Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “dioxide”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 937 records · Page 52
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Fossil fuel CO 2 emissions over metropolitan areas from space: A multi-model analysis of OCO-2 data over Lahore, Pakistan

Urban areas, where gathering more than 55% of the global population, alone contributed to more than 70% of anthropogenic fossil fuel carbon dioxide (CO 2ff ) emissions. Accurate quantification of CO 2ff emissions from urban areas is of great importance to the formulation of global warming mitigation policies to achieve carbon neutrality by 2050. Satellite-based inversion techniques are unique among “top-down” approaches, potentially allowing us to track CO 2ff emission changes over cities globally. However, its accuracy is still limited by incomplete background information, cloud blockages, aerosol contaminations, and uncertainties in models and emission inventories used as prior. To evaluate the current potential of space-based quantification techniques, we present the first attempt to monitor long-term changes in CO 2ff emissions based on the OCO-2 satellite measurements of column-averaged dry-air mole fractions of CO 2 (X CO2 ) over a fast-growing Asian metropolitan area: Lahore, Pakistan. We first examined the OCO-2 data availability at global scale. About 17% of OCO-2 soundings are marked as high-quality soundings by quality flags over the global 70 most populated cities over the period 2014-2019. Cloud blockage and aerosol contamination are the two main causes of data loss. As an attempt to recover additional soundings, we evaluated the effectiveness of OCO-2 quality flags at the city level by comparing three flux quantification methods (WRF-Chem, X-STILT, and flux cross-sectional integration method), all based on the Open-Data Inventory for Anthropogenic Carbon dioxide (ODIAC) product. The satellite/bottom-up emissions (OCO-2/ODIAC) ratios of the high-quality tracks better converged across the three methods compared to the all-data tracks with reduced uncertainties in emissions. Thus, OCO-2 quality flags are useful filters of low-quality OCO-2 retrievals at local scales, although originally designed for global-scale studies. All three methods consistently suggested that the ratio medians are greater than 1, which implies that the ODIAC slightly underestimated the CO2ff emissions over Lahore. Additionally, our estimation of the a posteriori CO2ff emission trend was about 734 kt C/year (i.e., an annual 6.7% increase). 10,000 Monte Carlo simulations of the Mann-Kendall upward trend test showed that less than 10% prior uncertainty for 8 tracks (or less than 20% prior uncertainty for 25 tracks) is required to achieve a greater-than-50% trend significant possibility at a 95% confidence level. It implies that the trend is driven by the prior and not due to the assimilation of OCO-2 retrievals. The key to improving the role of satellite data in CO 2 emission trend detection lies in collecting more frequent high-quality tracks near metropolitan areas to achieve significant constraints from X CO2 retrievals.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Reconciliation of asynchronous satellite-based $\mathrm{NO_2}$ and $\mathrm{XCO_2}$ enhancements with mesoscale modeling over two urban landscapes

Fossil fuel carbon dioxide (CO 2ff ), the main driver of global warming and climate change, is often co-emitted with nitrogen oxides (NO x ) and precursors to ground-level ozone from anthropogenic sources like power plants or vehicles. In urban and suburban areas, satellite-based NO 2 can be used as a proxy to track the emissions of CO 2ff . Because of NO 2 ’s shorter lifetime, urban NO 2 plumes are more distinguishable from backgrounds and more sensitive to variations in emissions. However, the combination of these two gases is limited by the asynchrony among NO 2 and CO 2 monitoring satellites. We used CO 2ff simulated by the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) model to reconcile the tropospheric NO 2 vertical column density (VCD) from the Tropospheric Monitoring Instrument (TROPOMI) and column-averaged dry-air mole fractions of carbon dioxide enhancements (ΔXCO 2 ) from Orbiting Carbon Observatory 3 (OCO-3) Snapshot Area Maps (SAMs) over a multicity area, Washington D.C.-Baltimore (DC-Balt), and a basin city, Mexico City. NO 2 /CO 2ff ratios over DC-Balt are smaller than Mexico City, indicative of stricter emission restrictions, a more combustion-efficient vehicle fleet, and higher combustion efficiency due to lower altitude in DC-Balt. For single-track cases, the spatial correlations between NO 2 and ΔXCO 2 over Mexico City are stronger than DC-Balt because the NO 2 and CO 2 are mostly trapped in the valley of Mexico City, while DC-Balt is severely affected by distant sources (i.e., US East Coast cities). Using multi-track averaging, spatial correlation coefficients increase with the number of days used for averaging. The correlations reached a maximum when averaging >12 continuous images for DC-Balt and > 10 continuous images for Mexico City. This finding indicates that multi-track averaging using modeled CO 2ff as a proxy is helpful to filter the noise in single-track images, to cancel the interference from distant sources, and to magnify correlations between NO 2 and CO 2ff . Mexico City showed stronger spatial correlations but weaker temporal correlations than DC-Balt due to biomass burning hot spots and large transport errors caused by the trapping effects of the surrounding mountains. Tracking the 20-day moving average of CO 2ff emissions using TROPOMI NO 2 seems technically feasible, considering the relationship between correlation coefficients and the number of available satellite images.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Volumetric efficiency and pressure pulsations of a triplex reciprocating supercritical CO 2 pump

