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Chemical variation and fractionation of KREEP basalt magmas

The fact that 53 Apollo 15 igneous KREEP basalts show a range of 100 Mg/(Mg + Fe) from 73 to 35, and that there are systematic variations in K2O and trace element abundances with the Mg/(Mg + Fe) ratio, suggests that the KREEP basalts are a magma series generated by fractional crystallization processes. Experimental and chemical evidence indicate that this magma series results from low-pressure, possibly subvolcanic, fractional crystallization of a magnesian parental liquid (100 Mg/(Mg + Fe) equal to approximately 72) by removal of low-Ca pyroxene and plagioclase, with eventual production of liquids similar in composition to 15405 quartz-monozodiorites. One soil sample, SAO 465-11, corresponds to the postulated parental liquid, which might have been a direct partial melt of troctolitic materials in the deep lunar crust.

Irving, A. J.↗

Reduction, partial evaporation, and spattering - Possible chemical and physical processes in fluid drop chondrule formation

The major chemical differences between fluid drop chondrules and their probable parent materials may have resulted from the loss of volatiles such as S, H2O, Fe, and volatile siderophile elements by partial evaporation during the chondrule-forming process. Vertical access solar furnace experiments in vacuum and hydrogen have demonstrated such chemical fractionation trends using standard rock samples. The formation of immiscible iron droplets and spherules by in situ reduction of iron from silicate melt and the subsequent evaporation of the iron have been observed directly. During the time that the main sample bead is molten, many small spatter spherules are thrown off the main bead, thereby producing many additional chondrule-like melt spherules that cool rapidly and generate a population of spherules with size frequency distribution characteristics that closely approximate some populations of fluid drop chondrules in chondrites. It is possible that spatter-produced fluid drop chondrules dominate the meteoritic fluid drop chondrule populations. Such meteoritic chondrule populations should be chemically related by various relative amounts of iron and other volatile loss by vapor fractionation.

King, E. A.↗

Trace elements in ocean ridge basalt glasses - Implications for fractionations during mantle evolution and petrogenesis

Seven documented and fresh glassy selvages from ocean floor basalt pillows were analyzed for trace elements including Ag, Au, Bi, Br, Ni, Pd, and Zn using radiochemical activation analysis. Glasses from DSDP leg 24, site 238 in the Indian Ocean have a trace element pattern which reflects secondary processes at a shallow depth. Chemical fractionations in petrogenesis of tholeiitic basalts indicate that (Ir, Os), Au, Pd, Ni, and Re are strongly fractionated in igneous processes; the unfractionated chondritic mantle pattern thus imposes constraints on mantle evolution models. Finally, the limited Rb/Cs fractionation in oceanic tholeiites reflects the low abundance of volatiles and hydrous silicates in normal ocean ridge basalts.

Hertogen, J.↗

A Simple Mechanism for Fractionating Oxygen Isotopes in the Solar Nebula

Lightning in the Solar Nebula is caused by the tribo-electric charging of dust grains carried by massive turbulent flows and driven by the accretion energy in the disk: it has long been one agent assumed responsible for the formation of chondrules. The degree to which charge separation can occur is dependent upon a number of factors, including the concentration of radioactive sources and the total level of ionization in the nebula, and these factors determine the maximum energy likely to be released by a single bolt. While chondrule formation requires a massive discharge, even a small lightning bolt can vaporize grains in the ionized discharge channel. Experimental studies have shown that silica, iron silicate and iron oxide grains formed from a high voltage discharge in hydrogen rich gas containing some oxygen produces solids that are enriched in O-17 and O-18 relative to the composition of the starting gas. Vaporization of silicates produces SiO, metal and free oxygen atoms in each discharge and these species will immediately begin to recondense from the hot plasma. Freshly condensed grains are incrementally enriched in heavy oxygen while the gas is enriched in O-16. Repeated evaporation and condensation of silicates in continuously occurring lightning discharges will monotonically increase the fractionation of oxygen isotopes between the O-17 and O-18 rich dust and the O-16 rich gas. The first mass independently fractionated refractory oxide particles were produced in the lab following the condensation of a flowing gas mixture containing variable amounts of hydrogen, silane, pentacarbonyl iron and oxygen that passed through a high voltage discharge powered by a Tesla coil. While the exact chemical pathway is still uncertain, the most probable reaction mechanisms involve oxidation of the growing refractory clusters by O3, OH or O atoms. This model has some interesting consequences for chemical processes in the early solar nebula. Chemical fractionation of recondensed dust evaporated via lightning discharges should be strongly time dependent. At earlier times, the accretion rate is maximal, thus driving strong turbulence, energetic grain-grain collisions, tribo-electric charging and charge separation, leading to frequent, powerful lightning discharges. As the accretion rate diminishes, turbulence decreases and lightning discharges will become both less powerful and less frequent, thus decreasing the rate of dust-gas fractionation. The most rapid increase in the formation of O-16 poor dust will occur early in nebular history. Generation of fractionated dust should be distributed throughout the inner disk. Once condensed, grain dispersal would average out any significant isotopic anomalies within the inner disk.

