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Buoyancy Effects on Flow Structure and Instability of Low-Density Gas Jets

A low-density gas jet injected into a high-density ambient gas is known to exhibit self-excited global oscillations accompanied by large vortical structures interacting with the flow field. The primary objective of the proposed research is to study buoyancy effects on the origin and nature of the flow instability and structure in the near-field of low-density gas jets. Quantitative rainbow schlieren deflectometry, Computational fluid dynamics (CFD) and Linear stability analysis were the techniques employed to scale the buoyancy effects. The formation and evolution of vortices and scalar structure of the flow field are investigated in buoyant helium jets discharged from a vertical tube into quiescent air. Oscillations at identical frequency were observed throughout the flow field. The evolving flow structure is described by helium mole percentage contours during an oscillation cycle. Instantaneous, mean, and RMS concentration profiles are presented to describe interactions of the vortex with the jet flow. Oscillations in a narrow wake region near the jet exit are shown to spread through the jet core near the downstream location of the vortex formation. The effects of jet Richardson number on characteristics of vortex and flow field are investigated and discussed. The laminar, axisymmetric, unsteady jet flow of helium injected into air was simulated using CFD. Global oscillations were observed in the flow field. The computed oscillation frequency agreed qualitatively with the experimentally measured frequency. Contours of helium concentration, vorticity and velocity provided information about the evolution and propagation of vortices in the oscillating flow field. Buoyancy effects on the instability mode were evaluated by rainbow schlieren flow visualization and concentration measurements in the near-field of self-excited helium jets undergoing gravitational change in the microgravity environment of 2.2s drop tower at NASA John H. Glenn Research Center. The jet Reynolds number was varied from 200 to 1500 and jet Richardson number was varied from 0.72 to 0.002. Power spectra plots generated from Fast Fourier Transform (FFT) analysis of angular deflection data acquired at a temporal resolution of 1000Hz reveal substantial damping of the oscillation amplitude in microgravity at low Richardson numbers (~0.002). Quantitative concentration data in the form of spatial and temporal evolutions of the instability data in Earth gravity and microgravity reveal significant variations in the jet flow structure upon removal of buoyancy forces. Radial variation of the frequency spectra and time traces of helium concentration revealed the importance of gravitational effects in the jet shear layer region. Linear temporal and spatio-temporal stability analyses of a low-density round gas jet injected into a high-density ambient gas were performed by assuming hyper-tan mean velocity and density profiles. The flow was assumed to be non parallel. Viscous and diffusive effects were ignored. The mean flow parameters were represented as the sum of the mean value and a small normal-mode fluctuation. A second order differential equation governing the pressure disturbance amplitude was derived from the basic conservation equations. The effects of the inhomogeneous shear layer and the Froude number (signifying the effects of gravity) on the temporal and spatio-temporal results were delineated. A decrease in the density ratio (ratio of the density of the jet to the density of the ambient gas) resulted in an increase in the temporal amplification rate of the disturbances. The temporal growth rate of the disturbances increased as the Froude number was reduced. The spatio-temporal analysis performed to determine the absolute instability characteristics of the jet yield positive absolute temporal growth rates at all Fr and different axial locations. As buoyancy was removed (Fr . 8), the previously existing absolute instability disappeared at all locations establhing buoyancy as the primary instability mechanism in self-excited low-density jets.

Pasumarthi, Kasyap Sriramachandra↗

Advancing Development of Emissions Detection (Final Report)