A reciprocating triplex pump has been integrated into a closed-loop supercritical carbon dioxide test facility. The pump is designed to compress liquid or supercritical carbon dioxide and has a maximum volumetric flow rate of 51 L/min. A sweep across the pump’s speed range of 100–1000 rev/min was performed with inlet conditions between 60 and 160 bar. The volumetric efficiency was found to increase as pump speed increased from 10 to 40 % before it plateaued at higher pump speeds. The mechanical efficiency increased linearly with pump speed and was not affected by system pressure. Pressure pulsations caused by the plungers and valves were also measured at each speed. Additionally, a 35-liter buffer volume, connected near the pump’s discharge was isolated at each speed to determine its effectiveness as a pulsation dampener. Overall the reciprocating pump was shown to perform exceptionally with liquid or supercritical inlet conditions applicable to many supercritical fluid applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Funding a Just Transition Away from Coal in the U.S. Considering Avoided Damage from Air Pollution

Abstract Coal is declining in the U.S. as part of the clean energy transition, resulting in remarkable air pollution benefits for the American public and significant costs for the industry. Using the AP3 integrated assessment model, we estimate that fewer emissions of sulfur dioxide, nitrogen oxides, and primary fine particulate matter driven by coal’s decline led to $300 billion in benefits from 2014 to 2019. Conversely, we find that job losses driven by less coal plant and mining activity resulted in $7.84 billion in foregone wages over the same timeframe. While the benefits were greatly distributed (mostly throughout the East), costs were highly concentrated in coal communities. Transferring a small fraction of the benefits to workers could cover these costs while maintaining societal net benefits. Forecasting coal fleet damages from 2020 to 2035, we find that buying out or replacing these plants would result in $589 billion in air quality benefits, which considerably outweigh the costs. The return on investment increases when policy targets the most damaging capacity, and net benefits are maximized when removing just facilities where marginal benefits exceed marginal costs. Evaluating competitive reverse auction policy designs akin to Germany’s Coal Exit Act, we find that adjusting bids based on monetary damages rather than based only on carbon dioxide emissions – the German design – provides a welfare advantage. Our benefit–cost analyses clearly support policies that drive a swift and just transition away from coal, thereby clearing the air while supporting communities needing assistance.

Dennin, Luke R. (ORCID:0000000205405520)↗
DOE OSTI2021

Thermal Energy Transport in Oxide Nuclear Fuel

To efficiently capture the energy of the nuclear bond, advanced nuclear reactor concepts seek solid fuels that must withstand unprecedented temperature and radiation extremes. In these advanced fuels, thermal energy transport under irradiation is directly related to reactor performance as well as reactor safety. The science of thermal transport in nuclear fuel is a grand challenge as a result of both computational and experimental complexities. Here we provide a comprehensive review of thermal transport research on two actinide oxides: one currently in use in commercial nuclear reactors, uranium dioxide (UO 2 ), and one advanced fuel candidate material, thorium dioxide (ThO 2 ). In both materials, heat is carried by lattice waves or phonons. Crystalline defects caused by fission events effectively scatter phonons and lead to a degradation in fuel performance over time. Bolstered by new computational and experimental tools, researchers are now developing the foundational work necessary to accurately model and ultimately control thermal transport in advanced nuclear fuels. We begin by reviewing research aimed at understanding thermal transport in perfect single crystals. The absence of defects enables studies that focus on the fundamental aspects of phonon transport. Next, we review research that targets defect generation and evolution. Here the focus is on ion irradiation studies used as surrogates for damage caused by fission products. We end this review with a discussion of modeling and experimental efforts directed at predicting and validating mesoscale thermal transport in the presence of irradiation defects. While efforts in these research areas have been robust, challenging work remains in developing holistic tools to capture and predict thermal energy transport across widely varying environmental conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Reactivity of CO 2 with Utica, Marcellus, Barnett, and Eagle Ford Shales and Impact on Permeability

