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Impact-induced devolatilization and hydrogen isotopic fractionation of serpentine: Implications for planetary accretion

Impact-induced devolatilization of porous serpentine was investigated using two independent experimental methods, the gas recovery and the solid recovery method, each yielding nearly identical results. For shock pressures near incipient devolatilization, the hydrogen isotopic composition of the evolved H2O is very close to that of the starting material. For shock pressures at which up to 12 percent impact-induced devolatilization occurs, the bulk evolved gas is significantly lower in deuterium than the starting material. There is also significant reduction of H2O to H2 in gases recovered at these higher shock pressures, probably caused by reaction of evolved H2O with the metal gas recovery fixture. Gaseous H2O-H2 isotopic fractionation suggests high temperature isotopic equilibrium between the gaseous species, indicating initiation of devolatilization at sites of greater than average energy deposition. Bulk gas-residual solid isotopic fractionations indicate nonequilibrium, kinetic control of gas-solid isotopic ratios. Impact-induced hydrogen isotopic fractionation of hydrous silicates during accretion can strongly affect the long-term planetary isotopic ratios of planetary bodies, leaving the interiors enriched in deuterium. Depending on the model used for extrapolation of the isotopic fractionation to devolatilization fractions greater than those investigated experimentally can result from this process.

Tyburczy, James A.↗

Infrared investigation of water in Comet P/Halley

The results of the investigation of gaseous water, detected in the IR spectra of the Comet Halley's coma taken by the NASA's Kuiper Airborne Observatory, are summarized. High-resolution spectra revealed, near the wavelength of 2.65 microns, solar-pumped fluorescent emission in the (001-000) band of H2O and three lines of the (011-010) 'hot' band. The absolute production rate of H2O and its spatial distribution, temporal variability, and outflow velocity were measured along with the H2O ortho/para ratio. The measured line intensities indicate that water in the coma is rotationally relaxed. The aperture-averaged excitation temperatures for the low-lying rotational transitions were about 40 K, indicating that the coma kinetic temperature is extremely cold. Significant short-term temporal variations in the H2O line intensities were detected together with a strong pre- to postperihelion asymmetry (a factor of about 7) in the water production rate at a heliocentric distance of about 1 AU.

Weaver, H. A.↗

Impact fracture experiments simulating interstellar grain-grain collisions

Oxide and silicate grains condensing during the early phases of the formation of the solar system or in the outflow of stars are exposed to high partial pressures of the low-z elements H, C, N and O and their simple gaseous compounds. Though refractory minerals are nominally anhydrous and non-carbonate, if they crystallize in the presence of H2O, N2 and CO or CO2 gases, they dissolve traces of the gaseous components. The question arises: How does the presence of dissolved gases or gas components manifest itself when grain-grain collisions occur. What are the gases emitted when grains are shattered during a collision event. Researchers report on fracture experiments in ultrahigh vacuum (UHV, approximately less than 10 to the -8th power mbar) designed to measure (by means of a quadrupole mass spectrometer, QMS, with microns to ms time resolution) the emission of gases and vapors during and after impact (up to 1.5 sec). Two terrestrial materials were chosen which represent structural and compositional extremes: olivine (San Carlos, AZ), a densely packed Mg-Fe(2+) silicate from the upper mantle, available as 6 to 12 mm single crystals, and obsidian (Oregon), a structurally open, alkaline-SiO2-rich volcanic glass. In the olivine crystals OH- groups have been identified spectroscopically, as well as H2 molecules. Obsidian is a water-rich glass containing OH- besides H2O molecules. Olivine from the mantle often contains CO2, either as CO2-rich fluid in fluid inclusions or structurally dissolved or both. By analogy to synthetic glasses CO2 in the obsidian may be present in form of CO2 molecules in voids of molecular dimensions, or as carbonate anions, CO3(2-). No organic molecules have been detected spectroscopically in either material. Results indicate that refractory oxide/silicates which contain dissolved traces of the H2O and CO/CO2 components but no spectroscopically detectable traces of organics may release complex H-C-O (possibly H-C-N-O) molecules upon fracture, plus metal vapor. This points: (1) at complex reaction mechanisms between dissolved H2O, CO/CO2 (and N2) components within the mineral structure or during fracture, and (2) at the possibility that similar emission processes occur following grain-grain collisions in interstellar dust clouds.

