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At least 19 records

Melt Redistribution in Dynamic Systems: Applications to Core Formation

Samples of olivine + Fe-S were fabricated by hot-pressing a mechanical mixture of the two phases. Olivine powders with a starting grain size of approx. 10 microns were prepared by crushing crystals of San Carlos olivine followed by pulverization in a fluid energy mill. Iron sulfide powder with a particle size of approx. 5 microns was prepared from a 2:1 mixture of reagent grade iron sulfide (FeS) plus iron. Rods 20 mm in length by 10 mm in diameter were cold-pressed into iron capsules with a uniaxial stress of approx. 200 MPa. These rods were then hot-pressed at 1523 K and 300 MPa for 4 h to obtain a starting material with <2% porosity. Samples for shear experiments were cut perpendicular to the long axis of these rods. The discs were shaped into ellipses approx. 6 mm by approx. 8 mm with a thickness ranging from 0.6 to 1.0 mm. An iron foil strain marker was inserted into a cut made along the minor axis. The sample was placed between two thoriated tungsten pistons cut at 45 deg to the long axis and then placed into an iron sleeve capped by alumina discs. The sample was then sheared in a gas pressure-medium apparatus at a temperature of 1523 K and a confining pressure of 300 MPa.

Hustoft, J. W.↗

Trace Element Partitioning in the Presence of Sulfur Under Reduced Conditions

Oxygen fugacity (fO2) plays an important role in thephysicochemical properties of that system because fO2 has asubstantial impact on the partitioning behavior between andsolubility of elements in various phases. The reduced nature ofMercury and the aubrite parent bodies (APB) have raised manyquestions regarding the geochemical behavior of typicallylithophile, heat-producing, and rare-earth elements (REE) inmagmas at low fO2. In fact, interpretations of magmaticprocesses on reduced rocky bodies are difficult at presentbecause of the small number of experimental studies relevant tothe extremely low fO2 and high sulfur content of Mercury andthe APB, and our only natural analogs are the highly reducedenstatite chondrites and aubrites [e.g., 1]. Preliminaryobservations suggest that major and minor elements exhibitdifferent geochemical affinities in highly reduced, S-richsystems compared to terrestrial rocks. The partitioning behavior of major, minor, and traceelements between silicate melt, sulfide melt, and metal underhighly reduced conditions will be determined in a suite of super-liquidus experiments at a range of pressures (1 bar to 4 GPa) atNASA Johnson Space Center (JSC). Based on previous studies,heat-producing elements U and Th become more chalcophile,while K becomes less chalcophile, with more reducingconditions [2]. The nominally lithophile elements Mg and Cabecoming more chalcophile and appear as minor elements in(Fe,Mg,Ca)-S with more reducing conditions [3]. Additionally, itappears that nominally siderophile elements become moresiderophile and chalcophile with more reducing conditions,although the partitioning behavior into Mg- and Ca-bearingsulfide melts, rather than FeS, is less understood. Current workis focused on investigating elements for which we currently haveMESSENGER data as well as a host of geochemically relevanttrace elements such as REE.

Brendan A Anzures↗

Acid-Sulfate-Weathering Activity in Shergottite Sites on Mars Recorded in Grim Glasses

Based on mass spectrometric studies of sulfur species in Shergotty and EET79001, [1] and [2] showed that sulfates and sulfides occur in different proportions in shergottites. Sulfur speciation studies in gas-rich impact-melt (GRIM) glasses in EET79001 by the XANES method [3] showed that S K-XANES spectra in GRIM glasses from Lith A indicate that S is associated with Ca and Al presumably as sulfides/sulfates whereas the XANES spectra of amorphous sulfide globules in GRIM glasses from Lith B indicate that S is associated with Fe as FeS. In these amorphous iron sulfide globules, [4] found no Ni using FE-SEM and suggested that the globules resulting from immiscible sulfide melt may not be related to the igneous iron sulfides having approximately 1-3% Ni. Furthermore, in the amorphous iron sulfides from 507 GRIM glass, [5] determined delta(sup 34)S values ranging from +3.5%o to -3.1%o using Nano-SIMS. These values plot between the delta(sup 34)S value of +5.25%o determined in the sulfate fraction in Shergotty [6] at one extreme and the value of -1.7%o obtained for igneous sulfides in EET79001 and Shergotty [7] at the other. These results suggest that the amorphous Fe-S globules likely originated by shock reduction of secondary iron sulfate phases occurring in the regolith precursor materials during impact [7]. Sulfates in the regolith materials near the basaltic shergottite sites on Mars owe their origin to surficial acid-sulfate interactions. We examine the nature of these reactions by studying the composition of the end products in altered regolith materials. For the parent material composition, we use that of the host shergottite material in which the impact glasses are situated.

