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NASA NTRS2014

Recent Advances in Water Analysis with Gas Chromatograph Mass Spectrometers

We report on progress made in developing a water sampling system for detection and analysis of volatile organic compounds in water with a gas chromatograph mass spectrometer (GCMS). Two approaches are described herein. The first approach uses a custom water pre-concentrator for performing trap and purge of VOCs from water. The second approach uses a custom micro-volume, split-splitless injector that is compatible with air and water. These water sampling systems will enable a single GC-based instrument to analyze air and water samples for VOC content. As reduced mass, volume, and power is crucial for long-duration, manned space-exploration, these water sampling systems will demonstrate the ability of a GCMS to monitor both air and water quality of the astronaut environment, thereby reducing the amount of required instrumentation for long duration habitation. Laboratory prototypes of these water sampling systems have been constructed and tested with a quadrupole ion trap mass spectrometer as well as a thermal conductivity detector. Presented herein are details of these water sampling system with preliminary test results.

quadrupole ion trap↗
NASA NTRSDate not supplied

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

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

Hiroshi Naraoka↗
NASA NTRS1998

Remote Sensing Measurements of Vertical and Horizontal Moisture Variations from Aircraft Instruments

The research in this paper focuses on describing vertical and horizontal of water vapor variability using two remote sensing aircraft instruments. To achieve this goal we will compare precipitable water and upper level humidity estimates derived from the each of the instruments. The Multispectral Atmospheric Mapping Sensor (MAMS) is a visible and infrared radiometer with similar channels to that of the GOES imager. MAMS has flown aboard the NASA ER-2 numerous times. It has been used to validate features observed with the previous series of GOES satellites. MAMS data has been used to study precipitable water and upper level water vapor as well as other geophysical parameters. MAMS provides the opportunity to obtain water vapor Imagery at 6.7 mm. Upper tropospheric humidity can be computed using this channel in a similar fashion to that of Soden and Bretherton. In addition to the water vapor channel, MAMS records data In 3 other Infrared channels and 8 visible and near Infrared bands at high spatial resolution (I 00 Abstract: m). The 1 1 and 12 mm infrared channels allow for the application of a split technique to derive total precipitable water. The Udar Atmospheric Sensing Experiment (LASE) which uses the Differential Absorption Udar (DIAL) technique for obtaining simultaneous water vapor and aerosol profiles through the entire troposphere. LASE operates In the 81 5 nm wavelength region and uses a double pulsed Ti:sapphire laser that is locked onto a water vapor line. LASE has good horizontal (IO km) and excellent vertical (300 m) resolution. MAMS and LASE collected data simultaneously on several ER-2 flights in September 1995. LASE mixing ratio profiles will be Integrated for comparison with MAMS precipitable water estimates and the upper tropospheric humidity will be computed for the layer observed by the MAMS 6.7 mm channel for comparison for this time period. Results show a significant correlation between the measurements of the two Instruments. Regions of high/low upper tropospheric humidity are apparent In measurements from both instruments. Also changes in boundary layer moisture depicted by LASE are reflected in the total precipitable water measured by MAMS.

Atkinson, R. J.↗
NASA NTRS2013

Multitemporal Cross-Calibration of the Terra MODIS and Landsat 7 ETM+ Reflective Solar Bands