We report that in order to reduce greenhouse gas emissions while recovering hydrocarbons from unconventional shale formations, processes that make use of carbon dioxide to enhance oil recovery while storing carbon dioxide (CO 2 ) should be considered. Here, we examine samples from three shale basins across the United States (Utica and Marcellus Shales in the Appalachian Basin, Barnett Shale in the Bend Arch-Ft. Worth Basin, and Eagle Ford in the Western Gulf Basin) to address the following questions: (1) do changes from reaction with CO 2 and fluids at the micrometer and nanometer scale alter flow pathways and, in turn, impact hydrocarbon production, CO 2 storage, and seal integrity and (2) can CO 2 or fluid reactivity be predicted based on physical or chemical properties of shale formations? Experiments were conducted at 40 °C and 10.3 MPa to characterize the interaction between CO 2 and shale using X-ray diffraction (XRD), carbon and sulfur analysis, in situ Fourier transform infrared spectroscopy (FT-IR), feature relocation scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), mercury (Hg) intrusion porosimetry, and Brunauer-Emmett-Teller (BET) surface area and pore size analysis coupled with density functional theory (DFT) methods. Changes in mechanical, physical, and flow properties of shale cores due to CO 2 exposure were addressed using a New England Research Autolab 1500 and Xenon X-ray computed tomography (CT) scanning. Results showed that CO 2 did not promote significant reactivity with the shale if water was not present; only shales with swelling clays or residual interstitial pore water reacted with dry CO 2 to promote reactivity in shale. When water was added as a reactant, CO 2 formed carbonic acid and reacted with the shale to dissolve carbonate pockets, etched and pitted the shale matrix surfaces, and increased the microporosity and decreased nanoporosity. Porosity and permeability increased appreciably in core shale samples after exposure to CO 2 saturated fluid due to dissolution of carbonate. Shale mechanical properties were not altered. Trends were not observed that could tie CO 2 or fluid reactivity to physical or chemical properties of the shale formations at the basin scale from the samples we examined. However, if the shale contained significant amounts of carbonate and water was available to react with the CO 2 , pore sizes were altered in the matrix and permeability and porosity increased.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2025

Diversifying the Materials and Technologies for the Future of Energy Storage

It is increasingly important to meet the growing global energy demand driven by factors such as population growth, electrification, and the rapid development of emerging economies, while minimizing the environmental harm caused by carbon dioxide emissions. Although fossil fuels remain an abundant and inexpensive energy source, there is a global consensus on the critical importance of addressing climate change and an increasing urgency to reduce carbon dioxide emissions without hindering economic growth. This challenge is particularly daunting due to the significant transformations required in electricity generation systems, transportation, and industrial processes. A significant portion of our energy still comes from burning fossil fuels, which poses harmful effects on the environment. Transitioning to renewable energy sources like solar and wind is essential, as these sources provide a low-carbon pathway for power generation and have become increasingly cost-competitive with fossil fuels. However, they face the inherent challenge of intermittency. Thus, energy storage systems (ESS) are essential not only to address this issue but also to accommodate the increasing adoption of electric vehicles (EVs). Lithium-ion batteries (LIBs) are still the predominant ESS used for these applications; however, they suffer from issues related to scarce and harmful resources, safety, and socio-economic impacts. This underscores the need for alternative energy storage systems beyond LIBs. Here, in this review, we discuss the diversification, repurposing, and recycling of ESS to meet the projected energy demand while minimizing environmental harm.

