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Soil crusts on Mars

Three distinct soillike materials sampled by the Viking landers (VL) on Mars are (in order of increasing strength): (1) drift; (2) crusty to cloddy; and (3) blocky. Relative strengths of these materials are manifested by footpad penetrations during landing (VL 1), depths of deep holes, motor currents during sampling, sampler backhoe penetrations, comminutor motor currents, impact pits, trench tailings, and successful acquisitions of the coarse fraction (only blocky material). Cementation by S Cl compounds probably contributes to the relative strengths. This is shown where the weight pct. of SO3 + Cl of each material is plotted against their relative strengths. A similar result is obtained using SO3 alone, but not with Cl which is deficient in VL 2 samples.

Moore, H. J.↗

Implications for volcanogenic volatile release on the weathering of Mars

Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the similarities are such that the suite of gases emitted from martian volcanic activity surely includes gases such as H2O, CO2, S-containing gases (H2S, SO3, or SO2), and Cl-containing gases (e.g. Cl or HCl). Both H2O and CO2 are present in the atmosphere of Mars; both are also present as surface condensates. Spectroscopic observations of the martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted. Likewise, there is no evidence of surface condensates of compounds of these elements. Within the soil, there is direct evidence of incorporation of H2O and some compounds of sulfur and chlorine. None of the resultant weathering products have been directly identified, but both clays and salts have been indirectly implicated. Other aspects of the implications for volcanogenic volatile release on the weathering of Mars are discussed.

Clark, Benton C.↗

Chemical and physical studies of chondrites. X - Cathodoluminescence and phase composition studies of metamorphism and nebular processes in chondrules of type 3 ordinary chondrites

The cathodoluminescence (CL) characteristics of eight type-3 ordinary chondrites and one L5 chondrite were investigated with particular emphasis on detailed compositions of the relevant phases in four of these chondrites: Semarkona (type-3.0); Krymka (3.1); Allan Hills A77214 (3.5); and Dhajala (3.8). By sorting the chondrules into eight groups according to the CL of mesostasis and to certain compositional criteria and by determining the number of chondrules in these groups as a function of petrological type, it was possible to deduce genetic/evolutionary sequences of the chondrules. It is shown that there are major compositional differences in chondrules, which account for their CL properties and the chondrule groups.

Dehart, John M.↗

A liquid-helium-cooled absolute reference cold load for long-wavelength radiometric calibration

Design, radiometric and thermal performance, and operation of a large diameter (78 cm) liquid-helium-cooled blackbody absolute reference cold load (CL) for the calibration of microwave radiometers is described. CL provides an absolute calibration near the liquid-helium (LHe) boiling point, with total uncertainty in the radiometric temperature of less than 30 mK over the 2.5-23 cm wavelength operating range. CL was used at several wavelengths at the South Pole, Antarctica and the White Mountain Research Center, California. Results show that, for the instruments operated at 20-, 12-, 7.9-, and 4.0 cm wavelength at the South Pole, the total corrections to the LHe boiling-point temperature (about 3.8 K) were 48 +/-23, 18 +/-10, 10 +/-18, and 15 +/-mK.

Bensadoun, Marc↗

Diamond film deposition using microwave plasmas under low pressures

Microwave plasma depositions of diamond films have been investigated under low pressures of 10 mTorr to 10 Torr, at low substrate temperatures of 400 to 750 C, using high methane concentrations of 5 to 15 percent and oxygen concentrations of 5 to 10 percent in hydrogen plasmas. The deposition system consists of a microwave plasma chamber, a downstream deposition chamber, and a RF induction-heated sample stage. The deposition system can be operated in either high-pressure microwave or electron cyclotron resonance (ECR) modes by varying the sample stage position. Cathodoluminescence (CL) studies on diamond films deposited at 10 Torr pressure show that CL emissions at 430, 480, 510, 530, 560, 570 and 740 nm can be employed to characterize the quality of diamond films. High-quality, well-faceted diamond films have been deposited at 10 Torr and 600 C using 5 percent CH4 and 5 percent O2 in H2 plasmas; CL measurements on these films show very low N impurities and no detectable Si impurities. Diamond nucleation on SiC has been demonstrated by depositing well-faceted diamond crystallites on SiC-coated Si substrates.

