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At least 541 records · Page 30

Support Effect Studied on Thin-Film Perovskites

Some functional oxides exhibit strong support effects but typically have low surface areas and stabilities that negate the promotional effects. The primary goal of our work in the past three years was to develop high-surface-area versions of these supports by Atomic Layer Deposition onto stable supports, then use these to understand how the oxide supports affect the metal catalytic properties. The primary application targeted for these materials was methane oxidation and related reactions for emissions control. Systems of particular interest were supported, precious metals on thin-film perovskites in order to develop “intelligent” catalysts in which the metal can reversibly ex-solve from perovskite lattices. This following report lists the papers that were published with the support of this DOE grant, together with a brief summary of the results from each paper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas Flare Technology Assessment and R&D Recommendations

The purpose of developing this report is to provide an assessment of gas flare technologies, with the intent of informing future high-impact R&D investments that can be used to realize significant reductions in methane and other greenhouse gas (GHG) emissions from U.S. oil and natural gas (ONG) operations

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Exhaust gas emissions of a vortex breakdown stabilized combustor

Exhaust gas emission data are described for a swirl stabilized continuous combustor. The combustor consists of confined concentric jets with premixed fuel and air in the inner jet and air in the outer jet. Swirl may be induced in both inner and outer jets with the sense of rotation in the same or opposite directions (co-swirl and counter-swirl). The combustor limits NO emissions by lean operation without sacrificing CO and unburned hydrocarbon emission performance, when commercial-grade methane and air fired at one atmosphere without preheat are used. Relative swirl direction and magnitude are found to have significant effects on exhaust gas concentrations, exit temperatures, and combustor efficiencies. Counter-swirl gives a large recirculation zone, a short luminous combustion zone, and large slip velocities in the interjet shear layer. For maximum counter-swirl conditions, the efficiency is low.

Yetter, R. A.↗

NASA DEVELOP’s Approach to Building Individual and Institutional Capacity to Use Earth Observations for Atmospheric Monitoring and Decision Making

NASA DEVELOP, an Applied Sciences’ Capacity Building program, introduces individuals and institutions to the applications of NASA Earth observation data in an effort to help inform decision making. The program employs early career professionals to conduct rapid feasibility studies tailored specific to partner needs. Each year, DEVELOP conducts 50-60 feasibility studies that highlight the capabilities of Earth observations for measuring and monitoring a wide range of environmental phenomena. For this presentation, example projects will be highlighted that focus on monitoring air quality and pollution, wildfire emissions, and greenhouse gasses such as methane. An overview of example projects, the user communities involved, satellite data used, and lessons learned will be shared.

Capacity Building↗

Sensitive Response of Atmospheric Oxidative Capacity to the Uncertainty in the Emissions of Nitric Oxide (NO) From Soils in Amazonia

Abstract Soils are a major source of nitrogen oxides, which in the atmosphere help govern its oxidative capacity. Thus the response of soil nitric oxide (NO) emissions to forcings such as warming or forest loss has a meaningful impact on global atmospheric chemistry. We find that the soil emission rate of NO in Amazonia from a common inventory is biased low by at least an order of magnitude in comparison to tower‐based observations. Accounting for this regional bias decreases the modeled global methane lifetime by 1.4%–2.6%. In comparison, a fully deforested Amazonia, representing a 37% decrease in global emissions of isoprene, decreases methane lifetime by at most 4.6%, highlighting the sensitive response of oxidation rates to changes in emissions of NO compared to those of terpenes. Our results demonstrate that improving our understanding of soil NO emissions will yield a more accurate representation of atmospheric oxidative capacity.

Geology↗

Production, fuel properties and combustion testing of an iso-olefins blendstock for modern vehicles

