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Research in planetary astronomy and operation of the Mauna Kea Observatory

Spectroscopic studies with ground-based telescopes at low resolution can give compositional information of the surfaces and atmospheres of planets, satellites, asteroids, and comets. Solid state absorptions in ices and minerals are measurable by the low-resolution spectrophotometric technique. This program includes spectroscopy of distant comets, asteroids of particular interest in various contexts (planet crossers, outer main belt, trojans, etc.), Pluto and Charon, and planetary satellites of particular interest (Iapetus, Io, Uranian satellites, etc.). In the case of planets, satellites, and comets, emphasis is placed on volatiles (ices and organics), while for asteroids the stress is on mineralogy and the connection with the meteorites. New spectra show that the IR signature of Triton has changed since 1980, in that the methane bands are significantly weaker. Spectral evidence for the presence of molecular nitrogen remains convincing. Also, the brightness of Triton throughout its orbital cycle was measured to higher precision than before and was found to be constant to better than 0.02 mag. Suggestive spectral evidence was found for the presence of the C-H stretching mode band in diffuse reflection on asteroid 130 Elektra.

Cruikshank, Dale P.↗

Investigating the Effects of Temperature on the Signatures of Shocks Propagated Through Impacts into Minerals Found in Comets and Asteroids

Comets and asteroids are subjected to extremely cold conditions throughout their lifetimes. During their sojourns in the solar system, they are subjected to collisions at speeds that are easily capable of generating shock waves in their constituent materials. In addition to ices, more common silicate minerals such as olivines and pyroxenes are important components of these objects. The collision-induced shocks could affect the spectral signatures of those mineral components, which could in turn be detected telescopically. We have embarked on a project to determine how impact-generated shock might affect the reflectance spectra and structures of select silicates as both impact speed and target temperature are varied systematically. While the effects of impact speed (in the form of shock stress) on numerous materials have been and continue to be studied, the role of target temperature has received comparatively little attention, presumably because of the operational difficulties it can introduce to experimentation. Our experiments were performed with the vertical gun in the Experimental Impact Laboratory of the Johnson Space Center. A liquid-nitrogen system was plumbed to permit cooling of the target container and its contents under vacuum to temperatures as low as -100 C (173 K). Temperatures were monitored by thermocouples mounted on the outside of the target container. Because those sensors were not in contact with the target material at impact, the measured temperatures are treated as lower limits for the actual values. Peridot (Mg-rich olivine) and enstatite (Mg-rich orthopyroxene) were used as targets, which involved the impact of alumina (Al2O3) spheres at speeds of 2.0 - 2.7 km s(exp -1) and temperatures covering 25 C to -100 C (298 K to 173 K). We have begun collecting and analyzing data in the near to mid-IR with a Fourier-transform infrared spectrometer, and preliminary analyses show that notable differences in absorption-band strength and position occur as functions of both impact speed (peak shock stress) and initial temperature.

Lederer, Susan M.↗

The Combustion Experiment on the Sample Analysis at Mars (SAM) Instrument Suite on the Curiosity Rover

The combustion experiment on the Sample Analysis at Mars (SAM) suite on Curiosity will heat a sample of Mars regolith in the presence of oxygen and measure composition of the evolved gases using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS). QMS will enable detection of combustion products such as CO, CO2, NO, and other oxidized species, while TLS will enable precise measurements of the abundance and carbon isotopic composition (delta(sup 13)C) of the evolved CO2 and hydrogen isotopic composition (deltaD) of H2O. SAM will perform a two-step combustion to isolate combustible materials below approx.550 C and above approx.550 C. The combustion experiment on SAM, if properly designed and executed, has the potential to answer multiple questions regarding the origins of volatiles seen thus far in SAM evolved gas analysis (EGA) on Mars. Constraints imposed by SAM and MSL time and power resources, as well as SAM consumables (oxygen gas), will limit the number of SAM combustion experiments, so it is imperative to design an experiment targeting the most pressing science questions. Low temperature combustion experiments will primarily target the quantification of carbon (and nitrogen) contributed by SAM wet chemistry reagants MTBSTFA (N-Methyl-N-tert-butyldimethylsilyltrifluoroacetamide) and DMF (Dimethylformamide), which have been identified in the background of blank and sample runs and may adsorb to the sample while the cup is in the Sample Manipulation System (SMS). In addition, differences between the sample and "blank" may yield information regarding abundance and delta(sup 13)C of bulk (both organic and inorganic) martian carbon. High temperature combustion experiments primarily aim to detect refractory organic matter, if present in Cumberland fines, as well as address the question of quantification and deltaD value of water evolution associated with hydroxyl hydrogen in clay minerals.