Shing, Y. H.↗

The (FHCl)- molecular anion - Structural aspects, global surface, and vibrational eigenspectrum

State of the art ab initio electronic structure methods have been used to investigate the (FHCl)- molecular anion. It is proposed that the geometric structure and binding energies of the complex are r(e)(H-F) = 0.963 +/- 0.003 A, R(e)(H-Cl) = 1.925 +/- 0.015 A, and D0(HF + Cl(-)) = 21.8 +/- 0.4 kcal/mol. A Morokuma decomposition of the ion-molecular bonding give the following electrostatic, polarization, exchange repulsion, dispersion, and charge-transfer plus higher-order mixing components of the vibrationless complexation energy: -27.3, -5.2, +18.3, -4.5, and -5.0 kcal/mol, respectively. A couples cluster single and doubles global surface is constructed from 208 and 228 energy points for linear and bent configurations, respectively, these being fit to rms errors of only 3.9 and 9.3/cm, respectively, below 8000/cm. Converged J = 0 and J = 1 variational eigenstates of the (FHCl)- surface to near the HF + Cl(-) dissociation threshold are determined. The fundamental vibrational frequencies are found to be nu1 = 247/cm, nu2 = 876/cm, and nu3 = 2884/cm. The complete vibrational eigenspectrum is analyzed.

Klepeis, Neil E.↗

Fundamental studies of gas phase ionic reactions by ion mobility spectrometry

Ion mobility spectrometry (IMS) provides a promising approach to the study of gas phase ionic reactions in buffer gases at unusually high pressures. This point is illustrated here by studies of the Sn2 nucleophilic displacement reaction, Cl(-) + CH3Br yields Br + CH3Br, using IMS at atmospheric pressure. The equilibrium clustering reaction, Cl(-)(CHCI3)(n - 1) + CHCI3 yields Cl(-)(CHCI3)(n), where n = 1 and 2, and the effect of clustering on the Sn2 reaction with CH3Br have also been characterized by this IMS-based kinetic method. Present problems and anticipated improvements in the application of ion mobility spectrometry to studies of other gas phase ionic processes are discussed.

Giles, K.↗

The evolution of enstatite and chondrules in unequilibrated enstatite chondrites: Evidence from iron-rich pyroxene

FeO-rich (Fs(sub 6)-34) pyroxene lacking cathodoluminescence (CL), hereafter black pyroxene, is a major constituent of some of the chondrules and fragments in unequilibrated (type 3) enstatite chondrites (UECs). It contains structurally oriented zones of Cr-, Mn-, V-rich, FeO-poor enstatite with red CL, associated with mm-sized blebs of low-Ni, Fe-metal and, in some cases, silica. These occurrences represent clear evidence of pyroxene reduction. The black pyroxene is nearly always rimmed by minor element (Cr, Mn, V)-poor enstatite having a blue CL. More commonly, red and blue enstatites, unassociated with black pyroxene, occur as larger grains in chondrules and fragments, and these constitute the major silicate phases in UECs. The rare earth element (REE) abundance patterns of the black pyroxene are LREE-depleted. The blue enstatite rims, however, have a near-flat to LREE-enriched pattern, approx. 0.5-4x chondritic. The petrologic and trace element data indicate that the black pyroxene is from an earlier generation of chondrules that formed in a nebular region that was more oxidizing than that of the enstatite chondrites. Following solidification, these chondrules experienced a more reducing nebular environment and underwent reduction. Some, perhaps most, of the red enstatite that is common throughout the UECs may be the product of solid-state reduction of black pyroxene. The blue enstatite rims grew onto the surfaces of the black pyroxene and red enstatite as a result of condensation from a nebular gas. The evolutionary history of some of the enstatite and chondrules in enstatite chondrites can be expressed in a four-stage model that includes: Stage 1. Formation of chondrules in an oxidizing nebular environment. Stage 2. Solid-state reduction of the more oxidized chondrules and fragments to red enstatite in a more reducing nebular environment. Stage 3. Formation of blue enstatite rims on the black pyroxene as well as on the red enstatite. Stage 4. Reprocessing, by various degrees of melting, of many of the earlier-formed materials.

