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At least 235 records · Page 13

Multi-Pass Quadrupole Mass Analyzer

Analysis of the composition of planetary atmospheres is one of the most important and fundamental measurements in planetary robotic exploration. Quadrupole mass analyzers (QMAs) are the primary tool used to execute these investigations, but reductions in size of these instruments has sacrificed mass resolving power so that the best present-day QMA devices are still large, expensive, and do not deliver performance of laboratory instruments. An ultra-high-resolution QMA was developed to resolve N2 +/CO+ by trapping ions in a linear trap quadrupole filter. Because N2 and CO are resolved, gas chromatography columns used to separate species before analysis are eliminated, greatly simplifying gas analysis instrumentation. For highest performance, the ion trap mode is used. High-resolution (or narrow-band) mass selection is carried out in the central region, but near the DC electrodes at each end, RF/DC field settings are adjusted to allow broadband ion passage. This is to prevent ion loss during ion reflection at each end. Ions are created inside the trap so that low-energy particles are selected by low-voltage settings on the end electrodes. This is beneficial to good mass resolution since low-energy particles traverse many cycles of the RF filtering fields. Through Monte Carlo simulations, it is shown that ions are reflected at each end many tens of times, each time being sent back through the central section of the quadrupole where ultrahigh mass filtering is carried out. An analyzer was produced with electrical length orders of magnitude longer than its physical length. Since the selector fields are sized as in conventional devices, the loss of sensitivity inherent in miniaturizing quadrupole instruments is avoided. The no-loss, multi-pass QMA architecture will improve mass resolution of planetary QMA instruments while reducing demands on the RF electronics for high-voltage/high-frequency production since ion transit time is no longer limited to a single pass. The QMA-based instrument will thus give way to substantial reductions of the mass of flight instruments.

Prestage, John D.↗

Development of a modulator to measure water vapor selectively in a gaseous mixture

Selective thermal modulation (STM) is a technique which produces a concentration-dependent pulse by selectively modulating a sample in a gas stream. Several types of modulation techniques, both chemical and physical, using adsorption, decomposition, and catalytic and mechanical methods have been developed for use with multiplex gas chromatography. Two of these applications involve selective modulation of the components present in the sample gas stream. The selective modulation of the concentration of specific sample molecules or classes of molecules provides additional analytical selectivity which can lead to selective detection. For some specific applications, the column may even be eliminated. Chemical modulation by absorption of a substance from the sample stream by a stationary phase will also produce a change in the signal intensity. Removal of a substance from the sample stream results in a signal containing a vacancy peak. In the work reported here, a selective thermal modulation technique has been developed as a method for determination of water vapor for possible use in Mars' atmosphere.

NASA Center ARC↗

Multiplex coherent raman spectroscopy detector and method

A multiplex coherent Raman spectrometer (10) and spectroscopy method rapidly detects and identifies individual components of a chemical mixture separated by a separation technique, such as gas chromatography. The spectrometer (10) and method accurately identify a variety of compounds because they produce the entire gas phase vibrational Raman spectrum of the unknown gas. This is accomplished by tilting a Raman cell (20) to produce a high-intensity, backward-stimulated, coherent Raman beam of 683 nm, which drives a degenerate optical parametric oscillator (28) to produce a broadband beam of 1100-1700 nm covering a range of more than 3000 wavenumber. This broadband beam is combined with a narrowband beam of 532 nm having a bandwidth of 0.003 wavenumbers and focused into a heated windowless cell (38) that receives gases separated by a gas chromatograph (40). The Raman radiation scattered from these gases is filtered and sent to a monochromator (50) with multichannel detection.

