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Geochemistry and cosmochemistry of fullerenes 3: Reaction of C60 and C70 with ozone

C60 and C70 dissolved in toluene were treated with O2 gas containing 2.6 volume percent ozone and with O3-free oxygen. No reaction products were detected for 0.1 mole of O2 passed through the solution, but destruction of C60 was clearly detectable for a dose of 10(exp -6) moles of O3. C70 was destroyed more slowly than C60. Among the substances remaining in solution, we identified C60O, C70O, C60O2, C60O3, and C60O4. C60 crystals exposed to O3 at room temperature became less soluble in toluene in a matter of days, but oxides were apparently not formed.

Heymann, D.↗

Magnesian anorthosites from the western highlands of the Moon: Isotope geochemistry and petrogenesis

Breccias from the Apollo 14 landing site have provided a wealth of information on the genesis of the lunar highlands. Various pristine rock-types have been discovered in relative abundance including rare ferroan anorthosites and alkali-suite and magnesian-suite rocks. Mineral-chemical and radiogenic isotopic data are reported here for a newly discovered Mg-suite anorthosite from Apollo 14, sample 14303,347. Meyer et al. reported U-Pb zircon analyses of Mg-suite highlands rocks from the western limb of the Moon. We have compiled these ages and generated a weighted average age of 4211 = 6 Ma; some 200 Ma younger than ferroan anorthosites. Utilizing this age for Mg-anorthosite 14303,347, our data results in an initial epsilon(sub Nd) value of -1.0 and initial Sr-87/Sr-86 of 0.69915. Based on trace-element, isotopic, and mineral-chemical data, the western highlands Mg-suite is interpreted to be crustal precipitates of a picritic magma, which assimilated KREEPy trapped liquid from upper-mantle cumulates during its transport to the crust.

Snyder, Gregory A.↗

Petrology and geochemistry of VLT glasses from double drive tube 79001/2

As a part of more general studies of soils from Apollo 17 double drive tube 79001/2, glasses from the 79001/2 core are being analyzed by a multidisciplinary approach including SEM/EDS and INAA. Efforts are currently focused on VLT (very low-Ti; TiO2 less than 1 wt%) mare glasses, which are common in 79001/2 and have also been found in other Apollo 17 soils. One of the primary objectives is to determine whether any or all of the Apollo 17 VLT glasses represent pristine volcanic compositions. In addition, the range of VLT glass compositions and possible relationships between the glasses and VLT lithic samples, for which some geochemical data have been obtained previously, is being defined.

Wentworth, Susan J.↗

The Lunar Scout Program: An international program to survey the Moon from orbit for geochemistry, mineralogy, imagery, geodesy, and gravity

The Lunar Scout Program was one of a series of attempts by NASA to develop and fly an orbiting mission to the moon to collect geochemical, geological, and gravity data. Predecessors included the Lunar Observer, the Lunar Geochemical Orbiter, and the Lunar Polar Orbiter - missions studied under the auspices of the Office of Space Science. The Lunar Scout Program, however, was an initiative of the Office of Exploration. It was begun in late 1991 and was transferred to the Office of Space Science after the Office of Exploration was disbanded in 1993. Most of the work was done by a small group of civil servants at the Johnson Space Center; other groups also responsible for mission planning included personnel from the Charles Stark Draper Laboratories, the Lawrence Livermore National Laboratory, Boeing, and Martin Marietta. The Lunar Scout Program failed to achieve new start funding in FY 93 and FY 94 as a result of budget downturns, the de-emphasis of the Space Exploration Initiative, and the fact that lunar science did not rate as high a priority as other planned planetary missions, and was cancelled. The work done on the Lunar Scout Program and other lunar orbiter studies, however, represents assets that will be useful in developing new approaches to lunar orbit science.

Morrison, Donald A.↗

Archean geochemistry of formaldehyde and cyanide and the oligomerization of cyanohydrin

The sources and speciation of reduced carbon and nitrogen inferred for the early Archean are reviewed in terms of current observations and models, and known chemical reactions. Within this framework hydrogen cyanide and cyanide ion in significant concentration would have been eliminated by reaction with excess formaldehyde to form cyanohydrin (glycolonitrile), and with ferrous ion to formferrocyanide. Natural reactions of these molecules would under such conditions deserve special consideration in modeling of primordial organochemical processes. As a step in this direction, transformation reactions have been investigated involving glycolonitrile in the presence of water. We find that glycolonitrile, formed from formaldehyde and hydrogen cyanide or cyanide ion, spontaneously cyclodimerizes to 4-amino-2-hydroxymethyloxazole. The crystalline dimer is the major product at low temperatue (approximately 0 C); the yield diminishes with increasing temperature at the expense of polymerization and hydrolysis products. Hydrolysis of glycolamide and of oxazole yields a number of simpler organic molecules, including ammonia and glycolamide. The spontaneous polymerization of glycolonitrile and its dimer gives rise to soluble, cationic oligomers of as yet unknown structure, and, unless arrested, to a viscous liquid, insoluble in water. A loss of cyanide by reaction with formaldehyde, inferred for the early terrestrial hydrosphere and cryosphere would present a dilemma for hypotheses invoking cyanide and related compounds as concentrated reactants capable of forming biomolecular precursor species. Attempts to escape from its horns may take advantage of the efficient concentration and separation of cyanide as solid ferriferrocyanide, and most directly of reactions of glycolonitrile and its derivatives.

