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NASA NTRS2016

Fluids During Diagenesis and Sulfate Vein Formation in Sediments at Gale Crater, Mars

We model the fluids involved in the alteration processes recorded in the Sheep bed Member mudstones of Yellowknife Bay (YKB), Gale crater, Mars, as revealed by the Mars Science Laboratory Curiosity rover investigations. We compare the Gale crater waters with fluids modeled for shergottites, nakhlites, and the ancient meteorite ALH 84001, as well as rocks analyzed by the Mars Exploration rovers, and with terrestrial ground and surface waters. The aqueous solution present during sediment alteration associated with phyllosilicate formation at Gale was high in Na, K, and Si; had low Mg, Fe, and Al concentrations relative to terrestrial ground waters such as the Deccan Traps and other modeled Mars fluids; and had near neutral to alkaline pH. Ca and S species were present in the 10(exp -3) to 10(exp -2) concentration range. A fluid local to Gale crater strata produced the alteration products observed by Curiosity and subsequent evaporation of this ground water- type fluid formed impure sulfate- and silica-rich deposits veins or horizons. In a second, separate stage of alteration, partial dissolution of this sulfate-rich layer in Yellowknife Bay,or beyond, led to the pure sulfate veins observed in YKB. This scenario is analogous to similar processes identified at a terrestrial site in Triassic sediments with gypsum veins of the Mercia Mudstone Group in Watchet Bay, UK.

Gale Crater↗
NASA NTRSDate not supplied

Low-Temperature Formation of Carbonaceous Grains from PAHs

Astronomical observations have detected interstellar carbon in the form of polycyclic aromatic hydrocarbons(PAHs) as well as carbonaceous dust, confirming its presence in both gaseous and solid phases. The goal of this study is to experimentally investigate low-temperature chemical pathways between these two phases in order to better understand the evolution of cosmic carbon. Cosmic dust analogs are produced in the supersonic expansion of an argon jet seeded with aromatic molecules: benzene, naphthalene, anthracene, phenanthrene, and pyrene. These are prototype aromatic molecules of compact and non compact structure, and are used to evaluate the effect of precursor structure on the molecular complexity of the resulting grains. The seeded jet is exposed to an electrical discharge and the carbonaceous grains are collected and probed ex situ via laser desorption mass spectrometry. Mass spectra reveal a rich molecular diversity within the grains, including fragments of the parent molecule but also growth into larger complex organic molecules (COMs). In all experiments, the largest number of products is found in the m/z range 200-250, and C16H10 (attributed to pyrene and/or its isomers) is found to be a dominant product, pointing at the formation of this stable PAH as a preferential route in the growth to larger PAHs. Comparison to mass spectra from the Murchison meteorite reveals a similar dominance of compounds related toC16H10 at m/z = 202. Evidence of the methyl addition-cyclization mechanism in the anthracene experiment is reported. PAH structure is found to impact the dust production yield, as seen by the greater yield for the anthracene compared to the phenanthrene experiment. PAH growth at low temperatures via barrierless routes involving the addition of alkyl- and phenyl-type radicals is suggested as a viable pathway to COMs. These results suggest that PAH growth and dust formation from PAHs are feasible at low temperatures in photon-dominated regions and circumstellar envelopes.

L Gavilan↗
NASA NTRS1991

High-pressure experiments on magnesian eucrite compositions - Constraints on magmatic processes in the eucrite parent body

Melting experiments were conducted on synthetic analogs of two magnesian eucrite clasts from howardites, Kapoeta clast rho and Yamato 7308 pigeonite-eucrite clast 1, at 1 atm and 1-kbar pressure at oxygen fugacities in the range of iron-wuestite (IW) to iron-quartz-fayalite (IQF). The compositions of liquids and coexisting minerals (olivine-low-Ca pyroxene-plagioclase spinel) were used to constrain possible melting and crystallization processes in the parent bodies of eucrite basalts. In agreement with previous studies, the experimental results at 1 atm indicate that the olivine-low-Ca pyroxene-plagioclase-spinel-liquid and olivine-low Ca pyroxene-spinel-liquid boundaries are reaction boundaries involving olivine. At 1 kbar, however, the olivine primary-phase volume shrinks, and the reaction relationship involving olivine disappears for both boundaries. The maximum pressure attained in a Vesta-sized eucrite parent body (EPB) is about 1 kbar, and these results provide important constraints on models relating the howardite-eucrite-diogenite (HED) meteorite association through melting and differentiation processes.

