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At least 703 records · Page 39

Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

Freund, Friedemann↗

Integrating transcriptomic and metabolomic analysis of the oleaginous yeast Rhodosporidium toruloides IFO0880 during growth under different carbon sources

Rhodosporidium toruloides is an oleaginous yeast capable of producing a variety of biofuels and bioproducts from diverse carbon sources. Despite numerous studies showing its promise as a platform microorganism, little is known about its metabolism and physiology. In this work, we investigated the central carbon metabolism in R. toruloides IFO0880 using transcriptomics and metabolomics during growth on glucose, xylose, acetate, or soybean oil. These substrates were chosen because they can be derived from plants. Significant changes in gene expression and metabolite concentrations were observed during growth on these four substrates. We mapped these changes onto the governing metabolic pathways to better understand how R. toruloides reprograms its metabolism to enable growth on these substrates. One notable finding concerns xylose metabolism, where poor expression of xylulokinase induces a bypass leading to arabitol production. Collectively, these results further our understanding of central carbon metabolism in R. toruloides during growth on different substrates. Furthermore, they may also help guide the metabolic engineering and development of better models of metabolism for R. toruloides.

59 BASIC BIOLOGICAL SCIENCES↗

Electrification of residential and commercial buildings integrated with hybrid renewable energy systems: A techno-economic analysis

Here, this study assesses the techno-economic viability of city-scale building electrification, comparing a base case scenario with conventional HVAC systems to an electrified scenario with heat pump systems. EnergyPlus simulations reveal a 28% increase in annual electricity consumption in the electrified scenario, shifting the peak consumption from summer to winter with a 49% surge. Hybrid renewable energy systems (HRESs) are then evaluated using HOMER Pro, considering renewable penetration from 0% to 100%. The net present cost (NPC) of the base case and electrified scenarios range from $\$10.34$ to $\$24.38$ billion and $\$8.79$ to $\$50.31$ billion, respectively. Sensitivity analysis explores the impact of carbon tax, fuel price, and renewable subsidies on HRESs in the electrified scenario. Results indicate that applying a carbon tax up to $\$120$/tonne of CO 2 increases the optimum renewable fraction from 5% to 26%, while higher fuel prices and renewable subsidies further enhance the feasibility by shifting the optimum renewable fraction to 60% and 54%, respectively, demonstrating the interplay between economic factors and renewable integration in electrified urban contexts.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Downstream Separation of Formic Acid with Anion-Exchange Resin from Electrocatalytic Carbon Dioxide (CO 2 ) Conversion: Adsorption, Kinetics, and Equilibrium Modeling

The electrocatalytic carbon dioxide reduction reaction (CO 2 RR) that produces liquid formic acid (FA) is one potential route to minimize the CO 2 concentration in the atmosphere by utilizing CO 2 as a feedstock. However, one of the main disadvantages of this route is the high energy demand required for purification through conventional distillation. This method of purification has been shown to result in a large carbon footprint in life-cycle analysis (LCA). Therefore, finding an alternative purification technique that can integrate with an electrochemical CO 2 RR process with the potential to lower the carbon footprint would be of great interest. Under the experimental conditions of the CO 2 RR, FA remains in its basic form as the formate anion in the catholyte. Anion exchange resins with their basic properties can separate the formate anion from the catholyte mixture as an alternative to energy intensive distillation. In this work, three anion exchange resins with increasing basicity order: Amberlite IRA-96 < Amberlite IRA-910 < Ambersep 900 are tested to separate FA in the presence of aqueous solution of potassium bicarbonate catholyte with varying levels of resin and FA. Kinetics and equilibrium studies data for the FA adsorption are interpreted using several kinetics and isotherm models. The kinetics data fit well with a pseudo-first-order model at high initial FA concentrations and a pseudo-second-order model at low initial FA concentrations. The experimental data can be best explained with the Freundlich isotherm model. The fitted results show that strongly basic Ambersep 900 is more effective at separating FA, with a maximum adsorption capacity of 336.7 mg/g compared to Amberlite IRA-96 (275.2 mg/g) and Amberlite IRA-910 (209.2 mg/g) in neutral water. However, weakly basic Amberlite IRA-96 (110.8 mg/g) can separate FA more efficiently from potassium bicarbonate catholyte than Amberlite IRA-910 (99.9 mg/g) and Ambersep 900 (40.0 mg/g). As a result, competitive adsorption occurs in the presence of potassium bicarbonate catholyte, but the formic acid adsorption capacity is still sufficient for adequate separation.

