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All sourcesNASA NTRSDOE OSTI
NASA NTRS2014

Up in the Air: Methane and Ozone over California

The Alpha Jet Atmospheric eXperiment (AJAX) at NASA Ames Research Center measures in-situ carbon dioxide, methane, and ozone concentrations in the Earth's atmosphere several times each month. The AJAX team studies local photochemical smog production, provides data for long-term studies of trans-Pacific transport of pollution, and supports the observation of greenhouse gases from satellites. The aircraft is stationed at Moffett Field and is outfitted with scientific instruments to measure trace gas concentrations and 3-D wind speeds. Vertical profiles from near the surface up to approximately 27,000 ft are routinely collected over locations such as: Merced, Edwards Air Force Base, Railroad Valley, NV, and over the Pacific Ocean. In addition, boundary layer measurements scout for surface sources such as fires, oil gas infrastructure, livestock, and urban pollution. This talk will focus on recent observations over dairy operations, fossil fuel infrastructure, and wildfires.

Trace Gas Concentrations↗
NASA NTRS2023

Observational Constraints Reduce Model Spread but Not Uncertainty in Global Wetland Methane Emission Estimates

The recent rise in atmospheric methane (CH 4 ) concentrations accelerates climate change and offsets mitigation efforts. Although wetlands are the largest natural CH 4 source, estimates of global wetland CH 4 emissions vary widely among approaches taken by bottom-up (BU) process-based biogeochemical models and top-down (TD) atmospheric inversion methods. Here, we integrate in situ measurements, multi-model ensembles, and a machine learning upscaling product into the International Land Model Benchmarking system to examine the relationship between wetland CH 4 emission estimates and model performance. We find that using better-performing models identified by observational constraints reduces the spread of wetland CH 4 emission estimates by 62% and 39% for BU- and TD-based approaches, respectively. However, global BU and TD CH 4 emission estimate discrepancies increased by about 15% (from 31 to 36 TgCH 4 year −1 ) when the top 20% models were used, although we consider this result moderately uncertain given the unevenly distributed global observations. Our analyses demonstrate that model performance ranking is subject to benchmark selection due to large inter-site variability, highlighting the importance of expanding coverage of benchmark sites to diverse environmental conditions. We encourage future development of wetland CH 4 models to move beyond static benchmarking and focus on evaluating site-specific and ecosystem-specific variabilities inferred from observations.

Kuang-Yu Chang↗
NASA NTRS1986

Atmospheric CH4, CO and OH from 1860 to 1985

Studies have shown that atmospheric methane, CO and the gaseous OH radical are interdependent: if CH4, CO or OH is perturbed, background concentrations of the other two constituents are affected. Perturbations to OH alter photooxidation rates of numerous natural and anthropogenic trace gases and affect lifetimes of those species that pass from the earth's surface to the free troposphere and stratosphere. It is now known that global atmospheric methane concentrations are increasing; less definite data suggest that carbon monoxide is also increasing. Even before the measurements reported in nine literature references, modeling studies of CH4-CO-OH coupling had led to predictions (Chameides, Liu and Ciceronne, 1977; Sze, 1977; and Hameed, Pinto and Stewart 1979) of future increases of CH4 and CO. A photochemical model is used to look backwards in time by simulating the trace-gas composition of the unpolluted troposphere at the start of the industrial era (taken as 1860) and at intervals up to 1985. It is found that the OH concentration in the background troposphere has decreased significantly and O3 has increased due to increases of CH4 and CO; calculated changes depend on temporal trends of NOx (NOx = NO + NO2), for which no historical data are available. The calculations allow recent trace-gas trends affecting background chemistry and climate to be viewed in a longer-term context.