This document is the final report to the U.S. Department of Energy (DOE for contract DE-FE0031873) awarded to Colorado State University (CSU). CSU and partners at Harrisburg University of Science and Technology, University of Texas Arlington, and University of Texas at Austin organized several testing rounds to provide knowledge focused on advancing the detection capabilities of emissions monitoring devices. With this funding opportunity the research group began by establishing the Advancing the Development of Emission Detection (ADED) program, with the goal focused on enhancing the accuracy, reliability, and field applicability of methane detection technologies. This effort aimed to address the critical challenges of identifying and quantifying methane emissions while enabling industry stakeholders to meet regulatory compliance and environmental sustainability goals. The program engaged with industry, government, and technology stakeholders to promote adoption and consensus on testing techniques for methane detection solutions. Methane, a potent greenhouse gas, contributes significantly to global warming, and the oil and natural gas (O&G) sector is a primary source of methane emissions. Regulatory measures such as leak detection and repair (LDAR) programs have been implemented to address emissions. However, traditional LDAR approaches, reliant on handheld and component-level measurements, are resource-intensive. To address these limitations and move with evolving regulations, advanced methane technologies are emerging. These solutions include ground-based sensors, mobile systems (e.g., drones, vehicles, and aircraft), and satellite-based platforms. They offer innovative capabilities for autonomous monitoring, larger spatial coverage, and emission quantification using methods such as tracer gas techniques and inverse modeling with Gaussian plume analysis. The ADED program began with creating protocols for methane controlled release (CR) testing these continuous monitoring (CM) and survey technologies that detect and monitor methane emissions at O&G facilities. The protocols were then implemented throughout testing of CM and survey devices at CSU’s Methane Emissions Technology Evaluation Center (METEC) facility from 2021 through 2024. As apart of the protocol, solutions that tested under the ADED program installed their solutions at METEC, documented their system under test, and provided detection reports to the METEC team for analysis. The METEC team would provide the solutions with analyzed reports of their emissions and ground truth data of the releases conducted during their testing session. Under the ADED program, CMs were also tested at O&G facilities for a six week test run of challenge release (ChR) releases. The findings from the ADED program underscore the critical role of collaborative research and innovation in tackling methane emissions, offering a pathway for the oil and gas sector to achieve significant environmental and economic benefits. Results from METEC testing saw improvement of performance and accuracy across all solutions over the extent of the ADED experiments. The results also showed a variance in CM solution performance between CRs and ChRs. That variance pushed the team to further analyze the differences between CR testing environments and field conditions. With the drive from regulations and that variance in field conditions, the ADED team began designing a new CR testing protocol and additions to the METEC testing facility. The METEC team is furthering the progress made through the ADED program with awarded funding from DE-FE0032276. This funding pushes the development of METEC’s addition with new equipment, allowing for an updated facility layout. METEC still facilitates for traditional facilities, with a legacy pad, while expanding an new design based on how O&G infrastructure has Final Report - Contract Number: DE-FE0031873 been changed over the last decade. Throughout the ADED program the team has also been working with international partners to ensure staying in the trend globally. International partners have been essential in moving the new protocol forward to implement into CR testing at the METEC facility in Spring 2025.

42 ENGINEERING↗

Determining the Local Abundance of Martian Methane and its 13-C/l2-C and D/H Isotopic Ratios for Comparison with Related Gas and Soil Analysis on the 2011 Mars Science Laboratory (MSL) Mission

Understanding the origin of Martian methane will require numerous complementary measurements from both in situ and remote sensing investigations and laboratory work to correlate planetary surface geophysics with atmospheric dynamics and chemistry. Three instruments (Quadrupole Mass Spectrometer (QMS), Gas Chromatograph (GC) and Tunable Laser Spectrometer (TLS)) with sophisticated sample handling and processing capability make up the Sample Analysis at Mars (SAM) analytical chemistry suite on NASA s 2011 Mars Science Laboratory (MSL) Mission. Leveraging off the SAM sample and gas processing capability that includes methane enrichment, TLS has unprecedented sensitivity for measuring absolute methane (parts-per-trillion), water, and carbon dioxide abundances in both the Martian atmosphere and evolved from heated soil samples. In concert with a wide variety of associated trace gases (e.g. SO2, H2S, NH3, higher hydrocarbons, organics, etc.) and other isotope ratios measured by SAM, TLS will focus on determining the absolute abundances of methane, water and carbon dioxide, and their isotope ratios: 13C/12C and D/H in methane; 13C/12C and 18O/17O/16O in carbon dioxide; and 18O/17O/16O and D/H in water. Measurements near the MSL landing site will be correlated with satellite (Mars Express, Mars 2016) and ground-based observations.

Webster, Christopher R.↗

Analytical methods for toxic gases from thermal degradation of polymers

Toxic gases evolved from the thermal oxidative degradation of synthetic or natural polymers in small laboratory chambers or in large scale fire tests are measured by several different analytical methods. Gas detector tubes are used for fast on-site detection of suspect toxic gases. The infrared spectroscopic method is an excellent qualitative and quantitative analysis for some toxic gases. Permanent gases such as carbon monoxide, carbon dioxide, methane and ethylene, can be quantitatively determined by gas chromatography. Highly toxic and corrosive gases such as nitrogen oxides, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and sulfur dioxide should be passed into a scrubbing solution for subsequent analysis by either specific ion electrodes or spectrophotometric methods. Low-concentration toxic organic vapors can be concentrated in a cold trap and then analyzed by gas chromatography and mass spectrometry. The limitations of different methods are discussed.

