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At least 703 records · Page 39

Kinetic and Mechanistic Understanding of Boron-Containing Catalysts for the Production of Light Olefins through Selective Oxidation

In recent years, an abundance of natural gas obtained from shale deposits has created opportunities for the US chemical industry to establish new and more efficient processes for the production of chemical intermediates and polymers. For example, the replacement of petroleum-derived naphtha as a to shale-derived ethane as feedstocks has made the production of ethylene/polyethylene less costly. However, this shift in feedstock has led to lower production of propylene from steam crackers, and new “on-purpose” light olefin production technologies have been implemented to bridge the gap between propylene supply and demand. The most important of these processes is direct propane dehydrogenation (PDH), but catalyst deactivation and high temperatures lead to high capital and operating costs. Oxidative dehydrogenation of propane (ODHP) is an efficient alternative to PDH, but high selectivity to CO2 from previous metal oxide catalyst prevents implementation. Hexagonal boron nitride (hBN) and other boron-containing materials have been recently developed as highly selective catalysts for both ODHP and oxidative cracking, surpassing previous systems. Much is still unknown in regard to the mechanism and the dynamic surface changes that occur under reaction conditions. This research project aims to combine in situ/operando spectroscopic investigation and kinetic studies to elucidate the interplay between the proposed gas-phase mechanism and the surface structures on the working catalyst. These insights will be leveraged to create a framework for optimizing reaction conditions and material synthesis for the next generation of boron-containing selective oxidation catalysts.

02 PETROLEUM↗

Fire and Thermal Experiments in Support of the Model Evaluation Protocol for LNG Facility Fires

The motivation for the experiments reported here pertains to the siting of Liquefied Natural Gas (LNG) facilities which requires assessing the potential adverse radiant thermal impacts of accidental fires on the public. The objective is to obtain data on jet fires, pool fires, fireballs, and concrete walls that could serve as thermal barriers for model validation. The fuels tested include ethane, ethylene, propane, and isopentane.

42 ENGINEERING↗

Fast-ion confinement in LHD and W7-X (Final Technical Report)

This project was the PhD thesis project for Wataru Hayashi, who graduated in December 2025. In work performed prior to the award while Heidbrink was a Guest Professor at NIFS, we had established conditions for the study of fast-ion confinement in the Large Helical Device (LHD) with fast-ion D-alpha (FIDA) diagnostics. Subsequently, we proposed new sightlines that could augment the existing FIDA measurements with ones that were more sensitive to the highest energy ions. During the project period, the new sightlines were installed by the LHD team and showed the expected enhanced sensitivity to high-energy ions. Many LHD experiments were led by UCI scientists remotely during the pandemic and in-person afterward. One of these, which was led by one of Professor Zhihong Lin’s PhD students (Ethan Green) in collaboration with Hayashi and Heidbrink, resulted in a Nuclear Fusion article on the effect of radial electric fields on fast-ion confinement. The main output of the project, however, is two detailed experimental papers by Hayashi et al. The first of these is a study of neoclassical fast ion confinement in MHD-quiescent plasmas, a key issue in stellarator research. The second is an initial study of the effect of Alfven eigenmodes on fast-ion confinement. In addition to these studies, the project also helped partially support stellarator research with the GTC code by members of Prof. Lin’s group.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A Moderator Test Station at ORNL

