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At least 127 records · Page 7

Analysis of LDEF experiment AO187-2 chemical and isotopic measurements of micrometeoroids by secondary ion mass spectrometry

#Experiment AO187-2, that was flown on board the Long Duration Exposure Facility(LDEF), was designed to measure the chemical and isotopic compositions of interplanetary dust impinging on the spacecraft from outer space. Information on the nature and composition of orbital debris was also anticipated. The spacecraft maintained a constant orientation with respect to its velocity vector thereby defining leading and trailing edges that faced respectively into and away from the direction of motion. Arrays of individual capture cells each 80.8 sq cm in size and totaling 237 in number were exposed on both the leading and trailing edges of LDEF. Each cell consisted of a pure Ge target surface slightly separated from a thin (2.5 micrometers) metallized plastic 'entrance foil.' The basic concept was that incoming projectiles would penetrate the foil, strike the Ge target plate at high velocity producing a vapor-liquid cloud that would re-deposit material on the underside of the plastic foil. This material would then be analyzed using the sensitive surface analysis technique of Secondary Ion Mass Spectrometry (SIMS). In practice, most of the plastic entrance foils failed during the extended period of orbital exposure probably due to a combination of UV embrittlement, large densities of impact events and (for the leading edge) the effects of atomic oxygen erosion in orbit. However the foils failed gradually and most remained in place on the capture cells for a significant fraction of the duration of the flight . Because most of the impactors were small (less than 10 micrometers) they were heated and dispersed in traversing the entrance foils producing clouds of molten droplets and vapor that produced easily identifiable 'extended impacts' on the Ge target plates. Fortunately, it proved possible to make ion probe measurements of projectile compositions from material deposited on the Ge in the extended impact structures.

Zinner, Ernst↗

Carbon isotopic analysis of atmospheric methane by isotope-ratio-monitoring gas chromatography-mass spectrometry

Less than 15 min are required for the determination of delta C(sub PDB)-13 with a precision of 0.2 ppt(1 sigma, single measurement) in 5-mL samples of air containing CH4 at natural levels (1.7 ppm). An analytical system including a sample-introduction unit incorporating a preparative gas chromatograph (GC) column for separation of CH4 from N2, O2, and Ar is described. The 15-min procedure includes time for operation of that system, high-resolution chromatographic separation of the CH4, on-line combustion and purification of the products, and isotopic calibration. Analyses of standards demonstrate that systematic errors are absent and that there is no dependence of observed values of delta on sample size. For samples containing 100 ppm or more CH4, preconcentration is not required and the analysis time is less than 5 min. The system utilizes a commercially available, high-sensitivity isotope-ratio mass spectrometer. For optimal conditions of smaple handling and combustion, performance of the system is within a factor of 2 of the shot-noise limit. The potential exists therefore for analysis of samples as small as 15 pmol CH4 with a standard deviation of less than 1 ppt.

Merritt, Dawn A.↗

Extraterrestrial Amino Acids in the C2 Ungrouped Carbonaceous Chondrite Tarda: A Unique Distribution

