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At least 307 records · Page 17

The measurement of carbon monoxide and methane in the national capital air quality control region. II - Meteorological conditions and chromatographic and spectrometric results

The meteorological conditions during this program consisted of a stagnant high pressure system which was subsequently replaced by southward moving Canadian air. This change in air masses produced distinct changes in the ambient CO concentrations. Ground level concentrations decreased from an average of 1.3 ppm at the beginning of the experiment to 0.2 ppm at the end. Vertical profiles obtained during the experiment showed decreases in the CO concentrations with altitude. Agreement of gas chromatography data for CO and CH4 by NASA and NRL was within 5% for the concentrations encountered. Results from NASA's Infrared Fourier Spectrometer agreed with the gas chromatographic results both in trends and concentrations of CO and CH4 observed with the passing frontal system.

Lamontagne, R. A.↗

Advanced acoustic cavity technology

A series of rocket motor firings was performed in a modified linear aerospike thrust chamber with the H2/O2 propellant combination to allow determination of the physical properties of the combustion gases in acoustic cavities located in the chamber side walls. A preliminary analytical study was first conducted to define theoretically both the appropriate cavity dimensions and the combustion gas flow field adjacent to the cavity openings. During the subsequent motor firings, cavity gas temperature profiles were measured and gas samples were withdrawn from the bottom of the cavities for compositional analysis by measurement of pressure/temperature variation and gas chromatography. Data were obtained with both radially and axially oriented cavities and with and without hydrogen bleed flow through the cavities. A simplified procedure was developed for predicting gas cavity and acoustic velocity for use in acoustic cavity design analyses.

Hines, W. S.↗

Parent Body Influences on Amino Acids in the Tagish Lake Meteorite

The Tagish Lake meteorite is a primitive C2 carbonaceous chondrite with a mineralogy, oxygen isotope, and bulk chemical. However, in contrast to many CI and CM carbonaceous chondrites, the Tagish Lake meteorite was reported to have only trace levels of indigenous amino acids, with evidence for terrestrial L-amino acid contamination from the Tagish Lake meltwater. The lack of indigenous amino acids in Tagish Lake suggested that they were either destroyed during parent body alteration processes and/or the Tagish Lake meteorite originated on a chemically distinct parent body from CI and CM meteorites where formation of amino acids was less favorable. We recently measured the amino acid composition of three different lithologies (11h, 5b, and 11i) of pristine Tagish Lake meteorite fragments that represent a range of progressive aqueous alteration in order 11h < 5b < 11i as inferred from the mineralogy, petrology, bulk isotopes, and insoluble organic matter structure. The distribution and enantiomeric abundances of the one- to six-carbon aliphatic amino acids found in hot-water extracts of the Tagish Lake fragments were determined by ultra performance liquid chromatography fluorescence detection and time of flight mass spectrometry coupled with OPA/NAC derivatization. Stable carbon isotope analyses of the most abundant amino acids in 11h were measured with gas chromatography coupled with quadrupole mass spectrometry and isotope ratio mass spectrometry.

Glavin, D. P.↗

An experimental and detailed kinetic modeling study of the pyrolysis and oxidation of allene and propyne over a wide range of conditions

Allene and propyne are important intermediates in the pyrolysis and oxidation of higher hydrocarbon fuels, and they are also a major source of propargyl radical formation, which can recombine into different C 6 H 6 isomers and finally produce soot. In a prior work (Panigrahy et al., “A comprehensive experimental and improved kinetic modeling study on the pyrolysis and oxidation of propyne”, Proc. Combust. Inst 38 (2021)), the pyrolysis, ignition , and laminar flame speed of propyne were investigated. To understand the kinetic features of initial fuel breakdown and oxidation of the two C 3 H 4 isomers, new measurements for allene pyrolysis and oxidation are conducted in the present paper at the same operating conditions as those studied previously for propyne. Ignition delay times of allene are measured using a high-pressure shock tube and a heated twin-opposed piston rapid compression machine in the temperature range 690– 1450 K at equivalence ratios of 0.5, 1.0 and 2.0 in ‘air’, and at pressures of 10 and 30 bar. Pyrolysis species measurements of allene and propyne are also performed using a gas chromatography integrated singlepulse shock tube in the temperature range 1000–1700 K at pressure of 2 and 5 bar. Furthermore, laminar flame speeds of allene are measured at elevated gas temperatures of 373 K at pressures of 1 and 2 bar for a wide range of equivalence ratios from 0.6 to 1.5. A newly updated kinetic mechanism developed for this study is the first model that can well reproduce all of the experimental results for both allene and propyne. It is observed that in the pyrolysis process, allene dissociates faster than propyne. Both isomers exhibit similar ignition delay times at high temperatures (>1000 K), while, at intermediate temperatures (770–1000 K) propyne is the faster to ignite, and at lower temperatures (< 770 K) allene becomes more reactive. Furthermore, laminar flame speeds for propyne are found to be slightly faster than those for allene under the conditions studied in this work

