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NASA NTRS2026

Glenn Research Center Propulsion Systems Laboratory 2026 Customer Guide

This guide describes the Propulsion Systems Laboratory (PSL) at the NASA Glenn Research Center. It was written to help customers understand the various components involved in conducting a test program within the PSL. The PSL complex supports two large-engine test cells that simulate altitude flight conditions for a wide range of research and experimental tests. These test cells operate at altitudes up to 90,000 ft and speeds from subsonic to above supersonic. Test points such as pressure, temperature, and Mach number can be set at the engine or test article inlet based on customer requirements. The facility’s support systems include the heated and cooled combustion air systems; altitude exhaust system; hydraulic system; nitrogen, oxygen, and hydrogen systems; thrust measurement system, which includes the facility’s single- and multi-axis thrust stands; inlet system; and electrical systems. In addition to providing a detailed description of PSL systems and capabilities, this guide discusses the facility’s history and past tests and addresses facility safety procedures, pretest requirements, and test operation standards.

Engine Icing Test Facility↗
NASA NTRS1988

In-situ measurements of total reactive nitrogen, total water vapor, and aerosols in polar stratospheric clouds in the Antarctic stratosphere

Measurements of total reactive nitrogen, NOy, total water vapor, and aerosols were made as part of the Airborne Antarctic Ozone Experiment. The measurements were made using instruments located onboard the NASA ER-2 aircrafts which conducted twelve flights over the Antarctic continent reaching altitudes of 18 km at 72 S latitude. Each instrument utilized an ambient air sample and provided a measurement up to 1 Hz or every 200 m of flight path. The data presented focus on the flights of Aug. 17th and 18th during which Polar Stratospheric Clouds (PSCs) were encountered containing concentrations of 0.5 to 1.0 micron diameter aerosols greater than 1 cm/cu. The temperature pressure during these events ranged as low as 184 K near 75 mb pressure, with water values near 3.5 ppm by volume (ppmv). With the exception of two short periods, the PSC activity was observed at temperatures above the frost point of water over ice. The data gathered during these flights are analyzed and presented.

Fahey, D. W.↗
NASA NTRS1989

In situ measurements of total reactive nitrogen, total water, and aerosol in a Polar Stratospheric Cloud in the Antarctic

Measurements of total reactive nitrogen, NOy, total water vapor, and aerosols were made as part of the Airborne Antarctic Ozone Experiment. The measurements were made using instruments located onboard the NASA ER-2 aircrafts which conducted twelve flights over the Antarctic continent reaching altitudes of 18 km at 72 S latitude. Each instrument utilized an ambient air sample and provided a measurement up to 1 Hz or every 200 m of flight path. The data presented focus on the flights of Aug. 17th and 18th during which Polar Stratospheric Clouds (PSCs) were encountered containing concentrations of 0.5 to 1.0 micron diameter aerosols greater than 1 cm/cu. The temperature pressure during these events ranged as low as 184 K near 75 mb pressure, with water values near 3.5 ppm by volume (ppmv). With the exception of two short periods, the PSC activity was observed at temperatures above the frost point of water over ice. The data gathered during these flights are analyzed and presented.

Fahey, D. W.↗
NASA NTRSDate not supplied

GC/MS Method Development for Separating Lunar Volatile Ice Simulant Headspace Gases