Rao, M. N.↗

Sulfide Stability of Planetary Basalts

The isotopic system, 187Re 187Os, can be used to determine the role of crust and mantle in magma genesis. In order to apply the system to natural samples, we must understand variations in Re/Os concentrations. It is thought that low [Os] and [Re] in basalts can be attributed to sulfide (FeS) saturation, as Re behaves incompatibly to high degrees of evolution until sulfide saturation occurs [1]. Previous work has shown that lunar basalts are sulfide under-saturated, and mid-ocean ridge, ocean-island and Martian (shergottites) basalts are saturated [2,3]. However, little is known about arc basalts. In this study, basaltic rocks were analyzed across the Trans-Mexican Volcanic Belt.

Caiazza, C. M.↗

Density of the mantle of Mars

The range of zero pressure densities of the Martian mantle which are compatible with the mean density and moment of inertia factor of Mars has been explored by: (1) considering the full range of plausible core compositions and densities, and (2) investigating the sensitivity of computed mantle densities to uncertainties in the input parameters. Ni, Fe, Fe3O4, and FeS cores were considered; corresponding zero pressure mantle densities range from 3.47 to 3.41 g/cu cm. Uncertainty in the mantle density of about 0.04 g/cu cm for the Fe core model and about 0.05 g/cu cm for the FeS core model results from uncertainties in the input parameters. The zero pressure density of the Martian mantle is estimated to be 3.44 plus or minus 0.06 g/cu cm.

Goettel, K. A.↗

Lunar evolution - How well do we know it now.

The currently known astronomical, chemical, and magnetic data are not uniquely indicative of an extensively and globally molten moon. It is argued that an accretional layering occurred in the moon, but at temperatures below solidus. The excess mass in the near side of the moon compatible with a 2-km displacement in the center of mass relative to the center of figure and the moment of inertia data is considered to be due to Fe-FeS liquid formation and inhomogeneous segregation. These Fe-FeS bodies, termed 'fescons,' are shown to be capable of accounting for the presently available magnetization data, by acting as small regenerative dynamos with a time-stability less than that of the terrestrial equivalent. The chemical characteristics of the highly differentiated materials, are considered to be due to small-scale localized melting caused by collisional events, from sources in which accessory phases play a significant role. Mare basalts are considered to be melts in the overlying material produced at a later time by K-40 radioactivity in the fescons. Some consequences of the present hypothesis are suggested. It is concluded that these and other characteristics of the lunar materials are reconcilable with a 'cold' moon, such as discussed by Urey over the past two decades.

Murthy, V. R.↗

Possible roles of manganese redox chemistry in the sulfur cycle

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

Nealson, K. H.↗

Opaque Minerals in the Matrix of the Bishunpur (LL3.1) Chondrite: Constraints on the Chondrule Formation Environment

The chemistry and mineralogy of a group of opaque mineral assemblages in the matrix of the Bishunpur LL3.1 ordinary chondrite provide insight into the nebular environment in which they formed. The assemblages consist of a kamacite (Fe,Ni) core that is rimmed by troilite (FeS) and fayalite (Fe2Si04). Accessory phases in the rims include silica (Si02), chromite (FeCr204), whitlockite (Ca3(P04)2), maricite (FeNaP04), magnetite (Fe304), and tetrataenite (FeNi). We suggest that the metal melted in and equilibrated with an igneous chondrule under high- temperature, reducing conditions. In this environment the molten alloys incorporated varied amounts of Si, Ni, P, Cr, and Co, depending on the oxygen fugacity and temperature of the melt. Some of the metal was subsequently expelled from the chondrule interiors into the surrounding nebular gas. As the temperature dropped, the alloy solidified and volatile elements corroded the metal. The main reaction products were troilite and fayalite. Thermodynamic equilibrium calculations are used to constrain the conditions under which these two phases can form simultaneously in the solar nebula. Kinetic factors are used to place a lower limit on the formation temperature. We determine that the metal corroded between 1173 and 1261 K at a total pressure in the range of 1025.0 to 1024.1 bars and a dust/gas ratio of 302 to 355 x relative to solar composition. These conditions are consistent with our model that the metal corroded in a dust- rich region of the solar nebula that was cooling after a chondrule formation event.