Introduction: Meteorites provide a record of the chemical processes that occurred in the early solar sys-tem. The delivery of organic matter by carbonaceous chondrites to the early Earth could have been an im-portant source of amino acids and other prebiotic or-ganic molecules required for the emergence of life [1]. To date, 96 amino acids have been named in meteor-ites, most of which are rare or absent in the biosphere [2]. The variability in amino acid concentrations and isomer distributions measured in carbonaceous chon-drites can be explained by differences in parent body chemistry and alteration conditions [3]. In addition, aqueous alteration was likely important in the amplifi-cation of some left-handed amino acids over their right-handed forms (L-excesses up to ~60%) in the Tagish Lake meteorite [3], suggesting that the origin of life on Earth and possibly elsewhere in the solar sys-tem was biased towards L-amino acids. On August 25, 2020, a fireball was witnessed in southern Morocco and the first pieces of the meteorite fall were recovered the following day near the town of Tarda [4]. Thousands of individual fragments were recovered from the strewn field totaling ~4 kg [4]. Based on petrographic observations, bulk mineralogy, and chemical and O-isotopic analyses, Tarda has been classified as a C2 ungrouped carbonaceous chondrite with similarities to Tagish Lake (though more primi-tive), as well as CI, CY, and CR chondrites [4,5]. The fall and rapid recovery of the Tarda stones provide an important opportunity to investigate a C-rich meteorite using the state-of-the-art techniques that will also be used to study the samples returned from asteroids Ryugu and Bennu by the Hayabusa2 and OSIRIS-REx missions, respectively. Here, we report the first amino acid analyses of the Tarda meteorite. The total concentrations, enantio-meric ratios and relative distributions of amino acids were determined using ultrahigh performance liquid chromatography with UV fluorescence and time-of-flight mass spectrometry (LC-FD/ToF-MS) at NASA GSFC. This analytical technique was employed on extracts from two different pre-rain Tarda meteorite fragments and a sample of sand collected from the Tarda fall site for the purpose of assessing potential terrestrial contamination. Bulk H, C, and N elemental and isotopic analyses were also conducted at the Car-negie Institution for Science (CIS) to assist with petro-logic type classification using elemental analysis iso-tope ratio mass spectrometry (EA-IRMS).

D P Glavin↗

Oxidation-chlorination of binary Ni-Cr alloys in flowing Ar-O2-Cl2 gas mixtures at 1200 K

Nickel-chromium alloys are resistant to oxidation because of the selective oxidation of chromium to form a protective Cr2O3 scale. In chlorine-containing environments, volatile corrosion products can also be formed. The mixed oxidation-chlorination of Ni-4.5Cr, Ni-13.8Cr, and Ni-26.5Cr (by weight) alloys in Ar-O2-Cl2 gas mixtures is investigated using thermogravimetric analysis and atmospheric-pressure-sampling mass spectrometry, followed by examination of the corrosion products using scanning electron microscopy and X-ray diffraction analysis. The overall kinetics of the corrosion are affected by the relative amounts of oxides and chlorides formed and the composition of the oxide corrosion products.

Mcnallan, M. J.↗

Mass Spectrometry on Future Mars Landers

Mass spectrometry investigations on the 2011 Mars Science Laboratory (MSL) and the 2018 ExoMars missions will address core science objectives related to the potential habitability of their landing site environments and more generally the near-surface organic inventory of Mars. The analysis of complex solid samples by mass spectrometry is a well-known approach that can provide a broad and sensitive survey of organic and inorganic compounds as well as supportive data for mineralogical analysis. The science value of such compositional information is maximized when one appreciates the particular opportunities and limitations of in situ analysis with resource-constrained instrumentation in the context of a complete science payload and applied to materials found in a particular environment. The Sample Analysis at Mars (SAM) investigation on MSL and the Mars Organic Molecule Analyzer (MOMA) investigation on ExoMars will thus benefit from and inform broad-based analog field site work linked to the Mars environments where such analysis will occur.

Brinckerhoff, W. B.↗

Mass spectrometry of aerospace materials

Mass spectrometry is used for chemical analysis of aerospace materials and contaminants. Years of analytical aerospace experience have resulted in the development of specialized techniques of sampling and analysis which are required in order to optimize results. This work has resulted in the evolution of a hybrid method of indexing mass spectra which include both the largest peaks and the structurally significant peaks in a concise format. With this system, a library of mass spectra of aerospace materials was assembled, including the materials responsible for 80 to 90 percent of the contamination problems at Goddard Space Flight Center during the past several years.

Colony, J. A.↗

Detection of soil microorganism in situ by combined gas chromatography mass spectrometry

Experimental tests were made to determine whether analysis of volatile metabolic products, formed in situ, is a viable procedure for an extraterrestrial life detection system. Laboratory experiments, carried out under anaerobic conditions with addition of carbon source, extended to include a variety of soils and additional substrates. In situ experiments were conducted without amendment using a vacuum sampling system.