Various investigators propose the lunar surface contains widely distributed volatiles, especially water- like species, i.e. OH and H2O. Surface volatiles are theorized to exist as a hydrated regolith layer, concentrated in extremely cold polar permanently shadowed regions (PSR), and/or solar wind implantation reservoirs in lunar glasses. The proposed sources of lunar surface volatiles range from cometary impacts, solar wind, or a supply present during moon formation. Future Artemis missions aim to collect and return the samples containing volatiles collected near lunar polar craters or PSRs. We, as advanced curation scientists, are responsible for developing techniques and methodologies for preserving returned sample integrity as much as possible. Pristine volatile-bearing samples are invaluable to the scientific community seeking to unravel the history of the solar system. Realistically, a sample will experience alteration during collection, transportation back to earth, and storage. The Planetary Exploration and Astromaterials Research Lab (PEARL) seeks to understand temperature and pressure effects on high-fidelity volatile-containing regolith simulants, the foundation for the future of cold curation. This abstract outlines the separation, identification, and quantification of headspace gases over volatile ice feed stock material using gas chromatography/mass spectrometry (GC/MS). Preliminary objectives concentrated on sample handling, reproducibility, and understanding the elution characteristics for each analyte. Initial GC/MS method development experiments utilized diluted static headspace sample preparation. Diluted samples were used because sampling headspace gases directly from a vial containing liquid analyte resulted in overloading of the column and detector. Overloading is evident based on chromatogram peak shapes and instrument contamination, or carry over, between experiments. A mixture of three alcohols were used for a majority of the sample handling and reproducibility studies. Reproducibility was tested via multiple users, calibration curves, and check standards. Stock solutions of condensed lunar volatile analytes included methanol, ammonia in methanol, hydrogen sulfide in water, and an equal volume mixture of methanol, ethanol, and isopropanol. Current samples use room air as the headspace sample matrix, however future experiments will incorporate an inert purge gas, such as argon or nitrogen. Three mL of each analyte solution were capped in separate 20 mL crimp top GC vials. Dilutions were carried out by removing an aliquot of headspace gases with a calibrated 1 mL gastight syringe and immediately transferring to a 20 mL capped crimp top vial. The GC/MS is a Thermo Fisher Trace 1310/ISQ 7000 with a TriPlus RSH autosampler and split/splitless injector module. The experiments outlined in this abstract use the following hardware: a 2.5 mL gastight headspace syringe tool, 1 mm ID x 78.5 mm length ultra-inert straight injection liner, and a TG-BondQ 30 m × 0.32 mm × 10 μm column. Various parameters, such as hardware selection and the temperature, pressure, and split ratio set points, continue to evolve as the overall experiment is refined. Diluted headspace chromatograms were collected for the individual stock solutions. Retention times, peak shapes, and mass spectra were evaluated and added to the data processing method for each molecule of interest. Figure 1 shows the total ion chromatograms for the three major lunar volatile simulant stock solutions: methanol, 7 N ammonia in methanol, and 0.4% hydrogen sulfide in water. Tailing peak shapes for ammonia (2.98 min rt) and water (4.06 min rt) indicate the molecules are not properly eluting from the selected column with the current separation method. Additionally, hydrogen sulfide and ammonia have overlapping peak windows, which could impact quantification. Ongoing experiments aim to address the peak shape and overlapping via the separation method and hardware selection. Sample preparation reproducibility experiments used stock solution containing equal volumes of a non- interactive mixture of methanol, ethanol, and isopropanol. Mass spectrum ion traces were used to identify and quantify all three alcohols. Peaks were automatically detected, identified, and integrated through the mass spectra detection and processing parameters. Calibration response curves and check standards were used to evaluate the validity of the sample preparation procedure. Figure 2 shows the methanol chromatogram peak area versus total headspace dilution volume transferred from the alcohol mixture vial. The calibration response curves and check standards validate sample preparation procedure. Continuing data analysis efforts are working towards correlating the peak area and instrument response factor to the headspace analyte concentration and condensed phase composition. Static headspace gas chromatography theory relies on Dalton’s law, Raoult’s law, Henry’s Law, and the Kolb and Ettre equation to associate peak area to the analyte composition in a non-ideal solution. Equation 1 is a simplified expression derived from the aforementioned theories. Future experiments involve liquid injections of the individual stock solutions, liquid and headspace analysis of various stock solution combinations, and the addition of regolith simulants to the mixtures. Temperature is another variable expected to affect reaction rates and will be explored.

Cecilia L. Amick↗
NASA NTRS2004

Workshop on Oxygen in the Terrestrial Planets

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Source record↗
NASA NTRS2011