Hsu, M.-T. S.↗

An In Situ , Automated High-Explosives Aging Method Utilizing Two-Dimensional Gas Chromatography–Mass Spectrometry

Understanding chemical changes that occur in high explosives as they age is of great importance to the safe employment and storage of these compounds. Traditional methods of aging high explosives even under accelerated aging conditions are time intensive with durations on the order of months to years. The nature of traditional aging analyses reduces each sample to a snapshot data point often separated widely in time, requiring many assumptions as to how the degradation products develop. Further complicating matters, several analytical techniques are typically employed for each sample analysis in order to ascertain an entire picture of the decomposition pathways. To address these shortcomings with existing methods, a new method of accelerated aging of high explosives utilizing comprehensive two-dimensional gas chromatography coupled to high-resolution mass spectrometry (GC × GC-HRMS) was developed using 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) as a model compound for method development. This in situ automated method reduces the time scale of aging to a matter of hours using the inlet of the GC × GC as the aging vessel. GC × GC in combination with HRMS allowed for the collection of both evolved gases and other decomposition products produced during the entire aging process in real time with HRMS providing far greater certainty in identification of explosives aging products. Additionally, this method allowed for a higher throughput of samples with greatly simplified sample preparation. Chemometric analysis of the GC × GC-HRMS data set via the alteration analysis (ALA) enabled discovery of statistically significant chemical changes providing insight into the variation of decomposition pathways with varying aging temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultraviolet spectroscopy of the recurrent nova U Scorpii during outburst

Observations of the recurrent nova U Sco during the 1979 outburst are presented, and the spectral evolution is found to differ from that of other recurrent novas. Spectra are dominated by emission lines, and the strong forbidden-line emission characteristic is conspicuously absent. A method to determine masses of nova shells is outlined, and an analysis of the emission lines shows an enrichment in N relative to C and O, and that the nova ejecta are rich in He relative to H. Optical spectra of U Sco obtained following its return to quiescence show predominantly He II emission lines, which suggests an enrichment of the preoutburst gas in He, and thus the presence of a highly evolved companion.

Williams, R. E.↗

HSR combustion analytical research

Increasing the pressure and temperature of the engines of a new generation of supersonic airliners increases the emissions of nitrogen oxides (NO(x)) to a level that would have an adverse impact on the Earth's protective ozone layer. In the process of evolving and implementing low emissions combustor technologies, NASA LeRC has pursued a combustion analysis code program to guide combustor design processes, to identify potential concepts of the greatest promise, and to optimize them at low cost, with short turnaround time. The computational analyses are evaluated at actual engine operating conditions. The approach is to upgrade and apply advanced computer programs for gas turbine applications. Efforts were made in further improving the code capabilities for modeling the physics and the numerical methods of solution. Then test cases and measurements from experiments are used for code validation.

Nguyen, H. Lee↗

Techniques for in situ collection and measurement of volatiles released during hypervelocity impact

The capability of the gas capture cell to collect particles and semivolatile species which were released during impact is examined. The proposed Comet Coma Sample Return (CCSR) payload contains a variety of instrumentation for characterizing and collecting cometary dust. In this suite of instruments the Gas Capture Cell (GCC) is unique in that it not only collects the vaporization products resulting from the dust particle impacts, but also provides chemical characterization information prior to return of the dust particles for analysis on Earth. The GCC provides near real-time characterization of the volatile species, such as low- and medium-molecular-weight organic compounds that evolve from dust particles on impact with metal targets. Instrument sensitivity is sufficient for analyzing the volatile impact products resulting from single, individual dust particles. This capability will enable characterization of near-pristine dust particles, including the CHON particles, to be performed at a level not previously possible. Its design concept, operation and performance are detailed.

Heppner, R. A.↗

Search for life on Mars: Evaluation of techniques

An important question for exobiology is, did life evolve on Mars? To answer this question, experiments must be conducted on the martian surface. Given current mission constraints on mass, power, and volume, these experiments can only be performed using proposed analytical techniques such as: electron microscopy, X-ray fluorescence, X-ray diffraction, a-proton backscatter, g-ray spectrometry, differential thermal analysis, differential scanning calorimetry, pyrolysis gas chromatography, mass spectrometry, and specific element detectors. Using prepared test samples consisting of 1% organic matter (bovine serum albumin) in palagonite and a mixture of palagonite, clays, iron oxides, and evaporites, it was determined that a combination of X-ray diffraction and differential thermal analysis coupled with gas chromatography provides the best insight into the chemistry, mineralogy, and geological history of the samples.