Mars↗

Nitrogen and light noble gases in Shergotty

Two samples of Shergotty and a sample of EETA 79001's lithology A have been analyzed for N, He, Ne, and Ar abundances and isotopic composition. After correcting for spallogenic nitrogen, the nitrogen isotopic ratios were found to be close to that of the terrestrial atmosphere. The spallogenic noble gas data are consistent with cosmic ray irradiation of both Shergotty and EETA 79001 at shallow shielding depths. Cosmic ray exposure ages were estimated to be in the range of 0.5-0.8 Myr for EETA 79001, and of 2.0-5.2 Myr for Shergotty, depending on the choice of object size and shielding. Among the two Shergotty samples, the contents of Ar-40 differed by a factor of 3. This difference can be attributed to either a small-scale mineralogical inhomogeneity or a significant variation in the degree of degassing of minerals during shock, although the presence of trapped argon with a high Ar-40/Ar-36 ratio and its heterogeneous distribution cannot be ruled out.

Becker, R. H.↗

Study of various NH4+/NO3- mixtures for enhancing growth of potatoes

Two experiments were conducted to determine the effects of various NH4(+)-N/NO3(-)-N percentages on growth and mineral concentrations in potato (Solanum tuberosum L.) plants using a non-recirculating nutrient film system in a controlled environment. The first experiment included six NH4(+)-N/NO3(-)-N percentages at 0/100, 20/80, 40/60, 60/40, 80/20, and 100/0 with the same total N concentration of 4 mM. The second experiment included six NH4(+)-N/NO3(-)-N percentages at 0/100, 4/96, 8/92, 12/88, 16/84, and 20/80 again with the same total N of 4 mM. In each experiment, plants were harvested 35 days after transplanting when tubers had been initiated and started to enlarge. Dry weights of shoots, tubers, and whole plant at the harvest were increased significantly with all mixed nitrogen treatments as compared with single NH4+ or NO3- form. The enhanced growth with mixed nitrogen was greatest at 8% to 20% NH4(+)-N. Also, the concentrations and accumulation of total N in the shoots and roots were greater with mixed nitrogen than with separate NH4+ or NO3- nutrition. With NH4+ present in the solutions, the concentrations of P and Cl in the shoots were increased compared to NO3- alone, whereas the tissue concentrations of Ca and Mg were decreased. It was concluded that nitrogen fertilization provided with combined NH4+ and NO3- forms, even at small proportions of NH4+, can enhance nitrogen uptake and productivity in potato plants.

NASA Program CELSS↗

Separation and Purification of Mineral Salts from Spacecraft Wastewater Processing via Electrostatic Beneficiation