Bartels, K. S.↗
NASA NTRS2004

Acquisition of a Gas Chromatograph/Mass Spectrometer System for Laboratory Study of Prebiotic Organic Geochemical Processes on the Early Earth, Mars, and Meteorites

This was a major equipment grant that provided funds ($72K) for purchase of a benchtop gas chromatograph-mass spectrometer (GC-MS) for use in experimental studies of prebiotic organic compounds. An Agilent model 689015973 GC-MS was purchased and installed in the PI's lab in August of 2003. The instrument is now being used for a variety of research projects. The primary use of the instrument is to analyze and quantify organic products of laboratory experiments conducted by the PI. One example is shown, which shows organic products (predominantly n-alkanes) formed during Fischer-Tropsch-type abiotic synthesis under hydrothermal conditions. The analytical capabilities of the GC- MS allowed identification of the numerous organic products of this as well as other laboratory experiments. A key use of the instrument in this research is that the mass spectrometer capabilities allow use of isotopically labeled reactants to trace the progress of reactions and evaluate background contaminants. collaborative projects with other scientists involved in exobiology & astrobiology research (e.g., Mitch Schulte, NASA Ames; Katrina Edwards, Woods Hole Oceanographic Institution). For instance, an analysis of membrane lipids of an lithoautotrophic iron-oxidizing bacteria being grown on basalt as a source of metabolic energy, a project where the instrument is being used to evaluate possible biomarker compounds from these organisms is shown. These iron oxidizers are thought to be similar to those living within the ocean crust, and are being investigated as possible analog organisms to those on the early Earth or crust of Mars. The instrument has also been used by an outside investigator (graduate student Brandon Canfeld, Arizona State University) for identification and isotopic characterization of experimental products of abiotic organic synthesis experiments he is conducting with Dr. John Holloway. analysis of quality control samples for other NASA-funded projects. For instance, an analysis of residual hydrocarbon contaminants on the internal surface of the shell of an atmospheric sounding rocket is shown. This analysis was used to help determine the source of the contaminating compounds. In the future, the instrument will continue to be used for quality control analysis in clean rooms and instrument construction facilities within the Laboratory for Atmospheric and Space Physics, where the GC-MS is housed.

McCollom, Thomas↗
NASA NTRS1999

Synthesis of Large Molecules in Cometary Ice Analogs: Physical Properties Related to Self-Assembly Processes

The combination of realistic laboratory simulations and infrared observations have revolutionized our understanding of interstellar dust and ice-the main component of comets. Since comets and carbonaceous micrometeorites may have been important sources of volatiles and carbon compounds on the early Earth, their organic composition may be related to the origin of life. Ices on grains in molecular clouds contain a variety of simple molecules. The D/H ratios of the comets Hale-Bopp and Hyakutake are consistent with a primarily interstellar ice mixture. Within the cloud and especially in the presolar nebula through the early solar system, these icy grains would have been photoprocessed by the ultraviolet producing more complex species such as hexamethylenetetramine, polyoxymethylenes, and simple keones. We reported at the 1999 Bioastronomy meeting laboratory simulations studied to identify the types of molecules which could have been generated in pre-cometary ices. Experiments were conducted by forming a realistic interstellar mixed-molecular ice (H2O, CH3OH, NH3 and CO) at approximately 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The gas mixture was typically 100:50:1:1, however when different ratios were used material with similar characteristics was still produced. The residue that remained after warming to room temperature was analyzed by HPLC, and by several mass spectrometric methods. This material contains a rich mixture of complex compounds with mass spectral profiles resembling those found in IDPs and meteorites. Surface tension measurements show that an amphiphilic component is also present. These species do not appear in various controls or in unphotolyzed samples. Residues from the simulations were also dispersed in aqueous media for microscopy. The organic material forms 10-40 gm diameter droplets that fluoresce at 300-450 nm under UV excitation. These droplets have a morphology and internal structure which appear strikingly similar to those produced by extracts of the Murchison meteorite. Together, these results suggest a link between organic material photochemically synthesized on the cold grains in dense, interstellar molecular clouds and compounds that may have contributed to the organic inventory of the primitive Earth. For example, the amphiphilic properties of such compounds permit self-assembly into the membranous boundary structures that required for the first forms of cellular life.

