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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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30 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Radiolytically reworked Archean organic matter in a habitable deep ancient high-temperature brine

Abstract Investigations of abiotic and biotic contributions to dissolved organic carbon (DOC) are required to constrain microbial habitability in continental subsurface fluids. Here we investigate a large (101–283 mg C/L) DOC pool in an ancient (>1Ga), high temperature (45–55 °C), low biomass (10 2 −10 4 cells/mL), and deep (3.2 km) brine from an uranium-enriched South African gold mine. Excitation-emission matrices (EEMs), negative electrospray ionization (–ESI) 21 tesla Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and amino acid analyses suggest the brine DOC is primarily radiolytically oxidized kerogen-rich shales or reefs, methane and ethane, with trace amounts of C 3 –C 6 hydrocarbons and organic sulfides. δ 2 H and δ 13 C of C 1 –C 3 hydrocarbons are consistent with abiotic origins. These findings suggest water-rock processes control redox and C cycling, helping support a meagre, slow biosphere over geologic time. A radiolytic-driven, habitable brine may signal similar settings are good targets in the search for life beyond Earth.

Science & Technology - Other Topics↗
DOE OSTI2020

Metal oxide supported Ni-impregnated bifunctional catalysts for controlling char formation and maximizing energy recovery during catalytic hydrothermal liquefaction of food waste

Nickel (Ni)-impregnated metal oxide catalysts, Ni/CeZrO x , Ni/ZrO 2 , and Ni/CeO 2 , were investigated to maximize energy recovery and reduce char yield during catalytic hydrothermal liquefaction (CHTL) of food waste. Yields of char, biocrude, water soluble products, and gas were measured at 300 °C and 1 hour for both the parent oxides (CeZrO x , ZrO 2 , and CeO 2 ) and the Ni-impregnated versions. Using Ni-based catalysts reduced the carbon-weighted char yield from 16–24% to <10% and decreased the energy recovery of char from 39–47% to <21%, as compared with control tests. In particular, using Ni/ZrO 2 resulted in the greatest biocrude yield, greatest reduction of char yield, and greatest energy recovered as biocrude (39.2%). After factoring in all forms of usable energy produced from food waste, the total energy recovery obtained for the catalysts studied here was >60%. Ni/ZrO 2 and Ni/CeO 2 show the greatest potential for controlling char growth and maximizing energy recovered from food waste. The crystalline structures of all three oxides were hydrothermally stable. Catalyst reuse tests indicate that the biocrude and char yields remained the same for the first and second use (within uncertainty) and that the catalyst retains its initial crystallinity and 93% of its initial Ni content. Molecular composition of biocrudes analyzed by the state-of-the-art analytical platforms (including GC-MS, GC × GC, FT-ICR MS, and 1H NMR) revealed minor differences in the chemical constituents of biocrudes obtained using different catalysts and provided some insight regarding reaction mechanism.

09 BIOMASS FUELS↗
DOE OSTI2022

Elucidating the role of reactive nitrogen intermediates in hetero-cyclization during hydrothermal liquefaction of food waste

Hydrothermal liquefaction (HTL) has emerged as a promising strategy for converting abundant, water-rich organic streams into an energy-dense, sustainable, biocrude. Despite major strides in improving oil yields and process intensification, a key underlying challenge persists in relating the composition of the feedstock to the ultimate fate of nitrogen, which is especially important for biocrude quality. To elucidate how nitrogen partitions into the respective gas, aqueous, oil and solid hydrothermal products, food waste was treated under HTL conditions (15 wt% solids, 575 K reaction temperature, and 1 hour reaction time) and elemental, chromatographic and mass spectroscopy analyses were performed on the products to establish dominant product classes and to close mass, carbon, and nitrogen balances. Liquid products (aqueous and biocrude) were found to contain nearly 60% of the nitrogen, with a majority of the biocrude-phase nitrogen in the form of amides. Ab initio thermodynamic and kinetic simulations on model reactants were used to evaluate potential reaction pathways involving reactive nitrogen intermediates. A subsequent kinetic model was evaluated at reaction temperatures ranging 300–1000 K and for a range of feedstock compositions to identify primary reaction pathways. The Maillard reaction is revealed to be the dominant pathway for converting reactive nitrogen intermediates into observed products, especially those in which nitrogen is present as a heterocyclic aromatic. Subsequent product analysis by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) confirms strong agreement among the experimental data, kinetic model and proposed Maillard pathways.