20 FOSSIL-FUELED POWER PLANTS↗

Data for Integrating Transcriptomic and Metabolomic Analysis of the Oleaginous Yeast Rhodosporidium toruloides IFO0880 During Growth under Different Carbon Sources

Rhodosporidium toruloides is an oleaginous yeast capable of producing a variety of biofuels and bioproducts from diverse carbon sources. Despite numerous studies showing its promise as a platform microorganism, little is known about its metabolism and physiology. In this work, we investigated the central carbon metabolism in R. toruloides IFO0880 using transcriptomics and metabolomics during growth on glucose, xylose, acetate, or soybean oil. These substrates were chosen because they can be derived from plants. Significant changes in gene expression and metabolite concentrations were observed during growth on these four substrates. We mapped these changes onto the governing metabolic pathways to better understand how R. toruloides reprograms its metabolism to enable growth on these substrates. One notable finding concerns xylose metabolism, where poor expression of xylulokinase induces a bypass leading to arabitol production. Collectively, these results further our understanding of central carbon metabolism in R. toruloides during growth on different substrates. They may also help guide the metabolic engineering and development of better models of metabolism for R. toruloides .

Conversion↗

Isotopic Composition of Carbon Dioxide Released from Confidence Hills Sediment as Measured by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

In October 2014, the Mars Science Laboratory (MSL) "Curiosity" rover drilled into the sediment at the base of Mount Sharp in a location namsed Cionfidence Hills (CH). CH marked the fifth sample pocessed by the Sample Analysis at Mars (SAM) instrument suite since Curiosity arrived in Gale Crater, with previous analyses performed at Rocknest (RN), John Klein (JK), Cumberland (CB), and Windjana (WJ). Evolved gas analysis (EGA) of all samples has indicated H2O as well as O-, C- and S-bearing phases in the samples, often at abundances that would be below the detection limit of the CheMin instrument. By examining the temperatures at which gases are evolved from samples, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases when their identities are unclear to CheMin. SAM may also detect gases evolved from amorphous material in solid samples, which is not suitable for analysis by CheMin. Finally, the isotopic composition of these gases may suggest possible formation scenarios and relationships between phases. We will discuss C isotope ratios of CO2 evolved from the CH sample as measured with SAM's quadrupole mass spectrometer (QMS) and draw comparisons to samples previously analyzed by SAM.

Franz, H. B.↗

Interpretation of wide-angle x-ray diffraction patterns from mesophase pitch-based carbon fibers – a simulation and experimental study

Carbon fiber is a critical material in a wide range of industries, where it is highly valued for its high specific strength/stiffness, excellent wear resistance, efficient electrical and thermal transport properties, chemical resistance, and low coefficient of thermal expansion. The properties of a specific carbon fiber are closely tied to its structural characteristics at all length scales. Here, in this work, we applied wide-angle x-ray diffraction to a set of heat-treated mesophase pitch-based carbon fibers, with the goal of elucidating the crystalline structures as a function of fiber orientation. To assist with analysis and interpretation of the experimental data, we employed diffraction pattern simulations using the scalar and vector forms of the Debye scattering equation to determine the influence of basal plane orientation, crystalline ordering (turbostratic-graphitic), and basal plane asymmetry on the diffraction patterns. The results presented here suggest that growth of the transverse crystallites in mesophase pitch-based carbon fiber is fixed until graphitization temperatures are reached. The work completed here provides a framework for the analysis of carbon fiber and other oriented carbon-based materials via diffraction.

36 MATERIALS SCIENCE↗

Carbon-Based Compounds and Exobiology

The Committee for Planetary and Lunar Explorations (COMPLEX) posed questions related to exobiological exploration of Mars and the possibility of a population of carbonaceous materials in cometary nuclei to be addressed by future space missions. The scientific objectives for such missions are translated into a series of measurements and/or observations to be performed by Martian landers. These are: (1) A detailed mineralogical, chemical, and textural assessment of rock diversity at a landing site; (2) Chemical characterization of the materials at a local site; (3) Abundance of Hydrogen at any accessible sites; (4) Identification of specific minerals that would be diagnostic of aqueous processes; (5) Textual examination of lithologies thought to be formed by aqueous activity; (6) Search for minerals that might have been produced as a result of biological processes; (7) Mapping the distribution, in three dimensions, of the oxidant(s) identified on the Martian surface by the Viking mission; (8) Definition of the local chemical environment; (9) Determination of stable-isotopic ratios for the biogenic elements in surface mineral deposits; (10) Quantitative analysis of organic (non-carbonate) carbon; (11) Elemental and isotopic composition of bulk organic material; (12) Search for specific organic compounds that would yield information about synthetic mechanisms, in the case of prebiotic evolution, and about possible bio-markers, in the case of extinct or extant life; (13) and Coring, sampling, and detection of entrained gases and cosmic-ray induced reaction products at the polar ice cap. A discussion of measurements and/or observations required for cometary landers is included as well.

