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DOE OSTI2024

A synthetic co-culture for bioproduction of ammonia from methane and air

Abstract Fixed nitrogen fertilizers feed 50% of the global population, but most fixed nitrogen production occurs using energy-intensive Haber–Bosch-based chemistry combining nitrogen (N2) from air with gaseous hydrogen (H2) from methane (CH4) at high temperatures and pressures in large-scale facilities sensitive to supply chain disruptions. This work demonstrates the biological transformation of atmospheric N2 into ammonia (NH3) using CH4 as the sole carbon and energy source in a single vessel at ambient pressure and temperature, representing a biological “room-pressure and room-temperature” route to NH3 that could ultimately be developed to support compact, remote, NH3 production facilities amenable to distributed biomanufacturing. The synthetic microbial co-culture of engineered methanotroph Methylomicrobium buryatense (now Methylotuvimicrobium buryatense) and diazotroph Azotobacter vinelandii converted three CH4 molecules to l-lactate (C3H6O3) and powered gaseous N2 conversion to NH3. The design used division of labor and mutualistic metabolism strategies to address the oxygen sensitivity of nitrogenase and maximize CH4 oxidation efficiency. Media pH and salinity were central variables supporting co-cultivation. Carbon concentration heavily influenced NH3 production. Smaller-scale NH3 production near dispersed, abundant, and renewable CH4 sources could reduce disruption risks and capitalize on untapped energy resources. One-Sentence Summary Co-culture of engineered microorganisms Methylomicrobium buryatense and Azotobacter vinelandii facilitated the use of methane gas as a sole carbon feedstock to produce ammonia in an ambient temperature, atmospheric pressure, single-vessel system.

Biotechnology & Applied Microbiology↗

DOE OSTI2020

Verification of diesel spray ignition phenomenon in dual-fuel diesel-piloted premixed natural gas engine

Dual-fuel (DF) engines, in which premixed natural gas and air in an open-type combustion chamber is ignited by diesel-fuel pilot sprays, have been more popular for marine use than pre-chamber spark ignition (PCSI) engines because of their superior durability. However, control of ignition and combustion in DF engines is more difficult than in PCSI engines. In this context, here we focus on the ignition stability of n-heptane pilot-fuel jets injected into a compressed premixed charge of natural gas and air at low-load conditions. To aid understanding of the experimental data, chemical-kinetics simulations were carried out in a simplified engine-environment that provided insight into the chemical effects of methane (CH4) on pilot-fuel ignition. The simulations reveal that CH4 has an effect on both stages of n-heptane autoignition: the small, first-stage, cool-flame-type, low-temperature ignition (LTI) and the larger, second-stage, high-temperature ignition (HTI). As the ratio of pilot-fuel to CH4 entrained into the spray decreases, the initial oxidization of CH4 consumes the OH radicals produced by pilot-fuel decomposition during LTI, thereby inhibiting its progression to HTI. Using imaging diagnostics, the spatial and temporal progression of LTI and HTI in DF combustion are measured in a heavy-duty optical engine, and the imaging data are analyzed to understand the cause of severe fluctuations in ignition timing and combustion completeness at low-load conditions. Images of cool-flame and hydroxyl radical (OH*) chemiluminescence serve as indicators of LTI and HTI, respectively. The cycle-to-cycle and spatial variation in ignition extracted from the imaging data are used as key metrics of comparison. The imaging data indicate that the local concentration of the pilot-fuel and the richness of the surrounding natural-gas air mixture are important for LTI and HTI, but in different ways. In particular, higher injection pressures and shorter injection durations increase the mixing rate, leading to lower concentrations of pilot-fuel more quickly, which can inhibit HTI even as LTI remains relatively robust. Decreasing the injection pressure from 80 MPa to 40 MPa and increasing the injection duration from 500 µs to 760 µs maintained constant pilot-fuel mass, while promoting robust transition from LTI to HTI by effectively slowing the mixing rate. This allows enough residence time for the OH radicals, produced by the two-stage ignition chemistry of the pilot-fuel, to accelerate the transition from LTI to HTI before being consumed by CH4 oxidation. Thus from a practical perspective, for a premixed natural gas fuel–air equivalence-ratio, it is possible to improve the “stability” of the combustion process by solely manipulating the pilot-fuel injection parameters while maintaining constant mass of injected pilot-fuel. This allows for tailoring mixing trajectories to offset changes in fuel ignition chemistry, so as to promote a robust transition from LTI to HTI by changing the balance between the local concentration of the pilot-fuel and richness of the premixed natural gas and air. This could prove to be a valuable tool for combustion design to improve fuel efficiency or reduce noise or perhaps even reduce heat-transfer losses by locating early combustion away from in-cylinder walls.