batteries↗
DOE OSTI2021

Methane Generation from CO 2 with a Molecular Rhenium Catalyst

The atomic-level tunability of molecular structures is a compelling reason to develop homogeneous catalysts for challenging reactions such as the electrochemical reduction of carbon dioxide to valuable C 1 –C n products. Of particular interest is methane, the largest component of natural gas. Herein, we report a series of three isomeric rhenium tricarbonyl complexes coordinated by the asymmetric diimine ligands 2-(isoquinolin-1-yl)-4,5-dihydrooxazole ( quin-1-oxa ), 2-(quinolin-2-yl)-4,5-dihydrooxazole ( quin-2-oxa ), and 2-(isoquinolin-3-yl)-4,5-dihydrooxazole ( quin-3-oxa ) that catalyze the reduction of CO 2 to carbon monoxide and methane, albeit the latter with a low efficiency. To our knowledge, these complexes are the first examples of rhenium(I) catalysts capable of converting carbon dioxide into methane. Re(quin-1-oxa)(CO) 3 Cl ( 1 ), Re(quin-2-oxa)(CO) 3 Cl ( 2 ), and Re(quin-3-oxa)(CO) 3 Cl ( 3 ) were characterized and studied using a variety of electrochemical and spectroscopic techniques. In bulk electrolysis experiments, the three complexes reduce CO 2 to CO and CH 4 . When the controlled-potential electrolysis experiments are performed at -2.5 V (vs Fc +/0 ) and in the presence of the Brønsted acid 2,2,2-trifluoroethanol, methane is produced with turnover numbers that range from 1.3 to 1.8. Isotope labeling experiments using 13 CO 2 atmosphere produce 13 CH 4 ( m / z = 17) confirming that methane originates from CO 2 reduction. Theoretical calculations are performed to investigate the mechanistic aspects of the 8e – /8H + reduction of CO 2 to CH 4 . Overall, a ligand-assisted pathway is proposed to be an efficient pathway in the formation of CH 4 . Delocalization of the electron density on the (iso)quinoline moiety upon reduction stabilizes the key carbonyl intermediate leading to additional reactivity of this ligand. These results should aid the development of more robust catalytic systems that produce CH 4 from CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Intramolecular Electrostatic Effects on O 2 , CO 2 , and Acetate Binding to a Cationic Iron Porphyrin

Noncovalent electrostatic interactions are important in many biological and chemical reactions, especially those that involve charged intermediates. There has been a growing interest in using electrostatic ligand designs—placing charges in the second coordination sphere—to improve molecular reactivity, catalysis, and electrocatalysis. For instance, an iron porphyrin bearing four cationic ortho -trimethylanilinium groups, Fe( o -TMA), has been reported to be an exceptional electrocatalyst for both the carbon dioxide reduction reaction (CO 2 RR) and the oxygen reduction reaction (ORR). These reactions involve many different steps, and it is not evident which steps are affected by the four positive charges, or why. By comparing Fe( o -TMA) with the related iron-tetraphenylporphyrin, this work examines how covalently positioned charged groups affect substrate binding and other key pre-equilibria of both the ORR and CO 2 RR, specifically acetate, dioxygen, and carbon dioxide binding. This study is among the first to directly measure the effects of electrostatics on ligand-binding. The results show that adding electrostatic groups to a catalyst design often results in a complex interplay of multiple effects, including changes in pre-equilibria prior to substrate binding, combinations of through-space and inductive contributions, and effects of ionic strength and solution dielectric. The inverse half-order dependence of binding constant on ionic strength is proposed as a clear marker for an electrostatic effect. Overall, the conclusions provide guidance for the increasingly popular electrostatic ligand designs in catalysis and other reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Oxidative Grafting for Catalyst Synthesis in Surface Organometallic Chemistry