Oak Ridge National Laboratory (ORNL) hosts two world-leading slow neutron sources, the Spallation Neutron Source (SNS) and the High Flux Isotope Reactor (HFIR), and is currently developing the technical design for a Second Target Station (STS) for the SNS. Upon completion of the STS project, ORNL will be uniquely positioned to optimize each of its three neutron sources, the SNS First Target Station (FTS), the STS, and HFIR, in a complementary way. Among the essential aspects of a reimagined FTS and the current STS concept are high-brightness parahydrogen moderators—moderators which are optimized for high per-unit-area neutron brightness rather than integrated-across-large-area neutron intensity. The high-brightness moderators proposed for the STS will significantly outperform the coupled moderators currently on the FTS for appropriately optimized neutron beamlines, provided the moderating hydrogen is converted to near-equilibrium levels of parahydrogen (approximately 99.8% at 20 K). The original FTS moderators, by contrast, were conservatively designed to be relatively insensitive to the exact ortho:para ratio, with a consequent loss in performance. As a result, a redesign of the FTS moderators assuming fully converted parahydrogen could result in significant performance improvements on the FTS coupled moderators, and more consistent performance over time for all hydrogen moderators. This “parahydrogen problem” is a long-standing challenge for the effective implementation of hydrogen cold moderators at high-power neutron sources. In addition, the development of new moderator concepts, whether based on previously unused materials, structured heterogeneous arrays, or even simply on changes in overall shape and size is significantly restricted at a large-scale production facility intended to use the neutron beams so produced. Accordingly, moderators for production neutron sources are often designed in a very conservative, low-risk fashion, even though this compromises the absolute neutronic performance. Advanced moderator concepts worthy of study include features that could not be tested without redesigning and redeploying the entire existing reflector, shielding, and neutron beamline installation, making such development efforts far more expensive than building a stand-alone test facility. We propose a Moderator Test Station (MTS) at the SNS with which we will verify such performance gains and test new moderator concepts. These concepts include both high-brightness and large-volume parahydrogen moderators, as well as moderators with tailored ortho:para hydrogen levels, heterogeneous moderator concepts such as the convoluted moderator or pelletized moderators, and moderators made of materials like ammonia, ethane, and oxygen clathrates, which have not been widely tested let alone deployed at neutron source facilities.

42 ENGINEERING↗

Sustainable Ethylene via Chemical Looping – Oxidative Dehydrogenation

This Phase I final report evaluates chemical looping–oxidative dehydrogenation as a lower-energy and cost-competitive alternative to conventional ethane steam cracking for ethylene production. The project combined catalyst development and experimental testing with process modeling, techno-economic analysis, and life-cycle assessment. Results indicate that the proposed process could improve olefin production, reduce energy use, and lower production costs, particularly when integrated with carbon capture and renewable electricity. The report also identifies remaining technical, environmental, and safety considerations and presents a technology maturation plan focused on longer-term catalyst evaluation and advancement toward pilot-scale demonstration.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Adhesion measurement of highly-ordered TiO 2 nanotubes on Ti-6Al-4V alloy

Self-assembled nanotubular arrays on Ti alloys could be used for more effective implantable devices in various medical approaches. In the present work, the adhesion of TiO 2 nanotubes (TiO 2 NTs) on Ti-6Al-4V (Ti64) was investigated by laser spallation and scratch test techniques. At first, electrochemical anodization was performed in an ammonium fluoride solution dissolved in a 90:10 ethane-1,2-diol (ethylene glycol) and water solvent mixture. This process was performed at room temperature (23 °C) at a steady potential of 60 V for 1 h. Next, the TiO 2 nanotubes layer was heat-treated to improve the adhesion of the coating. The formation of self-organized TiO 2 nanotubes as well as the microstructural evolution, are strongly dependent on the processing parameters and subsequent annealing. From microscopic analysis, highly oriented arrays of TiO 2 nanotubes were grown by thermal treatment for 90 min at 500 °C. Further heat treatment above 500 °C led to the detachment of the nanotubes and the complete destruction of the nanotubes occurred at temperature above 700 °C. Scratch test analysis over a constant scratch length (1000 μm) indicated that the failure point was shifted from 247.4 to 557.9 μm while the adhesion strength was increased from ~862 to ~1814 mN after annealing at 500 °C. Finally, the adhesion measurement determined by laser spallation technique provided an intrinsic adhesion strength of 51.4 MPa for the TiO 2 nanotubes on the Ti64 substrate.