42 ENGINEERING↗

DOE OSTI2024

Methane dynamics described through vegetation-soil interactions in bald cypress and other bottomland hardwood forests

Past estimates of CH4 fluxes from forested swamps ranged from 10 to 106 mg C m-2 d-1 in temperate regions and 44 to144 mg C m-2 d-1 in subtropical and tropical regions. However, climate change could alter these rates in wetlands where efflux is predominantly controlled by water level, temperature, and plant composition. While the Lower Mississippi Alluvial Valley has experienced the largest loss of forested wetlands in the U.S, supporting 21 to 25 million acres of bottomland hardwoods before European settlement, an estimated 5 million acres remain. This landscapes remain under-studied from a CH4 flux perspective, particularly in determining woody vegetation contributions to landscape CH4 emissions. Our overarching objective are to (1) improve our understanding of the controls on CH4 fluxes in forested mineral soil wetlands, and (2) to better understand the effects of landscape position and forest composition on the CH4 fluxes between terrestrial ecosystems and the atmosphere. Our main goal is to elucidate the

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Biogeochemical and plant trait mechanisms drive enhanced methane emissions in response to whole-ecosystem warming

Abstract. Climate warming perturbs ecosystem carbon (C) cycling, causing both positive and negative feedbacks on greenhouse gas emissions. In 2016, we began a tidal marsh field experiment in two vegetation communities to investigate the mechanisms by which whole-ecosystem warming alters C gain, via plant-driven sequestration in soils, and C loss, primarily via methane (CH4) emissions. Here, we report the results from the first 4 years. As expected, warming of 5.1 ∘C more than doubled CH4 emissions in both plant communities. We propose this was caused by a combination of four mechanisms: (i) a decrease in the proportion of CH4 consumed by CH4 oxidation, (ii) more C substrates available for methanogenesis, (iii) reduced competition between methanogens and sulfate-reducing bacteria, and (iv) indirect effects of plant traits. Plots dominated by Spartina patens consistently emitted more CH4 than plots dominated by Schoenoplectus americanus, indicating key differences in the roles these common wetland plants play in affecting anaerobic soil biogeochemistry and suggesting that plant composition can modulate coastal wetland responses to climate change.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

FLUXNET-CH 4 : a global, multi-ecosystem dataset and analysis of methane seasonality from freshwater wetlands