Aromatic Structure in Simulates Titan Aerosol

Observations of Titan by the Cassini Composite Infrared Spectrometer (CIRS) between 560 and 20 per centimeter (approximately 18 to 500 micrometers) have been used to infer the vertical variations of Titan's ice abundances, as well as those of the aerosol from the surface to an altitude of 300 km [1]. The aerosol has a broad emission feature centered approximately at 140 per centimeter (71 micrometers). As seen in Figure 1, this feature cannot be reproduced using currently available optical constants from laboratory-generated Titan aerosol analogs [2]. The far-IR is uniquely qualified for investigating low-energy vibrational motions within the lattice structures of COITIDlex aerosol. The feature observed by CIRS is broad, and does not likely arise from individual molecules, but rather is representative of the skeletal movements of macromolecules. Since Cassini's arrival at Titan, benzene (C6H6) has been detected in the atmosphere at ppm levels as well as ions that may be polycyclic aromatic hydrocarbons (PAHs) [3]. We speculate that the feature may be a blended composite that can be identified with low-energy vibrations of two-dimensional lattice structures of large molecules, such as PAHs or nitrogenated aromatics. Such structures do not dominate the composition of analog materials generated from CH4 and N2 irradiation. We are performing studies forming aerosol analog via UV irradiation of aromatic precursors - specifically C6H6 - to understand how the unique chemical architecture of the products will influence the observable aerosol characteristics. The optical and chemical properties of the aromatic analog will be compared to those formed from CH4/N2 mixtures, with a focus on the as-yet unidentified far-IR absorbance feature. Preliminary results indicate that the photochemically-formed aromatic aerosol has distinct chemical composition, and may incorporate nitrogen either into the ring structure or adjoined chemical groups. These compositional differences are demonstrated in the aerosol mass spectra shown in Figure 2. The aromatic aerosol also demonstrates strong chemical reactivity when exposed to laboratory air, indicating substantial stored chemical potential. Oxidatoin and solubility studies wil be presented and implicatoins for prebiotic chemistry o nTitan will be discussed.

Trainer, Melissa G.↗
NASA NTRS1996

Interaction of Peroxynitric Acid with Solid H2O Ice

The uptake of peroxynitric acid (PNA), HO2NO2 or HNO4, on solid H2O ice at 193 K (-80 C) was studied using a fast flow-mass spectrometric technique. An uptake coefficient of 0.15 +/- 0.10 was measured, where the quoted uncertainty denotes 2 standard deviations. The uptake process did not result in the production of gas phase products. The composition of the condensed phase was investigated using programmed heating (3 K/min) of the substrate coupled with mass spectrometric detection of desorbed species. Significant quantities of HNO, and HNO3 desorbed from the substrates at temperatures above 225 K and 246 K, respectively. The desorbed HNO3, which was less than 9% of the desorbed HNO, and remained unchanged upon incubation of the substrate, was likely due to impurities in the HNO4 samples rather than reaction of HNO, on the substrate. The onset temperatures for HNO4 desorption increased with increasing H2O to HNO4 ratios, indicating that HNO4, like HNO3, tends to be hydrated in the presence of water. These observations suggest possible mechanisms for removal of HNO4 or repartitioning of total odd nitrogen species in the Earth's upper troposphere and stratosphere.

Li, Zhuangjie↗
NASA NTRS2023

NASA Glenn Propulsion Systems Laboratory Customer Guide

This guide describes the Propulsion Systems Laboratory (PSL) at NASA Glenn Research Center (GRC) and was written to help customers utilizing the facility understand all the components of conducting a test program within the facility. The PSL complex supports two large engine test cells that simulate altitude flight conditions for a wide range of research and experimental tests. The test cells operate at altitudes up to 90,000 ft and speeds from subsonic to above supersonic. The way the facility sets test points at the engine or test article inlet, such as pressure, temperature, and Mach number is discussed. Support systems such as the heated and cooled combustion air system, the altitude exhaust system, the hydraulic system, the nitrogen, oxygen, and hydrogen systems, hydrogen burners, the engine exhaust gas-sampling system, and single- and multiple-axis thrust stands are addressed. Facility safety procedures, pre-test requirements, test operation standards are also stated in later sections. Past PSL tests and other capabilities are also discussed.

PSL Customer Guide↗
NASA NTRS2011

Spray-On Foam Insulations for Launch Vehicle Cryogenic Tanks

Spray-on foam insulation (SOFI) has been developed for use on the cryogenic tanks of space launch vehicles beginning in the 1960s with the Apollo program. The use of SOFI was further developed for the Space Shuttle program. The External Tank (ET) of the Space Shuttle, consisting of a forward liquid oxygen tank in line with an aft liquid hydrogen tank, requires thermal insulation over its outer surface to prevent ice formation and avoid in-flight damage to the ceramic tile thermal protection system on the adjacent Orbiter. The insulation also provides system control and stability with throughout the lengthy process of cooldown, loading, and replenishing the tank. There are two main types of SOFI used on the ET: acreage (with the rind) and closeout (machined surface). The thermal performance of the seemingly simple SOFI system is a complex of many variables starting with the large temperature difference of from 200 to 260 K through the typical 25-mm thickness. Environmental factors include air temperature and humidity, wind speed, solar exposure, and aging or weathering history. Additional factors include manufacturing details, launch processing operations, and number of cryogenic thermal cycles. The study of the cryogenic thermal performance of SOFI under large temperature differentials is the subject of this article. The amount of moisture taken into the foam during the cold soak phase, termed Cryogenic Moisture Uptake, must also be considered. The heat leakage rates through these foams were measured under representative conditions using laboratory standard liquid nitrogen boiloff apparatus. Test articles included baseline, aged, and weathered specimens. Testing was performed over the entire pressure range from high vacuum to ambient pressure. Values for apparent thermal conductivity and heat flux were calculated and compared with prior data. As the prior data of record was obtained for small temperature differentials on non-weathered foams, analysis of the different methods is provided. Recent advancements and applications of SOFI systems on future launch vehicles and spacecraft are also addressed.