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of Soot Growth Region of Laminar Premixed Methane/Oxygen Flames

The structure of the soot growth region of laminar premixed methane/oxygen flames (fuel-equivalence ratios of 1.60 - 2.77) was studied both experimentally and computationally. Measurements were carried out in flames stabilized on a flat flame burner operated at standard temperature and pressure, and included velocities by laser velocimetry, soot volume fractions by laser extinction, soot temperatures by multiline emission, gas temperatures (where soot was absent) by corrected fine-wire thermocouples, major gas species concentrations by sampling and gas chromatography, and hydrogen atom concentrations by the Li/LiOH technique in conjunction with atomic absorption to find the proportion of free lithium in the flames. The measured concentrations of major gas species were in reasonably good agreement with predictions based on the detailed mechanisms of Leung and Lindstedt, and Frenklach and coworkers. The measurements also confirmed predictions of both these mechanisms that H-atom concentrations are in local thermodynamic equilibrium throughout the soot growth region even through the concentrations of major gas species are not. Thus, present findings support recent evaluations of the hydrogen-abstraction/carbon-addition (HACA) soot growth mechanism in similar flames, where the approximation that H-atom concentrations were in local thermodynamic equilibrium was adopted, based on predictions using the two mechanisms, due to the absence of direct H-atom concentration measurements.

Xu, F.↗

Structure of the Soot Growth Region of Laminar Premixed Methane/Oxygen Flames

The structure of the soot growth region of laminar premixed methane/oxygen flames (fuel-equivalence ratios of 1.60-2.77) was studied both experimentally and computationally. Measurements were carried out in flames stabilized on a flat flame burner operated at standard temperature and pressure, and included velocities by laser velocimetry, soot volume fractions by laser extinction, soot temperatures by multiline emission, gas temperatures (where soot was absent) by corrected fine-wire thermocouples, major gas species concentrations by sampling and gas chromatography, and hydrogen atom concentrations by the Li/LiOH technique in conjunction with atomic absorption to find the proportion of free lithium in the flames. The measured concentrations of major gas species were in reasonably good agreement with predictions based on the detailed mechanisms of Leung and Lindstedt, and Frenklach and coworkers. The measurements also confirmed predictions of both these mechanisms that H-atom concentrations are in local thermodynamic equilibrium throughout the soot growth region even through the concentrations of major gas species are not. Thus, present findings support recent evaluations of the hydrogen-abstraction/carbon-addition (HACA) soot growth mechanism in similar flames, where the approximation that H-atom concentrations were in local thermodynamic equilibrium was adopted, based on predictions using the two mechanisms, due to the absence of direct H-atom concentration measurements.