With the increasing pressure to decarbonize the transportation sector, exploring strategies that can reduce emissions from light-duty vehicles (LDV) has become critical. Bioblendstocks that allow for higher engine efficiency and fuel economy could complement vehicle electrification and help reach carbon neutrality by 2050. In this context, the potential of a mixture of iso-olefins as a bioblendstock was investigated for multimode boosted spark-ignition (SI)/advanced compression ignition (ACI) engine operation designed to achieve higher overall vehicle fuel economy. By establishing the relationship between the molecular structure of iso-olefins and research octane number (RON), octane sensitivity (S) (i.e., the difference between RON and motor octane number [MON]), and phi-sensitivity a dimethyl-hexenes rich olefins mixture (DMHROM) was identified as a preferred blendstock for SI/ACI combustion engines. Here, a pathway for DMHROM production from biomass-derived ethanol was developed and scaled up. More than 1 gallon of DMHROM blendstock was produced for fuel properties assessment including engine testing. Measurements in a Cooperative Fuel Research Engine showed that the DMHROM blendstock possesses a RON of 94 and S of 13.5, and blends synergistically. Rapid compression machine tests coupled with single-cylinder gasoline direct injection engine measurements demonstrated the 20 vol.% DMHROM blend has higher phi-sensitivity than an olefin-free gasoline base fuel and a typical California Reformulated Gasoline Blendstock for Oxygenate Blending (CARBOB) gasoline fuel. These results demonstrate the potential of DMHROM for improving gasoline fuel performance and quality for operation under ACI conditions. The effectiveness of the aftertreatment system in mitigating emissions was verified and showed that the pure DMHROM blendstock and 20 vol.% blend would not increase non-methane organic gases, NO x , and carbon monoxide (CO) emissions. The DMHROM blendstock was found to slightly decrease sooting tendency when added to a gasoline-base fuel (i.e., ~6% reduction at 20 vol.% blending level). Oxidation stability and lubricant compatibility were both confirmed for the 20 vol.% blend. Overall, these results demonstrate that dimethyl-hexenes have potential for improving engine efficiency and fuel economy while meeting emissions regulations and ASTM specifications for gasoline fuel.

09 BIOMASS FUELS↗

Effective radiative forcing from emissions of reactive gases and aerosols - a multi-model comparison

This paper quantifies the pre-industrial (1850) to present-day (2014) effective radiative forcing (ERF) of anthropogenic emissions of NOX, volatile organic compounds (VOCs; including CO), SO2, NH3, black carbon, organic carbon, and concentrations of methane, N2O and ozone-depleting halocarbons, using CMIP6 models. Concentration and emission changes of reactive species can cause multiple changes in the composition of radiatively active species: tropospheric ozone, stratospheric ozone, stratospheric water vapour, secondary inorganic and organic aerosol, and methane. Where possible we break down the ERFs from each emitted species into the contributions from the composition changes. The ERFs are calculated for each of the models that participated in the AerChemMIP experiments as part of the CMIP6 project, where the relevant model output was available. The 1850 to 2014 multi-model mean ERFs (± standard deviations) are −1.03 ± 0.37 W/sq.m for SO2 emissions, −0.25 ± 0.09 W/sq.m for organic carbon (OC), 0.15 ± 0.17 W/sq.m for black carbon (BC) and −0.07 ± 0.01 W/sq.m for NH3. For the combined aerosols (in the piClim-aer experiment) it is −1.01 ± 0.25 W/sq.m. The multi-model means for the reactive well-mixed greenhouse gases (including any effects on ozone and aerosol chemistry) are 0.67 ± 0.17 W/sq.m for methane (CH4), 0.26 ± 0.07 W/sq.m for nitrous oxide (N2O) and 0.12 ± 0.2 W/sq.m for ozone-depleting halocarbons (HC). Emissions of the ozone precursors nitrogen oxides (NOx), volatile organic compounds and both together (O3) lead to ERFs of 0.14 ± 0.13, 0.09 ± 0.14 and 0.20 ± 0.07 W/sq.m respectively. The differences in ERFs calculated for the different models reflect differences in the complexity of their aerosol and chemistry schemes, especially in the case of methane where tropospheric chemistry captures increased forcing from ozone production.

radiative forcing↗

Chemical Characterization of Natural Gas Leaking from Abandoned Oil and Gas Wells in Western Pennsylvania

The U.S. Environmental Protection Agency estimates that there are over 3.2 million abandoned wells in the United States. Studies conducted on gas emissions from abandoned wells have been limited to methane, a powerful greenhouse gas, due to concerns regarding climate change. However, volatile organic compounds (VOCs), including benzene, a known human carcinogen, are known to be associated with upstream oil and gas development and hence could also be released when methane is emitted to the atmosphere. In this investigation, we analyze gas from 48 abandoned wells in western Pennsylvania for fixed gases, light hydrocarbons, and VOCs and estimate associated emission rates. We demonstrate that (1) gas from abandoned wells contains VOCs, including benzene; (2) VOCs are emitted from abandoned wells, the magnitude of which depends on the flow rate and concentration of VOCs in the gas stream; and (3) nearly one-quarter of abandoned wells are located within 100 m of buildings, including residences, in Pennsylvania. Together, these observations indicate that further investigation is necessary to determine whether emissions from abandoned wells pose an inhalation risk to people living, working, or congregating near abandoned wells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Workshop on the Impacts of Aviation on Climate Change