Methane (CH 4 ) emissions from natural landscapes constitute roughly half of global CH4 contributions to the atmosphere, yet large uncertainties remain in the absolute magnitude and the seasonality of emission quantities and drivers. Eddy covariance (EC) measurements of CH4 flux are ideal for constraining ecosystem-scale CH 4 emissions due to quasi-continuous and high-temporal-resolution CH 4 flux measurements, coincident carbon dioxide, water, and energy flux measurements, lack of ecosystem disturbance, and increased availability of datasets over the last decade. Here, we (1) describe the newly published dataset, FLUXNET-CH 4 Version 1.0, the first open-source global dataset of CH 4 EC measurements (available at https://fluxnet.org/data/fluxnet-ch4-community-product/, last access: 7 April 2021). FLUXNET-CH 4 includes half-hourly and daily gap-filled and non-gap-filled aggregated CH4 fluxes and meteorological data from 79 sites globally: 42 freshwater wetlands, 6 brackish and saline wetlands, 7 formerly drained ecosystems, 7 rice paddy sites, 2 lakes, and 15 uplands. Then, we (2) evaluate FLUXNET-CH 4 representativeness for freshwater wetland coverage globally because the majority of sites in FLUXNET-CH4 Version 1.0 are freshwater wetlands which are a substantial source of total atmospheric CH 4 emissions; and (3) we provide the first global estimates of the seasonal variability and seasonality predictors of freshwater wetland CH4 fluxes. Our representativeness analysis suggests that the freshwater wetland sites in the dataset cover global wetland bioclimatic attributes (encompassing energy, moisture, and vegetation-related parameters) in arctic, boreal, and temperate regions but only sparsely cover humid tropical regions. Seasonality metrics of wetland CH 4 emissions vary considerably across latitudinal bands. In freshwater wetlands (except those between 20°S to 20°N) the spring onset of elevated CH 4 emissions starts 3 d earlier, and the CH 4 emission season lasts 4 d longer, for each degree Celsius increase in mean annual air temperature. On average, the spring onset of increasing CH 4 emissions lags behind soil warming by 1 month, with very few sites experiencing increased CH 4 emissions prior to the onset of soil warming. In contrast, roughly half of these sites experience the spring onset of rising CH 4 emissions prior to the spring increase in gross primary productivity (GPP). The timing of peak summer CH 4 emissions does not correlate with the timing for either peak summer temperature or peak GPP. Our results provide seasonality parameters for CH 4 modeling and highlight seasonality metrics that cannot be predicted by temperature or GPP (i.e., seasonality of CH 4 peak). FLUXNET-CH 4 is a powerful new resource for diagnosing and understanding the role of terrestrial ecosystems and climate drivers in the global CH 4 cycle, and future additions of sites in tropical ecosystems and site years of data collection will provide added value to this database. All seasonality parameters are available at https://doi.org/10.5281/zenodo.4672601 (Delwiche et al., 2021). Additionally, raw FLUXNET-CH 4 data used to extract seasonality parameters can be downloaded from https://fluxnet.org/data/fluxnet-ch4-community-product/ (last access: 7 April 2021), and a complete list of the 79 individual site data DOIs is provided in Table 2 of this paper.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Data from: “Bald Cypress (Taxodium distichum) Knees Are Methane Sources Controlled by Geomorphology, Climate, and Hydrologic Extremes”

This dataset is associated with the manuscript “Bald Cypress (Taxodium distichum) Knees Are Methane Sources Controlled by Geomorphology, Climate, and Hydrologic Extremes”. Bald cypress “knees” (aboveground woody roots) have been shown to contribute to wetland methane (CH4) efflux, with large variation within and between studies. To explain this variation, we investigated spatial (i.e., across knee surface, within sites, between sites) and temporal dynamics of CH4 fluxes from knees. Methane fluxes were collected from September 2022 to August 2024 at three locations in western Kentucky, USA, within the Mississippi Alluvial Valley: a main channel (semi-permanently flooded), side channel (seasonally flooded), and reservoir edge (artificially flooded). Knee CH4 fluxes (“Ross_et_al_Knee_Flux_Data.csv”) were measured from multiple heights on knees (20, 40, and 60 cm) of various sizes (knee straight height ranged from 24 to 93 cm) using a LiCOR LI-7810 CH4/CO2/H2O Trace Gas Analyzer. The dataset also includes environmental variables collected with each knee measurement, including water level adjusted for knee-to-knee elevational differences, subsurface and air temperature, and humidity. Soil CH4 fluxes (“Ross_et_al_Soil_Flux_Data.csv”) were also collected adjacent to knees (starting in April 2023) when water levels didn’t overtop soil collars, using a LiCOR Smart Chamber and calculated in SoilFluxPro software. The soil flux dataset includes associated variables collected by the Smart Chamber. Three separate files (“*_Water_Level.csv”) are included for water level and subsurface temperature data collected at each site using HOBO U20L barometric pressure loggers. Each file type (knee flux, soil flux, water level) has an associated data dictionary (“*_dd.csv”). For specifics on methodology used and calculations, see the associated manuscript. The R script includes code used for figures and analyses reported in the manuscript.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2026

Microwave-Assisted Hydrogen Generation from Hydrocarbon-Bearing Reservoir Rocks: Stage-Dependent Thermal Runaway and In-Situ Carbonate Engineering