Thompson, A. M.↗
DOE OSTI2022

Porewater Geochemical Assessment of Seismic Indications for Gas Hydrate Presence and Absence: Mahia Slope, East of New Zealand’s North Island

We compare sediment vertical methane flux off the Mahia Peninsula, on the Hikurangi Margin, east of New Zealand’s North Island, with a combination of geochemical, multichannel seismic and sub-bottom profiler data. Stable carbon isotope data provided an overview of methane contributions to shallow sediment carbon pools. Methane varied considerably in concentration and vertical flux across stations in close proximities. At two Mahia transects, methane profiles correlated well with integrated seismic and TOPAS data for predicting vertical methane migration rates from deep to shallow sediment. However, at our “control site”, where no seismic blanking or indications of vertical gas migration were observed, geochemical data were similar to the two Mahia transect lines. This apparent mismatch between seismic and geochemistry data suggests a potential to underestimate gas hydrate volumes based on standard seismic data interpretations. To accurately assess global gas hydrate deposits, multiple approaches for initial assessment, e.g., seismic data interpretation, heatflow profiling and controlled-source electromagnetics, should be compared to geochemical sediment and porewater profiles. A more thorough data matrix will provide better accuracy in gas hydrate volume for modeling climate change and potential available energy content.

03 NATURAL GAS↗
NASA NTRS2017

Variability and Quasi-Decadal Changes in the Methane Budget over the Period 2000-2012

Following the recent Global Carbon Project (GCP) synthesis of the decadal methane (CH4) budget over 2000- 2012, we analyse here the same dataset with a focus on quasi-decadal and inter-annual variability in CH4 emissions. The GCP dataset integrates results from top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models (including process-based models for estimating land surface emissions and atmospheric chemistry), inventories of anthropogenic emissions, and data-driven approaches. The annual global methane emissions from top-down studies, which by construction match the observed methane growth rate within their uncertainties, all show an increase in total methane emissions over the period 2000-2012, but this increase is not linear over the 13 years. Despite differences between individual studies, the mean emission anomaly of the top-down ensemble shows no significant trend in total methane emissions over the period 2000-2006, during the plateau of atmospheric methane mole fractions, and also over the period 2008-2012, during the renewed atmospheric methane increase. However, the top-down ensemble mean produces an emission shift between 2006 and 2008, leading to 22 [16-32] Tg CH4 yr(exp -1) higher methane emissions over the period 2008-2012 compared to 2002-2006. This emission increase mostly originated from the tropics, with a smaller contribution from mid-latitudes and no significant change from boreal regions. The regional contributions remain uncertain in top-down studies. Tropical South America and South and East Asia seem to contribute the most to the emission increase in the tropics. However, these two regions have only limited atmospheric measurements and remain therefore poorly constrained. The sectorial partitioning of this emission increase between the periods 2002-2006 and 2008-2012 differs from one atmospheric inversion study to another. However, all top-down studies suggest smaller changes in fossil fuel emissions (from oil, gas, and coal industries) compared to the mean of the bottom-up inventories included in this study. This difference is partly driven by a smaller emission change in China from the top-down studies compared to the estimate in the Emission Database for Global Atmospheric Research (EDGARv4.2) inventory, which should be revised to smaller values in a near future. We apply isotopic signatures to the emission changes estimated for individual studies based on five emission sectors and find that for six individual top-down studies (out of eight) the average isotopic signature of the emission changes is not consistent with the observed change in atmospheric 13CH4. However, the partitioning in emission change derived from the ensemble mean is consistent with this isotopic constraint. At the global scale, the top-down ensemble mean suggests that the dominant contribution to the resumed atmospheric CH4 growth after 2006 comes from microbial sources (more from agriculture and waste sectors than from natural wetlands), with an uncertain but smaller contribution from fossil CH4 emissions. In addition, a decrease in biomass burning emissions (in agreement with the biomass burning emission databases) makes the balance of sources consistent with atmospheric 13CH4 observations. In most of the top-down studies included here, OH concentrations are considered constant over the years (seasonal variations but without any inter-annual variability). As a result, the methane loss (in particular through OH oxidation) varies mainly through the change in methane concentrations and not its oxidants. For these reasons, changes in the methane loss could not be properly investigated in this study, although it may play a significant role in the recent atmospheric methane changes as briefly discussed at the end of the paper.