Freund, Friedemann↗

Giotto IMS measurements of the production rate of hydrogen cyanide in the coma of Comet Halley

The ion composition measurements in the ionosphere of Comet Halley by the ion mass spectrometer (IMS) experiment on the Giotto spacecraft are used to estimate the relative abundance of HCN. From a comparison of the normalized number density of ions with mass-to-charge (M/q) ratio of 28 AMU/e with steady-state photochemical models, it can be determined that the production rate of HCN directly from the central nucleus is Q(HCN) is less than about 0.0002 Q(H2O) at the time of Giotto encounter. The related photochemical- model calculations also indicate that Q(NH3)/Q(H2O) at the time of Giotto encounter. The related photo-chemical model calculations also indicate that Q(HN3)/Q(H2O) equals about 0.005, in agreement with recent determination from ground-based observations. The estimated value of Q(HCN) is lower than the relative abundance of Q(HCN)/Q(H2O) of about 0.001, as derived from radio observations of the 88.6 GHz emission of the J = 1 - 0 transition of HCN. The difference may be the result of time variations of the coma composition and dynamics, as well as other model-dependent effects.

Ip, W.-H.↗

A coupled subsurface-boundary layer model of water on Mars

A 1D numerical model of the exchange of H2O between the atmosphere and subsurface of Mars through the PBL is employed to explore the mechanisms of H2O exchange and to elucidate the role played by the regolith in the local H2O budget. The atmospheric model includes effects of Coriolis, pressure gradient, and frictional forces for momentum: radiation, sensible heat flux, and advection for heat. It is suggested that in most cases, the flux through the Martian surface reverses twice in the course of each sol. The effects of surface albedo, thermal inertia, solar declination, atmospheric optical depth, and regolith pore structure are explored. It is proposed that higher thermal inertia forces more H2O into the atmosphere because the regolith is warmer at depth.

Zent, Aaron P.↗

Magmatic volatiles and the weathering of Mars

The sources for volatiles on Mars have been the subject of many hypotheses for exogenous influences including late accretion of volatile-enriched material, impact devolatilization to create massive early atmospheres, and even major bombardment by comets. However, the inventory of chemically active volatiles observable at the contemporary surface of Mars is consistent with domination by endogenous, subsequent planetary processes, viz., persistent magmatic outgassing. Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the geochemical similarities are such that the suite of gases emitted from Martian volcanic activity should include H2O, CO2, S-containing gases (e.g. H2S and/or SO2), and Cl-containing gases (e.g., Cl2 and/or HCl). H2O and CO2 exist in the atmosphere of Mars. Both are also present as surface condensates. However, spectroscopic observations of the Martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted, with upper limits of less than or equal to 10(exp -7) the abundance of CO2. Likewise, there is no evidence of polar condensates of compounds of these elements as there is for CO2 and H2O. Within the soil, on the other hand, there has been direct measurement of incorporated H2O and abundant compounds containing S and Cl. Barring some as yet implausible geochemical sequestering process, the S/Cl ratio of about 6:1 in Martian soils implies a limit of 5% on the contribution of matter of solarlike composition (e.g., carbonaceous chondrite or cometary material) to these volatiles. Hence, exogenous sources are minor or not yet observed. From analysis of elemental trends in Martian soils, it has been recently shown that a simple two-component model can satisfy the Viking in situ measurements. Component A includes Si and most or all the Al, Ca, Ti, and Fe. Component B, taken as 16 +/- 3% by weight of the total, contains S and most or all the Cl and Mg. These results constrain several models of Martian soil mineralogy but are consistent with a mixture of silicates (such as Fe-rich clays and accessory minerals and soluble salts). The overall element profile is notably like shergottites, with significant incorporation of chemically reactive atmospheric gases from magmatic degassing.