Weisberg, Michael K.↗

The Kinetic Nonequilibrium Processes in the Internal Flow and in the Plume of Subsonic and Supersonic Aircrafts

(1) Our results show that under combustion of thermal destruction products of n-C8H18, and other hydrocarbon fuels with air at the equivalent ratio -0.5 and less the chemical equilibrium is not realized at the exit plane of combustion chamber and in the gas turbine and nozzle for most of small components such as NO2, NO3, HNO, HNO2, HNO3, N(x)H(y), HO2, OH. The chemical equilibrium is not realized in the internal flow of ramjet hydrogen combustion engine too. So at the nozzle exit plane both of gas-turbine hydrocarbon combustion engine and of ramjet hydrogen combustion engine the relatively large values of concentration of such small components as NO3, HNO2, N2O, HNO3, HNO, NH, N2H, HO2, H2O2 may be realized. The exact definition of these component concentration as well as concentration of NO(x), OH, SO2, O, H, H2, H2O at the nozzle exit plane is very important for plume chemistry. (2) The results which were obtained for subsonic and hypersonic aircrafts indicate on the considerable change of the composition of the gas mixture along the plume. This change can be caused not only by the mixture of combustion products with the atmosphere air but by proceeding of whole complex of nonequilibrium photochemical reactions. The photodissociation processes begin to influence on the formation of the free atoms and radicals at flight altitude H greater than or equal to 18 km. Neglect of these processes can result in essential (up to 10(exp 4) times) mistakes of values gamma(sub OH), gamma(sub O), gamma(sub H), gamma(sub HSO3) and some products of CFC's disintegration. It was found that penetration of Cl-containing species from the atmosphere into the exhaust flow and its interaction with nitrogen oxides leads to essential increasing of the concentration of Cl, Cl2, ClO2, ClNO3, CH3Cl and sometimes HCl and the decreasing of ClO concentration by comparison with background values. The results of our analysis show that the plume aircraft with both hydrocarbon and hydrogen combustion engine may be source of various pollutant components such as HNO, HNO4,ClO2, CH3NO2, CH3NO3, CH2O, Cl, H2O2, but not only NO, NO2, HNO2, HNO3, N2O5, SO2, SO3, H2SO4 as it was supposed before.

Starik, Alexander M.↗

Thermally Mobile Trace Elements in Carbonaceous Chondrites from Cold and Hot Deserts

Some decades ago, Anders and co-workers used RNAA to classify a number of trace elements as being volatile during nebular condensation and accretion into primitive objects based upon their strong depletion in (equilibrated) ordinary chondrites relative to C1 chondrites. Such elements, e.g. Ag, Bi, Cd, Cs, In, Se, Te, Tl, Zn and others, exhibit nearly constant, C1-normalized atomic abundances in C2 (CM2) and in C3 chondrites. They interpreted the near-constancy of these abundances according to a 2-component model in which volatiles were introduced into carbonaceous (and other) chondrites as Cl material which was diluted with differing proportions of high-temperature (i.e. volatile-free) components. In this view, mean volatile element abundances of 0.48 in C2 and 0.24-0.29 x C1 in C3 chondrites indicated that C2 and C3 chondrites are, respectively, about 1:1 and 1:2-3 mixtures of Cl-like and high temperature materials. More recently, C1 normalized abundances of such volatile elements are nearly constant in most C2-6 chondrites (i.e. 25 non-Antarctic meteorites, nearly all falls, and 36 Antarctic finds) consistent with a 2- component mixing model. However, rather than being quantized, mean volatile element contents in each chondrite define a continuum from 0.92-0.14 x Cl for these 61 chondrites. A few carbonaceous chondrites - the first having been the NIPR consortium samples B-7904, Y-82162 and Y-86720 - show an altered pattern: many of the volatile elements in each exhibit the usual constancy of C1-normalized atomic abundances, but modified by further depletion of Cd and other elements like Tl and Bi. These are the most mobile trace elements, i.e. those most readily vaporized and lost from primitive meteorites during week-long heating at greater than or equal to 400 C under low ambient pressures (initially 10 (exp -5) atm H2), simulating metamorphic conditions in a primitive parent body. Similarities between mobile element data for B-7904, Y-82162 and Y-86720 with those for Murchison heated at 500-700 C suggest that these Antarctic C1 and C2-like chondrites were metamorphosed at temperatures like these in the interiors of their parent bodies. Metamorphic temperatures inferred from RNAA data and textural/mineralogic alterations are internally consistent, agreeing with those evident in heated Murchison samples. These 3 chondrites were also heated late in their histories since all have lost cosmogenic 3-He, presumably during close solar approach, and B-7904 and Y-86720 seem also to have lost substantial proportions of radiogenic He-4 and Ar-40, cf. data. Similarities in spectral reflectance data for C-, G-, B- and F- asteroids, for these meteorites and for heated Murchison samples suggest that thermally metamorphosed interior materials in these asteroids were excavated by impacts and re-deposited on them, forming their present surfaces. Establishment of the thermal metamorphic histories of carbonaceouis chondrites, then, is essential to establishing the evolution and present-day nature of C-type and related asteroids.