Alexander, M.↗

Gas analysis of Apollo 12, 14, and 15 samples by laser-probe mass spectrometry

Solar wind gases, cosmogenic gases from high energy spallation reactions from soxmic rays, and radiogenic gases from decay of radioactive potassium and from uranium and thorium isotopes were analyzed in lunar materials. Details are presented on two aspects of the studies: (1) The spatial distribution of Ar-40/Ar-38 ages in lunar breccia 14301 was determined. The ages of clasts within this breccia are 3.68 + or - 0.09 and 2.9 + or - 0.3 x 10 to the 9th power years. Parentless radiogenic Ar-40 exists within the fine-grained matrix. (2) The distribution of helium, neon, and argon isotopes within Apollo 15 samples results primarily from fractionated solar wind gases, accompanied by small quantities of cosmogenic gases. Comparison of this Apollo 15 data with Kapoeta and Fayetteville meteorite and Apollo 12 and 14 data indicates that solar wind implantation followed by fractionation of the gases was primarily responsible for incorporation of original gas phase within solid bodies of the solar system.

Imegrue, G. H.↗

Investigating Commercial Off-The-Shelf (COTS) Glovebox and Support Components Compared to Custom Curatorial Laboratories

There is a need envisioned to investigate the application of commercial off-the-shelf (COTS) systems as tools that could be used within commercial preliminary curation as the expected space economy is supported and begins to take flight. NASA is involved with supporting and developing the space economy [1] and therefore it’s feasible that at some point, a commercial space company would bring back materials and either store initially, or permanently, within COTS equipment as a stand-in for custom curation laboratories. While utilizing opportunities to explore this capability at NASA-Johnson Space Center (JSC) during the establishment of other laboratories [2] it was realized that cleanliness and/or other properties could be evaluated for these COTS systems during their installation in advanced research facilities that are not ISO-class rated clean rooms. Several aspects of a COTS-Curation system were explored including various gloves for curation manipulation within a negative pressure glovebox (Fig.1), Balazs organic and inorganic contaminant levels testing prior to glovebox ever being used, mode swapping comparison of recirculation vs. single pass, constant monitoring of oxygen (O2) and moisture (H2O) levels in various conditions, etc. To acquire inorganic and organic compound loads inside the glovebox, Balazs wafer testing and gas sampling were implemented. These are standardized analytical tests provided by Balazs™ NanoAnalysis, a division of Air Liquide USA. Deployment of 8-inch silicon wafer witness plates for 24-hours in an undisturbed environment capture the organic compound load and inorganic trace metal contents which can be obtained by Vapor Phase Decomposition Inductively Coupled Plasma Mass Spectrometry (VPD ICP-MS). Balazs gas sample analysis was also performed for better measurements of volatile organic compounds (VOC) in glovebox air analyzed by Thermal Desorption Gas Chromatography Mass Spectrometry (TD GC-MS). These analytical testings were carried out in a controlled ultra high pure (UHP) gaseous nitrogen (N2)-purged environment where oxygen and moisture contents were continuously monitored at certain temperature and pressure. The preliminary outcomes of these testings are promising. The COTS systems appear to maintain the steady-state controlled environment for days, if not weeks, with uninterrupted gaseous N2-supply which was operated from a standard medium pressure LN2 250L 230L dewar, exchanged as needed. The outgassing load can be maintained by selecting the glove materials that have the least outgassing and particle shedding performances. Further experiments will be considered to validate the preliminary findings. While this project is exploratory, it is not intended as an endorsement by NASA Curation for approved materials or usage for advanced curatorial activities. NASA does not endorse nor promote any one particular product or company. References: [1] McCubbin F. M. et al. (2019) Space Science Reviews 215:A48. [2] Lewis, E.K. et. al (2024) LPSC LV, Abstract #2457.

Curation↗

The Search for Organic Compounds of Martian Origin in Gale Crater by the Sample Analysis at Mars (SAM) Instrument on Curiosity