Microwave-assisted hydrogen generation from hydrocarbon-bearing reservoir rocks is strongly influenced by mineralogy, methane activation, carbonate reactions, and thermal runaway behavior. This study investigates a new approach in which carbonate phases are generated in-situ through the reaction of internally produced CO2 with Ca(OH)2 under microwave heating conditions. The objective is to evaluate how rock mineralogy, methane injection, and Ca(OH)2 addition influence hydrogen generation, carbon redistribution, and stage-dependent reaction pathways during microwave exposure. Microwave heating experiments were conducted using Permian Basin reservoir rocks under three experimental conditions: rock-only experiments under Ar atmosphere, CH4–Ar experiments without additive, and CH4–Ar experiments containing 5 wt% Ca(OH)2. Methane-assisted experiments were performed under continuous injection of 30 standard cubic centimeters per minute (sccm) CH4 and 30 sccm Ar. Based on thermal runaway behavior, each experiment was divided into three operational stages: Before Thermal Runaway (BR), After Thermal Runaway–Decrease in Microwave Power (ARD), and After Thermal Runaway– Increase in Microwave Power (ARI). Temperature and gas composition were continuously monitored throughout the experiments. The rock-only experiments demonstrated that hydrogen generation can occur intrinsically from hydrocarbon-bearing rocks under microwave heating, even without externally injected methane. However, hydrogen production did not correlate solely with kerogen content, indicating that mineralogy strongly influences hydrogen-generation pathways. Correlation analyses suggested that kerogen decomposition initially generated CH4, CO, and CO2, followed by secondary hydrocarbon reactions associated with H2 and C2 hydrocarbon formation. Methane-assisted experiments substantially increased hydrogen production; however, identical methane injection rates produced significantly different hydrogen yields among the rock samples, confirming that mineralogical composition controls methaneconversion behavior under microwave heating conditions. The addition of Ca(OH)2 significantly altered carbon evolution behavior in a stage-dependent manner. During the BR stage, Ca(OH)2 reduced gas-phase CO2 production, particularly in carbonate-rich rocks, indicating favorable conditions for in-situ carbonation and carbonate deposition prior to extensive thermal decomposition. The suppression of CO2 during BR became more pronounced with increasing carbonate content of the rock system. After thermal runaway, carbonate-containing systems exhibited enhanced hydrogen generation behavior, suggesting that carbonatederived mineral transformations and carbonate-mediated reactions contribute to high-temperature hydrogen-generation pathways. In carbonate-poor rocks, Ca(OH)2 addition enabled simultaneous URTeC 4493775 2 enhancement of hydrogen production and partial suppression of CO2 release during the post-runaway stages. Overall, the results demonstrate that microwave-assisted hydrogen generation is governed by dynamically evolving interactions among kerogen decomposition, methane activation, mineral transformations, carbonate formation/decomposition, and thermal runaway behavior. This work introduces in-situ carbonate engineering with Ca(OH)2 as a strategy for coupling hydrogen generation with partial insitu carbon management under microwave heating conditions.

03 NATURAL GAS↗

DOE OSTI2024

Reduction of Iron (III) Oxide in Microwaves Toward Gasification Studies

The purpose of this study is to reduce hematite (Fe2O3) using hydrogen (H2), carbon monoxide (CO), and methane (CH4) gases using microwave irradiation. Conventional temperature programmed reduction of iron phase transformation under H2, CO, and CH4 agree with the literature. Furthermore, the activation energy for the iron phase transformation in a conventional reactor was in the order of H2>CO>CH4, suggesting that CH4 was the best reductant to initiate the reduction at a much lower temperature than CO, and CO was significantly better than H2 atmosphere. Due to the uneven temperature distribution, the apparent activation energy of microwave reduction under H2 was approximately 1/4th when compared to the conventional reduction in H2. X-ray diffraction (XRD) analysis showed a mixed oxide phase in microwave reduction as opposed to the clear phase transformation in conventional studies. To combat the temperature measurement issues in microwave studies, fiber optic sensors and Forward Looking InfraRed (FLIR) sensors were used to acquire the actual temperature distribution in the catalyst bed. Therefore, a reasonably accurate activation energy estimation was achieved in the catalyst bed. Combining these with the characterization and quantification of the different iron phases in microwave reduction will provide a blueprint for future microwave-assisted gasification studies.