Arrhenius, T.↗

Trace Element Geochemistry of Martian Iddingsite in the Lafayette Meteorite

The Lafayette meteorite contains abundant iddingsite, a fine-grained intergrowth of smectite clay, ferrihydrite, and ionic salt minerals. Both the meteorite and iddingsite formed on Mars. Samples of iddingsite, olivine, and augite pyroxene were extracted from Lafayette and analyzed for trace elements by instrumental neutron activation. Our results are comparable to independent analyses by electron and ion microbeam methods. Abundances of most elements in the iddingsite do not covary significantly. The iddingsite is extremely rich in Hg, which is probably terrestrial contamination. For the elements Si, Al, Fe, Mn, Ni, Co, and Zn, the composition of the iddingsite is close to a mixture of approximately 50% Lafayette olivine + approximately 40% Lafayette siliceous glass + approximately 1O% water. Concordant behavior among these elements is not compatible with element fractionations between smectite and water, but the hydrous nature and petrographic setting of the iddingsite clearly suggest an aqueous origin. These inferences are both consistent, however, with deposition of the iddingsite originally as a silicate gel, which then crystallized (neoformed) nearly isochemically. The iddingsite contains significantly more magnesium than implied by the model, which may suggest that the altering solutions were rich in Mg(2+).

Treiman, Allan H.↗

Constraints on the Formation of the Terrestrial Planets from Experimental Geochemistry

The abundances of V, Cr, and Mn in the mantles of the Earth and Moon are very similar, and are distinct from all other sampled solar system bodies. This similarity has led to the suggestion that there is a genetic relationship between the Earth and Moon, more specifically, that the Moon was derived from the mantle of the Earth after formation of the core. This proposal is at odds with the Giant Impact paradigm of lunar origin and our current understanding of the formation of the terrestrial planets. During the award period, some of the necessary experimental procedures were developed. Specifically, an assembly design has been developed to permit heating of metal by insulating it from highly conducting diamond. A Nd-YAG laser was assembled, aligned and tested. The technique for preparation of the run products for electron microprobe analysis was developed, and an alternative approach has been identified. A scheme to carry out polybaric experiments on a single charge was developed. The experiments carried out did not lead to conclusive results, and the arguments advanced by Drake et aL (1989) and Drake (1990) remain the best summary of the status of the problem.

Drake, Michael J.↗

Isotope Geochemistry of Possible Terrestrial Analogue for Martian Meteorite ALH84001

We have studied the microdomain oxygen and carbon isotopic compositions by SIMS of complex carbonate rosettes from spinel therzolite xenoliths, hosted by nepheline basanite, from the island of Spitsbergen (Norway). The Quaternary volcanic rocks containing the xenoliths erupted into a high Arctic environment and through relatively thick continental crust containing carbonate rocks. We have attempted to constrain the sources of the carbonates in these rocks by combined O-18/O-16 and C-13/C-12 ratio measurements in 25 micron diameter spots of the carbonate and compare them to previous work based primarily on trace-element distributions. The origin of these carbonates can be interpreted in terms of either contamination by carbonate country rock during ascent of the xenoliths in the host basalt, or more probably by hydrothermal processes after emplacement. The isotopic composition of these carbonates from a combined delta.18O(sub SMOW) and delta.13C(sub PDB) standpoint precludes a primary origin of these minerals from the mantle. Here a description is given of the analysis procedure, standardization of the carbonates, major element compositions of the carbonates measured by electron microprobe, and their correlated C and O isotope compositions as measured by ion microprobe. Since these carbonate rosettes may represent a terrestrial analogue to the carbonate "globules" found in the martian meteorite ALH84001 interpretations for the origin of the features found in the Spitsbergen may be of interest in constraining the origin of these carbonate minerals on Mars.

Mojzsis, Stephen J.↗

Geochemistry and Organic Chemistry on the Surface of Titan

Titan's atmosphere produces a wealth of organic products from methane and nitrogen. These products, deposited on the surface in liquid and solid form, may interact with surface ices and energy sources to produce compounds of exobiological interest. Additional information is contained in the original extended abstract.

Lunine, J. I.↗

Petrology and Geochemistry of Paired Brachinites EET 99402 and EET 99407

Brachinites are considered a type of primitive achondrite, as are the acapulcoite-lodranite and winonaite-IAB iron silicate groups. However, this study shows that brachinites had a very different origin than the latter two groups. Additional information is contained in the original extended abstract.