Xu, F.↗

Structure of the Soot Growth Region of Laminar Premixed Methane/Oxygen Flames

The structure of the soot growth region of laminar premixed methane/oxygen flames (fuel-equivalence ratios of 1.60-2.77) was studied both experimentally and computationally. Measurements were carried out in flames stabilized on a flat flame burner operated at standard temperature and pressure, and included velocities by laser velocimetry, soot volume fractions by laser extinction, soot temperatures by multiline emission, gas temperatures (where soot was absent) by corrected fine-wire thermocouples, major gas species concentrations by sampling and gas chromatography, and hydrogen atom concentrations by the Li/LiOH technique in conjunction with atomic absorption to find the proportion of free lithium in the flames. The measured concentrations of major gas species were in reasonably good agreement with predictions based on the detailed mechanisms of Leung and Lindstedt, and Frenklach and coworkers. The measurements also confirmed predictions of both these mechanisms that H-atom concentrations are in local thermodynamic equilibrium throughout the soot growth region even through the concentrations of major gas species are not. Thus, present findings support recent evaluations of the hydrogen-abstraction/carbon-addition (HACA) soot growth mechanism in similar flames, where the approximation that H-atom concentrations were in local thermodynamic equilibrium was adopted, based on predictions using the two mechanisms, due to the absence of direct H-atom concentration measurements.

Xu, F.↗

GC/MS Gas Separator Operates At Lower Temperatures

Experiments show palladium/silver tube used to separate hydrogen carrier gas from gases being analyzed in gas-chromatography/mass-spectrometry (GC/MS) system functions satisfactorily at temperatures as low as 70 to 100 degrees C. Less power consumed, and catalytic hydrogenation of compounds being analyzed diminished. Because separation efficiency high even at lower temperatures, gas load on vacuum pump of mass spectrometer kept low, permitting use of smaller pump. These features facilitate development of relatively small, lightweight, portable GC/MS system for such uses as measuring concentrations of pollutants in field.

Sinha, Mahadeva P.↗

Hydrogen from low-density polyethylene via nonthermal plasma: Effects of energy density and process parameters

Nonthermal plasma processes are promising for the modular valorization of plastic waste, especially into hydrogen and carbon materials, due to their high intensity, lack of reliance on catalysts or consumables, and suitability to be directly powered by electricity. We investigate the production of hydrogen from low-density polyethylene (LDPE) as a plastic waste model using streamer Dielectric Barrier Discharge (sDBD) plasma in nitrogen at atmospheric pressure. Here, we examine the effects of process energy density (energy input per unit of feedstock mass), feedstock mass, and plasma intensity (electric voltage) on plasma properties, hydrogen yield and energy efficiency via gas chromatography, optical emission spectroscopy, and electrical diagnostics, together with reactor-scale and nonlinear electric circuit modeling. The characteristic temperature of free electrons in the sDBD plasma is approximately 15000 K (1.3 eV), and that of gas species 10 times lower, demonstrating strong thermal non-equilibrium that can lead to molecular bond scission via charged species impact rather than direct heating. Experimental results show that higher energy density leads to greater hydrogen production and diminishing energy efficiency, and that higher plasma intensity and larger feedstock mass lead to greater hydrogen yield due to higher plasma temperatures and enhanced energy fluxes to the feedstock.

08 HYDROGEN↗

Automated life-detection experiments for the Viking mission to Mars

As part of the Viking mission to Mars in 1975, an automated set of instruments is being built to test for the presence of metabolizing organisms on that planet. Three separate modules are combined in this instrument so that samples of the Martian surface can be subjected to a broad array of experimental conditions so as to measure biological activity. The first, the Pyrolytic Release Module, will expose surface samples to a mixture of C-14O and C-14O2 in the presence of Martian atmosphere and a light source that simulates the Martian visible spectrum. The assay system is designed to determine the extent of assimilation of CO or CO2 into organic compounds. The Gas Exchange Module will incubate surface samples in a humidified CO2 atmosphere. At specified times, portions of the incubation atmosphere will be analyzed by gas chromatography to detect the release or uptake of CO2 and several additional gases. The Label Release Module will incubate surface samples with a dilute aqueous solution of simple radioactive organic substrates in Martian atmosphere, and the gas phase will be monitored continuously for the release of labeled CO2.

