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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.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Gridded anthropogenic emissions inventory and atmospheric transport of carbonyl sulfide in the U.S.

Carbonyl sulfide (COS or OCS), the most abundant sulfur containing gas in the troposphere, has recently emerged as a potentially important atmospheric tracer for the carbon cycle. Atmospheric inverse modeling studies may be able to use existing tower, airborne, and satellite observations of COS to infer information about photosynthesis. However, such analysis relies on gridded anthropogenic COS source estimates that are largely based on industry activity data from over three decades ago. Here we use updated emission factor data and industry activity data to develop a gridded inventory with a 0.1 degree resolution for the U.S. domain. The inventory includes the primary anthropogenic COS sources including direct emissions from the coal and aluminum industries as well as indirect sources from industrial carbon disulfide emissions. Compared to the previously published inventory, we found that the total anthropogenic source (direct and indirect) is 47% smaller. Here, using this new gridded inventory to drive the STEM/WRF atmospheric transport model, we found that the anthropogenic contribution to COS variation in the troposphere is small relative to the biosphere influence, which is encouraging of carbon cycle applications in this region. Additional anthropogenic sectors with highly uncertain emission factors require further field measurements.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu-H: Different Rate-Limiting Steps as a Function of Electrophilicity

In this paper, we report mechanistic studies on the insertion reactions of [(NHC)Cu(H)] 2 complexes with carbonyl substrates by UV-vis and 1 H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X-ray crystallography. The results of these comprehensive studies show that the insertion of Cu-H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu-H monomer from Cu-H dimer for more electrophilic substrates and hydride transfer from a transient Cu-H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu-hemiacetalate and Cu-hemiaminalate moieties from the insertion of an ester and amide into the Cu-H bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Global gridded anthropogenic emissions inventory of carbonyl sulfide

Atmospheric carbonyl sulfide (COS or OCS) is the most abundant sulfur containing gas in the troposphere and is an atmospheric tracer for the carbon cycle. Gridded inventories of global anthropogenic COS are used for interpreting global COS measurements. However, previous gridded anthropogenic data are a climatological estimate based on input data that is over three decades old and are not representative of current conditions. Here we develop a new gridded data set of global anthropogenic COS sources that includes more source sectors than previously available and uses the most current emissions factors and industry activity data as input. Additionally, the inventory is provided as annually varying estimates from years 1980–2012 and employs a source specific spatial scaling procedure. We estimate a global source in year 2012 of 406 Gg S y -1 (range of 223–586 Gg S y -1 ), which is highly concentrated in China and is twice as large as the previous gridded inventory. Our large upward revision in the bottom-up estimate of the source is consistent with a recent top-down estimate based on air-monitoring and Antarctic firn data. Furthermore, our inventory time trends, including a decline in the 1990's and growth after the year 2000, are qualitatively consistent with trends in atmospheric data. Lastly, similarities between the spatial distribution in this inventory and remote sensing data suggest that the anthropogenic source could potentially play a role in explaining a missing source in the global COS budget.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Carbonyl cyanide 3-chlorophenylhydrazone (CCCP) suppresses STING-mediated DNA sensing pathway through inducing mitochondrial fission

Besides its important role in innate immune response to DNA virus infection, the regulatory function of STING in autoimmunity and cancer is emerging. Recently, multiple mechanisms regulating the activity of the STING pathway have been revealed. Previous study showed that carbonyl cyanide 3-chlorophenylhydrazone (CCCP), the protonophore, inhibited STING-mediated IFN-β production via disrupting mitochondrial membrane potential (MMP). However, how MMP dissipation leads to the suppression of the STING pathway remains unknown. Here, we show that CCCP inhibits activation of STING and its downstream signaling molecules, TBK1 and IRF3, but not STING translocation to the perinuclear region. We found that CCCP impairs the interaction between STING and TBK1 and concomitantly triggers mitochondria fission. Importantly, the knockout of the crucial mitochondria fission regulator Drp1 restored the STING activity, indicating that CCCP down-modulates the STING pathway through DRP1-mediated mitochondria fragmentation. Our findings highlight the coupling of the STING signaling platform to mitochondria dynamics. - Highlights: • CCCP inhibits IFN-β production induced by various types of the STING pathway activators. • CCCP suppresses the phosphorylation of STING, TBK1, and IRF3 via disrupting the association of STING and TBK1. • The mitochondria fission mediator DRP1 is essential for CCCP-induced suppression of the STING pathway.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Utilizing metal cation reactions with carbonyl sulfide to remove isobaric interferences in tandem inductively coupled plasma mass spectrometry analyses