Mittlefehldt, David W.↗

Making Intercontinental Burning Influences Quantitative: Lessons on Transport and Geochemistry From the 3-D Simulation of CO in PEM-T A and TRACE-A

We report on two aspects of the simulation of global transport of plumes originating from subtropical biomass fires. We use of meteorological assimilation (MM5) at 2-degree resolution with a Grail cloud parameterization and a Blackadar-based planetary boundary layer parameterization. Ames's GRACES model provides emissions, transport, and an appropriate level of simulated chemical transformation. We have worked with passive-tracer CO or linear chemistry. This is appropriate since we find major work to be done in evaluating CO source strengths and transport mechanisms before chemical integrations could be meaningful. First, we present mechanisms by which CO and other pollutants are introduced into the free troposphere, and are then transported with hate dilution from approx. 0 to approx. 180 degrees longitude. One principal conduit for these plumes is the vernal subtropical jet; however the plumes appear at various altitudes and latitudes as they influenced by frontal motions and (most likely) radiative processes. A common, repeated pattern of transport has pollutant plumes arriving in the distant Pacific Ocean from Africa and South America at 25 degrees south and 14 km altitude. Following this, there is then a general appearance of pollution at extending down to 5 kin at more equatorial (10 S) and polar latitudes (to 45 S). Second, we evaluate the quantitative success of our simulation. (Such success requires efforts considerably beyond trajectory analyses, and is necessary for our community to claim an understanding of the effects of biomass burning on global atmospheric chemistry and the planet's trend in oxidizing capacity.) We find that we simulate most pollution episodes sampled by Glenn Sachse's CO instrument and the Blake hydrocarbon analyses during PENT A. We will present our current ideas on why our general levels appear satisfactory when the observations are within 20 ppb of background levels, but substantially miss the variability associated with the most intense biomass burning plumes. As time allows, we will speculate on the origins of a class of plumes that appear in the mid-troposphere, but are missing from our simulations.

Chatfield, Robert↗

Remote Sensing and Geochemistry of Planetary Surfaces

We have been examining the resources required to support potential life on Mars, as a way of understanding the possible abundance and distribution of life. Based on our understanding of the Earth, the necessary requirements for the environment to allow it to support life are (i) presence of liquid water, (ii) access to the biogenic elements (C, H, O, N, S, P, Ca, Fe, etc.), and (iii) a source of energy to drive chemical disequilibrium, such that the reactions back toward equilibrium can release energy to support metabolism. While even demonstrating that all of these requirements have been met would not mean that life would necessarily exist on Mars, they provide the context in which a search for life or analysis of geochemical characteristics that might be indicative of life might be carried out. Our previous work has focused on the first and third of these characteristics determine where and when liquid water might have been present, and understanding the availability of chemical energy from weathering reactions that might ID support life. In the analysis supported by this grant (covering the time period 2/15/01-2/14/02), we have been examining the second requirement--the abundance of the necessary biogenic elements, their geographical distribution on Mars and the information on the possible vertical distribution within the crust, and their geochemical accessibility and mobility within the crust and at the surface. In particular, our work during the performance period has emphasized phosphorous.

Jakosky, Bruce M.↗

Geochemistry of Martian Meteorites and the Petrologic Evolution of Mars

Mafic igneous rocks serve as probes of the interiors of their parent bodies - the compositions of the magmas contain an imprint of the source region composition and mineralogy, the melting and crystallization processes, and mixing and assimilation. Although complicated by their multifarious history, it is possible to constrain the petrologic evolution of an igneous province through compositional study of the rocks. Incompatible trace elements provide one means of doing this. I will use incompatible element ratios of martian meteorites to constrain the early petrologic evolution of Mars. Incompatible elements are strongly partitioned into the melt phase during igneous processes. The degree of incompatibility will differ depending on the mineral phases in equilibrium with the melt. Most martian meteorites contain some cumulus grains, but nevertheless, incompatible element ratios of bulk meteorites will be close to those of their parent magmas. ALH 84001 is an exception, and it will not be discussed. The martian meteorites will be considered in two groups; a 1.3 Ga group composed of the clinopyroxenites and dunite, and a younger group composed of all others.

Mittlefehldt, D. W.↗

Geochemistry of Martian Meteorites and the Petrologic Evolution of Mars

Mafic igneous rocks serve as probes of the interiors of their parent bodies - the compositions of the magmas contain an imprint of the source region composition and mineralogy, the melting and crystallization processes, and mixing and assimilation. Although complicated by their multifarious history, it is possible to constrain the petrologic evolution of an igneous province through compositional study of the rocks. Incompatible trace elements provide one means of doing this. I will use incompatible element ratios of martian meteorites to constrain the early petrologic evolution of Mars. Incompatible elements are strongly partitioned into the melt phase during igneous processes. The degree of incompatibility will differ depending on the mineral phases in equilibrium with the melt. Most martian meteorites contain some cumulus grains, but nevertheless, incompatible element ratios of bulk meteorites will be close to those of their parent magmas. ALH 84001 is an exception, and it will not be discussed. The martian meteorites will be considered in two groups; a 1.3 Ga group composed of the clinopyroxenites and dunite, and a younger group composed of all others.

Mittlefehldt, D. W.↗