Aireddy, Divakar Reddy↗

DOE OSTI2025

Potential Risks Associated with Short-Term Hydrogen Storage in Methane Reservoirs

Hydrogen (H2) has been identified as a flexible energy carrier with zero emissions. It is possible to utilize H2 by storing Hyblend, or H2 blended with CH4, in existing natural gas infrastructure. However, the compatibility of adapting the current CH4 storage strategies to include H2 injection has not been fully demonstrated. It is essential that we understand the impact of H2 gas on the naturally occurring microbial community of subsurface storage reservoirs before deploying large-scale H2-CH4 storage. We designed a series of experiments that allowed us to identify potential challenges of HyBlend Storage in existing methane reservoirs (Figure 1). First, we characterized two field fluid samples from a methane reservoir located in Western United States. Next, we used these samples to complete a series of short-term reactor experiments at reservoir conditions for a natural gas (100% CH4) and HyBlend (80% CH4/20% H2) storage environment.

geomicrobiology↗

DOE OSTI2026

Upgrading Biogas through in situ Conversion of Carbon Dioxide to Biomethane in Anaerobic Digesters

Organic waste streams generated by wastewater treatment plants, agricultural operations, and food processing industries represent an important yet underutilized opportunity for renewable energy production in the United States. Through anaerobic digestion, these waste streams can produce biogas, a mixture primarily composed of methane (CH4) and carbon dioxide (CO2), that can be upgraded to pipeline-quality natural gas. However, most existing upgrading technologies remove CO2 from biogas rather than utilizing it, leaving a significant portion of the potential energy unused. This project investigates a novel biological upgrading approach that converts CO2 into additional CH4 by supplying hydrogen (H2) to specialized microorganisms capable of performing hydrogenotrophic methanation. The main challenges associated with biological biogas upgrading are related to hydrogen supply, gas-liquid mass transfer, and process stability. First, due to the high cost of hydrogen gas, it is preferable that H2 be produced on-site using renewable energy sources such as wind or solar power. Second, hydrogen has low solubility in liquids, which limits its availability to microorganisms and requires strategies to improve gas dissolution and transfer within the reactor. Third, process inhibition may occur as a result of increased pH caused by CO2 consumption or elevated H2 partial pressure, both of which can negatively affect methanogenic activity. Although research in these areas has advanced during the course of this project, these challenges have not yet been fully resolved. To date, the biological systems that have achieved the highest methane concentrations are typically ex-situ reactors, where operational conditions can be more easily controlled. For this reason, the findings of the present project remain highly relevant. The project goal was to develop an innovative system that can accomplish biogas upgrading via biological conversion of CO2 to CH4, in a novel hybrid approach that combines the advantages of both in-situ and ex-situ systems. The proposed system employs a three-phase upflow anaerobic bioreactor with H2 delivery through a gas-permeable membrane, enabling efficient hydrogen transfer and microbial conversion. Under optimized operating conditions, the system achieved 99% H2 consumption and 90% CO2 conversion. A subsequent gas cleaning stage was implemented to further improve gas quality and meet target purity standards. The upgraded gas composition reached 97.7% CH4, 2.2% CO2, and 0.97% O2, while H2S concentrations remained below detection limits. In addition, a flue gas-driven inorganic thermoelectric generator (TEG) system was designed and experimentally validated as a potential source of electricity for H2 production. The system consisted of six TEG modules connected in series and achieved an open-circuit voltage of 4.5 V and a maximum power output of 224 mW at a temperature difference of approximately 53.5 °C, demonstrating effective conversion of waste heat into electrical power under simulated flue gas conditions. Finally, a comprehensive techno-economic analysis was completed to evaluate the capital and operating costs associated with the proposed system. The results provide important insights to guide future scale-up, optimization, and potential deployment of integrated biological biogas upgrading technologies.