Clark, B. C.↗

Volatiles in the deep Earth: An experimental study using the laser-heated diamond cell

Experiments with the laser-heated diamond cell show that H2O and CO2 can be stabilized within crystalline mineral structures of the lower-mantle, and hence can be present at relatively non-volatile components of the Earth's deep interior. Samples quenched from high pressures and temperatures document that the MgCO3-FeCO3 magnesite-siderite solid-solution is stable and coexists with (Mg,Fe)SiO3 perovskite at 30-40 GPa and approximately 1500-2000 K. In contrast, H2O combines with the silicate to form (Mg,Fe)SiH2O4 phase D, coexisting with (Mg,Fe)SiO3 perovskite at these conditions. If enough water is present, phase D can become the predominant phase in the MgSiO3-H2O system at lower-mantle conditions. Our work extends previous studies to Fe-bearing compositions and to the pressures of the mid-lower mantle. Thus, the results of high-pressure experiments suggest that both H2O and CO2 can be abundant in the Earth's lower mantle, being present in stable hydroxisilicate and carbonate phases.

Li, Xiaoyuan↗

Is H20 present on Io? The detection of a new strong band near 3590/cm (2.79 micrometer)

A strong absorption band at 3590 +/- 20/cm (2.790 +/- 0.015 microns) has been discovered in the spectrum of Io using the Kuiper Airborne Observatory (KAO). The 2 nu(sub 1) + nu(sub 3) comination mode of solid SO2 falls at this position. Since SO2 is abundant on Io it must contribute to the new band. However, a band due to H2O was predicted near this frequency in Io's spectrum based on laboratory experiments of H2O:SO2 mixed Io ice analogs which were used to assign the two weak, variable features at 3370 and 3170/cm (2.97 and 3.15 microns) to trace amounts of H2O frozen in solid SO2 on Io. The new band probably originates from both SO2 and H2O. Unfortunately, the spectral resolution of the data is insufficient to settle the issue of whether there are two resolvable components.

Salama, F.↗

Recent lidar technology developments and their influence on measurements of tropospheric water vapor

In this paper the influences of recent technology developments in the areas of lasers, detectors, andoptical filters of a differential absorption lidar (DIAL) system on the measurenent of tropospheric water vapor (H2O) profiles are discussed. The lidar parameters selected are based upon a diode-seeded Ti:sapphire laser that is locked to an H2O line in the 820- or 930-nm band of H2O. To assess the influence of the mode of deployment on the measurement of tropospheric H2O, DIAL performance is evaluated for operation from a medium-altitude (12 km) aircraft, the ground, and space-based systems. It is found that incorporation of these developments could greatly enhance DIAL measurement capability.

Ismail, Syed↗

Chemical investigation of Titan and Triton tholins

We report chromatographic and spectroscopic analyses of both Titan and Triton tholins, organic solids made from the plasma irradiation of 0.9:0.1 and 0.999:0.001 N2/CH4 gas mixtures, respectively. The lower CH4 mixing ratio leads to a nitrogen-richer tholin (N/C greater than 1), probably including nitrogen heterocyclic compounds. Unlike Titan tholin, bulk Triton tholin is poor in nitriles. From high-pressure liquid chromatography, ultraviolet and infrared spectroscopy, and molecular weight estimation by gel filtration chromatography, we conclude that (1) several H2O-soluble fractions, each with distinct UV and IR spectral signatures, are present, (2) these fractions are not identical in the two tholins, (3) the H2O-soluble fractions of Titan tholins do not contain significant amounts of nitriles, despite the major role of nitriles in bulk Titan tholin, and (4) the H2O-soluble fractions of both tholins are mainly molcules containing about 10 to 50 (C + N) atoms. We report yields of amino acids upon hydrolysis of Titan and Triton tholins. Titan tholin is largely insoluble in the putative hydrocarbon lakes or oceans on Titan, but can yield the H2O-soluble species investigated here upon contact with transient (e.g., impact-generated) liquid water.