Fesmire, J. E.↗
NASA NTRS2015

Land Boundary Conditions for the Goddard Earth Observing System Model Version 5 (GEOS-5) Climate Modeling System: Recent Updates and Data File Descriptions

The Earths land surface boundary conditions in the Goddard Earth Observing System version 5 (GEOS-5) modeling system were updated using recent high spatial and temporal resolution global data products. The updates include: (i) construction of a global 10-arcsec land-ocean lakes-ice mask; (ii) incorporation of a 10-arcsec Globcover 2009 land cover dataset; (iii) implementation of Level 12 Pfafstetter hydrologic catchments; (iv) use of hybridized SRTM global topography data; (v) construction of the HWSDv1.21-STATSGO2 merged global 30 arc second soil mineral and carbon data in conjunction with a highly-refined soil classification system; (vi) production of diffuse visible and near-infrared 8-day MODIS albedo climatologies at 30-arcsec from the period 2001-2011; and (vii) production of the GEOLAND2 and MODIS merged 8-day LAI climatology at 30-arcsec for GEOS-5. The global data sets were preprocessed and used to construct global raster data files for the software (mkCatchParam) that computes parameters on catchment-tiles for various atmospheric grids. The updates also include a few bug fixes in mkCatchParam, as well as changes (improvements in algorithms, etc.) to mkCatchParam that allow it to produce tile-space parameters efficiently for high resolution AGCM grids. The update process also includes the construction of data files describing the vegetation type fractions, soil background albedo, nitrogen deposition and mean annual 2m air temperature to be used with the future Catchment CN model and the global stream channel network to be used with the future global runoff routing model. This report provides detailed descriptions of the data production process and data file format of each updated data set.

GEOS-5↗
NASA NTRS2016

40 Years of Processing Pieces of Space

This year marks the 40th year anniversary for the Antarctic Search for Meteorite (ANSMET) program. In 1976, the ANSMET program led the first expedition to Antarctica. The ANSMET program is a US-led field-based science project that recovers meteorite samples from Antarctica. Once a year from late November to late January, a field team consisting of 8 to 12 people, spends 6-8 weeks camping on the ice and collecting meteorites. Since 1976, more than 22,000 meteorite samples have been recovered. These meteorites come from asteroids, planets and other bodies of the solar system. Once collected, the Antarctic meteorites are shipped to NASA/Johnson Space Center (JSC) Houston, TX. in a refrigerated truck and are kept frozen to minimize oxidation until they are ready for initial processing. In Antarctica each meteorite is given a field tag which consists of numbers, once in the lab, this is replaced by an official tag, consisting of the Antarctic field location and year collected. The types and numbers of meteorites that have been classified include 849 carbonaceous chondrites, 135 enstatites, 512 achondrites, 64 stony, 115 irons, 48 others (27 R chondrites, 7 ungrouped), 6,161 H chondrites, 7,668 L chondrites, and 4,589 LL chondrites. Although 80-85 percent of the collected meteorites fall in the ordinary chondrite group, the other approximately 15 percent represent rare types of achondrites and carbonaceous chondrites. These rare meteorites include 25 lunar meteorites, 15 Martian meteorites, scores of various types of carbonaceous chondrites, and unique achondrites. The Antarctic meteorites that have been collected are processed in the Meteorite Processing Lab at JSC in Houston, TX. Initial processing of the meteorites begins with thawing/drying the meteorites in a nitrogen glove box for 24 to 48 hours. The meteorites are then photographed, measured, weighed and a description of the interior and exterior of each meteorite is written. The meteorite is broken and a representative sample, either a 1-3 gram chip or thin section is sent to the Smithsonian Institution for classification. After Antarctic meteorites have been classified and approved by the Nomenclature Committee of the Meteoritical Society, they are announced in the Antarctic Meteorite Newsletter, which is published twice per year (fall and spring) so that scientists may review which meteorites are available to study. Requests for Antarctic Meteorite samples are welcomed from research scientists, regardless of their current state of funding for meteorite studies. Since its inception over 3,300 requests have been made for pieces of these meteorites and over 400 investigators worldwide are active in the study of meteorites.. Research on these samples has been published in more than1500 peer reviewed articles; a listing of papers for any meteorite sample can be generated by accessing http://curator.jsc.nasa.gov/antmet/referencesearch.cfm. Antarctic meteorite samples requested by scientists are prepared several different ways. Most samples are prepared as chips, either using a rock splitter or using a chisel and chipping bowl. In special situations, a researcher may request a meteorite slab in which case the samples are cut using a diamond-bladed bandsaw inside of a dry nitrogen glove box. The meteorites are always cut in a 100 percent liquid-free environment. Additionally, thin/thick sections of Antarctic meteorites are also prepared at JSC. The meteorite thin section lab at JSC can prepare standard 30-micron thin sections, thick sections of variable thickness (100 to 200 microns), or demountable sections using superglue, all section are prepared without using water. Although many of the techniques used back in the '70's are still used today, advances in computers, software, databases, available tools and instrumentation have helped to streamline and shorten the duration of the classification process. In conjunction with present day missions to asteroids and other planets, meteorite studies have not only led to a better understanding of the complex histories of these bodies but have also tied certain meteorite groups to particular asteroid bodies. New meteorite discoveries by the ANSMET program provide a cost effective method for obtaining samples of previously unsampled bodies, allowing scientists to learn more about the origin, composition, and evolution of the solar system. Preservation in our cleanrooms at NASA allows material to be archived for future generations and advances in instrumentation and analysis.