09 BIOMASS FUELS↗

DOE OSTI2023

Biomethanation to Upgrade Biogas to Pipeline Grade Methane

NREL is working closely with DOE, Electrochaea GmbH, and Southern California Gas Company (SoCalGas) to reduce costs of a biomethanation process capable of megawatt-scale deployment that upgrades organic biogas waste streams to produce pipeline quality renewable natural gas (RNG). Biomethanation is a two-step process using a single-celled methanogenic archaea that converts low-carbon low-cost hydrogen (H2) and waste carbon dioxide (CO2) to produce renewable methane (CH4). The process upgrades the biogenic CO2 - while allowing the CH4 to pass through - from biogas sources like dairies, wastewater treatment plants, and landfills. The CH4 produced is a drop-in direct replacement fuel and producers can participate in the growing number of carbon markets; like California's Low Carbon Fuel Standard and the Federal Renewable Fuel Standard. NREL and Argonne National Laboratory have completed a life cycle analysis using the GREET model to show that the biomethanation process produces RNG that is carbon negative even when H2 production via low-temperature water electrolysis is driven by the existing carbon intensity of California's electricity grid. And of course, even further carbon negative (-233 kg CO2e/kWh) when the electricity is produced from low-carbon sources like wind and solar. Leveraging lessons learned from operating SoCalGas' 700L 18-bar bioreactor system, NREL is designing and building a flexible RD&D platform that will enable field trials at biogas and other CO2 sources. A custom 16' long trailer will house a 20L 18-bar bioreactor, 3 - 25 kW proton exchange membrane electrolyzer, and dosing, thermal, and controls systems to support operations with only power, biogas, and water feedstocks required by the field locations. The end-of-project goal is to demonstrate pipeline quality RNG production (> 95% CH4, < 4% H2, <1% CO2, < 0.2% O2 and < 4 parts per million H2 sulfide) using real biogas feedstocks - thereby recycling both greenhouse gases for injection into the natural gas network or to be used onsite.

biogas upgrading↗

DOE OSTI2026

Seasonal variation in methane ebullition in a temperate hydropower reservoir impacts annualized estimates

Estimates of ebullitive methane (CH4) emissions from reservoirs are highly uncertain, often based on spatial and temporal upscaling from a limited number of sampling sites and periods. While some of these estimates may adjust for seasonal variation in temperature, they rarely account for drawdown and the resulting changes in site depth and the areal extent of the reservoir. In Douglas Reservoir (Tennessee, USA), we conducted monthly sampling of 20 sites over 1 year to capture temporal and spatial variation in CH4 ebullition. We then compared various approaches for obtaining annualized, whole-reservoir ebullition estimates. CH4 ebullition fluxes were zero-inflated and highly skewed, with fluxes rising appreciably above zero in July and peaking in autumn. Estimates that did not account for drawdown overestimated annualized rates by 20%, though with high uncertainty. Seasonal variability and hotspots strongly influence annualized ebullition estimates and are important to account for in inventories and global upscaling.

Cardall, Anna [Brigham Young University]↗

DOE OSTI2026

Improving anaerobic digestion of sewage sludge to renewable natural gas by the Advanced Pretreatment & Anaerobic Digestion technology (APAD): Pilot testing

Conventional anaerobic digestion (AD) of sewage sludge in wastewater treatment facilities suffers from low carbon conversion efficiency (CCE = 40%) and requires costly CO2 removal for injection of the produced CH4 into the natural gas grid. To address these limitations, we developed the Advanced Pretreatment and Anaerobic Digestion (APAD) process. This integrates Advanced Wet Oxidation & Steam Explosion (AWOEx) pretreatment of residual sludge after conventional AD, followed by biogas upgradation using a novel methanogenic strain, Methanothermobacter wolfeii BSEL, converting CO2 with H2 into CH4 or RNG (renewable natural gas). Pilot-scale results demonstrated that AWOEx pretreatment achieved a CCE of 62% for the residual sludge, 68% higher than the conventional AD process. The CH4 production was further increased by 79%. Subsequent biogas upgrading in a trickling bed reactor with H2 further enhanced total methane output by 100% and resulted in a final CO2 concentration of =3%. The integrated APAD process achieved a remarkable overall CCE of 83%, resulting in a 200% increase in RNG output when compared to conventional AD. Techno-economic analysis revealed that AWOEx pretreatment alone reduced sludge treatment costs from $494 to $253 per ton of dry solids. The complete APAD process incurred a higher cost of treatment of $530 per ton, driven by prices for bottled H2. The process did, however, show gains in energy recovery and decarbonization. Renewable H2, which may reduce in price in the near future, can positively improve the economics of biogas upgrading for the APAD process.