Schwartz, D. E.↗

Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

Palmer, Peter T.↗

Techniques for the analysis of gases sequentially released from lunar samples

Description of two methods for the analysis of light gases that are sequentially evolved from 2 to 10 mg of lunar sample. A hydrofluoric acid hydrolysis of lunar material is achieved by repeated exposure of the sample to hydrogen fluoride. In the second technique, gases are evolved from lunar samples by the stepwise heating of these samples to 1400 C. The gases evolved by either hydrolysis or pyrolysis are analyzed in a gas chromatographic system using a helium ionization detector. The sensitivities of this detector for the gases, as analyzed, range from 20 picograms/sec for hydrogen to 0.2 picogram/sec for carbon dioxide.

Desmarais, D. J.↗

Granular instability in fluidized beds: A small-over-large instability

For different particle diameters arranged in a gas fluidized bed, a new gravitational instability is predicted. The first order stability analysis yields conditions for growth of the most unstable wavenumber both as a function of particle diameter and dimensionless Bond number. Gravity acts to distribute the greater fluid mass associated with smaller particles, while surface tension stabilizes the entire bed against accelerations. The phenomenon, called the 'Small-over-Large' (SL) instability, evolves somewhat akin to a Rayleigh-Taylor mechanism and in addition to fundamental interest, carries implications for predicting solute redistribution and gravitational alignments in particle beds and chemical separation columns.

Noever, David A.↗

NGC 5291: Implications for the Formation of Dwarf Galaxies

The possible formation and evolution of dwarf irregular galaxies from material derived from perturbed evolved galaxies is addressed via an H I study of a likely example, the peculiar system NGC 5291. This system, located in the western outskirts of the cluster Abell 3574, contains the lenticular galaxy NGC 5291 which is in close proximity to a disturbed companion and is flanked by an extensive complex of numerous knots extending roughly 4 min north and 4 min south of the galaxy. In an initial optical and radio study, Longmore et al. (1979, MNRAS, 188, 285) showed that these knots have the spectra of vigorous star-forming regions, and suggested that some may in fact be young dwarf irregular galaxies. High resolution 21-cm line observations taken with the VLA are presented here and reveal that the H I distribution associated with this system encompasses not only the entire N-S complex of optical knots, but also forms an incomplete ring or tail that extends approximately 3 min to the west. The H I associated with NGC 5291 itself shows a high velocity range; the Seashell is not detected. The formation mechanism for this unusual system is unclear and two models - a large, low-luminosity ram-swept disk, and a ram-swept interaction-are discussed. The H I in the system contains numerous concentrations, mostly along the N-S arc of the star-forming complexes, which generally coincide with one or more optical knots; the larger H I features contain several x 10(exp 9) solar mass of gas. Each of the knots is compared to a set of criteria designed to determine if these objects are bound against their own internal kinetic energy and are tidally stable relative to the host galaxy. An analysis of the properties of the H I concentrations surrounding the optical star-forming complexes indicates that at least the largest of these is a bound system; it also possesses a stellar component. It is suggested that this object is a genuinely young dwarf irregular galaxy that has evolved from the material associated with the system and that this entire complex contains several proto- or young dwarf irregular galaxies in various stages of development. We are therefore witnessing the early evolution of a number of genuinely young galaxies. Given the evident importance of the NGC 5291 system as a 'nursery' for young galaxies, careful modeling is required if we are to understand this remarkable galaxy.

Malphrus, Benjamin K.↗

The ever-evolving active site: transformation of single atoms to extended structures during the Rh-catalyzed reverse water–gas shift reaction

At low temperatures (< 400°C), single atoms of Rh supported on rutile TiO 2 (rTiO 2 ) are responsible for the formation of CO during the reverse water gas shift (RWGS), while methane production is associated with the Rh-TiO 2 interface due to the correlation between methane formation rates and the volume-averaged Rh nanoparticle diameter. As the temperature is increased to >540°C, there is a notable increase in CO selectivity and methane production rates tend towards zero. The time to reach zero depends on the temperature but independent of the initial Rh structure (single atoms and/or nanoparticles), which is controlled by the catalyst preparation method (wetness impregnation versus colloidal nanoparticles). At 600°C and > 4 h time on stream, the catalytic behaviour becomes completely agnostic to the initial Rh structure as well as weight loading, and the catalysts are highly selective for the reverse water gas-shift reaction. Post-reaction HR-TEM image analysis confirms Rh nanoparticles crystallize/order during the reaction; at 400°C, most of the Rh particles are disordered, while at 600°C, they are more ordered (i.e., development of defined faceting). Infrared spectroscopy of CO adsorption on Rh nanoparticles confirms the appearance of defined facets after annealing in nitrogen at high temperatures. Annealing the Rh/rTiO 2 catalysts prior to the RWGS reaction demonstrates the structural transformation of Rh depends only on time and temperature and not on reactant or product fugacity. Sites responsible for stabilizing Rh single atoms are no longer competent at higher temperatures, enabling their integration into existent nanoparticles. As the reaction temperature is increased to temperatures >540°C, the dominant active site for CO production evolves from single atoms to extended Rh structures.