Lauretta, D. S.↗

Examining Metasomatism in Low fO2 Environments: Exploring Sulfidation Reactions in Various Planetary Bodies

Hydrothermal systems are common on Earth in a variety of tectonic environments and at different temperature and pressure conditions. These systems are commonly dominated by H2O, and they are responsible for element transport and the production of ore deposits. Unlike the Earth (fO2~FMQ), many other planetary bodies (e.g., Moon and asteroids) have fO2 environments that are more reduced (IW+/-2), and H2O is not the important solvent responsible for element transport. One example of a texture that could result from element transport and metasomatism, which appears to occur on numerous planetary bodies, is sulfide-silicate intergrowths. These subsolidus assemblages are interpreted to form as a result of sulfidation reactions from a S-rich fluid phase. The composition of fluids may vary within and among parent bodies and could be sourced from magmatic (e.g. Moon) or impact processes (e.g. HED meteorites and Moon). For example, it has been previously demonstrated on the Moon that the interaction of olivine with a hydrogen- and sulfur-bearing vapor phase altered primary mineral assemblages, producing sulfides (e.g. troilite) and orthopyroxene. Formation of these types of "sulfidation" assemblages can be illustrated with the following reaction: Fe2SiO4(ol) + 1/2 S(2 system) = FeS(troi)+ FeSiO3(opx) + 1/2 O2 system. The products of this reaction, as seen in lunar rocks, is a vermicular or "worm-like" texture of intergrown orthopyroxene and troilite. Regardless of the provenance of the S-bearing fluid, the minerals in these various planetary environments reacted in the same manner to produce orthopyroxene and troilite. Although similar textures have been identified in a variety of parent bodies, a comparative study on the compositions and the origins of these sulfide-silicate assemblages has yet to be undertaken. The intent of this study is to examine and compare sulfide-silicate intergrowths from various planetary bodies to explore their petrogenesis and examine the nature of low fO2 (IW+/-2) element migration and sulfidation reactions.

Srinivasan, P.↗

Origin, Bulk Chemical Composition and Physical Structure of the Galilean Satellites of Jupiter: A Post-Galileo Analysis

The origin of Jupiter and the Galilean satellite system is examined in the light of the new data that has been obtained by the NASA Galileo Project. In particular, special attention is given to a theory of satellite origin which was put forward at the start of the Galileo Mission and on the basis of which several predictions have now been proven successful. These predictions concern the chemical composition of Jupiter's atmosphere and the physical structure of the satellites. According to the proposed theory of satellite origin, each of the Galilean satellites formed by chemical condensation and gravitational accumulation of solid grains within a concentric family of orbiting gas rings. These rings were cast off equatorially by the rotating proto-Jovian cloud (PJC which contracted gravitationally to form Jupiter some 4 1/2 billion years ago. The PJC formed from the gas and grains left over from the gas ring that had been shed at Jupiter's orbit by the contracting proto-solar cloud (PSC Supersonic turbulent convection provides the means for shedding discrete gas rings. The temperatures T (sub n) of the system of gas rings shed by the PSC and PJC vary with their respective mean orbital radii R (sub n) (n = 0, 1,2,...) according as T (sub n) proportional to R (sub n) (exp -0.9). If the planet Mercury condenses at 1640 K, so accounting for the high density of that planet via a process of chemical fractionation between iron and silicates, then T (sub n) at Jupiter's orbit is 158 K. Only 35% of the water vapour condenses out. Thus fractionation between rock and ice, together with an enhancement in the abundance of solids relative to gas which takes place through gravitational sedimentation of solids onto the mean orbit of the gas ring, ensures nearly equal proportions of rock and ice in each of Ganymede and Callisto. Io and Europa condense above the H20 ice point and consist solely of hydrated rock (h-rock). The Ganymedan condensate consists of h-rock and H20 ice. For Callisto, NH3 ice makes up -5% of the condensate mass next to h-rock (approximately 50%) and H2O ice (approximately 45%). Detailed thermal and structural models for each of Europa, Ganymede and Callisto are constructed on the basis of the above initial bulk chemical compositions. For Europa (E), a predicted 2-zone model consisting of a dehydrated rock core of mass 0.912 M (sub E) and a 150 km thick frozen mantle of salty H2O yields a moment-of-inertia coefficient which matches the Galileo Orbiter gravity measurement. For Ganymede (G), a 3-zone model possessing an inner core of solid FeS and mass approximately 0.116 M (sub G), and an outer H2O ice mantle of mass approximately 0.502 M (sub G) is needed to explain the gravity data. Ganymede's native magnetic field was formed by thermoremanent magnetization of Fe3O4. A new Callisto (C) model is proposed consisting of a core of mass 0.826 M (sub C) containing a uniform mixture of h-rock (60% by mass) and H2O and NH3 ices, and capped by a mantle of pure ice. This model may have the capacity to yield a thin layer of liquid NH3 (raised dot) 2H2O at the core boundary, in line with Galileo's discovery of an induced magnetic field.