Mcdonald, Gene D.↗

Spread of denitrification from 1987 Antarctic and 1988-1989 Arctic stratospheric vortices

Vertical profiles of N2O and NO(y) taken by the ER-2 outside the vortex are used to construct average vertical profiles of F(NO(y)) = NO(y)/(A-N2O), where A is the tropospheric content of N2O three years prior to the measurements. The southern hemisphere had less nitrous oxide in the range 400 less than Theta less than 470 K, by up to 25% relative to the northern hemisphere. F(NO(y)) is the ratio of NOy produced to N2O lost in a stratospheric air mass since entry from the troposphere. The profiles of F(NO(y)) have the following characteristics: (1) Relative to 1991-1992, a year without denitrification inside or outside the vortex, the northern hemisphere in 1988-1989 showed denitrification outside the vortex ranging up to 25% and averaging 17% above Theta = 425 K. (2) Relative to the northern hemisphere in 1991-1992, the southern hemisphere in 1987 showed denitrification outside the vortex ranging up to 32% and averaging 20% above Theta = 400 K. (3) Below Theta = 400 K the southern hemisphere showed enhancements of F(NO(y)) relative to the northern hemisphere in 1991-1992 ranging up to 200% at Theta = 375 K, outside the vortex. Corresponding profiles of residual water, R(H2O) = H2O - 2(1.6 - CH4), are considered and shown to be consistent with those of F(NO(y)) in the sense that they show deficits outside the Antarctic vortex, which was both dehydrated and denitrified, but not outside the 1988-1989 Arctic vortex, which was denitrified but not dehydrated. R(H2O) is the water content of stratospheric air with the contribution from methane oxidation subtracted. Comparison of F(NO(y)) and R(H2O) below 400 K outside the Antarctic vortex leads to the suggetion that dehydration in the Antarctic vortex occurs by the sedimentation of ice crystals large enough to fall out of the stratosphere, whereas denitrification occurs mainly on mixed nitric acid-water crystals which evaporate below the base of the vortex at Theta = 400 K but above the tropopause.

Tuck, A. F.↗

Spring dehydration in the Antarctic stratospheric vortex observed by HALOE

The distribution of dehydrated air in the middle and lower stratosphere during the 1992 Southern Hemisphere spring is investigated using Halogen Occultation Experiment (HALOE) observations and trajectory techniques. Comparisons between previously published Version 9 and the improved Version 16 retrievals on the 700-K isentropic surface show very slight (0.05 ppmv) increases in Version 16 CH4 relative to Version 9 within the polar vortex. Version 16 H2O mixing ratios show a reduction of 0.5 ppmv relative to Version 9 within the polar night jet and a reduction of nearly 1.0 ppmv in middle latitudes when compared to Version 9. The version 16 HALOE retrievals show low mixing ratios of total hydrogen (2CH4 + H2O) within the polar vortex on both 700 and 425 K isentropic surfaces relative to typical middle-stratospheric 2CH4 + H2O mixing ratios. The low 2CH4 + H2O mixing ratios are associated with dehydration. Slight reductions in total hydrogen, relative to typical middle-stratospheric values, are found at these levels throughout the Southern Hemisphere during this period. Trajectory calculations show that middle-latitude air masses are composed of a mixture of air from within the polar night jet and air from middle latitudes. A strong kinematic barrier to large-scale exchange is found on the poleward flank of the polar night jet at 700 K. A much weaker kinematic barrier is found at 425 K. The impact of the finite tangent pathlength of the HALOE measurements is investigated using an idealized tracer distribution. This experiment suggests that HALOE should be able to resolve the kinematic barrier, if it exists.