Carbonyl sulfide (OCS) was used as a reaction gas to investigate gas phase metal (M + ) ion-molecule reactions using the Agilent 8900 inductively coupled plasma tandem mass spectrometer (ICP-MS/MS) to yield insight on how this gas may be used to remove isobaric interferences in analytical measurements. The experimental work was paired with density functional theory (DFT) calculations of the reaction enthalpy to predict whether M + will react with OCS. A multi-element standard containing 46 elements ranging from 9 to 208 u was analyzed in the presence and absence of OCS. When a reaction was observed, the dominant product was the sulfide (MS + ). Oxide products were also observed for many M + but formation was less efficient with OCS than previously observed with other reaction gases. This is likely due to the weaker OC-S bond that makes MS + formation more favorable. Increasing the flow rate from 0.1 to 0.2 mL/min (corresponding to a change in reaction gas pressure from 0.35 to 0.53 Pa (2.6 to 4.0 mTorr)) generally resulted in greater MS + production, including the secondary product MS 2 + for a few cations. The early lanthanide series ions (La + , Ce + , Pr + and Nd + ) produced greater quantities of MO + at the higher pressure, although MS + products were still the dominant product. The DFT-predicted reaction enthalpies were consistent with the observed sulfide formation, with an accuracy >90%; however, model predictions were less accurate for the minor and higher order products (< 77% for MO + ). Finally, the work presented here continues a systematic study of ion-molecule reactions in ICP-MS/MS to understand and develop new and novel ways to analyze complex mixtures with minimal pre-analysis treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe 2 ) 4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe 2 ) n @MSN. Exhaustive characterization of Zr(NMe 2 ) n @MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe 2 ) 3 . The presence of these nitrogen-containing zirconium sites is supported by 15 N NMR spectroscopy, including natural abundance 15 N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe 2 ) n @MSN material reacts with pinacolborane (HBpin) to provide Me 2 NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1 H/ 2 H and 11 B SSNMR and infrared spectroscopy and through its reactivity with D 2 . The zirconium hydride material or the zirconium amide precursor Zr(NMe 2 ) n @MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. These supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Exploring the Potential of Using Carbonyl Sulfide to Track the Urban Biosphere Signal

Abstract Cities are implementing additional urban green as a means to capture CO 2 and become more carbon neutral. However, cities are complex systems where anthropogenic and natural components of the CO 2 budget interact with each other, and the ability to measure the efficacy of such measures is still not properly addressed. There is still a high degree of uncertainty in determining the contribution of the vegetation signal, which furthermore confounds the use of CO 2 mole fraction measurements for inferring anthropogenic emissions of CO 2 . Carbonyl sulfide (OCS) is a tracer of photosynthesis which can aid in constraining the biosphere signal. This study explores the potential of using OCS to track the urban biosphere signal. We used the Sulfur Transport and dEposition Model (STEM) to simulate the OCS concentrations and the Carnegie Ames Stanford Approach ecosystem model to simulate global CO 2 fluxes over the Bay Area of San Francisco during March 2015. Two observation towers provided measurements of OCS and CO 2 : The Sutro tower in San Francisco (upwind from the area of study providing background observations), and a tower located at Sandia National Laboratories in Livermore (downwind of the highly urbanized San Francisco region). Our results show that the STEM model works better under stable marine influence, and that the boundary layer height and entrainment are driving the diurnal changes in OCS and CO 2 at the downwind Sandia site. However, the STEM model needs to better represent the transport and boundary layer variability, and improved estimates of gross primary productivity for characterizing the urban biosphere signal are needed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Self-assembly of graphene oxide coated soft magnetic carbonyl iron particles and their magnetorheology