Satterwhite, C. E.↗
NASA NTRS2003

A Proposed Robotic Astronomy Mission to the Lunar South Polar Regions

This paper outlines a possible mission to emplace a robotic infrared / submillimeter wave interferometer array near the lunar south pole. This region has now been investigated by the Clementine and Lunar Prospector missions, and by Earth-based radar, and its topography and thermal environment are fairly well-known. The area would be exceptionally suitable for infrared / submillimeter astronomy because of the continually low temperatures, approaching that of liquid nitrogen (77K) in some places. A submillimeter spaceborne interferometer mission, Submillimeter Probe of the Evolution of the Cosmic Structure (SPECS) has been proposed by John Mather and others, covering the 40 - 500 micron region with 3 formation flying telescopes. The present paper proposes a lunar adaptation of the SPECS concept, LSPECS. This adaptation would involve landing 4 telescopes on the area north of Shackleton crater at zero degrees longitude. This is in nearly year round darkness but is continually radar visible from Earth. The landed payload of LSPECS would include a telerobotic rover, 4 three meter submm telescopes, a solar power array to be emplaced on the continually sunlit north rim of Shackleton crater, and an S-band antenna for data relay to Earth. Passive cooling without the use of expendable cryogenics. might be possible, trading long exposure time for instrument temperatures above that of liquid helium. The LSPECS would permit long-term study of an extremely wide range of cosmic and solar system phenomena in the southern celestial hemisphere. For complete sky coverage, a similar installation near the north pole would be required. The LSPECS site would also be suitable other types of observation, such as optical interferometry or centimeter wavelength radio astronomy. The lunar south pole is also of great interest because of its extensive ice deposits, which may represent cometary infall with pre-biotic compounds.