Dworkin, Jason P.↗
NASA NTRS1994

Cr, Mn, and Ca distributions for olivine in angritic systems: Constraints on the origins of Cr-rich and Ca-poor core olivine in angrite LEW87051

Angrite meteorites are a type of basaltic achondrites that are noted for their very old cyrstallization ages (4.55 b.y.) and unusual chemical and mineralogical properties. In spite of great interest, only four angrites have been found. LEW87051 is the smallest one which weighs 0.6 g. It is a porphyritic rock with coarse subhedral to euhedral olivines set in a fine-grained groundmass which clearly represents a crystallized melt. The largest uncertainty about the petrogenesis of LEW87051 is the relationship between the large olivine crystals and the groundmass. Prinz et al. suggests that olivines are xenocrysts, while McKay et al. proposed a fractional cyrstallization model based on experimental studies. However, the crystals have Cr-rich and Ca-poor cores which do not match experimental olivines. Although Jurewicz and McKay tried to explaine the zoning of the rim by diffusion, some features are not explained. There also exists a definite composition boundary of Fe(2+) and MnO between the core and the rim. To clarify the origin of these olivines, we have performed experiments using LEW87051 analogs to measure the effects of oxygen fugacity on distribution coefficients of various elements in an angritic system.

Mikouchi, T.↗
NASA NTRS2007

A New Method for Evaluating the Carbon Isotope Characteristics of Carbonate Formed Under Cryogenic Conditions Analogous to Mars

The two upcoming robotic missions to Mars, Phoenix and MSL, will both have the capability of measuring the carbon isotopic composition of CO2 in the martian atmosphere, as well as possible CO2 trapped in carbonate minerals in the Martian soil. Results from orbital and landed missions now clearly indicate that no large scale deposits of carbonate materials exist at the surface. However, some results from orbital remote sensing have been interpreted to indicate that carbonate minerals are present as fine particles interspersed at low concentrations (approx. 2%) in the martian dust. One likely mechanism for the production of these carbonates is during the freezing of transient water near the surface. Large deposits of near surface ice and photographic evidence for flowing water on the surface suggest that transient melting and refreezing of H2O is an active process on Mars. Any exposure of these fluids to the CO2 rich atmosphere should al-low the production of HCO3- solutions. Carbonates are likely precipitates from these solutions during freezing as extensive CO2 degassing, driven by the fluid s decreasing volume, drives CO2 out. This rapid CO2 degassing increases the pH of the solution and drives carbonate precipitation. It has been shown in previous studies that this rapid CO2 degassing also results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing a large isotope enrichment of C-13 in the precipitated carbonate. This kinetic isotope enrichment may be very common in the current martian environment, and may be a very important factor in understanding the very high deltaC-13 values of carbonates found in the martian meteorites. However, while previous studies have succeeded in generally quantifying the magnitude of this effect, detailed studies of the consistency of this effect, and the freezing rates needed to produce it are needed to understand any carbon isotope analyses from carbonate minerals in the martian soil or dust. This study demonstrates an innovative new method for measuring the isotopic composition of gas evolved from the freezing of carbonate solutions in real time, which allows for a much clearer view of the chemical processes involved. This method now sets the stage for detailed analysis of the chemical and isotopic mechanisms that produce cryogenic carbonates.