Electrostatic separation is a class of material processing technologies commonly used for the sorting of coarse mixtures by means of electrical forces acting on charged or polarized particles. Most if not all of the existing tribo-electrostatic separators had been initially developed for mineral ores beneficiation. It is a well-known process that has been successfully used to separate coal from minerals. Potash (potassium) enrichment where underground salt mines containing large amounts of sodium is another use of this techno logy. Through modification this technology can be used for spacecraft wastewater brine beneficiation. This will add in closing the gap be~een traveling around Earth's Gravity well and long-term space explorations. Food has been brought on all man missions, which is why plant growth for food crops continues to be of interest to NASA. For long-term mission considerations food productions is one of the top priorities. Nutrient recovery is essential for surviving in or past low earth orbit. In our advance bio-regenerative process instead of nitrogen gas produced; soluble nitrate salts that can be recovered for plant fertilizer would be produced instead. The only part missing is the beneficiation of brine to separate the potassium from the sodium. The use of electrostatic beneficiation in this experiment utilizes the electrical charge differences between aluminum and dried brine by surface contact. The helixes within the aluminum tribocharger allows for more surface contact when being agitated. When two materials are in contact, the material with the highest affinity for electrons becomes negatively charged, while the other becomes positively charged. This contact exchange of charge may cause the particles to agglomerate depending on their residence time within the tribocharger, compromising the efficiency of separation. The aim of this experiment is to further the development in electrostatic beneficiation by optimizing the separation of ersatz and possibly real wastewater brine residues. In doing so, ideally it will yield a high potassium enrichment for use in spacecraft plant systems.

Miles, John D., II↗

Modelling climate change impacts on maize yields under low nitrogen input conditions in sub‐Saharan Africa

Smallholder farmers in sub‐Saharan Africa (SSA) currently grow rainfed maize with limited inputs including fertilizer. Climate change may exacerbate current production constraints. Crop models can help quantify the potential impact of climate change on maize yields, but a comprehensive multimodel assessment of simulation accuracy and uncertainty in these low‐input systems is currently lacking. We evaluated the impact of varying [CO2], temperature and rainfall conditions on maize yield, for different nitrogen (N) inputs (0, 80, 160 kg N/ha) for five environments in SSA, including cool subhumid Ethiopia, cool semi‐arid Rwanda, hot subhumid Ghana and hot semi‐arid Mali and Benin using an ensemble of 25 maize models. Models were calibrated with measured grain yield, plant biomass, plant N, leaf area index, harvest index and in‐season soil water content from 2‐year experiments in each country to assess their ability to simulate observed yield. Simulated responses to climate change factors were explored and compared between models. Calibrated models reproduced measured grain yield variations well with average relative root mean square error of 26%, although uncertainty in model prediction was substantial (CV = 28%). Model ensembles gave greater accuracy than any model taken at random. Nitrogen fertilization controlled the response to variations in [CO2], temperature and rainfall. Without N fertilizer input, maize (i) benefited less from an increase in atmospheric [CO2], (ii) was less affected by higher temperature or decreasing rainfall and (iii) was more affected by increased rainfall because N leaching was more critical. The model inter-comparison revealed that simulation of daily soil N supply and N leaching plays a crucial role in simulating climate change impacts for low-input systems. Climate change and N input interactions have strong implications for the design of robust adaptation practices across SSA, because the impact of climate change will be modified if farmers intensify maize production with more mineral fertilizer.

Crop simulation model↗

Volatile element chemistry of selected lunar, meteoritic, and terrestrial samples

Using vacuum pyrolysis and high resolution mass spectrometry, a study is made of the gas release patterns of representative lunar samples, meteorites, terrestrial samples, and synthetic samples doped with various sources of carbon and nitrogen. The pyrolytic gas evolution patterns were intercorrelated, allowing an assessment of the possible sources of the volatilizable material in the lunar samples to be made. Lightly surface adsorbed species and more strongly chemisorbed species are released from ambient to 300 C and from 300 to 500 C, respectively. The low-temperature volatiles (less than 500 C) derived from various chondrites correlate well with the gas evolution patterns of volatile-rich samples, as for example 74220 and 61221. Solar wind entrapped species and molecules derived from reactions probably in the grain surfaces are evolved from about 500 to 700 C, respectively. Solar wind implanted C, N, and S species are generated from 750 to 1150 C, probably by reaction with the mineral matrix during the annealing process. Possible indigenous and/or refractory carbide, nitride, and sulfide C, N, and S are released in the region from 1200 C to fusion.