The development of new methods of catalyst synthesis with the potential to generate active site structures orthogonal to those accessible by traditional protocols is of great importance for discovering new materials for addressing challenges in the evolving energy and chemical economy. Here, in this work, the generality of oxidative grafting of organometallic and well-defined molecular metal precursors onto redox-active surfaces such as manganese dioxide (MnO 2 ) and lithium manganese oxide (LiMn 2 O 4 ) is investigated. Nine molecular metal precursors are explored, spanning groups 4–11 and each of the three periods of the transition metal series. The byproducts of the oxidative grafting reaction, a mixture of protodemetalation and ligand homocoupling for several organometallic precursors, was found to provide insights into the mechanism of the grafting reaction, suggesting oxidation of both the metal d-orbitals, as well as the metal–carbon σ-bonds, resulting in ejection of the ligand radical fragment. Analysis of the supported structures and oxidation state by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) suggests that several of the chemisorbed metal ions are intercalated into interstitial vacancies of the surface structure while other complexes form intact molecular fragments on the surface. Proof of concept for the use of this metalation protocol to generate diverse, metal-dependent catalytic performance is demonstrated by the application of these materials in the conversion of cyclohexane to K/A oil (cyclohexanol and cyclohexanone) with tert-butyl hydroperoxide, as well as in the low-temperature (T ≤ 50 °C) oxidation of carbon monoxide to carbon dioxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Optimizing Materials to Boost the Valorization of CO 2 : Tuning Cobalt–Cobalt Interactions on In 2 O 3 -Based Photothermal Catalysts

The valorization of CO 2 is an important challenge within the current panorama, since this molecule is probably the main contributor to climate change. In this study, the synthesis of materials based on a nanostructured batonnet-type indium oxide is carried out. In them, different amounts of Co are introduced, varying between 2 and 8% mol. It is verified that the most active sample in the transformation of carbon dioxide to carbon monoxide contains 6 mol %. of Co. This sample’s activity under dual excitation exceeds the thermal counterpart by more than 30%. After carrying out a complete physical and chemical characterization with the help of X-ray absorption spectroscopy and other techniques, it is shown that catalysts with amounts of cobalt equal to or below 4 mol % contain isolated single-atom species, while those with higher amounts of metal display a Co–Co interaction which triggers the evolution of the samples under reaction conditions. The optimum control of this Co–Co interaction and the nature of the final cobalt-containing species determine dual photothermal catalytic properties. In conclusion, this work establishes a structure–activity relationship to interpret the catalytic behavior of highly dispersed subnanometric cobalt species, and thus an avenue to optimize the photothermal valorization of carbon dioxide.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electrochemical CO2 Reduction over Metal-/Nitrogen-Doped Graphene Single-Atom Catalysts Modeled Using the Grand-Canonical Density Functional Theory

Renewably driven, electrochemical conversion of carbon dioxide into value-added products is expected to be a critical tool in global decarbonization. However, theoretical studies based on the computational hydrogen electrode largely ignore the nonlinear effects of the applied potential on the calculated results, leading to inaccurate predictions of catalytic behavior or mechanistic pathways. Here, we use grand canonical density functional theory (GC-DFT) to model electrochemical CO2 reduction (CO2R) over metal- and nitrogen-doped graphene catalysts (MNCs) and explicitly include the effects of the applied potential. We used GC-DFT to compute the CO2 to CO reaction intermediate energies at -0.3, -0.7, and -1.2 VSHE catalyzed by MNCs each doped with 1 of the 10 3d block metals coordinated by four pyridinic nitrogen atoms. Our results predict that Sc-, Ti-, Co-, Cu-, and Zn-N4Cs effectively catalyze CO2R at moderate to large reducing potentials (-0.7 to -1.2 VSHE). ZnN4C is a particularly promising electrocatalyst for CO2R to CO both at low and moderate applied potentials based on our thermodynamic analysis. Our findings also explain the observed pH independence of CO production over FeN4C and predict that the rate-determining step of CO2R over FeN4C is not *CO2- formation but rather *CO desorption. Additionally, the GC-DFT-computed density of states analysis illustrates how the electronic states of MNCs and adsorbates change non-uniformly with applied potential, resulting in a significantly increased *CO2- stability relative to other intermediates and demonstrating that the formation of the adsorbed *CO2- anion is critical to CO2R activation. This work demonstrates how GC-DFT paves the way for physically realistic and accurate theoretical simulations of reacting electrochemical systems.