Saunois, Marielle↗
NASA NTRS2020

Constraining Remote Oxidation Capacity with ATom Observations

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation in the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias with the exception of wintertime NOy, for which a model overestimate may indicate insufficient wet scavenging and/or missing loss on seasalt aerosol but large uncertainties remain that require further studies of NOy partitioning and removal in the troposphere. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by new estimates of ocean VOC sources and additional modeled reactivity in this region would be difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOC, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in modeled acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean VOC sources in the model increases annual surface cOHRmod by 10 % and improves model-measurement agreement for acetaldehyde particularly in winter but cannot resolve the model summertime bias. Doing so would require a 100 Tg yr−1 source of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Travis, Katherine R.↗
NASA NTRS1985

Causes of increasing atmospheric methane - Depletion of hydroxyl radicals and the rise of emissions

A combination of anthropogenic activities and a possible decline of global concentrations for the hydroxyl radicals that formerly removed methane from the atmosphere are cited as potential causes for the 1.3 percent/year rise of atmospheric methane levels. Calculations are presented which show that much of the methane increase over the last 200 years is probably to be divided among the two main sources in the proportions of 70 percent for anthropogenic generation and 30 percent for hydroxyl radical depletion. It is projected that in 20 years, average tropospheric concentrations of methane may be about 20 percent greater than 1980 levels. The current abundance of hydroxyl radicals may be 20 percent less than two centuries ago.

Khalil, M. A. K.↗
NASA NTRS2010

Lidar Measurements of Methane and Applications for Aircraft and Spacecraft

Atmospheric methane levels have remained relatively constant over the last decade around 1.78 parts per million (ppm) but observations since 2007 show that levels may be increasing. This trend may be caused by increased fossil fuel production, rice farming, livestock and landfills, but the underlying causes are quite uncertain. One hypothesis is that reservoirs of carbon trapped in the permafrost regions of northern Canada, Europe, and Siberia thaw as global temperatures rise and are releasing increasing amounts of methane. Another hypothesis points to increased production of methane by microbes as the permafrost warms. Currently most observations of greenhouse gases are limited to in-situ (surface and tower sites) and limited airborne in-situ measurements. Space column density measurements are starting to become available from the GOSAT mission. Although methane survives for a shorter time in the atmosphere than CO2, its impact on climate change per molecule is about 23 times than that of CO2. Accurate global observations of several greenhouse gases, including methane, are urgently needed in order to better understand climate change processes and to reduce the uncertainty in the carbon budget. Differential absorption lidar is a well-established technique to measure atmospheric gases, and methane has optical absorption bands near 1.65,2.2,3.4 and 7.8 micron. The near infrared overtones lines of CH4 near 1650 nm are relatively free of interference from other species. There are absorption lines near 1651 nm which are both temperature insensitive and have line strengths well suited for lidar measurements. We have developed a laser and demonstrated lidar measurements of CH4 using lines in this band. Our laser uses a narrow linewidth 1064 nm laser pulse passing through a nonlinear crystal. We generate the tunable laser signals near 1651 nm by using the optical parametric amplification (OPA) process. Inside the crystal the 1064 nm beam overlaps with an injection seed laser near 1651 nm from a wavelength tunable diode laser. Incident photons from the pump laser pulse are converted into two photons, with one at the wavelength of the injection seeder. The wavelength of the OPA output is tuned via the wavelength of diode laser. Our laser is tunable, operates near 1651 nm and generates approximately 4 uJ/pulse at 6 KHz. We vary the emission wavelengths within this band by tuning the diode laser's wavelength. We have used this OPA transmitter to make measurements of CH4 at various pressures in a gas cell and over open outdoor horizontal paths. We have measured the lineshape of methane in a 6 cm long cell at various energy levels with this transmitter, with excellent agreement with the lineshape calculated by HITRAN. We have also measured the absorption lineshape of atmospheric methane in an open 3 km outdoor path. The agreement between the measurements and HITRAN, for 1746 ppb and 760 Torr was quite good. We have also made pulsed two wavelength lidar measurements of methane line absorption in the column to a tower at 1.5 km range. These used on- and off-line wavelengths of 1650.957 nm, and 1651.072 nm, and a 20 cm diameter receiver telescope with an infrared PMT detector. The absorption of the on-line photons was 30%. The methane column absorption was estimated via HITRAN, and was in good agreement with the expected methane absorption for a concentration of 1750 ppm. Finally we have calculated the measurement performance of an airborne methane lidar using this transmitter, as well as the energy and telescope scaling needed for a lidar for space. These results, and more details of our experiments will be described in the presentation.

