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The chemical composition of a comet has always been considered to be a function of where it formed in the nebula. We suggest that the most important factor in determining a comet's chemistry might actually be when it formed. We present specific predictions of correlations between the dust and volatile components to test our hypothesis.
The chemical composition of a comet has always been considered to be a function of where it formed in the nebula. We suggest that the most important factor in determining a comet's chemistry might actually be when it formed. Specific predictions are presented.
Review of the crystallization histories suggested by the chemical, crystallographic, morphological, and paragenetic relationships observed in pyroxenes from basalts collected on the Apollo 11, 12, 14, 15, and Luna 16 missions. Although the final stages of lunar basalt crystallization appear to be rapid near-surface events, the initial stages are shown to vary considerably among the different basalt types.
Clinopyroxenes from Apollo 12 rocks studied by X ray diffraction and electron microprobe methods, noting phenocrysts, chemical composition and crystallization
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Dust grains in Herbig Ae/Be stars are continuously replenished by infalling comets. The IR spectra of these cometary grains appear to evolve temporally from initially amorphous astronomical silicates in young protostars to crystalline olivine in much older sources. Crystalline olivine can only be produced from amorphous silicates on a time scale of months-to-years via thermal annealing at temperatures near 1000 K. Since such sustained high temperatures only occur near the central star, dust annealed at 1000 K in inner nebular regions must be continuously transported beyond the nebular snowline to be incorporated into the next generation of cometesimals. The average formation age of a comet can therefore be measured as a ratio of the annealed crystalline olivine dust component to the total dust content of the comet. Comets formed from nearly pristine interstellar materials early in the protostellar nebula stage will contain very little crystalline dust whereas comets formed towards the end of the accretion period will incorporate a much higher percentage of annealed silicate. It is unlikely that only dust grains circulate from the inner to the outer nebula; the gas associated with such dust should also find its way beyond the snowline. Since this gas and dust will have equilibrated in the higher pressure-temperature regime of the inner nebula, it will contain a much higher proportion of hydrocarbons and ammonia than more pristine interstellar ices. Therefore, in addition to a higher fraction of crystalline dust, later forming comets should also contain higher ratios of hydrocarbons to CO and ammonia to N2 than do those formed early in the history of the nebula.
Radiochemical neutron activation analysis of Ag, As, Au, Bi, Co, Cs, Ga, In, Rb, Sb, Te, Tl, and Zn and major element data in 14 L4-6 and 3 LL5 chondrites indicates that the L group is unusually variable and may represent at least 2 subgroups differing in formation history. Chemical trends in the S/Fe rich subgroup support textural evidence indicating late loss of a shock formed Fe-Ni-S melt; the S/Fe poor subgroup seemingly reflects nebular fractionation only. Highly mobile In and Zn apparently reflect shock induced loss from L chondrites. However, contrasting chemical trends in several L chondrite sample sets indicate that these meteorites constitute a more irregular sampling of, or more heterogeneous parent material than do carbonaceous or enstatite chondrites. Data for 15 chondrites suggest higher formation temperatures and/or degrees of shock than for LL5 chondrites.
We have used a Green's function technique to calculate the energy levels and formation energy of deep defects in the narrow gap semiconductors mercury cadmium telluride (MCT), mercury zinc telluride (MZT) and mercury zinc selenide (MZS). The formation energy is calculated from the difference between the total energy with an impurity cluster and the total energy for the perfect crystal. Substitutional (including antisite), interstitial (self and foreign), and vacancy deep defects are considered. Relaxation effects are calculated (with molecular dynamics). By use of a pseudopotential, we generalize the ideal vacancy model so as to be able to consider relaxation for vacancies. Different charge states are considered and the charged state energy shift (as computed by a modified Haldane-Anderson model) can be twice that due to relaxation. Different charged states for vacancies were not calculated to have much effect on the formation energy. For all cases we find deep defects in the energy gap only for cation site s-like orbitals or anion site p-like orbitals, and for the substitutional case only the latter are appreciably effected by relaxation. For most cases for MCT, MZT, MZS, we consider x (the concentration of Cd or Zn) in the range appropriate for a band gap of 0.1 eV. For defect energy levels, the absolute accuracy of our results is limited, but the precision is good, and hence chemical trends are accurately predicted. For the same reason, defect formation energies are more accurately predicted than energy level position. We attempt, in Appendix B, to calculate vacancy formation energies using relatively simple chemical bonding ideas due to Harrison. However, these results are only marginally accurate for estimating vacancy binding energies. Appendix C lists all written reports and publications produced for the grant. We include abstracts and a complete paper that summarizes our work which is not yet available.