Prentice, A. J. R.↗

Aqueous Alteration Mineralogy in CM Carbonaceous Chondrites

Iron-nickel sulfides are found in most or all solar system environments, and are probably the only minerals found in all extraterrestrial materials on hand. Despite the ubiquity, they have not received the attention they deserve. The most common Fe-Ni sulfides in chondrites are troilite (FeS), pyrrhotite (Fe1- XS) and pentlandite (Fe,Ni)9S8. Troilite is believed to have resulted from sulfidation of metal (Fe-Ni) grains in an H2Scontaining environment. Pyrrhotite is produced when friable troilite grains, which are exfoliated from the metal nucleus, are submitted to continued sulfidation [1]. Some asteroids are known to have experienced aqueous alteration, forming products including new generations of sulfides (pyrrhotite and pentlandite). Pentlandite in particular is known to form during such alteration [1]. However, experimental work by Lauretta has indicated that pentlandite may also have been formed during the initial sulfidation process [2], due to the faster diffusion rate of nickel into the forming sulfide, as compared to iron. Finally, there is considerable evidence [1,3&4] for a family of phases intermediate between pyrrhotite and pentlandite, following the trend of the high temperature monosulfide solid solution [5], something not encountered in terrestrial rocks.

Chokai, J.↗

Affordable Development and Demonstration of a Small NTR Engine and Stage: How Small is Big Enough?

The Nuclear Thermal Rocket (NTR) derives its energy from fission of uranium-235 atoms contained within fuel elements that comprise the engine's reactor core. It generates high thrust and has a specific impulse potential of approximately 900 seconds - a 100% increase over today's best chemical rockets. The Nuclear Thermal Propulsion (NTP) project, funded by NASA's AES program, includes five key task activities: (1) Recapture, demonstration, and validation of heritage graphite composite (GC) fuel (selected as the "Lead Fuel" option); (2) Engine Conceptual Design; (3) Operating Requirements Definition; (4) Identification of Affordable Options for Ground Testing; and (5) Formulation of an Affordable Development Strategy. During FY'14, a preliminary DDT&E plan and schedule for NTP development was outlined by GRC, DOE and industry that involved significant system-level demonstration projects that included GTD tests at the NNSS, followed by a FTD mission. To reduce cost for the GTD tests and FTD mission, small NTR engines, in either the 7.5 or 16.5 klbf thrust class, were considered. Both engine options used GC fuel and a "common" fuel element (FE) design. The small approximately 7.5 klbf "criticality-limited" engine produces approximately 157 megawatts of thermal power (MWt) and its core is configured with parallel rows of hexagonal-shaped FEs and tie tubes (TTs) with a FE to TT ratio of approximately 1:1. The larger approximately 16.5 klbf Small Nuclear Rocket Engine (SNRE), developed by LANL at the end of the Rover program, produces approximately 367 MWt and has a FE to TT ratio of approximately 2:1. Although both engines use a common 35 inch (approximately 89 cm) long FE, the SNRE's larger diameter core contains approximately 300 more FEs needed to produce an additional 210 MWt of power. To reduce the cost of the FTD mission, a simple "1-burn" lunar flyby mission was considered to reduce the LH2 propellant loading, the stage size and complexity. Use of existing and flight proven liquid rocket and stage hardware (e.g., from the RL10B-2 engine and Delta Cryogenic Second Stage) was also maximized to further aid affordability. This paper examines the pros and cons of using these two small engine options, including their potential to support future human exploration missions to the Moon, near Earth asteroids, and Mars, and recommends a preferred size. It also provides a preliminary assessment of the key activities, development options, and schedule required to affordably build, ground test and fly a small NTR engine and stage within a 10-year timeframe.

Spacecraft design↗

Affordable Development and Demonstration of a Small Nuclear Thermal Rocket (NTR) Engine and Stage: How Small Is Big Enough?