Riris, Haris↗
DOE OSTI2020

Chamber Flux and Porewater Concentration of CH4, CO2 and N2O, 2018, Columbia River bank at the Hanford site, WA, USA

This is the corresponding observations data for the paper: Jorge A Villa; Garrett J Smith; Yang Ju; Lupita Renteria; Jordan C Angle; Evan Arntzen; Samuel F Harding; Huiying Ren; Xingyuan Chen; Audrey H Sawyer; Emily B Graham; James C Stegen; Kelly C Wrighton; Gil Bohrer (2020) Methane and nitrous oxide porewater concentrations and surface fluxes of a regulated river. Science of the Total Environment.Greenhouse gas (GHG) emissions from rivers are a critical missing component of current global GHG models. Their exclusion is mainly due to a lack of in-situ measurements and a poor understanding of the spatiotemporal dynamics of GHG production and emissions, which prevents optimal model parametrization. We combined simultaneous observations of porewater concentrations along different beach positions and depths, and surface fluxes of methane and nitrous oxide at a plot scale in a large regulated river during three water stages: rising, falling, and low. Our goal was to gain insights into the interactions between hydrological exchanges and GHG emissions and elucidate possible hypotheses that could guide future research on the mechanisms of GHG production, consumption, and transport in the hyporheic zone (HZ). Results indicate that the site functioned as a net source of methane. Surface fluxes of methane during river water stages at three beach positions (shallow, intermediate and deep) correlated with porewater concentrations of methane. However, fluxes were significantly higher in the intermediate position during the low water stage, suggesting that low residence time increased methane emissions. Vertical profiles of methane peaked at different depths, indicating an influence of the magnitude and direction of the hyporheic mixing during the different river water stages on methane production and consumption. The site acted as either a sink or a source of nitrous oxide depending on the elevation of the water column. Nitrous oxide porewater concentrations peaked at the upper layers of the sediment throughout the different water stages. River hydrological stages significantly influenced porewater concentrations and fluxes of GHG, probably by influencing heterotrophic respiration (production and consumption processes) and transport to and from the HZ. Our results highlight the importance of including dynamic hydrological exchanges when studying and modeling GHG production and consumption in the HZ of large rivers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Biological conversion of methane to methanol at high H 2 S concentrations with an H 2 S-tolerant methanotrophic consortium

To develop biological biogas to methanol conversion technology without costly hydrogen sulfide (H 2 S) removal, a high H 2 S tolerant methanotrophic consortium (HTMC), was enriched from an anaerobic digester effluent in presence of 5.64 g/m 3 H 2 S in the gas phase. The HTMC can grow stably and produce methanol under conditions with CH 4 /air mixtures containing 5.64 g/m 3 of H 2 S. There is no significant (p>0.05) difference in cell yield or CH 4 to methanol conversion efficiency between trials with different H 2 S concentrations from 0 g/m 3 to 5.64 g/m 3 . Further, under optimal conditions, a cell yield of 0.333 g cells/g CH 4 , a methanol concentration of 0.28 mg/mL, and a CH 4 to methanol conversion efficiency of 0.22 mol/mol were obtained, respectively. Besides methanotrophs (14.85%) and other bacteria, Cyanobacteria were also identified in the HTMC with a high abundancy (32.16%), which could broaden the application of HTMC for simultaneous utilization of CH 4 and CO 2 from raw biogas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