Niles, P. B.↗
NASA NTRS2016

Two-Step Resonance-Enhanced Desorption Laser Mass Spectrometry for In Situ Analysis of Organic-Rich Environments

A wide diversity of planetary surfaces in the solar system represent high priority targets for in situ compositional and contextual analysis as part of future missions. The planned mission portfolio will inform our knowledge of the chemistry at play on Mars, icy moons, comets, and primitive asteroids, which can lead to advances in our understanding of the interplay between inorganic and organic building blocks that led to the evolution of habitable environments on Earth and beyond. In many of these environments, the presence of water or aqueously altered mineralogy is an important indicator of habitable environments that are present or may have been present in the past. As a result, the search for complex organic chemistry that may imply the presence of a feedstock, if not an inventory of biosignatures, is naturally aligned with targeted analyses of water-rich surface materials. Here we describe the two-step laser mass spectrometry (L2MS) analytical technique that has seen broad application in the study of organics in meteoritic samples, now demonstrated to be compatible with an in situ investigation with technique improvements to target high priority planetary environments as part of a future scientific payload. An ultraviolet (UV) pulsed laser is used in previous and current embodiments of laser desorption/ionization mass spectrometry (LDMS) to produce ionized species traceable to the mineral and organic composition of a planetary surface sample. L2MS, an advanced technique in laser mass spectrometry, is selective to the aromatic organic fraction of a complex sample, which can provide additional sensitivity and confidence in the detection of specific compound structures. Use of a compact two-step laser mass spectrometer prototype has been previously reported to provide specificity to key aromatic species, such as PAHs, nucleobases, and certain amino acids. Recent improvements in this technique have focused on the interaction between the mineral matrix and the organic analyte. The majority of planetary targets of astrobiological interest are characterized by the presence of water or hydrated mineral phases. Water signatures can indicate a history of available liquid water that may have played an important role in the chemical environment of these planetary surfaces and subsurfaces. The studies we report here investigate the influence of water content on the detectability of organics by L2MS in planetary analog samples.

primitive asteroids↗
NASA NTRS2011

Macro vs. Micro: Relating the Spectral Properties of Vesta and the HED Meteorite

We present the main results obtained comparing the visible-near infrared (VIS-NIR) spectra Vesta s surface with howardites, eucrites, diogenites (HED). HEDs are commonly associated with Vesta s composition based on spectral similarities. Because of such association, much effort is being made to merge the information from HEDs as well as Vestoids - with that from Vesta to characterize the lithologic diversity of the surface of this asteroid and to infer clues regarding its thermal history. However, while the HEDs are a class of meteorites well studied in the laboratory, the only spectral data available for Vesta until now were telescopic observations which are limited in terms of observation conditions, spatial resolution and Signal to Noise Ratio. The Dawn spacecraft, orbiting around Vesta since July 2011, is performing detailed observations of this body and thus improving our knowledge of its properties. Dawn s scientific payload includes an imaging spectrometer, VIR-MS, sensitive to the VIS-NIR spectral range. VIR-MS began acquiring spectra during the approach phase started in May 2011 and will continue its observations through July 2012 when the spacecraft will depart Vesta to travel to Ceres. The VIR-MS spatial resolution depends upon the mission phase (approach, survey, high altitude, low altitude). However, spectra acquired by VIR-MS have already exceeded the spatial resolution of ground-based telescopic observations, with resolution in the approach phase ranging from 2.5 up to 0.8 km/pixel. Moreover, the observations are uniformly distributed in latitude and longitude allowing us to have a global view of Vesta s crust spectral properties. Using the information provided by VIR spectra, we studied the distribution of the spectral heterogeneities on the surface and we used our findings to perform a comparison with HEDs spectra in the VIS-NIR spectral range searching for analogies and/or incompatibilities. In our analysis, we focused on a method to compare the results obtained at microscopic scale on HEDs samples and the one obtained at macroscopic scale on the surface of Vesta. Finally, we discuss our results in the context of vestan thermal history. The intent of this study is to improve our understanding of the connection between Vesta and the HED samples, which is one of the primary Dawn scientific objectives. This work is supported by an Italian Space Agency (ASI) grant and by NASA through the Dawn project and a Dawn at Vesta Participating Scientist grant.