CO2 reduction↗
DOE OSTI2026

Spatially Mapping the CO 2 Alkaline Sorbent Diffuse Microenvironment Using Operando Raman Spectroscopy

When designing a chemical process, the local balance of transport and kinetics, collectively referred to as the diffuse microenvironment, plays a critical role in performance but is difficult to directly observe. This work demonstrates a method of two-dimensional spatial chemical mapping of the diffuse microenvironment in the context of alkali metal hydroxide direct air capture of carbon dioxide using a custom operando gas-absorption flow cell along with confocal Raman spectroscopy. Notably, we observe the concentration boundary layer near the gas–liquid interface and elucidate the interplay of carbonate and bicarbonate ions within it while inferring local hydroxide depletion through continuum modeling. These first of their kind observations provide a technique to compare the performance of direct air capture solvents based on diffuse microenvironment dynamics while also providing metrics important for air contactor design such as boundary layer thickness. Overall, this work showcases a new experimental platform to study interfacial diffuse microenvironments in and outside of the field of direct air capture of carbon dioxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Direct Air Capture and Sequestration of CO 2 by Accelerated Indirect Aqueous Mineral Carbonation under Ambient Conditions

Mineralization of gaseous carbon dioxide into solid carbonates using alkaline industrial residues such as coal fly ash has a dual advantage of reducing the carbon dioxide footprint of coal power plants and improving ash utilization. However, the slow mineral carbonation rate under atmospheric conditions is a major challenge, especially when using natural minerals or industrial residues for direct air capture (DAC) of CO 2 . In this study, using coal fly ash samples and concentrated alkali carbonate aqueous solutions as a recyclable solvent, we show the feasibility of coupling mineral carbonation with DAC under atmospheric conditions. Findings show that carbonation efficiency is best under alkaline conditions, achieving as high as ~80% conversion to calcium carbonates within 1 h in a 1.9 M sodium carbonate solution. Based on the experimental results, a process coupling DAC and mineral carbonation that operates entirely under ambient conditions is proposed. Here, the techno-economic and life cycle assessments for the proposed process project a levelized cost of $\$116$–133/t-CO 2 -sequestered (US $\$2019$) and process carbon emissions (GWP) in the range of 0.03–0.25 t-CO 2 e/t-CO 2 -sequestered. Considering the low cost, simplicity, and gigaton-scale sequestration potential, we believe that DAC based on alkaline industrial residue carbonation can be considered a “low-hanging fruit” in the pursuit of negative emissions to combat climate change.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Highlighting the Importance of Authentic Reference Chemicals in the Unambiguous Identification of Unknowns during Routine Sample Analysis─An OPCW Proficiency Test Case

The unequivocal identification of unknown chemicals during routine sample analysis is a constant occurrence in the field of analytical chemistry. The process can be painstakingly tedious, particularly in situations where a tentatively identified unknown may possess isomeric counterparts yielding identical accurate mass values and very similar mass spectra. In this work, we present the experimental process involved in the correct identification of 1,4-oxathiane 4,4-dioxide and differentiation from its constitutional isomer, 2-hydroxyethyl vinyl sulfone, when present in a silica gel matrix featured in the 54th Environmental Organisation for the Prohibition of Chemical Weapons (OPCW) proficiency test. After discovering that the library-generated mass spectrum for 2-hydroxyethyl vinyl sulfone in a preliminary gas chromatography–mass spectrometry (GC-MS) analysis did not match the one from an authentic reference chemical, we embarked on an unknown structure determination campaign involving GC-MS, liquid chromatography-tandem mass spectrometry (LC-MS-MS), and nuclear magnetic resonance (NMR) spectroscopy. All of the information obtained, coupled to the synthesis of an authentic reference chemical, was used to determine the identity of the unknown as 1,4-oxathiane 4,4-dioxide. The process described in this work highlights the important role played by authentic reference chemicals in the identification of unknown chemicals during routine sample analysis.

Chemistry↗
DOE OSTI2021

Atmospheric Carbon and Transport – America (ACT-America) Data Sets: Description, Management, and Delivery