09 BIOMASS FUELS↗
DOE OSTI2023

Applying the core-satellite species concept: Characteristics of rare and common riverine dissolved organic matter

Introduction: Dissolved organic matter (DOM) composition varies over space and time, with a multitude of factors driving the presence or absence of each compound found in the complex DOM mixture. Compounds ubiquitously present across a wide range of river systems (hereafter termed core compounds) may differ in chemical composition and reactivity from compounds present in only a few settings (hereafter termed satellite compounds). Here, we investigated the spatial patterns in DOM molecular formulae presence (occupancy) in surface water and sediments across 97 river corridors at a continental scale using the “Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems—WHONDRS” research consortium. Methods: We used a novel data-driven approach to identify core and satellite compounds and compared their molecular properties identified with Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Results: In this work, we found that core compounds clustered around intermediate hydrogen/carbon and oxygen/carbon ratios across both sediment and surface water samples, whereas the satellite compounds varied widely in their elemental composition. Within surface water samples, core compounds were dominated by lignin-like formulae, whereas protein-like formulae dominated the core pool in sediment samples. In contrast, satellite molecular formulae were more evenly distributed between compound classes in both sediment and water molecules. Core compounds found in both sediment and water exhibited lower molecular mass, lower oxidation state, and a higher degree of aromaticity, and were inferred to be more persistent than global satellite compounds. Higher putative biochemical transformations were found in core than satellite compounds, suggesting that the core pool was more processed. Discussion: The observed differences in chemical properties of core and satellite compounds point to potential differences in their sources and contribution to DOM processing in river corridors. Overall, our work points to the potential of data-driven approaches separating rare and common compounds to reduce some of the complexity inherent in studying riverine DOM.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Reviews and syntheses: Opportunities for robust use of peak intensities from high-resolution mass spectrometry in organic matter studies

Abstract. Earth's biogeochemical cycles are intimately tied to the biotic and abiotic processing of organic matter (OM). Spatial and temporal variations in OM chemistry are often studied using direct infusion, high-resolution Fourier transform mass spectrometry (FTMS). An increasingly common approach is to use ecological metrics (e.g., within-sample diversity) to summarize high-dimensional FTMS data, notably Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). However, problems can arise when FTMS peak-intensity data are used in a way that is analogous to abundances in ecological analyses (e.g., species abundance distributions). Using peak-intensity data in this way requires the assumption that intensities act as direct proxies for concentrations. Here, we show that comparisons of the same peak across samples (within-peak) may carry information regarding variations in relative concentration, but comparing different peaks (between-peak) within or between samples does not. We further developed a simulation model to study the quantitative implications of using peak intensities to compute ecological metrics (e.g., intensity-weighted mean properties and diversity) that rely on information about both within-peak and between-peak shifts in relative abundance. We found that, despite analytical limitations in linking concentration to intensity, ecological metrics often perform well in terms of providing robust qualitative inferences and sometimes quantitatively accurate estimates of diversity and mean molecular characteristics. We conclude with recommendations for the robust use of peak intensities for natural organic matter studies. A primary recommendation is the use and extension of the simulation model to provide objective guidance on the degree to which conceptual and quantitative inferences can be made for a given analysis of a given dataset. Broad use of this approach can help ensure rigorous scientific outcomes from the use of FTMS peak intensities in environmental applications.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1995

Association reactions at low pressure. 5: The CH3(+)/HCN system. A final word?

The reaction of the methyl cation with hydrogen cyanide is revisited. We have confidence that we have resolved a long standing apparent contradiction of experimental results. A literature history is presented along with one new experiment and a re-examination of an old experiment. In this present work it is shown that all of the previous studies had made consistent observations. Yet, each of the previous studies failed to observe all of the information present. The methyl cation does react with HCN by radiative association, a fact which had been in doubt. The product ions formed in the two-body and three-body processes react differently with HCN. The collisionally stabilized association product formed by a three-body mechanism, does not react with HCN and is readily detected in the experiments. The radiatively stabilized association product, formed by a slow two-body reaction, is not detected because it reacts with HCN by a fast proton transfer reaction forming the protonated HCN ion. Previous studies either 'lost' this product in the extremely large protonated HCN signal that is always present when HCN is used, or discounted it for various reasons. We have been able to show by ion cyclotron resonance (ICR) techniques (both FT-ICR and tandem ICR-dempster-ICR) that the radiative association product does react with the HCN to form the protonated HCN ion.