Ammannito, E.↗
NASA NTRS2016

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

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

Zeigler, R. A.↗
NASA NTRS2002

A IAB-Complex Iron Meteorite Containing Low-Ca Clinopyroxene: Northwest Africa 468 and its Relationship to Iodranites and Formation by Impact Melting

Northwest Africa 468 (NWA 468) is a new ungrouped, silicate-rich member of the IAB complex of nonmagmatic iron meteorites. The silicates contain relatively coarse (approximately 300 micron-size) grains of low-Ca clinopyroxene with polysynthetic twinning and inclined extinction. Low-Ca clinopyroxene is indicative of quenching from high temperatures (either from protoenstatite in a few seconds or high-temperature clinoenstatite in a few hours). It seems likely that NWA 468 formed by impact melting followed by rapid cooling to less than or equal to 660 C. After the loss of a metal-sulfide melt from the silicates, sulfide was reintroduced, either from impact-mobilized FeS or as an S2 vapor that combined with metallic Fe to produce FeS. The O-isotopic composition (delta O-17 = -1.39 %) indicates that the precursor material of NWA 468 was a metal-rich (e.g., CR) carbonaceous chondrite. Lodranites are similar in bulk chemical and O-isotopic composition to the silicates in NWA 468; the MAC 88177 lodranite (which also contains low-Ca clinopyroxene) is close in bulk chemical composition. Both NWA 468 and MAC 88177 have relatively low abundances of REE (rare earth elements) and plagiophile elements. Siderophiles in the metal-rich areas of NWA 468 are similar to those in the MAC 88177 whole rock; both samples contain low Ir and relatively high Fe, Cu and Se. Most unweathered lodranites contain approximately 20 - 38 wt. % metallic Fe-Ni. These rocks may have formed in an analogous manner to NWA 468 (i.e., by impact melting of metal-rich carbonaceous-chondrite precursors) but with less separation of metal-rich melts from silicates.

Rubin, Alan E.↗
NASA NTRSDate not supplied

Organic Matter in Itokawa Particles

The first Hayabusa mission returned samples from the near-Earth S-type asteroid 25143 Itokawa to Earth in 2010[1]. Although Itokawa has a lithology related to ordinary chondrites(OCs) that typically have low organic contents, several Itokawa particles were found to contain organic matter (OM)[2-5]. However, there was not an explicit conclusion to the origin of the observed OMin these early studies. We have extended our search for OM into other Itokawa grains. Here, we report extraterrestrial OM (macromolecular carbon and amino acids) observed in six Itokawa particles(including a category1 particle: RA-QD02-0162[#62; also nicknamed “Amazon”],and five category3 carbon-rich particles:RA-QD02-0012[#12], RA-QD02-0078[#78], RB-CV-0029[#29], RB-CV-0080 [#80] and RB-QD04-0052[#52]).All allocated Itokawa samples were initially analysed by spot and point-by-point mapping Raman spectroscopic analysis at the Open University, UK. Amazon was then transferred and mounted into indium on an aluminium stub, which was studied with a NanoSIMS 50L ion microprobe for its H,C,N isotopic compositions. The rest of the samples were mounted in sterile gold foils, and the amino acid contents of their acid hydrolysed hot water extracts were obtained with a liquid chromatography with tandem fluorescence and accurate mass detection at NASA Goddard Space Flight Center, USA. Based on the observation of the Raman parameters(e.g. the peak locations and widths of the defect (D) and graphite (G) bands)[6], a significant variety of carbonaceous materials has been observed in Amazon. The carbonaceous materials include primitive and unaltered OM that shares similarity with the IOM in primitive (CI,CM,CR) carbonaceous chondrites, as well as OM that has been heavily graphitised. The organic structure of the heated material is best represented by nanocrystalline graphite, comparable to that observed for metamorphosed meteorites (e.g., L3–6 Inman, Tieschitz and New Concord,CV3 Allende, and EH4 Indarch),suggesting peak metamorphic temperatures (PMT) of >~600°C. The thermal history recorded in the graphitic OM agrees with PMT estimates for returned Itokawa regolith grains (600–800°C)[7].We have obtained the H,C,N isotopic compositions for the primitive OM in Amazon, which exhibits unambiguously extraterrestrial isotopic signatures (δD = +4868±2288‰; δ13C = −24±5‰; δ15N = +344±20‰), contrasting to the typically negative isotopic values obtained for terrestrial organic matter[8]. The δD and δ13C values of the organic material in Amazon are comparable to OCs, however, the δ15N value is higher than that typically observed for OCs (δ15N = −47 to +36‰), and is similar to that of CRs (δ15N = +153 to +309‰)[9].Our data suggest a genetic link between the primitive organic material observed in Itokawa to CRs and IDPs for they share similar D, 13C and 15N enrichments[10].The high carbon contents of the five category 3 Itokawa particles suggest potentially higher OM abundances, hence we extracted and analysed amino acids in these samples. Although terrestrial contamination was observed primarily as L-protein amino acids, several terrestrially uncommon non-protein amino acids were also observed at low abundances, such as β-aminoisobutyric acid (β-AIB),β-amino-n-butyric acid (β-ABA), and β-alanine. Itokawa amino acid content observed here was dissimilar to thermally altered OCs, but preliminarily analogous to more aqueously altered CR2s.Continued evolution of Itokawa is evident by the in fall of primitive organic material derived from CRs/IDPs, accounting for a complex interplay between the remnant Itokawa silicates with exogenous organics. The results reported here are the first evidence of extraterrestrial OM in asteroid material from a sample-return mission, showcasing a working protocol for analysing samples returned by the Hayabusa2 and OSIRIS-REx missions