Nuth, Joseph A., III↗

Oxygen isotopic constraints on the composition of the moon

The mean oxygen isotopic composition of 5 Apollo 17 soils, one Apollo 17 breccia and one Apollo 12 soil is delta O-18 = 5.63 + or - .05 and delta O-17 = 3.8 + or - .2%. These values are within several tenths of a part permil of the composition of a large fraction of the lunar interior. High-temperature condensate aggregates from Allende and other C2 and C3 chondrites are vastly enriched in O-16 compared to this composition. The moon cannot be a mixture of ordinary chondrites and Allende inclusions, nor can it be derived from such a mixture by chemical fractionation processes. The moon's isotopic composition is consistent with a mixture of high- and low-temperature condensates but the refractory fraction would have to be free of the O-16-rich component so prevalent in the meteoritic aggregates, a fact which makes such models less attractive than they once seemed.

Grossman, L.↗

Observations of Nitrogen Fractionation in Prestellar Cores: Nitriles Tracing Interstellar Chemistry

Primitive materials provide important clues on the processes that occurred during the formation and early evolution of the Solar System. Space-based and ground-based observations of cometary comae show that comets appear to contain a mixture of the products of both interstellar and nebular chemistries. Significant 15-nitrogen enrichments have been measured in CN and HCN towards a number of comets and may suggest an origin of interstellar chemical fractionation. Additionally, large N-15 enhancements are found in meteorites and has also led to to the view that the N-15 traces material formed in the interstellar medium (ISM), although multiple sources cannot be excluded. Here, we show the results of observations of the nitrogen and carbon fractionation in prestellar cores for various N-bearing species to decipher the origin of primitive material isotopic enrichments.

Milam, S. N.↗

Chemical Evolution of Presolar Organics in Astromaterials

Sub-micron, hollow organic globules reported from several carbonaceous chondrites, interplanetary dust particles, and comet Wild-2 samples returned by NASA?s Stardust mission are enriched in N-15/N-14 and D/H compared with terrestrial materials and the parent materials [1-4]. These anomalies are ascribed to the preservation of presolar cold molecular cloud material from where H, C, and N isotopic constraints point to chemical fractionation near 10 K [5]. An origin well beyond the planet forming region and their survival in meteorites suggests submicrometer organic globules were once prevalent throughout the solar nebula. The survival of the membrane structures indicates primitive meteorites and cometary dust particles would have delivered these organic precursors to the early Earth as well as other planets and satellites. The physical, chemical, and isotopic properties of the organic globules varies to its meteorite types and its lithologies. For example, organic globules in the Tagish Lake meteorite are always embedded in fined grained (poorly crystallized) saponite, and hardly encapsulated in coarse grained serpentine, even though saponite and serpentine are both main components of phyllosilicate matrix of the Tagish Lake meteorite. The organic globules are commonly observed in the carbonate-poor lithology but not in the carbonate-rich one. In Tagish Lake, isolated single globules are common, but in the Bells (CM2) meteorite, globules are mostly aggregated. We will review the evolutions of the organic globules from its birth to alteration in the parent bodies in terms of its own physical and chemical properties as well as its associated minerals.

Nakamura-Messenger, K.↗

Vitrification darkening of rock powders - Implications for optical properties of the lunar surface

Laboratory experiments show that albedoes as low as those on the moon can be produced by vacuum vitrification and associated chemical fractionation of ordinary terrestrial basaltic material. Vitrification is established as an unequivocal process that can account for the low albedo and apparent local darkening with age of the lunar surface. The spectral reflectance curves of glass powders are significantly different than those of the parent rock mineralogy; thus, the presence of ubiquitous glass in lunar surface material complicates compositional determinations by interpretation of spectral reflectance curves. Vitrification of rocks on the moon may highly modify the chemical composition of the resulting glass; thus, glass fragments found in lunar fines cannot be assumed to represent bulk parent rock material. Progressive impact vitrification of lunar surface material throughout the moon's history may have led to a fine-grain, opaque, refractory-rich material we call 'ultimate glass.' This unidentified and, at this point, hypothetical component may exist in dark regolith material; if found, it may be a useful indicator of regolith maturity.