Projections indicate that demand for aviation transportation will increase by more than two fold over the next few decades. Timely action is needed to understand and quantify the potential climate impacts of aviation emissions particularly given the sustained lapse over the last several years in U.S. research activities in this area. In response to the stated needs, a group of international experts participated in the Workshop on the Impacts of Aviation on Climate Change during June 7-9, 2006 in Boston, MA. The workshop focus was on the impacts of subsonic aircraft emissions in the UT/LS region and on the potential response of the climate system. The goals of the workshop were to assess and document the present state of scientific knowledge, to identify the key underlying uncertainties and gaps, to identify ongoing and further research needed, to explore the development of climate impact metrics, and to help focus the scientific community on the aviation-climate change research needs. The workshop concluded that the major ways that aviation can affect climate, in agreement with the 1999 assessment by the Intergovernmental Panel on Climate Change (IPCC), are the direct climate effects from CO2 and water vapor emissions, the indirect forcing on climate resulting from changes in the distributions and concentrations of ozone and methane as a primary consequence of aircraft nitrogen oxide (NOx) emissions, the direct effects (and indirect effects on clouds) from emitted aerosols and aerosol precursors, and the climate effects associated with contrails and cirrus cloud formation. The workshop was organized in three subgroups: (1) Effects of aircraft emissions on the UT/LS chemical composition, (2) Effects of water and particle emissions on contrails and on cirrus clouds, and (3) Impacts on climate from aircraft emissions and identification of suitable metrics to measure these impacts. The workshop participants acknowledged the need for focused research specifically to address the uncertainties and gaps in our understanding of current and projected impacts of aviation on climate and to develop metrics to better characterize these impacts. This may entail coordination and/or expansion of existing and planned climate research programs, or new activities. Such efforts should include strong and continuing interactions among the science and aviation communities as well as policymakers to develop well-informed decisions.

Wuebbles, Don↗

Assessing Non-CO2 Climate-Forcing Emissions and Mitigation in Sub-Saharan Africa

There are few direct measurements of anthropogenic climate-forcing emissions in Africa, making it difficult to accurately assess current emissions and to anticipate changes in future emissions. Emissions databases suggest that sub-Saharan Africa (SSA), home to less than 15 of the world's population, is responsible for 11 of anthropogenic methane (CH4) and 18 of anthropogenic nitrous oxide (N2O) emissions globally, though this includes substantial emissions from biomass burning that would occur in the absence of contemporary anthropogenic activity, and which may be over-estimated. SSA is also an important source of precursors to the greenhouse gas tropospheric ozone, and of mineral dust, which has a range of impacts on climate. Eliminating food insecurity and poverty is likely to take priority over greenhouse gas mitigation in the region, so innovations in mitigation must focus on ways to reduce emissions as an ancillary benefit of improving livelihoods.

Africa↗

Gaseous emissions from Canadian boreal forest fires

CO2-normalized emission ratios for carbon monoxide (CO), hydrogen (H2), methane (CH4), total nonmethane hydrocarbons (TNMHC), and nitrous oxide (N2O) were determined from smoke samples collected during low-altitude helicopter flights over two prescribed fires in northern Ontario, Canada. The emission ratios determined from these prescribed boreal forest fires are compared to emission ratios determined over two graminoid (grass) wetlands fires in central Florida and are found to be substantially higher (elevated levels of reduced gas production relative to CO2) during all stages of combustion. These results argue strongly for the need to characterize biomass burning emissions from the major global vegetation/ecosystems in order to couple combustion emissions to their vegetation/ecosystem type.

Cofer, Wesley R., III↗

XMM-Newton X-Ray Observation of Jupiter

Soft X-ray emission has been observed from the disk of both Jupiter and Saturn as well as from the auroral regions of these planets. The low-latitude disk emission as observed by ROSAT, the Chandra X-Ray Observatory, and XMM-Newton appears to be uniformly distributed across the disk and to be correlated with solar activity. These characteristics suggest that the disk x-rays are produced by: (1) the elastic scattering of solar X-rays by atmospheric neutrals and (2) the absorption of solar X-rays in the carbon K-shell followed by fluorescent emission. The carbon atoms are found in methane molecules located below the homopause. In this paper we present the results of calculations of the scattering albedo for soft x-rays. We also show the calculated x-ray intensity for a range of atmospheric abundances for Jupiter and Saturn and for a number of solar irradiance spectra. The model calculations are compared with recent x-ray observations of Jupiter and Saturn. We conclude that the emission of soft x-rays from the disks of Jupiter and Saturn can be largely explained by the scattering and fluorescence of soft x-rays. We suggest that measured x-ray intensities from the disk regions of Jupiter