The Nuclear Thermal Rocket (NTR) derives its energy from fission of uranium-235 atoms contained within fuel elements that comprise the engine's reactor core. It generates high thrust and has a specific impulse potential of approximately 900 specific impulse - a 100 percent increase over today's best chemical rockets. The Nuclear Thermal Propulsion (NTP) project, funded by NASA's Advanced Exploration Systems (AES) program, includes five key task activities: (1) Recapture, demonstration, and validation of heritage graphite composite (GC) fuel (selected as the Lead Fuel option); (2) Engine Conceptual Design; (3) Operating Requirements Definition; (4) Identification of Affordable Options for Ground Testing; and (5) Formulation of an Affordable Development Strategy. During fiscal year (FY) 2014, a preliminary Design Development Test and Evaluation (DDT&E) plan and schedule for NTP development was outlined by the NASA Glenn Research Center (GRC), Department of Energy (DOE) and industry that involved significant system-level demonstration projects that included Ground Technology Demonstration (GTD) tests at the Nevada National Security Site (NNSS), followed by a Flight Technology Demonstration (FTD) mission. To reduce cost for the GTD tests and FTD mission, small NTR engines, in either the 7.5 or 16.5 kilopound-force thrust class, were considered. Both engine options used GC fuel and a common fuel element (FE) design. The small approximately 7.5 kilopound-force criticality-limited engine produces approximately157 thermal megawatts and its core is configured with parallel rows of hexagonal-shaped FEs and tie tubes (TTs) with a FE to TT ratio of approximately 1:1. The larger approximately 16.5 kilopound-force Small Nuclear Rocket Engine (SNRE), developed by Los Alamos National Laboratory (LANL) at the end of the Rover program, produces approximately 367 thermal megawatts and has a FE to TT ratio of approximately 2:1. Although both engines use a common 35-inch (approximately 89-centimeters) -long FE, the SNRE's larger diameter core contains approximately 300 more FEs needed to produce an additional 210 thermal megawatts of power. To reduce the cost of the FTD mission, a simple one-burn lunar flyby mission was considered to reduce the liquid hydrogen (LH2) propellant loading, the stage size and complexity. Use of existing and flight proven liquid rocket and stage hardware (e.g., from the RL10B-2 engine and Delta Cryogenic Second Stage) was also maximized to further aid affordability. This paper examines the pros and cons of using these two small engine options, including their potential to support future human exploration missions to the Moon, near Earth asteroids (NEA), and Mars, and recommends a preferred size. It also provides a preliminary assessment of the key activities, development options, and schedule required to affordably build, ground test and fly a small NTR engine and stage within a 10-year timeframe.

Spacecraft design↗

Day 640 infrared line and continuum measurements: Dust formation in SN 1987A

We have measured day 640-645 line and continuum spectra of (Ni II) 6.6 micrometer (Ne II) 12.8 micrometer (line emission was not detected), and (Fe II) 17.9 and 26.0 micrometer from SN 1987A. The high velocity feature at v(sub HVF) approximately 3900 km/sec found in both of our day 410 (Fe II) spectra is again detected in the day 640 (Ni II) spectrum, although the signal-to-noise of the day 640 (Fe II) spectra is insufficient to show this feature. The continuum fluxes provide clear evidence for the formation of dust between day 410 and day 640 and are best fitted by a graybody spectrum with a temperature of 342 +/- 17 K at day 640 and a surface area corresponding to a minimum dust velocity v(sub dust) = 1910 +/- 170 km/sec. Optically thin dust emissivity laws proportional to lambda(exp -1) or lambda(exp -2) are inconsistent with the data. Either the dust grains are large (radius a much greater than 4 micrometer and radiate like individual blackbodies, or else they are located in clumps optically thick in the 6-26 micrometer range. The (Ni II) 6.6 micrometer line flux yields a minimum Ni(+) mass of 5.8 +/- 1.6 x 10(exp -4) solar mass and a Ni/Fe abundance ratio of 0.06 +/- 0.02, equal to the solar value. The ratio of the two (Fe II) line profiles implies a gas temperature 2600 +/- 700 K, a drop of 1800 +/- 800 K from our day 410 measurement. The (Fe II) 26.0 micrometer line flux has decreased by a factor of 2 and the day 640 (Ni II) profile is blueshifted by -440 +/- 270 km/sec, relative to observations before day 500. We show that the decrease in the (Fe II) flux and the blueshift are not produced by a decrease in electron scattering optical depth, electron density, or temperature, but rather are probably due to obscuration by the same dust which produces the infrared continuum. This supports the interpretation that the dust spectrum is produced by optically thick clumps. We discuss possible explanations for the discrepancy between the mass of Fe(+) detected and the total iron mass required to power the light curve. The decrease in the (Fe II) fluxes relative to the decrease required to account for the blueshifts of optical lines from non-iron-group elements and the similarity between v(sub dust) and the Ni(+) expansion velocity imply a spatial association between the dust clumps and the iron-group elements. In addition, the larger blueshift observed for the near and far-infrared, heavy metal transitions relative to non-iron-group lines suggests that the iron-group elements are somewhat segregated from lighter elements such as the Mg(sup 0) and O(sup 0) responsible for shorter wavelength lines. We speculate that FeS may be an important constituent of the dust. A comparison of our line profiles with radiative transfer models shows that while power law and exponential density distributions yield reasonable fits to the data, polytrope distributions provided significantly worse agreement. The best fits require a substantial fraction of the iron to be undetectable, and are consistent with maximum expansion velocities of v(sub max) approximately 3000 km/sec.