Anicich, Vincent G.↗
NASA NTRSDate not supplied

Soluble Organic Matter (SOM) analysis of the Hayabusa2 samples: The first results

The Hayabusa2 spacecraft successfully collected the surface and possible sub-surface materials of the asteroid 162173 Ryugu. Ryugu is a C-type asteroid characterized by a low-albedo surface probably consisting of hydrous minerals and carbonaceous materials. [1] The direct optical and spectral analysis of the returned samples indicates that Ryugu material is dominated by hydrous carbonaceous chondrite-like matter (similar to CI chondrites) [2]. Since carbonaceous chondrites have generally yielded various types of organic matter, the collected Ryugu grains are expected to contain diverse types of organic compounds including bio-related molecules. The occurrence of organic compounds in the Ryugu surface will provide clues to the evolution of prebiotic molecules and their preservations associated with aqueous alteration of the primitive asteroid. The initial analysis of soluble organic matter (SOM) of the Hayabusa2-returned samples has been performed by an international team consisting of 32 members. Because the sample amount available for comprehensive SOM analyses is limited, and because the SOM is expected to be present as a complex mixture of various types of organic compounds with very small concentrations of each compound, high-sensitivity and high-resolution analytical techniques have been developed using carbonaceous meteorites [e.g. 3]. Two aggregate samples of the Ryugu grains (A106 and C107) were allocated for the solvent extractions and bulk carbon (C), hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) measurements. The A106 sample was collected during the 1st sampling in February 2019 and the C107 sample was collected during the 2nd sampling in July 2019 after the Small Carry Impactor (SCI) operation. They consist mainly of particles smaller than 1 mm in diameter, and each sample mass was 38-39 mg. They were firstly investigated spectroscopically in the near infrared wavelength range by the Stone Team prior to the solvent extractions. Other small grains (A0080 and C0057) were also allocated for this study to investigate the spatial distribution of organic compounds on the sample surface. The extraction and analytical measurements implemented by the SOM Team are summarized in Figure 1. Each powder sample was extracted sequentially with non-polar to polar solvents, i.e., hexane, dichloromethane (DCM), methanol (MeOH) and H2O, for non-targeted analysis to reveal the compound composition. Each solvent extract was analyzed by solution state nuclear magnetic resonance (NMR) spectroscopy [4], Fourier transform- ion cyclotron resonance/mass spectrometry (FT-ICR/MS) with ESI and APPI ionization [5] and by high-resolution mass spectroscopy using Orbitrap MS coupled with nano-liquid chromatography (nanoLC/Orbitrap MS) [6], and using two dimensional gas chromatography/mass spectrometry (GC×GC/MS). The extracted residues were passed to the Chemistry Team for further inorganic element analysis. The other powder sample was subjected to the hot water extraction for amino acid analyses including chiral isomer separation, which was performed by three-dimensional (3D) high-performance liquid chromatography (HPLC) with high-sensitivity fluorescence detection (FD) [7] and by HPLC/FD coupled with quadrupole-time of flight/mass spectrometry (QToF/MS) [8]. After the hot water extraction, the residue was split into two halves. One half was further extracted with hydrochloric acid (HCl) to analyze for amino acids in bound-form. The other half was sequentially extracted with DCM/MeOH (1/1) to analyze semi-polar compounds such as polycyclic aromatic hydrocarbons (PAHs) by GC/MS, followed by further extraction with formic acid to analyze polar heterocyclic compounds, and subsequent extraction with HCl to detect bound-form polar compounds. The extracted residues were passed to the IOM Team for the analysis of insoluble organic matter (IOM). Compound-specific stable isotope analyses will be performed using GC/combustion/isotope ratio mass spectrometry (GC/C/IRMS) if the compound concentration is high enough to enable such an isotopic measurement. All extraction procedures were performed on an ISO 6 (Class 100) clean bench inside an ISO 5 (Class 1000) clean room. Baked serpentine powder was also analyzed as a procedural blank. In situ organic compound analysis with the molecular imaging was performed using desorption electrospray ionization (DESI) equipped with Orbitrap MS [9, 10], followed by spatial imaging of organic compounds using ToF/secondary ion mass spectrometry (ToF/SIMS) [11]. The bulk chemical and isotopic compositions of CNS and HO were determined using nano-elemental analysis/isotope ratio mass spectrometry (nanoEA/IRMS) [12] and EA/pyrolysis/IRMS, respectively. We have identified a variety of indigenous organic compounds in the extracts of both A106 and C107 samples. The Ryugu grains host organic molecules under the high-vacuum and cosmic-ray irradiation environment of the asteroid surface. The analysis of extracted molecules is in progress, and the first results will be presented at the symposium.