Simoneit, B. R.↗

In-Situ Reaction Monitoring for Lunar Applications Utilizing a Single Quadrupole Residual Gas Analyzer

With a revived focus to create a permeant presence on the moon and in preparation for future Mars exploration, it is imperative that all re-sources are utilized to their fullest potential. In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable independent operation of missions while minimally relying on the complex supply chain created between the Earth, moon and Mars. One of the most critical resources that have been identified for ISRU is the creation of liquid oxygen (O2) for not only breathable air, but also for rocket fuel. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith. Although there are numerous minerals within regolith and various processes to extract O2, this is not the scope of this paper. Since the O2 extraction method can vary, a critical standardized analytical method is needed to verify O2 (or oxygenated precursor compounds) for extraction efficiency and purity. Our group utilizes a modified consumer off-the-shelf (COTS), Residual Gas Analyzer (RGA) Single Quadrupole Mass Spectrometer (QMS). Due to the current field mission requirements, the gas analysis module will need to rely only on mass-to-charge ratios (m/z) and peak intensities to differentiate and quantitate targeted gas-phase reactants or products, i.e. carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) and hydrogen (H2). However, due to solar wind implanted volatiles and various other compounds present in lunar regolith, such as nitrogen (N2), helium (He), and deuterium (D2), deconvolution and quantification of isobaric compounds becomes quite difficult. Specifically, the presence of N2 makes quantification of CO, an oxygenated precursor, difficult due to both compounds having a peak at m/z 28. Approaches to differentiate isobaric components: Initially, the solution to overcome isobaric overlap was to use isotopic ratios, particularly be-tween carbon-13 and nitrogen-15. Although limited literature discuss isotopic composition and attempt to quantify the ratios, variation is particularly high and limited to a few lunar regolith samples. The following were identified as potential approaches to quantify isobaric species, N2 and CO, using our RGA. Threshold Ionization. CO and N2 both have peaks at m/z 28, but only N2 is capable of producing a peak at m/z 7. While a N2 peak at m/z 7 is generally rare, instrument parameters can be optimized in order to maximize the peak intensity. Typically a standard ionization energy of 70 eV is used to monitor a batch process and would produce reliable results for a majority of the reactants or products that we are interested in quantifying. However, to analyze the rare molecular fragment of N2 (N2+ at m/z 7), a different ionization energy may be beneficial. Threshold Ionization Mass Spectrometry (TIMS) will be explored to optimize the N2+ peak at m/z 7 by varying parameters such as ionization energy and pressure. Therefore, a quantitative value at m/z 7 will be used to determine the product gas concentration of N2, which will be subtracted from the total concentration determined at m/z 28 enabling us to approximate the amount of CO. Secondary Detector (infrared gas detector, IR). Another approach to quantitate and differentiate be-tween isobaric components is to leverage alternative modes of detection. Unlike mass spectrometry, which generally uses a separation step prior to analysis (i.e. gas chromatography), IR produces energy that is specifically absorbed depending on the bond and configuration of the molecule. This technique could be leveraged since it is generally only active on non-symmetric molecules, i.e. CO. Utilizing concentrations of CO determined from another detector could help correct concentrations of CO obtained from the QMS. However, the inclusion of another detector adds additional mission requirements, such as power, software changes and avionics updates that add additional cost and schedule requirements.

mass spectrometry↗

In-Situ Reaction Monitoring for Lunar Applications Utilizing a Single Quadrupole Residual Gas Analyzer