36 MATERIALS SCIENCE↗

Anaerobic oxidation of short-chain alkanes in hydrothermal sediments: potential influences on sulfur cycling and microbial diversity

Short-chain alkanes play a substantial role in carbon and sulfur cycling at hydrocarbon-rich environments globally, yet few studies have examined the metabolism of ethane (C-2), propane (C-3), and butane (C-4) in anoxic sediments in contrast to methane (C-1). In hydrothermal vent systems, short-chain alkanes are formed over relatively short geological time scales via thermogenic processes and often exist at high concentrations. The sediment-covered hydrothermal vent systems at Middle Valley (MV Juan de Fuca Ridge) are an ideal site for investigating the anaerobic oxidation of C-1-C-4 alkanes, given the elevated temperatures and dissolved hydrocarbon species characteristic of these metalliferous sediments. We examined whether MV microbial communities oxidized C-1-C-4 alkanes under mesophilic to thermophilic sulfate-reducing conditions. Here we present data from discrete temperature (25, 55, and 75 degrees C) anaerobic batch reactor incubations of MV sediments supplemented with individual alkanes. Co-registered alkane consumption and sulfate reduction (SR) measurements provide clear evidence for C-1-C-4 alkane oxidation linked to SR over time and across temperatures. In these anaerobic batch reactor sediments, 16S ribosomal RNA pyrosequencing revealed that Deltaproteobacteria, particularly a novel sulfate-reducing lineage, were the likely phylotypes mediating the oxidation of C-2-C-4 alkanes. Maximum C-1-C-4 alkane oxidation rates occurred at 55 degrees C, which reflects the mid-core sediment temperature profile and corroborates previous studies of rate maxima for the anaerobic oxidation of methane (AOM). Of the alkanes investigated, C-3 was oxidized at the highest rate over time, then C-4, C-2, and C-1, respectively. The implications of these results are discussed with respect to the potential competition between the anaerobic oxidation of C-2-C(4)alkanes with AOM for available oxidants and the influence on the fate of C-1 derived from these hydrothermal systems.

Adams, MM↗

Overview of Diverse Methyl/Alkyl-Coenzyme M Reductases and Considerations for Their Potential Heterologous Expression

Methyl-coenzyme M reductase (MCR) is an archaeal enzyme that catalyzes the final step of methanogenesis and the first step in the anaerobic oxidation of methane, the energy metabolisms of methanogens and anaerobic methanotrophs (ANME), respectively. Variants of MCR, known as alkyl-coenzyme M reductases, are involved in the anaerobic oxidation of short-chain alkanes including ethane, propane, and butane as well as the catabolism of long-chain alkanes from oil reservoirs. MCR is a dimer of heterotrimers (encoded by mcrABG) and requires the nickel-containing tetrapyrrole prosthetic group known as coenzyme F430. MCR houses a series of unusual post-translational modifications within its active site whose identities vary depending on the organism and whose functions remain unclear. Methanogenic MCRs are encoded in a highly conserved mcrBDCGA gene cluster, which encodes two accessory proteins, McrD and McrC, that are believed to be involved in the assembly and activation of MCR, respectively. The requirement of a unique and complex coenzyme, various unusual post-translational modifications, and many remaining questions surrounding assembly and activation of MCR largely limit in vitro experiments to native enzymes with recombinant methods only recently appearing. Production of MCRs in a heterologous host is an important step toward developing optimized biocatalytic systems for methane production as well as for bioconversion of methane and other alkanes into value-added compounds. This review will first summarize MCR catalysis and structure, followed by a discussion of advances and challenges related to the production of diverse MCRs in a heterologous host.