In recent years, there has been a significant increase in the use of remotely sensed data to address global issues. With the open data policy, the data from the Moderate Resolution Imaging Spectroradiometer (MODIS) and Enhanced Thematic Mapper Plus (ETM+) sensors have become a critical component of numerous applications. These two sensors have been operational for more than a decade, providing a rich archive of multispectral imagery for analysis of mutitemporal remote sensing data. This paper focuses on evaluating the radiometric calibration agreement between MODIS and ETM+ using the near-simultaneous and cloud-free image pairs over an African pseudo-invariant calibration site, Libya 4. To account for the combined uncertainties in the top-of-atmosphere (TOA) reflectance due to surface and atmospheric bidirectional reflectance distribution function (BRDF), a semiempirical BRDF model was adopted to normalize the TOA reflectance to the same illumination and viewing geometry. In addition, the spectra from the Earth Observing-1 (EO-1) Hyperion were used to compute spectral corrections between the corresponding MODIS and ETM+ spectral bands. As EO-1 Hyperion scenes were not available for all MODIS and ETM+ data pairs, MODerate resolution atmospheric TRANsmission (MODTRAN) 5.0 simulations were also used to adjust for differences due to the presence or lack of absorption features in some of the bands. A MODIS split-window algorithm provides the atmospheric water vapor column abundance during the overpasses for the MODTRAN simulations. Additionally, the column atmospheric water vapor content during the overpass was retrieved using the MODIS precipitable water vapor product. After performing these adjustments, the radiometric cross-calibration of the two sensors was consistent to within 7%. Some drifts in the response of the bands are evident, with MODIS band 3 being the largest of about 6% over 10 years, a change that will be corrected in Collection 6 MODIS processing.

MODIS↗
NASA NTRSDate not supplied

Case Study for Lunar ISRU Systems Utilizing Polar Water

In-Situ Resource Utilization (ISRU) is key to long term presence at any extraterrestrial destination. Current NASA direction is to achieve a sustainable presence on the lunar surface by 2028. Mission plans currently target the lunar South Pole to leverage the extended periods of solar illumination and allows for potential access to water ice in the permanently shadowed areas around the poles. With water, it is possible to produce both fuel and oxidizer to fully refuel a vehicle. In order to address ISRU infusion into mission planning, a study of an end-to-end ISRU propellant production system was initiated to assess ISRU architectures and obtain mass and power estimates for each. The results of these case studies will be presented. For this study, The ISRU system architecture involved two sites; the mine site in a shadowed crater where water ice is excavated and extracted from the regolith and the propellant production site at an illuminated ridge where the water is processed into liquefied O2 and H2 propellants. Fixed hardware would be emplaced at each site, with two alternating water tankers to transport water between them. Notional lunar sites were identified for this architecture for baseline environmental parameters. Technology solutions for each subsystem were selected based on those with the highest fidelity models or those that have empirical laboratory data to anchor to. While power needs were identified for each location, a power solution was not prescribed, therefore the masses presented do not include surface power systems. The baseline case in this study assumed that 10 mT of oxygen, along with enough hydrogen to support a propulsion mixture ratio of 6, must be produced in 225 days. Therefore 15 mT of water would need to be collected and processed. The baseline solution resulted in a system mass of5 mT and a total required power of 68kW. The majority of the mass was split between the ridge site system and the two water tankers (2.6 mTand 1.8mTrespectively). The majority of the required power was with three subsystems at approximately 20 kW each: hydrogen liquefaction, electrolysis, and the water extractor subsystem. Trades for four key variables are also presented, namely production rate, water concentration, dry overburden depth, and number of water transport trips. This can be compared to a system that targets oxygen from the minerals in the surface regolith material. A carbothermal reduction reactor system was used for this comparison. The use of direct solar thermal energy to process the regolith and the ease of access of the resource resulted in significantly lower values for the oxygen case: approximately 2.7 mT and 11.8 kW. However, the mass trade would favor the water case over successive missions where the hydrogen up-mass of 2 mT per mission will accrue against the oxygen system.1Aerospace Research Engineer, Chemical and Thermal Propulsion Systems Branch, Senior Member.2Mechanical Engineer, Propulsion and Power Division/Energy Conversion Systems, 2101 Nasa Pkwy/Mailcode EP3 Houston, TX 77058, AIAA member.