Chen, Peter↗

Carbothermal Reduction Demonstration (CaRD) Gas Analysis Subsystem Development

The Carbothermal Reduction Demonstration (CaRD) project is currently developing a subscale system to demonstrate the operation and performance of the carbothermal reduction process and quantify the production of molar equivalent oxygen via carbon monoxide (CO) and carbon dioxide (CO2). Traditionally, gas chromatography (GC) systems are utilized to quantify gases due to their ability to separate volatile compounds within the gas mixture, followed by detection of the isolated component of interest. Despite their capabilities, GCs require carrier gas consumables for their operational mobile phase and consequently are not often considered a flight-forward option. An alternative analytical technique known as mass spectrometry measures the presence of gas phase molecules without the need of carrier gas. Residual gas analyzers (RGAs), which are smaller and rugged mass spectrometers, are not traditionally used to quantify analytes as they serve more as a monitoring tool. However, proper application and calibration can result in a flight-forward analytical instrument capable of direct quantification of volatile compounds of interest. Kennedy Space Center's role for the JSC led CaRD project is to design a gas analyzer system to detect and quantify the CO and CO2 gases produced during the carbothermal reaction utilizing a commercial version of the Mass Spectrometer observing lunar operations (MSolo) instrument. MSolo is a modified commercial off-the-shelf RGA, which consists of quadrupole mass filter and space rated electronics. MSolo is currently a TRL 6 technology and manifested on the PRIME-1 and VIPER missions. This paper describes leveraging MSolo based instrumentation to develop a gas analysis system for the work outlined in the 2023 International Conference on Environmental Systems (ICES) paper number 313.

Ryan P Gott↗

Precursor gases of aerosols in the Mount St. Helens eruption plumes at stratospheric altitudes

Nineteen stratospheric samples from the eruption plumes of Mount St. Helens were collected in five flight experiments. The plume samples were collected at various altitudes from 13.1 to 20.7 km by using the Ames cryogenic sampling system on board the NASA U-2 aircraft. The enriched, cryogenically collected samples were analyzed by chromatography. The concentrations of aerosols precursor gases (OCS, SO2, and CS2), CH3Cl, N2O, CF2Cl2, and CFCl3 were measured by gas chromatography. Large enhancement of the mixing ratio of SO2 and moderate enhancement of CS2 and OCS were found in the plume samples compared with similar measurement under pre-volcanic conditions. A fast decay rate of the SO2 mixing ratio in the plume was observed. Measurement of Cl(-), SO2(2-), and NO3(-) by ion chromatography was also carried out on water solutions prepared from the plume samples. The results obtained with this technique imply large mixing ratios of HCl, (NO + NO2 + HNO3), and SO2, in which these constituents are the respective sources of the anions. Measurement of the Rn222 concentration in the plume was made. Other stratospheric constituents in the plume samples, such as H2O, CO2, CH4, and CO, were also observed.

Inn, E. C. Y.↗

Sulfur gas exchange in Sphagnum-dominated wetlands

Sulfur gases are important components of the global cycle of S. They contribute to the acidity of precipitation and they influence global radiation balance and climate. The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S was investigated by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in trophic status. The effects of inorganic S input on the production and emission of gaseous S were also investigated. Experiments were conducted in wetlands in New Hampshire, particularly a poor fen, fens within the Experimental Lakes Area (ELA) in Ontario, Canada and in freshwater and marine tundra. Emissions were determined using Teflon enclosures, gas cryotrapping methods, and gas chromatography (GC) with flame photometric detection. Dynamic (sweep flow) and static enclosures were employed. Dissolved gases were determined by gas stripping followed by GC.

Hines, Mark E.↗

Improved Chromatographic Techniques for Sulfur Pollutants

This paper describes several improvements in instrumental techniques for the analysis of low ppb concentrations of sulfur gases using gas chromatography (G.C.). This work has focused on the analytical problem of ambient air monitoring of the two main sulfur gas pollutants, hydrogen sulfide and sulfur dioxide. The most significant technical improvement that will be reported here is the newly developed silica gel column for ppb concentrations of the light sulfur gases (COS, H2S, CS2, SO2, CH3SH). A simplified inlet system will be described which improves reliability of the GC system. The flame photometric detector is used as the means of selectively and sensitively detecting the low concentrations of sulfur gases. Improvements will be described which have yielded better performance than previously reported for this application of the detector. Also included in this paper will be a report of field monitoring using this improved GC system. Reliability and repeatability of performance at the low ppb concentrations of sulfur gases will be demonstrated.