59 BASIC BIOLOGICAL SCIENCES↗

Characterization of MoVTeNbO x catalysts during oxidation reactions using in situ/operando techniques: A review

The domestic fossil feedstock in recent years is shifting towards light hydrocarbons due to abundance of shale gas from hydraulic fracturing. This shift induces a need for greater flexibility in both new and existing processing plants to produce consumer products (polymers, paints, lubricants, etc.) from new feedstocks. The oxidative catalytic reactions operate at milder conditions than the processing of feedstocks through steam cracking. The conversion of light feedstocks (C3 and shorter hydrocarbons) to high value chemicals through highly selective catalysts in the presence of oxygen plays a crucial role in eliminating wastes, reducing greenhouse gas emissions and lowering market prices. Among all catalysts for light hydrocarbon processing through oxidation reactions, bulk mixed metal oxides such as MoVTe(Sb)NbO x catalysts are the most promising due to their performance under favorable reaction conditions (temperature, pressure, etc). Here, state-of-the-art in situ/operando techniques along with transient kinetics can revolutionize the development of catalysts by providing information about the nature of active sites, intermediates and kinetics under realistic industrial conditions. Only through detailed understanding of these catalyst behaviors can new synthesis methods be developed that will improve reactivity, selectivity and lifetimes of these catalysts. In this review, dynamic changes of this mixed oxide catalyst during the reaction (such as changes in surface composition, oxidation states, acidity, etc) are discussed mainly from knowledge and insights obtained from these in situ/operando approaches. The most common oxidation reactions driven by the MoVTeNbO x catalysts and studied under operando/in situ conditions to be discussed here are: (1) oxidative dehydrogenation of light alkanes (ethane and propane), (2) propane ammoxidation to acrylonitrile and (3) selective oxidation of propane to acrylic acid.

03 NATURAL GAS↗

Determining Coalbed Methane Production and Composition from Individual Stacked Coal Seams in a Multi-Zone Completed Gas Well

This work proposes a novel and cost-effective approach to determine coalbed methane (CBM) production and composition from individual coal seams in a multi-zone completed CBM well. The novel method uses water to cover individual coal seams in a low pressure CBM well followed by an Echometer fluid level survey to determine the water level. Corresponding gas flow measurements and natural gas chromatography analysis are used to determine gas production and composition from unique zones. A field test using this technology is conducted in Central Appalachia for a multi-zone CBM well containing 18 coal seams. Test results show that the shallow coal seams contribute the majority of the total CBM production in this multi-zone well, and the deeper coal seams contain more heavy hydrocarbons like ethane and propane.

01 COAL, LIGNITE, AND PEAT↗

Anomaly in the Chain Length Dependence of n-Alkane Diffusion in ZIF-4 Metal-Organic Frameworks

Molecular diffusion is commonly found to slow down with increasing molecular size. Deviations from this pattern occur in some host materials with pore sizes approaching the diameters of the guest molecules. A variety of theoretical models have been suggested to explain deviations from this pattern, but robust experimental data are scarcely available. Here in this paper, we present such data, obtained by monitoring the chain length dependence of the uptake of n-alkanes in the zeolitic imidazolate framework ZIF-4. A monotonic decrease in diffusivity from ethane to n-butane was observed, followed by an increase for n-pentane, and another decrease for n-hexane. This observation was confirmed by uptake measurements with n-butane/n-pentane mixtures, which yield faster uptake of n-pentane. Further evidence is provided by the observation of overshooting effects, i.e. by transient n-pentane concentrations exceeding the (eventually attained) equilibrium value. Accompanying grand canonical Monte Carlo simulations reveal, for the larger n-alkanes, significant differences between the adsorbed and gas phase molecular configurations, indicating strong confinement effects within ZIF-4, which, with increasing chain length, may be expected to give rise to configurational shifts facilitating molecular propagation at particular chain lengths.