With a revived focus to create a permanent presence on the moon and in preparation for future Mars exploration, it is imperative that all resources are utilized to their fullest potential.[1] In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable independent operation of missions while minimally relying on the complex supply chain created between the Earth, moon and Mars. One of the most critical resources that have been identified for ISRU is the creation of liquid oxygen(LO2) for not only breathable air, but also for rocket propellant. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith.[2],[3] Although there are numerous minerals within regolith and various processes to extract O2,this is not the scope of this paper. Since the O2 extraction method can vary, a critical standardized analytical method is needed to verify O2(or oxygenated precursor compounds) for extraction efficiency and purity. Our group utilizes a modified consumer off-the-shelf (COTS), Residual Gas Analyzer (RGA) Single Quadrupole Mass Spectrometer (QMS). Due to the current field mission requirements, the gas analysis module will need to rely only on mass-to-charge ratios (m/z) and peak intensities to differentiate and quantitate targeted gas-phase reactants or products, i.e. carbon monoxide(CO), carbon dioxide (CO2), methane (CH4) and hydrogen (H2). However, due to solar wind implanted volatiles and various other compounds present in lunar regolith, such as nitrogen (N2), helium (He), and deuterium (D2), deconvolution and quantification of isobaric compounds becomes quite difficult. Specifically, the presence of N2 makes quantification of CO, an oxygenated precursor, difficult due to both compounds having a peak at m/z 28.

Mass Spectrometry↗

Lunar and Planetary Science XXXVI, Part 13

Contents include the following: A Fast, Non-Destructive Method for Classifying Ordinary Chondrite Falls Using Density and Magnetic Susceptibility. An Update on Results from the Magnetic Properties Experiments on the Mars Exploration Rovers, Spirit and Opportunity. Measurement Protocols for In Situ Analysis of Organic Compounds at Mars and Comets. Piping Structures on Earth and Possibly Mars: Astrobiological Implications. Uranium and Lead in the Early Planetary Core Formation: New Insights Given by High Pressure and Temperature Experiments. The Mast Cameras and Mars Descent Imager (MARDI) for the 2009 Mars Science Laboratory. MGS MOC: First Views of Mars at Sub-Meter Resolution from Orbit. Analysis of Candor Chasma Interior Layered Deposits from OMEGA/MEX Spectra. Analysis of Valley Networks on Valles Marineris Plateau Using HRSC/MEX Data. Solar Abundance of Elements from Neutron-Capture Cross Sections. Preliminary Evaluation of the Secondary Ion/Accelerator Mass Spectrometer, MegaSIMS. Equilibrium Landforms in the Dry Valleys of Antarctica: Implications for Landscape Evolution and Climate Change on Mars. Continued Study of Ba Isotopic Compositions of Presolar Silicon Carbide Grains from Supernovae. Paleoenviromental Evolution of the Holden-Uzboi Area. Stability of Magnesium Sulfate Minerals in Martian Environments. Tungsten Isotopic Constraints on the Formation and Evolution of Iron Meteorite Parent Bodies. Migration of Dust Particles and Volatiles Delivery to the Inner Planets. On the Sitting of Trapped Noble Gases in Insoluble Organic Matter of Primitive Meteorites. Trapping of Xenon Upon Evaporation-Condensation of Organic Matter Under UV Irradiation: Isotopic Fractionation and Electron Paramagnetic Resonance Analysis. Stability of Water on Mars. A Didactic Activity. Analysis of Coronae in the Parga Chasma Region, Venus. Photometric and Compositional Surface Properties of the Gusev Crater Region, Mars, as Derived from Multi-Angle, Multi-Spectral Investigation of Mars Express HRSC Data. Mapping Compositional Diversity on Mars: Spatial Distribution and Geological Implications. A New Simulation Chamber for Studying Planetary Environments. Folded Structure in Terra Sirenum. Mars. Nitrogen-Noble Gas Static Mass Spectrometry of Genesis Collector Materials. Neon Isotope Heterogeneity in the Terrestrial Mantle: Implication for the Acquisition of Volatile Elements in Terrestrial Planets. The Cosmic Clock, the Cycle of Terrestrial Mass Extinctions.