Airborne tunable diode laser sensor for high-precision concentration and flux measurements of carbon monoxide and methane

An airborne tunable diode laser instrument is described that is capable of operating in two measurement modes. One mode provides high precision (0.1 percent CH4; 1 percent CO) measurements of CH4 and CO with a 5 second response time, and a second mode achieves the very fast response time that is necessary to make airborne eddy correlation flux measurements. Examples of data from atmospheric expeditions of the Global Tropospheric Experiment are presented.

Sachse, G. W.↗
DOE OSTI2023

Concentration fluctuations and flammability of cryo-compressed hydrogen and methane jets

Compressed hydrogen stored at cryogenic temperatures has a much higher density than room-temperature storage, which enables large-scale hydrogen storage and transport. An understanding of the release of cryogenic hydrogen from pressurized vessels is needed to evaluate the risk and safety concerns with the use of this fuel. Here, the present work extends the analysis of previous experimental studies that measured the gas concentrations of cryo-compressed hydrogen jets and methane jets using a laser Raman scattering diagnostic system. Since the Raman signals are very small, a denoising algorithm was applied to significantly reduce the noise to enable statistical analysis of the data. The transient features of the turbulent jets were characterized by their concentration intermittencies and probability density functions (PDFs). A two-part PDF was developed to predict the bimodal features of the jet concentration distributions. Then, the flammability factors of the cryogenic jets were calculated based on the intermittency and the PDF.

33 ADVANCED PROPULSION SYSTEMS↗
NASA NTRS2016

Tropospheric Ozone Change from 1980 to 2010 Dominated by Equatorward Redistribution of Emissions

Ozone is an important air pollutant at the surface, and the third most important anthropogenic greenhouse gas in the troposphere. Since 1980, anthropogenic emissions of ozone precursors methane, non-methane volatile organic compounds, carbon monoxide and nitrogen oxides (NOx) have shifted from developed to developing regions. Emissions have thereby been redistributed equatorwards, where they are expected to have a stronger effect on the tropospheric ozone burden due to greater convection, reaction rates and NOx sensitivity. Here we use a global chemical transport model to simulate changes in tropospheric ozone concentrations from 1980 to 2010, and to separate the influences of changes in the spatial distribution of global anthropogenic emissions of short-lived pollutants, the magnitude of these emissions, and the global atmospheric methane concentration. We estimate that the increase in ozone burden due to the spatial distribution change slightly exceeds the combined influences of the increased emission magnitude and global methane. Emission increases in Southeast, East and South Asia may be most important for the ozone change, supported by an analysis of statistically significant increases in observed ozone above these regions. The spatial distribution of emissions dominates global tropospheric ozone, suggesting that the future ozone burden will be determined mainly by emissions from low latitudes.

Zhang, Yuqiang↗
NASA NTRS1990

The effects of fire on biogenic emissions of methane and nitric oxide from wetlands

Enhanced emissions of methane (CH4) and nitric oxide (NO) were measured following three controlled burns in a Florida wetlands in 1987 and 1988. Wetlands are the major global source of methane resulting from metabolic activity of methanogenic bacteria. Methanogens require carbon dioxide, acetate, or formate for their growth and the metabolic production of methane. All three water-soluble compounds are produced in large concentrations during biomass burning. Postfire methane emissions exceeded 0.15 g CH 4/sq m per day. Preburn and postburn measurements of soil nutrients indicate significant postburn increases in soil ammonium, from 8.35 to 13.49 parts per million (ppm) in the upper 5 cm of the Juncus marsh and from 8.83 to 23.75 ppm in the upper 5 cm of the Spartina marsh. Soil nitrate concentrations were found to decrease in both marshes after the fire. These measurements indicate that the combustion products of biomass burning exert an important 'fertilizing' effect on the biosphere and on the biogenic production of environmentally significant atmospheric gases.