32 GCMC simulation↗

Preparing Lamellae from Vitreous Biological Samples using a Dual-Beam Scanning Electron Microscope for Cryo-Electron Tomography

Presented here is a protocol for preparing cryo-lamellae from plunge-frozen grids of Plasmodium falciparum-infected human erythrocytes, which could easily be adapted for other biological samples. The basic principles for preparing samples, milling, and viewing lamellae are common to all instruments and the protocol can be followed as a general guide to on-grid cryo-lamella preparation for cryo-electron microscopy (cryoEM) and cryo-electron tomography (cryoET). Electron microscopy grids supporting the cells are plunge-frozen into liquid nitrogen-cooled liquid ethane using a manual or automated plunge freezer, then screened on a light microscope equipped with a cryo-stage. Frozen grids are transferred into a cryo-scanning electron microscope equipped with a focused ion beam (cryoFIB-SEM). Grids are routinely sputter coated prior to milling, which aids dispersal of charge build-up during milling. Alternatively, an e-beam rotary coater can be used to apply a layer of carbon-platinum to the grids, the exact thickness of which can be more precisely controlled. Once inside the cryoFIB-SEM an additional coating of an organoplatinum compound is applied to the surface of the grid via a gas injection system (GIS). This layer protects the front edge of the lamella as it is milled, the integrity of which is critical for achieving uniformly thin lamellae. Regions of interest are identified via SEM and milling is carried out in a step-wise fashion, reducing the current of the ion beam as the lamella reaches electron transparency, in order to avoid excessive heat generation. A grid with multiple lamellae is then transferred to a transmission electron microscope (TEM) under cryogenic conditions for tilt-series acquisition. A robust and contamination-free workflow for lamella preparation is an essential step for downstream techniques, including cellular cryoEM, cryoET, and sub-tomogram averaging. Development of these techniques, especially for lift-out and milling of high-pressure frozen samples, is of high-priority in the field.

59 BASIC BIOLOGICAL SCIENCES↗

Hydrogenation and Deuteration of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} on Cold Grains: A Clue to the Formation Mechanism of C{sub 2}H{sub 6} with Astronomical Interest

We quantitatively investigated the hydrogen addition reactions of acetylene (C{sub 2}H{sub 2}) and ethylene (C{sub 2}H{sub 4}) on amorphous solid water (ASW) at 10 and 20 K relevant to the formation of ethane (C{sub 2}H{sub 6}) on interstellar icy grains. We found that the ASW surface enhances the reaction rates for C{sub 2}H{sub 2} and C{sub 2}H{sub 4} by approximately a factor of 2 compared to those on the pure-solid C{sub 2}H{sub 2} and C{sub 2}H{sub 4} at 10 K, probably due to an increase in the sticking coefficient and adsorption energy of the H atoms on ASW. In contrast to the previous proposal that the hydrogenation rate of C{sub 2}H{sub 4} is orders of magnitude larger than that of C{sub 2}H{sub 2}, the present results show that the difference in hydrogenation rates of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} is only within a factor of 3 on both the surfaces of pure solids and ASW. In addition, we found the small kinetic isotope effect for hydrogenation/deuteration of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} at 10 K, despite the requirement of quantum tunneling. At 20 K, the reaction rate of deuteration becomes even larger than that of hydrogenation. These unusual isotope effects might originate from a slightly larger number density of D atoms than H atoms on ASW at 20 K. The hydrogenation of C{sub 2}H{sub 2} is four times faster than CO hydrogenation and can produce C{sub 2}H{sub 6} efficiently through C{sub 2}H{sub 4} even in the environment of a dark molecular cloud.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Desorption Kinetics and Binding Energies of Small Hydrocarbons