Source record↗

Sierra Gorda 009: A New Member of the Metal-Rich G Chondrites Grouplet

We investigated the metal-rich chondrite Sierra Gorda (SG) 009, a member of the new G chondrite grouplet (also including NWA 5492, GRO 95551). G chondrites contain 23% metal, very reduced silicates, and rare oxidized mineral phases (Mg-chromite, FeO-rich pyroxene). G chondrites are not related to CH-CB chondrites, based on bulk O, C and N isotopic compositions, mineralogy and geochemistry. G chondrites have no fine-grained matrix or matrix lumps enclosing hydrated material typical for CH-CB chondrites. G chondrites’ average metal compositions are similar to H chondrites. Siderophile and lithophile geochemistry indicate sulfidization and fractionation of the SG 009 metal and silicates, unlike NWA 5492 and GRO 05551. The G chondrites have average O isotopic compositions DELTA 17O >0 ‰ ranging between bulk enstatite (E) and ordinary (O) chondrites. An Al-rich chondrule from SG 009 has DELTA 17O <0 ‰ indicating some heterogeneity in oxygen isotopic composition of G chondrite components. SG 009’s bulk carbon and nitrogen isotopic compositions correspond to E and O chondrites. Neon isotopic composition reflects a mixture of cosmogenic and solar components, and cosmic ray exposure age of SG 009 is typical for O, E, and R chondrites. G chondrites are closely related to O, E, and R chondrites and may represent a unique metal-rich parent asteroid containing primitive and fractionated material from the inner Solar System. Oxidizing and reducing conditions during SG 009 formation may be connected with a chemical micro-environment and possibly could indicate that G chondrites may have formed by a planetesimal collision resulting in the lack of matrix.

chondrite↗

Simulation of Helium-3 Extraction from Lunar Ilmenite

Knowledge of the trapping mechanisms and diffusion characteristics of solar-wind implanted isotopes in the minerals of the lunar regolith will enable the optimization of the processes to extract solar wind gases from regolith particles. Extraction parameters include the temperature and duration of extraction, particle size, and gas yield. Diffusion data will increase the efficiency and profitability of future mining ventures. This data will also assist in optimizing the evaluations of various potential mining sites based on remote sensing data. For instance, if magnesian ilmenite (Mg,Fel.,Ti03) is found to retain He better than stoichiometric ilmenite (FeTi03), remote sensing data for Mg could be considered in addition to Ti and maturity data. The context of the currently discussed work is the mining of helium-3 for potential use as a fuel for fusion energy generation. However, the potential resources deposited by the solar wind include hydrogen (and derived water), helium-4, nitrogen and carbon. Implantation experiments such as those performed for helium isotopes in ilmenite are important for the optimized extraction of these additional resources. These experiments can easily be reproduced for most elements or isotopes of interest.

Kuhlman, K. R.↗

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↗

Carbon and Oxygen Isotope Measurements of Ordinary Chondrite (OC) Meteorites from Antarctica Indicate Distinct Carbonate Species Using a Stepped Acid Extraction Procedure