Kerridge, John↗

Soil Moisture Active Passive Mission L4_C Data Product Assessment (Version 2 Validated Release)

The SMAP satellite was successfully launched January 31st 2015, and began acquiring Earth observation data following in-orbit sensor calibration. Global data products derived from the SMAP L-band microwave measurements include Level 1 calibrated and geolocated radiometric brightness temperatures, Level 23 surface soil moisture and freezethaw geophysical retrievals mapped to a fixed Earth grid, and model enhanced Level 4 data products for surface to root zone soil moisture and terrestrial carbon (CO2) fluxes. The post-launch SMAP mission CalVal Phase had two primary objectives for each science product team: 1) calibrate, verify, and improve the performance of the science algorithms, and 2) validate accuracies of the science data products as specified in the L1 science requirements. This report provides analysis and assessment of the SMAP Level 4 Carbon (L4_C) product pertaining to the validated release. The L4_C validated product release effectively replaces an earlier L4_C beta-product release (Kimball et al. 2015). The validated release described in this report incorporates a longer data record and benefits from algorithm and CalVal refinements acquired during the SMAP post-launch CalVal intensive period. The SMAP L4_C algorithms utilize a terrestrial carbon flux model informed by SMAP soil moisture inputs along with optical remote sensing (e.g. MODIS) vegetation indices and other ancillary biophysical data to estimate global daily net ecosystem CO2 exchange (NEE) and component carbon fluxes for vegetation gross primary production (GPP) and ecosystem respiration (Reco). Other L4_C product elements include surface (10 cm depth) soil organic carbon (SOC) stocks and associated environmental constraints to these processes, including soil moisture and landscape freeze/thaw (FT) controls on GPP and respiration (Kimball et al. 2012). The L4_C product encapsulates SMAP carbon cycle science objectives by: 1) providing a direct link between terrestrial carbon fluxes and underlying FT and soil moisture constraints to these processes, 2) documenting primary connections between terrestrial water, energy and carbon cycles, and 3) improving understanding of terrestrial carbon sink activity in northern ecosystems. There are no L1 science requirements for the L4_C product; however self-imposed requirements have been established focusing on NEE as the primary product field for validation, and on demonstrating L4_C accuracy and success in meeting product science requirements (Jackson et al. 2012). The other L4_C product fields also have strong utility for carbon science applications; however, analysis of these other fields is considered secondary relative to primary validation activities focusing on NEE. The L4_C targeted accuracy requirements are to meet or exceed a mean unbiased accuracy (ubRMSE) for NEE of 1.6 g C/sq m/d or 30 g C/sq m/yr, emphasizing northern (45N) boreal and arctic ecosystems; this is similar to the estimated accuracy level of in situ tower eddy covariance measurement-based observations (Baldocchi 2008).

Cal/Val↗

Using Separation-Enhanced Isotope Ratio Mass Spectrometry to Enable Increased Renewable Carbon Content in Transportation Fuels (CRADA 525)