Waite, J. Hunter↗

Infrared spectroscopy of Jupiter and Saturn

Infrared spectroscopy provides unique insights into the chemistry and dynamics of the atmospheres of Jupiter and Saturn -- and of Titan, the enigmatic satellite of Saturn. The 5 micron spectral region of these objects is transparent to deep levels, and is therefore particularly useful for the identification of molecules in the deep atmosphere at very low (parts per billion) concentrations. In 1991 we obtained data at J, H, K, and M and made repeated observations of Titan's albedo as the satellite orbited Saturn. The J albedo is 12 + -3% greater than the albedo measured in 1979; the H and K albedos are the same. There was no evidence for variations at any wavelength over the eastern half of Titan's orbit. We also obtained low resolution (R = 50) spectra of Titan between 3.1 and 5.1 microns. The spectra contain evidence for CO and CH3D absorptions. Spectra of Callisto and Ganymede in the 4.5 micron spectral region are featureless and give albedos of 0.08 and 0.04 respectively. If Titan's atmosphere is transparent near 5 microns, its surface albedo there is similar to Callisto's. In 1992 and 1993 we obtained further spectroscopic data of Titan with the UKIRT CGS4 spectrometer. We discovered two unexpected and unexplained spectral features in the 3-4 micron /spectrum of Titan. An apparent emission feature near the 3 micron (nu3) band of methane indicates temperatures higher than known to be present in Titan's upper stratosphere and may be caused by unexpected non-LTE emission. An absorption feature near 3.47 microns may be caused by absorption in solid grains or aerosol's in Titan's clouds. The feature is similar, but not identical to organics in the interstellar matter and in comets.

Knacke, Roger F.↗

Revolutionizing Methane Transformation with the Dual Production of Aromatics and Electricity in a Protonic Ceramic Electrocatalytic Membrane Reactor

Reducing the energy and carbon intensity of the conventional chemical processing industry can be achieved by electrochemically transforming natural gases into higher-value chemicals with higher efficiency and near-zero emissions. In this work, the direct conversion of methane to aromatics and electricity has been achieved in a protonic ceramic electrocatalytic membrane reactor through the integration of a proton-conducting membrane assembly and a trimetallic Pt–Cu/Mo/ZSM-5 catalyst for the nonoxidative methane dehydro-aromatization reaction. In this integrated system, a remarkable 15.6% single-pass methane conversion with an 11.4% benzene yield has been demonstrated, while a peak power density of 276 mW cm –2 is obtained at 700 °C. The enhanced 15.7% increase in conversion and 16.0% improvement in the yield are observed when compared with the thermochemical process, which is attributed to the shift of reaction equilibrium by the removal of hydrogen through the protonic membrane. Concurrently, the faster H2 removal at a higher electrical current gave rise to a higher methane conversion and benzene yield. Furthermore, the catalyst can be efficiently regenerated by eliminating carbon deposition. A stable cell potential is maintained for 45 h under a constant current load of 0.13 A cm –2 . Lastly, the dual production of aromatics and electricity in the electrocatalytic membrane reactor has been demonstrated to be an attractive approach for decarbonizing chemical processing.

aromatic compounds↗

Analysis of Present Day and Future OH and Methane Lifetime in the ACCMIP Simulations

Results from simulations performed for the Atmospheric Chemistry and Climate Modeling Intercomparison Project (ACCMIP) are analysed to examine how OH and methane lifetime may change from present day to the future, under different climate and emissions scenarios. Present day (2000) mean tropospheric chemical lifetime derived from the ACCMIP multi-model mean is 9.8+/-1.6 yr (9.3+/-0.9 yr when only including selected models), lower than a recent observationally-based estimate, but with a similar range to previous multi-model estimates. Future model projections are based on the four Representative Concentration Pathways (RCPs), and the results also exhibit a large range. Decreases in global methane lifetime of 4.5 +/- 9.1% are simulated for the scenario with lowest radiative forcing by 2100 (RCP 2.6), while increases of 8.5+/-10.4% are simulated for the scenario with highest radiative forcing (RCP 8.5). In this scenario, the key driver of the evolution of OH and methane lifetime is methane itself, since its concentration more than doubles by 2100 and it consumes much of the OH that exists in the troposphere. Stratospheric ozone recovery, which drives tropospheric OH decreases through photolysis modifications, also plays a partial role. In the other scenarios, where methane changes are less drastic, the interplay between various competing drivers leads to smaller and more diverse OH and methane lifetime responses, which are difficult to attribute. For all scenarios, regional OH changes are even more variable, with the most robust feature being the large decreases over the remote oceans in RCP8.5. Through a regression analysis, we suggest that differences in emissions of non-methane volatile organic compounds and in the simulation of photolysis rates may be the main factors causing the differences in simulated present day OH and methane lifetime. Diversity in predicted changes between present day and future OH was found to be associated more strongly with differences in modelled temperature and stratospheric ozone changes. Finally, through perturbation experiments we calculated an OH feedback factor (F) of 1.24 from present day conditions (1.50 from 2100 RCP8.5 conditions) and a climate feedback on methane lifetime of 0.33+-0.13 yr/K, on average. Models that did not include interactive stratospheric ozone effects on photolysis showed a stronger sensitivity to climate, as they did not account for negative effects of climate-driven stratospheric ozone recovery on tropospheric OH, which would have partly offset the overall OH/methane lifetime response to climate change.