The purpose of this study is to characterize the stable isotope values of terrestrial, secondary carbonate minerals from five Ordinary Chondrite (OC) meteorites collected in Antarctica. These samples were identified and requested from NASA based upon their size, alteration history, and collection proximity to known Martian meteorites. They are also assumed to be carbonate-free before falling to Earth. This research addresses two questions involving Mars carbonates: 1) characterize terrestrial, secondary carbonate isotope values to apply to Martian meteorites for isolating in-situ carbonates, and 2) increase understanding of carbonates formed in cold and arid environments with Antarctica as an analog for Mars. Two samples from each meteorite, each approximately 0.5 grams, were crushed and dissolved in pure phosphoric acid for 3 sequential reactions: a) R times 0 for 1 hour at 30 degrees Centigrade (fine calcite extraction), b) R times 1 for 18 hours at 30 degrees Centigrade (course calcite extraction), and c) R times 2 for 3 hours at 150 degrees Centigrade (siderite and/or magnesite extraction). CO (sub 2) was distilled by freezing with liquid nitrogen from each sample tube, then separated from organics and sulfides with a TRACE GC using a Restek HayeSep Q 80/100 6 foot 2 millimeter stainless column, and then analyzed on a Thermo MAT 253 Isotope Ratio Mass Spectrometer (IRMS) in Dual Inlet mode. This system was built at NASA/JSC over the past 3 years and proof-tested with known carbonate standards to develop procedures, assess yield, and quantify expected error bands. Two distinct species of carbonates are found: 1) calcite, and 2) non-calcite carbonate (future testing will attempt to differentiate siderite from magnesite). Preliminary results indicate the terrestrial carbonates are formed at approximately sigma (sup 13) C equal to plus 5 per mille, which is consistent with atmospheric CO (sub 2) sigma (sup 13) C equal to minus 7 per mille and fractionation of plus12 per mille based upon polar temperature of -20 degrees Centigrade. The oxygen values fractionate sigma (sup 18) O equal to minus 10-20 per mille lighter between the R times 0 and R times 1 reactions at 30 degrees Centigrade. The carbonate oxygen isotope measurements are consistently heavier than expected with meteoric water and temperatures from Antarctica, perhaps due to secondary carbonate formation during curation in Houston, TX.

Evans, Michael E.↗

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↗

Lunar and Planetary Science XXXV: Achondrite Mishmash

The session "Achondrite Mishmash" included teh following presentations:Constraining the Formation and Evolution of IAB Irons - High Precision; 40Ar/39Ar Ages on Plagioclase Separates from Silicate Inclusions of the Campo Del Cielo Meteorite; Radiogenic 129-Xenon in Silicate Inclusions in the Campo Del Cielo Iron Meteorite; Significance of Iron Isotope Mineral Fractionation in Pallasite and Iron Meteorites; An Experimental Study of Phosphoran Olivine and Its Significance in Main Group Pallasites; Characterization of the Distribution of Siderophile and Highly Siderophile Elements in the Milton and Eagle Station Pallasites; Relationships Between HED and Mesosiderite Meteorites: An Iron Isotope Perspective; Production Rates for Noble-Gas Isotopes in Eucrites; Evidence for Subsolidus Metasomatism in the Eucrite Parent Body; Possible Contact Metamorphism of the Polymict Eucrite Petersburg; Early and Late Stage Metals and Sulfides in Diogenites; Constraints on the Lithological Variation near the Surface of the HED Planetoid from the Petrology of 91 & 92 Series Antarctic Achondrites; Cosmic Ray Exposure Ages, Ar-Ar Ages, and the Origin and History of Eucrites; Trace Elements Abundances Vs Closure Temperature in Orthopyroxenes from Howardites; The First Mesosiderite-like Clast in a Howardite; 39Ar-40Ar Dating of Unusual Eucrite NWA 011: Is it from Vesta?; Trace Element Systematics of Northwest Africa 011: A "Eucritic" Basalt from a Non-Eucrite Parent Body ; 33S Anomaly in Acapulcoites and Lodranites; Magnetic Force Microscopy of Primitive Achondrites; Experimental Constraints on Ureilite Petrogenesis; Reflectance Spectra of Ureilites: Nature of the Mafic Silicate Absorption Features; Nitrogen and Noble Gases in Two Monomict Ureilites Acfer 277 and FRO 90036 from Hot and Cold Deserts; Solar Noble Gases in the Angrite Parent Body - Evidence from Volcanic Volatiles Trapped in D'Orbigny Glass; Trace Element Distribution Between Phases of the D'Orbigny Angrite ; Petrological Study of Six Angrites Including New Type; and Manganese-Chromium Isotope Systematics of Basaltic Achondrite Northwest Africa 011.