Q. H. S. Chan↗
NASA NTRS1995

Cogenetic Rock Fragments from a Lunar Soil: Evidence of a Ferroan Noritic-Anorthosite Pluton on the Moon

The impact that produced North Ray Crater, Apollo 16 landing site, exhumed rocks that include relatively mafic members of the lunar ferroan anorthositic suite. Bulk and mineral compositions indicate that a majority of 2-4 mm lithic fragments from sample 67513, including impact breccias and monomict igneous rocks, are related to a common noritic-anorthosite precursor. Compositions and geochemical trends of these lithic fragments and of related samples collected along the rim of North Ray Crater suggest that these rocks derived from a single igneous body. This body developed as an orthocumulate from a mixture of cumulus plagioclase and mafic intercumulus melt, after the plagioclase had separated from any cogenetic mafic minerals and had become concentrated into a crystal mush (approximately 70 wt% plagioclase, 30 wt% intercumulus melt). We present a model for the crystallization of the igneous system wherein "system" is defined as cumulus plagioclase and intercumulus melt. The initial accumulation of plagioclase is analogous to the formation of thick anorthosites of the terrestrial Stillwater Complex; however, a second stage of formation is indicated, involving migration of the cumulus-plagioclase-intercumulus-melt system to a higher crustal level, analogous to the emplacement of terrestrial massif anorthosites. Compositional variations of the lithic fragments from sample 67513 are consistent with dominantly equilibrium crystallization of intercumulus melt. The highly calcic nature of orthocumulus pyroxene and plagioclase suggests some reaction between the intercumulus melt and cumulus plagioclase, perhaps facilitated by some recrystallization of cumulus plagioclase. Bulk compositions and mineral assemblages of individual rock fragments also require that most of the mafic minerals fortned in close contact with cumulus plagioclase, not as separate layers. The distribution of compositions (and by inference, modes) has a narrow peak at anorthosite and a broader, larger peak at noritic anoilhosite. Characteristics of the samples and their geochemical trends imply an origin in a system that was large relative to the (unknown) size of the impact that produced the breccias of ferroan noritic-anorthosite composition that were excavated later by the formation of North Ray Crater, and they appear to be consistent with an origin of the suite within a perched plagioclase cumulate. If the Moon's crust formed by accumulation of plagioclase in a magma ocean, ferroan noritic anothosite, formed as an orthocumulate, is an alternative to extensive adcumulus formation of ferroan anorthosite (greater than 90 vol% plagiclase). This provides a relatively mafic ferroan anorthositic component (approximately 15 vol% mafics), which is required by mass-balance models of compositions of polymict lunar-crustal materials. The inferred bulk composition of the system of cumulus plagioclase and intercumulus melt is similar to that of ferroan regolith breccia MacAlpine Hills 88104/5, a lunar-highland meteorite, and may represent a common and widespread component of the Moon's early highland crust.