The surface of carbonyl iron (CI) microspheres was modified with graphene oxide (GO) as a coating material using 4-aminobenzoic acid as the grafting agent. The morphology, elemental composition, and magnetic properties of the GO-coated CI (GO/CI) particles were examined by scanning electron microscopy, energy dispersive X-ray spectroscopy and vibrating sample magnetometry, respectively, confirming their composite formation. The magnetorheological (MR) performance of the GO/CI particle-based suspension was examined using a rotational rheometer connected to a magnetic field supply. The GO/CI particles suspension exhibited typical MR properties with increasing shear stress and viscosity depending on the applied magnetic field strength.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Formation of high electrical-resistivity thin surface layer on carbonyl-iron powder (CIP) and thermal stability of nanocrystalline structure and vortex magnetic structure of CIP

This study focuses on the carbonyl-iron powder (CIP) used in the metal composite bulk magnetic core for high-efficient/light-weight SiC/GaN power device MHz switching dc-dc converter, where the fine CIP with a mean diameter of 1.1 μm is used to suppress the MHz band eddy current inside the CIP body. When applying the CIP to composite core together with the resin matrix, high electrical resistivity layer must be formed on the CIP-surface in order to suppress the overlapped eddy current between adjacent CIPs. In this study, tens nm thick silica (SiO{sub 2}) was successfully deposited on the CIP-surface by using hydrolysis of TEOS (Si(OC{sub 2}H{sub 5}){sub 4}). Also tens nm thick oxidized layer of the CIP-surface was successfully formed by using CIP annealing in dry air. The SiC/GaN power device can operate at ambient temperature over 200 degree-C, and the composite magnetic core is required to operate at such ambient temperature. The as-made CIP had small coercivity below 800 A/m (10 Oe) due to its nanocrystalline-structure and had a single vortex magnetic structure. From the experimental results, both nanocrystalline and single vortex magnetic structure were maintained after heat-exposure of 250 degree-C, and the powder coercivity after same heat-exposure was nearly same as that of the as-made CIP. Therefore, the CIP with thermally stable nanocrystalline-structure and vortex magnetic state was considered to be heat-resistant magnetic powder used in the iron-based composite core for SiC/GaN power electronics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Sulfur assimilation using gaseous carbonyl sulfide by the soil fungus Trichoderma harzianum

Fungi have the capacity to assimilate a diverse range of both inorganic and organic sulfur compounds. It has been recognized that all sulfur sources taken up by fungi are in soluble forms. In this study, we present evidence that fungi can utilize gaseous carbonyl sulfide (COS) for the assimilation of a sulfur compound. We found that the filamentous fungus Trichoderma harzianum strain THIF08, which has constitutively high COS-degrading activity, was able to grow with COS as the sole sulfur source. Cultivation with 34 S-labeled COS revealed that sulfur atom from COS was incorporated into intracellular metabolites such as glutathione and ergothioneine. COS degradation by strain THIF08, in which as much of the moisture derived from the agar medium as possible was removed, indicated that gaseous COS was taken up directly into the cell. Escherichia coli transformed with a COS hydrolase (COSase) gene, which is clade D of the β-class carbonic anhydrase subfamily enzyme with high specificity for COS but low activity for CO 2 hydration, showed that the COSase is involved in COS assimilation. Comparison of sulfur metabolites of strain THIF08 revealed a higher relative abundance of reduced sulfur compounds under the COS-supplemented condition than the sulfate-supplemented condition, suggesting that sulfur assimilation is more energetically efficient with COS than with sulfate because there is no redox change of sulfur. Phylogenetic analysis of the genes encoding COSase, which are distributed in a wide range of fungal taxa, suggests that the common ancestor of Ascomycota, Basidiomycota, and Mucoromycota acquired COSase at about 790–670 Ma.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Study of the structural features of ε-Co nanoparticles synthesized by cobalt carbonyl decomposition in the presence of surfactant

Cobalt nanoparticles (3–7 nm in size) obtained by cobalt carbonyl decomposition in 1,2-dichlorobenzene in the presence of surfactants (trioctylphosphine oxide and oleic acid) have been studied by a complex of structural methods: small-angle X-ray scattering, electron diffraction, and transmission electron microscopy. The nanoparticles synthesized are found to consist of the cubic ε-Со phase; their crystal structure is described within the sp. gr. P4{sub 1}32, a = 6.097 Å. Using small-angle X-ray scattering, the size and shape of nanoparticles have been determined directly in the liquid dispersion. Most of the particles have a spherical shape; their average size is ≈3.5 ± 0.5 nm, which agrees with the electron microscopy data. Possible factors causing the ε-phase formation during synthesis of metallic Co nanoparticles are discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Sonoluminescence of Suspensions of Insoluble Chromium Carbonyl Nanoparticles in Water and Inorganic Acids