Small hydrocarbons are a vital organic reservoir in protostellar and protoplanetary environments. Constraints on desorption temperatures and binding energies of such hydrocarbons are essential for accurate predictions of where these molecules exist in the ice versus gas phase during the different stages of star and planet formation. Here, through a series of temperature programmed desorption experiments, we constrain the binding energies of 2- and 3-carbon hydrocarbons (C 2 H 2 —acetylene, C 2 H 4 —ethylene, C 2 H 6 —ethane, C 3 H 4 —propyne, C 3 H 6 —propene, and C 3 H 8 —propane) to 2200–4200 K in the case of pure amorphous ices, to 2400–4400 K on compact amorphous H 2 O, and to 2800–4700 K on porous amorphous H 2 O. The 3-carbon hydrocarbon binding energies are always larger than the 2-carbon hydrocarbon binding energies. Within the 2- and 3-carbon hydrocarbon families, the alkynes (i.e., least-saturated) hydrocarbons exhibit the largest binding energies, while the alkane and alkene binding energies are comparable. Binding energies are ~5%–20% higher on water ice substrates compared to pure ices, which is a small increase compared to what has been measured for other volatile molecules such as CO and N 2 . Thus in the case of hydrocarbons, H 2 O has a less pronounced effect on sublimation front locations (i.e., snowlines) in protoplanetary disks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular characterization of free tropospheric aerosol collected at the Pico Mountain Observatory: a case study with a long-range transported biomass burning plume

Free tropospheric aerosol was sampled at the Pico Mountain Observatory located at 2225 m above mean sea level on Pico Island of the Azores archipelago in the North Atlantic. The observatory is located ~ 3900 km east and downwind of North America, which enables studies of free tropospheric air transported over long distances. Aerosol samples collected on filters from June to October 2012 were analyzed to characterize organic carbon, elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 ± 0.7 μg m -3 . On average, organic aerosol components represent the largest mass fraction of the total measured aerosol (60 ± 51%), followed by sulfate (23 ± 28%), nitrate (13 ± 10%), chloride (2 ± 3%), and elemental carbon (2 ± 2%). Water-soluble organic matter (WSOM) extracted from two aerosol samples (9/24 and 9/25) collected consecutively during a pollution event were analyzed using ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Approximately 4000 molecular formulas were assigned to each of the mass spectra in the range of m/z 100–1000. The majority of the assigned molecular formulas had unsaturated structures with CHO and CHNO elemental compositions. FLEXPART retroplume analyses showed the sampled air masses were very aged (average plume age > 12 days). These aged aerosol WSOM compounds had an average O/C ratio of ~ 0.45, which is relatively low compared to O/C ratios of other aged aerosol. The increase in aerosol loading during the measurement period of 9/24 was linked to biomass burning emissions from North America by FLEXPART retroplume analysis and Moderate Resolution Imaging Spectroradiometer (MODIS) fire counts. This was confirmed with biomass burning markers detected in the WSOM and with the morphology and mixing state of particles as determined by scanning electron microscopy. The presence of markers characteristic of aqueous-phase reactions of phenolic species suggests that the aerosol collected at the Pico Mountain Observatory had undergone cloud processing before reaching the site. Finally, the air masses of 9/25 were more aged and influenced by marine emissions, as indicated by the presence of organosulfates and other species characteristic of marine aerosol. The change in the air masses for the two samples was corroborated by the changes in ethane, propane, and ozone, morphology of particles, as well as by the FLEXPART retroplume simulations. This paper presents the first detailed molecular characterization of free tropospheric aged aerosol intercepted at a lower free troposphere remote location and provides evidence of low oxygenation after long-range transport. We hypothesize this is a result of the selective removal of highly aged and polar species during long-range transport, because the aerosol underwent a combination of atmospheric processes during transport facilitating aqueous-phase removal (e.g., clouds processing) and fragmentation (e.g., photolysis) of components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new aerial approach for quantifying and attributing methane emissions: implementation and validation