Hiroshi Naraoka↗
DOE OSTI2025

2025 ASMS Investigation of the Collision-Induced Dissociation Mechanism of Protonated TODGA with IRIS

Title (20 words): Investigation of the Collision-Induced Dissociation Mechanism of Protonated TODGA with IRIS Introduction (120 words): One of the challenges facing wide-spread adoption of nuclear power is the development of efficient separation processes for used nuclear fuel. The molecules in separation processes are subjected to an extreme environment due to the high radiation fields from the used fuel and highly acidic media used for fuel dissolution, which results in significant molecular degradation, leading to reduced process efficiency. These degradation products must be identified and studied so mitigation strategies can be developed to maintain process efficiency. However, complex systems can have many degradation products, complicating identification. Untargeted analysis tools could be used to understand radiation chemistry in complex systems. However, this would necessitate improved understanding of the gas-phase fragmentation mechanisms of fuel cycle molecules like tetraoctyldiglycolamide (TODGA). Methods (120 words): The gas-phase fragmentation of protonated TODGA was investigated using collision-induced dissociation (CID), resonance ejection, and infrared ion spectroscopy (IRIS). CID and resonance ejection experiments were conducted using a Bruker Daltonics (Bremen, Gemany) SolariX XR fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. IRIS spectra of protonated TODGA and its two CID fragmentation products were measured using a modified Bruker amaZon Speed ETD 3D quadrupole ion trap mass spectrometer coupled to the Free Electron Lasers for Infrared eXperiments (FELIX) free electron laser. Measured spectra were compared with density functional theory (DFT) calculations using the Gaussian 16, Revision C.02 software package with the ?B97X-D functional and def2-TZVPP basis sets. Candidate structures were generated using the CREST 3.0 conformational sampling software tool. Preliminary Data (300 words): Collision-induced dissociation of protonated TODGA ([C36H73N2O3]+, m/z=581.562) results two fragment ions, one at m/z=340.285 assigned as [C20H38NO3]+ and the other at m/z=312.290, assigned as [C19H38NO2]+. Based on the assigned formula and the structure of protonated TODGA, the fragment at m/z=340.285 is likely formed from elimination of neutral dioctylamine. Comparison of the IRIS spectrum of m/z=340.285 with DFT predictions suggests it contains a ring structure, and is assigned as N-octyl-N-(6-oxo-1,4-dioxan-2-ylidene)octan-1-aminium. Based on this structure and the structure of protonated TODGA, we hypothesize this fragment formed from elimination of neutral dioctylamine followed by a ring closure mechanism. Comparison of the IRIS spectrum of the fragment at m/z=312.290 with DFT predictions also indicated the presence of a ring structure, assigned as N-(1,3-dioxolan-4-ylidene)-N-octyloctan-1-aminium. This product could be formed from elimination of carbon monoxide from the ring of m/z=340.285 as a sequential fragmentation or formed directly from protonated TODGA via elimination of neutral N,N-dioctylformamide followed by a ring closure. Resonance ejection experiments where m/z=340 was continuously ejected from the IRC cell showed no decrease in intensity of m/z=312.290 across several collision energies, suggesting that the later, direct formation mechanism, dominates. The location of the ionizing proton in protonated TODGA is important for modeling the fragmentation mechanisms. DFT calculations suggested that the position of bands involving the coupled vibrations of the amide C—N and C=O bonds in TODGA are the most sensitive to proton location. Evaluation of the IRIS spectrum of protonated TODGA suggests that the ionizing proton is located between the two amid oxygens. This protonation location was calculated to lie approximately 30 kJ/mol lower in energy than the next lowest energy location, with the proton located solely on one of the amide oxygens. Novel aspect (20 words): Infrared ion spectroscopy combined with resonance ejection experiments and density functional theory to probe the collision-induced dissociation mechanism of tetraoctyldiglycolamide.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2020

A History of Molecular Level Analysis of Natural Organic Matter by FTICR Mass Spectrometry and The Paradigm Shift in Organic Geochemistry

Natural organic matter (NOM) is a complex mixture of biogenic molecules resulting from the deposition and transformation of plant and animal matter. It has long been recognized that NOM plays an important role in many geological, geochemical, and environmental processes. Of particular concern is the fate of NOM in response to a warming climate in environments that have historically sequestered carbon (e.g., peatlands and swamps) but may transition to net carbon emitters. In this review, we will highlight developments in the application of high-field Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) in identifying the individual components of complex NOM mixtures, focusing primarily on the fraction that is dissolved in natural waters (dissolved organic matter or DOM). We will first provide some historical perspective on developments in FTICR technology that made molecular-level characterizations of DOM possible. In conclusion, a variety of applications of the technique will then be described, followed by our view of the future of high-field FTICR MS in carbon cycling research, including a particularly exciting metabolomic approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Unveiling the dark matter of riverine dissolved organic matter and its role in molecular chemodiversity