Life Cycle Assessment (LCA)↗

DOE OSTI2021

Experimental and theoretical determinations of hydrogen isotopic equilibrium in the system CH 4 —H 2 —H 2 O from 3 to 200°C

The stable isotopic composition of methane (CH 4 ) is commonly used to fingerprint natural gas origins. Over the past 50 years, there have been numerous proposals that both microbial and thermogenic CH 4 can form in or later attain hydrogen isotopic equilibrium with water (H 2 O) and carbon isotopic equilibrium with carbon dioxide (CO 2 ). Evaluation of such proposals requires knowledge of the equilibrium fractionation factors between CH 4 and H 2 O or CO 2 at the temperatures where microbial and thermogenic CH 4 form in or are found in the environment, which is generally less than 200°C. Experimental determinations of these fractionation factors are only available above 200°C, requiring extrapolation of these results beyond the calibrated range or the use of theoretical calculations at lower temperatures. Here, we provide a calibration of the equilibrium hydrogen isotopic fractionation factor for CH 4 and hydrogen gas (H 2 ) ( D α CH4(g)–H2(g) ) based on experiments using γ-Al 2 O 3 and Ni catalysts from 3 to 200°C. Results were regressed as a 2 nd order polynomial of 1000 × ln D α CH4(g)–H2(g) vs. 1/T (K -1 ) yielding: 1000 × l n D α C H 4 ( g ) - H 2 ( g ) = 3.5317 × 10 7 T 2 + 2.7749 × 10 5 T - 179.48 We combine this calibration with previous experimental determinations of hydrogen isotope equilibrium between H 2 , H 2 O(g), and H 2 O(l) and we provide an interpolatable experimental calibration of 1000 × ln D α CH4(g)–H2O(l) from 3 to 200°C. Our resulting 4th order polynomial is the following equation: 1000 × l n D α C H 4 ( g ) - H 2 O l = - 7.9443 × 10 12 T 4 + 8.7772 × 10 10 T 3 - 3.4973 × 10 8 T 2 + 5.4398 × 10 5 T - 382.05 At 3°C, the value from our calibration differs by 93‰ relative to what would be calculated based on the extrapolation of the only experimental calibration currently available to temperatures below its calibrated range (lowest temperature of 200°C; Horibe and Craig, 1995). We additionally provide new theoretical estimates of hydrogen isotopic equilibrium between CH 4 (g), H 2 (g), and H 2 O(g) and carbon isotopic equilibrium between CH 4 (g) and CO 2 (g) using Path Integral Monte Carlo (PIMC) calculations. Our PIMC calculations for hydrogen isotopic equilibrium between CH 4 and H 2 agree 1:1 with our experiments. Finally, we compile carbon and hydrogen isotopic measurements of CH 4 , CO 2 , and H 2 O from various environmental systems and compare observed differences between carbon and hydrogen isotopes to those expected based on isotopic equilibrium. We find that isotopic compositions of some microbial gases from marine sedimentary, coalbed, and shale environments are consistent with those expected for CH 4 H 2 O(l) hydrogen and CH 4 CO 2 carbon isotopic equilibrium. In contrast, microbial terrestrial and pure culture gases are not consistent with both CH 4 H 2 O(l) hydrogen and CH 4 CO 2 carbon isotopic equilibrium. Overall, these results are explained qualitatively using previously developed conceptual models that link free energy gradients available to microorganisms to the degree that their enzymes can promote isotope-exchange reactions between CH 4 , CO 2 , and H 2 O.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

MgO Nanostructures on Au(111) as Catalysts for Low-Temperature Methane Activation and C-C Coupling

The selective conversion of methane (CH4) under mild conditions remains challenging due to strong C-H bonds and catalyst coking. We systematically investigated sub-monolayer MgO nanostructures on Au(111), where two-dimensional (2D) MgO islands with stable Mg-O-Au interfaces catalyze low-temperature CH4 activation and C-C coupling. Upon CH4 exposure at 300 K, surface-bound CHx and C2Hx intermediates formed and persisted post-evacuation, indicating robust CHx-O-Mg linkages. Temperature-programmed studies revealed that C-H activation and C-C coupling intensify with heat: the CHx signal grew continuously while the C2Hx signal reached a plateau at 400-500 K. O 1s and Mg 2p attenuation confirmed adsorption of the hydrocarbons on MgO. Catalytic tests at 500 K yielded C2H6 (70%) and C2H4 (30%) without coking, underscoring MgO's role as an active catalyst. These results offer new design principles for developing coke-resistant and low-temperature methane upgrading catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Chemical influence of ammonia on suppressing soot formation pathways