Methane (CH 4 ) is a powerful greenhouse gas that is produced by a diverse set of natural and anthropogenic emission sources. Biogenic methane sources generally involve anaerobic decay processes such as those occurring in wetlands, melting permafrost, or the digestion of organic matter in the guts of ruminant animals. Thermogenic CH 4 sources originate from the breakdown of organic material at high temperatures and pressure within the Earth's crust, a process which also produces more complex trace hydrocarbons such as ethane (C 2 H 6 ). Here, we present the development and deployment of an uncrewed aerial system (UAS) that employs a fast (1 Hz) and sensitive (1–0.5 ppb s -1 ) CH 4 and C 2 H 6 sensor and ultrasonic anemometer. The UAS platform is a vertical-takeoff, hexarotor drone (DJI Matrice 600 Pro, M600P) capable of vertical profiling to 120 m altitude and plume sampling across scales up to 1 km. Simultaneous measurements of CH 4 and C 2 H 6 concentrations, vector winds, and positional data allow for source classification (biogenic versus thermogenic), differentiation, and emission rates without the need for modeling or a priori assumptions about winds, vertical mixing, or other environmental conditions. The system has been used for direct quantification of methane point sources, such as orphan wells, and distributed emitters, such as landfills and wastewater treatment facilities. With detectable source rates as low as 0.04 and up to ~1500 kg h -1 , this UAS offers a direct and repeatable method of horizontal and vertical profiling of emission plumes at scales that are complementary to regional aerial surveys and localized ground-based monitoring.

54 ENVIRONMENTAL SCIENCES↗

Measurements of methane emissions from natural gas gathering facilities and processing plants: measurement methods

Increased natural gas production in recent years has spurred intense interest in methane (CH 4 ) emissions associated with its production, gathering, processing, transmission, and distribution. Gathering and processing facilities (G&P facilities) are unique in that the wide range of gas sources (shale, coal-bed, tight gas, conventional, etc.) results in a wide range of gas compositions, which in turn requires an array of technologies to prepare the gas for pipeline transmission and distribution. We present an overview and detailed description of the measurement method and analysis approach used during a 20-week field campaign studying CH 4 emissions from the natural gas G&P facilities between October 2013 and April 2014. Dual-tracer flux measurements and on-site observations were used to address the magnitude and origins of CH 4 emissions from these facilities. The use of a second tracer as an internal standard revealed plume-specific uncertainties in the measured emission rates of 20–47%, depending upon plume classification. Furthermore, combining downwind methane, ethane (C 2 H 6 ), carbon monoxide (CO), carbon dioxide (CO 2 ), and tracer gas measurements with on-site tracer gas release allows for quantification of facility emissions and in some cases a more detailed picture of source locations.