Lipschutz, M. E.↗

First Year Wilkinson Microwave Anisotropy Probe (WMAP)Observations: Preliminary Maps and Basic Results

We present full sky microwave maps in five frequency bands (23 to 94 GHz) from the WMAP first year sky survey. Calibration errors are less than 0.5% and the low systematic error level is well specified. The cosmic microwave background (CMB) is separated from the foregrounds using multifrequency data. The sky maps are consistent with the 7 in. full-width at half-maximum (FWHM) Cosmic Background Explorer (COBE) maps. We report more precise, but consistent, dipole and quadrupole values. The CMB anisotropy obeys Gaussian statistics with -58 less than f(sub NL) less than 134 (95% CL). The 2 less than or = l less than or = 900 anisotropy power spectrum is cosmic variance limited for l less than 354 with a signal-to-noise ratio greater than 1 per mode to l = 658. The temperature-polarization cross-power spectrum reveals both acoustic features and a large angle correlation from reionization. The optical depth of reionization is tau = 0.17 +/- 0.04, which implies a reionization epoch of t(sub r) = 180(sup +220, sub -80) Myr (95% CL) after the Big Bang at a redshift of z(sub r) = 20(sup +10, sub -9) (95% CL) for a range of ionization scenarios. This early reionization is incompatible with the presence of a significant warm dark matter density. A best-fit cosmological model to the CMB and other measures of large scale structure works remarkably well with only a few parameters. The age of the best-fit universe is t(sub 0) = 13.7 +/- 0.2 Gyr old. Decoupling was t(sub dec) = 379(sup +8, sub -7)kyr after the Big Bang at a redshift of z(sub dec) = 1089 +/- 1. The thickness of the decoupling surface was Delta(sub z(sub dec)) = 195 +/- 2. The matter density of the universe is Omega(sub m)h(sup 2) = 0.135(sup +0.008, sub -0.009) the baryon density is Omega(sub b)h(sup 2) = 0.0224 +/- 0.0009, and the total mass-energy of the universe is Omega(sub tot) = 1.02 +/- 0.02. There is progressively less fluctuation power on smaller scales, from WMAP to fine scale CMB measurements to galaxies and finally to the Ly-alpha forest. This is accounted for with a running spectral index, significant at the approx. 2(sigma) level. The spectral index of scalar fluctuations is fit as n(sub s) = 0.93 +/-0.03 at wavenumber k(sub o) = 0.05/Mpc ((sub eff) approx. = 700), with a slope of dn(sub s)/d I(sub nk) = -0.031(sup + 0.016, sub -0.018) in the best-fit model.