Colgan, Sean W. J.↗

Advanced Optical Measurement Techniques

This research analyzes four areas: (1) Improved Techniques for Optical Measurement; (2) KC-135 Low Gravity Simulation Flight Preparation; (3) In-Line Holographic Microscopy; and (4) Holographic Optical Schlieren System (HOSS). The first task provides for laboratory breadboarding of advanced optical measurement techniques which appear promising for use in Material Processing System (MPS) flight experiments. A laboratory schlieren system has been constructed which simulates a similar optical system on the Fluids Experiment System (FES) which is to be flown on Spacelab 3. The second task allows improved optical systems and breadboards to be built for experiments and hardware tests on the KC-135 aircraft. A new, more stable Mach-Zehnder interferometer has been developed and components have been ordered. The third task is concerned with improvements on the optical system being used to study immiscible fluids. Experiments studying the dynamics of nucleation and the separation of immiscible fluids have been conducted. The four task involves building breadboard reconstruction systems for holograms taken in the HOSS. The HOSS is an early prototype of the Fluids Experiments System (FES) which is scheduled to fly on Spacelab 3.

Owen, R. B.↗

The origin of KREEP

KREEP is a lunar material having very high concentrations of incompatible elements; its name is an acronym for the incompatibles K, rare-earth elements (REE), and P. Although a few pristine (endogenously igneous) KREEPy samples were returned from the Apollo 15 and 17 sites, most KREEPy samples are polymict breccias. Most models of KREEP petrogenesis have been based on partial melting of a variety of sources. Such models fail to explain the veritable absence of variations in incompatible element patterns over the sampled portion of the moon. We have defined a KREEP component based on the average composition of Apollo 14 breccias having extremely high concentrations of incompatible elements. Normalization of accurate incompatible data for KREEPy samples from the Apollo 12, 14, 15, 16, and 17 sites to this component virtually always shows no resolvable fractionation (e.g., <10% variation in the La/Lu ratio), whereas partial melting models typically produce larger fractionations (±20–25% in La/Lu) from a factor of 2 difference in degree of partial melting. Required is a single major source that could provide KREEP to widely separated locations on the nearside of the moon. The anorthositic crust of the moon is commonly attributed to the flotation of plagioclase on a deep, moon-wide magma ocean. Fractional crystallization of this magma ocean would have produced large enrichments of incompatibles in a residual liquid. No other plausible major source of incompatibles has been proposed. We borrow the German prefix ur—meaning primeval and designate this residual liquid ‘urKREEP.’ We propose that all KREEPy rocks originated by dilution of urKREEP with crustal or mantle materials during assimilation, or zone-refining (pristine samples), or impact-induced brecciation (breccias and melt rocks). The formation of urKREEP cannot be dated precisely. Correction of breccia Rb-Sr model ages for Rb loss or gain during the early intense bombardments yields ages that cluster in the range 4.4–4.5 Gy. This implies that crystallization of the magma ocean was essentially complete at this time and is in general agreement with U-Pb evidence indicating crustal formation at 4.4 Gy. Assuming that the moon had the composition of an H-group chondrite depleted in Fe-Ni and FeS and that half the incompatibles fractionated into materials other than urKREEP, the thickness of a moon-wide urKREEP layer was <2 km. Thorium concentrations determined by gamma ray spectroscopy indicate that about 4% of the incompatibles in an H chondritic moon are now in the outermost kilometer.

Paul H. Warren↗

Precision Oxygen Isotope Measurements of Two C-Rich Hydrated Interplanetary Dust Particles