One of the key objectives of the Mars Science Laboratory rover and the Sample Analysis at Mars (SAM) instrument suite is to determine the inventory of organic and inorganic volatiles in the atmosphere and surface regolith and rocks to help assess the habitability potential of Gale Crater. The SAM instrument on the Curiosity rover can detect volatile organic compounds thermally evolved from solid samples using a combination of evolved gas analysis (EGA) and gas chromatography mass spectrometry (GCMS) (Mahaffy et al. 2012). The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest, revealed several chloromethanes and a C4-chlorinated hydrocarbon derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tertbutyldimethylsilyl)- trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background (Glavin et al. 2013). After the analyses at Rocknest, Curiosity traveled to Yellowknife Bay and drilled two separate holes in a fluvio-lacustrine sediment (the Sheepbed unit) designated John Klein and Cumberland. Analyses of the drilled materials by both SAM and the CheMin X-Ray Diffraction instrument revealed a mudstone consisting of ~20 wt% smectite clays (Ming et al. 2013; Vaniman et al. 2013), which on Earth are known to aid the concentration and preservation of organic matter. Oxychlorine compounds were also detected in the Sheepbed mudstone during pyrolysis; however, in contrast to Rocknest, much higher levels of chloromethanes were released from the Sheepbed materials, suggesting an additional, possibly martian source of organic carbon (Ming et al. 2013). In addition, elevated abundances of chlorobenzene and a more diverse suite of chlorinated alkanes including dichloropropane and dichlorobutane detected in Cumberland compared to Rocknest suggest that martian or meteoritic organic carbon sources may be preserved in the mudstone (Freissinet et al. 2013). Chloromethane and dichloromethane were also identified after thermal volatilization of the surface soils by the GCMS instruments at the Viking landing sites, although no other chlorinated hydrocarbons were reported (Biemann et al. 1977). Here we focus on the origin of the chlorinated hydrocarbons detected in the Sheepbed mudstone by SAM and the implications for the preservation of organic matter in near-surface materials on Mars.

Mars Curiosity Rover↗

Minor and trace elements in some meteoritic minerals.

Despite the information available (Mason, 1971) on trace elements in different types of meteorites, relatively little is known about the distribution of these elements among the individual mineral phases. The mineral phases including olivine, orthopyroxene, clinipyroxene, troilite, nickel-iron, plagioclase, chromite, and the phosphates were separated from several meteorites. The purified minerals were analyzed for trace and minor elements by spark source mass spectrometry and instrumental neutron activation analysis. The elements are classified as siderophile, lithophile, and chalcophile.

Allen, R. O., Jr.↗

Effectiveness of solid lubricant coatings for friction in hard vacuum (10-9 tor)

A study was made of the efficiency of solid lubricating coatings, based on MoS2 with various binders, during friction and under highvacuum conditions. Mass spectrometry was used for an analysis of the composition of the gas evolved from the coatings in the friction process. It is shown that the vacuum level, loading, and sliding velocity influence coating effectiveness. In the friction process the solid lubricant coatings yield characteristic decay products associated with the chemical nature of the binders. The mechanism of coating breakdown during friction is associated with the binder breakdown mechanism.

Verkin, B. I.↗

Laser-induced volatilization and ionization of microparticles

A method for the laser vaporization and ionization of individual micron-size particles is presented whereby a particle is ionized by a laser pulse while in flight in the beam. Ionization in the beam offers a real-time analytical capability and eliminates any possible substrate-sample interferences during an analysis. An experimental arrangement using a high-energy Nd-YAG laser is described, and results are presented for ions generated from potassium biphthalate particles (1.96 micron in diameter). The method proposed here is useful for the chemical analysis of aerosol particles by mass spectrometry and for other spectroscopic and chemical kinetic studies.

Sinha, M. P.↗

Surface characterization in composite and titanium bonding: Carbon fiber surface treatments for improved adhesion to thermoplastic polymers

The effect of anodization in NaOH, H2SO4, and amine salts on the surface chemistry of carbon fibers was examined by X-ray photoelectron spectroscopy (XPS). The surfaces of carbon fibers after anodization in NaOH and H2SO4 were examined by scanning transmission electron microscopy (STEM), angular dependent XPS, UV absorption spectroscopy of the anodization bath, secondary ion mass spectrometry, and polar/dispersive surface energy analysis. Hercules AS-4, Dexter Hysol XAS, and Union Carbide T-300 fibers were examined by STEM, angular dependent XPS, and breaking strength measurement before and after commercial surface treatment. Oxygen and nitrogen were added to the fiber surfaces by anodization in amine salts. Analysis of the plasmon peak in the carbon 1s signal indicated that H2SO4 anodization affected the morphological structure of the carbon fiber surface. The work of adhesion of carbon fibers to thermoplastic resins was calculated using the geometric mean relationship. A correlation was observed between the dispersive component of the work of adhesion and the interfacial adhesion.