Stable isotope ratio measurements of carbon atoms using isotope ratio mass spectrometry (IRMS) can be an effective tool for quantifying biogenic carbon in co-processed fuels, with results approaching the precision and accuracy of accelerator mass spectrometry (AMS). The lower cost of an IRMS may enable deployment to refineries, improving access and analysis turnaround times (≤2 hours), and, by extension, provide data that can allow process optimization to maximize renewable carbon in desired refinery products. This project explored the integration of chemical separation with IRMS analyses to enable highly detailed tracking of biogenic carbon into fuel product streams separated by boiling point range, chemical class, or specific compound. Forty-nine fuels and fuel components of fossil and biogenic origin, spanning gasoline and diesel boiling point ranges, were received from three refiners and were analyzed for their δ 13 C values via IRMS. Results spanned a 13 C range from ca. 10‰ to 44‰ and reflect materials derived from sustainable sources (e.g., C4 or C3 plants, animal-based pathways, syngas) or from fossil-derived fuels. Common ranges are approximately 18‰ to 9‰ and approximately 30‰ to 20‰ for C4 and C3 plants, respectively, and approximately 34‰ to 24‰ and approximately 70‰ to 33‰ for petroleum-derived fuels and methane, respectively. Fuel-like standards were developed and tested using direct-injection elemental analyzer (EA) IRMS for liquid fuels. This method was compared with the published methods, yielding statistically similar results. Four blend curve sets were produced ranging from 0% to 100% of a fuel containing biogenic carbon, focusing on 0% to 10% biogenic carbon. Linear fits were the most applicable for two of the four blend curve sets; however, two sets were found to exhibit slightly quadratic behavior, which was more pronounced in low biogenic blend samples, necessitating second-order fits. The origin of the slight quadratic behavior remains unclear; however, the discussion points to possible interpretations. CanmetENERGY thoroughly characterized a majority of the samples using one- and two-dimensional gas chromatography (GC and GC×GC, respectively) and other analyses. Selected samples were subjected to solid phase extraction (SPE) for saturate, olefin, aromatic, and polar (SOAP) analysis, and the resulting solvent-diluted fractions containing saturates and aromatics were returned to Pacific Northwest National Laboratory (PNNL), where the solvent was removed via evaporation or physical separation using GC techniques. Characterization and separations provided an understanding of saturate and aromatic content, as well as boiling point ranges for each sample and sample fraction. Samples resulting from SPE were examined using EA-IRMS and gas chromatography combustion IRMS (GC-C-IRMS) analyses. Both approaches suggest that the range in values between end-members can be increased by selecting the paraffinic or aromatic fraction of the end-member or by selecting among individual compounds resulting from GC separation of the paraffinic fractions. Considerable work remains to put these approaches into practice and statistically validate the benefit for using a fraction or individual compound over bulk analysis of a sample. However, initial results suggest that separations provide advantages for samples having blend ratios of less than 10% biogenic blendstocks. 13 C results showed statistically similar biofuel blend results to those obtained at PNNL, although additional work is needed to obtain better reproducibility. Select samples were sent to Los Alamos National Laboratory (LANL) for IRMS measurements and Beta Analytics for AMS measurements. This work suggests that IRMS and AMS yield closely comparable results and in some circumstances, IRMS could serve as a surrogate for AMS. While additional work is needed to better resolve statistical advantages for separations and better show the comparable nature of IRMS and AMS in both the biogenic carbon analysis of bulk chemical classes, initial results from this study suggest that these should be pursued in order to proliferate this approach for quantifying biogenic carbon in transportation fuels to the refinery level, thereby potentially enabling process optimization in co-processing scenarios.

09 BIOMASS FUELS↗

Profiling of Mars Atmospheric Carbon Dioxide Isotopologues Using 2-Micron Orbiting Lidar

Mars atmospheric characterization is important for investigating the planet climate history and planning future missions. A feasibility study for implementing the 2-um lidar technology for measuring Martian atmospheric carbon dioxide isotopologues is presented in this paper. Instrument reconfigurations include transmitted wavelengths and detection for differential absorption lidar application using an orbiter platform. Spectral analysis focused on the major four carbon dioxide isotopologues using the 2035 nm wavelength range, which results in minimal interference from other molecular species. Lidar simulation indicated the capability of detecting 12C16O2, 13C16O2, and 18O12C16O near surface vertical profiles up to 20 km altitude. Sensing of 17O12C16O isotopologue is challenging due to lower abundance and Martian atmospheric dust. This orbiting lidar provides a valuable tool for future Mars missions.

Tamer F. Refaat↗

Profiling of Mars Atmospheric Carbon Dioxide Isotopologues Using 2-Micron Orbiting Lidar

Mars atmospheric characterization is important for investigating the planet climate history and planning future missions. A feasibility study for implementing the 2-um lidar technology for measuring Martian atmospheric carbon dioxide isotopologues is presented in this paper. Instrument reconfigurations include transmitted wavelengths and detection for differential absorption lidar application using an orbiter platform. Spectral analysis focused on the major four carbon dioxide isotopologues using the 2035 nm wavelength range, which results in minimal interference from other molecular species. Lidar simulation indicated the capability of detecting 12C16O2, 13C16O2, and 18O12C16O near surface vertical profiles up to 20 km altitude. Sensing of 17O12C16O isotopologue is challenging due to lower abundance and Martian atmospheric dust. This orbiting lidar provides a valuable tool for future Mars missions.

Tamer F. Refaat↗

A new solar carbon abundance based on non-LTE CN molecular spectra

A detailed non-LTE analysis of solar CN spectra strongly suggest a revised carbon abundance for the sun. We recommend a value of log carbon abundance = 8.35 plus or minus 0.15 which is significantly lower than the presently accepted value of log carbon abundance = 8.55. This revision may have important consequences in astrophysics.