There is interest in mixing ammonia (NH3) with hydrocarbons, as this decreases overall CO2 emissions from the fuel mixture when burned. Co-firing NH3 with hydrocarbons like methane (CH4) also enables stable combustion over a larger set of operating conditions in engines and gas turbines than firing only NH3 permits. When NH3 is co-fired with hydrocarbons, the influence of NH3 on soot formation chemistry becomes relevant. In this work, soot concentrations in laminar nonpremixed co-flow flames of NH3/CH4 and N2/CH4 were analyzed using color-ratio pyrometry. The concentrations of combustion species (CH4, CO2, H2O, O2, C2H2, C6H6, HCN) across the different flames were also determined using on-line electron-impact mass spectrometry. The flames were also interrogated with 2D CFD simulations, which employ a detailed chemical mechanism tailored to capturing fuel-nitrogen chemistry. Addition of NH3 to CH4 flames was found to decrease soot concentrations more significantly than N2-addition (Fig. 1). The NH3/CH4 flames were found to have higher flame temperatures than the N2/CH4 flames, implying the suppression of soot afforded by NH3 is due to a chemical influence of NH3, as opposed to thermal or dilution effects. Based on experimental and simulated soot volume fractions and species concentrations, soot formation pathways affected by NH3 are postulated.

10 SYNTHETIC FUELS↗

DOE OSTI2020

Observations of Greenhouse Gas Changes across Summer Frontal Boundaries in the Eastern United States

Our knowledge about synoptic-scale variations of atmospheric CO2 produced by interactions between mid-latitude cyclones and regional-scale surface fluxes remains limited by scarcity of observations. We synthesize observations of greenhouse gases (GHG) with respect to frontal passages to understand how GHG distributions change vertically and horizontally during a synoptic event. We use the airborne in-situ measurements of GHGs collected during the first Atmospheric Carbon and Transport–America (ACT) summer field campaign across three regions of the eastern US. We find that frontal structures are consistently and clearly associated with spatially coherent, significant changes in GHG composition. Warm sector CO2 mole fractions (henceforth, [CO2]) are significantly higher than those in the cold sector. The CO2 frontal differences (5-30 ppm) are largest in the atmospheric boundary layer (ABL) with smaller differences (3-5 ppm) in the free troposphere (FT). Bands of elevated CO2 (5-20 ppm enhancement compared to warm-sector mean [CO2]) repeatedly occurred in the ABL adjacent to the frontal boundary. Analyses of 84 vertical profiles reveal higher [CO2] in the FT than in the ABL in the cold-sector, the opposite pattern in the warm-sector. Average ABL-to-FT [CO2] differences are 12 ppm and -6 ppm in the warm and cold sectors, respectively. The same analysis for CH4 shows higher [CH4] in the ABL than in the FT in both warm and cold sectors with at least 30-ppb higher ABL-to-FT [CH4] differences in the warm-sector than in the cold-sector. The observational analyses presented here define new metrics for model evaluation of GHG transport.

Pal, Sandip↗

DOE OSTI2021

Soil metabolome response to whole-ecosystem warming at the Spruce and Peatland Responses under Changing Environments experiment

In this study, a suite of complementary environmental geochemical analyses, including NMR and gas chromatography-mass spectrometry (GC-MS) analyses of central metabolites, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) of secondary metabolites, and lipidomics, was used to investigate the influence of organic matter (OM) quality on the heterotrophic microbial mechanisms controlling peatland CO2, CH4, and CO2:CH4 porewater production ratios in response to climate warming. Our investigations leverage the Spruce and Peatland Responses under Changing Environments (SPRUCE) experiment, where air and peat warming were combined in a whole-ecosystem warming treatment. We hypothesized that warming would enhance the production of plant-derived metabolites, resulting in increased labile OM inputs to the surface peat, thereby enhancing microbial activity and greenhouse gas production. Because shallow peat is most susceptible to enhanced warming, increases in labile OM inputs to the surface, in particular, are likely to result in significant changes to CO2 and CH4 dynamics and methanogenic pathways. In support of this hypothesis, significant correlations were observed between metabolites and temperature consistent with increased availability of labile substrates, which may stimulate more rapid turnover of microbial proteins. An increase in the abundance of methanogenic genes in response to the increase in the abundance of labile substrates was accompanied by a shift toward acetoclastic and methylotrophic methanogenesis. Our results suggest that as peatland vegetation trends toward increasing vascular plant cover with warming, we can expect a concomitant shift toward increasingly methanogenic conditions and amplified climate–peatland feedbacks.

Wilson, Rachel M.↗