The ACT-America project is a NASA Earth Venture Suborbital-2 mission designed to study the transport and fluxes of greenhouse gases. The open and freely available ACT-America data sets provide airborne in situ measurements of atmospheric carbon dioxide, methane, trace gases, aerosols, clouds, and meteorological properties, airborne remote sensing measurements of aerosol backscatter, atmospheric boundary layer height and columnar content of atmospheric carbon dioxide, tower-based measurements, and modeled atmospheric mole fractions and regional carbon fluxes of greenhouse gases over the Central and Eastern United States. In this study, we conducted 121 research flights during five campaigns in four seasons during 2016–2019 over three regions of the US (Mid-Atlantic, Midwest and South) using two NASA research aircraft (B-200 and C-130). We performed three flight patterns (fair weather, frontal crossings, and OCO-2 underflights) and collected more than 1,140 h of airborne measurements via level-leg flights in the atmospheric boundary layer, lower, and upper free troposphere and vertical profiles spanning these altitudes. We also merged various airborne in situ measurements onto a common standard sampling interval, which brings coherence to the data, creates geolocated data products, and makes it much easier for the users to perform holistic analysis of the ACT-America data products. Here, we report on detailed information of data sets collected, the workflow for data sets including storage and processing of the quality controlled and quality assured harmonized observations, and their archival and formatting for users. Finally, we provide some important information on the dissemination of data products including metadata and highlights of applications of ACT-America data sets.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Benchmark calculations of radiative forcing by greenhouse gases

Changes in concentrations of greenhouse gases lead to changes in radiative fluxes throughout the atmosphere. The value of this change, the instantaneous radiative forcing, varies across climate models, due partly to differences in the distribution of clouds, humidity, and temperature across models, and partly due to errors introduced by approximate treatments of radiative transfer. This paper describes an experiment within the Radiative Forcing Model Intercomparision Project that uses benchmark calculations made with line–by–line models to identify parameterization error in the representation of absorption and emission by greenhouse gases. Clear–sky instantaneous forcing by greenhouse gases is computed using a set of 100 profiles, selected from a re–analysis of present–day conditions, that represent the global annual mean forcing from pre–industrial times to the present–day with sampling errors of less than 0.01 W m –2 . Six contributing line–by–line models agree in their estimate of this forcing to within 0.025 W m –2 while even recently–developed parameterizations have typical errors four or more times larger, suggesting both that the samples reveal true differences among line–by–line models and that parameterization error will be readily identifiable. Agreement among line–by–line models is better in the longwave than in the shortwave where differing treatments of the water vapor vapor continuum affect estimates of forcing by carbon dioxide and methane. The impacts of clouds on instantaneous radiative forcing are estimated from climate model simulations. Here, the adjustment due to stratospheric temperature change by assuming fixed dynamical heating. Adjustments are large only for ozone and for carbon dioxide, for which stratospheric cooling introduces modest non–linearity.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Development of the United States GReenhouse Gas and Air Pollutants Emissions System (GRA 2 PES)

In the U.S., emissions of greenhouse gases and air pollutants are often developed independently. Here, we describe the GReenhouse gas And Air Pollutants Emissions System (GRA 2 PES), which provides gridded emissions of fossil-fuel carbon dioxide (ffCO 2 ) and 93 air quality (AQ) species for 17 combustion and non-combustion sectors at 4 km × 4 km spatial resolution across the contiguous US. We find that the AQ emissions most spatially correlated with ffCO 2 are nitrogen oxides (NO x , ρ = 0.67), followed by sulfur dioxide (SO 2 , ρ = 0.51), carbon monoxide (CO, ρ = 0.44), and fine particulate matter (PM 2.5 , ρ = 0.38). We evaluate GRA 2 PES ffCO 2 emissions with an ensemble of publicly available regional and global inventories at national (Normalized Mean Bias (NMB) = +1.4%), state (NMB = +1.5%, R 2 = 0.98), and urban (NMB = +11.5%, R 2 = 0.97) scales. Nationally, the differences of publicly available inventories from the ensemble average range from −10.0% to +5.7%, and consistency diverges at state and urban scales. We simulate GRA 2 PES ffCO 2 in a particle dispersion model and compare to measurements of radiocarbon ( 14 C)-derived ffCO 2 collected in Los Angeles (August 2021), with results suggesting that GRA 2 PES ffCO 2 may be low by 19% for this city, but well within model-observation differences for other publicly available inventories (−43% to +94%). GRA 2 PES AQ/ffCO 2 ratios converted to concentration space generally agree with field observations (NMB = +4%, log R 2 = 0.90). Lastly, we present a method by which to utilize GRA 2 PES to derive AQ emission fluxes from ffCO 2 emissions.

Lyu, Congmeng [National Oceanic and Atmospheric Ad↗