Hartmann, C. H.↗

Carbothermal Reduction Demonstration (CaRD) Gas Analysis Subsystem Development

The Carbothermal Reduction Demonstration (CaRD) project is currently developing a subscale system to demonstrate the operation and performance of the carbothermal reduction process and quantify the production of molar equivalent oxygen (carbon monoxide (CO) and carbon dioxide (CO2)). Traditionally, gas chromatography (GC) systems are utilized to qualify gases due to their ability to separate the volatile compounds within the gas mixture, followed by quantification of the isolated component of interest. Despite these capabilities, GCs require consumables for their operational mobile phase and consequently are not often considered a flight-forward option. An alternative analytical technique known as mass spectrometry measures the presentence of gas phase molecules based on their mass-to-charge ratio. Residual gas analyzers (RGAs) which utilize mass spectrometry are not traditionally used to quantify analytes, but proper design and calibrations can result in a flight-forward analytical instrument capable of direct quantification of volatile gases of interest. Kennedy Space Center's role for the project is to design a gas analyzer system to detect and quantify the CO and CO2 gas produced during the carbothermal reaction utilizing a commercial version of the Mass Spectrometer Observing Lunar Operations (MSolo) instrument. MSolo is a modified commercial off-the-shelf mass spectrometer which consists of quadrupole mass filter and space rated electronics. MSolo is currently a TRL 6 technology and manifested on the PRIME-1 and VIPER missions. This paper describes leveraging MSolo based instrumentation to develop a gas analysis system for the work outlined in the 2023 International Conference on Environmental Systems (ICES) paper number 313. The design and testing of the brassboard phase of the project will be described along with the current work underway which will cover the design and preliminary test results of the prototype phase.

Ryan Patrick Gott↗

Leak Tester for Cryogenic Flowlines

Gas chromatography measures leakage into cavity surrounding joint under test. System surrounds joint being tested with sealed cavity. Presence of leakage gas in cavity monitored by gas chromatograph. Leakage rate found by multiplying relative leakage gas concentration by mass flow rate of purge as into cavity.

Mortensen, G. D.↗

Three field tests of a gas filter correlation radiometer

Test flights to remotely measure nonurban carbon monoxide (CO) concentrations by gas filter correlation radiometry are discussed. The inferred CO concentrations obtained through use of the Gas Filter Correlation Radiometer (GFCR) agreed with independent measurements obtained by gas chromatography air sample bottle analysis to within 20 percent. The equipment flown on board the aircraft, the flight test procedure, the gas chromatograph direct air sampling procedure, and the GFCR data analysis procedure are reported.

Campbell, S. A.↗

Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry

Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

Non-NASA Center↗

Particulate exhaust emissions from an experimental combustor

The concentration of dry particulates (carbon) in the exhaust of an experimental gas turbine combustor was measured at simulated takeoff operating conditions and correlated with the standard smoke-number measurement. Carbon was determined quantitatively from a sample collected on a fiberglass filter by converting the carbon in the smoke sample to carbon dioxide and then measuring the volume of carbon dioxide formed by gas chromatography. At a smoke of 25 (threshold of visibility of the smoke plume for large turbojets) the carbon concentration was 2.8 mg carbon/cu m exhaust gas, which is equivalent to an emission index of 0.17 g carbon/kg fuel.

Norgren, C. T.↗

Emissions of biogenic sulfur gases from northern bogs and fens

Sulfur gases are important components of the global cycle of S. They contribute to the acidity of precipitation and they influence global radiation balance and climate. The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in tropic status was investigated. Experiments were conducted in wetlands in New Hampshire, particularly a poor fen, and in Mire 239, a poor fen at the Experimental Lakes Area (ELA) in Ontario. Emissions were determined using Teflon enclosures, gas cryotrapping methods and gas chromatography (GC) with flame photometric detection. Dynamic (sweep flow) and static enclosures were employed which yielded similar results. Dissolved S gases and methane were determined by gas stripping followed by GC.

Demello, William Zamboni↗

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.↗

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.↗