Recent analysis analytical electron microscope study of lunar soils showed that the approximately 60-nm-wide amorphous rims surrounding many lunar soils grains exhibit distinct compositional differences from their hosts. On average, the amorphous rim compositions reflect the local bulk soil composition with the exceptions of Si and S, which are enriched relative to the bulk soil. These chemical trends led us to propose that the amorphous rims were in fact deposits of impact-generated vapors produced during regolith gardening, a hypothesis that runs contrary to the generally accepted view that the rims are produced through amorphization of the outer parts of mineral grains by interaction with the solar wind. Analytical data are reported for amorphous rims on individual minerals in lunar soils in order to show that the magnitude of the chemical differences between rim and host are so great that they require a major addition of foreign elements to the grain surfaces. The average composition of amorphous rims is listed as a function of host mineralogy as determined in microtone thin sections using energy-dispersive X-ray spectrometry in the transmission electron microscope. As the host mineral becomes chemically more complex, the chemical differences are not as clear. The average rim compositions are remarkably similar and are independent of the host grain mineralogy. Whether there are 'sputtering' or radiation effects superimposed on the vapor-deposited material can be debated. We do not explicitly exclude the effects of radiation damage as a contributing factor to the formation of amorphous rims; we are merely emphasizing the major role played by condensed vapors in the formation of amorphous rims on lunar soil grains.
Space shuttle and heavy lift launch vehicle concepts are described with attention to transportation cost trends. Chemical (LOX/LH2), nuclear, and electric propulsion systems are considered. Suggested space shuttle projects include the support of manned geosynchronous missions and the transfer of bulk cargo and large-delicate space structures from fabrication/assembly orbits to their operational locations. It is thought that development of the space shuttle will stimulate interest in space industrialization.
Tungsten concentrations have been determined by instrumental neutron activation in 104 iron meteorites, and range from 0.07 to 5 microg/g. In individual groups, concentrations vary by factors of between 1.5 and 8, but there are negative W-Ni correlations in 8 groups: IAB, IC, IIAB, IID, IIE, IIIAB, IIICD, and IIIF. The lowest W concentrations are found in groups IAB and IIICD, which also have the smallest slopes on a W-Ni plot. Eighteen anomalous irons have W concentrations between 5 microg/g (Butler) and 0.11 microg/g (Rafrueti). The distribution of W in irons shows similarities to that of other refractory sideophilic elements (except Mo), but is closest to the distribution of Ru and Pt. Assuming that chemical trends in group IIIAB were produced by fractional crystallization, a value of 1.6 can be deduced for the distribution coefficient of W between solid and liquid metal, as compared with 0.89 for Mo. Experimental evidence in support of these values is tenuous.
Equilibrium and controlled cooling rate experiments on a synthetic analog of Apollo 15 quartz normative basalt 15597 are reported. While the partitioning of the major elements Ca, Mg, and Fe between pyroxene and liquid is rate independent, the K sub D parameter for Fe/Mg, which is calculated for low-Ca pyroxene, is temperature dependent. It is suggested that chemical trends observed in lunar pyroxenes are a consequence of three rate processes. The processes are (1) rate-dependent suppression of crystallization of other phases until lower temperature alters liquid composition and, therefore, the composition of the pyroxene that crystallizes; (2) the efficiency of fractional crystallization and the extent of crystal zoning are rate dependent; and (3) the partitioning of Al2O3, TiO2, and Cr2O3 between pyroxene and liquid depends on cooling rate.