Lowman, Paul D., Jr.↗
NASA NTRS2016

Curating NASA's Past, Present, and Future Astromaterial Sample Collections

The Astromaterials Acquisition and Curation Office at NASA Johnson Space Center (hereafter JSC curation) is responsible for curating all of NASA's extraterrestrial samples. JSC presently curates 9 different astromaterials collections in seven different clean-room suites: (1) Apollo Samples (ISO (International Standards Organization) class 6 + 7); (2) Antarctic Meteorites (ISO 6 + 7); (3) Cosmic Dust Particles (ISO 5); (4) Microparticle Impact Collection (ISO 7; formerly called Space-Exposed Hardware); (5) Genesis Solar Wind Atoms (ISO 4); (6) Stardust Comet Particles (ISO 5); (7) Stardust Interstellar Particles (ISO 5); (8) Hayabusa Asteroid Particles (ISO 5); (9) OSIRIS-REx Spacecraft Coupons and Witness Plates (ISO 7). Additional cleanrooms are currently being planned to house samples from two new collections, Hayabusa 2 (2021) and OSIRIS-REx (2023). In addition to the labs that house the samples, we maintain a wide variety of infra-structure facilities required to support the clean rooms: HEPA-filtered air-handling systems, ultrapure dry gaseous nitrogen systems, an ultrapure water system, and cleaning facilities to provide clean tools and equipment for the labs. We also have sample preparation facilities for making thin sections, microtome sections, and even focused ion-beam sections. We routinely monitor the cleanliness of our clean rooms and infrastructure systems, including measurements of inorganic or organic contamination, weekly airborne particle counts, compositional and isotopic monitoring of liquid N2 deliveries, and daily UPW system monitoring. In addition to the physical maintenance of the samples, we track within our databases the current and ever changing characteristics (weight, location, etc.) of more than 250,000 individually numbered samples across our various collections, as well as more than 100,000 images, and countless "analog" records that record the sample processing records of each individual sample. JSC Curation is co-located with JSC's Astromaterials Research Office, which houses a world-class suite of analytical instrumentation and scientists. We leverage these labs and personnel to better curate the samples. Part of the cu-ration process is planning for the future, and we refer to these planning efforts as "advanced curation". Advanced Curation is tasked with developing procedures, technology, and data sets necessary for curating new types of collections as envi-sioned by NASA exploration goals. We are (and have been) planning for future cu-ration, including cold curation, extended curation of ices and volatiles, curation of samples with special chemical considerations such as perchlorate-rich samples, and curation of organically- and biologically-sensitive samples.

Zeigler, R. A.↗
DOE OSTI2021

The Story of 5d Metallocorroles: From Metal–Ligand Misfits to New Building Blocks for Cancer Phototherapeutics

Porphyrin chemistry is Shakespearean: over a century of study has not withered the field’s apparently infinite variety. Heme proteins continually astonish us with novel molecular mechanisms, while new porphyrin analogues bowl us over with unprecedented optical, electronic, and metal-binding properties. Within the latter domain, corroles occupy a special place, exhibiting a unique and rich coordination chemistry. The 5d metallocorroles are arguably the icing on that cake. New Zealand chemist Penny Brothers has used the word “misfit” to describe the interactions of boron, a small atom with a predilection for tetrahedral coordination, and porphyrins, classic square-planar ligands. Steve Jobs lionized misfits as those who see things differently and push humanity forward. Both perspectives have inspired us. The 5d metallocorroles are misfits in that they encapsulate a large 5d transition metal ion within the tight cavity of a contracted porphyrin ligand. Given the steric mismatch inherent in their structures, the syntheses of some 5d metallocorroles are understandably capricious, proceeding under highly specific conditions and affording poor yields. Three broad approaches may be distinguished. (a) In the metal–alkyl approach, a free-base corrole is exposed to an alkyllithium and the resulting lithio-corrole is treated with an early transition metal chloride; a variant of the method eschews alkyllithium and deploys a transition metal–alkyl instead, resulting in elimination of the alkyl group as an alkane and insertion of the metal into the corrole. This approach is useful for inserting transition metals from groups 4, 5, and, to some extent, 6, as well as lanthanides and actinides. (b) In our laboratory, we have often deployed a low-valent organometallic approach for the middle transition elements (groups 6, 7, 8, and 9). The reagents are low-valent metal–carbonyl or −olefin complexes, which lose one or more carbon ligands at high temperature, affording coordinatively unsaturated, sticky metal fragments that are trapped by the corrole nitrogens. (c) Finally, a metal acetate approach provides the method of choice for gold and platinum insertion (groups 10 and 11). This Account provides a first-hand perspective of the three approaches, focusing on the last two, which were largely developed in our laboratory. In general, the products were characterized with X-ray crystallography, electrochemistry, and a variety of spectroscopic methods. The physicochemical data, supplemented by relativistic DFT calculations, have provided fascinating insights into periodic trends and relativistic effects. An unexpected feature of many 5d metallocorroles, given their misfit character, is their remarkable stability under thermal, chemical, and photochemical stimulation. Many of them also exhibit long triplet lifetimes on the order of 100 μs and effectively sensitize singlet oxygen formation. Many exhibit phosphorescence in the near-infrared under ambient conditions. Furthermore, water-soluble ReO and Au corroles exhibit impressive photocytotoxicity against multiple cancer cell lines, promising potential applications as cancer phototherapeutics. We thus envision a bright future for the compounds as rugged building blocks for new generations of therapeutic and diagnostic (theranostic) agents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2019