Mount, G. H.↗

Black Carbon in Estuarine and Coastal Ocean Dissolved Organic Matter

Analysis of high-molecular-weight dissolved organic matter (DOM) from two estuaries in the northwest Atlantic Ocean reveals that black carbon (BC) is a significant component of previously uncharacterized DOM, suggesting that river-estuary systems are important exporters of recalcitrant dissolved organic carbon to the ocean.

Mannino, Antonio↗

Modern insights into the mechanisms of neptunium oxalate decomposition

Neptunium oxalate (Np(C 2 O 4 ) 2 ·6H 2 O) is a historically relevant solid phase used in nuclear processing as a precursor for neptunium dioxide (NpO 2 ). Although Np oxalate has been synthesized and used for NpO 2 production for decades, the thermal decomposition mechanism of this phase remains poorly understood and has not been evaluated in over 30 years. Conflicting reports in historical literature suggest either a direct conversion from anhydrous oxalate to NpO 2 or a decomposition that includes the formation of Np carbonate or oxidized Np intermediate phases. In this work, we reexamine the decomposition pathway of Np(C 2 O 4 ) 2 ·6H 2 O using thermal analysis coupled with evolved gas analysis and temperature-dependent Raman spectroscopy to elucidate decomposition mechanisms and intermediate phases using modern analytical techniques. Thermal analysis revealed a three-stage decomposition process, including dehydration below 200 °C, oxalate breakdown between 170 and 370 °C, and NpO 2 formation by 500 °C. However, an unidentified plateau in the thermal data was observed during measurements. Raman spectroscopy confirmed the stages of decomposition, and in the analysis of potential intermediate phases, no carbonate phases or Np 2 O 5 were identified. Raman data suggest that residual oxalate or nonstoichiometric oxide are present during decomposition before pure NpO 2 is formed. These findings clarify aspects of the Np oxalate decomposition mechanism and address longstanding discrepancies in the literature, with a specific focus on Np-specific materials chemistry.

Lawson, Kathryn M. [Oak Ridge National Laboratory ↗

Unraveling spectral shapes of adventitious carbon on gold using a time-resolved high-resolution X-ray photoelectron spectroscopy and principal component analysis

To extract chemical information reliably, we propose a new data processing method based both on the creation of information vectors and on a vector base change. The originality of this method is the combination of the different core XPS peaks, Auger and/or valence bands in a single vector. We show that the measurement of a sample upon its progressive chemical change, such as accumulation of the adventitious carbon, allows us to create a new vector basis using linear algebra and Principal Component Analysis. In this work, we demonstrate the application of this method using adventitious carbon films on Au foil utilizing Au 4f, C 1s and O 1s spectral envelopes. This method expands the possibilities of XPS measured chemical environment analysis and is an operator-unbiased solution for materials for which the reference XPS spectra are not available. In this demonstration, the emphasis is placed on identifying changes in a C 1s peak assumed to be adventitious carbon and highlight uncertainties associated with calibrating the binding energy scale using a simple peak model to identify a component C 1s assumed to be saturated hydrocarbon in origin.

36 MATERIALS SCIENCE↗

Using waste CO 2 from corn ethanol biorefineries for additional ethanol production: life‐cycle analysis

Abstract Corn ethanol plants generate high‐purity carbon dioxide (CO 2 ) while producing ethanol. If that CO 2 could be converted into ethanol by carbon capture and utilization technologies it would be possible to increase ethanol production more than 37% without additional corn grain inputs. Gas fermentation processes use microbes to convert carbon‐containing gases into ethanol and so have the potential to be used with the CO 2 from biorefineries for this purpose. However, as CO 2 utilization technologies for converting thermodynamically stable CO 2 are typically energy intensive, it is necessary to evaluate the related life‐cycle greenhouse gas (GHG) emissions (carbon intensities or CIs) to see whether there are actual emission reduction benefits. In this study, we evaluate the CIs of ethanol produced from high‐purity CO 2 in corn ethanol plants by gas fermentation plus electrochemical reduction. Our analysis shows that the sources of electricity and hydrogen are key drivers of CO 2 ‐based ethanol's GHG emissions. With wind electricity, the design cases show the potential of near‐zero CI ethanol (1.1 g CO 2 e/MJ), but that can increase to up to 331–531 g CO 2 e/MJ when today's U.S. Midwest electricity mix is used. To avoid the renewable electricity intermittency issue, we considered a power purchase agreement option using wind electricity 40% of the time and using the regional mix for the rest, which provides a 42% GHG emission reduction from the CI of gasoline. © 2020 The Authors and UChicago Argonne, LLC, Operator of Argonne National Laboratory. Biofuels, Bioproducts and Biorefining published by Society of Chemical Industry and John Wiley & Sons, Ltd.

09 BIOMASS FUELS↗