Klein, H. P.↗

Application of a Modified Gas Chromatograph to Analyze Space Experiment Combustion Gases on Space Shuttle Mission STS-94

A space experiment designed to study the behavior of combustion without the gravitational effects of buoyancy was launched aboard the Space Shuttle Columbia on July 1, 1997. The space experiment, designated as Combustion Module-1 (CM-1), was one of several manifested on the Microgravity Sciences Laboratory - 1 (MSL-1) mission. The launch, designated STS-94, had the Spacelab Module as the payload, in which the MSL-1 experiments were conducted by the Shuttle crewmembers. CM-1 was designed to accommodate two different combustion experiments during MSL-1. One experiment, the Structure of Flame Balls at Low Lewis-number experiment (SOFBALL), required gas chromatography analysis to verify the composition of the known, premixed gases prior to combustion, and to determine the remaining reactant and the products resulting from the combustion process in microgravity. A commercial, off-the-shelf, dual-channel micro gas chromatograph was procured and modified to interface with the CM-1 Fluids Supply Package and the CM-1 Combustion Chamber, to accommodate two different carrier gases, each flowing through its own independent column module, to withstand the launch environment of the Space Shuttle, to accept Spacelab electrical power, and to meet the Spacelab flight requirements for electromagnetic interference (EMI) and offgassing. The GC data was down linked to the Marshall Space Flight Center for near-real time analysis, and stored on-orbit for post-flight analysis. The gas chromatograph operated successfully during the entire SOFBALL experiment and collected 309 runs. Because of the constraints imposed upon the gas chromatograph by the CM-1 hardware, system and operations, it was unable to measure the gases to the required accuracy. Future improvements to the system for a re-flight of the SOFBALL experiment are expected to enable the gas chromatograph to meet all the requirements.

Coho, William K.↗

Combining micro dry column chromatography and mass spectrometry

Dry column chromatography principles applied in microscale produce technique to minimize time in preparing and analyzing colorless constituents of soluble mixtures. Glass pipette microcolumns filled with finely sieved adsorbents permit capillary attraction and separation in 3 to 15 minutes. Technique is adaptable to gas chromatography.

Bauman, A. J.↗

Isotopic and Geochemical Investigation of Two Distinct Mars Analog Environments Using Evolved Gas Techniques in Svalbard, Norway

The 2010 Arctic Mars Analog Svalbard Expedition (AMASE) investigated two distinct geologic settings on Svalbard, using methodologies and techniques to be deployed on Mars Science Laboratory (MSL). AMASErelated research comprises both analyses conducted during the expedition and further analyses of collected samples using laboratory facilities at a variety of institutions. The Sample Analysis at Mars (SAM) instrument suite on MSL includes pyrolysis ovens, a gas-processing manifold, a quadrupole mass spectrometer (QMS), several gas chromatography columns, and a Tunable Laser Spectrometer (TLS). An integral part of SAM development is the deployment of SAM-like instrumentation in the field. During AMASE 2010, two parts of SAM participated as stand-alone instruments. A Hiden Evolved Gas Analysis- Mass Spectrometer (EGA-QMS) system represented the EGA-QMS component of SAM, and a Picarro Cavity Ring Down Spectrometer (EGA-CRDS), represented the EGA-TLS component of SAM. A field analog of CheMin, the XRD/XRF on MSL, was also deployed as part of this field campaign. Carbon isotopic measurements of CO2 evolved during thermal decomposition of carbonates were used together with EGA-QMS geochemical data, mineral composition information and contextual observations made during sample collection to distinguish carbonates formation associated with chemosynthetic activity at a fossil methane seep from abiotic processes forming carbonates associated with subglacial basaltic eruptions. Carbon and oxygen isotopes of the basalt-hosted carbonates suggest cryogenic carbonate formation, though more research is necessary to clarify the history of these rocks.

Svalbard↗

Oil in Alaska North Slope Gas Hydrate Reservoir: Micro-CT and Flow Simulation Insights into Permeability

