episodic, seasonal, and location-dependent 13C depletion in CO in air samples from Barbados [J.E. Mak, G. Kra, T. Sandomenico, P. Bergamaschi, J. Geophys. Res. Atmos. 108 (2003)], which remained unexplained for decades. The production of Cl can also explain the anomaly in the CO:ethane ratio found at Cape Verde [K. A. Read et al., J. Geophys. Res. Atmos. 114 (2009)], in addition to explaining the observation of elevated HOCl [M. J. Lawler et al., Atmos. Chem. Phys. 11, 7617-7628 (2011)]. Our model finds that 3.8 Tg(Cl) y-1 is produced over the North Atlantic, making it the dominant source of chlorine in the region; globally, chlorine production increases by 41%. The shift in the methane sink budget due to the increased role of Cl means that isotope-constrained top-down models fail to allocate 12 Tg y-1 (2% of total methane emissions) to 13C-depleted biological sources such as agriculture and wetlands. Since 2014, an increase in North African dust emissions has increased the 13C isotope of atmospheric CH4, thereby partially masking a much greater decline in this isotope, which has implications for the interpretation of the drivers behind the recent increase of methane in the atmosphere.

Observed changes in China's methane emissions linked to policy drivers.

China is set to actively reduce its methane emissions in the coming decade. A comprehensive evaluation of the current situation can provide a reference point for tracking the country's future progress. Here, using satellite and surface observations, we quantify China's methane emissions during 2010-2017. Including newly available data from a surface network across China greatly improves our ability to constrain emissions at subnational and sectoral levels. Our results show that recent changes in China's methane emissions are linked to energy, agricultural, and environmental policies. We find contrasting methane emission trends in different regions attributed to coal mining, reflecting region-dependent responses to China's energy policy of closing small coal mines (decreases in Southwest) and consolidating large coal mines (increases in North). Coordinated production of coalbed methane and coal in southern Shanxi effectively decreases methane emissions, despite increased coal production there. We also detect unexpected increases from rice cultivation over East and Central China, which is contributed by enhanced rates of crop-residue application, a factor not accounted for in current inventories. Our work identifies policy drivers of recent changes in China's methane emissions, providing input to formulating methane policy toward its climate goal.

The case and context for atmospheric methane as an exoplanet biosignature.

Methane has been proposed as an exoplanet biosignature. Imminent observations with the James Webb Space Telescope may enable methane detections on potentially habitable exoplanets, so it is essential to assess in what planetary contexts methane is a compelling biosignature. Methane's short photochemical lifetime in terrestrial planet atmospheres implies that abundant methane requires large replenishment fluxes. While methane can be produced by a variety of abiotic mechanisms such as outgassing, serpentinizing reactions, and impacts, we argue that­in contrast to an Earth-like biosphere­known abiotic processes cannot easily generate atmospheres rich in CH4 and CO2 with limited CO due to the strong redox disequilibrium between CH4 and CO2. Methane is thus more likely to be biogenic for planets with 1) a terrestrial bulk density, high mean-molecular-weight and anoxic atmosphere, and an old host star; 2) an abundance of CH4 that implies surface fluxes exceeding what could be supplied by abiotic processes; and 3) atmospheric CO2 with comparatively little CO.

Very large fluxes of methane measured above Bolivian seasonal wetlands.

Methane (CH4) mole fractions from the large semiseasonal Llanos de Moxos wetlands (∼70,000 km2) in northern Bolivia were measured by aircraft flights and ground sampling during early March 2019 (late wet season). Daily fluxes of CH4 determined from the measurements using box models and inverse modeling were between 168 (± 50) and 456 (± 145) mg CH4⋅m-2⋅d-1 for the areas overflown, very high compared with those of previous Amazon basin studies. If the seasonality of the CH4 emissions is comparable to other parts of the Amazon Basin, the region could contribute as much as 8% of annual Amazonian CH4 emissions.