Jolliff, B. L.↗
NASA NTRS1993

Heliocentric zoning of the asteroid belt by aluminum-26 heating

Variations in petrology among meteorites attest to a strong heating event early in solar system history, but the heat source has remained unresolved. Aluminum-26 has been considered the most likely high-energy, short-lived radionuclide (half-life 0.72 million years) since the discovery of its decay product - excess Mg-26 - in Allende CAI's. Furthermore, observation of relict Mg-26 in an achondritic clast and in feldspars within ordinary chondrites (3,4) provided strong evidence for live Al-26 in meteorite parent bodies and not just in refractory nebular condensates. The inferred amount of Al-26 is consistent with constraints on the thermal evolution of both ordinary and carbonaceous chondrite parent objects up to a few hundred kilometers in diameter. Meteorites can constrain the early thermal evolution of their parent body locations, provided that a link can be established between asteroid spectrophotometric signature and meteorite class. Asteroid compositions are heliocentrically distributed: objects thought to have experienced high metamorphic or even melting temperatures are located closer to the sun, whereas apparently unaltered or mildly heated asteroids are located farther away. Heliocentric zoning could be the result of Al-26 heating if the initial amount of the radionuclide incorporated into planetesimals was controlled by accretion time, which in turn varies with semimajor axis. Analytic expressions for planetary accretion may be integrated to given the time, tau, required for a planetesimal to grow to a specified radius: tau varies as a(sup n), where n = 1.5 to 3 depending on the assumptions about variations in the surface density of the planetesimal swarm. Numerical simulations of planetesimal accretion at fixed semimajor axis demonstrate that variations in accretion time among small planetesimals can be strongly nonlinear depending on the initial conditions and model assumptions. The general relationship with semimajor axis remains valid because it depends only on the initial orbit properties and distribution of the planesimal swarm. In order to demonstrate the basic dependence of thermal evolution on semimajor axis, we parameterized accretion time across the asteroid belt according to tau varies as a(sup n) and calculated the subsequent thermal history. Objects at a specified semimajor axis were assumed to have the same accretion time, regardless of size. We set the initial Al-26/Al-27 ratio = 6 x 10(exp -5) and treated n and tau(sub 0) at a(sub 0) = 3 AU as adjustable parameters. The thermal model included temperature-dependent properties of ice and rock (CM chondrite analog) and the thermodynamic effects of phase transitions.

Grimm, R. E.↗
NASA NTRSDate not supplied

Simulating Ordinary Chondrite (Tamdakht) Ablation at the Hypersonic Materials Environmental Test System (HyMETS) Facility.

NASA’s Science Mission Directorate (SMD) created the Asteroid Threat Assessment Project (ATAP) to inform decision-makers of risks associated with Potentially Hazardous Objects (PHOs), which may pose an existential threat to human civilization. ATAP assesses risk, in part, by developing analytical physics-based damage models which draw upon data collected during material property characterization efforts, entry simulations, hazard simulations, and ground-based arc-jet testing. Therefore, a pathfinder test campaign was con-ducted at the Hypersonic Materials Environmental Test System (HyMETS) at the NASA Langley Re-search Center to investigate the ablation mechanisms of an ordinary chondrite (Tamdakht H5) and a terrestrial analog (basalt). The HyMETS facility is a 400 kW constricted arc heater used to screen material performance under simulated aerothermal conditions of hypersonic flow.1 Facility conditions were chosen to simulate Earth entry conditions be-tween the upper-mesosphere and the lower thermo-sphere. The ablation mechanisms of Tamdakht and bas-alt are illustrated with still images collected from high-speed video cameras (fig. 1, Tamdakht). Tamdakht produces a relatively stable melt flow, as evidenced by the perpetual growth of a flange at the sidewall and the exiguous detachment of molten material into the flow. Furthermore, an inspection of high-speed video and chemical analysis of the post-test melt layer suggests that the dominant mode of mass loss for Tamdakht, at these test conditions, is expressed through the vaporization of volatiles (e.g., iron, potassium, sodium, phosphorus, and sulfur). The vaporization rates of Tamdakht are greater than basalt under the most extreme test conditions, which leads to an enhanced blowing layer, in-creased thermal shielding, and reduced recession. The ablation mechanisms of basalt are markedly different from Tamdakht and are attributed to the presence of hydrated minerals dispersed at irregular intervals throughout the silicate matrix. Rapid de-composition of secondary minerals and the subsequent formation of water lead to the ejection of the subsurface and overlying melt layer. Furthermore, the presence of water is suspected of lowering the viscosity of the melt layer resulting in increased mass loss near the edge of the test article where drag forces overcome rheological properties (fig. 1, bas-alt). Finally, the results will be discussed in the broader context of meteorite-based material response model development and the potential impact on the Asteroid Threat Assessment Project (ATAP).