Chemodiversity of riverine dissolved organic matter (DOM) plays a crucial role in global elemental cycles and ecosystem function. However, DOM “dark matter”—molecules without assigned specific formulae—remain unexplored in the interpretation of chemodiversity. Here, we systematically investigated the characteristics and drivers of dark matter and its impacts on DOM chemodiversity using 551 river water and sediment samples. Compared to known matter with specific formulae, dark matter exhibited lower molecular weight and diversity, but higher compositional dissimilarity, with dissolved organic carbon (DOC) as the primary driver. Including dark matter into chemodiversity analysis changed mass, diversity, and compositional dissimilarity of DOM from –10.1 to –0.04 %, –0.7 to 4.9 %, and 0.4 to 28.8 % in waters, and from –17.5 to 5.7 %, –10.5 to 19.2 %, and –22.3 to 33.1 % in sediments, respectively. DOC mediated these ecosystem-dependent effects: lower DOC amplified the effects on chemodiversity in waters, whereas in sediments, the effects shifted from negative to positive with changing DOC. Furthermore, ignoring dark matter would overestimate the regulatory role of DOC on sediment DOM chemodiversity. In conclusion, collectively, our findings clarify the influence of dark matter on DOM chemodiversity assessments across environmental gradients, improving understanding of riverine DOM and refining its analytical framework.

Chemodiversity↗
DOE OSTI2021

Advanced spectrometric methods for characterizing bio-oils to enable refineries to reduce fuel carbon intensity during co-processing

A promising approach for supplementing petroleum-derived fuels to support reductions in green-house gas emissions is to convert abundant biomass feedstocks into renewable carbon-rich oils using pyrolysis. However, the resultant bio-oils contain various oxygenated compounds that can impart acidity, chemical and thermal instability, and immiscibility with petroleum derived fuels, necessitating further upgrading to derive fuel blendstocks. Co-processing bio-oils and petroleum-derived liquids in existing refineries is a potentially near-term, cost-effective approach for upgrading bio-oils while reducing refinery carbon intensities. However, one cause for hesitation in co-processing bio-oils is limited comprehensive characterization and speciation of the bio-oil components. Advanced analytical techniques are currently under investigation to enable identification of elusive species in bio-oils, enabling researchers to develop strategies to mitigate catalyst deactivation agents and contaminants. This review provides a brief overview of several analytical methods commonly used to analyze bio-oils and their limitations. In addition, advanced techniques currently under development are discussed to further elucidate bio-oil components that may limit its end use. This will help inform the technical and economic feasibility of co-processing bio-oils with petroleum-derived liquids, therefore, improving the overall downstream processes for biofuels blendstock production.

09 BIOMASS FUELS↗
DOE OSTI2023

Advanced Analytical Methodologies Enable Feedstock Screening and Correlation to Pyrolysis Yields and Catalytic Upgrading

Pyrolysis of lignocellulosic biomass can serve as a powerful pathway for the generation of renewable fuels and industrial products. However, procurement of some biomass may be costly, especially when there is competition for alternative uses. Forestry and agricultural byproducts may serve as valuable pyrolysis feedstocks due to their high availability and low cost. Although waste products may fill demand for affordable pyrolysis feedstocks, they are often high in ash and extractives which contribute to unfavorable changes in pyrolysis vapor composition, as well as end products. The work presented here investigates the correlations between various pine anatomical fractions to understand their effect on pyrolysis oil composition for forest residues. Analytical pyrolysis coupled to direct analysis by molecular beam mass spectrometry (MBMS) provides real-time monitoring of pyrolysis vapor composition, even for compounds that are not amenable to gas chromatography. Statistical analysis of MBMS data from the fast pyrolysis (FP) of clean pine, cambium, twigs and branches, needles, bark, and a forest residue samples revealed that bark and needles made the greatest differences in the vapor composition of forest residues during pyrolysis and were enriched in resin acids, furfural derivatives, and ions that have been previously observed from catalysis corresponding to ash content. These results were also compared to catalytic fast pyrolysis (CFP) using a platinum on titania catalyst, and correlations between FP and CFP products were observed for the anatomical fractions. The forest residues and corresponding anatomical fractions from a stand of 23-year-old pine will be converted by fast pyrolysis in a bench-scale 2-inch fluidized-bed reactor, and statistical correlations between the bench-scale products and analytical-scale pyrolysis vapors will be shown. This work highlights the power of advanced analytical methodologies in determining the contributions of vapor components to catalytic pyrolysis outcomes for mixed feedstocks and demonstrates the use of analytical methodologies to better screen feedstocks prior to pyrolysis.

analytical↗