Gas hydrate-bearing sands on the Alaska North Slope (ANS) host minor volumes of crude oil whose impact on formation permeability has never been quantified relative to a gas hydrate reservoir system. Here, we combine in situ pressure-core microcomputed-tomography (μ-CT), thermogravimetric analysis (TGA), gas-chromatography–mass-spectrometry (GC–MS), scanning-electron microscopy coupled with energy-dispersive spectroscopy (SEM-EDS), and Stokes-flow simulation to (i) quantify oil saturation, (ii) infer its source, and (iii) evaluate its influence on permeability after gas-hydrate dissociation. μ-CT and SEM-EDS imaging identify the host sediment as silty, with some grain-coating clay present. Eight representative 3003-voxel subvolumes extracted from a preserved pressure core (Core 15P-3c, from the B1 sand (unit B), HYDRATE 02 Geo Data Well (GDW), 886.96–887.29 m measured depth, MD) exhibit porosities of 0.34–0.37 and an average oil saturation of 0.09 ± 0.03, in comparison to an independent TGA-based estimate of 0.16. GC-MS fingerprints obtained from an adjacent depressurized core (Core 17P-1, 891.37–891.44 m MD), together with oil pore habit revealed by μ-CT, suggest that the oil is partly native but also includes contributions from mineral oil-based drilling fluid contamination. Further analysis of oil–porewater interactions and flushing tests confirms that native oil saturation in the analyzed samples ranges from 0.04 to 0.08 with an average of approximately 0.06, and the oil is highly immobile. Flow simulations demonstrate that the native oil saturation of ≈0.06 reduces permeability by approximately 50% due to both pore blockage and increased flow-path tortuosity. These findings reveal the potential presence of native oil within the ANS gas hydrate reservoir and suggest that future simulation models may need to account for its impact on permeability to improve long-term performance predictions of gas and water production.

02 PETROLEUM↗

Sustainable H 2 -Rich Syngas Production via Microwave-Assisted vs Conventional Catalysis of Pinewood

Catalytic gasification of biomass is a promising method for producing hydrogen-rich syngas, which is a valuable resource for cleanenergy applications. In this study, microwave-assisted biomass gasification was compared with conventional thermally driven biomass gasification using pinewood as the biomass without the use of external gasifying agents (such as air, steam, and CO 2 ), under non-catalytic and catalytic conditions. The catalysts consisted of either an iron or a nickel catalyst, and the pinewood used as biomass contained 42% oxygen. This comparative analysis explores the differences in reaction chemistry, product yields, and the role of key reactions such as the water gas shift (WGS) reaction, Boudouard reaction, etc. The gas-phase and liquid-phase products were analyzed using online gas chromatography, and the fresh and spent catalysts were analyzed using X-ray diffraction (XRD) techniques. It was found that microwave-assisted gasification offers advantages in terms of enhanced reaction efficiency, catalyst stability, and hydrogen yield. For the microwave-assisted reaction, the gas yield reached 87%, the char yield was 12.1%, and the tar yield was less than 1% (0.793%) at 550 °C. In contrast, thermal-assisted gasification using the same catalyst produced a gas yield of 85.796%, char yield of 11.438%, and higher tar yield of 2.8% at 900 °C. The higher microwave-assisted performance was attributed to faster heating and better control over reaction conditions, higher reaction rates, and more favorable conditions for hydrogen production.

biomass↗

Development and implementation of high-throughput proteomic and metabolomics assays by using advanced chromatographic and mass spectrometric systems (CRADA Final Report)

The mission of this CRADA with Agilent was to couple powerful MS platforms (QQQ, IM-QTOFMS) with Agilent’s novel Ultra-High-Performance Liquid Chromatography (UHPLC) fast metabolomic workflows and perform ABF Machine Learning (ML) to generated datasets. Agilent transferred UHPLC methods to PNNL and LBNL and methods were implemented and demonstrated in both labs, achieving total acquisition times of < 10 min. Metabolites analyzed using Agilent’s shared methods included metabolites from central carbon metabolism, common across hosts, and metabolites unique to engineered strains. Standards were acquired in an UHPLC-Drift Tube Ion Mobility Mass Spectrometer (DTIMS) system for the first time within the context of ABF and methods were optimized based on Agilent’s protocols. Samples from ABF hosts Pseudomonas putida, Aspergillus pseudoterreus, Aspergillus niger and Rhodosporidium toruloides were analyzed using the UHPLC-DTIMS platform for a total of 276 runs. A data analysis workflow compatible with the Experimental Data Depot (EDD) and completely shareable was developed for the acquired UHPLC-DTIMS data. Samples were analyzed using a Data Independent Acquisition Approach (DIA), which for most of the standards provided more transitions therefore increasing detection confidence. Using the data acquired by PNNL, LBNL, and Agilent’s specifications from previous ML projects, SNL applied an ensemble ML strategy to pick the best performing model for automated LC-method selection. Finally, with the contribution of the participant labs and Agilent, SNL developed an Automated Method Selection (AMS) software tool to predict the best liquid chromatography method for analysis of any new molecules of interest. Samples with novel pathways and new metabolite targets of interest are generated at a high pace in the ABF. Overall, the project advanced rapid metabolomics by combining liquid chromatography, ion mobility spectrometry, and data-independent mass spectrometry with machine learning. This multidimensional approach uses retention time, collision cross-section, precursor mass, and fragment-ion information to distinguish chemically similar metabolites that can be difficult to resolve using conventional liquid- or gas-chromatography methods. The resulting workflow also provided automated metabolite-identification error estimates, addressing a recognized need for statistical confidence measures in metabolomics.