Nash, D. B.↗

Chondritic Meteorites: Nebular and Parent-Body Formation Process

Chondritic meteorites are the products of condensation, agglomeration and accretion of material in the solar nebula; these objects are the best sources of information regarding processes occurring during the early history of the solar system. We obtain large amounts of high-quality chemical and petrographic data and use them to infer chemical fractionation processes that occurred in the solar nebula and on meteorite parent bodies during thermal metamorphism, shock metamorphism and aqueous alteration. We compare diverse groups of chondrites and model their different properties in terms of processes that differed at different nebular locations or on different parent-bodies. In order to expand our set of geochemically important elements (particularly Si, C, P and S) and to distinguish the different oxidation states of Fe, Greg Kallemeyn spent three months (1 Sept. - 30 Nov. 1995) at the Smithsonian Institution to learn Eugene Jarosewich's wet chemical techniques. Key specimens from the recently established CK, CR and R chondrite groups were analyzed.

Rubin, Alan E.↗

Earth and Venus - A comparative study

Two hypotheses attempting to account for the anomalously low intrinsic density of Venus in terms of chemical fractionation processes are entertained. Both assume similar relative abundances of major elements (Fe, Si, Mg, Al, Ca) in Venus and earth. One model assigns a larger proportion of the total Fe present in Venus to the planetary mantle, implying a core/mantle ratio lower than that of earth, and more extensive oxidation. The alternate hypothesis projects a Venus more reduced than the earth, with a mantle devoid of oxidized Fe; the difference in intrinsic densities is then attributed to the earth accreting at a lower temperature consonant with its greater distance from the sun. Large amounts of sulfur are presumed accreted on the earth but not on Venus, in the second model. Available chemical evidence tends to favor the first model.

Ringwood, A. E.↗

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.↗

Creation and Distribution of CAIs in the Protoplanetary Nebula

CaAl rich refractory mineral inclusions (CAIs) found at 1 - 10% mass fraction in primitive chondrites appear to be several million years older than the dominant (chondrule) components in the same parent bodies. A prevalent concern is that it is difficult to retain CAIs for this long against gas-drag-induced radial drift into the sun. We assess a hot inner (turbulent) nebula context for CAI formation, using analytical models of nebula evolution and particle diffusion. We show that outward radial diffusion in a weakly turbulent nebula can prevent significant numbers of CAI-size particles from being lost into the sun for times of 1 - 3 x 10(exp 6) years. To match the CAI abundances quantitatively, we advocate an enhancement of the inner hot nebula in silicate-forming material, due to rapid inward migration of very primitive, silicate and carbon rich, meter-sized objects. 'Combustion' of the carbon into CO would make the CAI formation environment more reduced than solar, as certain observations imply. Abundant CO might also play a role in mass-independent chemical fractionation of oxygen isotopes as seen in CAIs and associated primitive, high-temperature condensates.

Cuzzi, J. N.↗

Cosmochemistry

Cosmochemistry, discussing interdisciplinary nature, goals, nuclear roots, information sources, key concepts involving elements age and origin, nuclear species abundances, chemical fractionation, etc

Arnold, J. R.↗

Vanadium and copper in chondrites

V and Cu emission spectrographic analyses in chondrite types, noting distribution patterns between groups based on meteorite chemical fractionation mechanisms

Bingham, E.↗

Mineralogy, petrology and chemistry of lunar rock 12039.

Rock 12039 belongs to the olivine-depleted group of magmatic rocks characterized by normative and modal SiO2, absence or very low abundance of olivine, and high FeO/(FeO + MgO), Ti/Cr, and CaO/MgO ratios. Clinopyroxenes in this rock show a complex, essentially continuous, compositional zonation from augite cores through ferroaugite to ferrohedenbergite with an abrupt discontinuity at the pyroxferroite contact and, thus, are different from pyroxene in most other Apollo 12 rocks. Two grains contain thin subcalcic pigeonite zones. Texture, presence of very fine (less than 1 micron) exsolution lamallae, and pyroxene zoning indicate a relatively rapid cooling history and pronounced in situ chemical fractionation.

Bunch, T. E.↗

Are stellar surface heavy-element abundances systematically enhanced

Stellar surface heavy-element abundances may be substantially higher than interior abundances if there is appreciable accretion of chemically fractionated matter after Hayashi-phase convection has terminated. The plausibility of appreciable accretion is discussed, and some possible observational consequences of enhanced surface heavy-element abundances are investigated. These consequences include a reduced solar neutrino flux, systematic variations in surface abundance along the main sequence and along the giant branch, and relatively low heavy-element abundances among planetary nebulas and white dwarfs and in the interstellar medium. There is marginal observational evidence in support of the hypothesis of enhanced stellar surface heavy-element abundances.

Joss, P. C.↗

Melting behavior and phase relations of lunar samples

Cooling rate studies of 12002 were conducted and the results interpreted in terms of the crystallization history of this rock and certain other picritic Apollo 12 samples. Calculations of liquid densities and viscosities during crystallization, crystal settling velocities, and heat loss by the parent rock body are discussed, as are petrographic studies of other Apollo 12 samples. The process of magmatic differentiation that must have accompanied the early melting and chemical fractionation of the moon's outer layers was investigated. The source of regions of both high- and low-titanium mare basalts were also studied.

Hays, J. F.↗