Titan's Ionospheric Chemistry, Fullerenes, Oxygen, Galactic Cosmic Rays and the Formation of Exobiological Molecules on and within its Surfaces and Lakes

We discuss the formation of aerosols within Titan's thermosphere-ionosphere and the different chemical pathways. Negative ion measurements by the Cassini Plasma Spectrometer (CAPS) Electron Spectrometer (ELS) give evidence for formation of unsaturated anion carbon chains, while positive ion measurements of the Cassini Ion Neutral Mass Spectrometer (INMS) indicate formation of more aromatic cation hydrocarbons. There is presently no direct observational evidence for large neutral molecule growth in Titan's thermosphere-ionosphere. The hydrocarbon cations are expected to form Polycyclic Aromatic Hydrocarbons (PAH), those with the addition of nitrogen being called PAHNs. We theorize anion carbon chains can eventually become long enough to fold into fullerene C(60,70) carbon shells, of various charge states. Based on laboratory data the fullerenes can trap incoming O(sup +) magnetospheric ions that have relatively high energy collisions with the fullerenes and, once trapped, protect the oxygen atom from Titan's reducing thermosphere-ionosphere. The fullerenes can form into larger onion fullerenes and condense into larger embryo aerosols (i.e., m/q > 10,000 amu/q anions as observed by CAPS/ELS) eventually falling onto Titan's surface and precipitating to the bottom of its hydrocarbon lakes. Molecule production composed of H, C, N is known to occur in Titan's atmosphere with energy input from the magnetosphere, solar UV, and deeppenetrating irradiation from galactic cosmic rays (GCR). Space radiation effects by GCR irradiation of Titan's surface and lakes can lead to the manufacture of exobiological molecules with oxygen as the new ingredient. We have developed a model of galactic cosmic ray irradiation of Titan's atmosphere, surface, subsurface and bottoms of Titan lakes. GCR would provide further energy for processing of the aerosols into more complex organic forms such as tholins and precursor molecules for amino acids. A second process called hydrolysis then converts the precursor molecules into amino acids. Hydrolysis is provided via meteor impacts with size > 10 km and cryovolcanism both which can produce liquid water on Titan's surface for episodic periods > several 100 to 1000 years. Our model shows that GCR secondary particles can penetrate ~ 100 m below the ice surface (including the bottom of Titan's less dense hydrocarbon lakes ~ 150 m depths) and produce chemically significant dosages over very long timescales ~ 450 Myrs. The GCR model is combined with laboratory data from experiments in which dry methyl ices were irradiated to doses producing prebiotic amino acids such as glycine. The model calculations show glycine can form to ~ 2.5 ppb levels near the surface after ~450 Myrs of GCR proton irradiation and potentially to 5 ppb if heavy-ion GCRs up through Fe are included. If such molecules were detected, this would not only confirm this model but indicate that life forms different from ours may not be required.

Edward C. Sittler Jr↗
NASA NTRS2020

Titan's Ionospheric Chemistry, Fullerenes, Oxygen, Galactic Cosmic Rays and the Formation of Exobiological Molecules on and Within Its Surfaces and Lakes