03 NATURAL GAS↗

Global Methane Budget 2000–2020

Abstract. Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. CH4 is the second most important human-influenced greenhouse gas in terms of climate forcing after carbon dioxide (CO2), and both emissions and atmospheric concentrations of CH4 have continued to increase since 2007 after a temporary pause. The relative importance of CH4 emissions compared to those of CO2 for temperature change is related to its shorter atmospheric lifetime, stronger radiative effect, and acceleration in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in quantifying the factors responsible for the observed atmospheric growth rate arise from diverse, geographically overlapping CH4 sources and from the uncertain magnitude and temporal change in the destruction of CH4 by short-lived and highly variable hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to improve, synthesise, and update the global CH4 budget regularly and to stimulate new research on the methane cycle. Following Saunois et al. (2016, 2020), we present here the third version of the living review paper dedicated to the decadal CH4 budget, integrating results of top-down CH4 emission estimates (based on in situ and Greenhouse Gases Observing SATellite (GOSAT) atmospheric observations and an ensemble of atmospheric inverse-model results) and bottom-up estimates (based on process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). We present a budget for the most recent 2010–2019 calendar decade (the latest period for which full data sets are available), for the previous decade of 2000–2009 and for the year 2020. The revision of the bottom-up budget in this 2025 edition benefits from important progress in estimating inland freshwater emissions, with better counting of emissions from lakes and ponds, reservoirs, and streams and rivers. This budget also reduces double counting across freshwater and wetland emissions and, for the first time, includes an estimate of the potential double counting that may exist (average of 23 Tg CH4 yr−1). Bottom-up approaches show that the combined wetland and inland freshwater emissions average 248 [159–369] Tg CH4 yr−1 for the 2010–2019 decade. Natural fluxes are perturbed by human activities through climate, eutrophication, and land use. In this budget, we also estimate, for the first time, this anthropogenic component contributing to wetland and inland freshwater emissions. Newly available gridded products also allowed us to derive an almost complete latitudinal and regional budget based on bottom-up approaches. For the 2010–2019 decade, global CH4 emissions are estimated by atmospheric inversions (top-down) to be 575 Tg CH4 yr−1 (range 553–586, corresponding to the minimum and maximum estimates of the model ensemble). Of this amount, 369 Tg CH4 yr−1 or ∼ 65 % is attributed to direct anthropogenic sources in the fossil, agriculture, and waste and anthropogenic biomass burning (range 350–391 Tg CH4 yr−1 or 63 %–68 %). For the 2000–2009 period, the atmospheric inversions give a slightly lower total emission than for 2010–2019, by 32 Tg CH4 yr−1 (range 9–40). The 2020 emission rate is the highest of the period and reaches 608 Tg CH4 yr−1 (range 581–627), which is 12 % higher than the average emissions in the 2000s. Since 2012, global direct anthropogenic CH4 emission trends have been tracking scenarios that assume no or minimal climate mitigation policies proposed by the Intergovernmental Panel on Climate Change (shared socio-economic pathways SSP5 and SSP3). Bottom-up methods suggest 16 % (94 Tg CH4 yr−1) larger global emissions (669 Tg CH4 yr−1, range 512–849) than top-down inversion methods for the 2010–2019 period. The discrepancy between the bottom-up and the top-down budgets has been greatly reduced compared to the previous differences (167 and 156 Tg CH4 yr−1 in Saunois et al. (2016, 2020) respectively), and for the first time uncertainties in bottom-up and top-down budgets overlap. Although differences have been reduced between inversions and bottom-up, the most important source of uncertainty in the global CH4 budget is still attributable to natural emissions, especially those from wetlands and inland freshwaters. The tropospheric loss of methane, as the main contributor to methane lifetime, has been estimated at 563 [510–663] Tg CH4 yr−1 based on chemistry–climate models. These values are slightly larger than for 2000–2009 due to the impact of the rise in atmospheric methane and remaining large uncertainty (∼ 25 %). The total sink of CH4 is estimated at 633 [507–796] Tg CH4 yr−1 by the bottom-up approaches and at 554 [550–567] Tg CH4 yr−1 by top-down approaches. However, most of the top-down models use the same OH distribution, which introduces less uncertainty to the global budget than is likely justified. For 2010–2019, agriculture and waste contributed an estimated 228 [213–242] Tg CH4 yr−1 in the top-down budget and 211 [195–231] Tg CH4 yr−1 in the bottom-up budget. Fossil fuel emissions contributed 115 [100–124] Tg CH4 yr−1 in the top-down budget and 120 [117–125] Tg CH4 yr−1 in the bottom-up budget. Biomass and biofuel burning contributed 27 [26–27] Tg CH4 yr−1 in the top-down budget and 28 [21–39] Tg CH4 yr−1 in the bottom-up budget. We identify five major priorities for improving the CH4 budget: (i) producing a global, high-resolution map of water-saturated soils and inundated areas emitting CH4 based on a robust classification of different types of emitting ecosystems; (ii) further development of process-based models for inland-water emissions; (iii) intensification of CH4 observations at local (e.g. FLUXNET-CH4 measurements, urban-scale monitoring, satellite imagery with pointing capabilities) to regional scales (surface networks and global remote sensing measurements from satellites) to constrain both bottom-up models and atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) integration of 3D variational inversion systems using isotopic and/or co-emitted species such as ethane as well as information in the bottom-up inventories on anthropogenic super-emitters detected by remote sensing (mainly oil and gas sector but also coal, agriculture, and landfills) to improve source partitioning. The data presented here can be downloaded from https://doi.org/10.18160/GKQ9-2RHT (Martinez et al., 2024).

54 ENVIRONMENTAL SCIENCES↗