Bennett, C. L.↗

Space Radiation Cancer Risks

Space radiation presents major challenges to astronauts on the International Space Station and for future missions to the Earth s moon or Mars. Methods used to project risks on Earth need to be modified because of the large uncertainties in projecting cancer risks from space radiation, and thus impact safety factors. We describe NASA s unique approach to radiation safety that applies uncertainty based criteria within the occupational health program for astronauts: The two terrestrial criteria of a point estimate of maximum acceptable level of risk and application of the principle of As Low As Reasonably Achievable (ALARA) are supplemented by a third requirement that protects against risk projection uncertainties using the upper 95% confidence level (CL) in the radiation cancer projection model. NASA s acceptable level of risk for ISS and their new lunar program have been set at the point-estimate of a 3-percent risk of exposure induced death (REID). Tissue-averaged organ dose-equivalents are combined with age at exposure and gender-dependent risk coefficients to project the cumulative occupational radiation risks incurred by astronauts. The 95% CL criteria in practice is a stronger criterion than ALARA, but not an absolute cut-off as is applied to a point projection of a 3% REID. We describe the most recent astronaut dose limits, and present a historical review of astronaut organ doses estimates from the Mercury through the current ISS program, and future projections for lunar and Mars missions. NASA s 95% CL criteria is linked to a vibrant ground based radiobiology program investigating the radiobiology of high-energy protons and heavy ions. The near-term goal of research is new knowledge leading to the reduction of uncertainties in projection models. Risk projections involve a product of many biological and physical factors, each of which has a differential range of uncertainty due to lack of data and knowledge. The current model for projecting space radiation cancer risk relies on the three assumptions of linearity, additivity, and scaling along with the use of population averages. We describe uncertainty estimates for this model, and new experimental data that sheds light on the accuracy of the underlying assumptions. These methods make it possible to express risk management objectives in terms of quantitative metrics, i.e., the number of days in space without exceeding a given risk level within well defined confidence limits. The resulting methodology is applied to several human space exploration mission scenarios including lunar station, deep space outpost, and a Mars mission. Factors that dominate risk projection uncertainties and application of this approach to assess candidate mitigation approaches are described.

Cucinotta, Francis A.↗

Coatings on Atacama Desert Basalt: A Possible Analog for Coatings on Gusev Plains Basalt

Surface coatings on Gusev Plains basalt have been observed and may contain hematite and nanophase Fe-oxides along with enrichments in P, S, Cl, and K relative to the underlying rock. The Gusev coatings may be derived from the dissolution of adhering soil and/or parent rock along with the addition of S and Cl from outside sources. Transient water for dissolution could be sourced from melting snow during periods of high obliquity, acid fog, and/or ground water (Haskin et al., 2005). Coatings on basalt in the hyper-arid (less than 2mm y(sup -1)) Atacama Desert may assist in understanding the chemistry, mineralogy and formation mechanisms of the Gusev basalt coatings. The Atacama Desert climate is proposed to be analogous to a paleo-Mars climate that was characterized by limited aqueous activity when the Gusev coatings could have formed. The objectives of this work are to (i) determine the chemical nature and extent of surface coatings on Atacama Desert basalt, and (ii) assess coating formation mechanisms in the Atacama Desert. Preliminary backscattered electron imaging of Atacama basalt thin-sections indicated that the coatings are as thick as 20 m. The boundary between the coating and the basalt labradorite, ilmenite, and augite grains was abrupt indicating that the basalt minerals underwent no chemical dissolution. The Atacama coatings have been added to the basalt instead of being derived from basalt chemical weathering. Semi-quantitative energy dispersive spectroscopy shows the coatings to be chemically homogeneous. The coating is depleted in Ca (0.9 wt% CaO) and enriched in K (1.3 wt.% K2O) and Si (69.1 wt.% SiO2) relative to the augite and labradorite grains. A dust source enriched in Si (e.g., poorly crystalline silica) and K and depleted in Ca appears to have been added to the basalt surface. Unlike the Gusev coatings, no P, S, and Cl enrichment was observed. However, Fe (3.2 wt.% FeO) was present in the Atacama coatings suggesting the present of Fe-oxides. While the chemistry of Atacama coating does not mirror the Gusev coating, the coating formation mechanism may be similar. The Atacama coatings of surface basalt are derived completely from exogenous sources. If surface Mars rocks have experienced limited wetting conditions as in the Atacama, then Mars coatings may be derived only from dissolution of material adhering to rock.