Levine, Joel S.↗
NASA NTRS1984

Portable remote laser sensor for methane leak detection

A portable laser system for remote detection of methane gas leaks and concentrations is disclosed. The system transmitter includes first and second lasers, tuned respectively to a wavelength coincident with a strong absorption line of methane and a reference wavelength which is weakly absorbed by methane gas. The system receiver includes a spherical mirror for collecting the reflected laser radiation and focusing the collected radiation through a narrowband optical filter onto an optial detector. The filter is tuned to the wavelength of the two lasers, and rejects background noise. The output of the optical detector is processed by a lock-in detector synchronized to the chopper, and which measures the difference between the first wavelength signal and the reference wavelength signal.

Grant, W. B.↗
NASA NTRS2016

Martian Atmospheric Methane Plumes from Meteor Shower Infall: A Hypothesis

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

Fries, M.↗
NASA NTRS1975

Solar-wind interactions - Nature and composition of lunar atmosphere

The nature and composition of the lunar atmosphere are examined on the basis of solar-wind interactions, and the nature of the species in the trapped-gas layer is discussed using results of theoretical and experimental investigations. It is shown that the moon has a highly tenuous atmosphere consisting of various species derived from five sources: solar-wind interaction products, cosmic-ray interaction products, effects of meteoritic impacts, planetary degassing, and radioactive-decay products. Atmospheric concentrations are determined for those species derived from solar-wind protons, alpha particles, and oxygen ions. Carbon chemistry is briefly discussed, and difficulties encountered in attempts to determine quantitatively the concentrations of molecular oxygen, atomic oxygen, carbon monoxide, carbon dioxide, and methane are noted. The calculated concentrations are shown to be in good agreement with observations by the Apollo 17 lunar-surface mass spectrometer and orbital UV spectrometer.

Mukherjee, N. R.↗
DOE OSTI2022

LaNi x Fe 1–x O 3 as flexible oxygen or carbon carriers for tunable syngas production and CO 2 utilization

The current study reports LaFe 1–x Ni x O 3–δ redox catalysts as flexible oxygen or carbon carriers for CO2 utilization and tunable production of syngas at relatively low temperatures (~700 °C), in the context of a hybrid redox process. Specifically, perovskite-structured LaFe 1–x Ni x O 3–δ with seven different compositions (x = 0.4–1) were prepared and investigated. Cyclic experiments under alternating methane and CO 2 flows indicated that all the samples exhibited favorable reactive performance: CH 4 and CO 2 conversions varied between 85% and 98% and 70–88%, respectively. While H 2 /CO ratio from Fe-rich redox catalysts was ~2.3:1 in the methane conversion step, Ni-rich catalysts produced a concentrated (~ 93.7 vol%) hydrogen stream via methane cracking. The flexibility of LaFe 1–x Ni x O 3–δ to produce syngas (or hydrogen) with tunable compositions was found to be governed by the iron/nickel (Fe/Ni) ratio. Redox catalysts with higher Fe contents act as a lattice oxygen carrier via chemical looping partial oxidation (CLPOx) of methane whereas those with higher Ni contents function as a carbon carrier via chemical looping methane cracking (CLMC) scheme. XRD analysis and temperature-programmed reactions revealed that both types of catalysts involve the formation of La 2 O 3 and Ni 0 /Ni-Fe phases under the methane environment. The ability to re-incorporate La 2 O 3 and Ni/Fe into a perovskite structure gives rise to oxygen-carrying capacity whereas stable Ni 0 or Ni/Fe phases would catalyze methane cracking without lattice oxygen exchange in the reaction cycles. Here, temperature programmed oxidation and Raman spectroscopy indicated the presence of graphitic and amorphous carbon species, which were effectively gasified by CO 2 to produce concentrated CO. Stability tests over LaFe 0.5 Ni 0.5 O 3 and LaNiO 3 revealed that the redox performance was stable over a span of 50 cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