Devilbiss, T. A.↗

Reactions of silicon-based ceramics in mixed oxidation chlorination environments

The reaction of silicon-based ceramics with 2 percent Cl2/Ar and 1 percent Cl2/1 percent to 20 percent O2/Ar at 950 C was studied with thermogravimetric analysis and high-pressure mass spectrometry. Pure Si, SiO2, several types of SiC, and Si3N4 were examined. The primary corrosion products were SiCl4(g) and SiO2(s) with smaller amounts of volatile silicon oxychlorides. The reactions appear to occur by chlorine penetration of the SiO2 layer, and gas-phase diffusion of the silicon chlorides away from the sample appears to be rate limiting. Pure SiO2 shows very little reaction with Cl2, SiC with excess Si is more reactive than the other materials with Cl2, whereas SiC with excess carbon is more reactive than the other materials with Cl2/O2. Si3N4 shows very little reaction with Cl2. These differences are explained on the basis of thermodynamic and microstructural factors.

Marra, John E.↗

Use Of The Operational Air Quality Monitor (AQM) For In-Flight Water Testing Project

A primary requirement for manned spaceflight is Environmental Health which ensures air and water contaminants, acoustic profiles, microbial flora, and radiation exposures within the cabin are maintained to levels needed for crew health and for vehicle system functionality. The reliance on ground analyses of returned samples is a limitation in the current environmental monitoring strategy that will prevent future Exploration missions beyond low-Earth orbit. This proposal attempts to address this shortcoming by advancing in-flight analyses of water and air. Ground analysis of in-flight, air and water samples typically employ vapor-phase analysis by gas chromatography-mass spectrometry (GC-MS) to identify and quantify organic compounds present in the samples. We envision the use of newly-developed direct ionization approaches as the most viable avenue leading towards an integrated analytical platform for the monitoring of water, air, and, potentially bio-samples in the cabin environment. Development of an in-flight instrument capable of analyzing air and water samples would be the logical next step to meeting the environmental monitoring needs of Exploration missions. Currently, the Air Quality Monitor (AQM) on-board ISS provides this specific information for a number of target compounds in the air. However, there is a significant subset of common target compounds between air and water. Naturally, the following question arises, "Can the AQM be used for both air and water quality monitoring?" Previous directorate-level IR&D funding led to the development of a water sample introduction method for mass spectrometry using electrothermal vaporization (ETV). This project will focus on the integration of the ETV with a ground-based AQM. The capabilities of this integrated platform will be evaluated using a subset of toxicologically important compounds.

Macatangay, Ariel↗

Amino Acids Generated from Hydrated Titan Tholins: Comparison with Miller-Urey Electric Discharge Products

Various analogues of Titan haze particles (termed tholins) have been made in the laboratory. In certain geologic environments on Titan, these haze particles may come into contact with aqueous ammonia (NH3) solutions, hydrolyzing them into molecules of astrobiological interest. A Titan tholin analogue hydrolyzed in aqueous NH3 at room temperature for 2.5 years was analyzed for amino acids using highly sensitive ultra-high performance liquid chromatography coupled with fluorescence detection and time-of-flight mass spectrometry (UHPLC-FDToF-MS) analysis after derivatization with a fluorescent tag. We compare here the amino acids produced from this reaction sequence with those generated from room temperature Miller-Urey (MU) type electric discharge reactions. We find that most of the amino acids detected in low temperature MU CH4N2H2O electric discharge reactions are generated in Titan simulation reactions, as well as in previous simulations of Triton chemistry. This argues that many processes provide very similar mixtures of amino acids, and possibly other types of organic compounds, in disparate environments, regardless of the order of hydration. Although it is unknown how life began, it is likely that given reducing conditions, similar materials were available throughout the early Solar System and throughout the universe to facilitate chemical evolution.

Astrobiology aEuro" Titan↗