Brody K. Bessire↗
NASA NTRS2010

Oxidation States of Grim Glasses in EET79001 Based on Vanadium Valence

Gas-rich impact-melt (GRIM) glasses in SNC meteorites are very rich in Martian atmospheric noble gases and sulfur suggesting a possible occurrence of regolith-derived secondary mineral assemblages in these samples. Previously, we have studied two GRIM glasses, 506 and 507, from EET79001 Lith A and Lith B, respectively, for elemental abundances and spatial distribution of sulfur using EMPA (WDS) and FE-SEM (EDS) techniques and for sulfur-speciation using K-edge XANES techniques. These elemental and FE-SEM micro-graph data at several locations in the GRIM glasses from Shergotty (DBS), Zagami 994 and EET79001, Lith B showed that FeO and SO3 are positively correlated (SO3 represents a mixture of sulfide and sulfate). FE-SEM (EDS) study revealed that the sulfur-rich pockets in these glasses contain numerous micron-sized iron-sulfide (Fe-S) globules sequestered throughout the volume. However, in some areas (though less frequently), we detected significant Fe-S-O signals suggesting the occurrence of iron sulfate. These GRIM glasses were studied by K-edge microXANES techniques for sulfur speciation in association with iron in sulfur-rich areas. In both samples, we found the sulfur speciation dominated by sulfide with minor oxidized sulfur mixed in with various proportions. The abundance of oxidized sulfur was greater in 506 than in 507. Based on these results, we hypothesize that sulfur initially existed as sulfate in the glass precursor materials and, on shock-impact melting of the precursor materials producing these glasses, the oxidized sulfur was reduced to predominately sulfide. In order to further test this hypothesis, we have used microXANES to measure the valence states of vanadium in GRIM glasses from Lith A and Lith B to complement and compare with previous analogous measurements on Lith C (note: 506 and 507 contain the largest amounts of martian atmospheric gases but the gas-contents in Lith C measured by are unknown). Vanadium is ideal for addressing this re-dox issue because it has multiple valence states and is a well-studied element. Ferrous-dominated iron valences determined by microXANES on the Lith A and Lith B glasses provide little redox sensitivity. Vanadium valence measurements for impact glass in Lith C at three different locations yielded valence values of 3.1, 3.2 and 3.4 with inferred fO2 values of IW-0.7, IW-0.1 and IW+0.7, respectively. This range of oxygen-fugacity values is understandable because the glasses are shock-molten impact glasses which are heterogeneous in nature. Oxygen fugacity values obtained from the analysis of Fe-Ti oxides and Eu partitioning in pyroxenes from EET79001 Lith A and Lith B (host lithologies) were in the range of IW+0.3 to IW+1.9 suggesting that V in the Lith C impact glass was reduced in the impact process. Here, we examine whether the 506 from Lith A and 507 from Lith B GRIM glasses yield similar or different fO2 values from those of Lith C using the vanadium K-edge microXANES technique.

Sutton, S. R.↗
NASA NTRS1997

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