Introduction: Chondritic-smooth IDPs (Interplanetary Dust Particles) are low porosity objects whose mineralogy is dominated by aqueous alteration products such as Mg-rich phyllosilicates (smectite and serpentine group) and Mg-Fe carbonate minerals. Their hydrated mineralogy combined with low atmospheric entry velocities have been used to infer an origin largely from asteroidal sources. Spectroscopic studies show that the types and abundance of organic matter in CS IDPs is similar to that in CP IDPs. Although CS IDPs show broad similarities to primitive carbonaceous chondrites, only a few particles have been directly linked to specific meteorite groups such as CM and CI chondrites based on the presence of diagnostic minerals. Many CS IDPs however, have carbon contents that greatly exceed that of known meteorite groups suggesting that they either may derive from comets or represent samples of more primitive parent bodies than do meteorites. It is now recognized that many large, dark primitive asteroids in the outer main belt, as well as some trans-Neptunian objects, show spectroscopic evidence for aqueous alteration products on their surfaces. Some CS IDPs exhibit large bulk D enrichments similar to those observed in the cometary CP IDPs. While hydrated minerals in comets have not been unambiguously identified to date, the presence of the smectite group mineral nontronite has been inferred from infrared spectra obtained from the ejecta from comet 9P/Tempel 1 during the Deep Impact mission. Recent observations of low temperature sulfide minerals in Stardust mission samples suggest that limited aqueous activity occurred on comet Wild-2. All of these observations, taken together, suggest that the high-carbon hydrated IDPs are abundant and important samples of primitive solar system objects not represented in meteorite collections. Oxygen isotopic compositions of chondrites reflect mixing between a 16O-rich reservoir and a 17O,18O-rich reservoir produced via mass-independent fractionation. The composition of the 16O-rich reservoir is well constrained but material representing the 17O,18O-rich end-member is rare. Self-shielding models predict that cometary water, presumed to represent this reservoir, should be enriched in 17O and 18O by greater than 200 per mille. The high-carbon hydrated IDPs may be among the best materials available to search for preserved "cometary" H2O signatures. In order to better understand the origin and evolution of these particles, we have obtained 10 hydrated interplanetary dust particles for coordinated mineralogical, isotopic and organic analyses. We have previously reported the results of mineralogical and O isotopic measurements of two hydrated IDPs; here we present results of O isotopic measurements of three additional IDPs. Samples and Methods: Three interplanetary dust particles (L2079C35, L2083D46 and L2083E46) were embedded in S and partially ultramicrotomed into approximately 70 nanometer sections for analysis via transmission electron microscopy (TEM). The remainders of the unsliced particles were removed from S and pressed into high purity Au foil that was cleaned with HF acid and annealed at 800 degrees Centigrade. The pressed IDPs were analyzed via electron microprobe analysis (EPMA) for quantitative bulk chemical analysis. After EPMA analysis, the IDPs were subjected to precision O isotope analysis with the UCLA Cameca IMS-1270 ion probe. A 20 kiloelectronvolt, 0.5 nanoangstrom Cs+ primary beam of approximately 15 micrometers diameter was used for each measurement. Small particles of San Carlos olivine and Burma spinel were pressed into the Au foil for use as standards to correct for instrumental mass fractionation. The detection system was configured for multicollection, with 16O measured on a Faraday cup, and 17O and 18O measured on electron multipliers (EMs). Individual analyses consisted of 15 cycles of 10 seconds per cycle. Additionally, two microtome thin sections were measured for H isotopic compositions with the JSC NanoSIMS 50L ion probe. An 8 picoangstrom, 16 kiloelectronvolt Cs plus primary beam was used. Measurements consisted of H, C, 12C, 16O, and 18O collected with EMs in multicollection. Terrestrial biotite and kerogen were used for isotopic standards. A significant challenge in O isotope measurement of hydrated minerals is the interference from 16OH at mass 17O. We ensured that the 17O and 16OH peaks were fully resolved by using a mass resolution of greater than 7000 and by careful analyses of San Carlos olivine, Burma spinel and chlorite hydrated mineral standards. The hydride was further suppressed with a cold finger attached to an LN2 dewar to trap volatiles in the sample chamber. All sputtered ions were counted (i.e. presputtering was not used); after applying background, yield and deadtime corrections, we performed a change-point analysis on our data via R in order to determine when the sample reached sputtering equilibrium; data points collected prior to the change point were excluded. Change-point analysis was also used to determine whether the IDP had completely sputtered. Results: Mineralogy. IDPs C35 and E46 exhibited hydrated mineralogies, Fe-Ni sulfide grains, nanoglobules and occasional enstatite grains distributed throughout a fine-grained Mg-Fe saponite matrix. C35 also contained breunnerite (Mg,Fe)CO3; solar flare tracks were observed in enstatite, indicating minimal atmospheric entry heating. The mineralogy of D46 is dominated by a large FeS grain with a minor component of adhering silicate material. D46 was strongly heated during atmorpheric entry as evidenced by a well-developed magnetite rim. EPMA analyses show that both C35 and E46 have high carbon contents of 20 weight percentage (approximately 6X CI). D46 contains approximately 6 wt.weight percentage C. A significant amount of the carbon is present as carbon nanoglobules. Results: Hydrogen isotopes: Although the bulk delta D values of both sections of L2079C35 were within error of SMOW (minus 33 plus or minus 19 per mille, 1 plus or minus 14 per mille 1 sigma), several delta D-rich hotspots were also identified, reaching 2000 per mille. As shown in Fig. 1, these hotspots are clearly associated with discrete carbonaceous inclusions that are akin to nanoglobules found in many meteorites and other IDPs. Oxygen Isotopes. Results of the oxygen isotope measurements are shown in Figure 1. The oxygen isotope composition for L2079C35 was delta 18O equals plus11.6 plus or minus 1.9per mille, delta 17O equals plus 7.9 plus or minus 1.9per mille (2 standard errors). The oxygen isotope composition for L2083D46 was delta 18O equals minus 8.1 plus or minus 1.9 per mille, delta 17O equals minus 6.4 plus or minus 3.1 per mille (2 standard errors). The oxygen isotope composition for L2083E46 was delta 18O equals plus 12.0 plus or minus 1.9 per mille, delta 17O equals plus 9.2 plus or minus 2.0 per mille (2 standard errors). Discussion: Despite mineralogical similarities to highly aqueously altered carbonaceous chondrites, the hydrated IDPs we analyzed have oxygen isotopic compositions that are distinct from matrix materials in the CI, CM, and CR chondrites. The IDPs plot along the Young-Russell line, with delta 17O values for C35 and E46 suggestive of interaction with a 16O-poor reservoir. However, we have thus far not observed evidence of extreme 16O-poor reservoirs expected from self-shielding models and observed in Acfer 094 simplectite. The high carbon contents of the IDPs also set them apart from known meteoritic samples. The lack of atmospheric entry heating effects are consistent with low encounter velocities and suggest either an asteroidal source, or a low inclination, low eccentricity cometary origin. Conclusions: The unusual oxygen isotopic compositions, high carbon contents, and the abundance of Drich nanoglobules, together, suggest that the high-carbon, hydrated IDPs are derived from a primitive source that is not yet represented in meteorite collections.