The principal group of low-KREEP highlands rocks as indicated by quartz-olivine-anorthite pseudoternary phase diagrams shows chemical trends which violate the Bowen reaction principle, in that the greater the concentration of magnesian and mafic minerals, the more sodic the coexisting plagioclase tends to be. It is suggested that this trend was established during the primary differentiation of the lunar crust and is a result of crystallization in a vigorously convecting (well-stirred) system. Under these conditions all plagioclase crystals, all pyroxene crystals, and all of the residual liquid remain fairly uniform in composition until advanced crystallization immobilizes the system. The rock suite then established would vary continuously from anorthositic types at the top to ultramafic types at the bottom.
Radiochemical neutron activation analysis of Ag, As, Au, Bi, Co, Cs, Ga, In, Rb, Sb, Te, Tl and Zn and major element data in 14 L4-6 and 3 LL5 chondrites indicates that the L-group is unusually variable and may represent at least 2 sub-groups differing in formation history. Chemical trends in the S/Fe-rich sub-group support textural evidence indicating late loss of a shock-formed Fe-Ni-S melt; the S/Fe-poor sub-group seemingly reflects nebular fractionation only. Highly mobile In and Zn apparently reflect shock-induced loss from L-chondrites. Data for L5 chondrites suggest higher formation temperatures and/or degrees of shock than for LL5 chondrites.
Orbital X-ray data from the Apollo 16 region indicate that physiographic units identified before the lunar mission can be classified as chemical units as well. The Descartes Mountains, however, appear to be an extension of the Kant Plateau composition that is unusually anorthositic and resembles farside terra. The Cayley Plains have closer affinities to basaltic materials than terra materials, physically, spectrally and chemically. The Theophilus impact, 330 km east of the landing site, excavated magnesium-rich basalts from below less-magnesian flows in Mare Nectaris; but, mafic ejecta was substantially blocked from the Apollo 16 site by the Kant Plateau that rises 5 km above the level of the mare. Apollo 16 soil samples from stations selected to collect either Descartes Mountains material or Cayley Plains material were surprisingly similar. However, they do, indeed, show the chemical trends indicative of the two units as defined by the orbiting geochemistry detectors. The Kant Plateau and Descartes Mountains material may be among the rare nearside examples of a plagioclase-rich cumulate of the primordial magma ocean.
Trace element analyses using proton induced X-ray emission and synchrotron X-ray fluorescence have been made on metal and troilite from nine iron meteorites representing five geochemical groups. Nickel and copper distribution coefficients D (troilite/metal) vary by factors of 600 and 20, respectively, correlate positively with kamacite bandwidth and correlate negatively with bulk nickel content. Meteorites with bulk Ni of less than 10 percent have Cu-enriched troilite while those with Ni greater than 10 percent have Cu-depleted troilite. Since magmatic evolution and partial melting will produce Cu-enriched troilite only, the observation of Cu-depleted troilite in Ni-rich meteorites is evidence for subsolidus reequilibration, a process which reduces D(Cu) by transfer of Cu to exsolving metal. Elemental redistribution may have played an important role in establishing the present chemical trends in iron meteorites.
The investigation of defect interactions and properties related to semiinsulating behavior of III-V semiconductors resulted in about twenty original publications, six doctoral thesis, one masters thesis and numerous conference presentations. The studies of new compensation mechanisms involving transition metal impurities have defined direct effects associated with deep donor/acceptor levels acting as compensating centers. Electrical and optical properties of vanadium and titanium levels were determined in GaAs, InP and also in ternary compounds InGaAs. The experimental data provided basis for the verification of chemical trends and the VRBE method. They also defined compositional range for III-V mixed crystals whereby semiinsulating behavior can be achieved using transition elements deep levels and a suitable codoping with shallow donor/acceptor impurities.
The composition of 75 type-IA and type-II porphyritic olivine chondrules from nine LL type 3 to type 5 chondrites was determined and was compared with that of chondrules from the Semarkona type 3.0 meteorite. Chemical data for silicates in the LL3.3-5 chondrites indicated that porphyritic olivine chondrules in these chondrites could be derived from chondrules similar to those from the Semarkona LL3.0, the least metamorphosed one of the known LL chondrites. It is shown that the chemical trends defined by the minerals of type-IA and type-II chondrules can be satisfactorily accounted for by the process of solid-state diffusive equilibration between minerals in chondrules and the opaque matrix rather than by changes in conditions during chondrule crystallization.