Petzold, Christopher [Lawrence Berkeley National L↗

Co-processing catalytic fast pyrolysis oil in an FCC reactor

Here, studies of co-processing catalytic fast pyrolysis (CFP) oil with vacuum gas oil (VGO) are conducted in a Davison Circulating Riser (DCR). The CFP oil (CFPO) for this study was produced by upgrading fast-pyrolysis vapors from pine in an ex-situ fixed-bed reactor. CFPOs were co-processed at up to a volume fraction of 0.05 with VGO at 521 degrees C and 257 kPa. The yields of oil, aqueous phase, tail gas, and coke were measured. The amount of coke was determined from the carbon containing components in the regenerator flue gas. A compositional analysis was conducted with gas chromatography and elemental analyzers. The organic liquids were distilled into gasoline, jet-fuel, diesel, and resid fractions. A biocarbon analysis was conducted on the organic phase and its individual boiling-point fractions. The results show a small decrease in liquid yield and a generally increased gas yield when co-processing CFPO with VGO. The experiments showed that 75%-100% of biocarbon is incorporated into liquid fuels relative to fossil carbon, depending on catalyst and CFPO. The measurements indicate that cracked CFPO components are predominantly included in the jet-fuel and diesel fractions. A techno-economic analysis (TEA) estimated the minimum fuel selling price (MSFP) for fuel-range products derived from FCC co-processing of CFPO at 24 to 29 $\$$/GJ ($\$$2.90 to $\$$3.50 per gasoline-gallon equivalent; GGE) at a yield of 4.87-7.14 GJ/t(biomass) or 40-58 GGE/t.

09 BIOMASS FUELS↗

Co-Processing Catalytic Fast Pyrolysis Oil in an FCC Reactor

Studies of co-processing catalytic fast pyrolysis (CFP) oil with vacuum gas oil (VGO) are conducted in a Davison Circulating Riser (DCR). The CFP oil (CFPO) for this study was produced by upgrading fast-pyrolysis vapors from pine in an ex-situ fixed-bed reactor. CFPOs were co-processed at up to 5 vol% with VGO at 521°C and 2.57 bar. The yields of oil, aqueous phase, tail gas, and coke were measured. The amount of coke was determined from the carbon containing components in the regenerator flue gas. A compositional analysis was conducted with gas chromatography and elemental analyzers. The organic liquids were distilled into gasoline, jet-fuel, diesel, and resid fractions. A biocarbon analysis was conducted on the organic phase and its individual boiling-point fractions. The results show a small decrease in liquid yield and a generally increased gas yield when co-processing CFPO with VGO. For experiments with E-Cat as catalyst, approximately 70% of biocarbon is incorporated into liquid fuels relative to fossil carbon, while more of the biocarbon is contained in tail gas (as carbon dioxide or olefins) and/or coke. The measurements indicate that cracked CFPO components are predominantly included in the jet-fuel and diesel fractions. A techno-economic analysis (TEA) estimated the minimum fuel selling price (MSFP) for fuel-range products derived from FCC co-processing of CFPO at $3 to $4 per gasoline-gallon equivalent (GGE) at a yield of 51 GGE per ton of biomass.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