Sutter, B.↗

Observations of High-Redshift X-Ray Selected Clusters with the Sunyaev-Zel'dovich Array

We report measurements of the Sunyaev-Zel'dovich (SZ) effect in three high redshift (0.89 less than or equal to z less than or equal to 1.03), X-ray selected galaxy clusters. The observations were obtained at 30 GHz during the commissioning period of a new, eight-element interferometer - the Sunyaev-Zel'dovich Array (SZA) - built for dedicated SZ effect observations. The SZA observations are sensitive to angular scales larger than those subtended by the virial radii of the clusters. Assuming isothermality and hydrostatic equilibrium for the intracluster medium, and gas-mass fractions consistent with those for clusters at moderate redshift, we calculate electron temperatures, gas masses, and total cluster masses from the SZ data. The SZ-derived masses, integrated approximately to the virial radii, are 1.9 (sup +0.5)(sub -0.4) x 10(exp 14) solar mass for Cl J1415.1+3612, 3.4 (sup +0.6)(sub -0.5) x 10(exp 14) solar mass for Cl J1429.0+4241 and 7.2 (sup +1.3)(sub -0.9) x 10(exp 14) solar mass for Cl J1226.9+3332. The SZ-derived quantities are in good agreement with the cluster properties derived from X-ray measurements.

Muchovej, Stephen↗

Multimode and multistate ladder oscillator and frequency recognition device

A ladder oscillator composed of capacitive and inductive impedances connected together to form a ladder network which has a chosen number N oscillation modes at N different frequencies. Each oscillation mode is characterized by a unique standing wave voltage pattern along the nodes of the ladder oscillator, with the mode in which the ladder oscillator is oscillating being determinable from the amplitudes or phase of the oscillations at the nodes. A logic circuit may be connected to the nodes of the oscillator to compare the phases of selected nodes and thereby determine which mode the oscillator is oscillating in. A ladder oscillator composed of passive capacitive and inductive impedances can be utilized as a frequency recognition device, since the passive ladder oscillator will display the characteristic standing wave patterns if an input signal impressed upon the ladder oscillator is close to one of the mode frequencies of the oscillator. A CL ladder oscillator having series capacitive impedances and shunt inductive impedances can exhibit sustained and autonomous oscillations if active nonlinear devices are connected in parallel with the shunt inductive impedances. The active CL ladder oscillator can be synchronized to input frequencies impressed upon the oscillator, and will continue to oscillate after the input signal has been removed at a mode frequency which is, in general, nearest to the input signal frequency. Autonomous oscillations may also be obtained as desired from the active CL ladder oscillator at the mode frequencies.

Aumann, Herbert M.↗

Confirmation of a Radio-Selected Galaxy Overdensity at z=1.11

We report the discovery of a galaxy overdensity at z = 1.11 associated with the z = 1.110 high-redshift radio galaxy MG1 J04426+0202 (hereafter MG 0442+0202). The group, Cl 0442+0202, was found in a near-infrared survey of z > 1 radio galaxies undertaken to identify spatially coincident regions with a high density of objects red in I-K' color, typical of z > 1 elliptical galaxies. Spectroscopic observations from the Keck I telescope reveal five galaxies within 35" of MG 0442+0202 at 1.10 < z < 1.11. These member galaxies have broadband colors and optical spectra consistent with passively evolving elliptical galaxies formed at high redshift. Archival ROSAT observations reveal a 3 (sigma) detection of soft X-ray emission coincident with Cl 0442+0202 at a level 5 times greater than expected for the radio galaxy. These data suggest a rich galaxy cluster and inspired a 45 ks Chandra X-Ray Observatory observation. As expected, the radio galaxy is unresolved by Chandra but is responsible for approximately half the observed X-ray flux. The remaining ROSAT flux is resolved into four point sources within 15' of the radio galaxy, corresponding to a surface density 2 orders of magnitude higher than average for X-ray sources at these flux levels [S(0.5-2 keV) > 5 x 10(exp -16) ergs cm (exp -2) s(exp -1)]. One of these point sources is identified with a radio-quiet type II quasar at z = 1.863, akin to sources recently reported in deep Chandra surveys. The limit on an extended hot intracluster medium in the Chandra data is S(1-6 keV) < 1.9 x 10-15 ergs cm (exp -2) s(exp -1) (3 (sigma), 30" radius aperture). Though the X-ray observations do not confirm the existence of a massive bound cluster at z > 1, the success of the optical/near-infrared targeting of early-type systems near the radio galaxy validates searches using radio galaxies as beacons for high-redshift large-scale structure. We interpret Cl 0442+0202 as a massive cluster in the process of formation.