Pierce, R. Bradley↗

An examination of the total hydrogen budget of the lower stratosphere

We analyze the hydrogen budget of the lower stratosphere using simultaneous in situ measurements of northern hemispheric water vapor (H2O) and methane (CH4) obtained during the spring Stratospheric Photochemistry, Aerosols, and Dynamics Expedition (SPADE), as well as previously published in situ H2 data. Based on this data, we conclude that approximately two H2O molecules are produced for each CH4 molecule destroyed. This implies that H2 production from CH4 oxidation is balanced by H2 oxidation. The uncertainty in this analysis is greatly reduced by the use of multiple data sets. Additionally, we infer that, on an annual and global average, H2O enters the stratosphere with a mixing ratio of 4.2 +/- 0.5 ppmv, and that the quasi-conserved quantity 2 x CH4 + H2O has a value of 7.6 +/- 0.6 ppmv in these northern hemishere air parcels (where xi denotes the mixing ratio of the constituent xi).

Dessler, A. E.↗

New narrow infrared absorption features in the spectrum of Io between 3600 and 3100 cm (2.8-3.2 micrometers)

We report the discovery of a series of infrared absorption bands between 3600 and 3100/cm (2.8-3.2 micrometers) in the spectrum of Io. Individual narrow bands are detected at 3553, 3514.5, 3438, 3423, 3411.5, and 3401/cm (2.815, 2.845, 2.909, 2.921, 2.931, and 2.940 micrometers, respectively). The positions and relative strengths of these bands, and the difference of their absolute strengths between the leading and trailing faces of Io, indicate that they are due to SO2. The band at 3438/cm (2.909 micrometers) could potentially have a contribution from an additional molecular species. The existence of these bands in the spectrum of Io indicates that a substantial fraction of the SO2 on Io must reside in transparent ices having relatively large crystal sizes. The decrease in the continuum observed at the high frequency ends of the spectra is probably due to the low frequency side of the recently detected, strong 3590/cm (2.79 micrometer) feature. This band is likely due to the combination of a moderately strong SO2 band and an additional absorption from another molecular species, perhaps H2O isolated in SO2 at low concentrations. A broad (FWHM approximately = 40-60/cm), weak band is seen near 3160/cm (3.16 micrometers) and is consistent with the presence of small quantities of H2O isolated in SO2-rich ices. There is no evidence in the spectra for the presence of H2O vapor on Io. Thus, the spectra presented here neither provide unequivocal evidence for the presence of H2O on Io nor preclude it at the low concentrations suggested by past studies.

Sandford, Scott A.↗

The detection of a new strong band near 3590 cm(exp -1) (2.79 microns) in the spectrum of Io

A strong absorption band at 3590 +/- 20 cm(exp -1) (2.790 +/- 0.015 microns) has been discovered in the spectrum of Io using the Kuiper Airborne Observatory (KAO). The 2 nu(sub 1) + nu(sub 3) combination mode of solid SO2 falls at this position. Since SO2 is abundant on Io it must contribute to the new band. However, a band due to H2O was also predicted near this frequency in Io's spectrum based on laboratory experiments of H2O:SO2 mixed Io ice analogs which were used to assign the two weak, variable features at 3370 and 3170 cm(exp -1) (2.97 and 3.15 microns) to trace amounts of H2O frozen in solid SO2 on Io. The new band probably originates from both SO2 and H2O. Unfortunately, the spectral resolution of the data is insufficient to settle the issue of whether or not there are two resolvable components.

Salama, F.↗

Planetesimal Formation in the Outer Solar Nebula

A numerical investigation of the orbital trajectories of individual particles in the turbulent outer solar nebula has been performed. The (spherical) particle consists of an unchanging mm-sized 'dust' core surrounded by an H2O ice mantle; the density of both core and mantle is 0.5 g/cm(exp 3). The simulations include the effects of H2O condensation from the gas phase, H2O sublimation from the particle surface, and collisional growth via particle collisions with a background distribution of small H2O grains. The model nebula is an azimuthally symmetric minimum-mass nebula of solar composition with a vertical (and radial) temperature gradient. Particle evolution follows a pattern. A particle starting out in a cool region grows via condensation and collisional accretion until it is large enough (decimeter- to meter-sized) to decouple somewhat from the turbulence. (This growth occurs on a timescale of several thousand years at 10 AU; at 30 AU, the timescale is approx. 104 years.) The particle then moves rapidly inward toward the sun due to secular gas drag forces, sublimates much of its icy mantle, and slows its inward migration as it gets caught up in the turbulence again (due to its now-smaller size) at the 'sublimation boundary,' where the ambient gas temperature is approx. 150 K. Such a process could, on a short timescale (i.e., a timescale much shorter than the nebular gas lifetime of approx. 106 yr), generate a population of decimeter- to meter-sized bodies which would then collisionally accrete to form planetesimals.