The preparation and sonoluminescence of Cr(CO){sub 6} nanodispersed suspensions in water, 83% H{sub 2}SO{sub 4}, and 74% H{sub 3}PO{sub 4} are described for the first time. In the spectra of single- and multibubble sonoluminescence of these suspensions, chromium atom lines are found that are analogous to the corresponding lines in the sonoluminescence spectra of true Cr(CO){sub 6} solutions in dodecane. Sonoluminescence of nanodispersed suspensions of metal carbonyl, by which the electronic temperature reached in the bubbles under sonolysis (from 6500 to 16 000 K in water and acids) was measured, expands the scope of the sonochemical model of injection of nanodroplets of low volatile compounds into cavitation bubbles due to the inclusion of injection of suspensions of insoluble substances into it.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

SiB3 simulations of gross primary productivity(GPP) and carbonyl sulfide (COS) plant flux

This data set contains Simple Biosphere Model (SiB3) simulations of North American carbon dioxide (CO2) gross primary productivity (GPP) and carbonyl sulfide (OCS) plant flux (Fplant). There are two Fplant simulation methods included: a methodologically simpler LRU-based method, and a more mechanistic leaf enzyme kinetic approach. These methods are described in detail in the references included with the dataset.Time span: 1 July 2008 through 31 Aug 2008 Spatial extent: Coterminus USA and most of Canada SpatialResolution: 60 km by 60 km

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2013

Quantifying Carbon-Climate Processes at the Regional Scale Using Atmospheric Carbonyl Sulfide

Atmospheric carbonyl sulfide (COS) analysis has the potentially transformative capability for partitioning the regional carbon flux into respiration and photosynthesis components. This emerging approach is based on the observation that continental atmospheric CO2 gradients are dominated by net ecosystem fluxes while continental atmospheric COS gradients are dominated by photosynthesis-related plant uptake. Regional flux partitioning represents a critical knowledge gap due to a lack of robust methods for regional-scale flux partitioning and large uncertainties in forecasting carbon-climate feedbacks. Our completed project characterized the relationship between COS and CO2 surface fluxes using a novel measurement and modeling system in a winter wheat field at the U.S. Department of Energy?s Atmospheric and Radiation Measurement program Central Facility (DOE-ARM CF). The scope of this project included canopy flux measurements, soil flux measurements, regional atmospheric modeling, and analysis of COS and CO2 airborne observations at SGP. Three critical discoveries emerged from this investigation: (1) the new measurement system provided the first field evidence of a robust relationship between COS leaf fluxes and GPP; (2) a previously unknown seasonal soil source of COS was observed and characterized; (3) the regional atmospheric analysis of airborne measurements provided the first COS-based constraints on GPP parameterizations used in earth systems models. Dissemination of these results includes three publications [Billesbach et al., In Press; Campbell et al., In Preparation; Seibt et al., In Review], three presentations at the AGU Fall Meeting (2012), and four invited presentations to department seminars. We have leveraged this foundational project to continue our work on understanding carbon cycle processes at large scales through one funded project (DOE Lab Fee, 2012-2015) and one proposal that is under review (DOE/NASA/USDA/NOAA, 2014-2016).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Carbonyl Sulfide for Tracing Carbon Fluxes Field Campaign Report

The April-June 2012 campaign was located at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility Southern Great Plains (SGP) site Central Facility and had three purposes. One goal was to demonstrate the ability of current instrumentation to correctly measure fluxes of atmospheric carbonyl sulfide (COS). The approach has been describe previously as a critical approach to advancing carbon cycle science1,2, but requires further investigation at the canopy scale to resolve ecosystem processes. Previous canopy-scale efforts were limited to data rates of 1Hz. While 1 Hz measurements may work in a few ecosystems, it is widely accepted that data rates of 10 to 20 Hz are needed to fully capture the exchange of traces gases between the atmosphere and vegetative canopy. A second goal of this campaign was to determine if canopy observations could provide information to help interpret the seasonal double peak in airborne observations at SGP of CO 2 and COS mixing ratios. A third goal was to detect potential sources and sinks of COS that must be resolved before using COS as a tracer of gross primary productivity (GPP).

54 ENVIRONMENTAL SCIENCES↗