Snead, C. J.↗

Search for Fluid Inclusions in a Carbonaceous Chondrite Using a New X-Ray Micro-Tomography Technique Combined with FIB Sampling

Early solar system aqueous fluids are preserved in some H chondrites as aqueous fluid inclusions in halite (e.g., [1]). Although potential fluid inclusions are also expected in carbonaceous chondrites [2], they have not been surely confirmed. In order to search for these fluid inclusions, we have developped a new X-ray micro-tomography technique combined with FIB sampling and applied this techniqu to a carbanaceous chondrite. Experimental: A polished thin section of Sutter's Mill meteorite (CM) was observed with an optical microscope and FE-SEM (JEOL 7001F) for chosing mineral grains of carbonates (mainly calcite) and sulfides (FeS and ZnS) 20-50 microns in typical size, which may have aqueous fluid inclusions. Then, a "house" similar to a cube with a roof (20-30 microns in size) is sampled from the mineral grain by using FIB (FEI Quanta 200 3DS). Then, the house was atached to a thin W-needle by FIB and imaged by a SR-based imaging microtomography system with a Fresnel zone plate at beamline BL47XU, SPring-8, Japan. One sample was imaged at two X-ray energies, 7 and 8 keV, to identify mineral phases (dual-enegy microtomography: [3]). The size of voxel (pixel in 3D) was 50-80 nm, which gave the effective spatial resolution of approx. 200 nm. A terrestrial quartz sample with an aqueous fluid inclusion with a bubble was also examined as a test sample by the same method. Results and discussion: A fluid inclusion of 5-8 microns in quartz was clearly identified in a CT image. A bubble of approx. 4 microns was also identified as refraction contrast although the X-ray absorption difference between fluid and bubble is small. Volumes of the fluid and bubble were obtained from the 3D CT images. Fourteen grains of calcite, two grains of iron sulfide and one grain of (Zn,Fe)S were examined. Ten calcite, one iron sulfide and one (Zn,Fe)S grains have inclusions >1 micron in size (the maximum: approx. 5 microns). The shapes are spherical or irregular. Tiny inclusions (<1 micron) are also present in all the grains examined. These results show that mineral grains have more inclusions than expected from 2D observations. The X-ray absorption of the inclusions shows that they are not solid inclusions. No bubbles were observed inside, indicating that we cannot determine whether they are really aqueous fluids or merely voids. One calcite grain has an inclusion approx. 2 microns in size, which seems to have a bubble and a tiny solid daughter crystal inside (three-phase inclusion). As we know the exact 3D position of the inclusion, we will anlyze the inclusion by SIMS after freezing the sample as has been done for a halite sample [3]. The present technique is useful for finding small inclusions not only in carbonaceous chondrites but also for terrestrial materials.

Tsuchiyama, A.↗