Supulver, K. D.↗

A 2000 Solar Mass Rotating Molecular Disk Around NGC 6334A

We present millimeter and centimeter wave spectroscopic observations of the H II region NGC 6334A. We have mapped the source in several transitions of CO, CS, and NH3. The molecular emission shows a distinct flattened structure in the east-west direction. This structure is probably a thick molecular disk or torus (2.2 x 0.9 pc) responsible for the bipolarity of the near-infrared (NIR) and radio continuum emission which extends in two "lobes" to the north and south of the shell-like H II region. The molecular disk is rotating from west to east (omega approximately equals 2.4 km/s.pc) about an axis approximately parallel to the radio and NIR emission lobes. By assuming virial equilibrium, we find that the molecular disk contains approximately 2000 solar mass. Single-component gas excitation model calculations show that the molecular gas in the disk is warmer and denser (T(sub k) approximately equals 60 K, n approximately equals 3000/cc) than the gas to the north and south (T(sub k) approximately equals 50 K, n approximately equals 400/cc). High resolution (approximately 5 sec) NH3 (3, 3) images of NGC 6334A reveal several small (approximately 0.1 pc) clumps, one of which lies southwest of the radio continuum shell, and is spatially coincident with a near-infrared source, IRS 20. A second NH3 clump is coincident with an H2O maser and the center of a molecular outflow. The dense gas tracers, CS J = 5 approaches 4 and 7 approaches 6, peak near IRS 20 and the H2O maser, not at NGC 6334A. IRS 20 has a substantial far-infrared (FIR) luminosity L(sub FIR) approximately 10(exp 5) solar luminosity, which indicates the presence of an O 7.5 star but has no detected radio continuum (F(sub 6 cm) < 0.02 Jy). The combination of dense gas, a large FIR luminosity and a lack of radio continuum can best be explained if IRS 20 is a protostar. A third clump of NH3 emission lies to the west of IRS 20 but is not associated with any other molecular or continuum features. The star formation activity in the region has moved west of NGC 6334A to IRS 20 and the H2O maser position. We suggest that NGC 6334A, IRS 20, and the H2O maser spot are part of a "protocluster" of stars which is condensing from the massive molecular disk. The similarity between the structure around NGC 6334A and other large (r approximately 1 pc), massive (M approximately 10(exp 3) solar mass), rotating disks (K3-50A and G10.6-0.4) suggests that this may be a common mechanism by which open clusters form.

Kraemer, Kathleen E.↗

Kinetic Requirements for the Measurement of Mesospheric Water Vapor at 6.8 (microns) under Non-LTE Conditions

We present accuracy requirements for specific kinetic parameters used to calculate the populations and vibrational temperatures of the H2O(010) and H2O(020) states in the terrestrial mesosphere. The requirements are based on rigorous simulations of the retrieval of mesospheric water vapor profiles from measurements of water vapor infrared emission made by limb scanning instruments on orbiting satellites. Major improvements in the rate constants that describe vibration-to- vibration exchange between the H2O(010) and 02(1) states are required in addition to improved specification of the rate of quenching Of O2(1) by atomic oxygen (0). It is also necessary to more accurately determine the yield of vibrationally excited O2(l) resulting from ozone photolysis. A contemporary measurement of the rate of quenching of H2O(010) by N2 and O2 is also desirable. These rates are either highly uncertain or have never before been measured at atmospheric temperatures. The suggested improvements are necessary for the interpretation of water vapor emission measurements at 6.8 microns to be made from a new spaceflight experiment in less than 2 years. The approach to retrieving water vapor under non-LTE conditions is also presented.

Zhou, Daniel K.↗