Lunar↗
NASA NTRS1991

Conceptual study of on orbit production of cryogenic propellants by water electrolysis

The feasibility is assessed of producing cryogenic propellants on orbit by water electrolysis in support of NASA's proposed Space Exploration Initiative (SEI) missions. Using this method, water launched into low earth orbit (LEO) would be split into gaseous hydrogen and oxygen by electrolysis in an orbiting propellant processor spacecraft. The resulting gases would then be liquified and stored in cryogenic tanks. Supplying liquid hydrogen and oxygen fuel to space vehicles by this technique has some possible advantages over conventional methods. The potential benefits are derived from the characteristics of water as a payload, and include reduced ground handling and launch risk, denser packaging, and reduced tankage and piping requirements. A conceptual design of a water processor was generated based on related previous studies, and contemporary or near term technologies required. Extensive development efforts would be required to adapt the various subsystems needed for the propellant processor for use in space. Based on the cumulative results, propellant production by on orbit water electrolysis for support of SEI missions is not recommended.

Moran, Matthew E.↗
NASA NTRS1991

Conceptual study of on orbit production of cryogenic propellants by water electrolysis

The feasibility is assessed of producing cryogenic propellants on orbit by water electrolysis in support of NASA's proposed Space Exploration Initiative (SEI) missions. Using this method, water launched into low earth orbit (LEO) would be split into gaseous hydrogen and oxygen by electrolysis in an orbiting propellant processor spacecraft. The resulting gases would then be liquified and stored in cryogenic tanks. Supplying liquid hydrogen and oxygen fuel to space vehicles by this technique has some possible advantages over conventional methods. The potential benefits are derived from the characteristics of water as a payload, and include reduced ground handling and launch risk, denser packaging, and reduced tankage and piping requirements. A conceptual design of a water processor was generated based on related previous studies, and contemporary or near term technologies required. Extensive development efforts would be required to adapt the various subsystems needed for the propellant processor for use in space. Based on the cumulative results, propellant production by on orbit water electrolysis for support of SEI missions is not recommended.

Moran, Matthew E.↗
NASA NTRS2024

The Scientific Importance of the Lunar Environment

Many recent efforts to land robotic missions on the surface of the Moon are paving the way to return humans to the lunar surface and setting the stage for an ongoing human presence. Artemis is a NASA-led international effort to return humans to the Moon. One of the goals of Artemis is to use innovative technologies to address priority science objectives. At the same time, the European Space Agency (ESA) is exploring designs for a Moon base to enable ongoing human activity on the surface of the Moon. Furthermore, China plans to land humans on the Moon by 2030. In Situ Resource Utilization (ISRU) – the extraction of useful materials from the Moon itself – will be beneficial for efforts to sustain such human presence. ISRU could provide water that can be utilized by astronauts or split into hydrogen and oxygen rocket fuel for returning to Earth or moving forward to Mars, along with other vital resources. While this is exciting, it is critical that we recognize how human and robotic activity will impact the lunar environment and not having a global strategy to characterize lunar volatile materials before their scientific value is lost will significantly degrade the scientific potential of the Moon.

Kathleen E Mandt↗
NASA NTRS1991

Demonstration of Hazardous Hypervelocity Test Capability

NASA Johnson Space Center (JSC) White Sands Test Facility (WSTF) participated in a joint test program with NASA JSC Hypervelocity Impact Research Laboratory (HIRL) to determine if JSC was capable of performing hypervelocity impact tests on hazardous targets. Seven pressurized vessels were evaluated under hypervelocity impact conditions. The vessels were tested with various combinations of liquids and gasses at various pressures. Results from the evaluation showed that vessels containing 100-percent pressurized gas sustained more severe damage and had a higher potential for damaging nearby equipment, than vessels containing 75-percent liquid, 25-percent inert pressurized gas. Two water-filled test vessels, one of which was placed behind an aluminum shield, failed by bulging and splitting open at the impact point; pressure was relieved without the vessel fragmenting or sustaining internal damage. An additional water-filled test vessel, placed a greater distance behind an aluminum shield, sustained damage that resembled a shotgun blast, but did not bulge or split open; again, pressure was relieved without the vessel fragmenting. Two test vessels containing volatile liquids (nitro methane and hydrazine) also failed by bulging and splitting open; neither liquid detonated under hypervelocity test conditions. A test vessel containing nitrogen gas failed by relieving pressure through a circular entry hole; multiple small penetrations opposite the point of entry provided high velocity target debris to surrounding objects. A high-pressure oxygen test vessel fragmented upon impact; the ensuing fire and high velocity fragments caused secondary damage to surrounding objects. The results from the evaluation of the pressurized vessels indicated that JSC is capable of performing hypervelocity impact tests on hazardous targets.