Source record↗

Initial analysis of “stone” size Ryugu samples: current status

As a part of the initial analysis of the Ryugu samples, we perform a variety of analyses of millimeter-sized "stones". Our goals are to elucidate the entire formation process of C-type asteroid Ryugu from the viewpoint of petrology and mineralogy ande obtain necessary information by sample analysis, and then simulate the formation of Ryugu based on the evidencef obtained rom sample analysis. Eighteen stones (8 from Room A and 10 from Room C) were received from the ISAS curation facility on June 1, 2021, and brought into a fully nitrogen-displaced glove box at Tohoku University. At the same time, we also received the powder samples from Room A and Room C. To completely block the atmosphere from leaking into the container, all samples were put in the sample transport containers prepared by ISAS, transferred from the main chamber to the glovebox at ISAS, and then all containers were completely sealed in plastic bags with moisture and oxygen absorbers. No moisture or oxygen was detected when the bags were opened in the glove box at Tohoku University, so it was confirmed that there was no exposure to the atmosphere during transport. To date, a number of analyses have been carried out successfully and almost on schedule. The analysis started with the measurement of reflectance spectra, which are sensitive to atmospheric oxidation, hydroxylation, and adsorbed water. The visible, near-infrared, and mid-infrared reflectance spectra were measured while the samples were kept airtight. The spectra of powder samples and stone samples (as aggregates and as single stone) were successfully obtained. A major feature of the stone team's analysis is the use of synchrotron radiation facilities around the world. Since this analysis is non-destructive, stone samples whose reflectance spectra were measured were sent to KEK, SPring-8, ESRF (France), SOLEIL (France), DESY (Germany), and APS (USA). Using these synchrotron radiation facilities, high spatial resolution and sensitivity XRD, STXM, XANES, CT [1], IR-CT, FT-IR [2, 3], XRF, and Mössbauer analyses were performed. Most of the analyses were carried out under air-tight conditions on the stone samples and the particulates separated from the stone samples. These analyses allowed us to determine the three-dimensional distribution of minerals and elements, redox state, density and porosity of the stone samples. Furthermore, as a characteristic analysis of the stone team, light elemental analysis using negative Muon was performed at the MLF facility of J-PARC with an exceptionally long allocation of machine time. This is the only non-destructive method to measure the concentration of light elements in the whole (not the surface) of stone samples. Because the characteristic X-rays produced by muon irradiation are much higher in energy than the fluorescent X-rays produced by X-ray irradiation, there is little effect of self-absorption by the sample, and therefore, the concentration of light elements such as carbon, oxygen, and Na in the entire "stone" sample can be determined. Some stone samples are currently being measured for heat and strength physical properties in order to understand the physical properties of asteroid Ryugu. The data obtained from these measurements are useful for interpreting the remote-sensing data data taken from the surface layer of the asteroid Ryugu [4-7]. It is also important for understanding the behavior of the Ryugu material during impact events. The surfaces of many stone samples were observed by electron microscopy and other techniques, especially on natural “flat” surfaces formed on 5 stomes. As a result, characteristric mineral aggregates formed by the reactions with water and characteiristic impact features were observed on some of the samples. Based on the observations of surfaces and the synchrotron measurements of the whole stones, important objects such as characteristic structures and specific crystal aggregates for understanding the formation history of the asteroid were identified, and these parts were separated from the stone samples using an Xe beam (pFIB) and analyzed by various methods including transmission electron microscopy and synchrotron radiation analysis. Many stone samples, from which important objects have been separated, are embedded in epoxy resin and cut to produce many polished sections. Electron microscopy and spectroscopic measurements of the polished surfaces are being carried out to reveal the detailed mineralogical properties and elemental distribution inside the stone samples. In the fall, machine time for synchrotron radiation will begin, and we plan to analyze single crystals and characteristic objects separated from the stone samples.

Tomoki Nakamura↗