galaxies↗

Enrichment of the Amino Acid L-Isovaline by Aqueous Alteration on CI and CM Meteorite Parent Bodies

The distribution and enantiomeric composition of the 5-carbon (C(sub 5)) amino acids found in Cl-, CM-, and CR-type carbonaceous meteorites were investigated by using liquid chromatography fluorescence detection/TOF-MS coupled with o-phthaldialdehyde/Nacetyl- l-cysteine derivatization. A large L-enantiomeric excess (ee) of the a-methyl amino acid isovaline was found in the CM meteorite Murchison (L(sub ee) = 18.5 +/- 2.6%) and the Cl meteorite Orguell (L(sub ee) = 15.2 +/- 4.0%). The measured value for Murchison is the largest enantiomeric excess in any meteorite reported to date, and the Orgueil measurement of an isovaline excess has not been reported previously for this or any Cl meteorite. The L-isovaline enrichments in these two carbonaceous meteorites cannot be the result of interference from other C(sub 5) amino acid isomers present in the samples, analytical biases, or terrestrial amino acid contamination. We observed no L-isovaline enrichment for the most primitive unaltered Antarctic CR meteorites EET 92042 and QUE 99177. These results are inconsistent with UV circularly polarized light as the primary mechanism for L-isovaline enrichment and indicate that amplification of a small initial isovaline asymmetry in Murchison and Orgueil occurred during an extended aqueous alteration phase on the meteorite parent bodies. The large asymmetry in isovaline and other alpha-dialkyl amino acids found in altered Ct and CM meteorites suggests that amino acids delivered by asteroids, comets, and their fragments would have biased the Earth's prebiotic organic inventory with left-handed molecules before the origin of life.

Glavin, Daniel P.↗

Effect of Fluorine on Near-Liquidus Phase Equilibria of Basalts

Volatile species such as H2O, CO2, F, and Cl have significant impact in generation and differentiation of basaltic melts. Thus far experimental work has primarily focused on the effect of water and carbon dioxide on basalt crystallization, liquid-line of descent, and mantle melting [e.g., 1, 2] and the effects of halogens have received far less attention [3-4]. However, melts in the planetary interiors can have non-negligible chlorine and fluorine concentrations. Here, we explore the effects of fluorine on near-liquidus phase equilibria of basalt. We have conducted nominally anhydrous piston cylinder experiments using graphite capsules at 0.6 - 1.5 GPa on an Fe-rich model basalt composition. 1.75 wt% fluorine was added to the starting mix in the form of AgF2. Fluorine in the experimental glass was measured by SIMS and major elements of glass and minerals were analyzed by EPMA. Nominally volatile free experiments yield a liquidus temperature from 1330 C at 0.8GPa to 1400 at 1.6GPa and an olivine(Fo72)-pyroxene(En68)-liquid multiple saturation point at 1.25 GPa and 1375 C. The F-bearing experiments yield a liquiudus temperature from 1260 C at 0.6GPa to 1305 at 1.5GPa and an ol(Fo66)-pyx(En64)-MSP at 1 GPa and 1260 C. This shows that F depresses the basalt liquidus, extends the pyroxene stability field to lower pressure, and forces the liquidus phases to be more Fe-rich. KD(Fe-Mg/mineral-melt) calculated for both pyroxenes and olivines show an increase with increasing F content of the melt. Therefore, we infer that F complexes with Mg in the melt and thus increases the melt s silica activity, depressing the liquidus and changing the composition of the crystallizing minerals. Our study demonstrates that on a weight percent basis, the effect of fluorine is similar to the effect of H2O [1] and Cl [3] on freezing point depression of basalts. But on an atomic fraction basis, the effect of F on liquidus depression of basalts is xxxx compared to the effect of H. Future studies on kimberlitic and subduction zone magmas, which could have significant amount of fluorine, will need to consider the combined effects of F, Cl, and H on their stability and chemical evolution.

Filiberto, Justin↗