Rodriquez, Karen M.↗
NASA NTRS1985

High-speed compressible flow and other advection-dominated problems of fluid dynamics

Finite element methods are described for modeling high speed compressible flows with strong advection, problems important to aerodynamics. The situations are characterized by high pressure and temperature gradients, transients and the appearance of discontinuities, factors which require mesh refinement during computations. Techniques are developed for temporal and spatial discretization of a model problem. Several observations are made regarding the explicit and implicit features of the calculations, the use of the Lax-Wendroff scheme to produce a mass-matrix for obtaining accurate results for transients, methods of performing stability analyses, and simplification techniques. Examples are provided of solving the nonlinear shallow-water equations and describing compressible flows, particularly transonic flows. Domain splitting is defined for improving the calculations at each time step and in different parts of the flow regime while simultaneously advancing the calculations towards a solution.

Zienkiewicz, O. C.↗
NASA NTRS1990

Microwave spectra of van der Waals complexes of importance in planetary atmospheres

The Fourier-transform Fabry-Perot pulsed-molecular-beam microwave spectrometer at NIST was used to study the microwave spectra of a number of molecular dimers and trimers that may be present in planetary atmospheres. The weak van der Waals bonds associated with these species usually give rise to rotational-tunneling splittings in the microwave spectra. The microwave spectrum of the water dimer species was used to illustrate the complications that can arise in the study of the rotational spectra of these loosely bound species. In addition to the water dimer species, the microwave spectra of the following hydrogen-bonded and van der Waals complexes were studied: (CO2)2-H2O, CO2-(H2O)2, CO2-H2S, N2-H2O, CO-H2O, SO2-H2O, and O3-H2O.

Suenram, R. D.↗
NASA NTRS1994

Land surface temperature measurements from EOS MODIS data

A generalized split-window method for retrieving land-surface temperature (LST) from AVHRR and MODIS data has been developed. Accurate radiative transfer simulations show that the coefficients in the split-window algorithm for LST must depend on the viewing angle, if we are to achieve a LST accuracy of about 1 K for the whole scan swath range (+/-55.4 deg and +/-55 deg from nadir for AVHRR and MODIS, respectively) and for the ranges of surface temperature and atmospheric conditions over land, which are much wider than those over oceans. We obtain these coefficients from regression analysis of radiative transfer simulations, and we analyze sensitivity and error by using results from systematic radiative transfer simulations over wide ranges of surface temperatures and emissivities, and atmospheric water vapor abundance and temperatures. Simulations indicated that as atmospheric column water vapor increases and viewing angle is larger than 45 deg it is necessary to optimize the split-window method by separating the ranges of the atmospheric column water vapor and lower boundary temperature, and the surface temperature into tractable sub-ranges. The atmospheric lower boundary temperature and (vertical) column water vapor values retrieved from HIRS/2 or MODIS atmospheric sounding channels can be used to determine the range where the optimum coefficients of the split-window method are given. This new LST algorithm not only retrieves LST more accurately but also is less sensitive than viewing-angle independent LST algorithms to the uncertainty in the band emissivities of the land-surface in the split-window and to the instrument noise.