We discuss the formation of aerosols within Titan's thermosphere-ionosphere and the different chemical pathways. Negative ion measurements by the Cassini Plasma Spectrometer (CAPS) Electron Spectrometer (ELS) give evidence for formation of unsaturated anion carbon chains, while positive ion measurements of the Cassini Ion Neutral Mass Spectrometer (INMS) indicate formation of more aromatic cation hydrocarbons. There is presently no direct observational evidence for large neutral molecule growth in Titan's thermosphere-ionosphere. The hydrocarbon cations are expected to form Polycyclic Aromatic Hydrocarbons (PAHs), those with the addition of nitrogen being called PAHNs. We theorize anion carbon chains can eventually become long enough to fold into fullerene C60,70 carbon shells, of various charge states. Based on laboratory data the fullerenes can trap incoming O+ magnetospheric ions that have relatively high energy collisions with the fullerenes and, once trapped, protect the oxygen atom from Titan's reducing thermosphere-ionosphere. The fullerenes can form into larger onion fullerenes and condense into larger embryo aerosols (i.e., m/q (mass-to-charge ratio) greater than 10,000 amu/q (atomic mass unit-to-charge ratio) anions as observed by CAPS/ELS) eventually falling onto Titan's surface and precipitating to the bottom of its hydrocarbon lakes. Molecule production composed of H, C, N is known to occur in Titan's atmosphere with energy input from the magnetosphere, solar UV (ultraviolet), and deep-penetrating irradiation from galactic cosmic rays (GCR). Space radiation effects by GCR irradiation of Titan's surface and lakes can lead to the manufacture of exobiological molecules with oxygen as the new ingredient. We have developed a model of galactic cosmic ray irradiation of Titan's atmosphere, surface, subsurface and bottoms of Titan lakes. GCR would provide further energy for processing of the aerosols into more complex organic forms such as tholins and precursor molecules for amino acids. A second process called hydrolysis then converts the precursor molecules into amino acids. Hydrolysis is provided via meteor impacts with size greater than 10 kilometers and cryovolcanism both which can produce liquid water on Titan's surface for episodic periods more than several 100 to 1000 years. Our model shows that GCR secondary particles can penetrate ~100 meters below the ice surface (including the bottom of Titan's less dense hydrocarbon lakes ~150-meter depths) and produce chemically significant dosages over very long timescales ~450 million years. The GCR model is combined with laboratory data from experiments in which dry methyl ices were irradiated to doses producing prebiotic amino acids such as glycine. The model calculations show glycine can form to ~2.5 parts-per-billion levels near the surface after ~450 million years of GCR proton irradiation and potentially to 5 parts-per-billion if heavy-ion GCRs up through Fe are included. If such molecules were detected, this would not only confirm this model but indicate that life forms different from ours may not be required.

Edward C. Sittler Jr↗
DOE OSTI2023

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1995

Photochemistry of Triton's Atmosphere and Ionosphere

The photochemistry of 32 neutral and 21 ion species in Triton's atmosphere is considered. Parent species N2, CH4, and CO (with a mixing ratio of 3 x 10(exp -4) in our basic model) sublime from the ice with rates of 40, 208, and 0.3 g/sq cm/b.y., respectively. Chemistry below 50 km is driven mostly by photolysis of methane by the solar and interstellar medium Lyman-alpha photons, producing hydrocarbons C2H4, C2H6, and C2H2 which form haze particles with precipitation rates of 135, 28, and 1.3 g/sq cm/b.y., respectively. Some processes are discussed which increase the production of HCN (by an order of magnitude to a value of 29 g/sq cm/b.y.) and involve indirect photolysis of N2 by neutrals. Reanalysis of the measured methane profiles gives an eddy diffusion coefficient K = 4 x 10(exp 3)sq cm/s above the tropopause and a more accurate methane number density near the surface, (3.1 +/- 0.8)x IO(exp 11)/cu cm. Chemistry above 200 km is driven by the solar EUV radiation (lambda less than 1000 A) and by precipitation of magnetospheric electrons with a total energy input of 10(exp 8) W (based on thermal balance calculations). The most abundant photochemical species are N, H2, H, 0, and C. They escape with the total rates of 7.7 x 10(exp 24)/ s, 4.5 x 10(exp 25)/s, 2.4 x 10(exp 25)/s, 4.4 x 10(exp 22)/s, and 1.1 x 10(exp 24), respectively. Atomic species are transported to a region of 50-200 km and drive the chemistry there. Ionospheric chemistry explains the formation of an E region at 150-240 km with HCO(+) as a major ion, and of an F region above 240 km with a peak at 320 km and C(+) as a major ion. The ionosphere above 500 km consists of almost equal densities of C(+) and N(+) ions. The model profiles agree with the measured atomic nitrogen and electron density profiles. A number of other models with varying rate coefficients of some reactions, differing properties of the haze particles (chemically passive or active), etc., were developed. These models show that there are four basic unknown values which have strong impacts on the composition and structure of the atmosphere and ionosphere. These values and their plausible ranges are the CO mixing ratio f(sub co) = 10(exp -4) - 10(exp -3), the magnetospheric electron energy input (1 +/- 0.5) x 10(exp 8) W, the rate coefficient of charge-exchange reaction N2(+) + C(kappa) = 10(exp -11) - 10(exp -10)cu cm/s, and the ion escape velocity upsilon(sub i) approx. equals 150 cm/s.

Krasnopolsky, Vladimir A.↗