36 MATERIALS SCIENCE↗

Computational Methods for Modeling Electrospray Microdroplet Chemistry for Improved Quantitative Mass Spectrometry

This project aimed at enhancing the quantitative analysis capabilities of electrospray ionization mass spectrometry (ESI-MS) by developing advanced computational methods. The primary focus was to integrate continuum and molecular dynamics simulations to study the behavior of microdroplets in the ESI process, from formation to evaporation. Through this research, we sought to bridge significant length and time scales to provide a comprehensive understanding of how analyte concentrations evolve from bulk solutions into gas-phase ions. This understanding is crucial for addressing challenges such as ionization efficiency, solvent effects, and ion suppression, which currently limit the accuracy of quantitative ESI-MS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Detection of Evolved Carbon Dioxide in the Rocknest Eolian Bedform by the Sample Analysis at Mars(SAM) Instrument at the Mars Curiosity Landing Site

The Sample Analysis at Mars (SAM) instrument detected four releases of carbon dioxide (CO2) that ranged from 100 to 700 C from the Rocknest eolian bedform material (Fig. 1). Candidate sources of CO2 include adsorbed CO2, carbonate(s), combusted organics that are either derived from terrestrial contamination and/or of martian origin, occluded or trapped CO2, and other sources that have yet to be determined. The Phoenix Lander s Thermal Evolved Gas Analyzer (TEGA) detected two CO2 releases (400-600, 700-840 C) [1,2]. The low temperature release was attributed to Fe- and/or Mg carbonates [1,2], per-chlorate interactions with carbonates [3], nanophase carbonates [4] and/or combusted organics [1]. The high temperature CO2 release was attributed to a calcium bearing carbonate [1,2]. No evidence of a high temperature CO2 release similar to the Phoenix material was detected in the Rocknest materials by SAM. The objectives of this work are to evaluate the temperature and total contribution of each Rocknest CO2 release and their possible sources. Four CO2 releases from the Rocknest material were detected by SAM. Potential sources of CO2 are adsorbed CO2, (peak 1) and Fe/Mg carbonates (peak 4). Only a fraction of peaks 2 and 3 (0.01 C wt.%) may be partially attributed to combustion of organic contamination. Meteoritic organics mixed in the Rocknest bedform could be present, but the peak 2 and 3 C concentration (approx.0.21 C wt. %) is likely too high to be attributed solely to meteoritic organic C. Other inorganic sources of C such as interactions of perchlorates and carbonates and sources yet to be identified will be evaluated to account for CO2 released from the thermal decomposition of Rocknest material.

Sutter, B.↗

The implications and limitations of the findings of the Viking organic analysis experiment

The gas chromatograph mass spectrometer instrument of the Viking mission has demonstrated the absence of organic compounds in the immediate surface layer of the two landing sites. The demonstration of the successful operation of the instrument (comparison of ground-based test data with those obtained during interplanetary flight and the data from the surface of the planet) and its limitations (e.g., the detection of highly cross-linked polymers or polymeric carbon suboxide) are reviewed. The measurements for bound water are based on indirect data, the detectability of evolved carbon dioxide and ammonia is poor, and oxygen, liberated from the soil samples, can not be detected.

Biemann, K.↗

Discussion of flight experiments with an entry research vehicle

The focus of interest is the maneuvering flight of advanced entry vehicles operating at altitudes above 50 km and at velocities of 5 to 8 km/s. Information resulting in more accurate aerodynamic analysis is sought and measurement techniques that appear to be applicable are identified. Measurements discussed include: shock layer or boundary layer profiles of velocity, temperature, species mass fractions, and other gas properties associated with aerodynamic heating; surface energy transfer process; nonequilibrium flow processes and pressure distribution; separated, vortic leeside flow of nonequilibrium fluid; boundary layer transition on highly swept configurations; and shock and surface slip and gas/surface interaction. Further study should focus on evolving measurement techniques, installation requirements, and on identification of the portions of flights where successful results seem probable.

Potter, J. L.↗