Wan, Zhengming↗
NASA NTRS1992

Application of split window technique to TIMS data

Absorptions by the atmosphere in thermal infrared region are mainly due to water vapor, carbon dioxide, and ozone. As the content of water vapor in the atmosphere greatly changes according to weather conditions, it is important to know its amount between the sensor and the ground for atmospheric corrections of thermal Infrared Multispectral Scanner (TIMS) data (i.e. radiosonde). On the other hand, various atmospheric correction techniques were already developed for sea surface temperature estimations from satellites. Among such techniques, Split Window technique, now widely used for AVHRR (Advanced Very High Resolution Radiometer), uses no radiosonde or any kind of supplementary data but a difference between observed brightness temperatures in two channels for estimating atmospheric effects. Applications of Split Window technique to TIMS data are discussed because availability of atmospheric profile data is not clear when ASTER operates. After these theoretical discussions, the technique is experimentally applied to TIMS data at three ground targets and results are compared with atmospherically corrected data using LOWTRAN 7 with radiosonde data.

Matsunaga, Tsuneo↗
NASA NTRS2012

Performance Evaluation of Staged Bosch Process for CO2 Reduction to Produce Life Support Consumables

Utilizing carbon dioxide to produce water and hence oxygen is critical for sustained manned missions in space, and to support both NASA's cabin Atmosphere Revitalization System (ARS) and In-Situ Resource Utilization (ISRU) concepts. For long term missions beyond low Earth orbit, where resupply is significantly more difficult and costly, open loop ARS, like Sabatier, consume inputs such as hydrogen. The Bosch process, on the other hand, has the potential to achieve complete loop closure and is hence a preferred choice. However, current single stage Bosch reactor designs suffer from a large recycle penalty due to slow reaction rates and the inherent limitation in approaching thermodynamic equilibrium. Developmental efforts are seeking to improve upon the efficiency (hence reducing the recycle penalty) of current single stage Bosch reactors which employ traditional steel wool catalysts. Precision Combustion, Inc. (PCI), with support from NASA, has investigated the potential for utilizing catalysts supported over short-contact time Microlith substrates for the Bosch reaction to achieve faster reaction rates, higher conversions, and a reduced recycle flows. Proof-of-concept testing was accomplished for a staged Bosch process by splitting the chemistry in two separate reactors, first being the reverse water-gas-shift (RWGS) and the second being the carbon formation reactor (CFR) via hydrogenation and/or Boudouard. This paper presents the results from this feasibility study at various operating conditions. Additionally, results from two 70 hour durability tests for the RWGS reactor are discussed.

Vilekar, Saurabh A.↗
NASA NTRS2003

Mineralogical Characterization of Lunar Highland Soils

Ten pristine highland soils were selected for this study from Apollo 14 and 16 collections. These soils were chosen for their contrasting maturities, as reflected in their Is/FeO values [6]. For each soil, the 44- 20, 20-10, and < 10 m size fractions were obtained by wet sieving, with triply distilled water [7]. As outlined in Taylor et al. [2], each soil was split into appropriate sizes and distributed to LSCC members. The Tennessee team has characterized these soil size fractions both chemically and mineralogically, with detailed modal and phase compositional analyses, using techniques described previously by our group [8]. The results of the bulk chemistry of each size fraction of the highland soils was presented earlier.

Taylor, L. A.↗
NASA NTRS1992

The Zeeman effect in astrophysical water masers and the observation of strong magnetic fields in regions of star formation

The present study solves the transfer equations for the polarized radiation of astrophysical 22-GHz water masers in the presence of a magnetic field which causes a Zeeman splitting that is much smaller than the spectral line breadth. The emphasis is placed on the relationship between the recently detected circular polarization in this maser radiation and the strength of the magnetic field. When the observed spectral line breadth is smaller than about 0.8 km/s (FWHM), it is calculated that the uncertainty is less than a factor of about 2. The accuracy is improved significantly when the angle between the line of sight and the direction of the magnetic field does not exceed about 45 deg. Uncertainty in the strength of the magnetic field due to lack of knowledge about which hyperfine transition is the source of the 22-GHz masers is removed. The 22-GHz maser feature is found to be the result of a merger of the three strongest hyperfine components.

Nedoluha, Gerald E.↗