atmospheric composition↗

Valorizing the carbon byproduct of methane pyrolysis in batteries

While low-cost natural gas remains abundant, the energy content of this fuel can be utilized without greenhouse gas emissions through the production of molecular hydrogen and solid carbon via methane pyrolysis. In the absence of a carbon tax, methane pyrolysis is not economically competitive with current hydrogen production methods unless the carbon byproducts can be valorized. In this work, we assess the viability of the carbon byproduct produced from methane pyrolysis in molten salts as high-value-added anode or conductive additive for secondary Li-ion and Na-ion batteries. Raman characterization and electrochemical differential capacity analysis demonstrate that the use of molten salt mixtures with catalytically-active FeCl 3 - or MnCl 2 result in more graphitic carbon co-products. These graphitic carbons exhibit the best electrochemical performance (up to 272 mAh/g of reversible capacity) when used as Li-ion anodes. For all carbon samples studied here, disordered carbon domains and retained salt species trapped and/or intercalated into the carbon structure were identified by X-ray photoelectron and multinuclear solid-state nuclear magnetic resonance spectroscopy. The latter lead to reduced electrochemical activity and reversibility, and poorer rate performance compared to commercial carbon anodes. The electronic conductivity of the pyrolyzed carbons is found to be highly dependent on their purity, with the purest carbon exhibiting an electronic conductivity nearly on par with that of commercial carbon additives. These findings suggest that more effective removal of the salt catalyst could enable applications of these carbons in secondary batteries, providing a financial incentive for the large-scale implementation of methane pyrolysis for “low-carbon” hydrogen production.

08 HYDROGEN↗

Evolution of Ni-Mo/MgO during catalytic methane pyrolysis to produce base-growth nanotubes

Catalytic pyrolysis of methane is a promising approach for affordable hydrogen production without CO 2 emissions. While this process is thermodynamically appealing compared to steam reforming, the high stability of methane requires severe conditions, making catalyst stability challenging. Here, we report the behavior of a highly promising Ni-Mo/MgO catalyst, which greatly outperforms its Ni/MgO, Mo/MgO, and Ni-Mo/SiO 2 counterparts at atmospheric pressure. At 800°C, nearly 229 g of carbon nanotubes per gram of Ni are produced. We propose that this superior performance results from the phase evolution of the catalyst, which exsolves stable nickel catalyst particles under reaction conditions. We further reveal that molybdenum carbide formation reduces sintering and adheres the active catalytic particles to the support throughout the reaction, enabling catalyst reuse. Several characterization techniques (same-spot TEM, XPS, XRD, and Raman) are employed to examine catalyst morphology at every step, fostering a deeper understanding of its catalytic activity and stability.

36 MATERIALS SCIENCE↗

COMPASS-FME Synoptic Site Tree Greenhouse Gas Concentrations

These data are tree stem greenhouse gas concentrations collected from tree gas wells at some of the COMPASS-FME (Coastal Observations, Mechanisms, and Predictions Across Systems and Scales; see https://compass.pnnl.gov/) 'synoptic' sites in the Chesapeake Bay region: Moneystump (MSM), Goodwin Islands (GWI), and GCReW (GCW). The sap flow monitoring trees at these sites in the Upland (UP) and Transition (TR) zones were cored and had gas wells installed at breast height. There were also some dead standing trees cored, gas well installed, and sampled at MSM and GWI. The GCW UP samples overlap with the TEMPEST experiment control plot, so the GCW UP data was pulled from the TEMPEST page and included here. These data provide crucial information about possible pathways for the greenhouse gas (carbon dioxide and methane, CO2 and CH4 respectively) production and emission (or in the case of CH4, perhaps taken up from) the atmosphere.All data are plain text CSV (comma separated value) files and require no special software to read.Updated 2025-10-09 to fix two missing dates (lines 77 and 78 in the data file).

54 ENVIRONMENTAL SCIENCES↗